WO2005027861A1 - Agents for reducing scalp coloring during hair coloring processes - Google Patents

Abstract

The invention relates to agents which are used to pre-treat the scalp prior to a hair coloring process in order reduce coloring of the scalp, comprising at least one component from the group of physiologically compatible hydroxy carbolic acids, inorganic and organic reducing agents, quaternary ammonium compounds, amphoteric or zwitterionic surfactants, non-volatile silicon compounds, active anti-dandruff ingredients and/or from mixtures of said compounds and/or from the physiologically compatible salts of said compounds. Pre-treatment of the scalp and/or hair contours with said agents results in subsequent hair coloring with intensive and/or deep shades, wherein the scalp and the hair contours are not at all colored or are only slightly colored.

Description

 "Means for reducing scalp staining in hair dyeing processes"

The invention relates to an agent for treating the scalp, a method for pretreating the scalp and the use of special components for pretreating the scalp before a hair coloring process.

It also relates to a kit that contains a scalp pretreatment agent and a hair dye in two separate packages.

Today human hair is treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with dyes, tinting agents, waving agents and styling preparations. Means for changing or shading the color of the head hair play an outstanding role.

Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally sensitive to shampooing, so that a frequently undesirable shift in shades or even a visible "discoloration" can occur.

So-called oxidation dyes are used for permanent, intensive dyeings with appropriate fastness properties. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components. The oxidation coloring agents are characterized by excellent, long-lasting coloring results. Finally, another dyeing process has received great attention. In this process, precursors of the natural hair dye melanin are applied to the hair; These then form naturally analogous dyes in the hair as part of oxidative processes. Such a process with 5,6-dihydroxyindoline as a dye precursor was described in EP-B 1-530 229. When using agents with 5,6-dihydroxyindoline, in particular several times, it is possible for people with gray hair to reproduce the natural hair color. Coloring can take place with atmospheric oxygen as the only oxidizing agent, so that no further oxidizing agents have to be used. In people with originally medium blonde to brown hair, indoline can be used as the sole dye precursor. For use with people with originally red and in particular dark to black hair color, on the other hand, satisfactory results can often only be achieved by using additional dye components, in particular special oxidation dye precursors.

Another way to dye keratin-containing fibers is to use dyes that are a combination of components

A reactive carbonyl compounds, ie compounds with at least one reactive carbonyl group, and component B compounds selected from (a) CH-acidic compounds, (b) compounds with primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic Compounds and aromatic hydroxy compounds, (c) amino acids, (d) oligopeptides composed of 2 to 9 amino acids. The above-mentioned components A and B are generally not themselves dyes and are therefore not suitable for dyeing keratin fibers on their own. In combination, they form dyes in a non-oxidative process. Corresponding oxidation dye precursors of the developer and / or coupler type with or without the use of an oxidizing agent can, however, also be used among compounds of component B. This dyeing method (hereinafter called oxo dyeing) can thus be easily combined with the oxidative dyeing system. Components A and B are referred to below as oxo dye precursors. The oxo dyeing is described, for example, in the publications WO-A1-99 / 18916, WO-A1 -00/38638, WO-A1 -01/34106 and WO-A1 -01/47483.

The publications WO-A2-99 / 18916 and WO-A1 -01/47483 disclose the use of onium aldehydes and ketones, in particular 2- or 4-formyl-1-methylquinolinium compounds, for dyeing keratin-containing fibers in combination with compounds having a primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, and / or CH-active compounds.

The problem with temporary as well as permanent, oxidative or non-oxidative hair coloring is the coloring of the scalp, which often goes hand in hand with the coloring of the hair and is perceived as bothersome and unacceptable. This problem is particularly common among non-experienced consumers who want to dye their hair at home. But even the experienced hairdresser can often not avoid scalp staining, especially in the case of intensive and deep color tints, which leads to customer dissatisfaction, as it were.

There has therefore long been a need for an agent or method that is simple to use and with which the coloring of the scalp is avoided or at least reduced.

DE-A1-100 28 723 discloses a hair dyeing method in which the scalp and the hair contour area are first treated with a water-in-oil emulsion based on an oil component and a nonionic emulsifier to reduce scalp staining. The hair dye product is then applied to the hair. After a usual exposure time for hair coloring, the hair is washed thoroughly. In DE-A1-100 56 266 the W / O-emulsion according to DE-A1 -10028723 also includes a volatile silicone.

WO-A1 -96 / 18379 discloses a cosmetic and dermatological agent which contains at least one compound from the group of the flavonoids to protect the skin and hair from oxidative stress.

The subject of this application is an agent for "pretreating the scalp before a hair dyeing process which, in order to reduce the color of the scalp, comprises at least one component from the group of physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary ammonium compounds, amphoteric or zwitterionic surfactants, non-volatile silicone compounds, Contains office scale agents and / or from mixtures of these compounds and / or from the physiologically tolerable salts of these compounds.

The pretreatment of the scalp and hair with these agents has led in many attempts to a strong reduction in the scalp coloration in the case of color-intensive dyeings and in many cases to avoid the scalp coloration in the case of less color-intensive dyeings.

Hydroxycarboxylic acids and salts of hydroxycarboxylic acids in the context of the invention are lactic acid, mandelic acid, malic acid, tartaric acid, citric acid, salicylic acid and the salts of these acids.

It can be preferred according to the invention that the agents additionally have a physiologically tolerable content of aldonic acid, malonic acid, phosphonic acid, sulfonic acid, hydrochloric acid, phosphoric acid, dihydrogphosphate and oxydicarboxylic acids from monosaccharides such as glucose, mannose, galactose or the physiologically tolerable salts of these acids. Physiologically acceptable salts are to be understood as alkali and alkaline earth and ammonium salts.

The hydroxycarboxylic acids and / or the hydroxycarboxylic acid salts are usually used in the agents according to the invention in an amount of 0.05 to 10% by weight, based on the total weight of the agent. A total content of the acid or salt component in the range from 0.1 to 8% by weight, in particular in the range from 0.5 to 5% by weight, is preferred.

In a first preferred embodiment of the invention, the agents contain sodium salicylate.

Inorganic and organic reducing agents in the context of the invention include the compounds sodium metabisulfite, sodium dithionite, sodium salts of hydroxymethanesulfonic acid, the sulfinic acid derivatives listed in documents WO 02/039965 AI, WO 02 / 030369A1 and WO 02/015855, thiols such as cysteine, N-acetylcysteine, Cysteamine, the reduced form of glutathione, ascorbic acid, isoascorbic acid, 2,3-dihydroxy-2-cyclopenten-l-one or 6-0-palmitoyl ascorbate understood.

The inorganic reducing agents are usually used in the agents according to the invention in an amount of 0.05 to 10% by weight, preferably in an amount of 1 to 5% by weight, in each case based on the total weight of the agent.

In a second preferred embodiment of the invention, the agents contain ascorbic acid or isoascorbic acid.

Quaternary ammonium compounds in the sense of the invention can be selected from cationic polymers with quaternary ammonium group and from cationic surfactants with quaternary ammonium group. Cationic polymers suitable according to the invention are those under the INCI names Polyquaternium-2, Polyquaternium-4, Polyquaternium-6, Polyquaternium-7, Polyquaternium-10, Polyquaternium-11, Polyquaternium-16, Polyquaternium-22, Polyquaternium-28, Polyquatemium-29 , Polyquaternium-32, Polyquaternium-37, Polyquaternium-44, available polymers.

The cationic polymers are usually used in the agents according to the invention in an amount of 0.1 to 5% by weight, preferably in an amount of 0.1-3% by weight, in each case based on the total weight of the agent.

Cationic surfactants suitable according to the invention are cationic surfactants of the quaternary ammonium compound, esterquat and amidoamine type. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltriethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylarmnonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylarrimonium chloride, as well as the compounds known under the INCI names Quatemium-27 and Quatemium-83 imidazolium. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU 35 are examples of such esterquats.

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

The Linoleamidopropyl PG-Dimonium Chloride Phosphate, which is sold under the trade name Phospholipid EVA ^® (Uniqema) is a preferably used in the inventive compositions cationic surfactant.

In a third preferred embodiment of the invention, the agents contain linoleamidopropyl PG-dimonium chloride phosphates, alkyltrimethylammonium halides, dialkyldimethylammonium halides, trialkylmethylammonium halides or esterquats.

Preferred halides for the purposes of the invention are understood to mean chlorides and bromides; the chlorides are particularly preferred.

The cationic surfactants are preferably present in the agents according to the invention in amounts of 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight are particularly preferred.

Amphoteric or zwitterionic surfactants which are suitable according to the invention are selected from surface-active compounds which, in addition to a C ₈ -C ₂₄ -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SOaH group in the molecule and to form internal salts are qualified. Examples of suitable ampholytic or zwitterionic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N- Alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid, alkylaminoacetic acids and acylaminoalkylbetaines, each with about 8 to 24 carbon atoms in the alkyl group. Particularly preferred ampholytic or zwitterionic surfactants are the N-cocoalkylaminopropionate and dipropionate, the cocoacylaminoethylamino propionate, the C ₂ -Ciβ-acyl sarcosine and the cocoamidopropyl betaine.

In a fourth preferred embodiment of the invention, the agents contain cocoamphodipropionate or cocoamidopropylbetaine.

The amphoteric or zwitterionic surfactants are preferably present in the agents according to the invention in amounts of 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight are particularly preferred.

The non-volatile silicones suitable according to the invention are water-soluble surfactants based on silicone. In a preferred embodiment, these are nonionic.

Particularly preferred water-soluble surfactants based on silicone are selected from the group of dimethicone copolyols which are preferably alkoxylated, in particular polyethoxylated and / or polypropoxylated.

The water-soluble silicone surfactant is used in the compositions according to the invention in an amount of 0.01 to 10% by weight, in particular in an amount of 0.1 to 5% by weight.

Dimethicone copolyols are understood according to the invention to mean polyoxyalkylene-modified dimethylpolysiloxanes of the general formulas I or II: (I)

R'-Si- [OSi (CH ₃ ) ₂ ] _χ - (OC ₂ H ₄ ) _a - (OC ₃ H ₆ ) _b -OR '] ₃ (II)

wherein

the radical R can represent a hydrogen atom, an alkyl group with 1 to 12 C atoms, an alkoxy group with 1 to 12 C atoms or a hydroxyl group,

the radicals R 'and R "stand for alkyl groups with 1 to 12 carbon atoms,

x represents an integer from 1 to 100, preferably from 20 to 30,

- Y represents an integer from 1 to 20, preferably from 2 to 10, and

a and b are integers from 0 to 50, preferably from 10 to 30.

Compounds that fall within the above formulas are disclosed in the following explicitly referenced patent applications: US-A-4, 122,029; US-A-4,265,878; US-A-4,421, 769 and GB-A-2,066,659.

Particularly preferred dimethicone copolyols for the purposes of the invention are, for example, the products sold commercially under the trade names SILWET (Union Carbide Corporation) and DOW CORNING (Dow).

Dow Corning 190 and Dow Corning 193 are particularly preferred dimethicone copolyols according to the invention.

Antidandruff active substances which are suitable according to the invention are, for example, elementary colloidal sulfur, zinc pyridinthione and those of the Tradenames available from Octopirox and Climbazol. However, antidandruff agents based on natural substances, for example extracts from arnica, birch, burdock root, beard lichen, poplar, nettle and walnut shells can also be used according to the invention.

The antidandruff active ingredients are usually used in the agents according to the invention in a concentration of 0.05-5% by weight, preferably in a concentration of 0.1-2% by weight and in particular 0.15-1% by weight.

In a fifth preferred embodiment of the invention, the agents contain at least two components from the group of the physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary ammonium compounds, amphoteric or zwitterionic surfactants, non-volatile silicone compounds, antidandruff agents and / or mixtures of these compounds and / or from the physiologically tolerable salts of these compounds.

For the treatment of the scalp, the agents according to the invention can preferably be formulated in an aqueous or aqueous-alcoholic base. Lower alcohols such as ethanol and isopropanol are particularly suitable as alcohols. Aqueous-alcoholic bases can contain water-alcohol, preferably in a ratio of 1: 5 to 5: 1. A preferred aqueous-alcoholic base has an alcohol content of up to 15% by weight, based on the amount of water.

In a sixth preferred embodiment of the invention, the agents according to the invention are therefore formulated for treating the scalp as aqueous or aqueous-alcoholic agents.

Thickened formulations have proven to be particularly effective for the treatment of the hair contour area, since they adhere well to the skin and thus do not get into the eyes of the user. In a seventh preferred embodiment of the invention, the agents according to the invention are therefore formulated as thickened agents for treating the hair contour area.

To produce the agents thickened according to the invention, these consistency regulators and / or thickeners are added.

Suitable consistency agents are primarily fatty alcohols or hydroxyfatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxyfatty acids. A combination of these substances with alkyl oligoglucosides and or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred.

Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also hearing molecules

Polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (eg Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as, for example, pentaerythritol or trimethylolpropane with fatty alcohol narrow homolog distribution or alkyl oligoglucosides as well as electrolytes such as table salt and ammonium chloride.

The thickeners are usually used in a concentration of 0.1-10% by weight, preferably in a concentration of 0.2-5% by weight and in particular 0.3-2% by weight, in the agents according to the invention.

The agents according to the invention have a pH in the range of 0-10, preferably in the range of 0.5-7 and in particular in the range of 1-6. The pretreatment of the scalp and the hair contour area with the agents according to the invention is particularly useful and necessary if the hair is to be colored with deep and intense oxidative, direct or natural dyes. To prevent scalp staining, the agents can also be used prophylactically before each hair coloring.

The term dyeing process includes all processes known to the person skilled in the art, in which a dye is applied to the optionally moistened hair and either left on the hair for a period of between a few minutes and about 45 minutes and then rinsed out with water or a surfactant-containing agent or is left entirely on the hair. In this context, reference is expressly made to the known monographs, e.g. Kh. Schrader, Fundamentals and Recipes of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referring to the corresponding knowledge of the expert.

The composition of the colorants or tints is not subject to any fundamental restrictions.

Can as a dye (intermediate)

• natural and synthetic direct dyes

Oxidation dye precursors of the developer and coupler type,

• Precursors of nature-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives of one or more of these groups are used.

So-called reactive carbonyl compounds and the addition products of these compounds and The direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those with the international names 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 1 , 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- (ß-hydroxyethyl) -amino-2-nitrobenzene, 3-nitro-4- (ß-hydroxyethyl) aminophenol, 2- ( 2'-hydroxyethyl) amino-4,6-dinitrophenol, 1 - (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, l-amino-4- (2'-hydroxyethyl) amino-5-chloro 2-nitrobenzene, 4-amino-3-nitrophenol, 1 - (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, 6- Nitro-1, 2,3, 4-tetrahydroquinoxaline, 2-hydroxy-l, 4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2 -Chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Cationic direct dyes can also be used. Particular preference is given to (a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, (b) aromatic systems which are substituted by a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as (c) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as described, for example, in EP-A2-998 908, at this point explicit reference is made to claims 6 to 11.

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

CH3SO4^" (DZ1)

CH3SO4 ^" (DZ1)

er (DZ2)

he (DZ2)

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

Examples of developer type oxidation dye precursors are p-phenylenediamine derivatives or one of its physiologically tolerable salts. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

in which

- G ¹ represents a hydrogen atom, a d- to C ₄ -alkyl radical, a C-ι- to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C-ι- to C ₄ ) alkoxy - (Cr to C ₄ ) alkyl, a 4'-aminophenyl or a C ₁ - to C ₄ alkyl which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl group;

- G ² represents a hydrogen atom, a C to C ₄ alkyl radical, a C 1 -C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C1 to C ₄ ) alkoxy (i.e. - to C ₄ ) -alkyl radical or a C to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C to C ₄ alkyl radical, a C to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Cr to C ₄ hydroxyalkoxy radical, a C to C ₄ acetylaminoalkoxy radical, a C to C ₄ mesylaminoalkoxy radical or a C ₁ to C ₄ carbamoylaminoalkoxy radical;

G ⁴ represents a hydrogen atom, a halogen atom or a Cr to C ₄ alkyl radical or - If G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo group, such as an ethylenedioxy group.

Examples of the C 1 -C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Cr to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a Cr to C ₄ - hydroxyalkyl group are 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. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, Cr to C ₄ monoalkylamino groups, Cr to C ₄ dialkylamino groups, Cr to C ₄ trialkylammonium groups, Cr 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- (ß-hydroxyethyl) -amino-2-chloroaniline, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) -p-phenylenediamine, 2 -Fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N , N- (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N- (ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'- Aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-hydroxyethyloxy) -p-phenylenediamine, 2- (ß-acetylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically tolerable salts.

P-Phenylenediamine derivatives of the formula (E1) which are particularly preferred according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N -Bis- (ß-hydroxyethyl) -p-phenylenediamine.

It can also 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 coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:

wobei:

in which:

- Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a Cr to C ₄ alkyl radical, by a C to C ₄ hydroxyalkyl radical and / or by a bridging Y or which is optionally Is part of a bridging ring system, - The bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be and may be substituted by one or more hydroxyl or C to Cβ alkoxy groups, or a direct bond,

- G ⁵ and G ⁶ are each independently a hydrogen or halogen atom, a Cr to C ₄ alkyl group, a Cr to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C _\ - C ₄ - aminoalkyl radical or a direct connection to the bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridging Y or a C 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 the formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred dinuclear 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 (ß-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis - (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methyl-aminophenyl) tetramethylene diamine, N.N'-diethyl-N.N ' bis - ^ '- amino-S'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-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 tolerable salts.

Very particularly preferred dinuclear 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 tolerable salts.

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

wobei:

in which:

- G ¹³ represents a hydrogen atom, a halogen atom, a C to C ₄ alkyl radical, a C to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Cr to C ₄ ) alkoxy (C to C) alkyl group, a Cr to C ₄ aminoalkyl radical, a hydroxy (d- alkylamino-C), a Cr to C ₄ -Hydroxyalkoxyrest, a Cr to C ₄ - aminoalkyl hydroxyalkyl (Crbis C) or ( di- C to C ₄ alkylamino) - (d-C) alkyl, and

- G ¹⁴ represents a hydrogen or halogen atom, a Cr to C ₄ alkyl radical, a d to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Cr to C ₄ ) alkoxy (Cr to C ₄ ) alkyl, a C to C ₄ aminoalkyl or a C to C ₄ cyanoalkyl, G ¹⁵ represents hydrogen, a Cr to C alkyl radical, a C to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

- G ¹⁶ represents hydrogen or a halogen atom.

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

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

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

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

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

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

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

Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4.5 - diamino-1-methylpyrazole, 4,5-diamino-1- (ß-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 - (ß-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-isopropylipyrazole, 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- (ß-hydroxyethyl) -amino- 1-methylpyrazole.

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

in which:

- G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a Cr to C ₄ alkyl radical, an aryl radical, a Cr to C ₄ hydroxyalkyl radical, a C ₂ to d polyhydroxyalkyl radical a ( d- to C4) -alkoxy- (Cr to C ₄ ) - alkyl radical, a Cr to C ₄ -aminoalkyl radical, which can optionally be protected by an acetyl-ureide or a sulfonyl radical, a (Cr to C ₄ ) - Alkylamino- (Cr to C ₄ ) -alkyl radical, a di - [(Cr to C ₄ ) -alkyl] - (Cr to C ₄ ) -aminoalkyl radical, the dialkyl radicals optionally being a carbon cycle or a heterocycle with 5 or 6 chain links form a Cr to C ₄ - hydroxyalkyl or a di (Cr to C4) - [hydroxyalkyl] - (Cr to C4) - aminoalkyl radical,

- The X radicals independently of one another represent a hydrogen atom, ad- to C ₄ -alkyl radical, an aryl radical, a Cr to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a Cr to C ₄ - Aminoalkyl radical, a (Cr to C) alkylamino (Cr to C ₄ ) alkyl radical, a di - [(d to C ₄ ) alkyl] - (d to C ₄ ) aminoalkyl radical, the dialkyl radicals optionally a carbocycle or a heterocycle with 5 or 6 chain members, form a d- to C ₄ - hydroxyalkyl or a di- (d- d-up hydroxyalky aminoalkyl group, an amino group, a d- to C ₄ -alkyl- or di- (Cr 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 has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7); - if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7).

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

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

Among the pyrazolo [1, 5-a] pyrimidines of the formula (E4) above, one can mention 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-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino-pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino-pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino-pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol; 2- (7-amino-pyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) 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-dimethyl-pyrazolo [1,5-a] pyrimidine; as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.

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

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

Derivatives of 5,6-dihydroxyindoline of the formula purple are particularly well suited as precursors of naturally analogous hair dyes,

la) in der unabhängig voneinander

la) in the independently of each other

R ¹ represents hydrogen, a dd-alkyl group or a dd-hydroxyalkyl group,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,

R ³ represents hydrogen or a dd-alkyl group,

- R ⁴ stands for hydrogen, a dd-alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a dd-alkyl group, and

, R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid. Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5 , 6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and the 6-hydroxyindoline, the 6-aminoindoline and the 4-aminoindoline.

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

Derivatives of 5,6-dihydroxyindole of the formula IIIb are furthermore outstandingly suitable as precursors of nature-analogous hair dyes,

in der unabhängig voneinander R¹ steht für Wasserstoff, eine d-d-Alkylgruppe oder eine Crd-Hydroxyalkyl- gruppe,

in which R ¹ is independently hydrogen, a dd-alkyl group or a Crd-hydroxyalkyl group,

R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,

R ³ represents hydrogen or a dd-alkyl group,

- R ⁴ stands for hydrogen, a dd-alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a dd-alkyl group, and

R ⁵ stands for one of the groups mentioned under R ⁴ ,

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

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

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

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

Oxidation dye precursors of the coupler type which are preferred according to the invention

- m-Aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl -3-aminophenol, 3- trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino -2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3 - aminophenol,

o-aminophenol and its derivatives,

- m-Diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1, 3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene , 1, 3-bis (2 ', 4'-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,

o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene, di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5- Dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1, 2,4-trihydroxybenzene,

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

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

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

Quinoxaline derivatives such as 6-methyl-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.

Coupling components which are particularly preferred 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-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

Furthermore, the agents according to the invention can also contain naturally occurring dyes such as those in, for example, henna red, henna neutral, henna black, Chamomile flower, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root are included.

It is not necessary that the oxidation dye precursors or the direct dyes each represent uniform compounds. Rather, the coloring agents used may, due to the manufacturing processes for the individual dyes, contain minor components in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.

Reactive carbonyl compounds according to the invention as an oxo dye precursor of component A have at least one carbonyl group as a reactive group, which reacts with component B to form a covalent bond. Furthermore, compounds according to the invention can also be used as reactive carbonyl compounds in which the reactive carbonyl group is derivatized in such a way that the reactivity of the carbon atom of the derivatized carbonyl group with component B is always present. These derivatives are preferably addition compounds of a) amines and their derivatives to form hinen or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound to the carbon atom of the carbonyl group of the reactive carbonyl compound and c) of water to form hydrates.

The reactive carbonyl compound is preferably selected from compounds according to formula IV,

in which AR stands for benzene, naphthalene, pyridine, pyrimidine, pyrazine, pyridazine, carbazole, pyrrole, pyrazole, furan, thiophene, 1, 2,3-triazine, 1, 3,5-triazine, quinoline, isoquinoline, indole, indoline, Indolizine, indan, imidazole, 1, 2,4-triazole, 1, 2,3-triazole, tetrazole, benzimidazole, 1, 3-thiazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, quinolizine, cinnoline, acridine, julolidine, Acenaphthene, fluorene, biphenyl, diphenylmethane, benzophenone, diphenyl ether, azobenzene, chromone, coumarin, diphenylamine, stilbene, where the N-heteroaromatics can also be quaternized,

R ¹ represents a hydrogen atom, a dC _θ -alkyl, C ₂ -C ₆ -acyl, C ₂ -d-alkenyl, Crd-perfluoroalkyl, an optionally substituted aryl or heteroaryl group,

• R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a halogen atom, a CrC ₆ -alkyl, CrC ₆ -alkoxy, CrC ₆ -aminoalkyl, CrC ₆ - hydroxyalkyl group, a d-Ce-alkoxy- -C _ö alkyloxy group, a d-Cβ- acyl group, an acetyl, carboxyl, carboxylato, carbamoyl, sulfo, sulfato, sulfonamide, sulfonamido, C ₂ -C ₆ alkenyl, an aryl, an aryl-CrCβ-alkyl group, a hydroxy, a nitro, a pyrrolidino, a morpholino, a piperidino, an amino or ammonio or a 1-imidazole (in) io group, the last three groups with one or more CrCβ-alky!, CrCβ-carboxyalkyl, d-Cβ-hydroxyalkyl, C ₂ -C ₆ alkenyl, CrC ₆ alkoxy-CrC ₆ alkyl-, with optionally substituted benzyl groups, with sulfo- (CrC ₄ ) alkyl or heterocycle (CrC ₄ ) alkyl groups can be substituted, with two of the radicals from R ² , R ³ , R ⁴ and -ZYR ¹ together with the rest of the molecule forming a fused, optionally substituted 5-, 6th - or 7-ring, de r can likewise carry a fused aromatic ring, the system AR being able to carry, depending on the size of the ring, further substituents which, independently of one another, can represent the same groups as R ² , R ³ and R ⁴ ,

• Z represents a direct bond, a carbonyl, a carboxy (CrC ₄ ) alkylene, an optionally substituted C ₂ -C ₆ alkenylene, dC _δ alkadienylene, furylene, thienylene, arylene, Vinylene arylene, vinylene furylene, vinyl thienylene group, where Z together with the -YR ¹ group can also form an optionally substituted 5-, 6- or 7-ring, • Y stands for a group which is selected from carbonyl, a group according to formula V and a group according to formula \ / ι

wobei • R⁵ steht für ein Wasserstoffatom, eine Hydroxygrappe, eine CrC₄-Alkoxygmppe, eine CrC₆-Alkylgruppe, eine CrC₆-Hydroxyalkylgruppe, eine C₂-C₆- Polyhydroxyalkylgruppe, eine CrC₆-Alkoxy-CrC₆-alkylgmppe, • R und R stehen unabängig voneinander für eine CrC₆-Alkylgruppe, eine Arylgruppe oder bilden zusammen mit dem Strukturelement O-C-O der Formel IV einen 5- oder 6-gliederigen Ring.

where • R ⁵ represents a hydrogen atom, a hydroxy group, a CrC ₄ alkoxy group, a CrC ₆ alkyl group, a CrC ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a CrC ₆ alkoxy-CrC ₆ alkyl group, • R and R independently of one another represent a CrC ₆ -alkyl group, an aryl group or together with the structural element OCO of the formula IV form a 5- or 6-membered ring.

The reactive carbonyl compound is particularly preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-

Hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5- Trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone-diethyl ketal, 4-hydroxy-3-methoxyacetophenone, 3, 5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromoacetophenone, 4-hydroxy-3-nitroacetophenone carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4- Trihydroxybenzophenone, 2-hydroxy-l-acetonaphthon, l-hydroxy-2-acetonaphthon, chromon, chromon-2-carboxylic acid, flavon, 3-hydroxyflavon, 3,5,7-trihydroxyflav on, 4 ', 5,7-trihydroxyflavon, 5,6,7-trihydroxyflavon, quercetin, 1-indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3 -Methoxybenzaldehyde, 4- Methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-

Ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxy-benzaldehyde, 4-hydroxy-2,6-dimethoxy-benzaldehyde, 4-hydroxy-2-methyl-benzaldehyde, 4- Hydroxy-3-methyl-benzaldehyde, 4-hydroxy-2,3-dimethyl-benzaldehyde, 4-hydroxy-2,5-dimethyl-benzaldehyde, 4-hydroxy-2,6-dimethyl-benzaldehyde, 4-hydroxy-3, 5-dimethoxy-benzaldehyde, 4-hydroxy-3,5-dimethyl-benzaldehyde, 3,5-diethoxy-4-hydroxy-benzaldehyde, 2,6-diethoxy-4-hydroxy-benzaldehyde, 3-hydroxy-4-methoxy benzaldehyde, 2-hydroxy-4-methoxy-benzaldehyde, 2-ethoxy-4-hydroxy-benzaldehyde, 3-ethoxy-4-hydroxy-benzaldehyde, 4-ethoxy-2-hydroxy-benzaldehyde, 4-ethoxy-3-hydroxy- benzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-

Dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6- Trimethoxybenzaldehyde, 2,4,5-

Trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4- Dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3, 6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2, 5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholino-benzaldehyde 4- piperidinobenzaldehyde, 2-methoxy-l-naphthaldehyde, 4-methoxy-l-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-Hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimetho xy-l -naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4-dimethylamino cinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4- Diethylamino-cinnamaldehyde, 4-dibutylamino-benzaldehyde, 4-diphenylamino-benzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (l-imidazolyl) -benzaldehyde, piperonal, 2,3,6,7-tetrahydro-lH, 5H- benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene 1,3,3-trimethylindoline (Fi schers aldehyde or tribase aldehyde),

2-indolealdehyde, 3-indolealdehyde, l-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, l-methyl-3-acetylindole, 2- ^(l,, 3 ', 3'-trimethyl-2-indolinylidene) acetaldehyde, l-methylpyrrole-2-aldehyde, l-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine , 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinolin-3-aldehyde, quinoline-4-aldehyde, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoroacetone, chromon-3-aldehyde, 3 - (5'-Nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde,

1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) ace-tophenone and 2- (3 ^* -pyridoyl) -acetophenone,

Benzylidene acetone, 4-hydroxybenzylidene acetone, 2-hydroxybenzylidene acetone, 4-methoxybenzylidene acetone, 4-hydroxy-3-methoxybenzylidene acetone, 4-dimethylaminobenzylidene acetone, 3,4-methylenedioxybenzylidene acetone, 4-pyrrolidinobenzylidene acetone, 4-piperidinebenzone, 4-piper 4-diethylaminobenzylidene acetone, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylami- nobenzylidene) -2,4-pentanedione, 2-benzylidene cyclohexanone, 2- (4'-hydroxybenzylidene) -cyclohexanone, 2- (4'-dimethylaminobenzylidene) -cyclohexanone, 2-benzylidene-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -l, 3-cyclohexanedione , 3- (4'-Dimethylaminobenzylidene) - 1,3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-l, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-l , 3-cyclohexanedione, 2- (4'-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-l, 3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-l, 3-cyclohexanedione , 2-benzylidene cyclopentanone, 2 '- (4-hydroxybenzylidene) cyclopes ntanon, 2- (4'-dimethylaminobenzylidene) cyclopentanone,

5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3, 4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-Mθφholinophenyl ) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal, 6- (4-dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3, 5-dien-2-one, 6- (3, 4-dimethoxyphenyl) hexa-3, 5-dien-2- on, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa -3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3,5-dien-2- one, 5- (4-dimethylamino-l-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-

Nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy- 3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2- nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2, 5- dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9- Ethyl 3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, l, 4-dimethyl-3-carbazolaldehyde, 1,4,9-trimethyl-3-carbazolaldehyde,

4-formyl-1-methylpyridinium-, 2-formyl-1-methylpyridinium-, 4-formyl-1-ethylpyridinium-, 2-formyl-1-ethylpyridinium-, 4-formyl-1-benzylpyridinium-, 2-formyl-1 -benzylpyridinium-, 4-formyl-1, 2-dimethylpyridinium-, 4-formyl-1, 3-dimethylpyridinium-, 4-formyl-1-methylquinolinium-, 2-formyl-1-methylquinolinium-, 4-acetyl-1- methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8- Formyl-1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1 - ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6- formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquinolinium, 6-formyl-1-allylquinolinium, 7-formyl-1- allylquinolinium and 8-formyl-1-allylquinolinium, 5-acetyl-1-methylquinolinium, 6-acetyl-1-methylquinolinium, 7-acetyl-1-methylquinoli nium-, 8-acetyl-1-methylquinolinium, 5-acetyl-1-ethylquinolinium-, 6-acetyl-1 - ethylquinolinium-, 7-acetyl-1 -ethylquinolinium-, 8-acetyl-1 -ethylquinolinium, 5-acea tyl-1-benzylquinolinium, 6-acetyl-1-benzylquinolinium, 7-acetyl-1-benzylquinolinium, 8-acetyl-1-benzylquinolinium, 5-acetyl-1-allylquinolinium, 6-acetyl-1-allylquinolinium , 7-acetyl-1-allylquinolinium and 8-acetyl-1-allylquinolinium, 9-formyl-10-methylacridinium-, 4- (2'-formylvinyl) -1 - methylpyridinium-, 1, 3-dimethyl-2- ( 4'-formylphenyl) benzimidazolium, 1, 3- Dimethyl-2- (4'-formylphenyl) imidazolium-, 2- (4'-formylphenyl) -3-methylbenzothiazolium-, 2- (4'-acetylphenyl) -3-methylbenzothiazolium-, 2- (4'- Formylphenyl) -3-methylbenzoxazolium-, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium-, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium-, 2- (5 '-Formyl-2'-thienyl) -3-methylbenzothiazolium-, 2- (3'-formylphenyl) -3-methylbenzothiazolium-, 2- (4'-formyl-1 - naphthyI) -3-methylbenzothiazolium-, 5th -Chlor-2- (4'-formylphenyl) -3- methylbenzothiazolium-, 2- (4'-formylphenyl) -3,5-dimethylbenzothiazolium-benzenesulfonate, -p-toluenesulfonate, -methanesulfonate, -perchlorate, -sulfate, -chloride , - bromide, iodide, tetrachlorozincate, methyl sulfate, trifluoromethane sulfonate, tetrafluoroborate,

Isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitroisatin, 6-nitro-isatin, 5-sulfo-isatin, 5- Carboxy-isatin, cinisatin, 1-methylquinisatin, as well as any mixtures of the above compounds.

In a further embodiment, in order to expand the color spectrum and to improve the fastness properties, it can be advantageous to use at least one further compound as a component selected from (a) CH-acidic compounds and (b) compounds with primary or secondary to the hair dye used in addition to a reactive carbonyl compound Amino or hydroxy group, selected from aromatic hydroxy compounds, primary or secondary aromatic amines and nitrogen-containing heterocyclic compounds, (c) amino acids and (d) oligopeptides composed of 2 to 9 amino acids.

The CH-acidic compounds (a) of the oxo dye precursors of component B are preferably selected from the group consisting of 1,3,3,3-tetramethyl-3H-indolium iodide, 1,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H ~ indolium methanesulfonate, 1,3,3-trimethyl-2-methylene indoline (Fischer's base), 2,3-dimethyl-benzothiazolium iodide, 2,3 -Dimethyl-benzothiazolium-p-toluenesulfonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium-p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium -p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1.3 -Diethylbarbituric acid, oxindole, 3-ndoxyacetate, 2-coumaranone, 5-hydroxy-2-coumaranone, 6-hydroxy-2-coumaranone, 3-methyl-1-ρhenyl-pyrazolin-5-one, indan-l, 2-dione, indan-l, 3-dione, hιdan-1-one, benzoylacetonitrile, 3-dicyanomethylene indan-1-one, 2-amino-4-imino-l, 3-tlιiazolm hydrochloride, 5.5-

Dimethylcyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methyl-benzoxazolium iodide, 3-ethyl-2-methyl-benzothiazolium iodide, 1-ethyl-4-methyl quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1, 2,3-trimethylquinoxalinium iodide, 3-ethyl-2-methyl-benzoxazolium-p-toluenesulfonate, 3-ethyl-2-methyl-benzothiazolium-p-toluenesulfonate, 1-ethyl- 4-methyl-quinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p-toluenesulfonate, 1, 2,3-trimethylquinoxalinium p-toluenesulfonate 1, 2-dihydro-1, 3, 4,6-tetramethyl-2 -oxo-pyrimidinium chloride, 1, 2-dihydro-1, 3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium chloride, l, 2-dihydro-l, 3-dipropyl-4,6-dimethyl -2-oxo-pyrimidinium chloride, l, 2-dihydro-l, 3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4,6-dimethyl -2-oxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3,4-trimethyl-2 -oxo-pyrimidinium chloride, 1, 2-dihydrol, 3,4-trimeth yl-2-oxo-pyrimidinium hydrogen sulfate, l, 2-dihydro-l, 3-diethyl-4-methyl-2-oxo-pyrimidinium chloride, l, 2-dihydro-l, 3-diethyl-4-methyl 2-oxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4-methyl-2- oxo-pyrimidinium hydrogen sulfate, 1, 2-dihydro-1, 3, 4,6-tetramethyl-2-thioxo-pyrimidinium chloride, 1, 2-dihydro-l, 3-diethyl-4,6-dimethyl-2- thioxo-pyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2- thioxo-pyrimidim ^* um- hydrogen sulfate, 1, 2-dihydro-, 1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium- hydrogen sulfate, 1,2-dihydro-, 1,3-trimethyl-2- thioxo-pyrimidinium chloride, 1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium hydrogen sulfate, 1, 2-dihydro-1, 3-diethyl-4-methyl-2-thioxo-pyrimidinium- chloride, 1, 2-dihydro-1, 3-diethyl-4-methyl-2-thioxo-pyrimidinium hydrogen sulfate, 1, 2-dihydro-1, 3-dipropyl-4-methyl-2-thioxo-pyrimide inium chloride and l, 2-dihydro-l, 3-dipropyl-4-methyl-2-thioxo-pyrimidinixιm hydrogen sulfate.

The primary and secondary aromatic amines (b) of the oxo dye components of component B are preferably selected from the group consisting of N, N-dirnethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) - N-ethyl-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p- phenylene diamine, 2,3-dichloro-p-phenylene diamine, 2,4-dichloro-p-phenylene diamine, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, 2.5, -Diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethol, 4-amino-3-methylphenol, 2- (2,5-diaminophenyl) -ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) -ethanol, 3-amino-4- (2-hydroxyethyloxy) phenol, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloφhenol, 4-methylaminophenol, 2-methyl-5- aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-amino-4-chlorophenol, 5 - ( 2-hydroxyethylamino) -4-methoxy-2-methylphenol, 4-amino-2-hydroxymethylphenol, 2- (diethylaminomethyl) -4-aminophenol, 4-amino-1-hydroxy-2- (2-hydroxyethylaminomethyl) benzene, 1 - Hydroxy-2-amino-5-methyl-benzene, 1 -hydroxy-2-amino-6-methyl-benzene, 2-amino-5-acetamido-phenol, 1, 3-dimethyl-2,5-diaminobenzene, 5- (3-hydroxypropylamino) 2-methylphenol, 5-amino-4-methoxy-2-methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 5-amino-4-fluoro-2- methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino-5- (2-hydroxyethoxy) toluene, 2,4-diamino-5-methylphenetol, 3,5-diamino-2-methoxy-l- methylbenzene, 2-amino-4- (2-hydroxyoxyethylamino) anisole, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene, 1,3-diamino-2,4-dimethoxybenzene, 3,5-diamino- 2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenylacetic acid, 3-aminophenylacetic acid, 4-aminophenylacetic acid, 2,3-diaminobenzoic acid, 2,4-

Diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3-amino-4-hydroxy-benzoic acid, 4-amino-3-hydroxy-benzoic acid, 2 -Aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxy-naphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4 - hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-triaminobenzene, 1,2,4 -Triaminobenzene, 1,2,4,5-Tetraaminobenzene, 2,4,5-Triaminophenol, Pentaammobenzol, Hexaaminobenzene, 2,4,6-Triaminoresorcin, 4,5-Diaminobrenzcatechin, 4,6-Diaminopyrogallol, 1 - (2- Hydroxy-5-aminobenzyl) -2-imidazolidinone, 4-amino-2 - ((4- [(5-amino-2-hydroxyphenyl) methyl] piperazinyl) methyl) phenol, 3,5-diamino-4-hydroxy- catechol, 1,4-bis (4-aminophenyl) -1, 4-diazacycloheptane, aromatic nitriles such as 2-amino-4-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile, Amino compounds containing nitro groups, such as 3-amino-6-methylamino-2-nitro-pyridine, picraminic acid, [8 - [(4-amino-2-nitrophenyl) -azo] -7-hydroxy-naphth-2-yl] - trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) -azo) -7-hydroxy-naphth-2-yl] trimethylammonium chloride (Basic Brown 17), l-hydroxy-2-amino-4,6-dinitrobenzene , 1 -Ammo-2-nitro-4- [bis- (2-hydroxyethyl) amino] benzene, 1 -Amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5), l-Ammo-2-nitro-4 - [(2-hydroxyethyl) amino] benzene (HC Red No. 7), 2-chloro-5-nitro-N-2-hydroxyethyl-l, 4-phenylenediamine, 1 - [(2-Hydroxyethyl) amino] -2-nitτo-4-amino-benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro-o- toluidine, l-amino-3-methyl-4- [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet No. 1), l-amino-2-nitro-4 - [(2,3-dihy droxypropyl) amino] -5-chloro-benzene (HC Red No. 10), 2- (4-amino-2-nitroanilino) - benzoic acid, 6-nitro-2,5-diammopyridine, 2-amino-6-chloro 4-nitrophenol, l-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid disodium salt (Acid blue No. 29), 1-amino-2- (2-hydroxy-4 -nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (Palatinchrome green), l-amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt ( Gallion), 4-amino-4'-nitrostüben-2,2'-disulfonic acid disodium salt, 2,4-diamino-3 ', 5'-dmitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3 '-nitrobenzophenone-2-carboxylic acid, l-amino-4-nitro-2- (2-nitrobenzylideneamino) benzene, 2- [2-

(Diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-l-nitronaphthalene, 5 Amino-6-nitrobenzo-l, 3-dioxole, anilines, in particular anilines containing nitrograppen, such as 4-nitroaniline, 2-nitroaniline, l, 4-diamino-2-nitrobenzene, l, 2-diamino-4-nitrobenzene, 1- amino-2-methyl-6-nitrobenzene, 4-nitro-l, 3-phenylenediamine, 2-nitro-4-amino-l- (2-hydroxyethylamino) benzene, 2-nitτo-l-amino- 4- [bis- (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, l-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, aromatic Anilines or phenols with a further aromatic radical, as shown in formula VII

in the

• R ¹⁰ represents a hydroxy or an amino group, the -C _ö by -C ₆ alkyl, - hydroxyalkyl, -C ₆ alkoxy or -C ₆ -alkoxy-Cι-C ₆ alkyl groups may be substituted,

• R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ independently of one another for a hydrogen atom, a hydroxyl or an amino group, by -CC ₆ alkyl, d-Cβ-hydroxyalkyl, CrCβ-alkoxy -, D-Cβ-aminoalkyl or d-Ce-alkoxy-CrCβ-alkyl groups can be substituted, and

• Z "for a direct bond, a saturated or unsaturated carbon chain with 1 to 4 carbon atoms, optionally substituted by hydroxyl groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula VIII

in der • Q eine direkte Bindung, eine CH₂- oder CHOH-Gruppe bedeutet, • Q' und Q" unabhängig voneinander für ein Sauerstoffatom, eine NR²²- Gruppe, worin R²² ein Wasserstoffatom, eine d-C₆-Alkylgruppe oder CrCβ- Hydroxyalkylgruppe, wobei auch beide Gruppen zusammen mit dem Restmolekül einen 5-, 6- oder 7-Ring bilden können, bedeutet, die Gruppe 0-(CH₂)_P-NH oder NH-(CH₂)_p ^'-0, worin p und p' 2 oder 3 sind, stehen und • o eine Zahl von 1 bis 4 bedeutet,

in which • Q is a direct bond, a CH ₂ or CHOH group, • Q 'and Q "independently of one another for an oxygen atom, an NR ²² group, in which R ^{22 is} a hydrogen atom, a dC ₆ alkyl group or CrCβ- Hydroxyalkyl group, where both groups together with the rest of the molecule can form a 5-, 6- or 7-ring means the group 0- (CH ₂ ) _P -NH or NH- (CH ₂ ) _p ^' -0, where p and p 'are 2 or 3, are and • o is a number from 1 to 4,

such as 4,4'-diaminostilbene and its hydrochloride, 4,4 ^* -diaminostilbene-2,2'-disulfonic acid mono- or -di-Na salt, 4-amino-4 ^* -dimethylaminostilbene and its hydrochloride, 4, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenyl sulfoxide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3 ', 4,4'-tetraamino-benzophenone, 1,3-bis (2,4-diaminophenoxy) propane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,3-bis (4-aminophenylamino) propane, 1,3-bis (4-aminophenylamino) -2-propanol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino ] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methylamine, N-phenyl-1,4-phenylenediamine and bis- (5-amino-2-hydroxyphenyl) - methane.

The nitrogen-containing heterocyclic compounds (b) of the oxo dye components of component B are preferably selected from the group consisting of 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylammo) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamine-5-amino-pyridine, 2-methylamino-3-amino-6-methoxy- pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6-dihydroxy-3,4- dimethylpyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) amine, N- [2- (4-aminophenyl) aminoethyl] -N- (5-amino -2-pyridyl) amine, 2,4-dihydroxy-5,6-diaminopyrimidine, 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6- triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5,6-triaminopyrimidine, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy-6-methyl- pyrimidine, 3,5-diaminopyrazole, 3,5-diamino-l, 2,4-triazole, 3-ami nopyrazole, 3-amino-5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1 - (2-hydroxyethyl) -4,5-diaminopyrazole, 1-phenyl-3-methyl-4,5-diaminopyrazole, 4- Amino-2,3-dimethyl-l-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), l-phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8-aminoquinoline, 4 -Aminochinaldine, 2-aminonicotinic acid, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-moφ -aniline and indole and indoline derivatives, such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. According to the invention, the hydroxypyrimidines disclosed in DE-Ul-299 08 573 can also be used as heterocyclic compounds. The aforementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, e.g. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid. The aromatic hydroxy compounds (b) of the oxo dye component B are preferably selected from the group consisting of 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol , Hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3-dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3.4 Dihydroxybenzoic acid, 2,4-dihydroxyphenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, acetophenone, 2-chlonesorcinol, 4-chloreesorcinol, 1-naphthol, 1,5-dihydroxy-naphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

As amino acids (c) of the oxo dye components of component B, all naturally occurring and synthetic α-amino acids are preferred, e.g. obtained by hydrolysis from vegetable or animal proteins, e.g. Collagen, keratin, casein, elastm, soy protein, wheat gluten or almond protein accessible amino acids. Both acidic and alkaline amino acids can be used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), omithin, proline, lysine and tryptophan. But also other amino acids, e.g. 6-aminocaproic acid and β-alanine can be used.

The oligopeptides (d) of the oxo dye precursors of component B can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided that they have sufficient water solubility for use in the colorants according to the invention. Examples include glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Use together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds is preferred. With regard to the dyes which can be used in the hair dyeing and toning agents according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Gare, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European inventory of cosmetic raw materials", published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicines, Health Products and Personal Care Products, Mannheim.

Hair dyes, especially if the coloring is oxidative, be it with atmospheric oxygen or other oxidizing agents such as hydrogen peroxide, are usually weakly acidic to alkaline, i.e. H. adjusted to pH values in the range of about 5 to 11. For this purpose, the colorants contain alkalizing agents, usually alkali or alkaline earth metal hydroxides, ammonia or organic amines. Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1, 3-propanediol, 2-amino -2-methylbutanol and triethanolamine as well as alkali and alkaline earth metal hydroxides. Monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanedol are particularly preferred in this group. It is also possible to use ω-amino acids such as ω-aminocaproic acid as an alkalizing agent.

If the actual hair colors are formed as part of an oxidative process, customary oxidizing agents, such as in particular hydrogen peroxide or its adducts with urea, melamine or sodium borate, can be used. However, oxidation with atmospheric oxygen as the only oxidizing agent can be preferred. It is also possible to carry out the oxidation with the aid of enzymes, the enzymes being used both for producing oxidizing per compounds and for Enhancing the effect of a small amount of oxidizing agents present, or also enzymes which transfer electrons from suitable developer components (reducing agents) to atmospheric oxygen. Oxidases such as tyrosinase, ascorbate oxidase and laccase are preferred, but also glucose oxidase, uricase or pyruvate oxidase. Furthermore, the procedure should be mentioned to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

The preparation of the oxidizing agent is then expediently mixed with the preparation with the dye precursors immediately before dyeing the hair. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can be in a range between 15 and 40 ° C., preferably at the temperature of the scalp. After an exposure time of about 5 to 45, in particular 15 to 30, minutes, the hair dye is rinsed off the hair to be dyed. Washing with a shampoo is not necessary if a carrier with a high surfactant content, e.g. B. a coloring shampoo was used.

In an eighth particularly preferred embodiment of the invention, the scalp and hair contour area are treated with color-rich 5,6-dihydroxyindoline derivatives, in particular before the hair coloring, with the agents according to the invention.

In a ninth, particularly preferred embodiment of the invention, the scalp and hair contour area are treated with deep-colored reactive carbonyl compounds and their derivatives with the agents according to the invention, especially before hair coloring.

Further optional ingredients of the agents according to the invention are nonionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers, anionic polymers, such as polyacrylic and polymethacrylic acids in the form of their copolymers with acrylic and methacrylic acid esters and amides, polyoxycarboxylic acids, such as polyketo and polyhydrocarboxylic acids and their salts, and also polymers and copolymers of crotonic acid with esters and amides of acrylic and methacrylic acid, such as vinyl acetate-crotonic acid and vinyl acetate-vinyl propionate-crotonic acid copolymers, structurants such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, perfume oils,

Dimethyl isosorbide and cyclodextrins,

Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol and ethoxylated triglycerides,

- dyes,

Active ingredients such as bisabolol, allantoin, panthenol, niacinamide, tocopherol and plant extracts,

- light stabilizers,

- consistency agents such as sugar esters, polyol esters or polyol alkyl ethers,

Fats and waxes, such as walrus, beeswax, montan wax, paraffins, esters, glycerides and fatty alcohols,

- fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,

Swelling and penetration substances such as PCA, glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex or styrene / acrylamide copolymers,

Pearlizing agents such as ethylene glycol mono- and distearate or PEG-3 distearate,

- white pigments,

Propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air,

- Antioxidants, preservatives. The invention also relates to a method for reducing scalp staining, in which the scalp and / or the hair contours are treated before the hair coloring with an agent which quaternarily contains at least one component from the group of the physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents

Contains ammonium compounds, amphoteric or zwitterionic surfactants, silicone compounds, antidandruff agents and / or from mixtures of these compounds and / or from the physiologically tolerable salts of these compounds.

In a particularly preferred embodiment of the invention, the method is used before oxidative hair coloring.

In a further particularly preferred embodiment of the invention, the method is applied with deep shades of color before hair coloring.

According to the invention, color-deep shades are to be understood as shades which, when colored on white hair (code Kerling, natural white), result in a ΔL value of more than 30.

A hair contour area is to be understood as the transition area from an almost hairless skin area to skin areas with pronounced hair growth. The hair contour area on the head is therefore usually in the area of the hairline on the forehead, temples, over the ears and on the neck or neck, and comprises 1 to 3 cm of the hairy skin area and 1 to 3 cm of the hairless skin area. In the context of the method according to the invention, this transition region is preferably treated with the agent according to the invention. Depending on the hairstyle, the hairy areas of the skin can have areas where, although there is hair growth, the skin becomes visible. This is particularly the case with a crown or in the center of a so-called vortex-shaped hair growth. The agent according to the invention is preferably applied to such areas.

The agent according to the invention is preferably applied directly to the corresponding skin areas with the aid of applicators. Applicators in the sense of the method according to the invention are particularly suitable the narrow brushes referred to as appliqués in the hairdressing sector and in particular the bottles with a narrow application tip which are customary in the home application area. In addition, however, the agent can also reach the site of action with the help of the hands, for example by massaging. For this purpose, it can be present as a shampoo, for example.

Another object of the invention is the use of at least one component from the group of physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary

Ammonium compounds, amphoteric or zwitterionic surfactants, silicone compounds, antidandruff agents and / or from mixtures of these compounds and / or from the physiologically tolerable salts of these compounds in a physiologically acceptable medium for pretreating the scalp and the hair contours before a hair coloring process.

Another object of the invention is the use of at least one component from the group of physiologically compatible hydroxycarboxylic acids, inorganic reducing agents, quaternary ammonium compounds, amphoteric surfactants, silicone compounds and / or from mixtures of these compounds and / or from the physiologically compatible salts Reduction of scalp staining during oxidative hair coloring with deep shades.

Another object of the invention is a kit containing, in two separate packages, an inventive agent for pretreating the scalp and / or the hair contours as well as a hair dye.

The following examples are intended to describe the subject matter of the invention in more detail without restricting it thereto. Unless stated otherwise, the stated contents are based on% by weight, based on the total weight of the composition.

Examples

1) Lotions for the treatment of the entire scalp

The lotions were applied to the scalp with a pipette. Care was taken to ensure that the hair was wetted as little as possible. Lotions 1 to 5 as well as 11 and 12 were half-sided before hair coloring with a formulation which contained 1.5% dihydroxyindoline hydrobromide and was adjusted to a pH of 10.0 with 0.6% arginine and ammonia used. The scalp on the side that had been pretreated with the formulations according to the invention showed almost no scalp staining.

Lotions 6 to 10 were tested on one side with oxidation hair color formulations with shades of black and blue-black from the commercially available Poly Brillance Intensive Color Cream series. Here too, there was a significant reduction in the color of the scalp.

2) Formulations for the hair contours

Die Formulierungen 13 bis 15 für die Haarkonturen wurden vor der Coloration mit schwarzen Färbeprodukten im Bereich der Haarkonturen appliziert. Bei allen 3 Rezepturen war nach Beendigung des Färbeprozesses und Entfernung der erfindungsgemäßen Formulierungen aus dem Haarkonturenbereich praktisch keine Hautanfärbung bemerkbar.

Formulations 13 to 15 for the hair contours were applied before coloring with black coloring products in the area of the hair contours. With all 3 formulations, practically no skin staining was noticeable after the dyeing process had ended and the formulations according to the invention had been removed from the hair contour area.

3) Formulations for the hair contours

Liste der verwendeten Rohstoffe: 1 Trimethylhexadecylammoniumchlorid, 24-26 % WAS (Hersteller: Cognis)

List of raw materials used: 1 trimethylhexadecylammonium chloride, 24-26% WAS (manufacturer: Cognis)

2 hydroxyethyl cellulose (manufacturer: SHC Production Europe)

3 silicone glycol copolymer (INCI: PEG / PPG-18/18 Dimethicone; manufacturer: SHC)

4 silicone glycol copolymer (INCI: PEG-12 Dimethicone; manufacturer: SHC)

5 Ci ₆ -i ₈ fatty alcohol (manufacturer: Cognis)

6 Ci ₆ -i ₈ fatty acid mono-di-glyceride (INCI name: Glyceryl Stearate) (manufacturer: SHC)

7 C ₁₆ -i ₈ fatty alcohol + 12-EO (INCI name: Ceteareth-12) (manufacturer: Cognis)

8 Cetylstearyl alcohol + 20-EO (INCI name: Ceteareth-20) (manufacturer: COGNIS)

9 polydimethylsiloxane (INCI name: Dimethicone) (manufacturer: GE-Bayer-Silicones) 10 glycerol monostearate (INCI name: Glyderyl Stearate) (manufacturer: Cognis) 11 fatty acid triglyceride (INCI name: Caprylic / Capric Triglyceride) (manufacturer: Cognis) 12 Ci ₂ -i ₈ fatty alcohol (manufacturer: COGNIS) 13 2-octyldodecanol (INCI name: Octyldodecanol) (manufacturer: COGNIS) 14 Ci ₂ -i ₆ fatty alcohol-1,4-glucoside, (aqueous solution with 50% active substance) (INCI name: Lauryl Glucoside) (manufacturer: COGNIS) 15 Ci2-i4-fatty alcohol-4.5-EO acetic acid sodium salt, (aqueous solution with 21% active substance) (INCI name: Sodium Laureth-5 Carboxylate) (manufacturer: KAO ) 16 Lauryl myristyl ether sulfate sodium salt, (aqueous solution with 70% active substance) (INCI name: Sodium Myreth Sulfate) (manufacturer: COGNIS) 17 INCI name: Disodium Cocoamphodipropionate (manufacturer: RHODIA) Examination of the skin staining with 5,6-dihydroxyindoline revealed a clearly visible skin color after pretreatment of the scalp and the hair contours with agent 15 (without addition of an active ingredient according to the invention) after 30 minutes of exposure. This was almost completely eliminated by adding Miranol C2M SF in formulation 16. The addition of DC 190 and sodium salicylate in agents 17 and 18 also significantly reduced the coloring of the scalp and hair contours.

In a grading scale of 1 - 5 (1 = very good; 5 = standard without additives for comparison), the following grades were given subjectively: Miranol C2M: 1

Sodium salicylate: 2-3 DC 190: 3

Claims

claims 1. Agent for the pretreatment of the scalp before a hair dyeing process, characterized in that there is at least one component from the group of physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary ammonium compounds, amphoteric or zwitterionic surfactants, non-volatile silicone compounds, anti-scaling agents for reducing scalp staining and / or from mixtures of these compounds and / or from the physiologically tolerable salts of these compounds. 2. Composition according spoke 1, characterized in that the hydroxycarboxylic acids and the hydroxycarboxylic acid salts are selected from lactic acid, mandelic acid, malic acid, tartaric acid, citric acid and / or salicylic acid and from the physiologically tolerable salts of these hydroxycarboxylic acids. 3. Composition according to one of claims 1 or 2, characterized in that it contains sodium salicylate. 4. Composition according to one of claims 1 to 3, characterized in that the inorganic and organic reducing agents are selected from the compounds sodium metabisulfite, sodium dithionite, ascorbic acid, isoascorbic acid, sodium hydroxymethanesulfonic acid, cysteine, N-acetylcysteine and cysteamine. 5. Composition according spoke 4, characterized in that it contains ascorbic acid and / or isoascorbic acid. 6. Composition according to one of claims 1 to 5, characterized in that the quaternary ammonium compounds are selected from cationic polymers with quaternary ammonium group and from cationic surfactants with quaternary ammonium group. 7. Composition according to claim 6, characterized in that the quaternary surfactants are selected from linoleic amidopropyl PG-dimonium chloride phosphates, alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, trialkylmethylammonium chlorides and esterquats. 8. Composition according to one of claims 1 to 7, characterized in that the amphoteric surfactants are selected from cocoamphodipropionate or cocoamidopropylbetaine. 9. Composition according to one of claims 1 to 8, characterized in that the silicone compound is a water-soluble silicone surfactant. 10. Agent according to Anspmch 9, characterized in that the silicone surfactant is selected from the dimethicone copolyols. 11. Agent according to Anspmch 10, characterized in that the silicone surfactant is polyethoxylated and / or polypropoxylated. 12. Composition according to one of claims 1-11, characterized in that it contains elemental colloidal sulfur, zinc pyridinthione or the compounds obtainable under the trade names octopirox or climbazole as antidandruff active ingredient. 13. Means for pretreating the scalp before a hair coloring process, characterized in that it is used to reduce scalp staining, at least two components from the group of the physiologically tolerable Contains hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary ammonium compounds, amphoteric or zwitterionic surfactants, silicone compounds, antidandruff agents and / or from mixtures of these compounds and / or from the physiologically tolerable salts of these compounds. 14. A method for reducing scalp staining, characterized in that the scalp and / or the hair contours are treated before the hair coloring with an agent which contains at least one component from the group of the physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary ammonium compounds, amphoteric or contains zwitterionic surfactants, silicone compounds, antidandruff agents and / or from mixtures of these compounds and / or from the physiologically tolerable salts of these compounds. 15. The method according to Anspmch 14, characterized in that it is used before the oxidative coloring of hair. 16. The method according to Anspmch 14, characterized in that it is applied with deep shades of color before hair coloring. 17. Use of at least one component from the group of physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary ammonium compounds, amphoteric or zwitterionic surfactants, silicone compounds, antidandruff agents and or from mixtures of these compounds and or from the physiologically tolerable salts of these compounds in a physiologically acceptable medium for the pretreatment of the scalp and the hair contours before a hair coloring process. 18. Use of at least one component from the group of physiologically compatible hydroxycarboxylic acids, inorganic and organic reducing agents, quaternary ammonium compounds, amphoteric or zwitterionic surfactants, silicone compounds, antidandruff agents and or from mixtures of these compounds and / or from the physiologically compatible salts of these compounds in a physiologically acceptable Medium for the reduction of the head haxite coloring in the oxidative hair coloring with deep shades. 19. Kit containing, in two separate packages, an agent for pretreating the scalp and / or the hair contours according to one of claims 1 to 13 and a hair dye.