DE10343236A1 - Means for reducing scalp staining - Google Patents

Abstract

The invention relates to an agent for dyeing hair which minimizes skin discoloration, to a method for reducing skin staining in the context of a staining method and to the use of special components for reducing skin staining, in particular during hair coloring.

Description

The The invention relates to an agent for dyeing hair, which the skin staining minimizes a method of reducing skin staining in the Frame of a staining procedure and the use of special components to reduce the skin staining, especially during the hair coloring.

human Hair is becoming more diverse today Treated with hair cosmetic preparations. These include about Cleaning hair with shampoos, care and regeneration with rinses and Cures and bleaching, dyeing and deforming the hair with colorants, Tints, Wells and styling preparations. There are funds for change or nuancing the color of the head hair a prominent role.

For temporary dyeings become common dyeing or tinting agent used as dyeing Component so-called direct pullers included. This is it about dye molecules, which grow directly on the hair and no oxidative process to the formation of the color need. Belongs to these dyes for example, that from ancient times to the coloring of body and hairs known henna. These dyes are against shampooing usually sensitive, leaving a often undesirable nuance shift or even a visible "discoloration" can occur.

For lasting, intense colors with corresponding fastness properties become so-called oxidation colorants uses. Such colorants usually contain Oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidants or of atmospheric oxygen with one another or under coupling with one or more coupler components the actual Dyes off. The oxidation colorants are characterized by excellent, long-lasting staining results out.

Finally has further dyeing process size Attention found. In this process, precursors of the natural Hair dye melanin applied to the hair; these form then in the context of oxidative processes in the hair natural analog dyes. Such a process with 5,6-dihydroxyindoline as dye precursor has been described in EP-B1-530 229. In, in particular multiple, Application of agents with 5,6-dihydroxyindoline makes it possible for humans with gray hair the natural Reproduce hair color. The coloration can be done with atmospheric oxygen take place as the sole oxidant, so that no further oxidizing agents resorted must become. In persons with original Medium-blond to brown hair, indoline can be the sole dye precursor be used. For the application in persons with originally red and in particular Dark to black hair color, on the other hand, can be satisfying Results frequently only by the concomitant use of other dye components, in particular special oxidation dye precursors can be achieved.

• A reaktive Carbonylverbindungen, d.h. Verbindungen, mit mindestens einer reaktiven Carbonylgruppe, und Komponente
• B Verbindungen, ausgewählt aus (a) CH-aciden Verbindungen, (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen, (c) Aminosäuren, (d) aus 2 bis 9 Aminosäuren aufgebauten Oligopeptiden

enthalten. Die vorgenannten Komponenten A und B sind im Allgemeinen selbst keine Farbstoffe, und eignen sich daher jede für sich genommen allein nicht zur Färbung keratinhaltiger Fasern. In Kombination bilden sie in einem nichtoxidativen Prozess Farbstoffe aus. Unter Verbindungen der Komponente B können allerdings auch entsprechende Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kupplertyp mit oder ohne Einsatz eines Oxidationsmittels Verwendung finden. Somit läßt sich diese Färbemethode (im Folgenden Oxofärbung genannt) ohne weiteres mit dem oxidativen Färbesystem kombinieren. Die Komponenten A und B werden im Folgenden als Oxofarbstoffvorprodukte bezeichnet. Die Oxofärbung wird beispielweise in den Druckschriften WO-A1-99/18916, WO-A1-00/38638, WO-A1-01/34106 und WO-A1-01/47483 beschrieben.Another way to stain keratin-containing fibers is through the use of stains containing a combination of component

• A reactive carbonyl compounds, ie compounds having at least one reactive carbonyl group, and component
• B Compounds selected from (a) CH-acidic compounds, (b) compounds having 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) from 2 up to 9 amino acids oligopeptides

contain. The aforementioned components A and B are generally not themselves dyes, and therefore are not suitable alone for dyeing keratinhaltiger fibers alone. In combination, they form dyes in a non-oxidative process. However, it is also possible to use corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidizing agent under compounds of component B. Thus, this staining method (hereinafter called oxo staining) can be readily combined with the oxidative staining system. Components A and B are referred to below as Oxofarbstoffvorprodukte. 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 discloses the use of onium aldehydes and ketones, in particular of 2- or 4-formyl-1-methylquinolinium compounds, for dyeing keratin-containing fibers which 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.

Problematic in hair coloring, especially when using the oxo dyeing and staining with naturally-analogous dyes of indole or indoline derivatives staining the scalp, often with the coloring the hair goes along and as disturbing and unacceptable. Especially with the non-routine Consumers who want to dye their hair at home themselves face this problem increased on. But also the experienced Hairdressing can be especially intense and deep colorations a scalp stain often can not avoid what leads to customer dissatisfaction.

It is therefore the need for a remedy or a procedure that is easily applied can and with the staining the scalp as part of hair coloring prevented or at least reduced.

Out DE-A1-100 28 723 a hair dyeing method is known in which the scalp and hair contour area to reduce the scalp staining initially with a water-in-oil emulsion based on an oil component and a nonionic emulsifier. Subsequently, will the hair dye product applied to the hair. After a usual for hair coloring exposure time is the hair thoroughly washed.

In DE-A1-100 56 266 further comprises the W / O emulsion mandatory a fleeting Silicone.

In WO-A1-96 / 18379 becomes a cosmetic and dermatological agent discloses that for the protection of skin and hair against oxidative stress contains at least one compound from the group of flavonoids.

• (i) mindestens eine farbgebende Komponente, ausgewählt aus • Oxofarbstoffvorprodukten mit den Komponenten A mindestens eine reaktive Carbonylverbindung und B mindestens eine Verbindung ausgewählt aus (a) CH-aciden Verbindungen, (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen, • Indol- und/oder Indolin-Derivaten als Vorprodukte naturanaloger Farbstoffe, sowie aus Mischungen von Vertretern einer oder mehrerer dieser Gruppen und
• (ii) mindestens einen die Hautanfärbung verringernden Wirkstoff, ausgewählt aus • Hydroxycarbonsäuren, • emulgierend wirkenden Verbindungen, ausgewählt aus nicht-flüchtigen Silikonverbindungen, kationischen Tensiden und amphoteren Tensiden, • Antischuppenwirkstoffen, • anorganischen und organischen Redukionsmitteln und/oder aus Gemischen dieser Verbindungen und/oder aus den physiologisch verträglichen Salzen dieser Verbindungen

enthält.The first subject of this application is an agent for dyeing keratin-containing fibers, in particular human hair, the

• (I) at least one coloring component selected from Oxofarbstoffvorprodukten with the components A at least one reactive carbonyl compound and B at least one compound selected from (a) CH-acidic compounds, (b) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, • indole and / or indoline derivatives as precursors of natural-analogous dyes, as well as mixtures of representatives of one or more of these groups and
• (ii) at least one skin staining reducing agent selected from: hydroxycarboxylic acids, emulsifying compounds selected from non-volatile silicone compounds, cationic surfactants and amphoteric surfactants, antidandruff active ingredients, inorganic and organic reducing agents and / or mixtures of these compounds and / or or from the physiologically acceptable salts of these compounds

contains.

The Application of the agents according to the invention leads to a strong reduction of scalp staining in color intensive stains and to a complete one Prevention of scalp staining for non-color intensive dyeings.

When Reactive according to the invention Having carbonyl compounds as Oxofarbstoffvorprodukt the component A. at least one carbonyl group as a reactive group, which with the Component B to form a covalent bond to a coloring component reacts. When the agent of the invention contains a component A, is it preferred according to the invention that this inventive agent mandatory also contains at least one component B. The agent according to the invention contains then prefers no component B, if no component A contains is.

• a) Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Additionsverbindung
• b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Additionsverbindung an das Kohlenstoffatom der Carbonylgruppe der reaktiven Carbonylverbindung und
• c) von Wasser unter Bildung von Hydraten.

Furthermore, according to the invention, those compounds which are derivatized as reactive carbonyl compound of component A in which the reactive carbonyl group is derivatized in such a way that the reactivity of the Carbon atom of the derivatized carbonyl group over the component B is always present. These derivatives are preferably addition compounds of

• a) amines and derivatives thereof to form imines 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.

wobei
• AR steht für Benzol, Naphthalin, Pyridin, Pyrimidin, Pyrazin, Pyridazin, Carbazol, Pyrrol, Pyrazol, Furan, Thiophen, 1,2,3-Triazin, 1,3,5-Triazin, Chinolin, Isochinolin, Indol, Indolin, Indolizin, Indan, Imidazol, 1,2,4-Triazol, 1,2,3-Triazol, Tetrazol, Benzimidazol, 1,3-Thiazol, Benzothiazol, Indazol, Benzoxazol, Chinoxalin, Chinazolin, Chinolizin, Cinnolin, Acridin, Julolidin, Acenaphthen, Fluoren, Biphenyl, Diphenylmethan, Benzophenon, Diphenylether, Azobenzol, Chromon, Cumarin, Diphenylamin, Stilben, wobei die N-Heteroaromaten auch quaterniert sein können,
• R¹ steht für ein Wasserstoffatom, eine C₁-C₆-Alkyl-, C₂-C₈-Acyl-, C₂-C₄-Alkenyl-, C₁-C₄-Perfluoralkyl-, eine ggf. substituierte Aryl- oder Heteroarylgruppe,
• R², R³ und R⁴ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkyl-, C₁-C₆-Alkoxy-, C₁-C₆-Aminoalkyl-, C₁-C₆-Hydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₁-C₆-alkyloxygruppe, eine C₂-C₆-Acylgruppe, eine Acetyl-, Carboxyl-, Carboxylato-, Carbamoyl-, Sulfo-, Sulfato-, Sulfonamid-, Sulfonamido-, C₂-C₆-Alkenyl-, eine Aryl-, eine Aryl-C₁-C₆-alkylgruppe, eine Hydroxy-, eine Nitro-, eine Pyrrolidino-, eine Morpholino-, eine Piperidino-, eine Amino- bzw. Ammonio- oder eine 1-Imidazol(in)iogruppe, wobei die letzten drei Gruppen mit einer oder mehrerer C₁-C₆-Alkyl-, C₁-C₆-Carboxyalkyl-, C₁-C₆-Hydroxyalkyl-, C₂-C₆-Alkenyl-, C₁-C₆-Alkoxy-C₁-C₆-alkyl-, mit ggf. substituierten Benzylgruppen, mit Sulfo-(C₁-C₄)-alkyl- oder Heterozyklus-(C₁-C₄)-alkylgruppen substituiert sein können,
wobei auch zwei der Reste aus R², R³, R⁴ und -Z-Y-R¹ zusammen mit dem Restmolekül einen ankondensierten gegebenenfalls substituierten 5-, 6- oder 7-Ring, der ebenfalls einen ankondensierten aromatischen Ring tragen kann, bilden können,
wobei das System AR in Abhängigkeit von der Größe des Ringes weitere Substituenten tragen kann, die unabhängig voneinander für die gleichen Gruppen stehen können wie R², R³ und R⁴,
• Z steht für eine direkte Bindung, eine Carbonyl-, eine Carboxy-(C₁-C₄)-alkylen-, eine gegebenenfalls substituierte C₂-C₆-Alkenylen-, C₄-C₆-Alkadienylen-, Furylen-, Thienylen-, Arylen-, Vinylenarylen-, Vinylenfurylen-, Vinylenthienylengruppe, wobei Z zusammen mit der -Y-R¹-Gruppe auch einen gegebenenfalls substituierten 5-, 6- oder 7-Ring bilden kann,
• Y steht für eine Gruppe, die ausgewählt ist aus Carbonyl, einer Gruppe gemäß Formel II und einer Gruppe gemäß Formel III,

wobei
• R⁵ steht für ein Wasserstoffatom, eine Hydroxygruppe, eine C₁-C₄-Alkoxygruppe, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₁-C₆-alkylgruppe,
• R⁶ und R⁷ stehen unabängig voneinander für eine C₁-C₆-Alkylgruppe, eine Arylgruppe oder bilden zusammen mit dem Strukturelement O-C-O der Formel III einen 5- oder 6-gliederigen Ring.The reactive carbonyl compound is preferably selected from compounds according to formula I,

in which
• AR is 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 may also be quaternized,
R ¹ represents a hydrogen atom, a C ₁ -C ₆ alkyl, C ₂ -C ₈ acyl, C ₂ -C ₄ alkenyl, C ₁ -C ₄ 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 C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -aminoalkyl, C ₁ - C ₆ hydroxyalkyl, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy, C ₂ -C ₆ acyl, acetyl, carboxyl, carboxylato, carbamoyl, sulfo, sulfato, Sulfonamide, sulfonamido, C ₂ -C ₆ alkenyl, an aryl, an arylC ₁ -C ₆ alkyl group, a hydroxy, a nitro, a pyrrolidino, a morpholino, a piperidino, an amino or ammonio or a 1-imidazole (in) amino group, the last three groups having one or more C ₁ -C ₆ -alkyl, C ₁ -C ₆ -carboxyalkyl, C ₁ -C ₆ - Hydroxyalkyl, C ₂ -C ₆ alkenyl, C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, with optionally substituted benzyl groups, with sulfo (C ₁ -C ₄ ) alkyl or heterocycle - (C ₁ -C ₄ ) -alkyl groups may be substituted,
wherein also two of the radicals from R ² , R ³ , R ⁴ and -ZYR ¹ together with the remainder of the molecule can form a fused optionally substituted 5-, 6- or 7-ring, which may 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 stand for the same groups as R ² , R ³ and R ⁴ ,
Z is a direct bond, a carbonyl, a carboxy (C ₁ -C ₄ ) -alkylene, an optionally substituted C ₂ -C ₆ -alkenylene, C ₄ -C ₆ -alkadienylene, furylene, Thienylene, arylene, vinylenarylene, vinylenfururylene, vinylenthienylene group, wherein Z together with the -YR ¹ group can also form an optionally substituted 5-, 6- or 7-membered ring,
Y is a group which is selected from carbonyl, a group according to formula II and a group according to formula III,

in which
R ⁵ is hydrogen, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl group,
R ⁶ and R ⁷ independently of one another represent a C ₁ -C ₆ -alkyl group, an aryl group or together with the structural element OCO of the formula III form a 5- or 6-membered ring.

The reactive carbonyl compound is more 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-trihydroxyaceto phenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-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-1-acetonaphthone, 1-hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7-trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, 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-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxybenzaldehyde 2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy 4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3 Ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 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-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-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-dime thoxy-1-naphthaldehyde, 3,4-dimethoxy-1-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-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) benzaldehyde, piperonal, 2,3,6, 7-Tetrahydro-1H, 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 (Fischer's aldehyde or tribasic aldehyde),
2-indolealdehyde, 3-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ', 3 ', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine , 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, 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) acetophenone and 2- (3'-pyridoyl) acetophenone,
Benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4-diethylaminobenzylideneacetone, 3 Benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-Benzylidene-cyclohexanone, 2- (4'-hydroxybenzylidene) cyclohexanone, 2- (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) -1, 3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy-3 -methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) - cyclopentanone, 2- (4'-dimethyl aminobenzylidene) -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-morpholinophenyl ) 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-diene-2 on, 6- (2,4-dimethoxyphe nyl) hexa-3,5-dien-2-one, 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-diene-2 on, 6- (4-pyrrolidinophenyl) hexa-3,5-dien-2-one, 5- (4-dimethylamino-1-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, 1,4-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-methylquinolinium, 8-acetyl-1-methylquin olinium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl-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-naphthyl) -3-methylbenzothiazolium, 5-chloro 2- (4'-Formylphenyl) -3-methylbenzothiazolium, 2- (4'-Formylphenyl) -3.5 dimethylbenzothiazolium benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate,
Isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5- Carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures of the above compounds.

The CH-acidic compounds (a) of the oxo dye precursors of component B are preferably selected from the group consisting of 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium-p toluene sulfonate, 1,2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 2,3-dimethylnaphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methylnaphtho [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-indoxylacetate, 2-coumaranone , 5-hydroxy-2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1,2-dione, indan-1,3-dione, indan-1 -on, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5.5- Dimethylcyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methylbenzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methylquinolinium iodide, 1 Ethyl 2-methylquinolinium iodide, 1,2,3-trimethylquinoxaluminum iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-4-methyl- quinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p-toluenesulfonate, 1,2,3-trimethylquinoxaluminum p-toluenesulfonate, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxo pyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2- oxo-pyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2- oxo-pyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3,4-trimethyl-2-oxo pyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium hydrogen sulfate, 1,2 Dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro 1,3-dipropyl-4-methyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1 , 3,4,6-tetramethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1 , 3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium-hydro gensulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3,4-trimethyl-2-thioxo-pyrimidinium chloride, 1, 2-Dihydro-1,3,4-trimethyl-2-thioxo-pyrimidinium hydrogensulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium chloride, 1,2-dihydroxy 1,3-diethyl-4-methyl-2-thioxo-pyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium chloride and 1,2-dihydro-1, 3-dipropyl-4-methyl-2-thioxo-pyrimidinium hydrogensulphate.

in der
• R¹⁰ für eine Htdroxy- oder eine Aminogruppe, die durch C₁-C₆-Alkyl-, C₁-C₆-Hydroxyalkyl-, C₁-C₆-Alkoxy- oder C₁-C₆-Alkoxy-C₁-C₆-alkylgruppe substituiert sein, kann, steht,
• R¹¹, R¹², R¹³, R¹⁴ und R¹⁵ unabhänigig voneinander für ein Wasserstoffatom, eine Hydroxy- oder eine Aminogruppe, die durch C₁-C₆-Alkyl, C₁-C₆-Hydroxyalkyl-, C₁-C₆-Alkoxy- C₁-C₆-Aminoalkyl- oder C₁-C₆-Alkoxy-C₁-C₆-alkylgruppen substituiert sein kann, stehen, und
• Z'' für eine direkt Bindung, eine gesättigte oder ungesättigte, ggf. durch Hydroxygruppen substtuierte Kohlenstoffkette mit 1 bis 4 Kohlenstoffatomen, eine Carbonyl-, Sulfonyl- oder Iminogruppe, ein Sauerstoff- oder Schwefelatom, oder eine Gruppe mit der Formel V

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 C₁-C₆-Alkylgruppe oder C₁-C₆-Hydroxylkylgruppe, wobei auch beide Gruppen zusammen mit dem Restmolekül einen 5-, 6- oder 7-Ring bilden können, bedeutet, die Gruppe O-(CH₂)_p-NH oder NH-(CH₂)_p'-O, worin p' 2 oder 3 sind, stehen und
• o eine Zahl von 1 bis 4 bedeutet,
wie beispielsweise 4,4'-Diaminostilben und dessen Hydrochlorid, 4,4'-Diaminostilben-2,2'-disulfonsäure-mono- oder -di-Na-Salz, 4-Amino-4'-dimethylaminostilben und dessen Hydrochlorid, 4,4'-Diaminodiphenylmethan, 4,4'-Diaminodiphenylsulfid, 4,4'-Diaminodiphenylsulfoxid, 4,4'-Diaminodiphenylamin, 4,4'-Diaminodiphenylamin-2-sulfonsäure, 4,4'-Diaminobenzophenon, 4,4'-Diaminodiphenylether, 3,3',4,4'-Tetraaminodiphenyl, 3,3',4,4'-Tetraamino-benzophenon, 1,3-Bis-(2,4-diaminophenoxy)-propan, 1,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctan, 1,3-Bis-(4-aminophenylamino)propan, 1,3-Bis-(4-aminophenylamino)-2-propanol, 1,3-Bis-[N-(4-aminophenyl)-2-hydroxyethylamino]-2-propanol, N,N-Bis-[2-(4-aminophenoxy)-ethyl]-methylamin, N-Phenyl-1,4-phenylendiamin und Bis-(5-amino-2-hydroxyphenyl)-methan.The primary and secondary aromatic amines (b) of the oxo dye precursors of component B are preferably selected from the group consisting of N, N-dimethyl-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-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4- Dichloro-p-phenylenediamine, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 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-dichlorophenol, 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-methylphenol, 3,5-diamino-2-methoxy-1-methylbenzene , 2-amino-4- (2-hydroxyethylamino) -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-hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-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, penta-aminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobrcatechin, 4, 6-Diaminopyrogallol, 1- (2-hydroxy-5-amino-benzyl) -2-imidazolidinone, 4-amino-2 - ((4 - [(5-amino-2-hydroxyphenyl) -methyl] -piperazinyl) -methyl) phenol, 3,5-diamino-4-hydroxy-catechol, 1,4-bis (4-amine (n-phenyl) -1,4-diazacycloheptane, aromatic nitriles such as 2-amino-4-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile, nitro group-containing amino compounds such as 3-amino-6 -methylamino-2-nitro-pyridine, picramic 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), 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-amino-2-nitro-4- [ bis (2-hydroxyethyl) amino] benzene, 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5), 1-amino-2-nitro-4 - [( 2-hydroxyethyl) amino] -benzene (HC Red No. 7), 2-chloro-5-nitro-N-2-hydroxyethyl-1,4-phenylenediamine, 1 - [(2-hydroxyethyl) amino] -2-nitro 4-aminobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro-o-toluidine, 1-amino-3-methyl-4 - [( 2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4 - [(2,3-dihydroxypropyl) amino] -5-chlorobenzene (HC Red No. 10 ) 2- (4-amino-2-nitroanilino) benzoic acid, 6-nitro-2,5-diaminopyridine, 2-amino-6-chloro-4-nitrophenol, 1-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) , 1-Amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (gallium), 4-amino-4'-nitrostilbene-2,2'-disulfonic acid Disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino- 3'-nitrobenzophenone-2-carboxylic acid, 1-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-1-nitronaphthalene, 5-amino-6-nitrobgno-1,3-dioxole, anilines, especially nitro groups -containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nit robenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) - benzene, 2-nitro-1-amino-4- [bis- (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 1-amino-5-chloro-4 ( 2-hydroxyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as shown in the formula IV

in the
R ^{10 represents} a hydroxyl group or an amino group represented by C ₁ -C ₆ -alkyl, C ₁ -C ₆ -hydroxyalkyl, C ₁ -C ₆ -alkoxy or C ₁ -C ₆ -alkoxy-C ₁ C ₆ alkyl group may be substituted,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ independently of one another represent a hydrogen atom, a hydroxyl or an amino group which is represented by C ₁ -C ₆ -alkyl, C ₁ -C ₆ -hydroxyalkyl, C ₁ - C ₆ alkoxy C ₁ -C ₆ aminoalkyl or C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl groups may be substituted, and
Z '' is a direct bond, a saturated or unsaturated, optionally substituted by hydroxy-substituted carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group having the formula V

in the
Q signifies a direct bond, a CH ₂ or CHOH group,
• Q 'and Q''independently represent an oxygen atom, an NR ²² group in which R ^{22 is} a hydrogen atom, a C ₁ -C ₆ alkyl group or C ₁ -C ₆ hydroxyalkyl group, whereby both groups together with the remainder molecule may form a 5-, 6- or 7-membered ring, means the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _p '-O, wherein p' is 2 or 3, 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'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfoxide, 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 precursors Component B are preferably selected from the group consisting from 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamino-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-methylpyrimidine, 3,5-diaminopyrazole, 3,5-diamino-1,2,4-triazole, 3-aminopyrazole, 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-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 1-phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8-aminoquinoline 4-aminoquinaldine, 2-aminonicotinic acid, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-morpholino-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. Farther as heterocyclic compounds according to the invention in DE-U1-299 08 573 disclosed hydroxypyrimidines can be used. The aforementioned Connections can both in free form and in the form of their physiologically compatible Salts, e.g. B. used as salts of inorganic acids such as hydrochloric or sulfuric acid become.

The aromatic hydroxy compounds (b) of the oxo dye precursors of 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 , Hy droxyhydrochinon; 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3-dimethylamino-phenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxy-phenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2, 4-Dihydroxyphenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, acetophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-dimethylamino 4-hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

When Precursors of naturally-analogous dyes are preferably those indoles and indolines used as a coloring component, at least a hydroxy or amino group, preferably as a substituent on the six-membered ring, exhibit. These groups can bear further substituents, for. B. in the form of an etherification or Esterification of the hydroxy group or alkylation of the amino group.

in der unabhängig voneinander
– R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
– R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
– R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
– R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
– R⁵ steht für eine der unter R⁴ genannten Gruppen,
– sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula VIa,

in the independently of each other
R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
R ⁵ is one of the groups mentioned under R ⁴ ,
- As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

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

in der unabhängig voneinander
– R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
– R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
– R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
– R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
– R⁵ steht für eine der unter R⁴ genannten Gruppen,
– sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula VIb,

in the independently of each other
R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
R ⁵ is one of the groups mentioned under R ⁴ ,
- As well as physiologically acceptable salts of these compounds with an organic or inorganic Säu re.

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

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

The Indoline and indole derivatives can in the inventive compositions both as free bases and in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. The hydrochlorides, the sulfates and hydrobromides used. The indole or Indoline derivatives are common in these in amounts of 0.05-10 Wt .-%, preferably 0.2-5 Wt .-% included.

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

Under hydroxy and salts of hydroxycarboxylic acids Ascorbic acid, isoascorbic acid, lactic acid, mandelic acid, malic acid, tartaric acid, citric acid, salicylic acid, on acids of Pentoses, hexoses and heptoses (sugar acids), in particular derived of glucose, galactose, fructose and mannose, and the salts of all aforementioned acids Understood.

Ascorbic acid is suitable in particular for use in colorants containing at least an oxo dye precursor.

The hydroxy and / or the hydroxycarboxylic acid salts are commonly used in the compositions of the invention in an amount of 0.05 to 10 wt .-%, based on the total weight of the agent used. Preferably, a total content of the acid or Salt component in the range of 0.1 to 5 wt .-%, in particular in Range of 0.5 to 2 wt .-%.

In a preferred embodiment The invention includes the agents ascorbic acid, isoascorbic acid and Sodium salicylate.

Under inorganic and organic reducing agents in the context of the invention The compounds sodium metabisulfite, sodium dithionite, sodium salts hydroxymethanesulfonic acid, those in documents WO 02/039965 A1, WO 02 / 030369A1 and WO 02/015855 listed sulfinic acid derivatives, Thiols such as cysteine, N-acetylcysteine, cysteamine, the reduced form of glutathione, 2,3-dihydroxy-2-cyclopenten-1-one or 6-0-palmitoyl ascorbate.

The Inorganic reducing agents are commonly used in the compositions of the invention in an amount of 0.05 to 10 wt .-%, preferably in an amount from 1 to 5 wt .-% used, in each case based on the total weight of the agent.

Quaternary ammonium compounds in the sense of the invention selected be from cationic polymers with quaternary ammonium group and from cationic surfactants with quaternary ammonium group.

According to the invention suitable cationic polymers are such polymers and corresponding commercial products, under the INCI names (according to International Cosmetic Ingredient Dictionary and Handbook (Cosmetic, Toiletry and Fragrance Association (CTFA) (ed.)), 9th Edition, Washington, 2002) Polyquarternium-2, Polyquarternium-4, Polyquarternium-6, Polyquarternium-7, Polyquarternium-10, Polyquarternium-11, Polyquarternium-16, Polyquarternium-22, Polyquarternium-28, Polyquarternium-29, Polyquarternium-32, Polyquarternium-37, Polyquarternium-44 fall. The cationic polymers are commonly used in the compositions of the invention in an amount of 0.1 to 5 wt .-%, preferably in an amount of 0.1-3% by weight, in each case based on the total weight of the agent.

Cationic surfactants which are suitable according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, z. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

The Linoleamidopropyl PG-Dimonium Chloride Phosphate, which is sold under the trade name Phospholipid EVA ^® (Uniqema) is a particularly preferred cationic surfactant.

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

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

In a further preferred embodiment of the invention, the agents contain linoleic amidopropyl PG-dimonium Chloride phosphates, alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, Trialkyl-methylammonium chlorides or esterquats.

The Cationic surfactants are preferred in amounts in the compositions according to the invention from 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

at the invention suitable, non-volatile Silicones are silicone-based water-soluble surfactants. These are nonionic in a preferred embodiment.

Especially preferred water-soluble Silicone-based surfactants are selected from the group of dimethicone copolyols which is preferably alkoxylated, in particular polyethoxylated or polypropoxylated are.

Prefers is an amount used of 0.01 to 10 wt .-% of the water-soluble Silicone surfactant, particularly preferably an amount of 0.1 to 5% by weight.

worin
– der Rest R für ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 12 C-Atomen, eine Alkoxygruppe mit 1 bis 12 C-Atomen oder eine Hydroxylgruppe stehen kann,
– die Reste R' und R'' für Alkylgruppen mit 1 bis 12 C-Atomen stehen,
– x für eine ganze Zahl von 1 bis 100, bevorzugt von 20 bis 30 steht,
– Y für eine ganze Zahl von 1 bis 20, bevorzugt von 2 bis 10 steht und
– a und b stehen für ganze Zahlen von 0 bis 50, bevorzugt von 10 bis 30.Dimethicone copolyols are understood according to the invention to mean polyoxyalkylene-modified dimethylpolysiloxanes of the general formulas VII or VIII:

wherein
The radical R can be a hydrogen atom, an alkyl group having 1 to 12 C atoms, an alkoxy group having 1 to 12 C atoms or a hydroxyl group,
The radicals R 'and R "represent alkyl groups having 1 to 12 C atoms,
X is an integer from 1 to 100, preferably from 20 to 30,
Y is 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.

links which fall under the above formulas will be in the following Patent Applications, which are incorporated by reference, discloses: US-A-4,122,029; US-A-4,265,878; US-A-4,421,769 and GB-A-2,066,659.

Especially Preferred dimethicone copolyols according to the invention are, for example commercially available under the trade name SILWET (Union Carbide Corporation) and DOW CORNING (Dow) distributed products.

Particularly according to the invention preferred dimethicone copolyols are Dow Corning 190 and Dow Corning 193 (Dow).

Amphoteric surfactants which are suitable according to the invention are selected from surface-active compounds which, apart from a C ₈ -C ₂₄ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and which are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate and dipropionates, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

In a further preferred embodiment of the invention, the agents contain amphoteric surfactants with the INCI names sodium cocoamphodipropionate and / or disodium cocoamphodipropionate and / or cocobetainamido amphodipropionate. Sodium Cocoamphodipropionate is sold for example under the trade name Amphoterge K ^® (Lonza). Disodium Cocoamphodipropionate is sold for example under the tradenames Mackam ^® C 2SF (McIntyre Group Ltd.), Miranol ^® C2M SF Conc (Rhodia), MIRAPON ^® FBS (Rhone Poulenc), and Amphoterge ^® T2 (Lonza). Cocobetainamido Amphopropionate 50 (Goldschmidt) marketed for example under the trade name Rewoteric QAM ^®.

The Amphoteric surfactants are preferred in amounts in the compositions of the invention from 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

As anti-dandruff agents, the agent according to the invention preferably contains elemental colloidal sulfur, zinc-pyridinethione, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2- (1H) -pyridone-monoethanolamine salt (trade name: octopirox ^®) and / or 1- [1- (4-chlorophenoxy) -3,3-dimethyl-2-oxo-butyl] imidazole (trade name: climbazole ^®). However, natural-based antidandruff agents, for example extracts of arnica, birch, burdock root, bearded lichen, poplar, stinging nettle and walnut shells, may also be used according to the invention.

The Anti-dandruff agents are commonly used in a concentration of 0.05-5 Wt .-%, preferably in a concentration of 0.1-2 wt .-% and in particular 0.15-1 Wt .-% in the inventive compositions used.

In a further preferred embodiment According to the invention, the means comprise at least two components from the group of physiologically compatible hydroxycarboxylic acids, quaternary ammonium compounds, amphoteric surfactants, non-volatile Silicone compounds, anti-dandruff, inorganic and organic reducing agents and / or mixtures of these compounds and / or from the physiologically acceptable salts of these compounds.

The agents according to the invention are preferred in an aqueous or aqueous-alcoholic base formulated. In particular, lower alcohols, such as ethanol, are used as alcohols and isopropanol into consideration. Aqueous-alcoholic Basics can while water-alcohol, preferably in a ratio of 1: 5 to 5: 1, contain. A preferred aqueous-alcoholic Base has an alcohol content of up to 15 wt .-%, based on the amount of water, on.

• • natürlichen oder synthetischen Direktfarbstoffen und
• • Oxidationsfarbstoffvorprodukten vom Entwickler- und Kupplertyp,

sowie aus Mischungen von Vertretern einer oder mehrerer dieser Gruppen, enthalten.In addition to the coloring components contained in the agents according to the invention can additionally at least one further coloring component selected from

• • natural or synthetic direct dyes and
• Developer and coupler type oxidation dye precursors,

and mixtures of representatives of one or more of these groups.

The in the inventive compositions additionally contained direct dyes as a coloring component are usually Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those among 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 and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

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

Furthermore, the compositions according to the invention can contain as direct dye a cationic substantive dye. Particularly preferred are

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

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

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

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

wobei
– G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
– G² steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
– G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Acetylaminoalkoxyrest, einen C₁- bis C₄-Mesylaminoalkoxyrest oder einen C₁- bis C₄-Carbamoylaminoalkoxyrest;
– G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁- bis C₄-Alkylrest oder
– wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.It may be preferred according to the invention, in addition to use as the oxidation dye precursor of the developer type, a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which
G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkoxy radical (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
G ² represents a hydrogen atom, a C ₁ -C ₄ -alkyl radical, a C ₁ -C ₄ -monohydroxyalkyl radical, a C ₂ -C ₄ -polyhydroxyalkyl radical, a C ₁ -C ₄ -alkoxy radical (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - 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 ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl, C ₁ - to C ₄ -hydroxyalkoxy, C ₁ - to C ₄ -acetylaminoalkoxy, C ₁ - to C ₄ -mesylaminoalkoxy or C ₁ - to C ₄ -carbamoylaminoalkoxy;
- G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
When G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are, in particular, the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ -monohydroxyalkylamino groups, Imidazolinium and ammonium.

Especially preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isoprpropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-pherylendiamin, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-Acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable Salt.

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

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

wobei:
– Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
– die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
– G⁵ und G⁶ stehen, unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
– G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit den Maßgaben, daß
die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

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

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

Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-amino phenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxybenzyl) 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 acceptable salts.

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

wobei:
– G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁-bis C₄)-alkylaminorest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl-(C₁-bis C₄)-aminoalkylrest oder einen (Di- C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
– G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-, Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoalkylrest,
– G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
– G¹⁶ steht für Wasserstoff oder ein Halogenatom.Furthermore, it may be preferred according to the invention; to use as the oxidation dye precursor of the developer type a p-aminophenol derivative or one of its physiologically acceptable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:
- G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ Alkoxy (C ₁ to C ₄ ) alkyl, C ₁ to C ₄ aminoalkyl, hydroxy (C _{1 to} C ₄ ) alkylamino, C ₁ to C ₄ hydroxyalkoxy, C ₁ - to C ₄ -hydroxyalkyl- (C ₁ -C ₄ ) -aminoalkyl or a (di- C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄ ) -alkyl, and
- G ¹⁴ represents a hydrogen or halogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ -, alkoxy (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,
G ¹⁵ is hydrogen, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
- G ¹⁶ is hydrogen or a halogen atom.

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

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- (□ -hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) -phenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) -phenol as well as their physiologically tolerable Salts.

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

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

Farther For example, the developer component may be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, Pyrazole, pyrazole pyrimidine derivatives and their physiologically tolerable Salt.

Preferred pyridine derivatives are in particular the compounds described in the patents GB 1 026 978 and GB 1 153 196 such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) -amino-3-amino-pyri din, 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 described in the German patent DE 2 359 399 , the Japanese Patent Application JP 02019576 A2 or in the laid-open specification WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino 4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892 . DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988 such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3 dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl 3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-one 4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (D-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4, 5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

wobei:
– G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-, Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
– die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-( C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]- (C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)-aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
– i hat den Wert 0, 1, 2 oder 3,
– p hat den Wert 0 oder 1,
– q hat den Wert 0 oder 1 und
– n hat den Wert 0 oder 1,
mit der Maßgabe, daß
– die Summe aus p + q ungleich 0 ist,
– wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2, 3); (5, 6); (6, 7); (3, 5) oder (3, 7);
– wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2, 3); (5, 6); (6, 7); (3, 5) oder (3, 7).Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E4) and their tautomeric forms, if a tautomeric equilibrium exists:

in which:
- G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical is a (C ₁ - to C ₄ ) alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical optionally substituted by an acetyl-ureide or a sulfonyl radical may be protected, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl radical, a di - [(C ₁ - to C ₄ ) -alkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - ( C ₁ to C ₄ ) aminoalkyl radical,
- The X radicals independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) -aminoalkyl radical, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical , an amino radical, a C ₁ - to C ₄ -alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) -amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
- i has the value 0, 1, 2 or 3,
- p has the value 0 or 1,
- q has the value 0 or 1 and
- n has the value 0 or 1,
with the proviso that
The sum of p + q is not equal to 0,
If p + q equals 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5, 6); (6, 7); (3, 5) or (3, 7);
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 the positions (2, 3); (5, 6); (6, 7); (3, 5) or (3, 7).

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

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

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

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.In particular, among the pyrazolo [1,5-a] pyrimidines of the above formula (E4):

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

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

The Pyrazolo [1,5-a] pyrimidines of the above formula (E4) can be used as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

• – m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6-methylphenol, 5-Amino-4-chlor-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)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• – o-Aminophenol und dessen Derivate,
• – m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxyethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol und 1-Amino-3-bis-(2'-hydroxyethyl)aminobenzol,
• – o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• – Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• – Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• – Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Amino-benzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• - Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Indolderivate wie beispielsweise 4-Hydrpxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• – Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amirio-2,6-dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder
• – Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)amino-3,4-methylendioxybenzol.

According to the invention are preferred coupler type oxidation dye precursors

• - 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-diaminobenzene and its derivatives such as 3,4-diaminobenzoic 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, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyphenyl, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amirio-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino 4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly according to the invention preferred coupler components 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.

Farther can the agents according to the invention also occurring in nature dyes such as, for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre and alkano root are included.

It it is not necessary that the oxidation dye precursors or the direct dyes each represent uniform compounds. Rather, you can in the hair colorants according to the invention, due to the production process for the individual dyes, be contained in minor amounts still other components as far as these are not the dyeing result adversely affect or for other reasons, e.g. toxicological, must be excluded.

Regarding the in the hair dyeing and -tönungsmitteln applicable dyes is still expressly on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pp. 248-250; Dyes) and chapter 8, pages 264-267; Oxidation dye precursors) appeared as volume 7 of the series "Dermatology" (ed. Ch., Culnan and N. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of cosmetic raw materials ", issued by the European Community, available in diskette form from the German Association of Industrial and Trade Companies for Medicines, Health food and personal care products e.V., Mannheim.

hair dyes, especially if the coloration ozidatively, whether with atmospheric oxygen or other oxidizing agents such as hydrogen peroxide, usually become weakly acidic to alkaline, d. H. to pH values in the range of about 5 to 11, set. For this purpose, the colorants contain alkalizing agents, usually Alkali or alkaline earth hydroxides, ammonia or organic amines. Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylbutanol and triethanolamine and alkali and alkaline earth metal hydroxides. In particular, monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanediol are within this group prefers. Also, the use of ω-amino acids such as ω-aminocaproic acid as Alkalizing agent is possible.

He follows the training of the actual hair colors in the context of an oxidative Process, so common oxidants, in particular hydrogen peroxide or its addition products be used on urea, melamine or sodium borate. Farther Is it possible, to carry out the oxidation with the aid of enzymes, the enzymes both be used for the production of oxidizing per-compounds as well as for reinforcement the effect of a small amount of existing oxidizing agent, or also Enzymes the electrons from suitable developer components (reducing agent) transferred to atmospheric oxygen. Oxidases such as tyrosinase, ascorbate oxidase and Laccase but also glucose oxidase, uricase or pyruvate oxidase. Farther be the procedure mentioned, the effect of small amounts (eg 1% and less, based on total agent) of hydrogen peroxide to amplify by peroxidases.

The Oxidation with atmospheric oxygen as the sole oxidant can however, preferred according to the invention be. In a further embodiment are therefore the agents according to the invention free of oxidizing agents, in particular free of hydrogen peroxide.

Conveniently, the preparation of the oxidizing agent is then mixed with the preparation with the coloring components immediately prior to dyeing the hair. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 10. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures may be in a range between 15 and 40 ° C, preferably at the temperature of the scalp. After a contact time of about 5 to 45, especially 15 to 30, minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is eliminated if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere,
• – anionische Polymere, wie Polyacryl- und Polymethacrylsäuren in Form ihrer Copolymere mit Acrylsäure- und Methacrylsäureestern und -amiden, Polyoxycarbonsäuren, wie Polyketo- und Polyhydrocarbonsäuren und deren Salze, sowie Polymere und Copolymere der Crotonsäure mit Estern und Amiden der Acryl- und der Methacrylsäure, wie Vinylacetat-Crotonsäure- und Vinylacetat-Vinylpropionat-Crotonsäure-Copolymere,
• – Strukturanten wie Glucose und Maleinsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecithin und Kephaline,
• – Parfümöle,
• – Dimethylisosorbid und Cyclodextrine,
• – Lösungsvermittler, wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin, Diethylenglykol und ethoxylierte Triglyceride,
• – Wirkstoffe wie Bisabolol, Allantoin, Panthenol, Niacinmid, Tocopherol und Pflanzenextrakte,
• – Lichtschutzmittel,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse, wie Walrat, Bienenwachs, Montanwachs, Paraffine, Ester, Glyceride und Fettalkohole,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie PCA, Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex oder Styrol/Acrylamid-Copolymere,
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat oder PEG-3-distearat,
• – Weißpigmente,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Konservierungsmittel.

Further optional ingredients of the agents according to the invention are

• Nonionic polymers such as 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 esters and amides, polyoxycarboxylic acids, such as polyketo- and polyhydrocarboxylic acids and their salts, and 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 soya lecithin, egg lecithin and cephalins,
• - perfume oils,
• Dimethylisosorbide and cyclodextrins,
• Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol and ethoxylated triglycerides,
• - active substances such as bisabolol, allantoin, panthenol, niacinmide, tocopherol and plant extracts,
• - sunscreen,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• Fats and waxes, such as spermaceti, 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, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex or styrene / acrylamide copolymers,
• Pearlescing agents such as ethylene glycol mono- and distearate or PEG-3-distearate,
• - white pigments,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - preservative.

• (i) auf die mit Haaren bewachsene Hautpartie und/oder den Haarkonturenbereich gegebenenfalls ein Mittel (M1) aufgetragen und nach einer Einwirkzeit Z1 abgespült wird,
• (ii) auf die Fasern ein Mittel (M2) gemäß des ersten Gegenstandes der Erfindung aufgetragen und nach einer Einwirkzeit Z2 von den Fasern gespült wird.

A second object of the invention is a method of reducing scalp staining in which

• (i) if appropriate, a means (M1) is applied to the skin-covered area of the hair and / or the hair contour area and rinsed off after a contact time Z1,
• (ii) a medium (M2) according to the first aspect of the invention is applied to the fibers and rinsed by the fibers after a contact time Z2.

Under A hair contour area is the transition area from a nearly hairless skin in areas of skin with pronounced hair growth to understand. The hair contour area is therefore usually at the head in the region of the hairline on the forehead, the temples, over the Ears and neck or neck, and covers each 1 to 3 cm of the hairy Skin and 1 to 3 cm of the glabrous area of the skin. This transition area is in the context of the method according to the invention preferably treated with the agent (M1).

ever after hairstyle can the hairy skin areas have areas where, although Hair growth is present, the skin becomes visible. This is special at apex or in the center of a so-called vortex hair growth the case. The agent (M1) is preferably applied to such lots.

The Exposure time Z1 is preferably 1 to 60 minutes, more preferably 5 to 45 minutes. The reaction time Z2 is preferably 1 to 60 minutes, more preferably 5 to 45 minutes.

For further, additional Steps taken as part of a staining procedure can be applied expressly to the known monographs, e.g. Kh. Schrader, Basics and Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced the corresponding knowledge of the professional.

For the treatment In the hair contour area, thickened formulations have proven to be extra proven effective, as they adhere well to the skin and not into the eyes of the user. The agent M1 is preferred a viscosity from 5000-50000 mPa · s, especially preferably a viscosity of (measured at 20 ° C with a Brookfield viscometer, type RVT, spindle # 5 at 4 rpm).

For the application on the scalp are preferably almost water-thin to slightly thickened formulations of the agent (M1) in a viscosity range of 1-500 mPa · s (measured at 20 ° C with a Brookfield viscometer, type RVT, spindle # 1 at 20 rpm) The agent M1 is preferred directly by means of applicators applied to the appropriate areas of the skin. As applicators in the context of the present inventive method are suitable especially in the hairdressing area called Applizetten narrow to brush and in particular those used in the home field Bottles with a narrow application tip. Furthermore However, the agent M1 can also be massaged with the help of the hands, for example by get to the site of action. For example, M1 can be used as a shampoo available.

to Production of the invention thickened Means M1 become these consistency regulators and / or thickeners added.

When Bodying agents are primarily fatty alcohols or hydroxy fatty alcohols with 12 to 30 and preferably 16 to 22 carbon atoms and next to it Partial glycerides, fatty acids or hydroxy fatty acids in Consideration. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides same chain length and / or polyglycerol poly-12-hydroxy stearates.

Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also relatively high molecular weight polyethylene glycol mono- and diesters of fatty acids, Polyacrlate (eg Carbopol ^® of Goodrich or Synthalens ^® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or alkyl oligoglucosides and electrolytes such as saline and ammonium chloride. The thickening agents are preferably present in amounts of from 0.1 to 10% by weight, more preferably from 0.2 to 5% by weight, very particularly preferably from 0.3 to 2% by weight, based in each case on the entire composition.

One example for a formulation of an agent (M1) contains 2.0% by weight of ascorbic acid, 0.4 to 1.0% by weight of hydroxyethylcellulose, 0.1% by weight of salicylic acid, 0.1 % By weight of sorbic acid, ad 100% by weight of water.

The Pretreatment of the scalp and hair contour area with the Means M1 is especially useful and necessary if the hair to be dyed with color intensive dyes. To prevent the Kopfhautanfärbung can the funds but also used prophylactically before any hair coloring become.

In a particularly preferred embodiment the method according to the invention scalp and hair contours are especially with the hair coloring color-intensive indole and / or indoline derivatives as precursors of natural analogue Dyes treated with the agent M1.

A coloring or shade is to be described as intensively colored if, on coloration of the coloring agent on white hair (Kerling, natural white), the color has a ΔL value in the CIE-Lab system of at least 30 by colorimetric determination. The ΔL value is calculated from: L _reference - L _staining (see also DIN 6174, German standards, Benth Verlag GmbH, Berlin, 1975). The reference is the undyed original hair. To determine the CIE Lab values, for example, the measuring device Texflash DC 3881 from Datacolor is suitable.

In a further, particularly preferred embodiment of the method according to the invention scalp and hair contours are especially with the hair coloring the oxo dyeing with the invention used Means M1 treated.

In a further preferred embodiment The invention provides the method before hair coloring with deep shades of shade applied.

• • physiologisch verträglichen Hydroxycarbonsäuren,
• • emulgierend wirkenden Verbindungen, ausgewählt aus nicht-flüchtigen Silikonverbindungen, kationischen Tensiden und amphoteren Tensiden und
• • Antischuppenwirkstoffen,
• • anorganischen und organischen Redukionsmitteln

und/oder aus Gemischen dieser Verbindungen und/oder aus den physiologisch verträglichen Salzen dieser Verbindungen in einem physiologisch akzeptablen Medium zur Verminderung der Hautanfärbung durch farbgebende Komponenten.A third object of the invention is the use of at least one component selected from

• Physiologically acceptable hydroxycarboxylic acids,
• Emulsifying compounds selected from non-volatile silicone compounds, cationic surfactants and amphoteric surfactants and
• Antidandruff active ingredients,
• • inorganic and organic reducing agents

and / or from mixtures of these compounds and / or from the physiologically tolerable salts of these compounds in a physiologically acceptable medium for reducing skin staining by coloring components.

The preferred representatives of these components were already in the first Subject of the invention defined.

The following examples are intended to further describe the subject matter of the invention without limiting it thereto. Unless stated otherwise, the stated content data refer to% by weight, based on the total weight of the composition. EXAMPLES Table 1 1) Colorants for dyeing with nature-analogous dyes

The dye 1 contains no skin staining reducing agent and is therefore not according to the invention (comparative colorant). The colorants 2 to 4 are colorants according to the invention.

0.5 g of the respective hair dye 1 to 4 was applied to test the skin color on each of a 3 cm ² skin area of the forearm of a subject and left there for a period of 30 minutes. Subsequently, the agent was rinsed off the skin area with water. Finally, the An Color of the skin parts visually appraised and evaluated. On a grading scale of 1 - 5 (1 = no skin staining, 5 = skin staining corresponds to the degree of skin staining with the comparison dye), the following grades were subjectively awarded: active substance grade Miranol C2M SF conc. (Colorant 2): 1 Sodium salicylate (colorant 3): 2-3 DC 190 (colorant 4): 3

Table 2 2) Hair dyes for oxo dyeing

The coloring creams from Table 2 were used immediately before use in the weight ratio 1: 1 with the gel according to the table 3 mixed.

Table 3

The coloring cream 5 contains no skin staining reducing agent and is therefore not according to the invention (comparison dye cream). The coloring creams 6 to 11 are colorants according to the invention.

0.5 g of the respective mixture was applied to a 3 cm ² skin area of the forearm of a subject to test for skin staining and left there for a period of 30 minutes. Subsequently, the agent was rinsed off the skin area with water. Finally, the staining of the skin was visually assessed and evaluated. On a grading scale of 1 - 5 (1 = no skin staining, 5 = skin staining corresponds to the degree of staining of the comparative staining cream 5) the following grades were subjectively awarded: active substance grade Miranol C2M SF conc. (Coloring cream 6) 2 Sodium salicylate (coloring cream 7) 2 Climbazol (coloring cream 8) 2-3 Phospholipid EFA (Dye Cream 9) 3-4 Sodium tartrate (coloring cream 10) 3-4 Rewoteric QAM 50 (coloring cream 11) 3-4

Claims (15)

Dyeing agent for human hair, characterized in that it comprises (i) at least one coloring component selected from: • Oxofarbstoffvorprodukten with the components A at least one reactive carbonyl compound and B at least one compound 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, • indole and / or indoline derivatives as precursors of naturally occurring dyes and / or mixtures of these compounds and / or from the physiologically acceptable salts of these compounds and (ii) at least one skin color reducing agent selected from Physiologically compatible hydroxycarboxylic acids, emulsifying compounds selected from non-volatile silicone compounds, cationic surfactants and amphoteric surfactants and antidandruff active ingredients, inorganic and organic reducing agents and / or mixtures of these compounds and / or from the physiologically tolerated salts of these compounds. Composition according to Claim 1, characterized in that the component A of the oxo dye precursors is selected from compounds of the formula I,

where • AR is 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, wherein the N-heteroaromatics may also be quaternized, • R ¹ is a hydrogen atom, a C ₁ -C ₆ -alkyl- , C ₂ -C ₆ acyl, C ₂ -C ₄ alkenyl, C ₁ -C ₄ perfluoroalkyl, an optionally substituted aryl or heteroaryl group, • R ² , R ³ and R ⁴ are each independently a, hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -aminoalkyl, C ₁ -C ₆ -hydroxyalkyl group, a C ₁ -C ₆ - Alkoxy C ₁ -C ₆ alkyloxy group, e C ₂ -C ₆ acyl group, an acetyl, carboxyl, carboxylato, carbamoyl, sulfo, sulfato, sulfonamide, sulfonamido, C ₂ -C ₆ -alkenyl, an aryl, an aryl C ₁ -C ₆ alkyl group, a hydroxy, a nitro, a pyrrolidino, a morpholino, a piperidino, an amino or ammonio or a 1-imidazole (in) io group, where the last three groups with one or more C ₁ -C ₆ -alkyl, C ₁ -C ₆ -carboxyalkyl, C ₁ -C ₆ -hydroxyalkyl, C ₂ -C ₆ -alkenyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ alkyl, substituted with optionally substituted benzyl groups, with sulfo (C ₁ -C ₄ ) alkyl or heterocycle (C ₁ -C ₄ ) alkyl groups, wherein two of the radicals from R ² , R ³ , R ⁴ and -ZYR ¹ together with the remainder of the molecule can form a fused optionally substituted 5-, 6- or 7-ring, which may also carry a fused aromatic ring, the system AR depending on the size of the Ringes can carry additional substituents, the independent R ² , R ³ and R ⁴ may each be the same as R ² , R ³ and R ⁴ , • Z is a direct bond, a carbonyl, a carboxy (C ₁ -C ₄ ) -alkylene, an optionally substituted C ₂ - C ₆ alkenylene, C ₄ -C ₆ alkadienylene, furylene, thienylene, arylene, vinylenarylene, vinylenfurylene, vinylenthienylene group, wherein Z together with the -YR ¹ group also represents an optionally substituted 5-, 6 Y is a group which is selected from carbonyl, a group according to formula II and a group according to formula III,

where R ⁵ is hydrogen, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl group, R ⁶ and R ⁷ independently of one another represent a C ₁ -C ₆ -alkyl group, an aryl group or together with the, structural element OCO of the formula III form a 5- or 6-membered ring. Agent according to one of claims 1 or 2, characterized that the Indole and / or Indoline derivatives selected of 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, 4-aminoindole, 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, 6-hydroxyindoline, 6-aminoindoline, 4-aminoindoline and the physiologically acceptable Salts of the aforementioned compounds. Agent according to one of claims 1 to 3, characterized that the hydroxy selected are made of ascorbic acid, isoascorbic acid, Lactic acid, Mandelic acid, malic acid, tartaric acid, citric acid, salicylic acid, on acids of Pentoses, hexoses and heptoses (sugar acids), in particular derived of glucose, galactose, fructose and mannose, as well as the physiological acceptable Salts of all the aforementioned acids. Agent according to one of Claims 1 to 4, characterized in that the nonvolatile silicone ver compounds are selected from dimethicone copolyols. Agent according to one of claims 1 to 5, characterized that the cationic surfactants selected are made from linoleic amidopropyl PG-dimonium chlorides phosphates, alkyltin methylammonium chlorides, dialkyldimethylammonium chlorides, Trialkylmethylammonium chlorides, alkyltrimethylammonium halides and Esterquats. Agent according to one of claims 1 to 6, characterized that the amphoteric surfactants selected are made from sodium cocoamphodipropionate, disodium cocoamphodipropionate and cocobetainamido amphopropionate. Agent according to one of Claims 1 to 7, characterized in that the antidandruff active ingredients are chosen from elemental colloidal sulfur, zinc pyridinethione, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2- (1H ) -pyridone monoethanolamine salt (trade name: octopirox ^®) and 1- [1- (4-chlorophenoxy) -3,3-dimethyl-2-oxo-butyl] imidazole (trade name: climbazole ^®). Agent according to one of claims 1 to 8, characterized that the organic and inorganic reducing agents are selected of sodium metabisulfite, sodium dithionite, sodium salts of hydroxymethanesulfonic acid, in documents WO 02/039965 A1, WO 02 / 030369A1 and WO 02/015855 listed sulfinic acid derivatives, Thiols such as cysteine, N-acetylcysteine, cysteamine, the reduced Form of glutathione, 2,3-dihydroxy-2-cyclopenten-1-one and 6-0-palmitoyl ascorbate. Method for reducing skin staining in Frame of a hair coloring, in which (i) on the hair-covered area of the skin and / or the hair contour area optionally applied a means (M1) and after a contact time Z1 is rinsed off, (ii) on the Fibers a means (M2) according to a the claims 1 to 13 and after a contact Z2 of the fibers rinsed becomes. Method according to claim 12, characterized in that that this Means (M1) at least one skin-staining reducing agent according to claim 1 contains. Method according to one of claims 10 or 11, characterized that this Means (M1) a viscosity from 5000-50000 mPa.s (measured at 20 ° C with a Brookfield viscometer, type RVT, spindle # 5 at 4 rpm) has. Method according to one of claims 10 to 12, characterized that this Medium (M1) with an applicator directly on the hair-covered Skin part or the hair contours is applied. Method according to one of claims 10 to 13, characterized that this Medium (M1) in the form of a shampoo first on the hair fiber and then massage in on the hair-covered area of the skin or the hair contours is applied. Use a connection selected from • physiological acceptable hydroxy, • emulsifying acting compounds selected from non-volatile Silicone compounds, cationic surfactants and amphoteric surfactants, Antidandruff active ingredients, • inorganic and organic reducing agents, and / or mixtures of these Compounds and / or the physiologically acceptable salts of these compounds to reduce skin staining by coloring components.