WO2007048473A1 - Hair colouring and/or lightening method with improved efficiency achieved by uv light - Google Patents

Hair colouring and/or lightening method with improved efficiency achieved by uv light Download PDF

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WO2007048473A1
WO2007048473A1 PCT/EP2006/009125 EP2006009125W WO2007048473A1 WO 2007048473 A1 WO2007048473 A1 WO 2007048473A1 EP 2006009125 W EP2006009125 W EP 2006009125W WO 2007048473 A1 WO2007048473 A1 WO 2007048473A1
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acid
amino
red
hair
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PCT/EP2006/009125
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German (de)
French (fr)
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Kai Böge
Hans Dolhaine
Helmut Hoepfl
Astrid Kleen
Mustafa Akram
Wolfgang Wolff
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Henkel Kommanditgesellschaft Auf Aktien
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/347Phenols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • A61K8/411Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • A61K8/415Aminophenols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065Preparations for temporary colouring the hair, e.g. direct dyes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/08Preparations for bleaching the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/10Preparations for permanently dyeing the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/81Preparation or application process involves irradiation

Abstract

The invention relates to a method for treating keratin fibres, in particular human hair. According to said method, a hair colouring and/or lightening agent is applied to the hair and the hair thus treated is subsequently irradiated with UV radiation in the wavelength range of 200 to 600 nm for 1 to 60 minutes. Said method leads to reduced exposure times and to an improved colouring and/or lightening of the treated hair.

Description

Hair coloring AND / OR -AUFHELLVERFAHREN WITH IMPROVED EFFICIENCY BY UV LIGHT

The cosmetic treatment of skin and hair is an important part of human body care. So human hair is nowadays treated in diverse ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and treatments, as well as bleaching, dyeing and shaping the hair using colorants, tints, waving compositions and styling preparations. Here, media play an important role for changing or shading the color of the hair. Disregarding the bleaching compositions that cause oxidative lightening of the hair loss natural hair dyes, from, the hair dyeing essentially three types of hair dyes are of importance in the field:

For permanent, intensive colors with corresponding fastness properties, so-called oxidation can be used. Colorants normally contain oxidation dye precursors, so-called developer components and coupler components. The primary intermediates form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or by coupling with one or more coupler components. The oxidation colorants are characterized by excellent, long-lasting coloring results. For natural-looking colorations but a mixture of a large number must be used of oxidation dye precursors usually; In many cases, direct dyes for shading still be used. Have formed in the course of color formation or directly used dyes significantly different fastnesses (z. B. UV stability, perspiration fastness, wash fastness, etc.), so it may come in time to a recognizable and therefore undesirable color shift. This phenomenon tends to occur when the hair style hair or hair zones have different degrees of damage. An example of this are long hair, are where the long time exposed to all kinds of environmental influences hair ends damaged significantly more usually than the relatively freshly grown hair zones.

For temporary colorations, usually colorants or tints are used which contain as coloring component direct dyes. These are dye molecules which attach directly to the hair and require no oxidative process to develop the color. These dyes include, for example, already from the ancient times for coloring the body and hair known henna. These stains are much more sensitive than the oxidative colorations, so that then much more quickly enters an often undesired nuance shift or even a visible "decoloration" to shampooing rule. Finally, in recent years a new type of color process has received considerable attention. In this process, precursors of the natural hair melanin dye are applied to the hair; these then form the course of oxidative processes within the hair naturally analogous dyes. In such a method, for example, 5,6-dihydroxyindoline is used as dye precursor. In particular repeated, using products with a 5.6-Dihydroxyindolin it is possible to reproduce people with gray hair the natural hair color. The coloration can take place here with atmospheric oxygen as sole oxidizing agent so that must be resorted to no other oxidizing agent. In people with originally mid-blonde to brown hair, the indoline can be used as the sole dye precursor. however, satisfactory results can often be achieved only by use of further dye components, in particular specific oxidation dye precursors for use in people with originally red and in particular dark to black hair color.

In one application of oxidizing agents, the actual coloring agent is usually prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation comprising the dye precursors. predominantly aqueous hydrogen peroxide solutions there are used as the oxidant.

In hair dyeing - especially in the hair coloring by the Home Use - several problems occur. One problem lies in the exposure time of the means which should be as short as possible to avoid possible confusion and to make the application less time consuming. However, this case should not be affected by the dyeing the shortened reaction time.

The present invention has for its object to provide a hair dye and / or -aufhellverfahren that stands out from the prior art by advantages in terms of application (time of application) and / or the effects achieved (intensity and brilliance of the dyeings or cloudy). Particular attention should coloring effects amplified and / or Behandlungsbzw. Exposure times are shortened.

It has now been found that it is advantageous to apply agent for dyeing and / or lightening of hair on the hair and the hair thus treated to irradiate before rinsing of the composition with UV radiation.

A first object of the present invention is a method for treating keratin fibers, in particular human hair, which comprises applying an agent for dyeing and / or lightening of hair on the hair and the treated hair following the application of the agent is 1 to 60 minutes is irradiated with UV radiation in the wavelength range 200 to 600 nm. UV radiation (ultraviolet radiation) are electromagnetic waves of wavelength from about 380 to 10 nm or a frequency of about 790 THz to 30 PHz. The energy of a single photon is in the range of about 3.3 eV (380 nm) to about 124 eV (10 nm).

Ultraviolet radiation is not visible. However, it belongs to the group of optical wavelengths, so often the misleading term "UV light" is to be found. UV radiation can be broken as the light of other wavelengths or infrared radiation reflected, transmitted, absorbed and diffracted.

By fluorescent ultraviolet radiation can be made visible indirectly.

Below a wavelength of about 200 nm, the energy of a single ultraviolet photon is sufficient to release electrons from atoms or molecules, that is to ionize it. As well as gamma and x-radiation is therefore referred to short-wave ultraviolet radiation below about 200 nm as the ionizing radiation.

In the inventive method, a hair treatment agent is applied to the hair to be treated, and then irradiated with UV light. As the head of the person being treated, UV light is exposed to the usual precautions in dealing with ultraviolet radiation must be observed. In particular, a too long period of irradiation should be avoided. Here, processes according to the invention are preferred in which the treated hair following the application of the agent is 1 to 60 minutes, preferably 2 to 50 minutes, more preferably 5 to 40 minutes and in particular 10 to 30 minutes with an ultraviolet radiation UV-A (400-320 nm) and / or UV-B (320-280 nm) and / or UV-C (280-200 nm) is irradiated.

as part of the process of the invention particularly preferred is irradiation with UV-A radiation, as the short-wave radiation types can cause health irritations especially during prolonged irradiation time. Especially preferred is the use of UV radiation having wavelengths above 350 nm, for example those having wavelengths of 365 nm, those with wavelengths of 370-375 nm, those with wavelengths of 380-385 nm, those with wavelengths of 390-395 nm or such having a wavelength of 400 nm.

Following the irradiation, can be rinsed before irradiation on the hair applied agent from the hair. According to the invention, preferred methods are characterized in that the agent for dyeing and / or lightening of hair after irradiation is rinsed from the hair. The inventive approach, the exposure of hair dyes and / or brighteners can be significantly shortened with the same result compared to the conventional application (blonding). With comparable exposure times significantly improved performance is achieved by the inventive process, manifested among other things in brighter, more intense colorations and / or cloudy.

In the inventive method an agent for dyeing and / or lightening of hair is used.

Conventional hair dyes are generally of at least one developing and at least one coupling substance and optionally also contain direct dyes as shading agents. Coupler and developer components are also referred to as oxidation dye precursors.

The developer components primary aromatic amines are commonly used with another in the para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof.

Special representatives are, for example, p-phenylenediamine, p-tolylenediamine, 2,4,5,6-tetraamino pyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5 -Diaminophenyl) - ethanol, 2- (2,5-diaminophenoxy) -ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

The coupler components usually m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are used.

As coupler substances are in particular α-naphthol, 1, 5-, 2,7-, and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, 2,4 Resorcinmonomethyl- suitable ether, m-phenylenediamine, -Diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1, 3-bis - (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino pyridine and 3,5-diamino-2,6-dimethoxypyridine.

For temporary colorations, usually colorants or tints are used which contain as coloring component direct dyes. These are dye molecules which attach directly to the hair and require no oxidative process to develop the color. These dyes include, for example, already from the ancient times for coloring the body and hair known henna. These stains are much more sensitive than the oxidative colorations, so that then much more quickly enters an often undesired nuance shift or even a visible "decoloration" to shampooing rule.

With regard to further customary dye components, is made expressly to the series "Dermatology", edited by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, Cape. 7, pages 248-250 (Direct dyes), and chapter. 8, pages 264-267 (oxidation dyes), and the "European Inventory of Cosmetic Raw Materials", 1996, published by the European Commission, available in diskette form by the Federal Association of German Industries and Trading Firms for pharmaceuticals, health products and personal care products, Mannheim, reference is made ,

For temporary colorations, usually colorants or tints are used which contain as coloring component direct dyes. These are dye molecules which attach directly to the hair and require no oxidative process to develop the color. These dyes include, for example, already from the ancient times for coloring the body and hair known henna. These stains are much more sensitive than the oxidative colorations, so that then much more quickly enters an often undesired nuance shift or even a visible "decoloration" to shampooing rule.

Finally, another dyeing process has received considerable attention. In this process, precursors of the natural hair melanin dye are applied to the hair; these then form the course of oxidative processes within the hair naturally analogous dyes. One such method used, for example 5,6-Dihydroxyindolin as dye. In particular repeated, using products with a 5.6-Dihydroxyindolin it is possible to reproduce people with gray hair the natural hair color. The coloration can take place here with atmospheric oxygen as sole oxidizing agent so that must be resorted to no other oxidizing agent. In people with originally mid-blonde to brown hair, the indoline can be used as the sole dye precursor. however, satisfactory results can often be achieved only by use of further dye components, in particular specific oxidation dye precursors for use in people with originally red and in particular dark to black hair color. Here, too, problems regarding the authenticity of the staining can occur.

Another option keratin fibers to color, provides the use of colorants that a combination of component

A compounds which contain a reactive carbonyl group with component B compounds selected from (a) CH-acidic compounds, (b) compounds with primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) contain from 2 to 9 amino constructed oligopeptides. The corresponding staining hereinafter called oxo dyeing. The resulting colorations partially have color fastnesses on the keratin fibers, which are comparable to the oxidation coloring with them. The achievable with the gentle oxo dyeing shades spectrum is very wide and the dyeing obtained often has an acceptable brilliance and color depth. The above-mentioned components A and B generally are not themselves dyes, and are therefore each taken separately, are not keratin fibers for dyeing. In combination, they form dyes in a non-oxidative process. From compounds of the component B but also corresponding oxidation dye precursors of the developer and / or coupler type can be used with or without the use of an oxidizing agent. Thus, the method of oxo dyeing readily can be combined with the oxidative dyeing system.

Preferred agents contain at least one oxidation dye precursor of the developer type and / optionally at least one oxidation dye precursor of the secondary intermediate type.

With regard to the coloring agents usable in the invention further dye precursors, the present invention is subject to no restrictions. The colorants according to the invention may contain as further dye precursors

Oxidation dye precursors of the developer and / or coupler type, and

Precursors of nature-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives of these groups.

Before its application to human hair hair dye are mixed with oxidation dye precursors with dilute aqueous hydrogen peroxide solution. The period of action on the hair to achieve a full coloration is between about 30 and 40 minutes. It is obvious that in the users of hair dyes is a need to reduce this exposure time, which is achieved by the method according to the invention.

The method according to the invention, wherein the agent for dyeing and / or lightening of hair is formulated as oxidative hair dyeing, which based on its weight 0.01 to 15 wt .-%, preferably 0.05 to 10 wt .-%, more preferably 0, 1 to 7.5 wt .-% and in particular 0.2 to 5 wt .-% of one or more oxidation dye precursor (s) which are preferred. In a first preferred embodiment, the colorant contains at least one developer component. The developer components are usually primary aromatic amines with a further in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-amino-pyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives.

It may be preferable in the invention to use as the developer component is a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particularly preferably p-phenylenediamine derivatives of formula (E1)

Figure imgf000008_0001

in which

G 1 represents a hydrogen 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 J-AIkOXy- ( C 1 - to C 4) alkyl group, a 4'-aminophenyl radical or a C 1 - to C 4 -alkyl radical which is equipped with a nitrogen-containing group, a phenyl group or a 4'-aminophenyl group; G 2 represents a hydrogen atom , C r 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 J-AIkOXy- (C 1 - to C 4) alkyl group or a C 1 - to C 4 -alkyl, which is substituted with a nitrogenous 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, C 1 - to C 4 monohydroxyalkyl radical, a C 2 - to C 4 - polyhydroxyalkyl radical, a C 1 - to C 4 -Hydroxyalkoxyrest, a C 1 - to C 4 - Acetylaminoalkoxyrest, a C 1 - to C 4 - Mesylaminoalkoxyrest or a C 1 - to C 4 - Carbamoylaminoalkoxyrest;

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

Examples of the substituents mentioned as substituents in the compounds of the invention C 1 - to C 4 - alkyl radicals are the methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl groups. According to the invention, preferred C 1 - to C 4 -alkoxy are, for example, a methoxy or an ethoxy group. A hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl group are called a to C 4 -hydroxyalkyl group - In addition, preferred examples of a C. 1 A 2-hydroxyethyl group is particularly preferred. A particularly preferred C 2 - to C 4 -polyhydroxyalkyl group is the 1, 2-dihydroxyethyl. Examples of halogen atoms in the present invention F, Cl or Br atoms, chlorine atoms are 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 especially the amino groups, C 1 - to C 4 monoalkylamino, C 1 - to C 4 - dialkylamino, C 1 - to C 4 -Trialkylammoniumgruppen, C 1 - to C 4 - Monohydroxyalkylaminogruppen, imidazolinium and ammonium.

Especially preferred p-phenylenediamines of formula (E1) are selected from p-phenylenediamine, p-tolylenediamine, 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-dipropylene! -p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) aniline, N, N-bis (.beta.-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (.beta.-hydroxyethyl) amino-2 -methylanilin, 4-N, N-bis (.beta.-hydroxyethyl) amino-2-chloroaniline, 2- (.beta.

Hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (beta-hydroxypropyl) -p-phenylenediamine, 2 - hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, .beta.-hydroxyethyl) -p-phenylenediamine, N- (ß, γ-dihydroxypropyl) -p-phenylenediamine , N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (beta-hydroxyethyloxy) -p-phenylenediamine, 2- (.beta. Acetylaminoethyloxy) -p-phenylenediamine, N- (ß methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane, as well as their physiologically acceptable salts.

According to the invention particularly preferred p-phenylenediamine derivatives of formula (E1) are p-phenylenediamine, p-toluylenediamine, 2- (beta-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) - p-phenylenediamine, and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.

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

Among the binuclear developer components which can be used in the colorants according to the invention may in particular be mentioned the compounds corresponding to the following formula (E2), and their physiologically tolerable salts:

Figure imgf000010_0001
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 - C 4 hydroxyalkyl radical substituted by and / or by a bridge Y - to C 4 -alkyl radical, by a C 1 or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, by one or more nitrogenous groups and / or one or more hetero atoms such as oxygen , sulfur or nitrogen atoms may be interrupted or terminated, and possibly by one or more hydroxyl or C 1 - may be substituted to C 8 -alkoxy radicals, or a direct bond,

G 5 and G 6 are each independently a hydrogen or halogen atom, a C 1 - to C 4 alkyl, C 1 - to C 4 monohydroxyalkyl radical, a C 2 - to C 4 - polyhydroxyalkyl radical, a C 1 - to inoalkylrest C 4 -Am or a direct bond to the bridge 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 formula (E2) comprise only one bridge Y per molecule and the compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

In formula (E2) substituents used in the present invention are defined analogously to the above embodiments.

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

Very particularly preferred double bases of formula (E2) are N, N'-bis (.beta.-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 acceptable salts.

It may also be preferable in the invention to use as the developer component is a p-aminophenol derivative or one of its physiologically acceptable salts. Particularly preferably p-aminophenol derivatives of formula (E3) are

Figure imgf000011_0001
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 r to C 4) alkyl group, a C 1 - to C 4 aminoalkyl radical, a hydroxy ^ Cr to C 4) alkylamino group, a C 1 - to C 4 -Hydroxyalkoxyrest, a C 1 - to C ^ HydroxyalkyKd-to C 4) aminoalkyl radical or a (di-C 1 - to C ^ AlkylaminoHCr 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) - alkyl alkoxy (C r to C 4), a C 1 - to C 4 aminoalkyl radical or a C 1 - to C 4 -Cyanoalkylrest,

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

G 16 is hydrogen or a halogen atom.

In the formula (E3) substituents used in the present invention are defined analogously to the above embodiments.

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

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

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

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

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

Preferred pyrimidine derivatives are in particular 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 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (ß-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'- chlorobenzyl) pyrazole, 4,5-diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1 , 3-dimethyl-5-hydrazinopyrazol, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert. butyl-3-methylpyrazole, 4,5-diamino-1- (ß-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3 - (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1- isopropylpyrazol, 4,5-diamino-3-methyl-1-isopropylpyrazol, 4-amino-5- (beta-aminoethyl) amino-1, 3-dimethylpyrazole, 3,4,5-

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

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

Figure imgf000013_0001
in which

G 17, G 18, G 19 and G 20 are independently a hydrogen atom, a C 1 - to C 4 -alkyl radical, an aryl radical, a C 1 - to C 4 -hydroxyalkyl group, a C 2 - to C 4 - a polyhydroxyalkyl (C 1 - to C 4 alkyl group), a C 1 - - to C 4 J-AIkOXy- (C 1 to C 4 - aminoalkyl radical, which may optionally be protected by an acetyl ureide or a sulfonyl radical can, a (C 1 - to C 4) -Alkylam ino- (C 1 - to C 4) alkyl, a Dι - [(C r to C 4) alkyl] - (C 1 - to C 4) - amιnoalkylrest, wherein the dialkyl residues optionally form a carbocycle or a heterocycle with 5 or 6 chain links, a C 1 - to C 4 hydroxyalkyl or a di- (C 1 - to C 4) - [hydroxyalkyl] - (Cr to C 4) -amιnoalkylrest, the X radicals are each independently a hydrogen atom, a C 1 - to C 4 - alkyl radical, an aryl radical, a C 1 - to C 4 -hydroxyalkyl group, a C 2 - to C 4 - polyhydroxyalkyl group, a C 1 - to C 4 -Amιnoalky lrest, a (C 1 - to C 4) -Alkylamιno- (C 1 - to C 4) alkyl, a Dι - [(C r to C 4) alkyl] - (C 1 - to C 4) -amιnoalkylrest, wherein the dialkyl residues optionally form a carbocycle or a heterocycle with 5 or 6 chain links, a C 1 - to C 4 hydroxyalkyl or a di- (C 1 - to C 4 hydroxyalkyl) amιnoalkylrest, an amino group, a C 1 - to C 4 -alkyl- or di- (C 1 - to C 4 hydroxyalkyl) amιnorest, 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 is 0 or 1 and n is 0 or 1, with the proviso that the sum of p + q is not 0 when p + q is equal to 2, n has the value 0, and the groups NG 17 G 18 and G 20 NG 19 demonstrate the

Positions (2,3), (5,6), (6,7), (3,5) or (3,7) when p + q is equal to 1, n has the value 1, and the groups NG 17 G 18 (or 19 NG G 20) and the

Group OH occupy the positions (2,3), (5,6), (6,7), (3,5) or (3,7),

In formula (E4) substituents used to the invention are defined analogously to the above VERSIONS When the pyrazole [1, 5-a] pyrimidine of the above formula (E4) contains a hydroxy group at any of positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated in the following scheme, for example:

Figure imgf000014_0001

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

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

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

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

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

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

3-aminopyrazole [1, 5-a] pyrimidin-5-ol;

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

2- (7-aminopyrazole [1, 5-a] pyrimidine-3-ylamino) ethanol;

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

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

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

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

3-Amino-7-dimethylamino-2,5-dimethylpyrazole [1, 5-a] pyrimidine; and their physiologically tolerable salts and their tautomeric forms when a tautomeric equilibrium exists.

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

In summary method of the invention are preferred in which the oxidation hair dye as oxidation dye precursor, at least one

Contains developer component is preferably selected from p-phenylenediamine, p-toluenediamine, N, N-bis (2-hydroxyethyl) amino-p-phenylenediamine, 1, 3-bis - [(2-hydroxyethyl-4 '- aminophenyl ) amino] propan-2-ol, 1, 10-bis (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane, 4-aminophenol, 4-amino-3-methylphenol, bis (5-amino-2-hydroxyphenyl) methane, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4,5-diamino-1- (2-hydroxyethyl) pyrazole.

In a further preferred embodiment, the colorant used in the process of this invention contain at least one coupler component.

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

According to the invention, preferred secondary intermediates are 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-methyl-phenol, 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 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-amino-benzomorpholine,

Quinoxaline derivatives such as 6-methyl-1, 2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives, such as 1-phenyl-3-methylpyrazole-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine,

2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-

Amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or

Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-

Amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

According to the invention particularly preferred secondary intermediates 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.

In summary method of the invention are preferred in which the oxidation hair dye containing oxidation dye precursor as at least one coupling component which is preferably selected from resorcinol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, 5-aminophenol, 5-amino-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 3-amino-4-chloro-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-amino-2 , 4-dichlorophenol, 2,4-diaminophenoxyethanol, 2-amino-4- (2'-hydroxyethyl) amino-anisole, 1, 3-bis- propane (2,4-diaminophenoxy), 2-amino-3-hydroxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-naphthol, 2-methyl-1-naphthol, 1, 5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-phenyl-3-methylpyrazole-5-one, 2,6-bis - [(2 'hydroxyethyl) amino] toluene, 4-hydroxyindole, 6-hydroxyindole, 6- hydroxybenzomorpholine.

The precursors of nature-analogous dyes, such indoles and indolines are preferably used, which, preferably have at least one hydroxyl or amino group as substituent on the six-membered ring. These groups can carry further substituents such. Example in the form of an etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

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

Figure imgf000017_0001
in independently

R 1 represents hydrogen, a C 1 -C 4 alkyl group or a hydroxy-dC ^ alkyl group,

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

R 3 stands for hydrogen or a C r C 4 alkyl group,

R 4 represents hydrogen, an alkyl group or dC a group -CO-R 6 in which R 6 represents a Ci-C 4 alkyl group, and

R 5 represents one of the groups mentioned for R 4, and physiologically compatible salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline,

N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and the 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Of particular note are within the group of 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-Dihydroxyindolin.

As precursors of natural hair dyes, derivatives of 5,6-dihydroxyindole corresponding to formula are excellently suitable to continue (IIIb),

Figure imgf000017_0002

R 1 (IIIb) in which independently of one another

R stands for hydrogen, a Ci-C 4 alkyl group or a Ci-C 4 hydroxyalkyl group,

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

R 3 represents hydrogen or an alkyl group dd, R 4 stands for hydrogen, an alkyl group or dC a group -CO-R 6 in which R is a CrC t -alkyl group, and

R 5 represents one of the groups mentioned for R 4, and physiologically compatible salts of these compounds with an organic or inorganic acid.

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

Within this group, 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 -Dihydroxyindol.

The indoline and indole derivatives can be in used in the context of the inventive method colorants both as free bases and in the form of their physiologically compatible salts with inorganic or organic acids, eg. Example hydrochlorides, sulfates and hydrobromides be used. The indole or indoline derivatives are disclosed in this usually used in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

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

Preferred in the present process appropriation for dyeing hair are characterized in that they contain at least one dye precursor from the groups of aromatic and heteroaromatic diamines, aminophenols, naphthols, polyphenols, CH-acidic coupler components and their derivatives in quantities of 0.01 to 25th by weight, preferably from 0.5 to 10%.%, in particular from 1 to 5 wt .-%, each based on the total agent.

Besides the above compounds, the colorants used in the inventive method for shading can contain one or more direct dyes. Direct dyes are usually nitrophenylendiamines, Nitroaminophenole, azo dyes, anthraquinones or Indophenole. Preferred direct dyes are known under the International names or commercial names of HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red

11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue

12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1, 4-Diamino -2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis- (ß-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (ß-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl ) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4 amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphe- nylamin-2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picramic acid and salts thereof, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene ,

Corresponding method of the invention, wherein the agent for dyeing and / or lightening of hair based on its weight 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, particularly preferably from 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more reactive carbonyl compound (s) which are preferred.

A method according to any one of claims 1 to 7, characterized in that the agent for dyeing and / or lightening of hair based on its weight 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, particularly preferably 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more CH-acidic compound (s) contains.

A method according to any one of claims 1 to 8, characterized in that the agent for dyeing and / or lightening of hair at least one direct dye from the group of cationic (basic) dyes, preferably Basic Blue 6, CI -No. 51, 175; Basic Blue 7, CI-No. 42.595; Basic Blue 9, CI-No. 52.015; Basic Blue 26, Cl-No. 44.045; Basic Blue 41, CI No. 11, 154; Basic Blue 99, Cl-No. 56.059; Basic Brown 4, Cl-No. 21, 010; Basic Brown 16, Cl No. 12.250; Basic Brown 17, Cl-No. 12.251; Basic Green 1, Cl-No. 42.040; Basic Orange 31; Basic Red 2, Cl-No. 50.240; Basic Red 22, Cl-No. 11, 055; Basic Red 46; Basic Red 51; Basic Red 76, Cl-No. 12.245; Basic Violet 1, Cl-No. 42.535; Basic Violet 2; Basic Violet 3, CI-No. 42.555; Basic Violet 10, CI-No. 45.170; Basic Violet 14, CI-No. 42.510; Basic Yellow 57, Cl-No. 12.719; Basic Yellow 87 and / or anionic (acidic) dyes, and / or nonionic dyes, preferably Acid Black 1, Cl-No. 20.470; Acid Black 52; Acid Blue 7; Acid Blue 9, CI-No. 42.090; Acid Blue 74, Cl-No. 73,015, Acid Red 18, Cl-No. 16.255; Acid Red 23; Acid Red 27, Cl-No. 16.185; Acid Red 33; Acid Red 52; Acid Red 87, Cl-No. 45,380; Acid Red 92, Cl-No. 45,410; Acid Orange 3; Acid Orange 7; Acid Violet 43, Cl-No. 60.730; Acid Yellow 1, Cl No. 10.316; Acid Yellow 10; Acid Yellow 23, Cl-No. 19,140; Acid Yellow 3, Cl-No. 47.005; Acid Yellow 36; D & C Brown No. 1, Cl-No. 20.170 (Acid Orange 24); D & C Green No. 5, Cl-No. 61, 570 (Acid Green G); D & C Orange No. 4, Cl-No. 15,510 (Acid Orange II); D & C Orange No. 10, CI-No. 45,425: 1 (Solvent Red 73); D & C Orange No. 11, Cl-No. 45,425 (Acid Red 95); D & C Red No. 21, Cl-No. 45,380: 2 (Solvent Red 43); D & C Red No. 27, Cl-No. 45,410: 1 (Solvent Red 48); D & C Red No. 33, Cl-No. 17,200 (Acid Red 2A, Acid Red B); D & C Yellow No. 7, CI-No. 45,350: 1 (Solvent Yellow 94); D & C Yellow No. 8, Cl-No. 45,350 (Acid Yellow 73); FD & C Red No. 4, Cl-No. 14,700 (Food Red 4); FD & C Yellow No. 6, Cl-No. 15,985 (Food Yellow 3); Food Green 3; Pigment Red 57-1; Disperse Black 9; Disperse Blue 1; Disperse Blue 3; Disperse Violet 1; Disperse Violet 4; HC Orange 1; HC Red 1; HC Red 3; HC Red 13; HC Yellow 2; HC Yellow 4; Na Pikramat; 1, 4-bis (2 '-hydroxyethyl) amino-2-nitro-p-phenylenediamine; HC Yellow 5; HC Blue 2; HC Blue 12; 4-amino-3-nitrophenol; HC Yellow 6; HC Yellow 12; 2-Nitro-1- (2 'hydroxyethyl) amino-4-methyl benzene; 2-nitro-4-amino-diphenylamine-2-carboxylic acid; 2-amino-6-chloro-4-nitrophenol; HC Red BN; 6-nitro-1, 2,3,4-tetranitrochinoxalin; o-nitro-p-phenylenediamine; p-nitro-m-phenylenediamine; HC Red B 54; HC Red 10; HC Red 11; HC Red 13; 2- (2 '-hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene; 4-ethylamino-3-nitrobenzoic acid; 2-chloro-6-ethylamino-4-nitrophenol; 2-hydroxy-1, 4-naphthoquinone; amine-1-propene (4-amino-2-nitrophenyl); isatin; N-methylylisatin; HC Violet 1; HC Violet 2; 4-Nitrophenyl-aminoethylharnstoff used in amounts of 0.01 to 25.% By weight, preferably from 0.5 to 10.%, In particular from 1 to 5 wt .-%, each based on the total composition, contains.

Furthermore, the means used in the inventive process for dyeing hair can also contain a cationic direct dye. Particular preference is given

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

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

(C) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as they are called, for example, in EP-A2-998 908, referred to at this point explicit reference, in claims 6 to. 11

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

Figure imgf000021_0001

CH 3 SO 4 "

Figure imgf000021_0002
he

Figure imgf000021_0003
Figure imgf000022_0001

The compounds of formulas (DZ1), (DZ3) and (DZ5), which are also known under the names Basic Yellow 87, Basic Orange 31 and Basic Red 51 are especially preferred cationic direct dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ®, according to the invention are also very particularly preferred cationic direct dyes.

The means used in the invention according to this embodiment contain the dyes preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant.

Furthermore, the preparations used in the invention may also contain naturally occurring dyes such as, for example, in henna red, henna neutral, henna black, chamomile blossom, sandalwood, black tea, buckthorn bark, sage, logwood, madder root, catechu, cedar and alkanna contain. It is not necessary that the oxidation dye precursors or the substantive dyes to be single compounds. Rather, other components to be included due to the manufacturing processes for the individual dyes, in lesser amounts in the inventively used hair dye, to the extent they do not adversely affect the coloring result or toxicological for other reasons, for example, must be excluded.

In a further embodiment, the agent used in the invention for dyeing hair in addition contains a combination of component A compounds which contain a reactive carbonyl group with component B compounds selected from (a) CH-acidic compounds, (b) compounds with primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) constructed from 2 to 9 amino acids oligopeptides.

According to the invention usable compounds having a reactive carbonyl group (hereinafter also referred to as reactive carbonyl compounds or component A) have at least one carbonyl group as reactive group which reacts with the compounds of component B to form one of the two components linking chemical bond. Furthermore, such compounds as component A are according to the invention comprises in which the reactive carbonyl group is derivatized in such a way or masked, that the reactivity of the carbon atom of the derivatized or masked carbonyl group relative to the component B is always present. These derivatives are preferably the condensation of reactive carbonyl compounds with a) amines and derivatives thereof with the formation of imines or oximes as condensation compound b) of alcohols under formation of acetals or ketals as condensation compound.

Component A is preferably selected from the group which is formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-Hydroxybutyrophenon, 3-Hydroxybutyrophenon, 4-Hydroxybutyrophenon, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4, acetophenone 6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal-4-hydroxy-3-methoxy-, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-

Dimethylaminoacetophenone, 4-Morpholinoacetophenon, 4-Piperidinoacetophenon, 4- Imidazolinoacetophenon, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, A-

acetonaphthone hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1, 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-lπdanon, 9 -Fluorenon, 3-hydroxyfluorenone, anthrone, 1, 8-dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, A- methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, A- hydroxy-2,3 dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxy-benzaldehyde, 4-hydroxy-2,6-dimethoxy-benzaldehyde, 4-hydroxy-2-methyl-benzaldehyde, 4-hydroxy-3-methyl-benzaldehyde, A - hydroxy-2,3-dimethyl-benzaldehyde, 4-hydroxy-2,5-dimethyl-benzaldehyde, 4-hydroxy-2,6-dimethyl-benzaldehyde, 4-hydroxy-3,5-dimethoxy-benzaldehyde, 4-hydroxy -3,5-dimethyl-benzaldehyde, 3,5-diethoxy-4-hydroxy-benzaldehyde, 2,6-diethoxy-4-hy droxy-benzaldehyde, 3-hydroxy-4-methoxy- benzaldehyde, 2-hydroxy-4-methoxy-benzaldehyde, 2-ethoxy-4-hydroxy-benzaldehyde, 3-ethoxy-4-hydroxy-benzaldehyde, 4-ethoxy-2- hydroxy-benzaldehyde, 4-ethoxy-3-hydroxy-benzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxy, 2,3,5-trimethoxy, 2,3,6-trimethoxy, 2,4,6-trimethoxy, 2,4,5-trimethoxy, 2,5,6-trimethoxy, 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-dimethyl thylaminobe nzaldehyd, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, A- diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-Piperidinobenzaldehyd, 2-methoxy-1-naphthaldehyde, 4 c methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1 -naphthaldehyd, 2-hydroxy-4-methoxy-1 -naphthaldehyd, 3 -hydroxy-4-methoxy-1 -naphthaldehyd, 2,4-dimethoxy-1-naphthaldehyde, 3, 4-dimethoxy-1 -naphthaldehyd, 4-hydroxy-1 -naphthaldehyd, A- dimethylamino-1 -naphthaldehyd, 2-methoxy -zimtaldehyd, 4-methoxy-cinnamaldehyde, 4-hydroxy-3-methoxy-cinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino -2- methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylamino-benzaldehyde, 4-diphenylamino benzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) benzaldehyde, piperonal, 2,3,6,7 -Tetrah ydro-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 (Fischers aldehyde or aldehyde Tribasen), 2-lndolaldehyd, 3-lndolaldehyd, 1-methylindole-3-aldehyde, 2-Methylindo-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-pyridinealdehyde, 2-pyridinealdehyde, 3-pyridinealdehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromone-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,

Benzylidene acetone, 4-Hydroxybenzylidenaceton, 2-Hydroxybenzylidenaceton, 4-Methoxybenzyli- denaceton, 4-hydroxy-3-methoxybenzylidenaceton, 4-Dimethylaminobenzylidenaceton, 3,4-Me thylendioxybenzylidenaceton, 4-Pyrrolidinobenzylidenaceton, 4-Piperidinobenzylidenaceton, 4-mor- pholinobenzylidenaceton, 4-Diethylaminobenzylidenaceton, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2- Benzylidencyclohexanon, 2- (4'-hydroxybenzylidene) cyclohexanone, 2- (4'-Dimethylaminobenzy- liden) 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-meth oxybenzylidene) -5,5-dimethyl-1, 3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1, 3-cyclohexanedione, 2 -Benzylidencyclopentanon, 2 '- (4-hydroxybenzylidene) -cyclope ntanon, 2- (4'-dimethylaminobenzylidene) cyclopentanone,

5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-meth oxyphenyl) 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 -diene-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one , 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) - hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3 , 5-diene-2-one,

5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, A- 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-Dinitrosalicylaldehyd, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formyl- benzenesulfonic acid, 4-nitro -1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyd, 9-ethyl-3-carbazolaldehyd, 3-Acetylcarbazol, 3,6-diacetyl-9-ethylcarbazole, S-acetyl -θ-methylcarbazol, 1, 4-dimethyl-3-carbazolaldehyd, 1, 4,9-TriMeth yl-3-carbazolaldehyd,

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-methylchinolinium-, 2-formyl-1-methylchinolinium-, 4-acetyl-1- methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1 -methylchinolinium-, 5-formyl-1 -methylchinolinium-, 6-formyl-1 -methylchinolinium-, 7-formyl-1 - methylchinolinium-, 8- formyl-i-methylquinolinium, 5-formyl-i-ethylchinolinium-, 6-formyl-1- ethylchinolinium-, 7-formyl-i-ethylchinolinium-, 8-formyl-i-ethylchinolinium, benzylchinolinium- 5-formyl-1, 6-formyl-i-benzylchinolinium-, 7-formyl-i-benzylchinolinium-, 8-formyl-1- benzylchinolinium, 5-formyl-i-allylchinolinium-, 6-formyl-i-allylchinolinium-, 7-formyl-1- allylchinolinium- and 8-formyl-i-allylchinolinium-, 5-acetyl-1 -methylchinolinium-, 6-acetyl-1- methylchinolinium-, 7-acetyl-1 -methylchinolinium-, 8-acetyl-1-methylquinolinium, 5-acetyl-1- ethylchinolinium-, 6-acetyl-1-ethylchinolinium-, 7-acetyl-1-ethylchinolinium-, 8-acetyl-1- ethylchinolinium, 5-acetyl-1-benzylchinolinium -, 6-acetyl-1-benzylchinolinium-, 7-acetyl-1- benzylchinolinium-, 8-acetyl-1-benzylchinolinium, 5-acetyl-1-allylchinolinium-, 6-acetyl-1- allylchinolinium-, 7-acetyl- 1 -allylchinolinium- and δ-acetyl-1-allylchinolinium, 9-formyl-10-methyl-acridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1, 3-dimethyl-2- (4'- formylphenyl) -benzimidazo- lium-, 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-, 4'-formyl-1-naphthyl 2- ( ) -3-methylbenzothiazolium-, 5-chloro-2- (4'-formylphenyl) -3-methylb ! Enzothiazolium-, 2- (4'-formylphenyl) -3,5-ium dimethylbenzothiazo benzenesulfonate, toluenesulfonate -p, methane sulfonate, perchlorate, sulfate, chloride, bromide, iodide, -tetrachlorozinkat - methyl sulfate -, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methyl-isatin, 1-allyl isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitroisatin, 6-nitroisatin, 5 -Sulfo-isatin, 5-carboxy-isatin, Chinisatin, 1-Methylchinisatin, as well as any mixtures of the above compounds.

CH-acidic such compounds are generally considered to carry a bonded to an aliphatic carbon atom of hydrogen, with a result of electron-withdrawing substituents, activation of the corresponding carbon-hydrogen bond is effected. From CH-acidic compounds according to the invention also fall enamines resulting from alkaline treatment of quaternized N-heterocycles having a quaternary nitrogen in property for conjugation CH-acidic alkyl group.

The CH-acidic compounds 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-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1, 3,3-trimethyl-2-methyleneindoline (Fischer's Base), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl benzothiazolium-p-toluenesulfonic sulfonate, 2,3-dimethyl-naphtho [1, 2-d] thiazolium p-toluenesulphonate, 3-ethyl-2-methyl-naphtho [1, 2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3- acid, 1, 4-dimethylquinolinium iodide, 1, 2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1, 3-Dimethylthiobarbitursäure, 1, 3-Diethylthiobarbitursaure, 1, 3-diethylbarbituric acid, oxindole, 3-lndoxylacetat, 2-coumaranone, 5-hydroxy-2-coumaranone, 6-hydroxy-2-coumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1, 2-dione, indan-1, 3-dione, indan-1- one, benzoylacetonitrile, 3-dicyanomethylene-1-one, 2-amino-4-imino-1, 3- thiazoline hydrochloride, 5,5-Dimethylcycl ohexan-1, 3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methyl-benzoxazolium iodide, 3-ethyl-2-methyl-benzothiazolium iodide, 1-ethyl-4-methyl- quinolinium iodide, i-ethyl-2-methyl quinolinium iodide, 1, 2,3-Trimethylchinoxaliniumiodid, 3-ethyl-2-methyl-benzoxazolium p-toluenesulfonate, 3-ethyl-2-methyl-benzothiazolium-p-toluenesulfonate, 1-ethyl 4-methylquinolinium-p-toluenesulfonate, i-ethyl-2-methylquinolinium-p-toluenesulfonate, and 1, 2,3- Trimethylchinoxalinium p-toluenesulfonate.

In addition, the means employed in this invention for dyeing hair may contain other ingredients. A use of certain metal ions or complexes, for example, be preferred to obtain intense colorations. Here are preferred agent of the invention which additionally contain Cu, Fe, Mn, Ru ions or complexes of these ions.

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

As a further component, the means used in the invention for dyeing hair at least one ammonium compound selected from the group ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium in an amount of 0.5 to 10, preferably 1 to 5 wt .-%, based on the total composition containing.

The means used in this invention for dyeing hair may also contain any known for such preparations active ingredients, additives and auxiliaries. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases it has proved advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Anionic surfactants suitable for use on the human body anionic surfactants are useful in the inventively used formulations. These are characterized by a water solubilizing anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having approximately 10 to 22 C-atoms. In addition polyglycol ether groups, ester, ether and amide groups and also hydroxyl groups may be contained in the molecule or glycol. Examples of suitable anionic surfactants, each in the form of sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group: linear fatty acids having 10 to 22 carbon atoms (soaps )

Ether carboxylic acids of formula RO- (CH 2 -CH 2 O) x -CH 2 -COOH, in which R is a linear

Alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 16,

Acyl sarcosides having 10 to 18 carbon atoms in the acyl group,

Acyl taurides having 10 to 18 carbon atoms in the acyl group,

Acyl isethionates having from 10 to 18 carbon atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and

Sulfosuccinic acid esters having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates having 12 to 18 C atoms, linear alpha-olefin sulfonates having 12 to 18 carbon atoms,

Alpha-sulfofatty acid methyl esters of fatty acids having 12 to 18 carbon atoms,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH 2 -CH 2 O) x -SO 3 H, = in which R is a preferably linear alkyl group having 10 to 18 carbon atoms and x is 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene propylene glycol ethers according to

DE-A-37 23 354,

Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols which are addition products of approximately

represent 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and, in particular, salts of saturated and especially unsaturated C 8 -C 22 - carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid , Non-ionic surfactants contain as hydrophilic group, for. B. a polyol group, a polyalkylene glycol ether or a combination of polyol and polyglycol ether. Such compounds are for example

Addition products of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, onto fatty acids having 12 to 22 carbon atoms and

Alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C 12 -C 22 fatty acid monoesters and diesters of addition products of 1 to 30 mol

Ethylene oxide onto glycerol,

C 8 -C 22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof and

Addition products of 5 to 60 mol ethylene oxide onto castor oil and hydrogenated castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R 1 O- (Z) x. These compounds are characterized by the following parameters.

The alkyl group R 1 contains from 6 to 22 carbon atoms and may be both linear and branched. primary linear and methyl-branched in the 2-position, aliphatic radicals are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Especially preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. Where so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain.

The alkyl polyglycosides used according to the invention may contain only one particular alkyl group R 1, for example. Usually these compounds are oils from natural fats and mineral oils or produced. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or to the particular working of these compounds.

Particularly preferred alkyl polyglycosides are those in which R 1 consists essentially of C 8 - and C 10 alkyl groups, mainly of C 12 - and Cu-alkyl groups essentially of C 8 - to C 16 -alkyl groups or consists essentially of C 12 - consists to C 16 alkyl groups.

Sugar building blocks Z Any mono- or oligosaccharides can be used. Usually, sugars having 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar units are glucose, fructose, galactose, arabinose and sucrose; Glucose is especially preferred. The usable in this invention include alkyl polyglycosides in section 1, 1 to 5 sugar units. Alkyl polyglycosides with x values ​​of 1, 1 to 1, 6 are preferred. Very particular preference is given to alkyl glycosides in which x 1, 1 to 1, 4.

The alkyl glycosides can also serve to improve the fixing of fragrance components to the hair in addition to their surfactant. The skilled artisan will therefore in the event that an excess of the duration of the hair treatment effect of the perfume oil is desired on the hair, preferably to fall back to this class of substances as an additional ingredient of the preparations according to the invention.

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

Furthermore, zwitterionic surfactants can be, in particular as co-surfactants can be used. Zwitterionic surfactants are those surface active compounds which contain in the molecule at least one quaternary ammonium group and at least one -COO '' '- 3 bear ^ group or -SO. Particularly suitable zwitterionic surfactants are the betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate Gly, N-acyl-aminopropyl-N, N-dimethylammonium glycinates, for example, the aminopropionate nopropyl- dimethylammonium, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group ethylcarboxymethylglycinat and the Kokosacylaminoethylhydroxy-. A preferred zwitterionic surfactant is known under the INCI name Cocamidopropyl Betaine fatty acid amide derivative.

Likewise particularly suitable as cosurfactants are ampholytic surfactants. Under rule ampholytic surfactants are surface-active compounds which, apart from a C 8 - containing COOH or -SO 3 H group and are capable of forming inner salts - at least one free amino group and at least one C 18 alkyl or acyl group in the molecule are. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-Alkylaminobutter- acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut, cocoacylaminoethyl aminopropionate and C 12-i 8 acyl sarcosine.

According to the invention be used as cationic surfactants in particular those of the quaternary ammonium compounds, esterquats, and amidoamines. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for. B. cetyl trimethylammonium chloride, Stearyltri- methylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethyl ammonium chloride, as well as those known under the INCI names Quaternium-27 and Quaternium-83 imidazolium compounds. The long alkyl chains of the above surfactants preferably have 10 to 18 carbon atoms.

Ester quats are known substances which contain both at least one Esterfunktion and at least one quaternary ammonium group as structural element. Preferred esterquats are quaternized Estersalze of fatty acids with triethanolamine, quaternized Estersalze of fatty acids with diethanol alkylamines and quaternized Estersalze of fatty acids with 1, 2-dihydroxypropyl. Such products are marketed under the trade names Stepantex® ®, ® and Dehyquart® Armocare® ®. The products Armocare ® VGH-70, a N 1 N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ® F-75 and Dehyquart ® AU-35 are examples of such esterquats.

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

Further inventively usable cationic surfactants are the quaternized protein hydrolysates.

According to the invention are also suitable cationic silicone oils such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethicone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® quat 3270 and 3272 (manufacturer: Th Goldschmidt; di- quaternary polydimethylsiloxanes, quaternium-80.).

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

When used as surfactants, compounds having alkyl groups may be single compounds. However, it is generally preferred to proceed in the preparation of these substances from native vegetable or animal raw materials so that mixtures of substances obtained with different alkyl chain lengths dependent upon the particular raw material.

The surfactants which are addition products of ethylene and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products having a "normal" homologue distribution or those may be used with a narrow homolog distribution. "Normal" homologue distribution are mixtures of homologues are understood to be obtained as catalysts in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali. Narrowed homolog distributions are obtained, however, if hydrotalcite, alkaline earth salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or - alcoholates are used as catalysts. The use of products with a narrow homolog distribution may be preferred.

Furthermore, the means employed in this invention for dyeing hair more active,

Auxiliaries and additives, such as non-ionic polymers, for example vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes having quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyl diallyl ammonium chloride copolymers quaternized with diethyl sulfate dimethylamino-ethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone lmidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl trimethyl ammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert Butylaminoethylmethaciγlat ^ -Hydroxypropylmethacrylat copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers

Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert.butyl acrylamide terpolymers, thickeners, such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya Pastes, locust bean flour, linseed, dextrans, cellulose derivatives, eg. Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as. For example, bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants, such as maleic acid and lactic acid, hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and cephalins, protein hydrolysates, especially elastin, collagen, keratin, milk protein, soya protein and wheat protein, condensation products thereof with fatty acids and quaternized protein hydrolysates,

Perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fruit sugar and lactose, quaternized amines, such as methyl-1-alkylamidoethyl-2 -alkylimidazolinium methosulfate defoamers such as silicones, dyes for coloring the composition,

Antidandruff active ingredients such as piroctone olamine, zinc omadine and climbazole, light stabilizers, particularly derivatized benzophenones, cinnamic acid derivatives and triazines, substances for adjusting the pH, such as conventional acids, in particular edible acids and bases,

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

Plant extracts such as extracts from green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock, horsetail, hawthorn, linden blossom, almond, aloe vera, pine needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lemon, wheat, kiwi , melon, orange, grapefruit, sage, rosemary, birch, mallow, lady's smock, creeping thyme, yarrow, thyme, balm, restharrow, coltsfoot, marshmallow, meristem, ginseng and ginger root ,. Cholesterol,

Thickeners like Zuckerester, polyol esters or polyol, fats and waxes, such as spermaceti, beeswax, montan wax and paraffins, fatty acid,

Complexing agents such as EDTA, NTA, .beta.-alanine diacetic acid and phosphonic acids, swelling and penetration substances, such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, opacifiers, such as latex, styrene / PVP and styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, pigments,

Stabilizing agent for Wassserstoffperoxid and other oxidizing agents, propellants such as propane-butane mixtures, N 2 O, dimethyl ether, CO2 and air, antioxidants regard contain further optional components and the amounts of these components is expressly made to the well-known to those skilled einschlagigen manuals, e.g. , B. Kh. Schrader, bases and Formulations of Cosmetics, 2nd edition, Hüthig Verlag, Heidelberg, 1989, directed.

The means used in the invention for dyeing hair contain the active ingredients preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For coloring hair, such carriers are, for example, creams, emulsions, gels or even surfactant, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. but it is also conceivable to integrate the dye precursors in a powdery or tablet-shaped formulation.

Under aqueous-alcoholic solutions are aqueous solutions containing 3 to 70 wt .-% of a C r C 4 -alcohol, in particular ethanol or isopropanol, to be understood within the meaning of the present invention. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. All water-soluble organic solvents are preferred.

Agent preferred according to the invention used for dyeing hair are characterized in that they additionally contain a non-aqueous solvent, particularly preferred composition of the invention, the solvent in a concentration from 0.1 to 30 weight percent, preferably in a concentration of 1-20 percent by weight, very particularly preferably in a concentration from 2 to 10 percent by weight, based on the composition.

In further preferred agents used in the invention for dyeing hair, the solvent is selected from ethanol, n-propanol, Isoropanol, n-butanol, propylene glycol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, phenoxyethanol and benzyl alcohol as well as their mixtures.

The pH value of the compositions used in the invention for dyeing hair can be adjusted by suitable ingredients such as acidifiers or alkalizing agents in a wide range. Preferred compositions according to the invention are characterized in that the pH value of the agent from 6 to 11, preferably from 7.5 to 10 and is particularly preferably from 8 -9.

An oxidative dyeing of the fibers can take place in the presence of oxidation dye precursors in principle with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially when a lightening effect is desired on human hair besides the color. This whitening effect may be desirable irrespective of the staining method. The presence of Oxidationsfarbstoffvorprdukten is therefore not a prerequisite for use of oxidizing agents in the inventive compositions. Suitable oxidizing agents are persulfates, chlorites and, in particular hydrogen peroxide or its addition products onto urea, melamine and sodium borate in question.

According to the invention however, the oxidation can also be applied to the hair together with a catalyst that activates the oxidation of the dye precursors, for example by air oxygen. Such catalysts are for example metal ions, iodides, quinones or specific enzymes.

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

Suitable enzymes are, for example, peroxidases, which can amplify small amounts of hydrogen significantly the effect. Furthermore, such enzymes are useful in this invention, the oxidized directly with the aid of atmospheric oxygen, the oxidation dye precursors, such as laccases, or produce hydrogen peroxide in situ small amounts and enable in this way the oxidation of the dye precursors biocatalytically. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, for example,

Pyranose oxidase and as D-glucose or galactose,

Glucose oxidase and D-glucose,

Glycerol oxidase and glycerol,

Pyruvate oxidase and pyruvic acid or salts thereof, - alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and salts thereof,

Tyrosinase oxidase and tyrosine,

Uricase and uric acid or salts thereof,

Choline and choline,

Amino acid oxidase and amino acids.

In one application of oxidizing agents, the actual colorant is advantageously prepared immediately before use by mixing the preparation of the oxidizing agent with the formulation containing the compounds of formula I and, if dye precursors. The resulting ready-to-use hair coloring preparation should preferably have a pH in the range 6 to 12 Particularly preferably, the application of the hair dye in a weakly alkaline milieu. The application temperatures may be in a range between 15 and 40 0 C. After an exposure time of 5 to 45 minutes, the hair colorant is removed by rinsing from the hair to be dyed. The washing with a shampoo is unnecessary when a carrier of high surfactant, for example a coloring shampoo, has been used.

Especially with difficult to dye hair an inventively used technique for coloring hair can also optionally applied with additional dye precursors without prior mixing with the oxidation component to the hair. The oxidation component is applied - after a contact time of 20 to 30 minutes is then - optionally after intermediate rinsing. After another contact time of 10 to 20 minutes, is then rinsed and if desired, shampooed. In this embodiment, according to a first variant in which the previous application of the dye precursors is intended to better penetration into the hair, the corresponding agent adjusted to a pH of about 4 to 7th According to a second variant, an air oxidation is first sought, wherein the applied agent preferably has a pH value of 7 to 10 In the subsequent accelerated post-oxidation to use acidified peroxydisulfate solutions may be preferred as the oxidant.

Claims

claims
1. A method for treating keratin fibers, in particular human hair, characterized in that a means for color and / or lightening of hair is applied to the hair and the treated hair following the application of the agent is 1 to 60 minutes with UV radiation is irradiated in the wavelength range 200 to 600 nm.
2. The method according to claim 1, characterized in that the treated hair following the application of the agent is 1 to 60 minutes, preferably 2 to 50 minutes, more preferably 5 to 40 minutes and in particular 10 to 30 minutes with a UV-radiation UV-A (400-320 nm) and / or UV-B f320-280 nm) and / or UV-C (280-200 nm) is irradiated.
3. A method according to any one of claims 1 or 2, characterized in that the agent for dyeing and / or lightening of hair after irradiation is rinsed from the hair.
4. The method according to any one of claims 1 to 3, characterized in that the agent for dyeing and / or lightening of hair is formulated as oxidative hair dyeing, which based on its weight 0.01 to 15 wt .-%, preferably 0.05 to contains 10 wt .-%, particularly preferably 0.1 to 7.5 wt .-% and in particular 0.2 to 5 wt .-% of one or more oxidation dye precursor (s)
5. The method according to claim 4, characterized in that the oxidation hair dye as oxidation dye precursor contains at least one developer component is preferably selected from p-phenylenediamine, p-toluenediamine, N, N-bis (2-hydroxyethyl) amino-p-phenylenediamine , 1, 3-bis - [(2-hydroxyethyl-4 '-aminophenyl) amino] - propan-2-ol, 1, 10-bis (2', 5'-diaminophenyl) -1, 4,7,10 -tetraoxadecan, 4-aminophenol, 4-amino-3-methyl phenol, bis (5-amino-2-hydroxyphenyl) methane, 2,4,5,6-tetraaminopyrimidine triaminopyrimidine, 2-hydroxy-4,5,6, 4,5-diamino-1- (2-hydroxyethyl) pyrazole.
6. The method according to any one of claims 4 or 5, characterized in that the oxidation hair dye as oxidation dye precursor contains at least one coupler component, which is preferably selected from resorcinol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 4-chlororesorcinol , resorcinol monomethyl ether, 5-aminophenol, 5-amino-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 3-amino-4-chloro-2-methylphenol, 3-amino-2-chloro-6- methylphenol, 3-amino-2,4-dichlorophenol, 2,4-diaminophenoxyethanol, 2-amino-4- (2 'hydroxyethyl) -amino-anisole, 1, 3-bis (2,4-diaminophenoxy) propane, 2 amino-3-hydroxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-naphthol, 2-methyl -1- naphthol, 1, 5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-phenyl-3-methylpyrazole-5-one, 2,6-bis - [(2'-hydroxyethyl) amino] toluene, 4-hydroxyindole , 6-hydroxyindole, 6-
Hydroxybenzomorpholine.
7. A method according to any one of claims 1 to 6, characterized in that the agent for dyeing and / or lightening of hair based on its weight 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, more preferably 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more reactive carbonyl compound (s) contains.
8. A method according to any one of claims 1 to 7, characterized in that the agent for dyeing and / or lightening of hair based on its weight 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, more preferably 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more CH-acidic compound (s) contains.
9. The method according to any one of claims 1 to 8, characterized in that the agent for dyeing and / or lightening of hair at least one direct dye from the group of cationic (basic) dyes, preferably Basic Blue 6, CI -No. 51, 175; Basic Blue 7, CI-No. 42.595; Basic Blue 9, CI-No. 52.015; Basic Blue 26, Cl-No. 44.045; Basic Blue 41, Cl-No. 11, 154; Basic Blue 99, Cl-No. 56.059; Basic Brown 4, Cl-No. 21, 010; Basic Brown 16, Cl-No. 12.250; Basic Brown 17, Cl-No. 12.251; Basic Green 1, Cl-No. 42.040; Basic Orange 31; Basic Red 2, Cl-No. 50.240; Basic Red 22, Cl-No. 11, 055; Basic Red 46; Basic Red 51; Basic Red 76, Cl-No. 12.245; Basic Violet 1, Cl-No. 42.535; Basic Violet 2; Basic Violet 3, CI-No. 42.555; Basic Violet 10, CI-No. 45.170; Basic Violet 14, Cl No. 42.510; Basic Yellow 57, Cl-No. 12.719; Basic Yellow 87 and / or anionic (acidic) dyes, and / or nonionic dyes, preferably Acid Black 1, Cl- No. 20.470; Acid Black 52; Acid Blue 7; Acid Blue 9, CI-No. 42.090; Acid Blue 74, Cl-No. 73,015, Acid Red 18, Cl-No. 16.255; Acid Red 23; Acid Red 27, Cl-No. 16.185; Acid Red 33; Acid Red 52; Acid Red 87, Cl-No. 45,380; Acid Red 92, Cl-No. 45,410; Acid Orange 3; Acid Orange 7; Acid Violet 43, Cl-No. 60.730; Acid Yellow 1, Cl-No. 10.316; Acid Yellow 10; Acid Yellow 23, Cl-No. 19,140; Acid Yellow 3, Cl-No. 47.005; Acid Yellow 36; D & C Brown No. 1, Cl-No. 20.170 (Acid Orange 24); D & C Green No. 5, Cl-No. 61, 570 (Acid Green G); D & C Orange No. 4, Cl-No. 15,510 (Acid Orange II); D & C Orange No. 10, CI-No. 45,425: 1 (Solvent Red 73); D & C Orange No. 11, Cl-No. 45,425 (Acid Red 95); D & C Red No. 21, No. Cl- 45,380: 2 (Solvent Red 43); D & C Red No. 27, Cl-No. 45,410: 1 (Solvent Red 48); D & C Red No. 33, Cl-No. 17,200 (Acid Red 2A, Acid Red B); D & C Yellow No. 7, CI-No. 45,350: 1 (Solvent Yellow 94); D & C Yellow No. 8, Cl-No. 45,350 (Acid Yellow 73); FD & C Red No. 4, Cl-No. 14,700 (Food Red 4); FD & C Yellow No. 6, Cl-No. 15,985 (Food Yellow 3); Food Green 3; Pigment Red 57-1; Disperse Black 9; Disperse Blue 1; Disperse Blue 3; Disperse Violet 1; Disperse Violet 4; HC Orange 1; HC Red 1; HC Red 3; HC Red 13; HC Yellow 2; HC Yellow 4; Na-Pikramat; 1, 4-bis (2 '-hydroxyethyl) amino-2-nitro-p-phenylenediamine; HC Yellow 5; HC Blue 2; HC Blue 12; 4-amino-3-nitrophenol; HC Yellow 6; HC Yellow 12; 2-Nitro-1- (2 'hydroxyethyl) amino-4-methyl benzene; 2-nitro-4-amino-diphenylamine-2-carboxylic acid; 2-amino-6-chloro-4-nitrophenol; HC Red BN; 6-nitro-1, 2,3,4-tetranitrochinoxalin; o-nitro-p-phenylenediamine; p-nitro-m-phenylenediamine; HC Red B 54; HC Red 10; HC Red 11; HC Red 13; 2- (2 '-hydroxyethyl) amino-1-hydroxy-4,6-dinitrobenzene; 4-ethylamino-3-nitrobenzoic acid; 2-chloro-6-ethylamino-4-nitrophenol; 2-hydroxy-1, 4-naphthoquinone; 1-propene (4-amino-2-nitrophenyl) amine; isatin; N-methylylisatin; HC Violet 1; HC Violet 2; 4-nitrophenyl aminoethylharnstoff in amounts of 0.01 to 25 wt.%, Preferably from 0.5 to 10.%, In particular from 1 to 5 wt .-%, each based on the total composition, contains.
PCT/EP2006/009125 2005-10-28 2006-09-20 Hair colouring and/or lightening method with improved efficiency achieved by uv light WO2007048473A1 (en)

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WO2015082184A1 (en) * 2013-12-06 2015-06-11 Henkel Ag & Co. Kgaa Means for dyeing hair, containing specific combinations of developers and couplers
WO2015082228A1 (en) * 2013-12-06 2015-06-11 Henkel Ag & Co. Kgaa Agents for oxidatively dyeing hair containing specific combinations of developers and couplers
WO2015165949A1 (en) 2014-04-30 2015-11-05 L'oreal Process for bleaching or dyeing keratin fibres using an oxidizing composition and uv-visible radiation

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ES2350080B1 (en) * 2009-05-12 2011-12-19 Jose Luis Jose Chafer Reformulation for hair dye.
FR2954118B1 (en) * 2009-12-23 2012-04-13 Oreal Process for dyeing keratin fibers using at least one derivative of an ortho particular metal oxide, an alkalizing agent under photoirradiation
FR2990944A1 (en) * 2012-05-23 2013-11-29 Oreal coloring of keratin fibers comprising a colorant / pigment, a photoactive compound, and a light source
DE102013225193A1 (en) 2013-12-06 2015-06-11 Henkel Ag & Co. Kgaa Means for oxidative dyeing of hair comprising specific combinations of developers and couplers
DE102013225185A1 (en) * 2013-12-06 2015-06-11 Henkel Ag & Co. Kgaa Means for oxidation dyeing hair comprising specific combinations of developers and couplers

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