DE10256382A1 - Hair dye with encapsulated care substances - Google Patents

Abstract

The invention relates to agents for oxidative hair dyeing with continuous release of at least one care substance, which contain the care substance in one of two separately packaged components A and B, which is released from the time the components are mixed, immediately before use.

Description

The invention relates to a Agents for oxidative hair coloring, that during continuously releases care substances during the application period.

Preparations for tinting and To dye of hair is an important type of cosmetic. she can serve the natural Hair color according to the wishes and needs to nuance the person in question more or less, a completely new one Achieve hair color or unwanted shades, such as for example shades of gray, to cover. Usual hair dye depending on the desired color and durability of the color, either on the basis of oxidation dyes or on the basis formulated by direct dyes. Combinations are also common of oxidation dyes and direct dyes to achieve special nuances used.

Good dyes are characterized a high color strength out. Furthermore, good welding, Warmth-, Perm, wash and light fastness desired. They should also be in toxicologically and dermatologically harmless. It is also beneficial if the substances have high solubility in different basic formulations.

dye based on oxidation dyes lead to brilliant and long-lasting Colors. she are, however, in the usual today Formulations usually at alkaline pH values from 8 to 11 on what is to be colored Hair applied and with before or after application to the hair a chemical oxidizer, mostly hydrogen peroxide, one Per compound or a hydrogen peroxide adduct, activated, i.e. polymerized oxidatively to the dye. Such treatment can especially with repeated use or when the hair is already is damaged by other treatments, damage to the Hair structure result in poor combability and formability, as well as a loss of gloss, elasticity and tear resistance. Furthermore Such a treatment can leave the hair as a whole unkempt and give it an unattractive look.

In practice this problem counteracted that the hair immediately after the oxidative coloring treated with funds, the care and restructuring components contain. You can but only treats existing hair damage, the real one damage during the dyeing but cannot be prevented. Furthermore, a subsequent treatment participates Hair care and Restructuring the entire dye treatment for the consumer toilsome and time consuming. With this in mind, attempts have been made to Hair care and Incorporate restructuring agent directly into the oxidation paint mixture, however, which is due to the instability of the majority of hair care and restructuring agents in an oxidative and / or alkaline environment could not be implemented satisfactorily.

The disclosure of WO 89/06531 is the oxidative coloring of hair with an alkaline agent, that is created immediately before use by mixing two components, one containing the oxidation dye precursors and the other the oxidizer. At the time, this means continues to contain its creation microencapsulated active substances, which after the Dissolve the mixture and gentle oxidative hair coloring with weakly alkaline pH values guaranteed.

This principle was tried Microencapsulate hair care and restructuring ingredients with it they released immediately before the oxidative staining and immediately while of the dyeing process could work. However, this again posed the problem of low stability of the active ingredients. A large number of the care substances have already decomposed while the application time, which in turn means greater protection of the hair during the prevented oxidative treatment.

The object of the invention was therefore a means for the oxidative hair coloring to develop with the hair while avoiding the above Disadvantages gently colored oxidatively can be. The method should in particular damage healthy, and / or the further damage already pre-damaged Hair minimized by the oxidative treatment and hair without another, time-consuming step with hair care and restructuring products to be additionally supplied hair damage counteract.

This task was solved by an oxidative hair dye that the continuous release of intact hair care and restructuring components during guaranteed the entire application time and thus the hair damage during the oxidative treatment.

The object of the invention is thus a means of oxidative hair coloring with continuous release of at least one care substance. The care fabric is packaged separately in one of two and too components A and B included in a sales unit and becomes immediate by mixing the two components released before use.

According to the invention, an agent is preferred in which component A is an alkaline coloring formulation represents. A pH> 7 is understood as alkaline in the sense of the invention. The required pH values are usually adjusted with an alkalizing agent.

Preferred alkalizing agents are Ammonia, monoethanolamine, isopropylamine, isopropanolamine, 2-amino-2-methylpropan-1-ol, an alkali metal hydroxide, especially sodium hydroxide or potassium hydroxide, and especially arginine, lysine and histidine. According to the invention particularly colorants are preferred, the monoethanolamine, 2-amino-2-methylpropan-1-ol, an alkali metal hydroxide, in particular sodium hydroxide or potassium hydroxide, and especially contain arginine, lysine and histidine.

Also preferred according to the invention is an agent in which component B is an acidified developer emulsion, containing the encapsulated care substance. As angry in According to the invention, a pH in the range from 1.0 to 6.9 Roger that. A pH of component B is particularly preferred Range from 3.9 to 4.5.

Also preferred according to the invention is an agent in which component B additionally contains the care substance contains encapsulated form.

Preferred in the sense of the invention is also a means in which the encapsulation material in the acidic environment, at a pH <7, is stable and dissolves or swells in the alkaline range at a pH> 7.

In a particularly preferred embodiment the pH difference should be 2 pH levels, so that an optimal resolution of the encapsulation material guaranteed becomes.

Are preferred according to the invention Agent in which the care substances in an alkaline environment or in the presence of oxidizing agents are not, or are only stable for a short time. Under not or only for According to the invention, a time window of about a short time becomes stable an hour understood.

Also means in which the care substances selected are from the group that is formed from vitamins, provitamins and / or UV filters, protein hydrolyzates, and the physiological acceptable Derivatives of these compounds are preferred according to the invention.

According to the invention, such are Vitamins, pro-vitamins and vitamin precursors are preferred, which are common be assigned to groups A, B, C, E, F and H.

To the group of those designated as vitamin A. Substances belong retinol (vitamin A1) and 3,4-didehydroretinol (vitamin A2). The β-carotene is the provitamin of retinol. Coming as a vitamin A component according to the invention, for example Vitamin A acid and their esters, vitamin A aldehyde and vitamin A alcohol and its Esters such as the palmitate and the acetate. The preparations according to the invention ent contain the vitamin A component preferably in amounts of 0.05-1% by weight, based on the entire preparation.

The vitamin B group or vitamin B complex includes vitamin B ₁ (thiamine), vitamin B ₂ (riboflavin) and vitamin B ₃ . The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. According to the invention, preference is given to nicotinamide, which is preferably present in the agents according to the invention in amounts of 0.05 to 1% by weight, based on the total agent.

Vitamin B ₅ (pantothenic acid and panthenol): Within this group, panthenol is preferred. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and cationically derivatized panthenols. Individual representatives are, for example, panthenol triacetate, panthenol monoethyl ether and its monoacetate and the cationic panthenol derivatives disclosed in WO 92/13829. The compounds of the vitamin B ₅ type mentioned are preferably present in the agents according to the invention in amounts of 0.05-10% by weight, based on the total agent. Amounts of 0.1-5% by weight are particularly preferred.

Another representative of the vitamin B group is vitamin B ₆ (pyridoxine, pyridoxamine and pyridoxal).

Vitamin C (ascorbic acid): vitamin C is in the agents according to the invention preferably in amounts of 0.1 to 3% by weight, based on the total Funds used. Use in the form of the palmitic acid ester can be preferred.

Vitamin E (tocopherols, especially α-tocopherol). Tocopherol and its derivatives, including esters such as the acetate, the nicotinate, the phosphate and the succinate fall, are in the agents according to the invention preferably in amounts of 0.05-1 % By weight, based on the total composition.

Vitamin F: The term "vitamin F" is commonly used essential fatty acids, especially linoleic acid, linolenic and arachidonic acid, Roger that.

Vitamin H: Vitamin H is called Compound (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-d] -imidazole-4-valeric acid, for the In the meantime, the trivial name biotin has become established. Biotin is in the agents according to the invention preferably in amounts of 0.0001 to 0.1% by weight, in particular in amounts from 0.001 to 0.01% by weight.

The agents according to the invention preferably contain Vitamins, provitamins and vitamin precursors from groups A, B, E and H.

Panthenol (B ₅ ) and its derivatives, as well as nicotinamide (B ₃ ), pyridoxine (B ₆ ) and biotin (H) are particularly preferred caring active ingredients.

A very particularly preferred care component according to the invention is panthenol or one of its physiologically acceptable derivatives.

Organic UV filters are used according to the invention Substances that are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, e.g. To give off heat again. UVB filters can be oil-soluble or water soluble his.

Examples of oil-soluble substances are:
3-benzylidene camphor and its derivatives, for example 3- (4-methylbenzylidene) camphor;
4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3-phenylcinnamate (octocrylene);
Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-meth-oxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;
Triazine derivatives such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyltriazone.
Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione;

Possible water-soluble substances are:
2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;
Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid and their salts;
Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidenemethyl) benzenesulphonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

In particular come as typical UV-A filters Derivatives of benzoylmethane in question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione or 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione. The UV-A and UV-B filters can Of course can also be used in mixtures. In addition to the soluble Fabrics come for this purpose also insoluble Pigments, namely finely dispersed Metal oxides or salts, such as titanium dioxide, Zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (Talc), barium sulfate and zinc stearate. The particles should be there an average diameter of less than 100 nm, preferably have between 5 and 50 nm and in particular between 15 and 30 nm. You can a spherical Have shape, it can however, particles are also used that have an ellipsoid or in any other way deviating from the spherical shape have. In addition to the two aforementioned groups of primary light protection substances can also secondary light stabilizers of the type of antioxidants that are used in photochemical Interrupt reaction chain, which is triggered when UV radiation penetrates the skin. Typical examples are superoxide dismutase, Tocopherols (vitamin E) and ascorbic acid (vitamin C).

UV light protection filters are particularly preferred, selected from the group formed by 3-benzylidene camphor and its Derivatives, 4-aminobenzoic acid derivatives, cinnamic, Salicylsäurestern, Benzophenone derivatives, benzalmalonic acids, triazine derivatives, propane-1,3-diones, 2-phenylbenzimidazole-5-sulfonic acids, benzophenone sulfonic acids, benzoylmethane derivatives, finely dispersed metal oxides, superoxide dismutase, tocopherols (vitamin E) and ascorbic acid (Vitamin C).

UV light protection filters are in the agents according to the invention preferably in an amount of 0.001 to 5% by weight, in particular in Contain amounts of 0.01 to 3 wt .-%.

The oxidation coloring agent can in principle any oxidation colorant known in the art or common in practice his. Such preparations contain oxidation dye precursors in an aqueous carrier and are used immediately before use with an oxidizer preparation mixed. In the dyeing batch formed by the oxidizing agent an oxidation of the so-called developer compounds to polymerizable Intermediates initiated by polymerization - if necessary with the installation of the so-called coupler connections (color modifier) - to the actual one React the dye.

As a rule, it does not succeed alone with a developer component, one that looks natural on the hair To get a shade. In practice, therefore, combinations are mostly used with coupler components and / or with other developer components used.

The as oxidation dye precursors known developer compounds are usually primary aromatic Amines, which are at least one further one in the para or ortho position have free or substituted amino or hydroxyl group. Further known developers are heterocyclic hydrazones, 4-aminopyrazolone derivatives, 2,4,5,6-tertaaminopyrimidine and its derivatives and analogues.

wobei

• – G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• – G² steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• – G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Acetylaminoalkoxyrest, einen C₁- bis C₄-Mesylaminoalkoxyrest oder einen C₁- bis C₄-Carbamoylaminoalkoxyrest;
• – G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁- bis C₄-Alkylrest oder
• – wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

It can be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as developer component. P-Phenylenedia are particularly preferred minor derivatives of the formula (E1)

in which

• G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy radical (C ₁ to C ₄ ) alkyl, a 4'-aminophenyl group or a C ₁ to C ₄ alkyl group which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl group;
• G ² represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy radical (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C _4- polyhydroxyalkyl, a C ₁ to C ₄ hydroxyalkoxy, a C ₁ to C ₄ acetylaminoalkoxy, a C ₁ to C ₄ mesylaminoalkoxy or a C ₁ to C ₄ carbamoylaminoalkoxy;
• - G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
• - If G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo group, such as an ethylenedioxy group.

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

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

Very particularly preferred according to the invention p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenidiamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine. It can continue according to the invention be preferred to use compounds as developer components, which contain at least two aromatic nuclei with amino and / or hydroxyl groups are substituted.

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit den Maßgaben, daß
• – die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• – die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

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

in which:

• Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ to C ₄ alkyl radical, by a C ₁ to C ₄ hydroxyalkyl radical and / or by a bridging Y. is or is possibly part of a bridging ring system,
• - The bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms and may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ aminoalkyl radical or a direct connection to the bridge Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that
• - The compounds of formula (E2) contain only one bridging Y per molecule and
• - The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylene diamine, Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically tolerable Salts.

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

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁- bis C₄)-alkylaminorest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyal kyl-(C₁-bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoalkylrest,
• – G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G¹⁶ steht für Wasserstoff oder ein Halogenatom.

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

in which:

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

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

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethylaminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) -phenol as well as their physiologically tolerable Salts.

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

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

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

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

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

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

wobei:

• – G¹⁷, G¹⁸, G^{1 9} und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁-bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄- Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]- (C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)-aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, daß
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

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

in which:

• - G ¹⁷ , G ¹⁸ , G ^{1 9} and G ²⁰ independently represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - bis C ₄ -polyhydroxyalkyl radical is a (C ₁ - to C ₄ ) -alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical which is optionally substituted by an acetyl-ureide or a sulfonyl radical can be protected, a (C ₁ - to C ₄ ) -alkylamino (C ₁ - to C ₄ ) -alkyl radical, a di - [(C ₁ - to C ₄ ) -alkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links, a C ₁ -bis C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical,
• - The X radicals independently of one another represent a hydrogen atom, a C ₁ to C ₄ alkyl radical, an aryl radical, a C ₁ to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle 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) aminoalkyl radical , an amino radical, a C ₁ to C ₄ alkyl or di (C ₁ to C ₄ hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1, with the proviso that
• - the sum of p + q is not equal to 0,
• - if p + q is 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);
• - if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

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

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

• – Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-7-ol;
• – 3-Aminopyrazol-[1,5-a]-pyrimidin-5-ol;
• – 2-(3-Aminopyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazol-[1,5-a]-pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.Among the pyrazole- [1,5-a] pyrimidines of the above formula (E4), one can mention in particular:

• - pyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - 2,5-dimethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole- [1,5-a] pyrimidine-3,5-diamine;
• - 2,7-dimethylpyrazole- [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] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazole- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;
• - 2 - [(7-aminopyrazole- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) 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;

as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.

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

As coupler components are in usually m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, Pyrazolone and m-aminophenol derivatives used.

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

Coupler components preferred according to the invention 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-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) - amino-2-methylphenol, 3- (diethylamino) phenol, 1,3-dihydro xy-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, 1,3-bis (2', 4'-diaminophenyl) propane , 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• O-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as, for example, 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-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino -4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly preferred further coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 5- (2'-hydroxyethylamino) -2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 2,4-diaminophenoxyethanol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2-methyl-4-chloro-5-aminophenol and their physiologically tolerable salts.

The developer components are in the agents according to the invention preferably in amounts of 0.005 to 20% by weight, preferably 0.1 to 5% by weight and the coupler components are preferred in amounts of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on all the means included.

It may also be preferred to use precursors of natural analog dyes as color components.

As precursors to natural dyes such indoles and indolines are preferably used, which at least a hydroxyl or amino group, preferably as a substituent on the six-membered ring, exhibit. These groups can carry further substituents, e.g. B. in the form of etherification or Esterification of the hydroxyl group or alkylation of the amino group.

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

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

Particularly preferred derivatives of Indolins 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 as well as the 6-hydroxyindoline, the 6-aminoindoline and the 4-aminoindoline.

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

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

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

Particularly preferred derivatives of Indoles 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.

To be highlighted within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5,6-dihydroxyindole.

The indoline and indole derivatives can in in the context of the inventive method colorants used both as free bases and in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. B. the hydrochloride, of sulfates and hydrobromides. The indole or Indoline derivatives are common in these in amounts of 0.05-10 % By weight, preferably 0.2-5 % By weight.

Especially when using Dye precursors of the indoline or indole type have been found to be advantageous proven as an alkalizing agent, an amino acid and / or an oligopeptide use.

In addition to the dye precursors agents according to the invention contain direct dyes for further shading. This are common selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 13, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 7, Basic Blue 26, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Basic Violet 2, Basic Violet 14, Acid Violet 43, Disperse Black 9, Acid Black 52, Basic Brown 16 and Basic Brown 17 are known Compounds and 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) -aminophenol, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. The agents according to the invention according to this embodiment contain the substantive dyes preferably in an amount from 0.01 to 20% by weight, based on the total colorant.

The preparations according to the invention can also dyes occurring in nature such as, for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, Sedre and alkanna root occur.

It is not necessary that the oxidation dye precursors or the substantive dyes each represent uniform compounds. Rather, in the hair colorants according to the invention, due to the manufacturing process for the individual dyes, even more in minor amounts Components are included, provided that they do not adversely affect the coloring result or must be excluded for other reasons, e.g. toxicological.

Regarding in the hair dyeing and -tönungsmitteln usable dyes will continue to expressly on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive Dyes) and Chapter 8, pages 264–267; Oxidation dye precursors) published as Volume 7 of the series "Dermatology" (Ed .: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the “European inventory of cosmetic raw materials " published by the European Community, available in floppy form from the Federal Association of German Industry and Trade Companies for Medicines, Health food and personal care products e.V., Mannheim, referred to.

The agents according to the invention contain dye precursors preferably in a suitable aqueous, alcoholic or aqueous-alcoholic Carrier. For the purpose of coloring hair are such carriers for example creams, emulsions, gels or surfactants foaming Solutions, such as shampoos, foam aerosols or other preparations, the for are suitable for use on the hair. But it is also conceivable the dye precursors in a powdery or tablet-like formulation to integrate.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing 3 to 70% by weight of a C ₁ -C ₄ alcohol, in particular ethanol or isopropanol. The agents according to the invention can additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred.

The encapsulated active ingredients lie preferably in a component with an aqueous or oily medium, which is then added to the application mixture.

• – Pyranose-Oxidase und z. B. D-Glucose oder Galactose,
• – Glucose-Oxidase und D-Glucose,
• – Glycerin-Oxidase und Glycerin,
• – Pyruvat-Oxidase und Benztraubensäure oder deren Salze,
• – Alkohol-Oxidase und Alkohol (MeOH, EtOH),
• – Lactat-Oxidase und Milchsäure und deren Salze,
• – Tyrosinase-Oxidase und Tyrosin,
• – Uricase und Harnsäure oder deren Salze,
• – Cholinoxidase und Cholin,
• – Aminosäure-Oxidase und Aminosäuren.

The actual oxidative coloring of the fibers can basically be done with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and sodium borate are suitable as oxidizing agents. But you can also apply the oxidation dye together with a catalyst on the hair, the oxidation of the dye precursors, for. B. activated. Such catalysts are e.g. B. transition metal compounds, iodides, quinones or certain enzymes. Suitable enzymes are e.g. B. peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as for example the laccases, or generate small amounts of hydrogen peroxide in situ and in this way activate 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 substrates specific for them, e.g. B.

• - Pyranose oxidase and z. B. D-glucose or galactose,
• Glucose oxidase and D-glucose,
• Glycerin oxidase and glycerin,
• Pyruvate oxidase and pyruvic acid or its salts,
• - alcohol oxidase and alcohol (MeOH, EtOH),
• Lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or its salts,
• Choline oxidase and choline,
• - Amino acid oxidase and amino acids.

• – sie sollten sich gegebenenfalls in einer Farbe einfärben lassen, um die Pflegestoffe und die damit verbundene Schonung der Haare während des oxidativen Haarfärbeprozesses für den Verbraucher sichtbar zu machen,
• – sie sollten undurchlässig für die gecoateten Haarpflege- und Restrukturierwirkstoffe sein (inaktivierter Zustand),
• – sie sollten inert gegenüber den gecoateten Wirkstoffen sein,
• – sie sollten in dem vorliegenden Medium stabil und undurchlässig für die gecoateten Wirkstoffe sein,
• – das Coatingmaterial sollte durch schonende Verfahren (beispielsweise das Wirbelschichtverfahren) gleichmäßig um den Wirkstoff gebracht werden können,
• – es sollte durch den sogenannten Schaltermechanismus vom inaktivierten in den aktivierten Zustand, bei dem die Wirkstoffe in freier Form vorliegen, gebracht werden können,
• – die Schichtdicke des Coatingmaterials sollte derart gewählt werden können, dass die Wirkstoffe ausgelöst durch den Schaltermechanismus und durch die unterschiedliche Auflöse- bzw. Quellgeschwindigkeit während der gesamten Applikationszeit intakt auf die Haare wirken können.

As encapsulation material according to the invention, preference is given to those substances which meet the following claims:

• - if necessary, they should be able to be colored in one color in order to make the care substances and the associated protection of the hair visible to the consumer during the oxidative hair dyeing process,
• - they should be impermeable to the coated hair care and restructuring active ingredients (inactivated state),
• - they should be inert to the coated active ingredients,
• - they should be stable and impermeable to the coated active substances in the medium at hand,
• The coating material should be able to be brought evenly around the active substance by gentle processes (for example the fluidized bed process),
• It should be able to be brought from the inactivated to the activated state, in which the active substances are present in free form, by means of the so-called switch mechanism,
• - The layer thickness of the coating material should be chosen so that the active ingredients are triggered can act intact on the hair during the entire application time due to the switch mechanism and the different dissolution or swelling speeds.

The capsules are produced according to the so-called fluidized bed process. This procedure is known and adequately described in the literature. It will for example, explicitly to the monograph Römpp's Chemie Lexikon, 9th edition, Georg Thieme Verlag Stuttgart (1995), Vol. 6, page 5051.

A switch mechanism preferred according to the invention is the so-called pH switch mechanism. The coating material through a sudden change of the pH value a value in the range of 8.5 to 10 when the components are mixed A and B resolved or swollen and the care and restructuring agents can leak.

The usual application time of one oxidative hair coloring is 5-40 minutes. While this time should be continuous according to the invention intact care substance emerge from the capsules in order to protect the hair guarantee.

This condition is determined by the layer thickness of the encapsulation material and the associated variable dissolution or Swelling speed controlled.

Encapsulation materials according to the invention are, for example, chitosans, polyvinylamide, polyacrylates, cellulose, as well as the physiologically tolerable Derivatives of these compounds.

• – Eudragit^®S oder Eudragit^®L der Firma Röhm, die auf der Grundlage von anionischen Polymeren aus Acrylat- und Methacrylateinheiten beruhen und erst ab einem pH-Wert größer als 7 löslich sind,
• – Celluloseacetatphthallat (CAP) oder Hypromellosephthallat, die ab einem pH-Wert größer als 7 löslich und
• – Ethylcellulose oder Eudragit^®RL bzw. Eudragit^®RS, die leicht im alkalischen Medium in einem pH-Bereich von 8 bis 11 quellbar sind.

The following coating materials are particularly preferably used according to the invention:

• - Eudragit ^® S or Eudragit ^® L from Röhm, which are based on anionic polymers made from acrylate and methacrylate units and are only soluble from a pH greater than 7,
• - Cellulose acetate phthalate (CAP) or hypromellose phthalate, which are soluble and from a pH greater than 7
• - Ethyl cellulose or Eudragit ^® RL or Eudragit ^® RS, which are easily swellable in an alkaline medium in a pH range of 8 to 11.

The application of the agents according to the invention is preferably carried out in such a way that first the dye preparations A and B are mixed and preferred using an application tool a brush on spread the hair and leave for 5 to 40 minutes.

The agents according to the invention can continue all for such preparations contain known active ingredients, additives and auxiliaries. In many cases these agents contain at least one surfactant, in principle both anionic as well as zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases However, it has proven advantageous to use anionic, select zwitterionic or nonionic surfactants.

• – lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x -CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030 ,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354 ,
• – Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344 ,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2–15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Monosulfonic acid and dialkyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates with 12 to 18 carbon atoms,
• Linear alpha olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,
• - Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030 .
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23 354 .
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344 .
• - esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules len ethylene oxide and / or propylene oxide on fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid ,

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C_{1 2}-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowie
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.

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

• Addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,
• C _{1 2} -C ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,
• - C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues as well
• - Adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R'O (Z) _X. These connections are characterized by the following parameters.

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

The alkyl polyglycosides which can be used according to the invention can for example, contain only a certain alkyl radical R '. Usually these connections but starting from natural Greases and oils or mineral oils manufactured. In this case, mixtures of alkyl radicals R are correspondingly the starting compounds or according to the respective workup of these connections.

• – im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• – im wesentlichen aus C₁₂- und C_{1 4}-Alkylgruppen,
• – im wesentlichen aus C₈-C_{1 6}-Alkylgruppen oder
• – im wesentlichen aus C₁₂-C₁₆-Alkylgruppen besteht.

Alkylpolyglycosides in which R '

• Essentially from C ₈ and C ₁₀ alkyl groups,
• Essentially from C ₁₂ and C _{1 4} alkyl groups,
• - essentially of C ₈ -C _{1 6} alkyl or
• - consists essentially of C ₁₂ -C ₁₆ alkyl groups.

Any sugar block Z can be used Mono- or oligosaccharides can be used. Usually sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides used. Examples of such sugars are glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, Gulose, Idose, Talose and Sucrose. Preferred sugar building blocks are Glucose, fructose, galactose, arabinose and sucrose; Is glucose particularly preferred.

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

The alkyl glycosides can besides their surfactant effect also serve to fix fragrance components to improve on the hair. The specialist is therefore in the event that one about the Effect of the perfume oil on the duration of the hair treatment the hair desired is preferred to this class of substances as a further ingredient of the preparations according to the invention To fall back on.

Even the alkoxylated homologues of the alkyl polyglycosides mentioned can be used according to the invention become. These homologues can on average up to 10 ethylene oxide and / or propylene oxide units included per alkyl glycoside unit.

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

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, apart from a C ₈ to C _{1 8} alkyl or acyl group in the molecule ent at least one free amino group and at least one -COOH or -SO ₃ H group hold and are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C _{1 2 1 8} acyl sarcosine.

According to the invention as cationic surfactants in particular those of the quaternary ammonium compound type, the Esterquats and the Amidoamine used.

Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as Alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants are preferred 10 to 18 carbon atoms.

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

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

Further usable according to the invention cationic surfactants are the quaternized protein hydrolyzates represents.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer : General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

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

For the compounds used as surfactants alkyl groups can be uniform substances act. However, it is usually preferred in manufacturing of these substances from native vegetable or animal raw materials going out so that one Mixtures of substances with different raw materials dependent alkyl chain lengths receives.

In the case of surfactants, the add-on products of ethylene and / or propylene oxide to fatty alcohols or derivatives of these addition products can be both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood as mixtures of homologues that are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. On the other hand, narrow homolog distributions are obtained if, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates can be used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Furthermore, the agents according to the invention preferably a conditioning agent selected from the group of cationic surfactants, cationic polymers, Alkylamidoamines, paraffin oils, vegetable oils and synthetic oils is formed.

Preferred as conditioning agents could be cationic polymers. These are usually polymers that have a quaternary nitrogen atom, for example in the form of an ammonium group.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• – polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Acrylsäure sowie Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)), Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) und Merquat^® 280 (Dimethyldiallyl-ammoniumchlorid-Acrylsäure-Copolymer im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• – Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• – quaternierter Polyvinylalkohol sowie die unter den Bezeichnungen
• – Polyquaternium 2,
• – Polyquaternium 17,
• – Polyquaternium 18 und
• – Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.
• - polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. The under the names Merquat ^® 100 (poly (dimethyldiallylam monium chloride)), Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer) commercially available products are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol and those under the names
• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Cationic ones are particularly preferred Polymers of the first four groups, very particularly preferred are Polyquaternium-2, Polyquaternium-10 and Polyquaternium-22.

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

Can also be used as conditioning Active ingredients are paraffin oils, synthetically produced oligomeric alkenes as well as vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil.

Also suitable hair conditioning Compounds are phospholipids, for example soy lecithin, egg lecithin and cephaline.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z.B. Polyvinylalkohol,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,.
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styro/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien.

Other active ingredients, auxiliaries and additives are, for example

• Non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• - zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• - anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl-acrylamide terpolymers
• Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. 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 soy lecithin, egg lecithin and cephalins,
• Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• - Quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• - defoamers like silicones,
• Dyes for coloring the agent,
• - anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol,
• Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• - Substances for adjusting the pH, such as customary acids, especially edible acid bases and bases,
• Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts 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 the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, hake, coltsfoot, marshmallow, meristem, ginseng and ginger root.
• - cholesterol,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as walrus, beeswax, montan wax and paraffins,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• - opacifiers such as latex, styrene / PVP and styro / acrylamide copolymers
• Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,
• - pigments,
• - stabilizing agents for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

Regarding other optional Components as well as the amounts used of these components expressly to the relevant manuals known to those skilled in the art, e.g. B. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

• I) Vermischen der Komponenten A und B unmittelbar vor der Anwendung,
• II) Auftragen der Färbemischung auf das Haar und
• III) Spülen des Haares.

A second subject of the invention is a process for coloring keratin fibers, in particular hair, using an oxidation coloring agent according to the invention, which comprises the following process steps:

• I) mixing components A and B immediately before use,
• II) applying the dye mixture to the hair and
• III) Rinsing the hair.

The application temperatures can be in a range between 15 and 40 ° C lie. After an exposure time of 5 to 40 minutes, it will Hair Dye by rinsing of the one to be colored Hair removed. Washing with a shampoo is not necessary if a high tenside carrier, e.g. a coloring shampoo, was used.

A third object of the invention is the use of the agent according to the invention for gentle oxidative hair coloring.

Claims (10)

Agent for oxidative hair dyeing with continuous release of at least one care substance, characterized in that the care substance is contained in one of two separately packaged components A and B and combined into a sales unit and is released from the time the two components are mixed immediately before use. Agent according to claim 1, characterized in that component A is an alkaline coloring formulation. Agent according to one of claims 1 or 2, characterized in that that component B is an acidic developer emulsion with a pH range of 1.0 to 6.9 containing the encapsulated Care fabric. Agent according to one of claims 1 to 3, characterized in that that component B also contains the care substance in unencapsulated form contains. Agent according to one of claims 1 to 4, characterized in that that the encapsulation material is stable in an acidic environment at a pH <7 and at a pH shift by at least 2 pH levels in the alkaline range, at one pH> 7, dissolves or swells. Agent according to one of claims 1 to 5, characterized in that that the care substances in an alkaline environment, at a pH> 7, or in the presence of oxidizing agents not, or only stable for up to an hour are. Agent according to one of claims 1 to 6, characterized in that that the care substances are selected from the group that is formed from vitamins, provitamins and / or UV filters and the physiologically compatible derivatives of these substances. Agent according to one of claims 1 to 7, characterized in that the care substance panthenol (provitamin B ₅ ) and its derivatives, nicotinamide (vitamin B ₃ ), pyridoxine (vitamin B ₆ ), vitamin E, vitamin F, biotin (vitamin H) , Silk protein hydrolyzate or ascorbic acid. Process for oxidative hair coloring using a Means according to one of the claims 1 to 9, comprising the following process steps  I) Mix components A and B immediately before use,  II) Apply the dye mixture on the hair and  III) Rinse of the hair. Use of an agent according to any one of claims 1 to 9 for gentle oxidative hair coloring.