WO2004050048A1

WO2004050048A1 - Hair-dyeing agent comprising encapsulated care products

Info

Publication number: WO2004050048A1
Application number: PCT/EP2003/013144
Authority: WO
Inventors: Astrid Kleen; Christa Rohland; Detlef Hollenberg
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2002-12-02
Filing date: 2003-11-22
Publication date: 2004-06-17
Also published as: DE10256382A1; EP1567118A1

Abstract

The invention relates to agents for oxidatively dyeing hair while at least one care product is continuously released. Said agents contain the care product in one of two separately packaged components B and B which are combined in a retail unit. Said care product is set free from the moment that the components are mixed immediately before being applied.

Description

Hair dye with encapsulated care substances "

The invention relates to an agent for oxidative hair coloring, which continuously releases care substances during the application time.

Preparations for tinting and coloring hair are an important type of cosmetic products. They can be used to shade the natural hair color slightly or more depending on the wishes and needs of the person concerned, to achieve a completely new hair color or to cover up undesirable shades, such as shades of gray. Depending on the desired color and the durability of the dye, conventional hair dyes are formulated either on the basis of oxidation dyes or on the basis of substantive dyes. Combinations of oxidation dyes and direct dyes are often used to achieve special shades.

Good dyes are characterized by a high color strength. Good sweat, heat, perm, wash and light fastness are also desired. They should also be safe from a toxicological and dermatological point of view. It is also advantageous if the substances have a high solubility in various base formulations.

Colorants based on oxidation dyes lead to brilliant and lasting shades. However, in the formulations common today, they are generally applied to the hair to be colored at alkaline pH values from 8 to 11 and before or after application to the hair with a chemical oxidizing agent, usually hydrogen peroxide, a per-compound or a hydrogen peroxide adduct , activated, ie polymerized oxidatively to the dye. Such treatment, particularly with repeated use or if the hair has already been damaged by other treatments, can result in damage to the hair structure, resulting in poor combability and malleability and a loss of shine. Elasticity and tear-resistant activity expresses. In addition, such a treatment can give the hair an overall unkempt and unattractive appearance.

In practice, this problem is countered by treating the hair immediately after the oxidative coloring with agents that contain care and restructuring components. However, only existing hair damage can be treated, but the actual damage during the dyeing process cannot be prevented. Furthermore, a subsequent treatment with hair care and restructuring agents makes the entire coloring treatment laborious and time-consuming for the consumer. From this point of view, attempts have been made to incorporate hair care and restructuring agents directly into the oxidation color mixture, but this has not been able to be implemented satisfactorily due to the instability of the majority of hair care and restructuring agents in the oxidative and / or alkaline environment.

The disclosure of WO89 / 06531 shows the oxidative coloring of hair with an alkaline agent which is formed immediately before use by the mixing of two components, one containing the oxidation dye precursors and the other the oxidizing agent. At the time of its creation, this agent also contains microencapsulated active ingredients, which dissolve after mixing and ensure gentle oxidative hair coloring at weakly alkaline pH values.

An attempt was made according to this principle to microencapsulate hair care and restructuring ingredients so that they were released immediately before the oxidative dyeing and could act directly during the dyeing process. However, this again posed the problem of the poor stability of the active ingredients. A large number of the care substances already decomposed during the application period, which in turn prevented the hair from being spared during the oxidative treatment.

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

This object has been achieved by developing an oxidative hair dye which ensures the continuous release of intact hair care and restructuring components during the entire application time and thus reduces hair damage during the oxidative treatment.

The invention thus relates to an agent for oxidative hair dyeing with continuous release of at least one care substance. The care substance is contained in one of two separately packaged components A and B, which are combined to form a sales unit, and is released by mixing the two components immediately before use.

According to the invention, an agent is preferred in which component A is an alkaline coloring formulation. In the sense of the invention, alkaline is understood to mean a pH value> 7. The required pH values are usually set with an alkalizing agent.

Preferred alkalizing agents are ammonia, monoethanolamine, isopropylamine, isopropanolamine, 2-amino-2-methylpropan-l-ol, an alkali metal hydroxide, in particular sodium hydroxide or potassium hydroxide, and in particular arginine, lysine and histidine. Colorants containing monoethanolamine, 2-amino-2-methylpropan-l-ol, an alkali metal hydroxide, in particular sodium hydroxide or potassium hydroxide, and in particular arginine, lysine and histidine are particularly preferred according to the invention.

Also preferred according to the invention is an agent in which component B is an acidic developer emulsion containing the encapsulated care substance. Acid in the sense of the invention is understood to mean a pH in the range from 1.0 to 6.9. A pH of component B in the range from 3.9 to 4.5 is particularly preferred. Also preferred according to the invention is an agent in which component B additionally contains the care substance in unencapsulated form.

For the purposes of the invention, preference is also given to an agent in which the encapsulation material is stable in an acidic environment, at a pH <7, 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 dissolution of the encapsulation material is guaranteed.

Also preferred according to the invention are agents in which the care substances are not stable or only stable for a short time in an alkaline environment or in the presence of oxidizing agents. According to the invention, not stable or only stable for a short time means a time window of approximately one hour.

Agents in which the care substances are selected from the group formed from vitamins, provitamins and / or UV filters, protein hydrolyzates and the physiologically tolerable derivatives of these compounds are also preferred according to the invention.

Vitamins, pro-vitamins and vitamin precursors which are usually assigned to groups A, B, C, E, F and H are preferred according to the invention.

The group of substances called vitamin A includes retinol (vitamin AI) and 3,4-didehydroretinol (vitamin A2). The ß-carotene is the provitamin of retinol. According to the invention, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as palmitate and acetate come into consideration as vitamin A components. The preparations according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the entire preparation.

The vitamin B group or vitamin B complex includes vitamin Bi (thiamine), vitamin B ₂ (riboflavin) and vitamin B ₃ . The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. Erfmdungsgemäß preference is given to the 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 used in the agents according to the invention preferably in amounts of 0.1 to 3% by weight, based on the total agent. Use in the form of the palmitic acid ester may be preferred.

Vitamin E (tocopherols, especially α-tocopherol). Tocopherol and its derivatives, which include in particular the esters such as acetate, nicotinate, phosphate and sucinate, are preferably present in the agents according to the invention in amounts of 0.05-1% by weight, based on the total agent. contain.

Vitamin F: The term "vitamin F" usually means essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.

Vitamin H: The compound (3aS, 4S, 6aR) -2-oxohexa- hydrothienol [3,4-d] -imidazole-4-valeric acid is designated as vitamin H, but for which the trivial name biotin has now become established. Biotin is contained in the agents according to the invention preferably in amounts of 0.0001 to 0.1% by weight, in particular in amounts of 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 tolerable derivatives.

According to the invention, organic substances which are able to absorb ultraviolet rays and which absorb the energy in the form of longer-wave radiation, e.g. To give off heat again. UVB filters can be oil-soluble or water-soluble.

As oil-soluble substances e.g. to call:

3-benzylidene camphor and its derivatives, e.g. 3- (4-methylbenzylidene) camphor;

4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4-

(Dimethylamino) benzoesäureamylester;

Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4-

Propyl 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, e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-hexyloxy) -l, 3,5-triazine and

Octyl.

Propane-1,3-dione, e.g. l- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-l, 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, e.g. 4- (2-oxo-3-bornylidene-methyl) benzenesulphonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane are particularly suitable as typical UV-A filters, such as, for example, l- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-l, 3-dione or 1-phenyl- 3- (4'-isopropylphenyl) -propane-l, 3-dione. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble pigments, namely finely dispersed metal oxides or salts, such as, for example, titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate are also suitable for this purpose. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape. In addition to the two aforementioned groups of primary light stabilizers, it is also possible to use secondary light stabilizers of the antioxidant type which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples are superoxide dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C).

Particularly preferred are UV light protection filters selected from the group formed by 3-benzylidene camphor and its derivatives, 4-aminobenzoic acid derivatives, cinnamic acid esters, salicylic acid esters, benzophenone derivatives, benzalmalonic acids, triazine derivatives, propane-1,3-dione, 2 -Phenylbenzimida-zol-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 contained in the agents according to the invention preferably in an amount of 0.001 to 5% by weight, in particular in amounts of 0.01 to 3% by weight. The oxidation coloring agent can in principle be any oxidation coloring agent known in the prior art or customary in practice. Such preparations contain oxidizing dye precursors in an aqueous carrier and are mixed with an oxidizing agent preparation immediately before use. In the dyeing batch formed in the process, the oxidizing agent initiates an oxidation of the so-called developer compounds to polymerizable intermediates, which react to the actual dye by polymerization, optionally with the incorporation of the so-called coupler compounds (color modifier).

As a rule, it is not possible to get a color shade that looks natural on the hair with just one developer component. In practice, therefore, combinations with coupler components and / or with other developer components are mostly used.

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

According to the invention, it may be preferred to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

in which

G ¹ represents a hydrogen atom, ad- to C -alkyl radical, a C _\ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (- to C) -alkoxy- (C _\ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C 1 -C 4 -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical; G ² represents a hydrogen atom, a Q to C alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C polyhydroxyalkyl radical, a (Ci to C ₄ ) alkoxy (to C ₄ ) alkyl radical or a C _\ - to C -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 Cp to C alkyl radical, a C to C monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a Cr to C -hydroxyalkoxy, a C _\ - to C - acetylaminoalkoxy, a C _\ - to C ₄ - mesylaminoalkoxy or a Cr to C ₄ - carbamoylaminoalkoxy;

G ⁴ represents a hydrogen atom, a halogen atom or a - to C ₄ -alkyl radical or if G ³ and G ^{4 are} in the ortho position to one another, they can together form a bridging α, ω-alkylenedioxo group, such as, for example, an ethylenedioxy group.

Examples of the - 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. Cr to C alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C ₁ -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 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 formula (El) are especially the amino groups, C to C monoalkylamino, C _\ - to C ₄ dialkylamino, Ci to C -Trialkylammoniumgruppen, C to C -Monohydroxyalkylaminogruppen, imino dazolinium 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-diethyι) aniline, N, N-bis (ß-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (ß-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (ß-hydroxyethyl) - amino-2-chloroaniline, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (ß-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, ß-hydroxyethyl) -p- phenylene diamine, N- (β, γ-dihydroxypropyl) -p-phenylene diamine, N- (4'-aminophenyl) -p-phenylene diamine, N-phenyl-p-phenylene diamine, 2- (ß-hydroxyethyloxy) -p -phenylenediamine, 2- (ß-acetylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically tolerable salts.

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

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

in which: Z and Z independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a Cr to C alkyl radical, by a Cr to C ₄ hydroxyalkyl radical and / or by a bridging Y or which is optionally part of a bridging ring system is the bridge Y represents an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is formed by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms can be interrupted or terminated and possibly substituted by one or more hydroxyl or Cr 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 Cr to C alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, a C ₂ ~ to C ₄ polyhydroxyalkyl radical, a Cr 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 bridging Y or a Cr to C -alkyl radical, with the provisos that the compounds of the formula (E2) contain only one bridge Y per molecule and the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-ammophenyl) -l, 3-diamino-propan-2-ol, N, N'-bis (ß-hydroxyethyl) -N, N ^, -bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyi) - tetramethylene diamine, N, N'-bis - (ß-hydroxyethyl) -N, N'-bis- (4-aminophenyl) -tetramethylene-diamine, N, N'-bis- (4-methyl-aminophenyl) -tetramethylene-diamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -l, 4th -diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and l, 10-bis (2 ', 5'- diaminophenyl) -l, 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) -l, 4-diazacycloheptane and l, 10-bis (2 ', 5'-diaminophenyl) - l, 4,7,10-tetraoxadecane or one of its physiologically tolerable salts.

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

in which:

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

G ¹⁴ represents a hydrogen or halogen atom, a Cr to C ₄ alkyl radical, a Cj to C ₄ monohydroxyalkyl radical, a C ₂ to C polyhydroxyalkyl radical, a (Cr to C ₄ ) alkoxy (Cr to C ₄ ) alkyl radical, a Cr to C ₄ aminoalkyl radical or a Cr to C ₄ cyanoalkyl radical,

G ¹⁵ represents hydrogen, a Cr to C ₄ alkyl radical, a Cr to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ represents hydrogen or a halogen atom. According to the invention, the substituents used in formula (E3) are defined analogously to the above statements.

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

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

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

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

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

Preferred pyrimidine derivatives are, in particular, the compounds which are described in German patent DE 2,359,399, Japanese laid-open patent publication JP 02019576 A2 or in 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-dimethyl amino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-pyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4.5 -Diamino-l-methylpyrazole, 4,5-di-amino-1 - (ß-hydroxyethyl) -pyrazole, 3, 4-diarninopyrazole, 4,5-diamino-1 - (4'-chlorobenzyl) - pyrazole, 4, 5-diamino-l, 3-dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-l, 3-dimethyl-5- hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-l-methylpyrazole, 4,5-diamino-l-tert-butyl-3-methylpyrazole, 4,5-diamino-l- (ß-hydroxyethyl) -3-methylpyrazole, 4,5-di-amino-1-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3- (4'- methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4.5 -Diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (ß-aminoethyl) -amino-l, 3-dimeth ylpyrazole, 3,4,5-triamino-pyrazole, 1-methyl-3, 4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl ) amino-l-methylpyrazole.

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

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a Cr to C ₄ alkyl radical, an aryl radical, a Cr to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical a ( Cr to C) alkoxy- (Cr to C ₄ ) -alkyl, a Cr to C ₄ -aminoalkyl, which can optionally be protected by an acetyl-ureide or a sulfonyl residue, a (Cr to C ₄ ) -alkylamino - (Cr to C) alkyl radical, a di - [(Cr to C) alkyl] - (Cr to C) aminoalkyl radical, the dialkyl radicals optionally having one Form carbon cycle or a heterocycle with 5 or 6 chain links, a - to C -hydroxyalkyl or a di- (Cr to C) - [hydroxyalkyl] - (Cr to C) aminoalkyl radical, the X radicals independently of one another a hydrogen atom, a Cr to C alkyl radical, an aryl radical, a Cr to C hydroxyalkyl radical, a C ₂ to C polyhydroxyalkyl radical, a Cr to C ₄ aminoalkyl radical, a (Cr to C ₄ ) alkylamino - (Cr to C ₄ ) -alkyl radical, a di - [(Cr to C) alkyl] - (Cj- to C ₄ ) -aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a Cr to C ₄ hydroxyalkyl or a di (Cr to C ₄ hydroxyalkyl) aminoalkyl radical, an amino radical, a Cr to C ₄ alkyl or di (Cr to C ₄ hydroxyalkyl) - amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not 0, if p + q is 2, n is 0, and the groups NG ¹⁷ G ¹⁸ and NG ^I9 G ²⁰ occupy the positions (2nd , 3); (5,6); (6,7); (3.5) or (3.7); if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

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

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

Among the 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-dimethyl-pyrazol [l, 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 [l, 5-a] pyrimidine-3-ylamino) ethanol;

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

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

5,6-dimethylpyrazole [l, 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 tolerable salts and their tautomeric forms when there is a tautomeric equilibrium.

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

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components.

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-di-hydroxy-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, for example, 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-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-l-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydro- xynaphthalene and 2,3-dihydroxynaphthalene,

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

Quinoxaline derivatives such as 6-methyl-1, 2,3, 4-tetrahydroquinoxaline, pyrazole derivatives such as l-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-dihydroxy-pyrimidine, 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 l-hydroxy-3,4-methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l- (2'-hydroxyemyl) amino-3,4-methylenedioxy-benzene.

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-pyrazolon-5, 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 physiological tolerable salts.

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

It can furthermore be preferred to use precursors of nature-analogous dyes as color components.

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

Derivatives of 5,6-dihydroxyindoline of the formula (V) are particularly suitable as precursors of naturally analogous hair dyes,

in the independently of each other

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

R 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 stands for hydrogen or a CrC ₄ alkyl group, ^' R ⁴ stands for hydrogen, a Cι- C-alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a CrC ₄ alkyl group, and R ⁵ stands for one of the groups mentioned under R ⁴ , and physiologically tolerable salts of these compounds with an organic or inorganic acid.

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

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

Derivatives of 5,6-dihydroxyindole of the formula (VI) are also outstandingly suitable as precursors of natural hair dyes,

(VI)

R ¹ in independently

R ¹ represents hydrogen, a CrC 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 Cj- alkyl group,

R ⁴ represents hydrogen, a CrC ₄ alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a C ₁ -C ₄ alkyl group _;) and

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

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-di-hydroxyindole, 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 5.6 are to be emphasized -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants used in the process according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochloride, the sulfates and hydrobromides can be used. The indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

In particular when using dye precursors of the indoline or indole type, it has proven to be advantageous to use an amino acid and / or an oligopeptide as the alkalizing agent.

In addition to the dye precursors, the agents according to the invention can contain direct dyes for further shading. These are usually selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those 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 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-l, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-l, 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 in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain dyes which occur naturally, such as, for example, in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the substantive dyes each represent uniform compounds. Rather, the hair colorants according to the invention, due to the production process for the individual dyes, may also contain minor components in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.

With regard to the dyes which can be used in the hair dyeing and tinting agents according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (Ed .: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European inventory of cosmetic raw materials" , published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicinal Products, Health Care Products and Personal Care Products, Mannheim. The agents according to the invention preferably contain dye precursors in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as, for example, shampoos, foam aerosols or other preparations which are suitable for use on the hair. However, it is also conceivable to integrate the dye precursors into a powdery or tablet-like formulation.

For the purposes of the present invention, aqueous-alcoholic solutions are understood to mean aqueous solutions containing 3 to 70% by weight of an 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 are preferably present in a component with an aqueous or oily medium, which is then added to the application mixture.

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 thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are So-called 2-electron oxidoreductases in combination with the specific substrates, e.g. B.

Pyranose oxidase and e.g. 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.

As encapsulation material according to the invention, preference is given to those substances which meet the following claims: they should, if appropriate, 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 agents (inactivated state), they should be inert to the coated agents, they should be stable and impermeable to the coated agents in the medium at hand, the coating material should be evenly around the by gentle processes (e.g. the fluidized bed process) Active substance should be brought, it should be able to be brought from the inactivated to the activated state, in which the active substances are in free form, by the so-called switch mechanism, the layer thickness of the coating material should be d It can be selected that the active ingredients triggered by the switch mechanism and the different dissolution or swelling speeds can act intact on the hair during the entire application time. The capsules are produced using the so-called fluidized bed process. This method is known in the literature and is sufficiently described. For example, reference is explicitly made to the monograph Römpp's Chemie Lexikon, 9th edition, Georg Thieme Verlag Stuttgart (1995), Vol. 6, page 5051.

A preferred switch mechanism according to the invention is the so-called pH switch mechanism. The coating material is dissolved or swelled by a sudden change in the pH to a value in the range from 8.5 to 10 when components A and B are mixed, and the care and restructuring agents can escape.

The usual application time for oxidative hair coloring is 5-40 minutes. During this time, according to the invention, intact care substance should emerge from the capsules in order to ensure gentle hair coloring.

This condition is controlled by the layer thickness of the encapsulation material and the associated variable dissolving or swelling speed.

Encapsulation materials according to the invention are, for example, chitosans, polyvinyl amide, polyacrylates, cellulose, and the physiologically tolerable derivatives of these compounds.

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 based on 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 agents according to the invention are preferably used by first mixing the dye preparations A and B and distributing them on the hair with the aid of an application tool, preferably a brush, and allowing them to act for 5 to 40 minutes.

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

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 with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and 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 C- 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,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester 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-3725 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers 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, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with 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.

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

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group, C ₁₂ -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

Addition products 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 RO- (Z) _χ . These connections are characterized by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds. Alkylpolyglycosides in which R consists essentially of C - and C ₁₀ -alkyl groups, essentially of C ₁ - and C ₁₄ -alkyl groups, essentially of C ₈ -C ₁₆ -alkyl groups or essentially of -C ₂ -Cι are particularly preferred ₆ alkyl groups.

Any mono- or oligosaccharides can be used as the sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar components are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The skilled person is therefore in the event that an effect of the perfume oil beyond the duration of the hair treatment the hair is desired, preferably to this substance class as another. Access ingredient of the preparations according to the invention.

The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units 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 -Sθ 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 coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammoniumglycmat, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each with 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, in addition to a C ₈ -C ₈ -alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylaminopropionate and C _12-18 acyl sarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound, esterquat and amidoamine type. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the compounds known under the INCI names quatemium-27 and quaternium-83 compounds. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

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

The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethylsilylamodimethicone), Dow Coming 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer ler: 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".

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates. By contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal 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 can be preferred.

Furthermore, the agents according to the invention can preferably also contain a conditioning agent selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils.

Cationic polymers can be preferred as conditioning agents. These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. 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. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)), Merquat ^® 550 (di- methyldiallylammoniumchlorid-acrylamide copolymer) and Merquat ^® 280 (di- methyldiallylammoniumchlorid-acrylic acid copolymer are commercially available products available examples of such cationic polymers ,

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755. Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol and under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain. Cationic polymers of the first four groups are particularly preferred; polyquaternium-2, polyquaternium-10 and polyquaternium-22 are very particularly preferred.

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 Coming under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 as well as the commercial products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethylsilylamodimethicone), Dow ^Coming® 929 emulsion (containing a hydroxyl-amino-modified silicone, which is also known as amodimethicone is drawn), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents.

Likewise suitable hair-conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephalins.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate acrylamide copolymers methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobolymethyl acrylate, isobomyyl acrylate - reanhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl-acrylamide terpolymers,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic cum, 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 e.g. 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 intermediates such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin 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 l-alkylamidoethyl -2-alkylimidazolinium methosulfate defoamers such as silicones, dyes for coloring the agent,

Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, such as customary acids, in particular edible acids and bases, active substances such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,

- Plant extracts such as the extracts from green tea, oak bark, nettle, hamamis, hops, chamomile, burdock root, horsetail, white dome, linden flowers, almond, aloe vera, spruce needles, 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 agents 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, ß-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 styrofoam / 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, blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, e.g. B. Kh. Schrader, Fundamentals and Recipes of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

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. Application temperatures can range between 15 and 40 ° C. After an exposure time of 5 to 40 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high surfactant content, such as a coloring shampoo, has been used.

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

Claims

claims

1. 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 and released from the time the two components are mixed immediately before use becomes.

2. Composition according spoke 1, characterized in that component A is an alkaline coloring formulation.

3. Composition according to one of claims 1 or 2, characterized in that component B is an acidic developer emulsion having a pH range from 1.0 to 6.9, containing the encapsulated care substance.

4. Composition according to one of claims 1 to 3, characterized in that component B additionally contains the care substance in unencapsulated form.

5. Agent according to one of claims 1 to 4, characterized in that the encapsulation material in an acidic environment, at a pH <7, is stable and at a pH shift by at least 2 pH levels in the alkaline range , at a pH> 7, dissolves or swells.

6. Agent according to one of claims 1 to 5, characterized in that the care substances in an alkaline environment, at a pH> 7, or in the presence of oxidizing agents are not, or are only stable for up to one hour.

7. Composition according to one of claims 1 to 6, characterized in that the care substances are selected from the group which is formed from vitamins, provitamins and / or UV filters and the physiologically tolerable derivatives of these substances.

8. 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.

9. A method for oxidative hair coloring using an agent according to any one of claims 1 to 9, comprising 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.

10. Use of an agent according to one of claims 1 to 9 for gentle oxidative hair coloring.