DE19756455A1 - Oxidation dyeing agent especially for hair containing dye-precursor and oxygen enriched zeolite in anhydrous medium - Google Patents

Abstract

An oxidation dyeing agent comprising a component (A) containing a conventional oxidation dye precursor (I) also contains another component (B) containing an oxygen-enriched zeolite (II) in an anhydrous medium. An Independent claim relates to dyeing keratin fibers by oxidative development of a dye precursor using oxygen released from an oxygen-enriched zeolite immediately prior to the dyeing process.

Description

The present invention relates to oxidation coloring agents with oxygen enriched zeolites and a process for dyeing keratin fibers in which oxygen released immediately before from oxygenated zeolite as Oxidizing agent is used.

For dyeing keratin fibers, e.g. B. wool, furs and in particular human hair, generally come either direct dyes or Oxidation dyes by oxidative coupling of one or more developers components with each other or with one or more coupler components Application.

Direct dyes are applied under gentle conditions. However, their disadvantage is that the dyeings often have inadequate fastness properties. With oxidation dyes it is possible to achieve intense dyeings with good fastness properties, but the development of the color usually takes place under the influence of H ₂ O ₂ or H ₂ O ₂ adducts, which can damage the fibers.

Oxidation dyes with atmospheric oxygen as a very mild oxidizing agent have also been used already proposed; in general, however, the oxidations run with atmospheric oxygen not completely off. Especially in oxidation hair dyes, which are usually in one If the cream-like cosmetic carrier is applied, the atmospheric oxygen strikes significant diffusion barriers.

It is therefore an object of the present invention to provide oxidation colorants, in particular Oxidation hair dye to provide that alone with oxygen as an oxidizer result in intense colors. The task was solved by using Zeolites as oxygen stores.

The present invention therefore relates to oxidation colorants consisting of a component A, containing conventional oxidation dye precursors, and one Component B, which is characterized in that it is in an anhydrous medium contains oxygen-enriched zeolite.

According to the invention, developer sub are conventional oxidation dye precursors stamping and to understand coupler substances.

Developer substances are usually aromatic or heterocyclic ring systems, by two reactive groups in ortho or para positions to each other, i.a. Hydroxy or amino groups are characterized. Such connections are for example primary aromatic amines with a further one in the para or ortho position located free or substituted hydroxy or amino group, further diamino pyrldinderlvate, heterocyclic hydrazone derivatives or 4-aminopyrazolone derivatives.

Preferred developer components according to the invention are p-phenylenediamine, p-Toluy lendiamine, p-aminophenol, 2- (2,5-diaminophenyl) ethanol, N, N-bis (2-hydroxyethyl) -p- phenylenediamine, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino pyrazolon-5, 4-amino-3-methylphenol, 2-hydroxymethyl-4-aminophenol, 2-arnino methyl-4-aminophenol, 2-hydroxyethylaminomethyl-4-aminophenol and 4,4'-diamino diphenylamine.  

Coupler substances are often aromatic or heterocyclic ring systems, the two have reactive groups in the meta position. Examples of such substances are Phenyiendiamindvate, m-aminophenols, naphthols, resorcinol derivatives and pyrazolones.

Coupler components preferred according to the invention are 1-naphthol, 1,5-, 2,7- and 1,7- Dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, Re sorcinol, resorcinol monomethyl ether, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3- aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2- Chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylre sorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyrtdine, 2-amino-3-hydroxypyrldine, 2,6-dihy doxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-bis- (2-hydro xyethylamino) toluene, 2,4-diaminophenoxyethanol, 2-amino-4-hydroxyethylamino-anisole.

Usually developer components and coupler components become approximately molar Quantities used to each other. Even if the molar use turned out to be expedient has a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components preferably in one Molar ratio of 1: 0.5 to 1: 2 may be contained in the colorant.

The total amount of oxidation dye precursors is preferably from 0.01 to 20 % By weight, in particular 0.1 to 5% by weight, based on the entire oxidation colorant.

According to the invention, the types zeolite NaA, zeolite are particularly suitable as zeolites KA, zeolite CaA, zeolite MgA, zeolite NaX, zeolite H-ZSM5, zeolite NaY and zeolite Na-ZSM5. Further details on these types of zeolites can be found in the monograph by D.W. Breck, Zeolite molecular sieves, John Wiley & Sons, New York, London, Sidney, Toronto, 1974, can be seen; to the corresponding passages in this monograph expressly referred.

According to the invention, the volume of oxygen stored in the zeolite is 1.5- up to 50 times, in particular 3 to 30 times the volume of zeolite. The specified  The volume of oxygen here and below refers to a temperature of 20 ° C and a pressure of 1 bar. The methods for enriching the zeolite with oxygen are known to the person skilled in the art; reference is still made to the example part.

According to a preferred embodiment, the zeolite can contain, in addition to the stored oxygen, catalytically active metal ions such as Ag⁺, Cu ²⁺ and Mn ions.

The oxidation colorants according to the invention contain the oxygen-enriched Zeolite preferably in an amount of 5 to 80% by weight, in particular 5 to 50% by weight, based on the entire oxidation colorant.

The oxygen-enriched zeolite is packaged and stored in one anhydrous medium; anhydrous in the sense of the present invention means that the Content of water in the agent according to the invention at most 2% by weight, based on the Component B is; preferably the water content is less than 1% by weight, in particular less than 0.5% by weight. Evidence of the residual water content in the zeolite can be done by determining the loss on ignition (800 ° C; 1 h).

According to a first preferred embodiment, component B is in the form of a dry powder. In this case, component B may contain other powdery substances in addition to the acid-enriched zeolite. These are preferably:

• Polymeric swelling agents such as xanthan gum, derivatized cellulose, guar gum, Polyacrylates,
• - surfactants,
• - wetting agents and
• - emulsifiers.

According to a second, particularly preferred embodiment, component B is in Form of an anhydrous paste. This paste is preferred based on a natural one or synthetic oils, for example a paraffin or silicone oil, a liquid  Wax such as jojoba oil, a higher dialkyl ether or a cyclic Formulated hydrocarbon. According to the invention, higher dialkyl ethers are used in Room temperature (20 ° C) liquid dialkyl ethers, in which the alkyl groups are independent are linear or branched from one another, saturated or mono- or polyunsaturated and each have 4 to 18 carbon atoms. A preferred representative according to the invention This group is the one sold by the applicant under the name Cetiol® OE Dioctyl ether. A preferred example of a cyclic according to the invention Hydrocarbon is the one sold by the applicant under the name Cetiol® S. 1,3-bis (2-ethylhexyl) cyclohexane.

If component B is present as an anhydrous paste, the proportion of acid is substance-enriched zeolite preferably 10 to 85% by weight, in particular 15 to 85% by weight, based on component B.

Component A, which contains the oxidation dye precursors, is according to a first preferred embodiment of the invention as a water-containing preparation con assembled. In this case, the two components A and B are spatially separated kept apart, especially in two separate containers. The components A and B are mixed with one another immediately before application and then onto the Hair applied. As water enters the zeolite crystals, the sorbed oxygen is released or exchanged for water and stands as Oxidizers available.

According to a second embodiment, components A and B can also be in one shared containers are kept. In this case, make sure that next to component B, component A is also anhydrous. The release of the zeolite In this case, bound oxygen occurs immediately before adding water the application on the hair.

When components A and B are stored separately in two different ones Containers is the component A in containing the oxidation dye precursors formulated a conventional cosmetic carrier. Such carriers are e.g. B. creams,  Emulsions, gels or surfactant-containing, foaming solutions, e.g. B. shampoos, Foam aerosols or other preparations that are suitable for use on the hair are.

The agents according to the invention can furthermore all known for oxidation colorants contain further substances, which are preferably part of component A. The Incorporation of these substances, especially if they are in powder form, in the However, component B should not be excluded in principle.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, Anthraquinones or indophenols. Preferred substantive dyes are those among international names or trade names HC Yellow 2, HC Yellow 4, HC Yel low 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as 4- Amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, Hy hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol and 4-N- Ethyl 1,4-bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride. The inventive Agents according to this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20 wt .-%, based on the total colorant.

Furthermore, the preparations according to the invention can also occur in nature Dyes such as henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, Contain sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the substantive ones Dyes each represent uniform compounds. Rather, in the inventions hair colorants according to the manufacturing process for the individual Dyes, minor components may be included, so far these do not adversely affect the coloring result or for other reasons, e.g. B. toxi ecological, must be excluded.  

Regarding those that can be used in the hair coloring and tinting agents according to the invention Dyes continue to be expressly referred 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 "Dermato logy "(Ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the European Community, available in disk form from the Federal Association of German Industrial and trading company for pharmaceuticals, health products and personal care tel e.V., Mannheim, referred to.

Surfactants which can be used according to the invention are, for example:

• - Anionic surfactants such as soaps from fatty acids, alkyl sulfates, alkyl poly glycol 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, sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfons mono-alkyl polyoxyethylsuccinate with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, alkane sulfonates and α-olefin sulfonates,
• - Nonionic surfactants such as, in particular, adducts 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, with alkylphenols with 8 to 15 C atoms in the alkyl group and on fatty acid alkanolamides, 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 as adducts from 5 to 60 Moles of ethylene oxide to castor oil and hardened castor oil,
• - zwitterionic surfactants, especially the so-called betaines such as the N-alkyl N, N-dimethylammomum glycinate, for example coconut alkyl dimethylammo nium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-car boxylmethyl-3-hydroxyethyl-imidazolines each with 8 to 18 carbon atoms in the Al  kyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethyl glycinate,
• - Ampholytic surfactants such as N-alkylglycine, N-alkylpropionic acid, N-alkylamino butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycine, N-alkyl taurine, N-alkyl sarcosine, 2-alkyl aminopropionic acid and alkyl aminoacetic acids each having about 8 to 18 carbon atoms in the alkyl group,
• - Quaternary ammonium compound type cationic surfactants, e.g. B.Amtnoni halides, in particular chlorides and bromides, such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and trialkylmethylammonium chloride, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distea ryldimethylarnmonium chloride, lauryldimethylarnmonium chloride, lauryldimethyl benzylammonium chloride and tricetylmethylammonium chloride, behenyltrime thylammonium methosulfate and those under the INCI names Quaternium-27 and quaternium-83 known imidazolium compounds. Also as a cationic Alkylamidoamines such as that under the name Tegoamid® can be used as surfactants S 18 commercially available stearamidopropyldimethylamine and so-called esters quats like the N, N- commercially available under the name Armocare® VGH-70 Bis (2-palmitoyloxyethyl) dimethylammonium chloride

Depending on the type of agent and the type of surfactant, the surfactants in the invention Agents in a total amount of 0.5 to 30% by weight, based on the total agent, be included; Agents that are formulated as so-called concentrates can also be higher Contain surfactant levels.

Furthermore, the agents according to the invention can preferably also be a conditioning agent Active ingredient selected from the group consisting of cationic surfactants, cationic Polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils is formed.

Cationic polymers can be preferred as conditioning agents. These are in usually polymers that have a quaternary nitrogen atom, for example in the form of an Am monium group.  

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, such as those under the names Celquat® and Po lymer JR® are commercially available. The connections Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
• - polymeric dimethyldiallyl ammonium salts and their copolymers with esters and Amides of acrylic acid and methacrylic acid. The under the designations Mer quat® 100 (poly (dimethyldiallylammonium chloride)) and Merquat®550 (dimethyldial lylammonium chloride-acrylamide copolymer) are commercially available products Examples of such cationic polymers.
• - Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as vinyl quaternized with diethyl sulfate pyrrolidone-dimethylaminomethacrylate copolymers. Such connections are under the names Gaftquat®734 and Gaftquat®755 commercially available.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as described under the designation Luviquat® can be offered.
• - quaternized polyvinyl alcohol

as well as those under the designations

• - polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the Po lymer main chain.

Cationic polymers of the first four groups are particularly preferred.

Also suitable as conditioning agents are silicone oils, especially dialkyl and alkylarylsiloxanes such as dimethylpolysiloxane and methylphenylpolysi loxane, and their alkoxylated and quaternized analogues. Examples of such silicones are those of Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 distributed products 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 can also be called 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 and vegetable oils can also be used as conditioning agents such as sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil.

Suitable hair conditioning compounds are phospholipids, for example wise soy lecithin, egg lecithin and cephaline.

Other common constituents of the preparations according to the invention can be:

• - Anionic, zwitterionic, amphoteric and nonionic polymers such as wise vinyl acetate / crotonic acid copolymers, polydimethylsiloxanes, Vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl-acrylic lat copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked and crosslinked with polyols, acrylic amidopropyl trime thylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert. Butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrolidone / dimethyl aminoethyl methacrylate / vinyl caprolactam terpolymers and optionally derivatized based cellulose ether.
• - Symmetrical and asymmetrical, linear and branched dialkyl ethers with a total between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, for example di n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether and di-n-dodecy ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-unde cyl-n-dodecyl ether and n-hexyl-n-undecyl ether as well as di-tert-butyl ether, di-iso-pen tyl ether, di-3-ethyl decyl ether, tert-butyl-n-octyl ether, isopentyl-n-octyl ether and 2- Methyl pentyl n-octyl ether,
• - defoamers like silicones,
• - Thickeners such as agar agar, guar gum, alginates, xanthan gum, plants gumm, starch, gelatin, pectins, methyl or hydroxyethyl cellulose and poly acrylamides and their copolymers,  
• Structurants such as maleic acid, mono-, di- and oligosaccharides,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• - Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glyce rin and diethylene glycol,
• - anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol,
• - substances for adjusting the pH,
• - Animal and vegetable protein hydrolyzates, especially elastin, collagen, kera tin, milk protein, soy protein, almond protein and wheat protein hydrolyzates, see above such as their fatty acid condensation products and quaternized derivatives,
• Vitamins and precursors such as panthenol, its derivatives and biotin,
• - Plant and honey extracts, such as in particular extracts from oak bark, distillate sel, witch hazel, hops, chamomile, burdock root, horsetail, linden flowers, man del, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, Orange, grapefruit, sage, rosemary, birch, cuckoo flower, quendel, sheep sheaf, harrow, meristem, ginseng and ginger root,
• Further active ingredients such as ceramides, allantoin, pyrrolidone carboxylic acids and bisabolol,
• - light stabilizers,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• Fats and waxes, such as walrus, beeswax, montan wax, fatty alcohols, fatty acids, Fatty acid esters and paraffins,
• - fatty acid alkanolamides,
• - Swelling and penetration substances such as glycerin, propylene glycol monoethyl ether, carbo nates, hydrogen carbonates, guanidines, ureas and primary, secondary and ter tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers,
• Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - Reducing agents such. B. thioglycolic acid and its derivatives, thiolactic acid, Cy steamin, thio malic acid and α-mercaptoethanesullonic acid,
• - Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ , N ₂ and air such as
• - antioxidants.

Regarding further components and quantity ranges for the individual ingredients is based on the manuals known to those skilled in the art, e.g. B. K. Schrader, Basics and Recipes for cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

Another object of the invention is a process for dyeing keratin fibers, especially human hair, through oxidative development of oxidation dye precursors with oxygen, in which the oxygen immediately before the Dyeing process is released from an oxygen-enriched zeolite.

The oxidative development of the dyeing takes place in that component B with the oxygen-enriched zeolite is mixed with component A immediately before the dyeing process and, if component A is not a water-containing preparation, with water, and the subsequent oxidation by that released from the zeolite Oxygen occurs. In cases in which the oxidation of the dye precursors does not proceed completely, small amounts of an oxidizing agent, in particular an H ₂ O ₂ preparation, can also be added as additional oxidizing agents. In the case of an aqueous 12% by weight H ₂ O ₂ solution, this addition is preferably not more than 10% by weight, based on the total colorant.

The use of the finished colorants for coloring human beings is particularly preferred Hair in a neutral to weakly alkaline environment. The application temperatures can be in a range between 15 and 40 ° C. After an exposure time of The dye is rinsed off the hair to be dyed for about 30 minutes. Rinsing with a shampoo can be omitted if a strong surfactant Carrier, e.g. B. a coloring shampoo was used.

The oxidation dyeing process described can of course also be applied to others Use fibers as human hair. As keratin fibers are except human To name hair, for example, feathers, furs or wool.

Examples 1. Production of Oxygenated Zeolites

Commercially available zeolite is optionally known by a cation exchange reaction Process converted into the desired composition. Then the zeolite dried at a temperature at which it has not yet lost its crystallinity is destroyed (the drying temperatures for preferred zeolites are in Table 1 listed). The dehydrated zeolite is then dried in vacuo. After this the zeolite is completely saturated with oxygen, if necessary not in one suspended aqueous phase and stored dry.

Table 1

Zeolites

2. Examples of use

Oxidation dyes according to the invention in the form of a hair dye Cream emulsion of the following compositions prepared (all quantities, unless otherwise noted, parts by weight are:

Component A

Component B Zeolite CaA with 25 times the volume of oxygen

10 g each of components A according to Examples A1 and A2 were mixed with 3 g of Component B mixed (Examples B1 and B2). Corresponding were for comparison Mixtures made with non-oxygen-loaded zeolite CaA (comparative examples V1 and V2).

The oxidative development of the color took place immediately after mixing the Components A and B on strands of hair weighing approximately 0.5 g (type "Virgin White" of Alkinco) at room temperature. The ratio of dye to hair was approximately 4: 1 The hair was rinsed for 30 minutes, washed with a conventional shampoo and then dried in an air stream at approx. 40 ° C. The assessment of the coloring results took place immediately after drying. The individual staining results are shown in Table 2 refer to:

Table 2

Dyeing results

The results show that the dyeings with the colorants according to the invention have a half the color shade turned out to be more intense than with the colors with not oxygenated zeolite.

Claims (10)

1. Oxidation dye consisting of a component A, containing conventional oxidation dye precursors , and a component B, characterized in that component B contains oxygen-enriched zeolite in an anhydrous medium. 2. Oxidation dye according to claim 1, characterized in that the Oxidation dye precursors in amounts of 0.01 to 20 wt .-%, preferably 0.1 to 5 wt .-%, and the oxygenated zeolite in an amount of 5 to 80 wt .-%, preferably 5 to 50 wt .-%, each based on the total Oxidation colorants are included. 3. Oxidation dye according to claim 1 or 2, characterized in that the volume of oxygen stored by the oxygen-enriched zeolite up to 50 times, preferably 3 to 30 times, the volume of zeolite. 4. Oxidation dye according to one of claims 1 to 3, characterized in that the zeolite is selected from the group consisting of zeolite NaA, zeolite KA, Zeolite CaA, Zeolite MgA, Zeolite NaX, Zeolite H-ZSM5, Zeolite NaY and Zeolite Na-ZSM5 is formed. 5. Oxidation coloring agent according to one of claims 1 to 4, characterized in that component B is at 25 ° C in the form of a dry powder. 6. oxidation dye according to one of claims 1 to 4, characterized in that component B is in the form of an anhydrous paste up to 25 ° C. 7. oxidation dye according to claim 6, characterized in that the Component B a paste based on a natural or synthetic oil,  a liquid wax, a higher dialkyl ether or a cyclic Is hydrocarbon. 8. oxidation dye according to one of claims 1 to 7, characterized in that components A and B are kept separate from each other. 9. oxidation dye according to one of claims 1 to 7, characterized in that components A and B are kept in a common container become. 10. Process for dyeing keratin fibers by oxidative development of Oxidation dye precursors with oxygen, characterized in that the Oxygen immediately before the dyeing process from an oxygen-enriched Zeolite is released.