DE19827366A1 - Oxidation dye for keratin fibers giving fast, intense orange-brown colors - Google Patents

Abstract

An oxidation dyeing agent for keratin fibers, especially human hair, contains, in addition to oxidation dye precursors, a 2-amino-3-hydroxy-5-halo-pyridine or one of its salts. An oxidation dyeing agent for keratin fibers, especially human hair, contains, in addition to oxidation dye precursors, a 2-amino-3-hydroxy-5-halo-pyridine of formula (I) or one of its salts R<1> and R<2> = H, Me or Et; and X = halogen.

Description

This invention relates to colorants which contain pyridine derivatives as the coupler component, and their use for dyeing keratin fibers.

For the coloring of keratin fibers, especially human hair, they play so-called oxidation dyes because of their intense colors and good quality Fastness properties play a preferred role. Such colorants contain oxidation dye precursors, so-called developer components and coupler components. the Developer components form under the influence of oxidizing agents or of Atmospheric oxygen with one another or with coupling with one or more couplers components make up the actual dyes.

Good oxidation dye precursors should primarily meet the following requirements fulfill: You must have the desired color nuances in develop sufficient intensity and authenticity. You must also have a good one Have the ability to be absorbed by the fiber, especially in the case of human hair no noticeable differences between damaged and newly grown hair may exist (equalizing ability). They should be resistant to light, heat, Friction and the influence of chemical reducing agents, e.g. B. Permanent wave fluids. After all, if they are used as a hair dye, they should be used on the scalp do not stain too much, and above all they should be toxicological and dermatological Respect to be harmless. Furthermore, the coloring achieved by bleaching should be light can be removed from the hair again if they are not the individual Corresponds to the wishes of the individual and should be reversed.

Alone with a developer component or a special coupler / developer combination nation does not usually succeed in creating a natural color shade on the hair obtain. In practice, therefore, combinations of different Developer and / or coupler components used. There is therefore a constant need for new, improved dye components.

Primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4- Aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives are included puts.

Special representatives are, for example, p-phenylenediamine, p-tolylenediamine, 2,4,5,6-Te traaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2.5- Diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4- amino-pyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-Hy droxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4- hydroxypyrimidine and 1,3-N, N'-bis (2'-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -diamino propan-2-ol.

As a rule, m-phenylenediamine derivatives, naphthols, Re sorcin and resorcinol derivatives, pyrazolones and m-aminophenols are used. as Coupler substances are particularly suitable 1-naphthol, 1,5-, 2,7- and 1,7- Dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resor cinmonomethylether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3- aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4- chloro-5-aminophenol.

From DE-A1-27 14 831 are aminopyridine derivatives as coupler substances in Hair dye known. As a representative of this group, the 2-amino-3- hydroxypyridine has recently gained in importance. So in the EP-A1-0 766 958, EP-A2-0 818 191 and EP-A1-0 818 192 describe hair dyes which contain 2-amino-3-hydroxypyridine as a mandatory component. The colorations achieved are, however, not with regard to the range of nuances and the fastness properties fully satisfactory.

The object of the present invention was therefore to provide new coupler components develop that remedy these shortcomings.

It has now been found that certain derivatives of 2-amino-3-hydroxypyridine with usual developers for intense colorations, especially in the orange-brown area excellent fastness properties.

The invention therefore first relates to oxidation dyes for dyeing keratin fibers, containing oxidation dye precursors in a medium suitable for dyeing, which contain at least one pyridine derivative of the general formula (I) as the coupler component

in which the substituents R ¹ and R ² independently represent hydrogen, a methyl or an ethyl group and the substituent X represents a halogen atom, e.g. B. a fluorine, a chlorine or a bromine atom, or contains one of the corresponding physiologically acceptable salts of these compounds.

Keratin fibers include fur, wool, feathers and, in particular, human hair to understand. Although the oxidation colorants of the invention are primarily used for Dyeing of keratin fibers are suitable, in principle, one use is also possible In other areas, especially in color photography, there is nothing against it.

Oxidation colorants in are particularly preferred for the purposes of the present invention an aqueous vehicle or in powder form.

Oxidation colorants are particularly preferred, the compounds of the formula (I) in which the substituent X is a chlorine atom.

Oxidation colorants which contain compounds of the formula (I) in which the radicals R ¹ and R ^{2 represent} hydrogen are also preferred.

Oxidation hair dyes which are used as the coupler component of the Formula (I) contain 2-amino-3-hydroxy-5-chloropyridine.

These compounds are prepared by known organic processes Synthetic chemistry. An example is the production of 2-amino-3-hydroxy-5- halopyridines at this point expressly refer to the essays in Helv. Chim. Acta, 60 (1977), pages 2062-2070.

Since all substances according to the invention are amino compounds, read The known acid addition salts can be prepared from these in the usual way. All Statements in this document and accordingly the scope of protection claimed relate to this forward both to the diaminophenol derivatives according to formula (I) present in free form as well as their water-soluble, physiologically compatible salts. Examples of such Salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates.

The oxidation colorants according to the invention contain at least one coupler component nents according to formula (I) and one or more developer components and can if desired, contain further coupler components.

Developer components preferred according to the invention are p-phenylenediamine, p-Toluy lenediamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2-hydroxyethyl) p-phenylenediamine, 2- (2,5-diaminophenoxy) ethanol, 1-phe nyl-3-carboxyamido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2,4,5,6-tetraamino pyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4- Dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-hydroxy ethylaminomethyl-4-aminophenol, 4,4'-diaminodiphenylamine, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, bis- (2-hydroxy-5- aminophenyl) methane, 1,4-bis (4-aminophenyl) diazacycloheptane, 1,3-bis (N (2-hydroxy ethyl) -N (4-aminophenylamino)) -2-propanol, 4-amino-2- (2-hydroxyethoxy) phenol and 4,5-diaminopyrazole derivatives according to EP 0 740 741 or WO 94/08970 such as e.g. B. 4,5-Di amino-1- (2'-hydroxyethyl) pyrazole.

Particularly preferred developer components are p-phenylenediamine, p-tolylenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-tri aminopyrimidine, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 2-aminomethyl-4-amino phenol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, bis- (2-hydroxy-5-aminophenyl) - methane and o-aminophenol.

According to the invention preferred coupler components are 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophe nol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazo ion-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylre sorcin, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dihy hydroxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hy hydroxytoluene, 2,6-bis- (2-hydroxyethylamino) -toluene, 2,4-diaminophenoxyethanol, 1-meth oxy-2-amino-4- (2-hydroxyethylamino) benzene, 2-methyl-4-chloro-5-aminophenol, 6-Me ethyl 1,2,3,4-tetrahydroquinoxaline, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 2,6-dimethyl-3-aminophenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4- aminophenoxyethanol, 2-methyl-5- (2-hydroxyethylamino) -phenol and 2,6-dihydroxy-3,4- dimethyl pyridine.

Particularly preferred coupler components for the purposes of the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylre sorcin, 2,6-dihydroxy-3,4-diaminopyridine, methyl-1,2,3,4-tetrahydroquinoxaline, m- Aminophenol, o-aminophenol and 2-chlororesorcinol.

These further developer and coupler components are usually in free form used. In the case of substances with amino groups, however, it may be preferred to use them in Salt form, especially in the form of hydrochlorides and sulfates, to be used.

The hair colorants according to the invention contain both the developer components the coupler components are also preferably present in an amount of from 0.005 to 20% by weight preferably 0.1 to 5% by weight, based in each case on the total oxidation colorant. Here, developer components and coupler components are generally approximately molar amounts used to each other. If even the molar stake is an endeavor has been shown to be moderate, so is a certain excess of individual oxidation dye precursors not disadvantageous, so that developer components and Coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2, may be included.

In a preferred embodiment, the hair colorants according to the invention contain for further modification of the color nuances in addition to the oxidation dye precursors additional standard direct dyes. Direct dyes are common Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophe nole. Preferred substantive dyes are those under the international designation or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, 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 and 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, Hydroxyethyl-2-nitro-toluidine, picric acid, 2-amino-6-chloro-4-nitrophenol 4- Ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

The agents according to the invention according to this embodiment contain the substantive dyes preferably in an amount of 0.01 to 20 wt .-%, based on all of the dye.

Furthermore, the preparations according to the invention can also occur naturally Dyes such as red henna, neutral henna, black henna, chamomile blossom, Sandalwood, black tea, buckthorn bark, sage, blue wood, madder root, catechu, Contains sedre and alkanna root.

Further dye components contained in the colorants according to the invention can also indoles and indolines, as well as their physiologically tolerable salts. Preferred Examples are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihy droxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6- Dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Also preferred 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, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

It is not necessary that the oxidation dye precursors or the substantive Dyes each represent uniform compounds. Rather, in the inven proper hair dyes, due to the manufacturing process for the individual dyes, contain other components in subordinate quantities insofar as these do not adversely affect the dyeing result or from others Reasons, e.g. B. toxicological, must be excluded.

With regard to those which can be used in the hair coloring and tinting compositions according to the invention Dyes is also expressly referred to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive dyes), and Chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the series "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 European Community, available in diskette form from the Bundesverband Deutscher Industrial and trading company for pharmaceuticals, health foods and personal care products tel e.V., Mannheim.

A second object of this invention is the use of the aforementioned means for Dyeing of keratin fibers.

Oxidation dyes can be used to produce the colorants according to the invention precursors are incorporated into a suitable water-containing carrier. Such Carriers are for the purpose of hair coloring z. B. creams, emulsions, gels or th foaming solutions containing sides, e.g. B. shampoos, foam aerosols or other preparations tings that are suitable for use on the hair.

The colorants according to the invention can also all be used for such preparations contain known active ingredients, additives and auxiliaries. In many cases, the coloring agents contain at least one surfactant, in principle both anionic and zwitterionic, am pholytic, nonionic and cationic surfactants are suitable. In many cases it has but proved to be advantageous, the surfactants from anionic, zwitterionic or select nonionic surfactants.

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

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

Zwitterionic surfactants are surface-active compounds which have at least one quaternary ammonium group and at least one —COO ^(-) or —SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example cocoacylaminopropyl-dimethylammonium glycinate, and alkyl -3-carboxymethyl-3-hydroxyethyl-imidazolines, each with 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacylaminoethylhydroxyethylcarboxymethylgly cinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C _8-18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, cocacylaminoethylaminopropionate and C _12-18 acylsar cosine.

Nonionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide of linear fatty alcohols with 8 to 22 carbon atoms, of fatty acids with 12 to 22 carbon atoms and to alkylphenols with 8 to 15 carbon atoms in the alkyl group,
• - C _12-22 fatty acid mono- and diesters of addition products of 1 to 30 mol ethylene oxide with glycerol,
• - C _{8-22 -alkyl} mono- and oligoglycosides and their ethoxylated analogues,
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated Rizi nut oil,
• - Addition products of ethylene oxide with sorbitan fatty acid esters
• - Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of those which can be used in the hair treatment compositions according to the invention Cationic surfactants are, in particular, quaternary ammonium compounds. Are preferred Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammo niumchloride and trialkylmethylammoniumchloride, e.g. B. Cetyltrimethylammo nium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methylammonium chloride. Further cationic surfactants which can be used according to the invention represent the quaternized protein hydrolysates.

Also suitable according to the invention are cationic silicone oils such as, for example, those im Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trim thylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxyl-amino-mo differentiated silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines like that under the name Tego Amid®S 18 available stearylamidopropyldimethylamine, stand out next to one good conditioning effect, especially due to their good biodegradability. Quaternary ester compounds, so-called, are also very readily biodegradable "Esterquats" such as the methyl-hydroxyal sold under the trademark Stepantex® kyldialkoyloxyalkyl-ammonium methosulfate and those under the trademark De hyquart® such as Dehyquart® AU-46.

An example of a quaternary sugar derivative that can be used as a cationic surfactant is provided the commercial product Glucquat © 100, according to INCI nomenclature a "Lauryl Methyl Glu ceth-10 Hydroxypropyl Dimonium Chloride ".

The compounds with alkyl groups used as surfactants can each be act uniform substances. However, it is usually preferred in manufacturing of these substances from native vegetable or animal raw materials, so that one Mixtures of substances with different, depending on the respective raw material Maintains alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide with fatty al represent alcohols or derivatives of these addition products, both products can a "normal" homolog distribution as well as those with a narrowed homolog distribution can be used. Under "normal" homolog distribution, Mi Understood chings of homologues that one in the implementation of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates obtained as catalysts. Narrowed homolog distributions are on the other hand, if, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates as catalysts be used. The use of products with a narrow homolog distribution may be preferred.

Further active ingredients, auxiliaries and additives are, for example

• - nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,
• - Cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary Groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl ammonium chloride copolymers, dimethylamino quaternized with diethyl sulfate ethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• - zwitterionic and amphoteric polymers such as acrylamidopropyl-tri methylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacryl lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• - anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide Terpolymers,
• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum ara bicum, karaya gum, locust bean gum, linseed gums, dextrans, cellu lose derivatives, e.g. Methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose lulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, Clays such as B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol get,
• - structurants such as glucose and maleic acid,
• - hair conditioning compounds such as phospholipids, e.g. soy lecithin, Egg lecithin and cephalins, as well as silicone oils,
• - Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids as well as quaternized protein hydrolysates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• - Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerine and diethylene glycol,
• - Anti-dandruff ingredients such as Piroctone Olamine and Zinc Omadine,
• - other substances to adjust the pH value,
• - Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - light stabilizers,
• - Consistency factors such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as whale rat, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• - fatty acid alkanolamides,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerine, propylene glycol monoethyl ether, carbo nates, hydrogen carbonates, guanidines, ureas as well as primary, secondary and tertiary Phosphates,
• - opacifiers such as latex,
• - pearlescent agents such as ethylene glycol mono- and distearate,
• - Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air as well
• - antioxidants.

The constituents of the water-containing carrier are used to produce the inventive ßen colorants used in amounts customary for this purpose; z. B. are emulsifiers medium in concentrations of 0.5 to 30% by weight and thickener in concentrate nen from 0.1 to 25 wt .-% of the total colorant used.

The oxidative development of the color can in principle take place with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially when In addition to the coloring, a lightening effect on human hair is desired. As an oxidation medium come persulfates, chlorites and especially hydrogen peroxide or its type storage products of urea, melamine and sodium borate in question. Furthermore it is possible to carry out the oxidation with the help of enzymes. The enzymes for transferring atmospheric oxygen to the developer component or for amplification serve the effect of small amounts of oxidizing agents present. An example of a enzymatic process represents the procedure, the effect of small amounts (e.g. 1% and less, based on the total agent) hydrogen peroxide by peroxidases strengthen.

Appropriately, the preparation of the oxidizing agent is immediately before Hair coloring mixed with the preparation from the oxidation dye precursors. That The resulting ready-to-use hair dye preparation should preferably have a pH value in Range from 6 to 10. The use of hair coloring is particularly preferred medium in a weakly alkaline environment. The application temperatures can be in ei range between 15 and 40 ° C. After an exposure time of approx. 30 minutes th, the hair dye is removed from the hair to be colored by rinsing. That After washing with a shampoo is not necessary if a strong surfactant-containing carrier, z. B. a Coloring shampoo.

The following examples are intended to explain the subject matter of the invention in more detail.

Embodiments

All quantitative data in the examples are parts by weight.

1. Preparation of the coloring cream 1.1 Partial mix A

Hydrenol® D ¹ 8.50 g Lorol® tech. ² 2.00 g Eumulgin® B2 ³ 0.75 g Texapon® NSO ⁴ 20.00 g Dehyton® K ⁵ 12.50 g water 30.00 g

¹ C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (HENKEL)
² C _12-18 fatty alcohol (INCI name: Coconut alcohol) (HENKEL)
³ cetostearyl alcohol with approx. 2 EO units (INCI name: Ceteareth-20) (HENKEL)
⁴ Lauryl ether sulfate, sodium salt (approx. 27.5% active ingredient; INCI name: Sodium Laureth Sulfate) (HENKEL)
⁵ N, N-Dimethyl-N- (C _8-18 cocamidopropyl) ammonium acetobetaine (approx. 30% active ingredient; INCI name: Aqua (Water), Cocamidopropyl Betaine) (HENKEL)
The substances Hydrenol D, Lorol and Eumulgin B2 were melted at 80 ° C., mixed with the 80 ° C. hot water containing Texapon NSO and Dehyton K, and emulsified with vigorous stirring. The emulsion was then cooled with gentle stirring.

1.2 Partial mix B

Sodium sulfite 1.00 g Ammonium sulfate 1.00 g Dye precursors 7.5 mmol each Ammonia (25% solution) ad pH = 10.0 water 10.00 g

The dye precursors were in the 50 ° C hot water with the addition of Dissolved sodium sulfite, ammonium sulfate and ammonia.

The dye precursor solution (partial mixture B) became an emulsion (partial mixture A) given, adjusted to pH = 10 with ammonia and to 100 parts by weight with water filled up. Stirring was continued until room temperature was reached.

2. Coloring of the keratin fibers

The coloring cream obtained in this way was mixed in a ratio of 2: 1 with a 3% H ₂ O ₂ solution and applied to 5 cm long strands of standardized 80% gray but not specially pretreated human hair (Kerling). After a contact time of 30 minutes at 32 ° C., the hair was rinsed, washed out with a conventional shampoo and then dried.

The result of the dyeing tests is shown in Table I.

Table I.

Claims (9)

1. Oxidation dyes for dyeing keratin fibers, especially human hair, containing oxidation dye precursors in a medium suitable for dyeing, characterized in that it contains at least one pyridine derivative of the general formula (I)
in which the substituents R ¹ and R ² independently of one another represent hydrogen, a methyl or ethyl group and the substituent X represents a halogen atom or contains one of the physiologically acceptable salts of these compounds. 2. Oxidation colorant according to claim 1, characterized in that the substituent X in the compound of formula (I) is a chlorine atom. 3. Oxidation colorant according to claim 1, characterized in that the radicals R ¹ and R ² in the compound of formula (I) represent hydrogen. 4. Oxidation coloring agent according to one of claims 1 to 3, characterized in that the compound of formula (I) is 2-amino-3-hydroxy-5-chloropyridine. 5. Oxidation coloring agent according to one of claims 1 to 4, characterized in that there is at least one developer component selected from the group consisting of p- Phenylenediamine, p-tolylenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-dia minobenzene, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 4,5-diamino-1- (2- hydroxyethyl) pyrazole, 2-aminomethyl-4-aminophenol, N, N-bis- (2-hydroxyethyl) -p- phenylenediamine, bis (2-hydroxy-5-aminophenyl) methane and o-aminophenol will contain. 6. Oxidation coloring agent according to one of claims 1 to 5, characterized in that there is at least one further coupler component selected from the group which is formed from 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2- methylphenol, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-diaminopyridine, Methyl-1,2,3,4-tetrahydroquinoxaline, m-aminophenol, o-aminophenol and 2- Contains chlororesorcinol. 7. Oxidation coloring agent according to one of claims 1 to 6, characterized in that Developer components in an amount of 0.005 to 20% by weight, preferably 0.1 up to 5% by weight, and coupler components in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, based in each case on the total oxidation dye means, are included. 8. Oxidation colorant according to any one of claims 1 to 7, characterized in that at least one substantive dye is included. 9. Use of agents according to one of claims 1 to 8 for dyeing keratinous Fibers.