DE19750303A1 - Hair dye compositions containing direct dye - Google Patents

Abstract

Use of 3,7-diaminophenothiazines of formula (I) for dyeing keratin-containing fibres is new: R1 and R2 = NH2, NHR8 or NR8R9; R3-R6 = H or 1-4C alkyl; R7 = H, halogen or NO2; R8 and R9 = 1-4C alkyl; X = a mineral or organic acid anion; provided that at least one of R3-R6 is alkyl when R1 and R2 are both NR8R9. Also claimed is a composition for dyeing keratin-containing fibres, especially human hair, comprising (A) one or more compounds (I), (B) oxidation dye precursors selected from developers and couplers, and/or (C) condensation dye precursors selected from reactive carbonyl compounds, primary or secondary aromatic amines, N-containing heterocyclic compounds and aromatic hydroxy compounds.

Description

The invention relates to the use of alkylated phenothiazines for dyeing kera fibers containing ink, in particular human hair, an agent for coloring keratin containing fibers containing alkylated phenothiazines, and a process for dyeing fibers containing keratin.

For dyeing keratin fibers, e.g. B. hair, wool or furs come in general either direct dyes or oxidation dyes caused by oxida tive coupling of one or more developer components with each other or with one or several coupler components are created for use. Coupler and developer compo nenten are also referred to as oxidation dye precursors.

The direct dyes form the color directly on the fiber due to their egg gene color. The color on the fiber will fade over time or will change during washing washed out. Compared with the oxidation dyes are the intensity of the color and the fastness properties are lower.

With oxidation dyes intensive dyeings with good fastness properties can be achieved, but the development of the color is usually done under the influence of oxidizing agents such. B. H ₂ O ₂ , which in some cases can damage the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on people with sensitive skin. Direct dyes are applied under gentler conditions. They are often used in combination with oxidation dyes to obtain certain color shades.

The published patent application DE 33 05 305 A1 describes a method for dyeing hair described basic dyes, in which the hair is changed so that more than  75% of the cystine bonds of the hair keratin peptide chain in S-sulfocysteine groups are converted, the major part of the peptide chains having a molecular weight between approximately 1100 and approximately 7500. As a basic colorant, for example wise methylene blue used. In the process described, the keratin-containing Fibers are first pretreated to obtain a color. The real one The properties of the copies obtained by this process are not satisfactory presenting.

The object of the present invention is to provide coloring agents for keratin-containing fibers, in particular to provide human hair, which is used as a direct colorant that can, and that in terms of color depth, gray coverage and authenticity are qualitatively at least equivalent to the usual oxidation hair dyes. A Another object of the present invention is to provide colorants with which can be preserved in a wide variety of color shades. A coloring of the Skin areas should be avoided if possible. In addition, the colorants may not or only have a very low sensitization potential.

Surprisingly, it was found that the alkylated used according to the invention Phenothiazines are excellent as direct substances for coloring keratin containing fibers. They result in colors with excellent brilliance and depth of color and lead to diverse shades of color. The use of oxidizing agents is not him required, but it should not be excluded in principle.

The present invention accordingly relates to the use of alkylated phenothiazines of the following formula I.

wherein R ¹ and R ^{2 are} each independently an NH ₂ , NHR ⁸ or NR ⁸ R ⁹ group in which R ⁸ and R ^{9 represent} a (C ₁ -C ₄ ) alkyl group,
R ³ to R ^{6 are} each independently a hydrogen atom or a (C ₁ -C ₄ ) alkyl group,
R ^{7 is} a hydrogen atom, a halogen atom or a nitro group and X represents the anion of a mineral acid or organic acid,
with the proviso that if R ¹ and R ^{2 are} both an NR ⁸ R ⁹ group, then at least one of the radicals R ³ to R ^{6 is} a (C ₁ -C ₄ ) alkyl group,
for dyeing keratin fibers.

The present invention therefore furthermore relates to an agent for dyeing fibers containing keratin, in particular human hair, which contains

• (A) one or more alkylated phenothiazines of the following formula I
  wherein
  R ¹ and R ^{2 are} each independently an NH ₂ , NHR ⁸ or NR ⁸ R ⁹ group in which R ⁸ and R ^{9 represent} a (C ₁ -C ₄ ) alkyl group,
  R ³ to R ^{6 are} each independently a hydrogen atom or a (C ₁ -C ₄ ) alkyl group,
  R ^{7 is} a hydrogen atom, a halogen atom or a nitro group and
  X represents the anion of a mineral acid or organic acid,
  with the proviso that if R ¹ and R ^{2 are} both an NR ⁸ R ⁹ group, then at least one of the radicals R ³ to R ^{6 is} a (C ₁ -C ₄ ) alkyl group,
• (B) one or more oxidation dye precursors from the group of developers and Coupler connections, and / or
• (C)) one or more condensation dye precursors from the reactive group Carbonyl compounds as well as those with primary or secondary amino group or hydroxy group selected from primary or secondary aromatic Amines, nitrogen-containing heterocyclic compounds and aromatic Hydroxy compounds.

Among keratin fibers are wool, furs, feathers and especially human hair to understand. In principle, however, the colorants according to the invention can also be used for dyeing other natural fibers, such as. B. cotton, jute, sisal, linen or silk, modified nature fibers such as B. regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as B. polyamide, polyacrylonitrile, polyurethane and polyester fibers be used.

Suitable compounds of the formula I which can be used as component A are Azur A, Azur B, Azur C, 1,9-dimethylmethylene blue, toluidine blue, new methylene blue N, Thionine, methylene green and methylene green zinc chloride double salt.

The compounds of the formula I are preferably in the agents according to the invention in an amount of 0.03 to 65, in particular 1 to 40 mmol, based on 100 g of the total Colorant included.

The oxidation dye precursors or condensates mentioned as components B and C ons dye precursors are well known in the hair dye field. Condensate Onsfarbstoffvorprodukte are for example in the German patent application 1 97 17 224.5.

Preferred developer components according to the invention are p-phenylenediamine, p-Toluy lendiamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2-hydroxyethyl) -p-phen ylenediamine, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyra zolon-5, 4-amino-3-methylphenol, 2-methylamino-4-aminophenol, 2,4,5,6-tetra aminopyrimidine, 2-hydroxy-4,5,6-triaminopynmidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopynmidine, 2-dimethylamino-4,5,6-triaminopynmidine, 2-hydroxyethylaminomethyl-4-aminophenol and 4,4'-diaminodiphenylamine.

Coupler components preferred according to the invention are 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, Resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5,2,4-di chloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 4-chlororesorcinol, 2-chloro-6-meth yl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dihydroxy-3,4-di aminopyridine, 3-amino-2-methylamino-6-methoxypyndine, 4-amino-2-hydroxytoluene, 2,6-bis- (2-hy  hydroxyethylamino) toluene, 2,4-diaminophenoxyethanol and 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 a molar Ver ratio of 1: 0.5 to 1: 2 may be contained in the colorant. The total amount of Oxidation dye precursors are usually at most 20 wt .-%, based on the total funds.

It is not necessary for the oxidation dye precursors to be uniform in each case Represent connections. Rather, in the hair colorants according to the invention, due to the manufacturing process for the individual dyes, in subordinate Amounts of other components may be included, provided that these do not affect the coloring result adversely affect or for other reasons, e.g. B. toxicological, excluded Need to become.

In all colorants, several different coloring substances can also be formulated with For mel I and various compounds from components B and C together to Come into play. This embodiment also includes the use of such substances zen, the reaction products of the individual components, namely the phenothiazines and the Represent oxidation dye precursors or the condensation dye precursors.

The compounds of components B and C can each in the agents according to the invention Weil in an amount of 0.03 to 65, especially 1 to 40 mmol, based on 100 g of entire colorant.

The colorants according to the invention result in a wide range of color shades in the range from yellow to yellow brown, orange, brown orange, medium brown, dark brown, violet, dark violet up to blue-black and black; the authenticity properties are excellent, the Sensibi potential for very little.

In a preferred embodiment, the colorants according to the invention contain white teren modification of the color shades in addition to the compounds contained according to the invention  additionally conventional direct dyes, e.g. B. from the group of nitrophenylenediamines, Nitroaminophenols, anthraquinones, indophenols or the one known as Arianore Connections such as B. under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 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, Basic Brown 17, Picramic Acid and 2-amino-6-chloro-4-nitrophenol known compounds and 4-amino-2-nitrodiphenyla min-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis (2'-hydroxyethylami no) -2-nitrobenzene hydrochloride and 1-methyl-3-nitro-4- (2'-hydroxyethyl) aminobenzene. The Agents according to the invention according to this embodiment contain the direct agents Dyes preferably in an amount of 0.01 to 20 wt .-%, based on the total Colorants.

Furthermore, the colorants according to the invention can also occur naturally Dyes such as henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and contain alkanna root.

With regard to other conventional dye components, it is expressly mentioned "Dermatology", edited by Ch. Culnan, H. Maibach, published by Marcel Dekker Inc., New York, Basel, 1986, vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, pages 248-250 (Direct dyes), and Chap. 8, pages 264-267 (oxidation dyes), and the "European inventory of cosmetic raw materials", 1996, published by the European Commission, available in diskette form from the Federal Association of German Industrial and Trading company for pharmaceuticals, health products and personal care products, Mannheim, Referred.

It is not necessary that the optional components, namely the oxidati ons dye precursors or the direct dyes, each uniform connection represent gene. Rather, in the colorants according to the invention, due to the Manufacturing process for the individual dyes, in minor quantities even more Components may be included as far as they do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.  

The colorants according to the invention already result at a physiologically compatible temperature temperatures of less than 45 ° C intense coloring. They are therefore particularly suitable for dyeing of human hair. The dye can be used on human hair agents are usually incorporated into a water-containing cosmetic carrier. Ge Suitable water-containing cosmetic carriers are e.g. B. creams, emulsions, gels or surfactant-containing foaming solutions such as B. shampoos or other preparations for the application on the keratin fibers are suitable. If necessary, it is too possible to incorporate the colorants in anhydrous carriers.

Furthermore, the colorants according to the invention can all be known in such preparations contain active ingredients, additives and auxiliary substances. In many cases, the colorants contain at least Mostly a surfactant, in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases it has turned out to be Proven partially, the surfactants from anionic, zwitterionic or nonionic surfactants to select.

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 carb oxylate, 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 as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH _2- CH ₂ O) _x -CH _2- COOH, in which R is a linear alkyl group having 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,
• - Monosulfonic succinate 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 alkanesulfonates with 12 to 18 carbon atoms,
• linear alpha-olefin sulfonates with 12 to 18 carbon atoms,  
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
• - esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules 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 in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and Palmitic acid.

Zwitterionic surfactants are surface-active compounds that carry 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 be taine such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2 -Alkyl-3-carboxymethyl-3-hy droxyethyl-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 CTFA 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 in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C atoms in the alkyl group. Be particularly preferred ampholytic surfactants are the N-cocoalkylaminopropionate, the Ko kosacylaminoethylaminopropionat and the C _12-18 acyl sarcosine.

Nonionic surfactants contain z as a hydrophilic group. 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 linear fatty alcohols with 8 to 22 carbon atoms, fatty acids with 12 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group,
• C _12-22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,
• C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,
• - Adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil oil,
• - Addition products of ethylene oxide with sorbitan fatty acid esters
• - Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cationi which can be used in the hair treatment compositions according to the invention In particular, surfactants are quaternary ammonium compounds. Ammo are preferred nium halides such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl monium chlorides and tri alkylmethylammonium chlorides, e.g. B. Cetyltrimethylammonium chloride, stearylrimethylammo nium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldime thylbenzylammonium chloride and tricetylmethylammonium chloride. Further according to the invention usable cationic surfactants are the quaternized protein hydrolyzates.

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino modified Silicon, which is also called Amodimethicone), SM-2059 (Manufacturer: General Elec tric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Gold schmidt; diquaternary polydimethylsiloxanes, Quaternium-80).  

Alkylamidoamines, especially fatty acid amidoamines such as that under the name Tego Amear®S 18 available stearylamidopropyldimethylamine, stand out in addition to a good one conditioning effect especially due to its good biodegradability.

Quaternary ester compounds are also very readily biodegradable "Esterquats", such as the methylhydroxyalkyl sold under the trademark Stepantex® dialkoyloxyalkylammonium methosulfates.

This is an example of a quaternary sugar derivative that can be used as a cationic surfactant Commercial product Glucquat®100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride ".

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

In the case of surfactants, the addition products of ethylene and / or propylene oxide with fatty alcohol hole or derivatives of these investment products, both products with a normal "homolog distribution as well as those with a narrow homolog distribution be used. Under "normal" homolog distribution, mixtures of Homologues understood that one under the implementation of fatty alcohol and alkylene oxide Use of alkali metals, alkali metal hydroxides or alkali metal alcoholates as kata lysators receives. On the other hand, narrow homolog distributions are obtained if at for example hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, -hy hydroxides or alcoholates can be used as catalysts. The use of pro Products with a narrow homolog distribution can be preferred.

Other active ingredients, auxiliaries and additives are, for example

• - Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, Po lyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,
• - cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary Groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammoni umchloride copolymers, dimethylaminoethyl methacrylate vin quaternized with diethyl sulfate  ylpyrrolidone copolymers, vinylpyrrolidone imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• - zwitterionic and amphoteric polymers such as acrylamidopropyl trimethyl ammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butyl aminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• - Anionic polymers such as polyacrylic acids, cross-linked polyacrylic acids, Vi nyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinylace tat / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride co polymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers,
• Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, Karaya gum, locust bean gum, linseed gums, dextrans, cellulose deriva te, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch-Frak ions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,
• Structurants such as glucose and maleic acid,
• hair-conditioning compounds such as phospholipids, for example soy lecithin, Egg lecithin and cephaline, as well as silicone oils,
• - Protein hydrolyzates, especially elastin, collagen, keratin, milk protein, soy protein and Wheat protein hydrolyzates, their condensation products with fatty acids and qua ternized protein hydrolyzates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• - Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and Diethylene glycol,
• - anti-dandruff agents such as Piroctone Olamine and Zink Omadine,
• - other substances for adjusting 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 enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as walrus, 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 glycerol, propylene glycol monoethyl ether, carbonates, Hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phos phate, imidazole, tannins, pyrrole,
• Opacifiers such as latex,
• - pearlescent agents such as ethylene glycol mono- and distearate,
• - blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air and
• - antioxidants.

The constituents of the water-containing carrier are used to produce the inventive Colorants used in amounts customary for this purpose; e.g. B. are emulsifiers in Concentrations from 0.5 to 30 wt .-% and thickeners in concentrations from 0.1 to 25 wt .-% of the total colorant used.

For the coloring result, it may be advantageous to add ammonium or metal salts to the coloring agents. Suitable metal salts are e.g. B. formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, Strontium or barium, or of aluminum manganese, iron, cobalt, copper or zinc, with sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, ZnCl ₂ double salts, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate being preferred . These salts are preferably in an amount of 0.03 to 65, in particular from 1 to 40 mmol, based on 100 g of the total colorant.

The pH value of the ready-to-use coloring preparations is usually between 2 and 11, preferably between 5 and 9.

For dyeing keratin fibers, especially for dyeing human hair ren, the compounds of formula I used according to the invention are usually in Presence of an aqueous cosmetic carrier in an amount of 0.03 to 65, ins particularly 1 to 40 mmol, based in each case on 100 g of the total colorant, on the Hair applied, left there for about 30 minutes and then rinsed out or with a commercial hair shampoo washed out. Other optional colorants can, if they are used, be applied in the same amount as that Compounds of the formula I used according to the invention  

The compounds of formula I and other colorants can either be used simultaneously can be applied to the hair or one after the other, whereby it is irrelevant which of the components is applied first. The optional ammonium or Metal salts can be added to the first or the second component. It can take up to 30 minutes between applying the first and second components Time interval. Pretreatment of the fibers with the saline solution is also possible.

The compounds with the formula I and further colorants of the agents according to the invention can either be stored separately or together, either in a liquid up pasty preparation (aqueous or anhydrous) or as a dry powder. Will the comm components stored together in a liquid preparation, this should be for the avoidance tion of a reaction of the components to be largely anhydrous. At the separate location The reactive components only become available with one another immediately before use intimately mixed. In dry storage, a de is usually used before use Finished amount of warm (50 to 80 ° C) water added and a homogeneous mixture manufactured.

Examples Preparation of a coloring solution

It became an aqueous solution of 10 mmoles of a coloring component, 10 mmoles of sodium acetate and a drop of a 20% fatty alkyl ether sulfate solution in 100 ml of water. The The solution was briefly heated to about 80 ° C. and, after cooling, the undissolved was filtered; of the The pH was then adjusted to 6.

A streak of 90% was not grayed in this dyeing solution at 30 ° C. for 30 minutes, not pretreated human hair introduced. The colored streak then turned 30 Rinsed with lukewarm water, dried in a warm (30-40 ° C) air stream and turned on combed out. The colorations were then assessed visually in daylight.

The respective color shades and color depths are shown in the following table ben.

The color depth was rated on the following scale:
-: no or very pale color (+): weak intensity
+: medium intensity
+ (+): medium to strong intensity
++: strong intensity
++ (+): strong to very strong intensity
+++: very strong intensity.

Table 1

Claims (9)

1. Use of alkylated phenothiazines of the following formula I
wherein R ¹ and R ^{2 are} each independently an NH ₂ , NHR ⁸ or NR ⁸ R ⁹ group in which R ⁸ and R ^{9 represent} a (C ₁ -C ₄ ) alkyl group,
R ³ to R ^{6 are} each independently a hydrogen atom or a (C ₁ -C ₄ ) alkyl group,
R ^{7 is} a hydrogen atom, a halogen atom or a nitro group and
X represents the anion of a mineral acid or organic acid,
with the proviso that if R ¹ and R ^{2 are} both an NR ⁸ R ⁹ group, then at least one of the radicals R ³ to R ^{6 is} a (C ₁ -C ₄ ) alkyl group,
for dyeing keratin fibers. 2. Agent for dyeing keratin-containing fibers, especially human hair that contains

• (A) one or more alkylated phenothiazines having the following formula I.
  wherein R ¹ and R ^{2 are} each independently an NH ₂ , NHR ⁸ or NR ⁸ R ⁹ group in which R ⁸ and R ⁹ stand for a (C ₁ -C ₄ ) alkyl group,
  R ³ to R ^{6 are} each independently a hydrogen atom or a (C ₁ -C ₄ ) alkyl group,
  R ^{7 is} a hydrogen atom, a halogen atom or a nitro group and
  X represents the anion of a mineral acid or organic acid,
  with the proviso that if R ¹ and R ^{2 are} both an NR ⁸ R ⁹ group, then at least one of the radicals R ³ to R ^{6 is} a (C ₁ -C ₄ ) alkyl group,
• (B) oxidation dye precursors selected from the group of developer and coupler compounds, and / or
• (C) condensation dye precursors from the group of reactive carbonyl compounds and compounds with primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.

3. Composition according to claim 2, characterized in that component A is out is selected from the group consisting of Azure A, Azure B, Azure C, 1,9-dimethylmethylene blue, toluidine blue, new methylene blue N, thionine, methylene green and methylene green zinc chloride double salt. 4. Agent according to one of claims 2 or 3, characterized in that the Ver Compounds of component A in an amount of 0.03 to 65, in particular 1 up to 40 mmol, each based on 100 g of the total colorant, are contained. 5. Agent according to one of claims 2 to 4, characterized in that the verb Component B and C each in an amount of 0.03 to 65, in particular whose 1 to 40 mmol, based on 100 g of the total colorant, are contained. 6. Agent according to one of claims 2 to 5, characterized in that Oxidati onsmittel in an amount of 0.01 to 6 wt .-%, based on the application solution, be used. 7. Composition according to one of claims 2 to 6, characterized in that H ₂ O _{2 is} used as the oxidizing agent. 8. Composition according to one of claims 2 to 7, characterized in that anionic, zwitterionic and / or nonionic surfactants are used. 9. A process for dyeing keratin-containing fibers, wherein a colorant containing (A) one or more alkylated phenothiazines having the following formula I.
wherein
R ¹ and R ^{2 are} each independently an NH ₂ , NHR ⁸ or NR ⁸ R ⁹ group in which R ⁸ and R ^{9 represent} a (C ₁ -C ₄ ) alkyl group,
R ³ to R ^{6 are} each independently a hydrogen atom or a (C ₁ -C ₄ ) alkyl group,
R ^{7 is} a hydrogen atom, a halogen atom or a nitro group and
X represents the anion of a mineral acid or organic acid,
with the proviso that if R ¹ and R ^{2 are} both an NR ⁸ R ⁹ group, then at least one of the radicals R ³ to R ^{6 is} a (C ₁ -C ₄ ) alkyl group,

• (B) one or more oxidation dye precursors from the group of developer and coupler compounds, and / or
• (C) one or more condensation dye precursors from the group of the reactive carbonyl compounds and the compounds having a primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds,
  

as well as the usual cosmetic ingredients and possibly other coloring agents are applied to the keratin fibers, left on the fibers for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.