WO1999025314A1

WO1999025314A1 - Use of alkylated phenothiazines for dyeing keratinous fibres

Info

Publication number: WO1999025314A1
Application number: PCT/EP1998/007162
Authority: WO
Inventors: Bernd Meinigke; Hinrich Möller; David Rose
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1997-11-13
Filing date: 1998-11-10
Publication date: 1999-05-27
Also published as: DE19750303A1; AU1233999A

Abstract

Alkylated phenothiazines of formula (I) are used for dyeing keratinous fibres. In the formula, R?1 and R2¿ independently represent an NH¿2?, NHR?8 or NR8R9¿ group, in which R?8 and R9¿ stand for a (C¿1?-C4)-alkyl group; R?3-R6¿ independently represent a hydrogen atom or a (C¿1?-C4)-alkyl group; R?7¿ stands for a hydrogen atom, a halogen atom or a nitro group; and X is the anion of a mineral or organic acid, provided that when both R?1 and R2¿ stand for a NR8R9 group, at least one of the radicals R3-R6 be a (C¿1?-C4)-alkyl group.

Description

"Use of alkylated phenothiazines for dyeing keratin fibers"

The invention relates to the use of alkylated phenothiazines for dyeing keratin-containing fibers, in particular human hair, an agent for dyeing keratin-containing fibers which contains alkylated phenothiazines, and a method for dyeing keratin-containing fibers.

For dyeing keratin fibers, e.g. B. hair, wool or fur, generally either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with one another or with one or more coupler components, are used. Coupler and developer components are also referred to as oxidation dye precursors.

The direct dyes form the color directly on the fiber due to their own color. The color on the fiber fades over time or is washed out during washing. Compared to the oxidation dyes, the intensity of the coloring and the fastness properties are lower.

Intensive dyeings with good fastness properties can be achieved with oxidation dyes, but the development of the color generally takes place under the influence of oxidizing agents such as H ₂ O ₂ , which in some cases can damage the fibers. Furthermore, some oxidation dye precursors or certain mixtures of

Oxidation dye precursors 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 process for dyeing hair with basic dyes, in which the hair is changed in such a way that more than 75% of the cystine bonds of the peptide chain of the keratin of the hair are converted into S-sulfocysteine groups, the larger one Part of the peptide chains Molecular weight between about 1100 and about 7500. Methylene blue, for example, is used as the basic colorant. In the process described, the keratin-containing fibers first have to be pretreated in a complex manner in order to obtain a coloration. The authenticity properties of the copies obtained by this process are unsatisfactory.

The object of the present invention is to provide colorants for keratin-containing fibers, in particular human hair, which can be used as direct colorants and which are at least equivalent in quality to conventional oxidation hair colorants in terms of color depth, gray coverage and fastness properties. Another object of the present invention is to provide colorants with which a wide variety of color shades can be obtained. Staining of the skin areas should be avoided if possible. In addition, the colorants may have no or only a very low sensitization potential.

Surprisingly, it was found that the alkylated phenothiazines used according to the invention are outstandingly suitable as substantive substances for dyeing keratin-containing fibers. They result in colors with excellent brilliance and depth of color and lead to a wide range of shades. The use of oxidizing agents is not necessary, but it should not be excluded in principle.

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

(l) 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, -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 _r C ₄ ) alkyl group for dyeing keratin fibers.

The present invention therefore furthermore relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains (A) one or more alkylated phenothiazines of the following formula I.

(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 _r C ₄ ) alkyl group, R ³ to R ⁶ each are independently a hydrogen atom or a (CC 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 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.

Keratin-containing fibers are wool, furs, feathers and in particular human hair. In principle, however, the colorants according to the invention can also be used to dye other natural fibers, such as Cotton, jute, sisal, linen or silk, modified natural fibers, e.g. Regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as e.g. Polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used.

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

The compounds of the formula I are preferably present in the compositions 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.

The oxidation dye precursors or condensation dye precursors mentioned as components B and C are well known in the field of hair colorants. Condensation dye precursors are described, for example, in German patent application 197 17 224.5.

Preferred developer components according to the invention are p-phenylenediamine, p-toluylenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine , 2- (2,5-diaminophenoxy) -ethanol, 1 -pheny! -3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-methylamino-4-aminophenol, 2,4, 5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-thaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4, 5,6-triaminopyrimidine, 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-amino- phenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-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-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2, 6-dihydroxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2,6-bis (2-hydroxyethylamino) toluene, 2,4-diaminophenoxyethanol and 2-amino-4-hydroxyethylamino anisole.

Developer components and coupler components are usually used in approximately molar amounts to one another. If the molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components can preferably be present in the colorant in a molar ratio of 1: 0.5 to 1: 2. The total amount of

Oxidation dye precursors are generally at most 20% by weight, based on the total agent.

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

Several different coloring substances with the formula I and different compounds from components B and C can also be used together in all coloring agents. This embodiment also includes the use of such substances, the reaction products of the individual components, namely the phenothiazines and the oxidation dye precursors

Represent condensation dye precursors.

The compounds of components B and C can each be present 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. 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 to blue-black and black; the fastness properties are excellent, the sensitization potential is very low.

In a preferred embodiment, the colorants according to the invention contain, in addition to the compounds contained according to the invention, customary direct dyes, e.g. from the group of the nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenols or the compounds known as Arianors, such as e.g. under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yeliow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HCBIue 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 as well as 4-amino-2-nitrodiphenylamine-2 'carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1, 4-bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride and 1-methyl-3-nitro- 4- (2'-hydroxyethyl) aminobenzene. 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 colorants according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.

With regard to other conventional dye components, reference is expressly made to the “Dermatology” series, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, Chapter 7, pages 248 - 250 (direct dyes), and Chapter 8, pages 264 - 267 (oxidation dyes), as well as the "European inventory of cosmetic raw materials", 1996, published by the European Commission, available in disk form from the Federal Association of German Industrial and handicraft companies for pharmaceuticals, health products and body care products eV, Mannheim. It is not necessary for the optionally contained components, namely the oxidation dye precursors or the substantive dyes, to be uniform compounds. Rather, in the colorants according to the invention, due to the production processes for the individual dyes, further components may also be present in minor amounts, provided that these do not adversely affect the coloring result or must be excluded for other reasons, for example toxicological reasons.

The colorants according to the invention produce intensive colorations even at physiologically tolerable temperatures of below 45 ° C. They are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants can usually be incorporated into a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are e.g. Creams, emulsions, gels or also surfactant-containing foaming solutions such as Shampoos or other preparations that are suitable for use on the keratin fibers. If necessary, it is also possible to incorporate the colorants into water-free carriers.

Furthermore, the colorants according to the invention can contain all active ingredients, additives and auxiliaries known in such preparations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven 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 trium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts

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 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group,

Mono and dialkyl sulfosuccinic acid with 8 to 18 carbon atoms in the alkyl group and mono alkyl polyoxyethyl sulfosuccinate 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-37 25 030, 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.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(" '- or -SO ^ group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl -3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethyl-hydroxyethylcarboxymethylglycinate. 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-alkyltauhne, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and 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 with linear fatty alcohols with 8 to 22 carbon atoms, with 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 from 1 to 30 mol

Ethylene oxide on glycerol,

C ₈ . ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened

Castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters

Addition products of ethylene oxide with fatty acid alkanolamides. Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides are preferred,

Dialkyldimethylmonium chlorides and trialkylmethylammonium chlorides, e.g. B.

Cetyltrimethylammonium chloride, stearylrimethylammonium chloride,

Distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethyiammonium chloride. 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 Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quatemium-80).

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid®S 18, are characterized in particular by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", hydroxyalkyldialkoyloxyalkylammoniummethosulfate such as those sold under the trademark Stepantex ^® methyl.

An example of a quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat®100, according to the CTFA nomenclature a "lauryl methyl gluceth-10 hydroxypropyl dimonium chloride".

The compounds with alkyl groups used as surfactants can each be uniform substances. However, it is usually preferred in the manufacture of these substances from native vegetable or animal raw materials to go out, so that substance mixtures with different, depending on the respective raw material alkyl chain lengths 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 from the reaction of fatty alcohol and alkylene oxide 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.

Further 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, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonyl dimethyldiallyl - methyldiallylammonium chloride copolymers, dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone-

Imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyacrylic acids, for example, anionic polymers, such as anionic polymers , Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidoneΛ / inylacrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers,

Thickening agents such as agar agar, guar gum, alginates, xanthan gum, gum arabic cum, karaya gum, locust bean gum, linseed gums, dextrans, cellulose loose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol,

Structurants such as 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 quaternized 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 zinc 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 whale, 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 phosphates, imidazoles, tannins, pyrrole,

Opacifiers like 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 as well

Antioxidants.

The constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; for example Emulsifiers in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant used.

For the coloring result it can be advantageous to add ammonium or metal salts to the coloring agents. Suitable metal salts are, for example, formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates from 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, preference being given to 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 are. These salts are preferably present in an amount of 0.03 to 65, in particular 1 to 40 mmol, based on 100 g of the total colorant.

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

For dyeing the keratin-containing fibers, in particular for dyeing human hair, the compounds of the formula I used according to the invention are generally used in the presence of a water-containing cosmetic carrier in an amount of 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the entire colorant, applied to the hair, left there for about 30 minutes and then rinsed out or washed out with a commercially available hair shampoo. Further optional colorants, if used, can be applied in the same amount as the compounds of formula I used according to the invention.

The compounds with the formula I and further colorants can either be applied to the hair simultaneously or else in succession, it being irrelevant which of the components is applied first. The optionally contained ammonium or metal salts can be added to the first or the second component. Between the application of the first and the second Components can be up to 30 minutes apart. 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 to pasty preparation (aqueous or anhydrous) or as a dry powder. If the components are stored together in a liquid preparation, this should be largely anhydrous to reduce a reaction of the components. When stored separately, the reactive components are only intimately mixed with one another immediately before use. In dry storage, a defined amount of warm (50 to 80 ° C) water is usually added before use and a homogeneous mixture is produced.

Examples

Preparation of a coloring solution

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

A strand of 90% gray, untreated human hair was placed in this coloring solution at 30 ° C. for 30 minutes. The colored streak was then rinsed for 30 seconds with lukewarm water, dried in a warm (30-40 ° C.) air stream and then combed out. The colorations were then assessed visually in daylight.

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

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

Component B shade nuance

Color depth

AzurA bright dark blue +++

AzurB bright blue +++

1, 9-dimethylmethylene blue dark blue +++

Thionine acetate dark purple blue +++

New methylene blue N green blue + (+)

Toluidine blue O bright dark blue +++

Methylene green dark green blue +++

Methylene green ZnCI ₂ double salt turquoise +++

Claims

claims

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 ** - C ₄ ) alkyl group, R ³ to R ^{6 are} each independently a hydrogen atom or a (C. * - C ₄ ) alkyl group,

Agent for dyeing keratin fibers, especially human

Hair that contains

(A) one or more alkylated phenothiazines having the following formula I.

(l) 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 _r 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 _r 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 selected from the group consisting of 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 .

4. Composition according to one of claims 2 or 3, characterized in that the compounds of component A are contained in an amount of 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the total colorant.

5. Composition according to one of claims 2 to 4, characterized in that the compounds of components B and C are each present in an amount of 0.03 to 65, in particular 1 to 40 mmol, based on 100 g of the total colorant.

6. Agent according to one of claims 2 to 5, characterized in that oxidizing agents are used in an amount of 0.01 to 6 wt .-%, based on the application solution.

7. Agent 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, which contains a colorant

(A) one or more alkylated phenothiazines having the following formula I.

(l)

wherein

R ¹ and R ^{2 are} each independently an NH ₂ -, NHR ⁸ - or NR ⁸ R ⁹ -

Are groups in which R ⁸ and R ^{9 represent} a (C * -C ₄ ) -alkyl group,

R ³ to R ⁶ each independently represent a hydrogen atom or a

Are (C * -C ₄ ) alkyl groups,

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 (C1-C4) alkyl group is

(B) one or more oxidation dye precursors from the group of

Developer and coupler connections, and / or

(C) one or more condensation dye precursors from the group of reactive carbonyl compounds and compounds with primary ones 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 usual cosmetic ingredients and possibly other colorants 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.