WO1999020233A1

WO1999020233A1 - Use of phenazinium salts for dyeing fibres containing keratin

Info

Publication number: WO1999020233A1
Application number: PCT/EP1998/006399
Authority: WO
Inventors: Hinrich Möller; Bernd Meinigke
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1997-10-18
Filing date: 1998-10-09
Publication date: 1999-04-29
Also published as: DE19746137A1; AU1226899A

Abstract

The invention relates to the use of phenazinium salts for dyeing fibres containing keratin, especially human hair, said phenazinium salts being of formula (I), wherein R?1 and R2¿ each represent, independently of each other, an NH¿2?-, NHR?8- or NR8R9¿- group, R?8 and R9¿ representing a C¿1?-C4-alkyl- or aryl group; R?3 and R6¿ each represent, independently of each other, a hydrogen atom, a C¿1?-C4-alkyl group, an NH2-, NHR?10- or NR10R11¿- group, R?10 and R11¿ representing a C¿1?-C4-alkyl- or aryl group; R?4 and R5¿ each represent, independently of each other, a hydrogen atom or a C¿1?-C4-alkyl group, R?7¿ represents a C¿1?-C4 alkyl or aryl group and X represents the anion of a mineral or organic acid, on the condition that neutral red and neutral violet are excluded.

Description

"Use of phenazinium salts for dyeing keratin fibers"

The invention relates to the use of phenazinium salts for dyeing keratin-containing fibers, in particular human hair, an agent for dyeing keratin-containing fibers that contains phenazinium salts, 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. From the international patent application WO 95/15144, cationic colorants for fibers containing keratin, in particular human hair, are known. Neutral red and neutral violet are mentioned as examples. These colorants are phenazinium salts which have no substituents on the aromatic nitrogen and in the 9 and 10 positions. The coloring properties of the compounds mentioned are not always satisfactory.

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 has been found that certain phenazinium salts are outstandingly suitable for dyeing fibers containing keratin. The compounds can be applied in organic, aqueous or organic-aqueous preparations. 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 should not be excluded in principle. The phenazinium salts used according to the invention can be combined with other substantive colorants and oxidation colorants.

The present invention accordingly relates to the use of phenazinium salts of the following formula I.

wherein

R ¹ and R ² each independently of one another an NH ₂ -, an NHR ⁸ - or an NR ⁸ R ⁹ -

Are a group, where R ⁸ and R ^{9 are} a C 1 -C 4 alkyl or aryl group,

R ³ and R ⁶ each independently represent a hydrogen atom, a C ^ C ,, -

Is an alkyl group, an NH ₂ , an NHR ¹⁰ or an NR ¹⁰ R ¹¹ group, where R ¹⁰ and R ^{11 are} a CC ₄ alkyl or aryl group,

R ⁴ and R ⁵ each independently represent a hydrogen atom or a C 1 -C ⁴ alkyl

Group mean

R ^{7 represents} a C ^ C ^ alkyl or aryl group and

X stands for the anion of a mineral or organic acid, with the proviso that neutral red and neutral violet are excluded, for dyeing keratin fibers, in particular human hair.

Another object of the present invention is an agent for dyeing keratin-containing fibers, in particular human hair, which contains phenazinium salts with the following formula I.

wherein

R ¹ and R ² each independently represent an NH ₂ , an NHR ⁸ or an NR ⁸ R ⁹ group, where R ⁸ and R ^{9 represent} a C ₁ -C ₄ alkyl or aryl group, R ³ and R ^{6 are} each independently a hydrogen atom, a C ^ C ^

Is an alkyl group, an NH ₂ , an NHR ¹⁰ or an NR ¹⁰ R ¹¹ group, where R ⁰ and R ^{11 are} a C _r C ₄ alkyl or aryl group,

R ⁴ and R ⁵ each independently represent a hydrogen atom or a CrC alkyl

Group mean

R ^{7 represents} a C ₁ -C ₄ alkyl or aryl group and

X stands for the anion of a mineral or organic acid, with the proviso that neutral red and neutral violet are excluded.

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 of the formula I are in particular those in which, when R ^{3 is} hydrogen or a methyl group and R ^{4 is} hydrogen, R ⁵ and / or R ^{6 are} not hydrogen. Furthermore, compounds are preferred in which R ¹ and R ^{2 are} identical groups. Preferred anions X ^" are the salts of hydrohalic acids, in particular chloride. The compounds known under the international names methylene violet 3RAX, Brilliant Heliotrop 2R, indulin, basic violet 5, phenosafranine and safranin T are particularly preferably used.

The compounds of the formula I are preferably 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 variety of shades and the color fastness of the compounds of the formula I used according to the invention can be expanded by combining these compounds with the oxidation dye precursors which are well known in the field of hair dyes. Several different coloring substances can also be used together in all coloring agents; Likewise, several different components from the groups of compounds having a primary or secondary amino group, nitrogen-containing heterocycles, aromatic hydroxy compounds or amino acids can also be used together, as are described, for example, in German patent application 197 17 224.5.

The colorants according to the invention result in a wide range of color shades in the range from red to violet; 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 Yeliow 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 Vioiet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphenyiamine 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, it is expressly referred to with regard to the individual dye components that can be used "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag 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), as well as "European Inventory of Cosmetic Raw Materials", 1996, published by the European Commission, available in floppy form from the Federal Association of German Industrial and Commercial Enterprises for Medicinal Products, Health Care Products and Personal Care Products eV, Mannheim, referred to.

It is not necessary that the optional oxidation dye precursors or the substantive dyes each represent 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 for other reasons, e.g. toxicological, must be excluded.

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 anhydrous carriers.

Furthermore, the colorants according to the invention can contain all active substances, 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, 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 with 10 to 22 C 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,

Mono and dialkyl sulfosuccinic acid with 8 to 18 carbon atoms in the

Alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 C-

Atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 C atoms, linear alpha-olefin sulfonates with 12 to 18 C 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, 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 those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^H or -SO ₃ ^w group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl -3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also coconut acylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C ₈ . ₁₈ -alkyl or -acyl group in the molecule contain at least one free amino group and at least one -COOH or -SO ₃ H group 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. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, the

Coconut acylaminoethyl aminopropionate 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 mol of ethylene oxide and / or 0 to 5 mol

Propylene oxide to linear fatty alcohols with 8 to 22 carbon atoms, to 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 monoesters and diesters of adducts from 1 to 30 mol

Ethylene oxide on glycerin,

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

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

Castor oil,

Addition products of ethylene oxide onto 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,

Dialkyldimethylammoniumchloride and Trialkylmethylammoniumchloride, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride,

Distearyldimethylammonium chloride, lauryldimethylammonium chloride,

Lauryldimethylbenzylammonium chloride and tricetylmethylammonium 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, Quaternium-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 particularly characterized by their good biodegradability. Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as those sold under the trademark Stepantex ^® methylhydroxyalkyldialkoyloxyalkylammonium.

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 generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

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

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidoneΛ 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

Dimethyldiallylammonium chloride copolymers, quaternized with diethyl sulfate Dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, 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, anionic polymers such as polyacrylic acids, crosslinked

Polyacrylic acids, vinyl acetate / crotonic acid copolymers,

VinylpyrrolidonΛ acrylate copolymers, vinyl acetate / butyl maleate / isobomylacrylate

Copolymers, methyl vinyl ether / maleic anhydride copolymers 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 De vate, e.g. B. methyl cellulose, hydroxyalkyl cellulose and

Carboxymethyl cellulose, starch fractions and derivatives such as amylose,

Amylopectin and dextrins, clays such as e.g. B. bentonite or fully synthetic

Hydrocolloids such as Polyvinyl alcohol,

Structurants such as giucose 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 walnut, 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; e.g. emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant.

For the coloring result it can be advantageous to add ammonium or metal salts to the coloring agents. Suitable metal salts are e.g. 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, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate being preferred. 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 colorants are generally applied to the hair in the form of the water-containing, cosmetic carrier in an amount of 100 g, left there for about 30 minutes and then rinsed out or with a commercially available one Washed out hair shampoo.

The compounds used according to the invention and the oxidation dye precursors used, if appropriate, can either be applied to the hair simultaneously or else in succession, it being irrelevant which of the three components is applied first. The optionally contained ammonium or metal salts can be added to the first or the second component. There may be an interval of up to 30 minutes between the application of the first and the second component. Pretreatment of the fibers with the saline solution is also possible.

The compounds used according to the invention and any oxidation dye precursors used in 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

Production of a coloring cream

To prepare a coloring cream, 1.0 g of cetearyl alcohol, 1.0 g of coconut alcohol, 1.1 g of sodium laureth-5-carboxylate, 0.05 g of propyl paraben and 0.15 g of methyl paraben were melted at 80 ° C. and at 70 g at 80 ° C hot water mixed and emulsified with vigorous stirring. The emulsion was then allowed to cool with gentle stirring, x g of colorant was dissolved in 10 g of water at 50 ° C. with the addition of 3.0 g of ammonium sulfate and ammonia. The dye solution was added to the emulsion, adjusted to pH 9 with ammonia and made up to 100 g with water. The cream was then cooled to room temperature with stirring.

The resulting coloring cream was applied to a strand of blonde hair 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.

In Examples 1 to 3, colorants were examined as individual substances and in Examples 4 to 8 mixtures of several colorants. The respective color shades and color depths are shown in Table 1 below.

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

claims

1. Use of phenazinium salts of the following formula

wherein R ¹ and R ² each independently represent an NH ₂ , an NHR ⁸ or an NR ⁸ R ⁹ group, where R ⁸ and R ^{9 represent} a C 1 -C 4 alkyl or aryl group,

R ³ and R ⁶ each independently represent a hydrogen atom, a C ₁ -C ₄ alkyl group, an NH ₂ -, an NHR ¹⁰ - or an NR ⁰ R ¹¹ group, where R ¹⁰ and R ^{11 are} a C ₁ - C ₄ alkyl or aryl group,

R ⁴ and R ⁵ each independently represent a hydrogen atom or a C _r C ₄ alkyl group, R ^{7 represents} a C 1 -C ₄ alkyl or aryl group and X represents the anion of a mineral or organic acid, with the proviso that neutral red and neutral violet are excluded, for dyeing keratin fibers, especially human hair.

Agent for dyeing keratin-containing fibers, in particular human hair, which, as a coloring component, phenazinium salts having the following formula I

wherein R ¹ and R ² each independently represent an NH ₂ , an NHR ⁸ or an NR ⁸ R ⁹ group, where R ⁸ and R ^{9 represent} a CC ₄ alkyl or aryl group,

R ³ and R ⁶ each independently represent a hydrogen atom, a CrC-alkyl group, an NH ₂ -, an NHR ¹⁰ - or an NR ¹⁰ R ¹¹ group, where R ¹⁰ and R ^{1 are} a C ¹ -C ₄ -alkyl - or aryl group,

R ⁴ and R ⁵ each independently represent a hydrogen atom or a C _r C ₄ alkyl group, R ^{7 represents} a C _r C ₄ alkyl or aryl group and X represents the anion of a mineral or organic acid with which Provided that neutral red and neutral violet are excluded.

3. Composition according to claim 2, characterized in that when in formula R ^{3 is} hydrogen or a methyl group and R ⁴ and R ^{7 are} hydrogen, R ⁵ and / or R ^{6 are} not hydrogen.

4. Composition according to claim 3, characterized in that the compounds having the formula I are selected from methylene violet 3 RAX, brilliant heliotrope 2R, indulin, basic violet 5, phenosafranine, safranine T.

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

6. Composition according to one of claims 2 to 5, characterized in that anionic, zwitterionic and / or nonionic surfactants are used.

7. A process for dyeing keratin-containing fibers, wherein a colorant containing phenazinium salts of the following formula I

R ³ and R ⁶ each independently represent a hydrogen atom, a CC ^ alkyl group, an NH ₂ -, an NHR ¹⁰ - or an NR ¹⁰ R ¹¹ group, where R ¹⁰ and R ^{11 represent} a CrC-alkyl or aryl group ,

R ⁴ and R ⁵ each independently represent a hydrogen atom or a CrC ^ alkyl group, R ^{7 represents} a CC ₄ alkyl or aryl group and X represents the anion of a mineral or organic acid, with the proviso that neutral red and Neutralvioiett are excluded, as well as usual cosmetic ingredients applied to the keratin fibers, left on the fiber for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.