DE10118271A1 - Hair-dyeing compositions contain new and known diazo-thiazole derivatives as direct dyes, optionally in combination with oxidation dyes - Google Patents

Abstract

An agent for dyeing or tinting keratin fibers (especially human hair) contains a disazo-thiazole derivative (I) in a cosmetically-acceptable carrier. An agent for dyeing or tinting keratin fibers (especially human hair) contains a disazo-thiazole derivative of formula (I) or a salt in a cosmetically-acceptable carrier. A = H, halogen, NO2 or 1-4C alkyl; B' = N or CH; X = 4-(NRR')-phenyl or 4-(NRR')naphthyl (both further ring substituted by C'); C' = halogen, 1-4C alkyl, 3-8C cycloalkyl, 1-4C alkoxy or -COOM; M = H or a suitable cation; and R, R' = H, 1-4C alkyl, allyl, 2-5C polyhydroxyalkyl, 3-8C cycloalkyl,1-4C amino- or hydroxy-alkyl, 1-4C alkoxy-1-4C alkyl, 1-4C alkoxy-1-4C hydroxyalkyl or 1-4C trialkylammonium-1-4C alkyl Also included is an Independent claim for 4 new compounds (I) i.e. 3-methoxy-1-((4-(5-nitro-(1,3-thiazol-2-yl)diazenyl)phenyl)(2-trimethy lammonium)ethyl)amino) propan-2-ol iodide, 2-((4-(5-nitro-(1,3-thiazol-2-yl)diazenyl)phenyl)(2-trimethylammonium) ethyl)amino) propan-2-ol iodide, 3-methoxy-1-((4-(1,3-thiazol-2-yldiazenyl)phenyl) (2-trimethylammonium)ethyl)amino) propan-2-ol iodide and 4-(1,3,4-thiadiazol2-yldiazenyl)naphthylamine.

Description

The invention relates to agents for dyeing and tinting keratin fibers with special ones Diazothiazole derivatives as direct dyes, their use and new Dyes.

Preparations for tinting and dyeing hair are an important type of cosmetic Means. They can serve the natural hair color according to the wishes of the to slightly or more intensely nuance the corresponding person, a completely different hair color too or mask unwanted hues such as grays. usual Hair dyes are, depending on the desired color or durability of the dyeing, either on the basis of oxidation dyes or on the basis of substantive Formulated dyes. Often, combinations of oxidation dyes and direct dyes used to achieve special nuances.

Good dyes are characterized by high color strength. Furthermore, good welding, Heat, perming, washing and light fastness desired. Furthermore, they should be in be toxicologically and dermatologically harmless. It's also an advantage when the substances have high solubility in various base formulations.

Dyes based on oxidation dyes lead to brilliant and lasting Colors. However, they require the use of strong oxidants such as Hydrogen peroxide solutions. This can damage the hair to be dyed. this Damage must then be counteracted with appropriate care products. In addition, contacts of the skin with these stains can be very sensitive Lead to adverse reactions.  

Colorants based on direct dyes do without oxidizing agents and can be formulated at pH values around the neutral point. Among the direct-acting dyes play an important role nitrobenzene derivatives. In particular, the nitroanilines and their derivatives are characterized by intense colorations with good light fastness. A major disadvantage of the known nitroaniline dyes However, the unsatisfactory wash fastness, d. H. that the stains after repeated Washing the hair to lose intensity.

There is therefore a constant need for new substantive dyes that by improved absorption on the hair and / or by staining with characterized improved wash fastness.

In addition, substantive dyes are also used for shading Oxidation hair colors used. Therefore, direct dyes should be a good Compatibility with oxidation dye precursors and with the in Oxidation hair dyes have conventional components. In particular, a high Stability to reducing and oxidizing agents is necessary for one direct dye, if this is to be used in Oxidationsfärbemitteln.

To develop fashionable tints, it is necessary to have the color palette in each one Cover color range sufficiently. In many areas this was due to variation various dyes, for. B. by the use of 2-nitro-p-phenylenediamine derivatives in Red area reached; however, there is still a certain gap in the blue area.

It has now surprisingly been found that specially substituted Diazothiazole derivatives the requirements placed on direct dyes in high Measures meet.

A first subject of the present invention are therefore agents for dyeing and tinting keratinic fibers, in particular human hair, containing in a cosmetically acceptable carrier as substantive dye at least one diazothiazole derivative of the formula (I) or its corresponding physiologically acceptable salts,

in which
A represents hydrogen, a halogen atom, a nitro group or a C ₁ -C ₄ -alkyl group,
B represents a nitrogen atom or a = CH group,
X represents a group of the formula (a) or (b) in which
C is a halogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₈ -cycloalkyl group, a C ₁ -C ₄ -alkoxy group or a -COOM group, in which M is hydrogen or a physiologically tolerated cation, stands,
R and R 'independently of one another represent hydrogen, a C ₁ -C ₄ -alkyl group, an allyl group, a C ₂ -C ₅ -polyhydroxyalkyl group, a C ₃ -C ₈ -cycloalkyl group, a C ₁ -C ₄ -aminoalkyl group, a C ₁ C ₄ -C ₄ hydroxyalkyl group, C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy C ₁ -C ₄ hydroxyalkyl group or C ₁ -C ₄ trialkylammonium C; ₁ -C ₄ alkyl group.

Examples of the C ₁ -C ₄ -alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl groups. Examples of a cycloalkyl group are cyclopentyl and cyclohexyl. An inventively preferred C ₁ - to C ₄ alkoxy group, for example, a methoxy or ethoxy group, more preferably is a methoxy group. Examples of a halogen atom are according to the invention an F, a Cl or a Br atom, a Cl atom is particularly preferred. Preferred hydroxyalkyl groups according to the invention are hydroxyethyl and hydroxypropyl groups and particularly preferably hydroxyethyl groups. Examples of C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl groups which are preferred according to the invention are methoxy and ethoxyethyl and -propyl groups, but especially methoxypropyl is particularly preferred. Illustrative of the invention, preferred C ₁ - C ₄ alkoxy-C ₁ -C ₄ hydroxyalkyl groups, and Methoxyhydroxyethyl- Methoxyhydroxypropyl to give 3-methoxy-2-hydroxypropyl is particularly preferred. Preferred C ₁ -C ₄ -trialkylammonium C ₁ -C ₄ -alkyl groups according to the invention are trialkylammoniumethyl and -propyl groups, the trimethylammoniumethyl group being particularly preferred. Examples of physiologically acceptable cations are the alkali metal cations sodium, potassium and lithium and the ammonium ion. Particularly preferred is the sodium cation and the ammonium ion.

Preference according to the invention is given to compounds of the formula (I) in which A is hydrogen or a nitro group.

Furthermore, compounds of the formula (I) are preferred in which B is a = CH group stands.

Furthermore, preference is given to those compounds of the formula (I) in which C represents Hydrogen stands.

Particularly preferred compounds of formula (I) are 2- {ethyl [4- (1,3-thiazole-2- yldiazenyl) phenyl] amino} ethan-1-ol, 4- (1,3-thiazol-2-yldiazenyl) naphthylamine, diethyl {4- [(5-nitro (1,3-thiazol-2-yl)) diazenyl] phenyl} amine, 4 - [(5-nitro (1,3-thiazol-2-yl)) diazenyl] naphthylamine, 2- (ethyl {4 - [(5-nitro (1,3-thiazol-2-yl) diazenyl] phenyl} amino) ethane-1-ol, 3 Methoxy-1 - ({4 - [(5-nitro (1,3-thiazol-2-yl)) diazenyl] phenyl} [2- (trimethylammonium) ethyl] amino) propan-2-ol iodide, 2 - ({4 - [(5-nitro (1,3-thiazol-2-yl)) diazenyl] phenyl} [2- (trimethyl ammonium) ethyl] amino) ethane-1-ol-iodide, 3-methoxy-1 - [[4- (1,3-thiazol-2-yldiazenyl)] phe nyl] [2- (trimethylammonium) ethyl) amino} propan-2-ol iodide, 5- (diethylamino) -2- (1,3-) thiazol-2-yldiazenyl) benzoic acid or 4- (1,3,4-thiadiazol-2-yldiazenyl) naphthylamine. The utility of the compounds of formula (I) in dyeing and tinting agents of keratinic fibers is in principle subject to no restrictions.  

According to a first preferred embodiment of the invention are those Means that should only cause a temporary coloration of the fiber. Such means are often referred to as toning agents. This embodiment includes, for example also such hair treatment products, with which the hair is not only temporarily colored, but also to be styled to a particular hairstyle. In this case one speaks of tinting fixatives.

Since the coloring of the keratinic fibers by such means usually without the With the aid of oxidizing components, in particular hydrogen peroxide, takes place, the agents according to the invention according to this embodiment are preferably free of Oxidation dye precursors.

Although the compounds according to formula (I) are also used as sole dye components can be used, the means according to this embodiment preferably contain at least one further dye of the direct draw type.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, Azo dyes, anthraquinones or indophenols. Preferred substantive dyes are under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 9 known compounds as well as 1,4-diaminobenzene, 2- Amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4 (β-) hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'- Hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro 2-nitrobenzene, 4-amino-3-nitrophenol, 2- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2- nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4- naphthoquinone, hydroxyethyl-2-nitro-toluidine, picramic acid and its salts, 2-amino-6- chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1 hydroxy-4-nitrobenzene. The agents according to the invention according to this embodiment the other direct dyes preferably contain in an amount of 0.01 to 20 wt .-%, based on the total colorant.  

Furthermore, the preparations according to the invention can also occur in nature Dyes contain, for example, in henna red, henna neutral, henna black, Chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and Alkana root are included.

In the case of oxidation colorants without the oxidizing agent preparation, the agents according to the invention, the compound of formula (I) usually in amounts of 0.05 to 5.0 wt .-%, based on the colorant. Amounts of 0.1 to 3 wt .-% are preferred.

According to a second preferred embodiment, the claimed Remedies for hair dye for the permanent coloring of hair. These funds included at least one oxidation dye precursor of the developer type. These, as a rule colorless compounds react under the action of oxidants or Atmospheric oxygen, optionally with the aid of special enzymes or metal ions as Catalyst, with the formation of the desired dyes. In particular to However, training natural hair colors are usually combinations of several developer components used. Furthermore, in addition usually so-called couplers used under the influence of oxidizing agents with the Developer components react, resulting in new colors or a nuance of color leads. According to the invention, both one or more coupler components in Combination with one or more developer components are used.

Developer components preferred according to the invention are p-phenylenediamine, p- Toluenediamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) -2,5-dia minobenzene, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenoxy) - ethanol, 1-phenyl-3-carboxamido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2,4,5,6- Tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6- triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6- triaminopyrimidine, 2-hydroxymethylamino-4-aminophenol, bis (4-aminophenyl) amine, 4- Amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 4-amino-2 - ((diethylamino) -methyl) -phenol, bis (2-hydroxy-5-aminophenyl) -methane, N, N'- Bis (4'-aminophenyl) -1,4-diazacycloheptane, 1,3-bis (N (2-hydroxyethyl) -N (4-aminophenyl amino)) - 2-propanol, 4-amino-2- (2-hydroxyethoxy) phenol, 1,10-bis (2,5-diaminophenyl) -  1,4,7,10-tetraoxadecane and 4,5-diaminopyrazole derivatives according to EP 0 740 931 and WO 94/08970, respectively such as B. 4,5-diamino-1- (2'-hydroxyethyl) pyrazole.

Particularly preferred developer components according to the invention are p-phenylenediamine, p- Toluenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 4-amino-3-ol methylphenol, 2-aminomethyl-4-aminophenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine.

According to preferred coupler components are

• 3-aminophenol and its derivatives such as 5-amino-2-methylphenol, 5- (3 Hydroxypropylamino) -2-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 3-amino 6-methoxy-2-methylaminophenol, 2,6-dimethyl-3-aminophenol, 3-trifluoro acetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4 methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethyl amino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) benzene, 3- (ethylamino) -4-methylphenol and 2,4-dichloro-3-aminophenol,
• 2-aminophenol and its derivatives,
• 1,3-diaminobenzene and its derivatives such as 2,4- Diaminophenoxyethanol, 1,3-bis- (2,4-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) propane, 2,6-bis (2-bis) hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis- (2'- hydroxyethyl) aminobenzene,
• - 1,2-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as resorcinol, Resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-Amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6- Dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-  Dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7- Dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• - Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-amino benzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Methylene dioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylene dioxybenzene.

Coupler components preferred according to the invention are furthermore 3-dimethylaminophenol, 2,4-dihydroxyaniline, 8-amino-6-methoxy-quinoline, 2-amino-5-naphthol-1,7-disulfonic acid, 3-Amino-1-phenyl-5-pyrazolone, 3,5-diaminobenzamide, 3-methylsulfonylamino-2- methylaniline, 5,6-dihydroxybenzimidazole, 2,2'-dihydroxybenzylamine, 3,5,3 ', 5'-tetraamino 2,2'-dimethoxy-diphenyl, 3,5-diamino-p-chlorobenzotrifluoride, 4-methyl-3-aminophenol, 2,4-diamino-3-chlorophenol, 1-amino-3-di- (2-hydroxyethylamino) -4-ethoxybenzene, 2,4- Dimethylresorcinol, bis (2,4-diaminophenoxy) -methane, 2,6-bis (hydroxyethyl) -pyridine, 4- Hydroxy-3-methoxybenzyl alcohol, 8-hydroxyquinoline, 4-hydroxy-3-methoxybenzylamine, 4-ethylresorcinol, 2-methylthio-5-aminophenol, 5 [(3-hydroxypropyl) amino] -2-methyl phenol, 2,6-dimethoxy-3-aminophenol and 2,6-diamino-3-methylthiotoluene.

Particularly preferred coupler components according to the invention are 1-napthithol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3- hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2- Methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4- dimethylpyridine.

According to the invention, those developer and coupler components which are suitable for the Forming the dyeing no oxidizing agents except atmospheric oxygen, preferably his.  

The hair colorants of the invention contain both the developer components as also the coupler components preferably in an amount of 0.005 to 20 wt .-%, respectively based on the colorant without the oxidizing agent preparation. It will be Developer components and coupler components generally in about molar Quantities used to each other. If the molar use as appropriate has proven, so is a certain excess of individual oxidation dye precursors not disadvantageous, so that developer components and coupler components in a molar Ratio of 1: 0.5 to 1: 2 may be included.

The agents of this embodiment of the invention may except the compounds according to formula (I), the developer and optionally coupler components about to Nuancierung still further substantive dyes included. It was up at this point the above directed.

Furthermore, in the colorants according to the invention precursors of natural dyes, in particular indoles and indolines, and their physiologically acceptable salts his. Preferred examples are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N- Ethyl 5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6- Dihydroxyindole-2-carboxylic acid, 6-hydroxyindole-6-aminoindole and 4-aminoindole. Also preferred are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl 5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6- Dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

It is not necessary that the oxidation dye precursors, the direct Dyes or the precursors of natural dyes each have uniform compounds represent. Rather, in the hair colorants according to the invention, due to the Production process for the individual dyes, in minor amounts more Components are included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. As toxicological, must be excluded.

With regard to the hair dyeing and tinting compositions according to the invention Dyes is still expressly based on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250, direct dyes) and Chapter 8, pages 264-267;  Oxidation dye precursors), published as volume 7 of the series "Dermatology" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials", published by the European Community, available in disk form from the Bundesverband Deutscher Industrial and commercial enterprise for pharmaceuticals, health products and personal care products e.V., Mannheim.

Furthermore, it is possible to carry out the oxidation by means of enzymes. there The enzymes (class 1: oxidoreductases) can be selected from suitable electrons Developer components (reducing agent) transferred to atmospheric oxygen. Preferred would be Oxidases such as tyrosinase and laccase but also glucose oxidase, uricase or Pyruvate. Furthermore, the enzymes for enhancing the effect of less Used quantities of existing oxidizing agents. An example of such an enzymatic Procedure represents the procedure, the effect of small amounts (eg 1% and less, relative to the total agent) to amplify hydrogen peroxide by peroxidases.

According to a preferred embodiment, the agents according to the invention contain, in particular if they still have conditioning or firming properties, continue anionic, nonionic or in particular cationic polymers.

As conditioning agents suitable cationic polymers contained within the Polymeric cationic groups. These groups can be part of the polymer chain, But they can also be located in side chains, the intermediate links with a Main chain are connected. Common cationic groups include quaternary nitrogen or Phosphorus atoms. Groups with quaternary nitrogen atoms are preferred. The Quaternary nitrogen atoms can be both 4 different or z. T. same Wear substituents, as well as be part of a ring system. Preferred cationic groups are ammonium and imidazolium groups.

Examples of such polymers are:

• - Quaternized cellulose derivatives, such as those under the names Celquat® and polymer JR® are commercially available. The compounds Celquat® H 100, Celquat L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.  
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino alkyl acrylate and methacrylate, such as quaternized with diethyl sulfate Vinylpyrrolidone-Dimethylaminoalkylmethacrylat copolymers and the vinyl pyrrolidone-methacrylamidopropyltrimethylammonium chloride copolymers. Such Compounds are known under the names Gafquat®734, Gafquat®755 and Gafquat® HS100 commercially available.
• - Copolymers of vinylpyrrolidone with vinylimidazolium methochloride, as described in the name Luviquat® be offered.
• - Dimethyldiallylammoniumsalze polymeric and their copolymers with acrylic acid and Esters and amides of acrylic acid and methacrylic acid. The under the names Merquat®100 (poly (dimethyldiallylammonium chloride)), Merquat®550 (dimethyldi allylammonium chloride-acrylamide copolymer) and Merquat® 280 (dimethyldiallyl ammonium chloride-acrylic acid copolymer are commercially available products Examples of such cationic polymers.
• - quaternized guar derivatives, as they are known under the names Cosmedia Guar® and Jaguar® are commercially available. Preferred guar derivatives are, for example Cosmedia Guar® C-261 and Jaguar® C 13-S.
• Cationically derivatized silicone oils, such as those commercially available Products Q2-7224 (Manufacturer: Dow Corning, a stabilized trimethylsilyl amodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino modified silicone, 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).
• - Chitosan and its derivatives
• - Quaternized polyvinyl alcohol
  as well as those under the designations
• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• Polyquaternium 27 known polymers with quaternary nitrogen atoms in the Polymer backbone.

Particularly preferred are cationic polymers of the first four groups, completely Polyquaternium-2, polyquaternium-10 and polyquaternium-22 are particularly preferred.

Preferred amounts of the cationic polymers in the invention are 0.1-5 wt .-%, based on the entire preparation.

Suitable nonionic polymers are, for example:

• - Vinylpyrrolidone / vinyl ester copolymers, such as those under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, respectively Vinyl pyrrolidone / vinyl acetate copolymers are preferred nonionic polymers.
• Cellulose ethers such as hydroxypropylcellulose, hydroxyethylcellulose and methyl hydroxypropyl cellulose, such as those sold under the trademarks Culminal® and Benecel® (AQUALON).
• - Gramophone
• Polyvinylpyrrolidones, as described, for example, under the name Luviskol® (BASF) to be expelled.

Examples of suitable anionic polymers are:

• - Copolymers of acrylic acid and / or methacrylic acid or esters thereof with C _10-30 - alkyl acrylates, such as those sold under the name Pemulen®.
• - Polymers and copolymers of crotonic acid with esters and amides of acrylic and Methacrylic acid, such as vinyl acetate-crotonic acid and vinyl acetate-vinyl propionate Crotonic acid copolymers. Compounds of this type are under the brand name Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF) in the Trade; the products Luviset®CA-66 and Luviset®CAP may be preferred.
• Vinylpyrrolidone / vinyl acrylate copolymers, available for example under the Trademark Luviflex® (BASF). A preferred polymer is that under the Designation Luviflex® VBM-35 (BASF) available vinylpyrrolidone / acrylate Terpolymers.
• - Acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers, for example, under the name Ultrahold® strong (BASF), as well as  Methacrylic acid / ethyl acrylate / t-butyl acrylate terpolymers sold under the name Luvimer® 100P (BASF).

The use of anionic, nonionic or cationic polymers can be found in preference is given to those hair colorants which are free of oxidation dye precursors.

To prepare the colorants of the invention are the substantive dyes and optionally the oxidation dye precursors in a suitable hydrous Carrier incorporated. For the purpose of hair coloring such carrier z. Creams, Emulsions, gels or surfactant-containing foaming solutions, eg. Shampoos, Foam aerosols or other preparations suitable for use on the hair are.

The colorants according to the invention can furthermore all be used for such preparations contain known active ingredients, additives and excipients. In many cases, the included Colorant at least one surfactant, where in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In In many cases, however, it has proven to be advantageous to use anionic surfactants, select zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. 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 having 2 or 3 C 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 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,  
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• - Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters having 8 to 18 carbon atoms in the Alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 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 having 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 hydroxyalkylpolyethylene and / or hydroxyalkylenepropylene glycol ether according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double compounds 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 with fatty alcohols having 8 to 22 Represent C atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and in particular salts of saturated and especially unsaturated C ₈ -C ₂₂ carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammoniumglycinate, for example, the cocoalkyl dimethylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example Kokosacylaminopropyl-dimethylammoniumglycinat, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylgly cinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocami dopropyl Betaine.

Ampholytic surfactants are understood to mean those surface-active compounds which, apart from 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 which are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylamino propionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

Nonionic surfactants contain as hydrophilic group z. As a polyol group, a Po lyalkylenglykolethergruppe or a combination of polyol and Polyglykolethergruppe. Such compounds are, for example

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

Examples of the kationi usable in the hair treatment compositions of the present invention surfactants are in particular quaternary ammonium compounds. Preferred are Am monium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and Trialkylmethylammoniumchloride, z. Cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl  ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammoni monium chloride. Further cationic surfactants which can be used according to the invention are the quaterni siert protein hydrolysates.

Alkylamidoamines, in particular fatty acid amidoamines such as that under the name Tego Amid®S 18 available stearylamidopropyldimethylamine, in addition to a good conditioning effect especially by their good biodegradability. Also very readily biodegradable are quaternary ester compounds, so-called "Esterquats", such as methylhydroxyal sold under the trademark Stepantex® kyldialkoyloxyalkyl-ammonium Methosulfate and under the trademark De hyquart® distributed products such as Dehyquart® AU-46.

An example of a cationic surfactant usable quaternary sugar derivative is the Commercial product Glucquat®100, according to INCI nomenclature a "Lauryl methyl gluceth- 10 hydroxypropyl dimonium chlorides ".

The compounds used as surfactants with alkyl groups may be in each case act uniform substances. However, it is usually preferred in the production These substances are based on native plant or animal raw materials, so that one Substance mixtures with different alkyl chains depending on the respective raw material length receives.

In the case of the surfactants, the addition products of ethylene oxide and / or propylene oxide with fatty al can represent alcohols or derivatives of these addition products, both products with a "normal" homolog distribution as well as those with a narrow homologue distribution can be used. Under "normal" homolog distribution Mi understood by homologues, which in the implementation of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or alkali obtained metal alkoxides as catalysts. Narrow homolog distributions become however, when, for example, hydrotalcites, alkaline earth metal salts of ether carbon are obtained acids, alkaline earth metal oxides, hydroxides or alcoholates used as catalysts become. The use of products with restricted homolog distribution can be be preferred.  

Furthermore, the hair treatment compositions according to the invention may preferably have one conditioning agent selected from the group consisting of cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetics is formed.

Cationic polymers may be preferred as conditioning agents. In this Connection is made to the above polymers.

Further suitable conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes such as dimethylpolysiloxane and methylphenylpolysi loxan, as well as their alkoxylated and quaternized analogs. Examples of such silicones are those of Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 distributed products and the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxyl-amino modified silicone, also called amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quater nium-80).

Also usable as conditioning agents are paraffin oils, synthetic prepared oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, Orange oil, almond oil, wheat germ oil and peach kernel oil.

Likewise suitable hair conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephaline.

Other active ingredients, auxiliaries and additives are, for example

• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum ara bicum, karaya gum, locust bean gum, linseed gums, dextran, cellu loose derivatives, e.g. Methylcellulose, hydroxyalkylcellulose and carboxymethylcel cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as glucose and maleic acid,  
• - Protein hydrolysates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• - Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine,
• - other substances for adjusting the pH,
• - Active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - light stabilizers,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid ester,
• - fatty acid,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, Hydrogencarbonates, guanidines, ureas as well as primary, secondary and tertiary phosphates,
• Opacifiers such as latex,
• Pearlescing agents such as ethylene glycol mono- and distearate,
• - Propellants 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 for the preparation of the inventive Colorants used in customary amounts for this purpose; z. B. become emulsifiers in Concentrations of 0.5 to 30% by weight and thickening agents in concentrations of 0.1 used to 25 wt .-% of the total colorant.

A second subject of the application is the use of an inventive Means for dyeing and tinting keratinic fibers, in particular human ones Hair.  

It is in principle possible to formulate the agents according to the invention so that they either remain on the hair or be rinsed out of the hair again.

According to a preferred embodiment, the agents according to the invention are so formulated that they can remain on the hair. This is especially so-called Tinting the case, but also with funds that also have a firming function to exercise.

New and thus also the subject of the invention are the following dyes:
3-Methoxy-1 - ({4 - [(5-nitro- (1,3-thiazol-2-yl) -diazenyl] -phenyl} [2- (trimethyl-ammonium) -ethyl] -amino) -propan-2-ol-iodide.
2 - ({4- [5-nitro (1,3-thiazol-2-yl)) diazenyl] phenyl} [2- (trimethyl-ammonium) ethyl] -amino) -ethan-1-ol-iodide.
3-Methoxy-1 - {[4- (1,3-thiazol-2-yldiazenyl) phenyl] [2- (trimethylammonium) ethyl] amino} propan-2-ol iodide.
naphthylamine 4- (1,3,4-thiadiazol-2-yldiazenyl).

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

Examples 1. Synthesis examples

The synthesis proceeds analogously to a literature-known protocol for the preparation of Diazothiazole derivatives, as disclosed for example in JP 57/136580 A2; here will be an example of the synthesis of the new compound 4- (1,3,4-thiadiazole-2) yldiazenyl) naphthylamine described:

4- (1,3,4-thiadiazol-2-yldiazenyl) naphthylamine

124 mmol of 2-aminothiazole were dissolved with stirring in hot H ₂ SO ₄ , the resulting reaction solution was cooled to -10 ° C and diazotized rapidly with an aqueous solution of 124 mmol NaNO ₂ . Subsequently, 124 mmol of 1-naphthylamine dissolved in 50% acetic acid were added at a temperature <5 ° C and the mixture was stirred for 10 minutes. It was diluted with water and adjusted to a pH of 5. The precipitated dye was filtered off, washed with water until neutral and then dried. Recrystallization took place from ethanol.
Yield: 70-75%

2. hair dyes Partial mixture A

cetearyl 1.00 g Fatty alcohol mixture based on coconut oil 1.00 g Akypo® RLM 45N ¹ 1.10 g p-hydroxybenzoate 0.05 g p-hydroxybenzoate 0.15 g water 70.00 g ¹ lauryl alcohol with about 4.5 mol of ethylene oxide-acetic acid sodium salt (about 82% of active ingredient, INCI name: sodium laureth-6 carboxylates) (KAO, Chem-Y). The substances were melted at 80 ° C, mixed with 80 ° C hot water and emulsified with vigorous stirring. Thereafter, the emulsion was cooled with gentle stirring.

Partial mixture B

ammonium sulfate 1.00 g Direct dye according to formula (I) 1.00 g Ammonia (25% solution) ad pH = 9.0 water 10.00 g

The dye was dissolved in 50 ° C hot water with the addition of ammonium sulfate and Ammonia dissolved.

The dye solution (part mixture B) was added to the emulsion (part mixture A), with Adjust ammonia to pH = 9 and make up to 100 g with water. It was up to the Reaching room temperature stirring.

The dyeing cream thus obtained was standardized on strands of 5 cm length, to 80% applied gray hair, but not particularly pretreated human hair, and there Leave at 32 ° C for 30 minutes. Thereafter, the hair was rinsed, with a usual Washed out shampoo and then dried.

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

Table I

D1: 2- {ethyl [4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} ethan-1-ol
D2: 4- (1,3-thiazol-2-yldiazenyl) naphthylamine
D3: diethyl {4 - [(5-nitro (1,3-thiazol-2-yl)) diazenyl] phenyl} amine
D4: 4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] naphthylamine
D5: 2- (Ethyl {4 - [(5-nitro (1,3-thiazol-2-yl) diazenyl] phenyl} amino) ethan-1-ol
D6: 3-Methoxy-1 - ({4- [5-nitro (1,3-thiazol-2-yl) diazenyl] phenyl} [2- (trimethylammonium) ethyl] amino) propan-2-ol iodide
D7: 2 - ({4 - [(5-nitro (1,3-thiazol-2-yl) -diazenyl] -phenyl} [2- (trimethyl-ammonium) -ethyl] -amino) -ethan-1-ol-iodide
D8: 3-Methoxy-1 - {[4- (1,3-thiazol-2-yldiazenyl) phenyl] [2- (trimethylammonium) ethyl] amino} propan-2-ol iodide
D9: 5- (Diethylamino) -2- (1,3-thiazol-2-yldiazenyl) benzoic acid
D10: 4- (1,3,4-thiadiazol-2-yldiazenyl) naphthylamine

Claims (21)

1. Composition for dyeing and tinting keratinic fibers, in particular of human hair, characterized in that it contains in a cosmetically acceptable carrier as substantive dye at least one diazothiazole derivative of the formula (I),
in the
A represents hydrogen, a halogen atom, a nitro group or a C ₁ -C ₄ -alkyl group,
B represents a nitrogen atom or a = CH group,
X is formula (a) or (b), where
C is a halogen atom, a C ₁ -C ₄ -alkyl group, a C ₃ -C ₈ -cycloalkyl group, a C ₁ -C ₄ -alkoxy group or a -COOM group, in which M is hydrogen or a physiologically tolerated cation, stands,
R and R 'independently of one another represent hydrogen, a C ₁ -C ₄ -alkyl group, an allyl group, a C ₂ -C ₅ -polyhydroxyalkyl group, a C ₃ -C ₈ -cycloalkyl group, a C ₁ -C ₄ -aminoalkyl group, a C ₁ -C ₄ - hydroxyalkyl group, a C ₁ -C ₄ -alkoxy-C ₁ -C ₄ alkyl group, a C ₁ -C ₄ - alkoxy-C ₁ -C ₄ -hydroxyalkyl group or a C ₁ -C ₄ -Trialkylammonium- C ₁ -C ₄ alkyl group,
or one of the corresponding physiologically acceptable salts. 2. Composition according to claim 1, characterized in that A is hydrogen or a Nitro group is. 3. Composition according to one of claims 1 and 2, characterized in that B for a = CH Group stands. 4. Composition according to one of claims 1 to 3, characterized in that the rest of C Is hydrogen. 5. Composition according to one of claims 1 to 4, characterized in that the radicals R and R 'are hydrogen. 6. Composition according to one of claims 1 to 4, characterized in that at least one the radicals R and R 'is an ethyl group or a hydroxyethyl group. 7. Composition according to one of claims 1 to 4, characterized in that at least one the radicals R and R 'is a 2-hydroxy-3-methoxy-propyl group. 8. Composition according to one of claims 1 to 4, characterized in that at least one R and R 'is an N-trimethylammoniumethyl group. 9. Composition according to one of claims 1 to 8, characterized in that the compound (I) is selected from 2- {ethyl (4- (1,3-thiazol-2-yldiazenyl) phenyl] amino} ethan-1-ol, 4- (1,3-thiazol-2-yldiazenyl) naphthylamine, diethyl {4 - [(5-nitro (1,3-thiazol-2-yl)) diazenyl] phenyl} amine, 4 - [(5-nitro-1,3-thiazol-2-yl) diazenyl] naphthylamine, 2- (ethyl {4 - [(5-nitrobenzene) (1,3-thiazol-2-yl) diazenyl] phenyl} amino) ethan-1-ol, 3-methoxy-1 - ({4- [5-nitro- (1,3-) thiazol-2-yl) diazenyl] phenyl} [2- (trimethylammonium) ethyl] amino) propan-2-ol iodide, 2- ({4 - [(5-nitro (1,3-thiazol-2-yl)) diazenyl] phenyl} [2- (trimethylammonium) ethyl] amino) - ethan-1-ol iodide, 3-methoxy-1 - {[4- (1,3-thiazol-2-yldiazenyl) phenyl] [2- (trimethyl ammonium) ethyl] amino} propan-2-ol iodide, 5- (diethylamino) -2- (1,3-thiazol-2-yl diaze nyl) benzoic acid or 4- (1,3,4-thiadiazol-2-yldiazenyl) naphthylamine.   10. Composition according to one of claims 1 to 9, characterized in that it at least contains another direct dye. 11. Composition according to one of claims 1 to 10, characterized in that it is free from Oxidation dye precursors is. 12. Composition according to claim 11, characterized in that it remains on the hair. 13. Composition according to one of claims 1 to 12, characterized in that it is a hair fixative agent. 14. Composition according to one of claims 1 to 10, characterized in that it continues contains at least one developer component. 15. Composition according to claim 14, characterized in that the developer component is selected from p-phenylenediamine, p-toluenediamine, p-aminophenol, 1- (2'- Hydroxyethyl) -2,5-diaminobenzene, 4-amino-3-methylphenol, 2-aminomethyl-4 aminophenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine and 4- Hydroxy-2,5,6-triaminopyrimidine. 16. Composition according to one of claims 14 or 15, characterized in that it at least one coupler component selected from the group consisting of 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5- Methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-diaminopyridine formed will, contains. 17. Composition according to one of claims 1 to 16, characterized in that it further comprises anionic, nonionic or cationic polymer. 18. Composition according to one of claims 1 to 17, characterized in that it continues contains at least one surfactant.   19. Use of a composition according to any one of claims 1 to 18 for dyeing and tinting of hair. 20. Use of a composition according to any one of claims 1 to 18 for dyeing and tinting hair, characterized in that the agent is an oxidation hair dye. 21. Compounds according to formula (I), according to claim 1, characterized by the following substituent combinations: