DE60124889T2 - Hair dyes containing pyrazoloazole dyes - Google Patents

Description

technical area

These Invention relates to a hair dye composition, the at least one substantive dye for dyeing includes human hair, and also a method of dyeing human hair through this composition.

State of technology

hair dye compositions, containing several anionic or cationic substantive dyes, have been known for a long time and require as opposed to permanent ones hair dyeing with oxidative dye intermediates no coupling reaction by oxidizing agent. This type of substantive dyeing compositions becomes common in the hair as a so-called tinting shampoo together with surface-active Components or as a lotion, emulsion or thickened solution, i. Gels applied.

These direct hair dyeing composition should, however, regarding the color permanence and in particular intensity as well like uniformity the coloring and the color gloss can be improved.

Additionally have the substantive dyes described in general the Disadvantage that they are with alkaline peroxides are incompatible, so that the dyeing compositions with direct dyes generally on the hair without Peroxide are applied. As a result, the direct hair dye composition has no bleaching effect on the hair.

epiphany the invention

One The aim of this invention is to provide a hair dye composition on the Indicate the basis of substantive dyes that are excellent dyeing properties shows and gives the hair a lasting and vibrant color over one extended Time period and in the form of a lotion, emulsion, solution, gel, Suspension or aerosol by adding propellants to the hair can be applied. Another object of this invention is in it, a hair dye composition indicate that also has a hair bleaching performance, coupled with the performance described above, based on the substantive dyes.

The solution of these objects lies in the provision of such a composition, comprising at least one specific substantive dye, the good hair dyeing performance and compatibility having peroxides.

These Inventors have found that then, when the substantive pyrazolazole dye described below As a hair dye is used, surprisingly, the resulting hair dye gives the hair a livelier and more lasting shade than general oxidative hair dye compositions can lend. additionally These inventors have found that the substantive Pyrazolazole dye has excellent stability to alkaline Having peroxides and the hair coloring effect of this composition comprising at least one of the substantive ones described below Pyrazolazole dyes can be further improved if one this composition with a pH of 7.5 to 12.5 together with applying at least one peroxide, because the hair bleaching effect that comes from an alkaline peroxide, makes the hair more alive.

worin R¹ ein Wasserstoffatom, Halogenatom, C_1-5-Alkyl-Gruppe, die wahlweise durch ein oder mehr als ein Halogenatom(e), Hydroxy-Gruppe(n), Alkoxy-Gruppe(n), Aryloxy-Gruppe(n), Amino-Gruppe(n), Alkylamino-Gruppe(n), Acyl-Gruppe(n), Acylamino-Gruppe(n) substituiert sein kann; C_1-4-Alkoxygrouppe, C_1-4-Alkylthio-Gruppe, Arylthio-Gruppe, Benzylthio-Gruppe, Acyl-Gruppe, Acylamino-Gruppe, Acyloxy-Gruppe, Carbamoyl-Gruppe, Phenyl-Gruppe, die wahlweise durch ein oder mehrere Halogenatom(e), Nitro-Gruppe(n), Sulfonyl-Gruppe(n), C_1-4-Alkyl-Gruppe(n), C_1-4-Alkoxy-Gruppe(n), C_1-3-Trifluor-alkyl-Gruppe(n), Amino-Gruppe(n) oder Alkylamino-Gruppe(n) substituiert sein kann; Alkoxycarbonyl-Gruppe; Aryloxycarbonyl-Gruppe, Cyano-Gruppe, Nitro-Gruppe, Dialkylphosphinyl-Gruppe, Alkylsulfinyl-Gruppe, Arylsulfinyl-Gruppe, Sulfamoyl-Gruppe, Carboxyl-Gruppe, Sulfo-Gruppe, Aryloxy-Gruppe, C_1-4-Alkylamino-Gruppe, Ureido-Gruppe, Sulfamoylamino-Gruppe, Sulfonamido-Gruppe, Alkoxycarbonylamino-Gruppe, Aryloxycarbonylamino-Gruppe, Heteroarylthio-Gruppe oder eine Phosphonyl-Gruppe ist; worin Za, Zb and Zc jeweils unabhängig ein Stickstoffatom oder Kohlenstoffatom sind, das eine Gruppe aufweist, die oben für R¹ angegeben ist; und wobei nur eines von Zb und Zc das Kohlenstoffatom ist, wobei R² und R³ jeweils unabhängig ein Wasserstoffatom oder eine Elektronen ziehende Gruppe sind.Thus, in one aspect of this invention, there is provided a hair dye composition comprising

wherein R ^{1 is} hydrogen, halogen, C _1-5 alkyl optionally substituted by one or more halogen (s), hydroxy group (s), alkoxy group (s), aryloxy group (s) Amino group (s), alkylamino group (s), acyl group (s), acylamino group (s) may be substituted; C _1-4 alkoxy group, C _1-4 alkylthio group, arylthio group, benzylthio group, acyl group, acylamino group, acyloxy group, carbamoyl group, phenyl group, optionally by one or more Halogen atom (s), nitro group (s), sulfonyl group (s), C _1-4 alkyl group (s), C _1-4 alkoxy group (s), C _1-3 trifluoro- alkyl group (s), amino group (s) or alkylamino group (s) may be substituted; Alkoxycarbonyl group; Aryloxycarbonyl group, cyano group, nitro group, dialkylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, sulfamoyl group, carboxyl group, sulfo group, aryloxy group, C _1-4 alkylamino group, ureido Group, sulfamoylamino group, sulfonamido group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroarylthio group or a phosphonyl group; wherein Za, Zb and Zc are each independently a nitrogen atom or carbon atom having a group given above for R ¹ ; and wherein only one of Zb and Zc is the carbon atom, wherein R ² and R ^{3 are} each independently a hydrogen atom or an electron withdrawing group.

According to one Another aspect is thus a method of dyeing the hair by use the described hair dye composition specified.

Best kind to carry out the invention

worin R¹ und R⁴ unabhängig ein Wasserstoffatom, Halogenatom, C_1-5-Alkyl-Gruppe, die wahlweise durch ein oder mehrere Halogenatom(e), Hydroxy-Gruppe(n), Alkoxy-Gruppe(n), Aryloxy-Gruppe(n), Amino-Gruppe(n), Alkylamino-Gruppe(n), Acyl-Gruppe(n), Acylamino-Gruppe(n) substituiert sein kann; C_1-4- Alkoxy-Gruppe, C_1-4-Alkylthio-Gruppe, Arylthio-Gruppe, Benzylthio-Gruppe, Acyl-Gruppe, Acylamino-Gruppe, Acyloxy-Gruppe, Carbamoyl-Gruppe, Phenyl-Gruppe, die wahlweise durch ein oder mehrere Halogenatom(e), Nitro-Gruppe(n), Sulfonyl-Gruppe(n), C_1-4-Alkyl-Gruppe(n), C_1-4-Alkoxy-Gruppen, C_1-3-Trifluor-alkyl-Gruppe(n), Amino-Gruppe(n) oder Alkylamino-Gruppe(n) substituiert sein kann; Alkoxycarbonyl-Gruppe, Aryloxycarbonyl-Gruppe, Cyano-Gruppe, Nitro-Gruppe, Dialkylphosphinyl-Gruppe, Alkylsulfinyl-Gruppe, Arylsulfinyl-Gruppe, Sulfamoyl-Gruppe, Carboxyl-Gruppe, Sulfo-Gruppe, Aryloxy-Gruppe, C_1-4-Alkylamino-Gruppe, Ureido-Gruppe, Sulfamoylamino-Gruppe, Sulfonamido-Gruppe, Alkoxycarbonylamino-Gruppe, Aryloxycarbonylamino-Gruppe, Heteroarylthio-Gruppe oder Phosphonyl-Gruppe sind;
wobei R² und R³ jeweils unabhängig ein Wasserstoffatom oder eine Elektronen ziehende Gruppe sind.In particular, as the substantive pyrazoloazole dye of this invention, one having the formula (2) or (3) having a pyrazolotriazole structure or a salt thereof is preferable:

wherein R ¹ and R ^{4 are} independently a hydrogen atom, halogen atom, C _1-5 alkyl group optionally substituted by one or more halogen atom (s), hydroxy group (s), alkoxy group (s), aryloxy group ( n), amino group (s), alkylamino group (s), acyl group (s), acylamino group (s) may be substituted; C _1-4 alkoxy group, C _1-4 alkylthio group, arylthio group, benzylthio group, acyl group, acylamino group, acyloxy group, carbamoyl group, phenyl group, optionally by a or more halogen atom (s), nitro group pe (n), sulfonyl group (s), C _1-4 alkyl group (s), C _1-4 alkoxy groups, C _1-3 trifluoroalkyl group (s), amino group (n) or alkylamino group (s) may be substituted; Alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, sulfamoyl group, carboxyl group, sulfo group, aryloxy group, C _1-4 alkylamino Group, ureido group, sulfamoylamino group, sulfonamido group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroarylthio group or phosphonyl group;
wherein R ² and R ^{3 are} each independently a hydrogen atom or an electron withdrawing group.

The definitions of R ¹ to R ⁴ in the above formulas (1), (2) and (3) are described below in detail.

Examples of the halogeno group represented by R ¹ or R ⁴ include a fluorine atom, chlorine atom, bromine atom and iodine atom, in particular, chlorine and bromine atoms are preferable. Examples of the C _1-5 alkyl group represented by R ¹ or R ⁴ include methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, t-butyl and n-pentyl.

Examples of the substituent which may substitute the described C _1-5 alkyl group include chloro, bromo, hydroxy, methoxy, ethoxy, phenoxy, amino, methylamino, dimethylamino, 2-hydroxyethylamino, Bis (2-hydroxyethyl) ymino, acetyl and acetylamino group. In particular, hydroxy, methoxy, ethoxy, amino, methylamino, dimethylamino, 2-hydroxyethylamino and bis (2-hydroxyethyl) amino are preferred in view of the solubility of the dye.

Examples of the C _1-4 alkoxy group represented by R ¹ or R ⁴ include methoxy, ethoxy, n-propyloxy, 1-methylethoxy, n-butoxy, 1-methylpropyloxy and t-butoxy Group. In particular, methoxy and ethoxy group are preferred.

Examples of the C _1-4 alkylthio group represented by R ¹ or R ⁴ include methylthio and ethylthio groups.

Examples of the arylthio group represented by R ¹ or R ⁴ include phenylthio, 1-naphthylthio, 2-naphthylthio, 2-pyridylthio, 3-pyridylthio and 4-pyridylthio group.

Examples of the acyl group represented by R ¹ or R ⁴ include formyl, acetyl, hydroxyacetyl, aminoacetyl and propionyl group.

Examples of the acylamino group represented by R ¹ or R ⁴ include formylamino, acetylamino and propionylamino groups.

Examples of the acyloxy group represented by R ¹ or R ⁴ include acetyloxy and propionyloxy groups.

Examples of the substituent which can optionally substitute the phenyl group represented by R ¹ or R ⁴ include fluorato, chlorato, bromine atom, iodine atom, nitro, sulfonyl, methyl, ethyl, methoxy, ethoxy, trifluoromethyl , Amino group, methylamino group, dimethylamino group, 2-hydroxyethylamino group and bis (2-hydroxyethyl) amino group. In particular, chlorine atom, bromato, amino, methylamino, dimethylamino, 2-hydroxyethylamino and bis (2-hydroxyethyl) amino group are preferred.

Examples of the alkoxycarbonyl group represented by R ¹ or R ⁴ include methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl and 2-hydroxyethoxycarbonyl.

Examples of the aryloxycarbonyl group represented by R ¹ or R ⁴ include phenoxycarbonyl, 1-naphthyloxycarbonyl, 2-naphthyloxycarbonyl, 2-pyridyloxycarbonyl, 3-pyridyloxycarbonyl and 4-pyridyloxycarbonyl.

Examples of the dialkylphosphinyl group represented by R ¹ or R ⁴ include dimethylphosphinyl and diethylphosphinyl.

Examples of the alkylsulfinyl group represented by R ¹ or R ⁴ include methylsulfinyl and ethylsulfinyl.

Examples of the arylsulfinyl group represented by R ¹ or R ⁴ include phenylsulfinyl.

Examples of the aryloxy group represented by R ¹ or R ⁴ include 1-naphthyloxy, 2-naphthyloxy, 2-pyridyloxy, 3-pyridyloxy and 4-pyridyloxy.

Examples of the C _1-4 alkylamino group represented by R ¹ or R ⁴ include methylamino, ethylamino, n-propylamino and n-butylamino.

Examples of the alkoxycarbonylamino group represented by R ¹ or R ⁴ include methoxycarbonylamino and ethoxycarbonylamino.

Examples of the aryloxycarbonylamino group represented by R ¹ or R ⁴ include phenoxycarbonylamino group.

Examples of the heteroarylthio group represented by R ¹ or R ⁴ include 2-pyridylthio, 2-imidazolothio and 3-pyrazolothio.

The group represented by R ¹ or R ⁴ may be a hydrogen atom. Furthermore, in view of the hair dyeing intensity, C _1-5 alkyl groups which may be optionally substituted by one or more than two hydroxy groups, alkoxy groups, amino group or alkylamino groups are phenyl group optionally substituted by one or more is substituted as halogen atoms, C _1-4 alkyl groups, C _1-4 alkoxy groups, amino groups or alkylamino groups.

Particularly suitable examples of the electron withdrawing group represented by R ² and R ³ are fluorine, chlorine, bromine, iodine, carboxylic acid group, carboxylate group, alkoxycarbonyl group, substituted or unsubstituted aminocarbonyl group or acyl group, wherein fluorine , Chlorine, bromine, iodine, carboxylic acid group and C _2-5 alkoxycarbonyl group are particularly preferable in view of the hair dyeing intensity.

Examples the directing pyrazoloazole dye having the formula (1) according to this Invention include the following structures:

each of the compounds of formulas (1), (2) and (3) of this invention a salt of an organic or inorganic acid or organic or inorganic be alkaline substance. Examples of organic or inorganic Acid include Hydrochloric acid, Sulfuric acid, Phosphoric acid, Acetic acid, propionic acid, lactic acid and citric acid. Examples of the organic or inorganic substance include ammonium hydroxide, 2-ethanolammonium hydroxide, sodium hydroxide and potassium hydroxide.

The Generation of the direct-acting pyrazolazole dyes described above is already known and will be over oxidative coupling of the corresponding substituted pyrazolazole achieved with the corresponding substituted aminophenol derivatives.

The resulting colors are in the range of intense red to the intense magenta color, but they can be further added by Colors are varied.

The proportion of substantive pyrazolazole dyes in the compositions of this invention is variable and depends on the structure and also the desired chroma; in general it is within about 0.001 to about 5, preferably 0.01 to 2.5, in particular 0.1 to 1 wt .-%, based on the total composition.

Next The substantive pyrazolazole dye of the formula (1) may additionally contain other direct hair dye for The Haas are used together to create color nuances.

Regarding such direct dyes are so-called "Arianor dyes" preferred, cf. K. Schrader, "Basics and Recipes of cosmetics ", 2nd edition (1989), p. 811.

Particularly suitable basic (cationic) dyes are:
Basic Blue 6, CI No. 51,175; Basic Blue 7, CI No. 42,595; Basic Blue 9, CI No. 52,015; Basic Blue 26, CI No. 44,045; Basic Blue 41, CI No. 11,154; Basic Blue 99, CI No. 56,059; Basic Brown 4, CI No. 21,010; Basic Brown 16, CI No. 12,250; Basic Brown 17, CI No. 12,251; Basic Brown 7, CI No. 75,500; Basic Green 1, CI No. 42,040; Basic Red 2, CI No. 50,240; Basic Red 12, CI No. 48,070; Basic Red 22, CI No. 11,055; Basic Red 76, CI No. 12,245; Basic Violet 1, CI No. 42,535; Basic Violet 3, CI No. 42,555; Basic Violet 10, CI No. 45,170; Basic Violet 14, CI No. 42,510; Basic Yellow 57, CI No. 12,719; as well as the dyes according to EP 0 618 464 B1 ,

of course is also the use of direct dyes of plants and / or anionic (acidic) substantive dyes for the hair possible.

The following dyes can be used as anionic suitable dyes:
Acid Black 1, CI No. 20,470; Acid Blue 1, CI No. 42,045; Food Blue 5, CI No. 42,051; Acid Blue 9, CI No. 42,090; Acid Blue 74, CI No. 73,015; Acid Red 18, CI No. 16,255; Acid Red 27, CI No. 16,185; Acid Red 87, CI No. 45,380; Acid Red 92, CI No. 45,410; Acid Orange 7, CI No. 15,510; Acid Violet 43, CI No. 60,730; Acid Yellow 1, CI No. 10,316; Acid Yellow 23, CI No. 19,140; Acid Yellow 3, CI No. 47,005; Food Yellow No. 8, CI No. 14,270; D & C Brown No. 1, CI No. 20,170; D & C Green No. 5, CI No. 61,570; D & C Orange No. 4, CI No. 15,510; D & C Orange No. 10, CI No. 45,425: 1; D & C Orange No. 11, CI No. 45,425; D & C Red No. 21, CI No. 45,380: 2; D & C Red No. 27, CI No. 45,410: 1; D & C Red No. 33, CI No. 17,200; D & C Yellow No. 7, CI No. 45,350: 1; D & C Yellow No. 8, CI No. 45,350; FD & C Red No. 4, CI No. 14,700; FD & C Yellow No. 6, CI No. 15,985.

As well The use of vegetable dyes is possible, such as for example Henna (red or black), Alkana root, Laccainsäure (Stocklack), Indigo, bluegore root powder, drought root and rhubarb powder, etc. alone or in combination with synthetic direct dyes.

These direct dyes can equally in an amount of about 0.005 to about 5, preferably about 0.05 to about 2.5, in particular about 0.1 to about 1 wt .-%, based on the Whole composition used in the form of a Solution, Dispersion, emulsion, gel, aerosol intended for use becomes.

The Compositions of this invention may also include at least one oxidative dye intermediate, i. Developer and / or coupler substance contain.

Examples of the developer include in particular 1,4-diaminobenzene, 2,5-diaminotoluene, Tetraaminopyrimidine, triaminohydroxypyrimidine, 1,2,4-triaminobenzene, 2- (2,5-diaminophenyl) ethanol, 2- (2-hydroxyethylamino) -5-aminotoluene, 1-amino-4-bis (2-hydroxyethyl) aminobenzene or water-soluble Salts thereof.

Examples of the coupler include 2-methylresocrin, 4-chlororesorcinol, 2-amino-4-chlorophenol, 4- (N-methylamino) phenol, 2-aminophenol, 3-aminophenol, 1-methyl-2-hydroxy-4-aminobenzene, 3- (N, N-dimethylamino) phenol, 4-amino-3-methylphenol, 5-amino-2-methylphenol, 6-amino-3-methylphenol, 3-amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 4-aminodiphenylamine, 4,4'-diaminodiphenylamine, 2-dimethylamino-5-aminopyridine, 2,6-diaminopyridine, 1,3-diaminobenzene, 1-amino-3- (2-hydroxyethylamino) benzene, 1-amino-3- [bis (2-hydroxyethyl) amino) benzene, alpha-naphthol, 1,4-diamino-2-chlorobenzene, 4,6-dichlororesorcinol, 1,3-diaminotoluene, 1-hydroxynaphthalene, 4-hydroxy-1,2-methylenedioxybenzene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-diamino-3-chlorophenol and / or 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene. However, the examples described are not intended to be in this invention restrict.

developer and couplers are preferably in a molar ratio of 1: 3 to 5: 1, in particular about 1: 1 to about 3: 1, and their proportion in the hair dye composition of the invention may be from about 0.05 to about 5 weight percent and depends on the one desired Color off.

Of the described direct-pulling pyrazolazole dye has an excellent stability against alkaline Peroxide, so he is compatible with peroxide, which simultaneously with the hair coloring a hair bleaching can result. For this purpose, the hair dye composition of this invention can be at least a peroxide having at least one described substantive pyrazolazole dye included, and the hair dye composition may preferably be at a pH of 7.5 to 12.5 to achieve a sufficient Hair bleaching can be adjusted.

When Peroxides for the described hair dye composition can diluted Solutions, Emulsions or gels of hydrogen peroxide are used, however other peroxides such as alkaline earth peroxides, for example magnesium peroxide, Urea peroxides or melamine peroxide, etc., may be in appropriate stoichiometric Quantities are used. To increase the hair bleaching effect additionally in particular persulfates such as ammonium persulfate, potassium persulfate or sodium persulfate in the composition having a pH of about 7.5 to approximately 12.5, preferably about 8 to 11 are inserted. The combined use of hydrogen peroxide and the described persulfates is contemplated the achievement of a good bleaching effect.

Preferred alkalizing agents are ammonia, monoethanolamine and alkali carbonates and bicarbonates, such as sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Different alkalizing agents such as di- and triethanolamine as well as other hydroxyalkanolamines can be used. As hair components containing persulfate, the components which are mixed as a powder with the aqueous hydrogen peroxide, for example, 6 wt .-% of an aqueous H ₂ O ₂ solution are particularly preferred, with the monograph by K. Schrader, "Basics and formulations of cosmetics ", 2nd Edition (1989), pp. 815-823.

The described hair dye composition, which contains at least one oxidizing agent can be known in all known Haarfärbemedien especially solutions, creams, emulsions, Pastes, gels (foam) aerosols, etc.

The hair dye composition of the invention can also be surface-active Contain substances, and these should be used if they are a tinting shampoo concerns.

nonionic, anionic, cationic, amphoteric or zwitterionic surfactants can in the hair dye composition added become.

For tinting shampoos other than amphoteric or zwitterionic and cationic surfactants are preferably used in an amount of about 0.5 to about 5 wt .-%, based on the total composition. Suitable nonionic surfactants are selected from the class of alkylpolyglucosides having the general formula: RO- (CH ₂ CH ₂ O) _n -Z _x , wherein R is a C _8-20 -, preferably C _10-14 alkyl group, Z is a C _5-6 saccharide, n is a number from 0 to 10 and x is a number between 1 and 5, preferably 1, 1 to 2.5. Other suitable nonionic surfactants for the composition of this invention are C _10-22 fatty alkyl ethoxylates.

Particularly suitable C _10-22 fatty alcohol ethers are available under the trade names "Laureth", "Myristeth", "Oleth", "Ceteth", "Ceceth", "Steareth" and "Ceteareth" according to the CTFA nomenclature, which are included with a number of ethylene oxides, for example laureth-16. The average number of ethylene oxides is suitably between about 2.5 and about 25, preferably about 10 to about 20.

Other nonionic surfactants additionally shareable include sorbitan esters such as polyethylene glycol Sorbitanstearylsäureester, fatty acid, and also esters of fatty acid and mixed-polymerized polyglycol from ethylene oxide and propylene oxide, as they are obtainable for example under the trade name "Pluronics ^®" on the market. In addition, another useful surfactant is amine oxide.

Such amine oxides, which have long been state of the art, are, for example, C _12-18 -alkyldi methyl amine oxide such as lauryl dimethyl amine oxide, C _12-18 -Alkylamidopropylaminoxid or Alkylamidoethylenaminoxide, C _12-18 alkyl di (hydroxyethyl) amine oxide or alkyldi (hydroxypropyl) amine oxide, and also amine oxides which have groups of ethylene oxides and / or propylene oxides in their alkyl chains. Suitable amine oxides are on the market, for example under the names "Ammonyx ^®", "Aromox ^®" or "Genaminox ^®".

Further optionally surfactant components are fatty acid mono- and dialkanolamide, such as coco fatty acid monoethanolamide and myristic monoisopropanolamide.

suitable amphoteric and zwitterionic surfactants are especially those of known betaines such as fatty acid amidoalkylbetaine and sulfobetaine, for example, lauryl hydroxysulfobetaine; also long-chain alkyl amino acids such as cocoaminoacetate, cocoaminopropionate, sodium cocoamphopropionate and sodium cocoamphoacetate.

worin R eine C_8-18-Alkyl-Gruppe und n 1 bis 3 ist,

worin R eine C_8-18-Alkyl-Gruppe und n 1 bis 3 sind,

worin R eine C_8-18-Alkyl-Gruppe und n 1 bis 3 ist, verwendet werden.In particular, betaines or sulfobetaines having the structure:

wherein R is a C _8-18 alkyl group and n is 1 to 3,

wherein R is a C _8-18 alkyl group and n is 1 to 3,

wherein R is a C _8-18 alkyl group and n is 1 to 3 are used.

preferred fatty acid amidoalkyl In particular, cocoamidopropyl betaine, cocoamphoacetate and cocoamphopropionate are and sodium salts thereof.

The preferred mixing ratio of cocoamidopropyl betaine and cocoamphoacetate is 3: 1 to 1: 3 and in particular 2: 1 to 1: 1 as a weight ratio.

suitable Cationic surfactants are, for example, long-chain quaternized Ammonium compounds, alone or in combination with each other can be used such as cetyltrimethylammonium chloride, dimethylstearylammonium chloride, Trimethylcetylammonium bromide, stearyltrimethylammonium chloride, dimethylstearylbenzylammonium chloride, Benzyltetradecyldimethylammonium chloride, dihydrogenated dimethyltallow ammonium chloride, Lauryldimethylbenzylammonium chloride, behenyltrimethylammonium chloride, Lauryltrimethylammonium chloride, tris (oligooxyethyl) alkylammonium phosphate, Cetylpyridinium chloride, etc.

quaternized Ammonium salts according to EP-A-472,107 are also suitable.

worin R¹ und R² unabhängig eine C_8-22-Alkyl-Gruppe oder -Alkenyl-Gruppe sind, die wahlweise durch Hydroxy-Gruppe substituiert sein können, R³ und R⁴ unabhängig eine C_1-3-Alkyl-Gruppe oder eine Gruppe -CH₂-CH₂-O-[EO]_z-H sind, worin x, y und z jeweils unabhängig 0 bis 5 und Y^– ein Anion und EO Ethylenoxid bedeuten.Further suitable long-chain ammonium compounds are esters of quaternized ammonium compounds having the general formula (4):

wherein R ¹ and R ^{2 are} independently a C _8-22 alkyl group or alkenyl group optionally substituted by hydro xy group, R ³ and R ^{4 are} independently a C _1-3 alkyl group or a group -CH ₂ -CH ₂ -O- [EO] _z -H where x, y and z are each independently 0 to 5 and Y ^- an anion and EO denote ethylene oxide.

It is particularly preferred that in the formula (4), R ¹ and R ^{2 are} each an oleyl group or C _12-18 alkyl group, R ^{3 is} a methyl group and R ^{4 is} a group -CH ₂ -CH ₂ -O- [EO] _{z is} -H.

The anion Y ^- is preferably a halide such as Cl ^- or Br ^- , lower alkyl sulfate, for example methyl sulfate and ethyl sulfate or an alkyl phosphate, but various anions can also be used.

These compounds are known and available in the market under the trade name "Schercoquat® ^®", "Dehyquart® F30 ^®" and "Tetranyl ^®". The use of these "esterquats" as hair preservatives is well known and disclosed, for example, in WO-A 96/10748, WO-A 94/16677.

worin R¹ und R² eine C_8-22-Alkyl- oder -Alkenyl-Gruppe sind, die wahlweise durch eine Hydroxy-Gruppe substituiert sein kann, R³ und R⁴ eine C_1-3-Alkyl-Gruppe oder eine Gruppe -CH₂-CH₂-[EO]_x-H sind, x 0 bis 5 und Y^– ein Anion ist.Also suitable amides of quaternized ammonium compounds are represented by the formula (5):

wherein R ¹ and R ^{2 are} a C _8-22 alkyl or alkenyl group which may be optionally substituted by a hydroxy group, R ³ and R ^{4 are} a C _1-3 alkyl group or a group CH ₂ -CH ₂ - [EO] _x -H, x is 0 to 5 and Y ^{- is} an anion.

Generally known other surfactants can can also be used and the surfactants described can be compatible be used together.

Another desired ingredient for the hair dye composition of this invention is a C _3-6 alkanediol or its ether, especially a mono C _1-3 alkyl ether.

Preferred solvents for the composition are 1,2- and 1,3-propanediol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1,3- and 1,4-butanediol, diethylene glycol and its monomethyl and Monoethyl ether and its monomethyl and monoethyl ethers as well as dipropylene glycol and its monomethyl and monoethyl ether. The proportion of these diols is preferably from 0.5 to 30, more preferably from about 1 to about 15, and most preferably from about 5 to about 10 percent by weight, based on the total composition. In addition to the C _3-6 alkanediols or their ethers, monoalcohols such as ethanol, 1-propanol and 2-propanol; Polyhydric alcohols such as glycerol and hexanetriol; Ethylcarbitol, benzyl alcohol, benzyloxyethanol as well as propylene carbonate (4-methyl-1,3-dioxan-2-one), n-alkylpyrrolidone and urea are additionally used. Other possible additional ingredients are cationic, anionic, nonionic and amphoteric polymers and may preferably be introduced in an amount of from about 0.1 to about 5, especially about 0.25 to 2.5 percent by weight of the total dyeing composition. These compositions may also contain other preservatives such as oils and fats. Such are, for example, sunflower oil, almond oil, peach kernel oil, wheat germ oil, macadamia nut oil, evening primrose oil, jojoba oil, castor oil and also olive or soybean oil, lanolin and its derivatives, as well as mineral oils such as paraffin oil and Vaseline.

Synthetic oils and waxes, for example, silicone oils, Polyethylene glycols, etc. can be used. Furthermore you can suitable hydrophobic compounds, in particular fatty acid esters such as isopropyl myristate, palmitate, stearate and isostearate, oleyl oleate, Isocetylstearate, hexyl laurate, dibutyl adipate, dioctyl adipate, myristyl myristate, Oleyl erucate, polyethylene glycol and polyglyceryl fatty acid esters such as PEG-7-glyceryl cocoate, cetyl palmitate etc. are also used.

When the composition of this invention is in the form of an emulsion, it may contain commonly used emulsifying agents. The composition of this invention may also contain long-chain fatty acids. C _10-24 - in particular C _12-22 -fatty acids are preferred as fatty acids and may be present in an amount of about 0.5 to 15% by weight, in particular 1 to 10% by weight, based on the total amount of be inserted. Behenic acid and stearic acid are particularly suitable, but other fatty acids, for example myristic acid, palmitic acid, oleic acid or mixtures of natural or synthetic fatty acids such as coconut fatty acid may also be incorporated.

The Composition according to the invention has a viscosity of about 1000 to about 60,000, in particular about 5,000 to 50,000, in particular about 10 000 to 40 000 mPa · s at 20 ° C, measured by a Brookfield rotary viscometer with a spindle No. 5 at 5 rpm.

Of the pH is preferably set to a basic range between about 7.5 and 12.5, for example 7.8 and 12, in particular between about 8 and 11 set. If the composition concerns tinting shampoos, can they generally in addition to the listed surface active Substances contain an anionic surfactant.

suitable anionic surfactants are present in the composition in an amount of at least 5 to about 50 wt .-%, preferably 10 to 25 wt .-%.

Examples of the anionic surfactant include those of the sulfate, sulfonate, carboxylate and alkyl phosphate type, all of which are commonly used in shampoos. For example, the known C _10-18 alkyl sulfates, and in particular the appropriate ether sulfates, for example C _12-14 alkyl ether sulfates, lauryl ether sulfate, in particular having 1-4 ethylene oxide groups in the molecule can be given. Further, monoglyceride (ether) sulfate, fatty acid amide sulfates produced by ethoxylation and subsequent sulfate incorporation into the corresponding fatty acid alkanolamide and their alkali salts as well as salts of long chain mono- and dialkyl phosphates, which are mild detergents and applied to the skin, may also be used.

Further Suitable anionic surfactants are α-olefinsulfonates and its salts and in particular alkali metal salts of sulfosuccinic monoesters, for example Disodium salt of Monooctylsulfosuccinates and alkali salts of long-chain Monoalkylethoxysulfo.

worin R und X die gleichen Bedeutungen wie oben beschrieben aufweisen und n insbesondere eine Zahl von 1 bis 10, bevorzugt 2,5 bis 5 ist.A suitable carboxylate-type surfactant is alkyl polyether carboxylic acid or its salts having the following formula: R- (C ₂ H ₄ O) _n -O-CH ₂ COOX wherein R is a C _8-20 alkyl group is preferably C _12-14 alkyl group, n is a number from 1 to 20, preferably 2 to 17 and X is a hydrogen atom or cation of sodium, potassium, magnesium or ammonium and which may optionally be substituted hydroxyalkyl, as well as alkamidopolyethercarboxylic acid of the following general formula:

wherein R and X have the same meanings as described above and n is in particular a number from 1 to 10, preferably 2.5 to 5.

Such products are known and have long been available, for example under the name "AKYPO ^®" and "AKYPO-SOFT ^®".

Also, C _8-20 acyl isethionate and similar sulfofatty acids and their esters may be used in admixture with other surfactants.

As well can Mixtures of several anionic surfactants, for example mixtures an α-olefin sulphate and sulfosuccinates, preferably in a proportion of 1: 3 to 3: 1 or an ether sulfate and a polyether carboxylic acid or alkylamidoether carboxylic acid become.

Examples of anionic surfactants used as liquid personal cleansers in the monograph by K. Schrader, "Grundlagen und Rezepturen of cosmetics ", 2nd Edition (1989, Huethig Buchverlag), pp. 683-691.

With respect to the concentration of the anionic surfactant, the preferred amount in tinting shampoos according to this invention is between about 5 and about 30% by weight, more preferably about 7.5 to about 25 wt .-%, more preferably between about 10 and about 20 wt .-%, based on the total composition.

A preferred form of the tinting shampoos of this invention preferably contains a mixture of at least one anionic surfactant as mentioned above and a C _8-22 acylaminocarboxylic acid or its water-soluble salts, preferably in an amount of 0.5 to 10, in particular 1 to 7.5 wt .-%, based on the total composition.

Particularly preferred is N-lauroylglutamate, especially the sodium salt thereof. Further suitable N-acylaminocarboxylic acids are, for example, N-lauroyl sarcosinate, NC _12-18 -acylaspartic acid, N-myristoyl sarcosinate, N-oleylsarcosinate, N-lauroylmethylalanine, N-lauroyllysine and N-lauroylaminopropylglycine, preferably in the form of the water-soluble alkali metal or ammonium salts, in particular sodium salts.

The Composition according to the invention can also known starting materials for cosmetics such as thickeners, perfumes, Stabilizers, solubility aids, natural and / or synthetic polymers, chelating agents, etc. The composition of these substances is basically known and, for example in the monograph by K. Schader, L.c., pp. 796-798. The hair dye composition of the invention can be conventionally used as a one-part, two-part composition with a first part comprising an alkalizing agent, and a second part, comprising an oxidizing agent or as a three-part Composition produced in addition to these two components a powdery one Contains oxidizing agent, like persulphate. The direct-acting pyraolazole dye (1) can be in one or both these components of the two- or three-part composition are inserted. The one-piece composition is applied directly to the hair, while the two- or three-part composition after mixing these parts when dyeing hair is applied to the hair.

The Application time of this hair dye composition is preferably about 10 to 30 minutes; it can be reduced by thermal action become. Thereafter, the hair is washed and rinsed and dried.

The The following examples serve to illustrate this invention.

The Compounds obtained according to Synthesis Examples I to V. and the examples using the dyes of I, II, III, IV and V are according to this invention. On the other hand serve the compounds of the examples obtained according to the Synthesis Examples VI and VII, not of this invention and serve for comparison purposes only.

Examples

production example I

6-methyl-3-phenyl-1H-pyrazolo (5,1-c) (1,2,4) triazole (0.5 g) was dissolved in alkaline water at pH 12 (50 ml). To was stirring 4-Amino-2,6-dichlorophenol (0.5 g) was added. To this mixture was Potassium persulfate (0.2 g) was added, whereupon the solution turned dark red. The mixture was stirred for 2 h, before the resulting precipitate was collected by filtration. The dark brown precipitate was dried and taken up in acetone again. The acetone solution was used to remove the Impurities filtered and then evaporated to give Pyrzolotriazole (I) as a dark brown crystalline powder.

production examples II-V

6-methyl (3- (2-chlorophenyl) -1H-pyrazolo (5,1-c) (1,2,4) triazole (0.5 g) was dissolved in alkaline water at pH 12 (50 ml). To 4-amino-2,6-dichlorophenol (0.5 g) was added with stirring. To this mixture Potassium persulfate (0.2 g) was added, whereupon the mixture became dark red has been. The mixture was stirred for 2 h before the resulting Precipitate via filtration was collected. The dark brown precipitate was dried and then taken up in acetone. The acetone solution was used to remove Impurities filtered and then evaporated to give Pyrazolotriazole (II) as a dark brown crystalline powder.

The Compounds (III), (IV) and (V) were similar to the production examples (I) and (II) produced.

Production Example VI (not according to this Invention)

6-Methyl-3- (2-chlorophenyl) -1H-pyrazolo (5,1-c) (1,2,4) triazole (0.5 g) was dissolved in alkaline water at pH 12 (50 ml). To was stirring 2,5-diaminotoluene (0.5 g) was added. To this mixture was potassium persulfate (0.2 g) was added, whereupon the solution turned dark red. The mixture was stirred for 2 h, before the resulting precipitate was collected by filtration. The dark brown precipitate was dried and taken up in acetone again. The acetone solution was used to remove the Impurities filtered and then evaporated to give Pyrzolotriazole (VI) as a dark brown crystalline powder.

Production Example VII (not according to this Invention)

6-Methyl-3- (2-chlorophenyl) -1H-pyrazolo (5,1-c) (1,2,4) triazole (0.5 g) was dissolved in alkaline water at pH 12 (50 ml). To was stirring N, N-diethyl-p-phenylenediamine (0.5 g) was added. To this mixture was added potassium persulfate (0.2 g) was added, whereupon the solution was dark red. The mixture was stirred for 2 h before the resulting precipitate was collected by filtration. The dark brown precipitate was dried and taken up in acetone again. The acetone solution was filtered to remove impurities and then evaporated, to give pyrazolotriazole (VII) as a dark brown crystalline Powder.

Examples 1 and 2 - staining

example 1

One direct-acting pyrazolotriazole dye (I) (0.01 g) was used in the minimal amount of ethanol (0.5 g) dissolved. The dark magical solution became in a second aqueous solution Benzyl alcohol (0.5 g) and water (9 g) and ammonia adjusted to pH 10. An undamaged white goat hair strand was into the solution at 30 ° C 20 Minutes submerged. Thereafter, the strand was shampooed, rinsed and dried.

Example 2

One direct-acting pyrazolotriazole dye (II) (0.01 g) was dissolved in the minimum amount of ethanol (0.5 g) dissolved. The dark magical solution became in a second aqueous solution Benzyl alcohol (0.5 g) and water (9 g) and ammonia adjusted to pH 10. An undamaged white goat hair strand was into the solution at 30 ° C Dipped for 20 minutes. Thereafter, the strand was shampooed, rinsed and dried.

Comparative Example 1 (not according to this Invention)

A substantive pyrazolotriazole dye (VI) (0.005 g) was dissolved in the minimum amount of ethanol (0.5 g). The dark magenta solution was transferred to a second aqueous solution of benzyl alcohol (0.5 g) and water (9 g) and adjusted to pH 10 with ammonia. An undamaged white goat hair tress was immersed in the solution at 30 ° C for 20 minutes. Thereafter, the strand was shampooed, ge rinses and dried.

Comparative Example 2 (not according to this Invention)

One direct-acting pyrazolotriazole dye (VII) (0.005 g) was dissolved in the minimum amount of ethanol (0.5 g) dissolved. The dark magical solution became in a second aqueous solution Benzyl alcohol (0.5 g) and water (9 g) and ammonia adjusted to pH 10. An undamaged white goat hair strand was into the solution at 30 ° C Dipped for 20 minutes. Thereafter, the strand was shampooed, rinsed and dried.

The Lab values of the resulting stained strands was made by a Minolta color meter measured, and the delta E value, a measure of the chroma is, was on usual Way for each example is calculated (the same applies to all examples below).

The Table 1 shows the results.

Table 1

each Composition of Examples 1 and 2 resulted in a bright vivid Magenta while the Composition of Comparative Examples 1 and 2 only a blunt Color with very faint pink hue.

These Comparative examples show the excellent superiority of substantive Dyes according to this Invention in contrast to the structurally similar substantive dye Comparative Examples 1 and 2.

Examples 3 to 8 - staining

A Base of the following composition was prepared.

Table 2

each Composition was on white goat tresses 15 minutes at 50 ° C applied. Then the strand was shampooed, rinsed and then dried.

table 3 shows the results.

Table 3

each Composition gave a vibrant color with red-pink to magenta shades.

Examples 9 and 10 - Dyeing with hydrogen peroxide

Example 9

One direct-acting pyrazolotriazole dye (I) (0.012 g) was dissolved in the minimum amount of ethanol (0.5 g) dissolved. The dark magical solution became in a second aqueous solution Benzyl alcohol (0.5 g) and water (9 g) and ammonia adjusted to pH 10. To this was added 50% hydrogen peroxide (0.65 g) and the pH adjusted again to 10 with ammonia. A non-damaged white Goat hair strand was in the solution 20 minutes at 30 ° C dipped. After this time, the strand was shampooed, rinsed and then dried.

Example 10

A direct-acting pyrazolotriazole dye (II) (0.01 g) was dissolved in the minimum amount of ethanol (0.5 g). The dark magenta solution was transferred to a second aqueous solution of benzyl alcohol (0.5 g) and water (9 g) and adjusted to pH 10 with ammonia. To this was added 50% hydrogen peroxide (0.65 g) and the pH adjusted again to 10 with ammonia. An undamaged white goat hair tress was immersed in the solution at 30 ° C for 20 minutes. After this time, the strand was shampooed, rinsed and then dried.

table 4 shows the results.

Table 4

each Composition of Example 9 and Example 10 imparted to the hair a bright vibrant magenta color.

Example 11 - Compatibility with the oxidative technology

A Base having the following composition was prepared.

Table 5

Both Compositions were on white goats 15 Minutes was 50 ° C applied. Then the strand was shampooed, rinsed and then dried.

table 6 shows the results.

Table 6

The The composition of Example 11 gave a red-maroon color, while the Composition of Comparative Example 3 a light brown without red Sounds lent.

Examples 12 and 13 - Compatibility with persulfate

A Base having the following composition was prepared.

Table 7

The Compositions 12 and 13 were applied to Chinese black hair tresses and 30 minutes at 50 ° C calmly. After this time, the strand was shampooed, rinsed and then dried.

table 8 shows the results.

Table 8

The The composition of Example 12 gave a bright red color while the Composition of Example 13 lent a vibrant magenta color. Both compositions gave significant bleaching intense red color.

Surprisingly have the direct dyes according to this invention better properties compared to structurally similar ones Links.

The hair dyeing This invention also gives a longer lasting brilliante Color based on the properties of the substantive pyrazolazole dyes against hair washing and environmental influences like exposing to Sunlight, sweat, Rain, etc. compared to conventional direct dyes.

Claims (11)

A hair dye composition comprising, as a direct dye, a direct-pulling pyrazolazole dye represented by the following general formula (1) or a salt thereof:

wherein R ^{1 represents} a hydrogen atom, halogen atom, C _1-5 alkyl group optionally substituted by one or more halogen atoms, hydroxy group (s), alkoxy group (s), aryloxy group (s), amino group (s), alkylamino group ( n), acyl group (s), acylamino group (s) may be substituted; C _1-4 alkoxy group, C _1-4 alkylthio group, arylthio group, benzylthio group, acyl group, acylamino group, acyloxy group, carbamoyl group, phenyl group optionally substituted by one or more halogen atom (s), nitro group (s), sulfonyl group (s), C _1-4 alkyl group (s), C _1-4 alkoxy group (s), C _1-3 trifluoroalkyl group (s), amino group (s) or alkylamino group (s); alkoxycarbonyl; Aryloxycarbonyl, cyano, nitro, dialkylphosphinyl, alkylsulfinyl, arylsulfinyl, sulfamoyl, carboxyl, sulfo, aryloxy, C _1-4 -alkylamino, ureido, sulfamoylamino, sulfonamido, alkoxycarbonylamino, aryloxycarbonylamino, heteroarylthio or phosphonyl; wherein Za, Zb and Zc are each independently a nitrogen atom or carbon atom having a group given above for R ¹ ; and wherein only one of Zb and Zc is the carbon atom, wherein R ² and R ^{3 are} each independently a hydrogen atom or an electron withdrawing group. A hair-dyeing composition according to claim 1, wherein the direct-pulling pyrazolazole dye or the salt thereof is defined by the following general formula (2) or (3) or a salt thereof:

wherein R ¹ and R ^{4 are} independently a hydrogen atom, halogen atom, C _1-5 alkyl group optionally substituted by one or more halogen atom (s), hydroxy group (s), alkoxy group (s), aryloxy group (s), amino group (s), Alkylamino group (s), acyl group (s), acylamino group (s) may be substituted; C _1-4 alkoxy group, C _1-4 alkylthio group, arylthio group, benzylthio group, acyl group, acylamino group, acyloxy group, carbamoyl group, phenyl group optionally substituted by one or more halogen atom (s), nitro group (s), sulfonyl group (s), C _1-4 alkyl group (s), C _1-4 alkoxy groups, C _1-3 trifluoroalkyl group (s), amino group (s) or alkylamino group (s); Alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, dialkylphosphinyl, alkylsulfinyl, arylsulfinyl, sulfamoyl, carboxyl, sulfo, aryloxy, C _1-4 -alkylamino, ureido, sulfamoylamino, sulfonamido, alkoxycarbonylamino, aryloxycarbonylamino, heteroarylthio or phosphonyl; wherein R ² and R ^{3 are} each independently a hydrogen atom or an electron withdrawing group. A hair dye composition according to claim 2, wherein in the general formula (2) or (3), R ¹ and R ^{4 are} independently a hydrogen atom, a C _1-5 alkyl group optionally substituted by one or more hydroxy group (s), alkoxy group (s), Amino group (s) or alkylamino group (s) may be substituted; or a phenyl group which may be optionally substituted by one or more than two halogen atom (s), C _1-4 alkyl group (s), C _1-4 alkoxy group (s), amino group (s) or alkylamino group (s) ; R ² and R ^{3 are} each independently hydrogen, fluorine, chlorine, bromine, iodine, carboxylic acid or C _1-4 alkoxycarbonyl. A hair dye composition according to any one of claims 1-3, wherein the direct dye is represented by the following formulas:

hair dye according to one of the claims 1-4, comprising From 0.001 to 5% by weight of at least one direct-pulling pyrazolazole dye, based on the entire composition. hair dye according to one of the claims 1-5, the further comprising at least one oxidative dye intermediate. hair dye according to one of the claims 1-6, the further comprises at least one peroxide and a pH of about 7.5 to approximately 12.5. hair dye according to claim 7, comprising hydrogen peroxide as peroxide. hair dye according to claim 7, comprising at least one ammonium persulfate, sodium persulfate or potassium persulfate as peroxide. hair dye according to claim 7, comprising both hydrogen peroxide and at least one of ammonium persulfate, sodium persulfate and potassium persulfate as peroxide. Dyeing process of hair with a hair dye composition according to any one of claims 1-10.