WO2000038636A1 - Agent for dying keratin fibers - Google Patents

Agent for dying keratin fibers

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Publication number
WO2000038636A1
WO2000038636A1 PCT/EP1999/009998 EP9909998W WO0038636A1 WO 2000038636 A1 WO2000038636 A1 WO 2000038636A1 EP 9909998 W EP9909998 W EP 9909998W WO 0038636 A1 WO0038636 A1 WO 0038636A1
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WO
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Patent type
Prior art keywords
amino
group
hydroxy
acid
c4
Prior art date
Application number
PCT/EP1999/009998
Other languages
German (de)
French (fr)
Inventor
Hinrich Möller
Doris Oberkobusch
Horst Höffkes
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/10Preparations for permanently dyeing the hair

Abstract

The invention relates to an agent for dying keratin fibers, especially human hair, containing; A) nitroisatins with formula (I), in which R1 represents hydrogen, a C¿1?-C4-alkyl group, C1-C4-alkenyl group, C1-C4-alkoxy group, hydroxy-C1-C4-alkyl group, amino-C1-C4-alkyl group, which can be substituted on the nitrogen, an optionally substituted aryl-C1-C4-alkyl group; R?2 and R3¿ represent hydrogen, halogen, C¿1?-C14-alkyl group, C1-C4-alkenyl group, C1-C4-alkoxy group, hydroxy-C1-C4-alkyl group, a hydroxy group, carboxy group, sulfo group, nitro group or amino group, which can be substituted by one or two C1-C4-alkyl group(s), or a C1-C4-acyl group, whereby two of the radicals, together, can also form a fused, aromatic ring; and B) at least one compound selected from compounds with a primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogenous, heterocyclic compounds, amino acids, oligopeptides constructed from 2 to 9 amino acids and aromatic hydroxy compounds, and/or from CH-active compounds.

Description

"Formulations for coloring keratin-containing fibers"

The present invention relates includes a means for coloring keratin-containing fibers, in particular human hair, the Nitroisatine in combination with oxidation dye precursors, the use of this combination as a coloring in hair dye system and a method for dyeing keratinous fibers, in particular human hair.

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

The developer components primary aromatic amines are commonly used with another in the para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-AminopyrazoIonderivate and 2,4,5,6-tetraaminopyrimidine and derivatives thereof.

Special representatives are, for example, p-phenylenediamine, p-toluylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5 -Diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) -ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2-amino-methyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine. The secondary intermediates used are generally m-phenylenediamine derivatives, thole naphthalene, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives. As coupler substances are in particular α-naphthol, 1, 5-, 2,7-, and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol suitable , 2-amino-4- (2-hydroxyethylamino) - anisole (Lehmann Blue), 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-amino-phenol, 1, 3-bis ( 2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino-pyridin and 3,5-diamino-2,6-dimethoxy.

With regard to further customary dye components, is made expressly to the series "Dermatology", edited by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, Cape. 7, pages 248-250 (Direct dyes), and chapter. 8, pages 264-267 (oxidation dyes), and the "European Inventory of Cosmetic Raw Materials", 1996, published by the European Commission, available in diskette form by the Federal Association of German Industries and Trading Firms for pharmaceuticals, health products and personal care products, Mannheim, reference is made ,

With oxidation dyes intensive colors with good fastness properties can indeed be achieved, however, the development of color is generally under the influence of oxidizing agents such. As H 2 O 2, which may in some cases damage to the fibers. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can occasionally have a sensitizing effect in people with sensitive skin. Direct dyes are applied under more conditions, but their disadvantage is that the colors often have inadequate fastness properties. From the prior art the use of isatin in combination with oxidation dye precursors is known. In the European patent application 497,697 a process for dyeing keratin-containing fibers is described, a combination of isatin and indole derivatives is used wherein as the coloring component.

In European patent applications 502 783 and 502 784 processes are described for coloring keratin fibers, which are used as coloring components in each case a combination of isatin and pyridine derivatives or aniline derivatives.

In the international patent application WO94 / 24988 Formulations for coloring keratin-containing fibers are disclosed as a coloring component isatin or any derivative according to the illustrated general formula in combination with certain primary aliphatic amines, heterocyclic aromatic compounds, aromatic carboxylic and sulfonic acids, aniline derivatives, Dianilinderivaten or amino sugars included. The use of the Nitroisatine described in more detail below in combination with oxidation dye precursors for coloring keratin-containing fibers is not described explicitly.

Object of the present invention is to provide colorants for keratin fibers, especially human hair, which the conventional oxidation are at least equivalent in terms of color depth, the gray coverage and fastness properties qualitatively, without necessarily to oxidants such. As H 2 0 2 to be instructed. In addition, the colorants must have no or only a very low sensitization potential. Surprisingly, it has now been found that a combination of those shown in the formula I and oxidation dye precursors Nitroisatinen particularly highly suitable for dyeing keratin fibers and in the absence of oxidizing agents. They give colorations with excellent brilliance and depth and lead to various shades. However, the use of oxidizing agents should not be ruled out in principle. Furthermore, the colorations compared with the unsubstituted isatin are much more intense was found.

The invention relates to an agent for coloring keratin fibers, in particular human hair, comprising A) Nitroisatine of the formula I,

alkyl group in which R 1 represents hydrogen, a C 4 alkyl group, C 1 -C 4 -alkenyl, CC 4 -alkoxy, hydroxy-C C4, amino-C C 4 - alkyl group which may be substituted on the nitrogen, a optionally substituted AryI C-C 4 alkyl group, R 2 and R 3 is hydrogen, halogen, CrC ^ alkyl group, C r C 4 alkenyl group, CC 4 -alkoxy, hydroxy-C 1 -C 4 alkyl, a hydroxy, carboxy, sulfo, nitro or amino group which may be substituted by one or two C 1 -C 4 alkyl group (s) or a C-O, - acyl group, where two of the radicals can form a fused aromatic ring together, and B) at least one compound selected from compounds having primary or secondary amino group or hydroxy group chosen from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, constructed from 2 to 9 amino acids in oligopeptides and aromatic Hydraulic oxy compounds, and / or CH-active compounds.

Keratin fibers wool, furs, feathers and in particular human hair to understand. The colorants according to the invention can in principle also for dyeing other natural fibers such. As cotton, jute, sisal, linen or silk, modified natural fibers such. B. regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such. As polyacrylonitrile, polyurethane and polyester fibers are used.

Preferably, the compounds of formula I are selected from the group of the following Nitroisatine: 5-nitroisatin, 1-methyl-5-nitroisatin, 1-benzyl-5-nitroisatin, 1- (4-chlorobenzyl) -5-nitroisatin, 7-chloro -5-nitroisatin, 5-chloro-7-nitroisatin, 5-bromo-5-nitroisatin, 5-methoxy-7-nitroisatin, 5,7-Dinitroisatin, 6- nitroisatin, and any mixtures thereof.

These substances are known from the literature or commercially available.

The compounds of component B are one hand, compounds which stain only weakly on its own keratin fibers and will result, together with the Nitroisatinen of formula I brilliant colorations. On the other hand are including compounds that are already being used as oxidation dye precursors.

The Nitroisatine mentioned above having formula I and the compounds of component B are preferably used in the inventive compositions each in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant. Dyes containing as coloring component a combination of Nitroisatinen of formula I and the compounds of component B are preferred maroon for dyeings in shades ranging from brown-red, brown orange, dark brown, dark violet, blue violet to use black.

In all colorants several different Nitroisatine of formula I can work in conjunction; Likewise, several different compounds of component B may be used together. Among the object of the present invention also provides the use of such substances, the reaction products of Nitroisatinen of formula I with the above-mentioned compounds of the component B falls represent, as substantive colorant.

Suitable compounds having primary or secondary amino group as component B z. , Primary aromatic amines such as N, N-dimethyl, N, N-diethyl-, N- (2-hydroxyethyl) -N-ethyl-, N, N-bis (2-hydroxyethyl) -, N- (2 -Methoxye- thyl-), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, 2-amino nomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-Phenylendia- min, o-toluene diamine, 2,5-diaminotoluene, -phenol, -phenethol, 4-amino-3-me- thylphenol, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 4-methylamino-, 3-amino-4 - (2'-hydroxyethyloxy) -, 3,4-Methylendiamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4-methylamino-, 2-methyl-5-amino-, 3-methyl -4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 6-methyl-3-amino-2-chloro-, 2-methyl-5-amino-4-chloro-, 3,4-methylenedioxy -, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-hydroxymethylphenol, 1, 3- diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, - phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxy-benzoic acid, 2-, 3-, 4- aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4- amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthenic thoesäure, 3-aminophthalic acid, 5-aminoisophthalic acid, 1 3,5, 1 2,4-triamino benzene, 1, 2 , 4,5-tetraaminobenzene, 2,4,5-Triaminophenol, Pentaaminobenzol, Hexaaminobenzol, 2,4,6-Triaminoresorcin, 4,5-Diaminobrenzcatechin, 4,6-diamino nopyrogallol, 3,5-diamino-4-hydroxybrenzcatechin , aromatic nitriles, anilines, in particular nitro group-containing anilines, such as 4-nitroaniline, 4-nitro-1, 3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) -benzene, 2-nitro-1 -Ami--4- [bis (2-hydroxyethyl) -amino] -benzene, 4-amino-2-nitrodiphenylamine-2'-car- bonsäure, 2-amino-6-chloro-4-nitrophenol, 1 - amino-5-chloro-4- (2 hydrogencarbonates droyethylamino) -2-nitrobenzene, 4-amino-4 '- [bis- (2-hydroxyethyl) amino] - azobenzene, aromatic anilines or phenols with a further aromatic radical as shown in Formula II

in which R 4 is a hydroxy or an amino group which droxyalkyl- by C ^ alkyl, C 1-4 hydrogencarbonates, C ^^ C ^ AIkoxy- or alkoxy-C ^ alkyl groups may be substituted, .

R 4, R 6, R 7, R 8 and R 9 is hydrogen, a hydroxy or an amino group represented by

C ^ alkyl, C ^^ hydroxyalkyl, C ^^ AIkoxy-, C ^^ aminoalkyl or C ^ -alkoxy-O, ^ - alkyl groups may be substituted, stand, and

X is a direct bond, a saturated or unsaturated, optionally by

Hydroxy-substituted carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group of the formula III Z- (CH 2 -Y-CH 2 -Z ') 0 (III)

in which Y is a direct bond, a CH 2 - or CHOH group,

Z and Z 'independently represent an oxygen atom, an NR 10 - group, wherein R 10 is hydrogen, C ^ alkyl or a hydroxy-C ,.4 - alkyl group, the group O- (CH 2) p -NH or NH- (CH 2) p '-O where p and p' are 2 or 3, and are o is a number from 1 to 4, such as dimethylaminostilben for example, 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, mono- or di-Na salt, 4-amino-4'and its hydrochloride, 4 , 4'-diaminodiphenylmethane, - sulfide, sulfoxide, -amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, 3,3 ', 4,4'-Tetraaminodiphenyl, 3, 3 ', 4,4'-tetraamino-benzophenone, 1, 3-bis (2,4-diaminophenoxy) propane, 1, 8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane, 1, 3-bis (4-aminophenylamino) propane, -2-propanol, 1 3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis [2- ( 4-aminophenoxy) ethyl] methylamine, N-phenyl-1, 4-phenylenediamine.

The abovementioned compounds may exist in free form and in the form of their physiologically acceptable salts, especially salts of inorganic acids such as hydrochloric or sulfuric acid, are used.

Suitable nitrogen-containing heterocyclic compounds are, for. B. 2-, 3-, 4- amino-, 2-amino-3-hydroxy-, 2,6-diamino-, 2,5-diamino-, 2,3-diamino-, 2-dimethylamino-5-amino -, 2-methylamino-3-amino-6-methoxy-, 2,3-diamino-6-methoxy-, 2,6-dimethoxy-3,5-diamino-, 2,4,5-triamino-2, 6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino-, 4,5,6-triamino-4-hydroxy-2,5,6-triamino-2-hydroxy-4 , 5,6-triamino, 2,4,5,6-tetraamino, 2-methylamino-4,5,6-triamino, 2,4-, 4,5-diamino-, 2-amino-4- methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, -1, 2,4-triazole, 3-amino-, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-aminobenzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. The abovementioned compounds may exist in free form and in the form of their physiologically acceptable salts, for. B. be used as salts of inorganic acids such as hydrochloric or sulfuric acid.

Suitable aromatic hydroxy compounds are, for. B. 2-, 4-, 5-methylresorcinol, 2,5 dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol; hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-Trihy- droxybenzoesäure, -acetophenone, 2-, 4-chlororesorcinol , 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

As a CH-active compounds can be exemplified 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1, 2,3,3-tetramethyl -3H-indolium methanesulfonate, Fischer's base (1, 3,3-trimethyl-2-methyleneindoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl benzothiazolium-p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid , 1-methyl-2-quinaldinium iodide, 1-ethyl-2-quinaldinium iodide, 1, 4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1, 3-Dimethylthiobarbitursäure, 1, 3-diethylthiobarbituric acid, diethylthiobarbituric acid, oxindole , 3-lndoxylacetat, coumaranone and 1-methyl-3-phenyl-2-pyrazoiinon.

As amino acids, preferably all naturally occurring and synthetic α-amino acids are suitable, for example. B. obtained by hydrolysis from vegetable or animal proteins, eg. As collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein, accessible amino acids. This case, both acidic and alkaline amino acids einge- sets are. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan. But other amino acids such. B. 6-aminocaproic acid can be used.

The oligopeptides can thereby be naturally occurring or synthetic oligopeptides, but also the oligopeptides present in polypeptide or protein, provided they have one for use in the inventive colorants sufficient water solubility. As examples z. to name as glutathione and the oligopeptides present in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. this means, containing the compounds of the formula I together with compounds with a primary or secondary amino group or with aromatic hydroxy compounds are preferred.

The compounds of component B are especially preferably selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phe nylendiamin, N, N-bis (2-hydroxyethyl) -p- phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diaminophenyl) -ethanol, 2,5-diaminotoluene, 3,4-Me thylendioxyanilin, 2-amino-4- (2-hydroxyethylamino) -anisole, 2- (2,4

Diaminophenoxy) ethanol, 3-amino-2,4-dichloro-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl -5-amino-4-chloro-, 6-methyl-3-amino-2-chloro-, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 3,4-MethylendioxyphenoI, 3.4 -Diaminobenzoesäure, 2,5-diamino-, 2-dimethylamino-5-amino-, 3-amino-2-methylamino-6-methoxy-, 2,3-diamino-6-me thoxy-, 3.5 diamino-2,6-dimethoxy-, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-4-hydroxy-2,5,6-triamino, 2, 4,5,6-tetraamino, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxy-pyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline and their formed with inorganic acids preferably physiologically tolerable salts. In the presence of oxidants such. B. H 2 O 2l can be dispensed with. However, it may u. U. be desirable, the agents of the invention for achieving the nuances that are lighter than the keratin-containing fibers to be dyed, to add hydrogen peroxide or other oxidizing agents. Oxidizing agents are generally used in an amount of 0.01 to 6 wt .-%, based on the application solution. A preferred for human hair oxidant is H 2 O 2.

In a preferred embodiment, the colorants according to the invention to further modify the color nuance additionally contain customary direct dyes in addition to the compounds according to the invention contained, z. B. from the group of nitrophenylendiamines, Nitroaminophenole, anthraquinones or Indophenole such. As known under the International names or commercial names of HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 and also picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphe - nylamin-2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1, 4-bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride and 1 -methyl- 3-nitro-4- (2'-hydroxyethyl) aminobenzene. The agents of the invention according to this embodiment contain the dyes preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant.

The preparations according to the invention can be black included, chamomile blossom, sandalwood, black tea, buckthorn bark, sage, logwood, madder root, catechu, cedar and alkanet also contain naturally occurring dyes such as henna red, henna neutral, henna. It is not necessary that the oxidation dye precursors or the substantive dyes optionally present to be single compounds. Rather, other components can be used in the inventive dyes, due to the manufacturing processes for the individual dyes, in small quantities to be included to the extent they do not adversely affect the coloring result or for other reasons such. B. toxicological must be excluded.

The colorants according to the invention already provide intense colorations even at physiologically compatible temperatures of less than 45 ° C. They are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants may be typically incorporated into an aqueous cosmetic carrier. Suitable water-containing cosmetic carriers are, for. For example, creams, emulsions, gels or even surfactant such. As shampoos or other preparations which are suitable for use on keratin fibers. it is also possible if necessary to incorporate the colorants into anhydrous carriers.

The colorants of the invention can include all known in such preparations active ingredients, additives and auxiliaries. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases it has proved advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Anionic surfactants suitable for use on the human body anionic surfactants are present in inventive preparations. These are characterized by a water solubilizing anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having approximately 10 to 22 C-atoms. In addition polyglycol ether groups, ester, ether and amide groups and also hydroxyl groups may be contained in the molecule or glycol. Examples of suitable anionic surfactants, each in the form of sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group:

linear fatty acids having 10 to 22 carbon atoms (soaps),

Ether carboxylic acids of formula R-0- (CH 2 -CH 2 O) x -CH 2 -COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 16, acyl sarcosides having 10 to 18 carbon atoms in the acyl group, acyl taurides having 10 to 18 carbon atoms in the acyl group, acyl isethionates containing 10 to 18 carbon atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates having 12 to 18 C atoms, linear alpha-olefin sulfonates containing 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 12 to 18 carbon atoms , alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH 2 -CH 2 0) x - SO 3 H, = in which R is a preferably linear alkyl group having 10 to 18 carbon atoms and x is 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or Hydroxyalkylenpropylenglykol- ether according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Represent ester of tartaric acid and citric acid with alcohols which are addition products of around 2 to 15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon 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 surface-active compounds which have in the molecule at least one quaternary ammonium group and at least one -COO () - Wear 3 () group or -SO. Particularly suitable zwitterionic surfactants are the betaines such as N-alkyl-N, N-di- methyl ammonium glycinates, for example cocoalkyl dimethylammonium, N-acyl-aminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines glycinate each having 8 to 18 carbon atoms in the alkyl or acyl group as well as the Kokosacylaminoethylhydroxyethylcarboxymethyl-. A preferred zwitterionic surfactant is known under the CTFA name Cocamidopropyl Betaine fatty acid amide derivative.

Ampholytic surfactants are surface-active compounds which, apart from a C. 8 18 alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -S0 3 H group and are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylamino butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylg- lycine, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkyl aminoacetic acids with in each case about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl aminopropionate the, cocoacylaminoethyl aminopropionate and C 12-18 - sarcosine. Non-ionic surfactants contain as hydrophilic group, for. B. lyglykolethergruppe a polyol group, a polyalkylene glycol ether group or a combination of polyol and Po. Such compounds are for example

Addition products of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, onto fatty acids having 12 to 22 carbon atoms and onto alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C 12 _ 22 fatty acid monoesters and diesters of addition products of 1 to 30 mol ethylene oxide onto glycerol,

C. 8 22 -AlkyImono- mono- and oligoglycosides and ethoxylated analogs thereof, addition products of 5 to 60 mol ethylene oxide onto castor oil and hydrogenated castor oil,

Addition products of ethylene oxide with sorbitan addition products of ethylene oxide with fatty acid.

Examples of the usable in the inventive hair treatment compositions cationic surfactants are especially quaternary ammonium compounds. Ammonium are preferred such as alkyl, dialkyl and trialkyl such. As cetyltrimethylammonium chloride, stearyltrimethylammonium, Distea- ryldimethylammoniumchlorid, lauryl, lauryl dimethyl benzyl ammonium chloride and tricetylmethylammonium chloride. Further inventively usable cationic surfactants are the quaternized protein hydrolysates.

According to the invention are also suitable cationic silicone oils such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone which thicone as Amodime- hereinafter) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquatemäre polydimethylsiloxanes, quaternium-80.).

Alkylamidoamine, particularly fatty acid as the stearylamidopropyldimethylamine obtainable under the name Tego Amid ® S 18, are distinguished by a good conditioning effect particularly by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as the methyl hydroxyalkyl marketed under the trademark Stepantex ®.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercially available product Glucquat ® 100 is, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

When used as surfactants compounds with alkyl groups may be single compounds. However, it is generally preferred to proceed in the preparation of these substances from native vegetable or animal raw materials so that substance mixtures with different alkyl chain lengths dependent upon the particular raw material.

The surfactants which are addition products of ethylene and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products having a "normal" homologue distribution or those may be used with a narrow homolog distribution. "Normal" homologue distribution are mixtures of homologues are understood to be obtained as catalysts in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali. Narrowed homolog distributions are obtained, however, if hydrotalcite, alkaline earth salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution may be preferred.

Other active substances, auxiliaries and additives are, for example, nonionic polymers such as VinylpyrrolidonΛ / inylacrylat copolymers, polyvinylpyrrolidone and VinylpyrrolidonΛ / inylacetat copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes having quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide -Dimethyldiallylammoniumchlorid copolymers with diethyl square ternierte dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers,

Imidazoliniummethochlorid vinylpyrrolidone copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as Acrylamidopro- propyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-Hydroxypropylmeth- acrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, men Leinsamengum-, dextrans, cellulose derivatives, eg. For example, methyl cellulose, Hydroxyalkylcellu- loose and carboxymethyl cellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as. For example, bentonite or fully synthetic hydrocolloids such. Polyvinyl alcohol, structurants, such as glucose and maleic acid, hair-conditioning compounds, such as phospholipids, for example solar jalecithin, egg lecithin and cephalins, and silicone oils,

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein, their condensation products with fatty acids and quaternized protein hydrolysates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizing agents such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,

Antidandruff active ingredients such as piroctone olamine and zinc Omadine, further substances for adjusting the pH,

acids active ingredients such as panthenol, pantothenic acid, allantoin, Pyrrolidoncarbon- and salts thereof, plant extracts and vitamins, cholesterol, light stabilizers,

Thickeners like Zuckerester, polyol esters or polyol alkyl ethers, fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid ester, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA and phosphonic acids, swelling and penetration substances, such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, opacifiers, such as latex,

Pearlizing agents such as ethylene glycol mono- and distearate, propellents, such as propane-butane mixtures, N 2 O, dimethyl ether, CO2 and air and antioxidants.

The components of the water-containing carrier are used for the preparation of the colorants according to the invention in amounts customary for this purpose; z. Emulsifiers are used in concentrations of 0.5 to 30 wt .-%, and thickeners in concentrations of from 0.1 to 25 wt .-% of the total colorant.

For the coloring result, it may be advantageous to add the colorants ammonium or metal salts. Suitable metal salts are, for. B. formates, carbonates, halides, sulfates, butyrates, valerates, caproates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals such as potassium, sodium or lithium, alkaline earth metals such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate are preferred. These salts are preferably present in an amount of 0.03 to 65, particularly 1 to 40 mmol based on 100 g of the colorant as a whole.

The pH of the ready to use dyeing preparations is usually from 2 to 11, preferably 5 to 9

Another object of the present invention relates to the use of A) one or more Nitroisatinen of the formula I,

in which R 1 is hydrogen, a C r C 4 alkyl, C 1 -C 4 alkenyl, C ϊ -C AIkoxygruppe, hydroxy-C C4-alkyl, amino-C, -. C 4 - alkyl group which may be substituted on the nitrogen, alkyl an optionally substituted aryl-C 1 -C 4, R 2 and R 3 is hydrogen, halogen, C r C 4 alkyl group, C r C 4

Alkenyl group, C 1 -C 4 alkoxy, hydroxy-C 1 -C 4 alkyl, hydroxy, carboxy, sulfo, nitro or amino group which may be substituted by one or two C 4 alkyl group (s) or C ^ C ^ -acyl group are, where two of the radicals can form a fused aromatic ring together, in combination with

B) at least one compound selected from compounds having primary or secondary amino group or hydroxy group chosen from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, constructed from 2 to 9 amino acids in oligopeptides and aromatic hydroxy compounds and / or CH-active compounds as a coloring component in hair colorants.

Yet another object of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, in which a colorant containing A) at least one nitroisatin with the formula I,

in which R 1 represents hydrogen, a C 4 alkyl group, C r C 4 -alkenyl, CC 4 -alkoxy, hydroxy-C C4-alkyl, amino-C, - ^ - alkyl group which may be substituted on the nitrogen, a alkyl optionally substituted aryl-C r C 4, R 2 and R 3 is hydrogen, halogen, CC 4 alkyl group, CC 4 alkenyl group, C r C 4 alkoxy group, hydroxy-C C 4 alkyl group, a hydroxy, carboxy, sulfo, nitro or amino group which may be substituted by one or two C 1 -C 4 alkyl group (s), or a C 4 - acyl group, where two of the radicals together form a fused- can form aromatic ring and B) at least one compound selected from compounds having primary or secondary amino group or hydroxy group chosen from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, constructed from 2 to 9 amino acids and oligopeptides aromatic Hydrox yverbindungen, and / or CH-active compounds, and customary cosmetic ingredients, is applied to the keratin-containing fibers, for some time, usually about 30 minutes, it is left on the fibers and then rinsed out again or washed out with a shampoo.

The Nitroisatine of formula I and the compounds of component B can either be applied simultaneously to the hair or else one after the other, it being immaterial which of the two components applied first. The ammonium or metal salts optionally present can thereby be added to the first or the second component. may be an interval of up to 30 minutes between the application of the first and the second component. Also, a pretreatment of the fibers with the salt solution is possible.

The Nitroisatine of formula I and the compounds of component B may be either separately or stored together, either (anhydrous or aqueous) in a liquid to paste-like preparation or as a dry powder. If the components are stored together in a liquid preparation, they should be substantially anhydrous in order to reduce reaction of the components. In the separate storage of the reactive components are intimately mixed with one another only immediately before use. In the dry storage, a defined amount of hot (from 30 to 80 ° C) water is usually added prior to the application and a homogeneous mixture prepared.

Examples

Preparing a staining solution

It ever B and 5 mmol of sodium acetate and one drop of a 20% fatty alkyl ether sulfate solution in 50 ml of water at 60 ° C a slurry of 5 mmol nitroisatin with the formula I, 5 mmol of a Oxidationsfarbstoffvorprodukt.es the component. The Aufschiämmungen were mixed at 30 ° C and adjusted to have a pH of 6 with dilute sodium hydroxide solution or hydrochloric acid.

In this dye solution, a strand of 90% non-pretreated human hair graying was at 30 ° C for 30 minutes, is introduced. The tress was then 30 sec. Rinsed with lukewarm water, dried with hot air and then combed.

The respective color shades and color depths are given in the Table 1 below.

The color depth was it rated on the following scale:

no or a very pale coloration

(+) Weak intensity

+ Average intensity

+ (+) Moderate to severe intensity

++ strong intensity

strong ++ (+) to very strong intensity

+++ very strong intensity Sheetl

Colorations with 5-nitroisatin

Colorations with 6-nitroisatin

Colorations with 5.7-Dinitroisatin

Claims

Patentansprüche1. Formulations for coloring keratin-containing fibers, especially human hair, containing as coloring component A) Nitroisatine of the formula I, in which R 1 is hydrogen, C C4 alkyl, C C4-alkenyl, C ^ C ^ alkoxy, hydroxy-C1 -C4 alkyl group, amino-C C4-alkyl group which may be substituted on the nitrogen, an optionally substituted aryl-C C4-alkyl group, are, R2 and R3 is hydrogen, halogen, CRC-4 alkyl group, C C4 alkenyl, C C4 alkoxy, hydroxy-C, -C 4 alkyl group, a hydroxy, carboxy, sulfo, nitro or amino group which may be substituted by one or two C-C4 alkyl group (s), or a C ^ C ^ acyl group are, where two of the radicals can form a fused aromatic ring together, and B) at least one compound selected from compounds having primary or secondary amino group or hydroxy group chosen from primary or secondary aliphatic or aromatic amines, nitrogen-containing n heterocyclic compounds, amino acids, constructed from 2 to 9 amino acids and oligopeptides aromatic hydroxy compounds and / or CH-active compounds. 2. Composition according to claim 1, characterized in that as compounds of the formula I 5-nitroisatin, 1-methyl-5-nitroisatin, 1-benzyl-5-nitroisatin, 1- (4-chlorobenzyl) -5-nitroisatin, 7 -chloro-5-nitroisatin, 5-chloro-7-nitroisatin, 5-bromo-5-nitroisatin, 5-methoxy-7-nitroisatin, 5,7-Dinitroisatin, 6-nitroisatin, and any mixtures thereof werden.3 used. Agent according to one of claims 1 to 2, characterized in that the Nitroisatine of formula I and the compounds of component B are each in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total dyeing agent sind.4. Agent according to one of claims 1 to 3, daurch in that the compounds of component B are selected from primary or secondary amines from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, N- (2-methoxyethyl -), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2 , 5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4- aminophenol, o-, m-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) -ethanol, 2 , 5-diaminotoluene, -phenol, -phenethol, 4-methylamino-, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-Methylendiamino-, 3,4-methylenedioxyaniline, 3-amino-2,4 dichloro, 4-methylamino-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4- chloro-, 6-methyl-3-amino-2-chloro-, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-aminomethyl-phenol, 4-amino-2-hydroxymethyl phenol, 1, 3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4- aminobenzoic acid, -phenylessigs äure, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-dia- minobenzoesäure, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino- 3-hydroxy-benzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7- amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5-, 1, 2 , 4-triaminobenzene, 1, 2,4,5-tetraaminobenzene tetrahydrochloride, 2,4,5-triamino-phenol trihydrochloride, Pentaaminobenzol-penta hydrochloride, Hexaaminobenzol-hexahydrochlorid, 2,4,6-Triaminoresorcin trihydrochloride, 4.5 -Diaminobrenzcatechinsulfat, 4,6-Diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxybrenzcatechin sulfate, aromatic nitriles, anilines, in particular nitro group-containing anilines, such as 4-nitroaniline, 4-nitro-1, 3- phenylenediamine, 2 -nitro-4-amino-1- (2-hydroxyethylamino) -benzene, 2-nitro-1-amino-4- [bis- (2 hydroxyethyl) -amino] -benzene, 4-amino-2-nitrodiphenylamine 2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino-5-chloro-4- (2- hydroyethylamino) - 2-nitrobenzoI, 4-amino-4 '- [bis- (2-hydroxyethyl) amino] - azobenzene, aromatic anilines or phenols with a further aromatic radical, such as 4,4'-diaminostilbene dihydrochloride, 4,4'- Diaminostil- ben-2,2'-disulfonic acid, Na salt, 4,4'-diaminodiphenylmethane, sulfide, - sulfoxide, -amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, benzophenone, 4,4'-diamino- , diphenyl ether, 3,3 \ 4,4'-Tetraaminodiphenyl tetrahydrochloride, 3,3 ', 4,4'-tetraamino-benzophenone, 1, 3-bis (2,4-diaminophenoxy) -propane tetrahydrochloride, 1 , 8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane-tetrahydro- chloride, 1, 3-bis- (4-aminophenylamino) -propane, -2-propanol, 1, 3-bis [N - (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis [2- (4-aminophen- oxy) -ethyl] methylamine trihydrochloride, nitrogen-containing heterocyclic compounds selected from the group consisting of 2 -, 3-, 4-Am ino-, 2-amino-3-hydroxy-, 2,6-diamino-, 2,5-diamino-, 2,3-diamino-, 2-dimethylamino-5-amino-, 3-amino-2-methylamino 6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethacrylate oxy, 2,4,5-triamino-2,6-dihydroxy-3,4- dimethylpyridine, 4,5,6-triamino, 2-hydroxy-4,5,6-triamino-4-hydroxy-2,5,6-triamino, 2,4,5,6-tetraamino, 2- methylamino-4,5,6-triamino, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-me- thyl-pyrimidine, 2,3,4-trimethylpyrrole, 2,4 dimethyl-3-ethyl-pyrrol, 3,5-diamino pyrazole, -1, 2,4-triazole, 3-amino-, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4 -amino-quinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, thiazole -benzo, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 4-, 5-, 6-, 7-hydroxyindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, and in each case from the with preferably inorganic acids formed physiologically acceptable salts di eser compounds, aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxy benzoic acid, - acetophenone, 2-, 4-chlororesorcinol, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2 , naphthalenesulfonic acid 7-, and CH-active compounds selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, Fischer's base (1, 3,3-trimethyl-2-methyleneindoline), 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl benzothiazolium-p-toluenesulfonate, rhodanine, rhodanine-3-es- sigsäure, 1-methyl- 2-quinaldinium iodide, 1-ethyl-2-quinaldinium iodide, 1, 4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, thiobarbituric acid, 1, 3-dimethyl-1, 3-diethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-lndoxylacetat, coumaranone and 1-methyl-3-phenyl-2-pyrazolinon.5. Composition according to claim 4, characterized in that the compounds of component B are selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis (2- hydroxyethyl) - p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-Diaminophe- nyl) ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 2-amino-4- (2- hydroxyethylamino) -anisole, 2- (2,4-diaminophenoxy) ethanol, 3-amino-2,4-dichloro-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl- 5- (2-hydro- xyethylamino) -, 2-methyl-5-amino-4-chloro-, 6-methyl-3-amino-2-chloro-, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4 aminophenol, 3,4-methylene lendioxyphenol, 3,4-diaminobenzoic acid, 2,5-diamino-, 2-dimethylamino-5-amino-, 3-amino-2-methylamino-6-methoxy-, 2,3- diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-4-hydroxy-2 , 5,6-triamino, 2,4,5,6-tetraamino, 2-methylamino 4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyr azole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline and in each case from the formed preferably with inorganic acids physiologically acceptable salts of these Verbindungen.6. Agent according to one of claims 1 to 5, characterized in that it aminophenols direct dyes from the group of nitrophenylenediamines, nitro, anthraquinones or indophenols, preferably all the in an amount of 0.01 to 20 wt .-%, based dye, enthält.7. Agent according to one of claims 1 to 6, characterized in that ammonium or metal salts selected from the group of formates, carbonates, halides, sulfates, butyrates, valerates, caproates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates , phosphates and phosphonates of alkali metals such as potassium, sodium or lithium, alkaline earth metals such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc admit werden.8. Agent according to one of claims 1 to 7, characterized in that it contains oxidizing agents, in particular H2O2, in an amount of 0.01 to 6 wt .-%, based on the application solution. 9. A composition according to any one of claims 1 to 8, characterized in that it contains anionic, zwitterionic or nonionic surfactants enthält.10. Use of a combination of A) Nitroisatinen of the formula I in which R1 represents hydrogen, a CRC-4 alkyl group, CROT alkenyl group, C | -C4-alkoxy, hydroxy-CRC4 alkyl group, amino-CRC4 alkyl group substituted on the nitrogen may be an optionally substituted aryl-C C4-alkyl group, are, R2 and R3 is hydrogen, halogen, CRC-4 alkyl group, alkenyl group CRC4, CRC-4 alkoxy, hydroxy-C C4-alkyl group, a hydroxy, carboxy, sulfo -, nitro or amino group by one or two C-C4 alkyl group (s) may be substituted or a CRC-4 acyl group, where two of the radicals can form a fused aromatic ring together, and B) selected at least one compound built up from compounds containing a primary or secondary amino group or hydroxy group chosen from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, from 2 to 9 amino acids n oligopeptides and aromatic hydroxy compounds and / or CH-active compounds, as a coloring component in hair colorants.
1. A method for dyeing keratinous fibers, especially human hair, in which a colorant containing A) Nitroisatine of the formula I,
in which R 1 is hydrogen, a C, -C 4 alkyl, C, -C 4 -alkenyl, CC 4 -alkoxy, hydroxy-C ^ C ^ alkyl, amino-C r C 4 - alkyl group substituted on the nitrogen may be an optionally substituted aryl-C ^ C ^ alkyl group, R 2 and R 3 is hydrogen, halogen, CC -AIkylgruppe 4, C r C 4 - alkenyl group, CC 4 -alkoxy, hydroxy-C, -C 4 -alkyIgruppe, hydroxy, carboxy, sulfo, nitro or amino group which may be substituted by one or two C 1 -C 4 alkyl group (s), or a C, -C, 4 are also acyl group wherein two of the radicals together form a fused aromatic ring and B) at least one compound with a primary or secondary amino group or hydroxy group chosen from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, constructed from 2 to 9 amino acids in oligopeptides and aromatic hydroxy compounds, and / or minimum ens a CH-active compound, and customary cosmetic ingredients, is applied to the keratin-containing fibers, for some time, usually about 30 minutes, it is left on the fibers and then rinsed out again or washed out with a shampoo.
PCT/EP1999/009998 1998-12-23 1999-12-16 Agent for dying keratin fibers WO2000038636A1 (en)

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