EP1083869A1

EP1083869A1 - Colorants containing 4-amino-2( (diethylamino) methyl)phenol and their use for coloring keratin fibers

Info

Publication number: EP1083869A1
Application number: EP00922573A
Authority: EP
Inventors: Horst Höffkes; Doris Oberkobusch; Melanie Hitz
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1999-04-09
Filing date: 2000-03-30
Publication date: 2001-03-21
Also published as: WO2000061087A1; DE19916029A1; AU4291700A

Abstract

The invention relates to agents for coloring fibers containing keratin. Said agents contain 4-amino-2-((diethylamino)methyl)phenol as the developer component and 2-amino-3-hydroxypyridin as the coupler component. The inventive agents produce coloring results that are characterised by excellent light- and shampoo-fastness, especially in the yellow-orange range.

Description

4-Amino-2 ((DIETHYLAMINO) METHYL) PHENOL CONTAINING COLORANTS AND THEIR USAGE _¬ DUNG FOR DYING KERATIN FIBERS

The present invention relates to colorants which contain 4-amino-2- ((diethylamino) methyl) phenol in combination with 2-amino-3-hydroxypyridine as a coupler component and their use for dyeing keratin fibers.

For the coloring of keratin fibers, especially human hair, the so-called oxidation coloring agents play a preferred role because of their intense colors and good fastness properties. Such colorants contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with one or more coupler components.

Good oxidation dye products should meet the following requirements in the first place: They must develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. They must also have a good ability to draw onto the fiber, whereby there must be no noticeable differences between stressed and freshly regrown hair, especially with human hair (leveling ability). After all, if they are used as a hair dye, they should not stain the scalp too much, and above all they should be harmless from a toxicological and dermatological point of view.

Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and their derivatives are usually used as developer components .

Special representatives are, for example, p-phenylenediamine, p-toluenediamine, 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-aminopyrazolon-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2 -Hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis- (2nd '-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) diamino-propan-2-ol.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components. 1-Naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomino methyl ether, m-phenylenediamine, l-phenyl are particularly suitable as coupler substances -3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl -3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

With a developer component or a special coupler / developer combination alone, it is usually not possible to obtain a color shade that looks natural on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. There is therefore a constant need for new, improved dye combinations. The dyeings that can be achieved by the dye combinations should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. Perm fluids. Furthermore, the coloration obtained should be easily removed from the hair again by bleaching, if it does not correspond to the individual wishes of the individual and should be reversed. Therefore, there was still the task of developing new developer-coupler combinations with which expressive, brilliant shades, especially in the yellow-orange range, can be achieved and which are also a step ahead of the state of the art in toxicological terms.

Surprisingly, it has now been found that the developer-coupler combinations 4-amino-2 - ((diethylamino) methyl) phenol / 2-amino-3-hydroxypyridine fulfill the tasks placed on such combinations to a high degree. The present invention therefore relates to compositions for dyeing keratin fibers which contain 4-amino-2 - ((diethylamino) methyl) phenol as the developer component and 2-amino-3-hydroxypyridine as the coupler component.

According to the invention, keratin fibers are to be understood as furs, wool, feathers and in particular human hair. Although the colorants according to the invention are primarily suitable for dyeing keratin fibers, there is in principle nothing to prevent their use in other fields.

The dyeings obtained with the developer / coupler combination according to the invention are notable for great brilliance and high fastness to light and shampooing.

The use of 4-amino-2-aminomethyl derivatives in hair dyes has already been described in the literature. For example, DE-Al-35 43 345 generally deals with derivatives of 4-amino-2-aminomethylphenols. Furthermore, EP-AI-857 479 describes hair colorants which contain 4-amino-2 - ((diethylamino) methyl) phenol in combination with 5-amino-2-methoxyphenol. From this rather vague information, however, there is no indication of the effects that can be achieved with the combination according to the invention.

In one embodiment of the present invention, the colorants can also contain further developer components. Preferred developer components according to the invention are p-phenylenediamine, p-toluenediamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2-hydroxyethyl) -p -phenylene diamine, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2,4,5, 6 -Tetraamino-pyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6 -triaminopyrimidine, 2-hydroxyethylaminomethyl-4-amino-phenol, 4,4'-diaminodiphenylamine, .4-amino-3-fluorophenol, 2-aminomethyl-4-amino-phenol, 2-hydroxymethyl-4-aminophenol, bis - (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4-aminophenyl) diazacycloheptane, 1,3-bis (N- (2-hydroxyethyl) -N (4-aminophenylamino) ) -2-propanol, 4-amino-2- (2-hydroxyethoxy) phenol, 1.10- Bis- (2,5-diaminophenyl) -l, 4,7,10-tetraoxadecane and 4,5-diaminopyrazole derivatives according to EP 0 740 931 or WO 94/08970 such as 4,5-di-amino-l- (2'-hydroxyethyl) pyrazole.

Particularly preferred developer components are p-phenylenediamine, p-toluenediamine, p-aminophenol, 1 - (2'-hydroxyethyl) -2,5-diaminobenzene, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2 -Hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 4,5-diamino-1 - (2-hydroxyethyl) pyrazole, 2-aminomethyl-4-aminophenol , N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, bis- (2-hydroxy-5-aminophenyl) methane, l, 10-bis (2,5-diaminophenyl) -1, 4.7 , 10-tetraoxadecane and o-aminophenol.

To nuance the color tones that can be achieved, the agents according to the invention can also contain one or more further coupler components. Coupler substances are often aromatic or heterocyclic ring systems which have two reactive groups in the meta position. M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as coupler components.

Coupler components preferred according to the invention are m-aminophenol and its derivatives such as 5-amino-2-methylphenol. 5-

(3-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-

Hydroxy-4-aminophenoxyethanol, 3-amino-6-methoxy-2-methylaminophenol, 2,6-

Dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino

4-chloro-2-methylphenol, 5 - amino-4-methoxy-2-methylphenol, 5 - (2 '-hydroxyethyl) - amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3- aminophenol, 1,3-

Dihydroxy-5- (methylamino) benzene, 3- (ethylamino) -4-methylphenol and 2,4-dichloro-

3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4-

Diaminophenoxyethanol, 1,3-bis- (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-

4- (2'-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -l-methylbenzene and 1-amino-3-bis- (2'-hydroxyethyl) aminobenzene, o-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and

2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol,

Resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol,

2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,

Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy -3, 4-diaminopyridine, 2,6-dihydroxy-4-methylpyridine,

2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-

Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene,

1, 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-

Dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Moφholinderivate such as 6-hydroxybenzomoφholin and 6-amino-benzomoφholin,

Quinoxaline derivatives such as 6-methyl-l, 2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives such as, for example, l-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-

Hydroxyindole,

Methylenedioxybenzene derivatives such as 3,4-methylenedioxyphenol, 1-

Hydroxy-3,4-methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l- (2'-

Hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly preferred coupler components in the sense of the invention are 1-naphthol, 1,5-, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, 3-amino-2-methylamino-6-methoxypyridine, resorcinol, 4-chlororesorcinol, 2-methylresorcinol, 2,5-dimethylresorcinol, m-aminophenol, o-aminophenol and 2-chlororesorcinol.

The developer and coupler components are usually used in free form. For substances with amino groups, however, it can be preferred to use them in salt form, in particular in the form of the hydrochlorides and sulfates. The hair colorants according to the invention preferably contain both the developer components and the coupler components in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, in each case based on the total oxidation colorant. Developer components and coupler components are generally used in approximately molar amounts to one another. If the molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can be included.

In a preferred embodiment, the hair colorants according to the invention contain, in addition to the oxidation dye products, customary direct dyes for further modification of the color shades. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, 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 known compounds and 4-amino-2-nitrodiphenylamine-2 ' -carboxylic acid, 6-nitro-l, 2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol 4-ethylamino-3-nitrobenzoic acid and 2-chloro 6-ethylamino-1-hydroxy-4-nitrobenzene.

The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten bark, sage, blue wood, madder root, catechu, sedre and alkanna root. Further dye components contained in the colorants according to the invention can also be indoles and indolines, and also their physiologically tolerable salts. Preferred examples are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole , 5.6-

Dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Also preferred are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5 , 6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

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

In a further embodiment of the present invention, the hair colorants furthermore contain at least one dye of the reactive carbonyl compound type, selected from the group of aromatic, heteroaromatic or unsaturated aldehydes or ketones, dialdehydes or diketones or acetals, semi-aminals or imine derivatives of such reactive carbonyl compounds.

Hair dyes of the reactive carbonyl compound type have been known for a long time. Suitable compounds of the aromatic aldehyde type are e.g. described in the German patent applications DE 196 30 274 AI and DE 196 30 275 AI. Suitable compounds are e.g. the 2-hydroxybenzaldehyde, the 4-hydroxy-3-methoxy-benzaldehyde (vanillin) and the 4-hydroxy-3-methoxy-cinnamaldehyde (coniferyl aldehyde).

Suitable compounds of the heteroaromatic aldehyde type are described, for example, in German Offenlegungsschrift DE 197 17 280 AI. Particularly suitable dyes are, for example, trans-β- (2-furyl) acrolein, l-methylindole-3-aldehyde, 2- (1,3,3-trimethyl-2-indolinylidene) acetaldehyde or antipyrin-4-aldehyde. Special products of this type with a pyridinium group are in the German patent application DE 197 45 356.2 describes, for example, the very suitable 4-formyl-1-methylpyridinium benzenesulfonate and 4-formyl-1-methylquinolinium methane sulfonate or methyl sulfate.

Suitable dyes of the unsaturated aldehyde type are e.g. described in German Offenlegungsschrift DE 197 17 224 AI. Glutaconaldehyde in the form of its salts, e.g. its alkali or tetrabutylammonium salt or the 2-chloro-3-hydroxymethylene-l-cyclohexene-l-aldehyde.

Dialdehydes and diketones and their derivatives which are suitable as dyes according to the invention are e.g. alicyclic and cyclic 1,2- and 1,3-dicarbonyl compounds, such as isatin, ninhydrin, alloxan, isobarbituric acid, p- and o-quinones, 1,3-indanediones and their derivatives. Such dyes are found e.g. in the German patent application DE 43 35 627 AI. Suitable compounds are e.g. the malonic dialdehyde, preferably in the form of its dimethyl acetal, the 2-nitro-l, 3-indanedione or the 2-acetyI-l, 3-cyclo-hexanedione.

The diketones suitable according to the invention also include cyclic dicarbonyl compounds such as e.g. the isatin and its derivatives, e.g. are described in German Offenlegungsschrift DE 44 09 143 AI. According to the invention, e.g. the isatinic acid potassium salt, the isatin-5-sulfonic acid potassium salt, the N-allylisatin, the 1-piperidinomethylisatin, the 1-hydroxymethylisatin and the 1-diethylaminomethylisatin.

Another suitable cyclic dicarbonyl compound is e.g. also dehydro-ascorbic acid, the suitability of which as a hair dye is known from German patent application DE 197 45 354.6. Finally, the acetals, imine derivatives and semi-aminals of the reactive carbonyl compounds mentioned are also suitable. Such compounds are obtained by reaction of the carboxyl group with primary alcohols or amines and optionally elimination of water.

Starting from the unsaturated dialdehydes and diketones, one arrives in the group of merocyanine and azomethine dyes. Suitable imine derivatives of Glutacondialdehyds are, for example, the mono-N-methylaniline derivative of glutaconaldehyde (5-N-methylanilinopentadienal) or the N- (5-anilino-2,4-pentadien-l-ylidene) anilinium chloride. Another suitable vinylogous cyanine dye is 7-dimethylamino-2,4,6-heptatrienylidene-dimethylammonium perchlorate. Such compounds are known as hair dye components, for example from German published application DE 197 17 223 AI.

Many of the reactive carbonyl compounds mentioned dye keratin-containing fibers with a wide variety of color nuances particularly intensively only in combination with one or more color-enhancing compounds with a primary or secondary amino or hydroxy group, selected from the group of amino acids and peptides, aromatic amines, phenols, aminophenols and nitrogen-containing ones Heterocycles.

In many cases, deeper (darker) shades are obtained.

Suitable amino acids are e.g. the naturally occurring and synthetic amino acids, e.g. Arginine, histidine, phenylalanine, dihydroxyphenylalanine, ornithine, lysine. Suitable peptides are above all oligo- and polypeptides which have sufficient water solubility in the preparations according to the invention for keratin reduction. Examples are e.g. Glutathione or the oligopeptides contained in the hydrolysates of collagen, keratin, elastin, casein and vegetable proteins such as soy protein, wheat gluten or almond protein.

Suitable aromatic amines and aminophenols are N, N-dimethyl-, N, N-diethyl-, N- (2-hydroxyethyl) -N-ethyl-, N, N-bis- (2-hydroxyethyl) -, N- (2 -Methoxyethyl-), 2-chloro, 2,3-, 2,4- and 2,5-dichloro-p-phenylenediamine, 2,5-dihydroxy-4-moφholinoaniline dihydrobromide, 2-, 3- and 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o- and p-phenylenediamine, o- and m-toluenediamine, 2,5-diamino-phenol, -toluene and -phenethol, 4- Amino-3-methylphenol, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 4-methylamino, 3-amino-4- ( 2'hydroxyethyloxy) -, 3,4-methylenediamino- and 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-methylene dioxy-, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl- and 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-naphthoic acid, 3 - aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1, 2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobenzate catechol, 4,6-diaminopyrogallol, 3,5-diamino-4-hydroxycatechol, aromatic anilines or phenols with a further aromatic radical, as shown in the formula (I)

in the R ¹ for a hydroxy or an amino group, which by Cι _-4 alkyl, Cμ- hydroxyalkyl or may be substituted, R ² , R ³ , R ⁴ , R ⁵ and R ^{6 represents} hydrogen, a hydroxy or an amino group which is substituted by C 4 alkyl, C ₄ hydroxyalkyl, or may be substituted, represent a carbon or sulfonic acid group, and X represents a direct bond, a saturated or unsaturated carbon chain with 1 to 4 carbon atoms optionally substituted by hydroxyl groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom , or a group with the formula (II)

Z- (CH ₂ -Y-CH ₂ -Z ') ₀ (II),

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

Z and Z 'independently of one another are an oxygen atom, an NR ⁷ group, in which R ^{7 is} hydrogen, a C _-4 alkyl or hydroxy C _{4 -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 o is a number from 1 to 4, for example 4,4'-diaminostilbene, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 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 can be used both in free form and in the form of their physiologically tolerable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.

Suitable phenols are e.g. 2-, 3- or 4-methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl) - and 3,4-methylenedioxyphenol, resorcinol and 2-, 4- and 5-methylresorcinol, 2- and 4-chlororesorcinol, 2,5-dimethylresorcinol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, hydroxyhydroquinone, 2,4- or 3,4-dihydroxybenzoic or phenylacetic acid, gallic acid, 2,4, 6-trihydroxybenzoic acid or 2,4,5-trihydroxyacetophenone, 1-naphthol, 1,5-, 2,3- and 2,7-dihydroxy-naphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid or the 3,6-dihydroxy-2,7-naphthalenedisulfonic acid.

Suitable nitrogen-containing heterocyclic compounds are, for example, 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 - and 2,6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino, 4,5,6-triamino, 4-hydroxy-2,5,6-triamino-, 2nd -Hydroxy-4,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino- and 2- Amino-4-methoxy-6-methyl-pyrimidine, 3-amino, 3-amino-5-hydroxy- and 3,5-diaminopyrazole, 2-, 3-, 8-aminoquinoline, 4-amino-quinaldine, 2- , 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5- and 7-amino-benzimidazole and benzothiazole, 2,5-dihydroxy-4-moφholinoaniline and indole and indoline derivatives such as 4-, 5-, 6- and 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. The aforementioned Bonds can be in both free form and in the form of their physiologically acceptable salts, e.g. B. as salts of inorganic acids such as hydrochloric or sulfuric acid.

These coloring systems can be further strengthened by suitable nitrogen-containing heterocycles such as e.g. Piperidine, piperidine-2-, -3- or -4-carboxylic acid, pyridine, 2-, 3- or 4-hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrolidine, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazine and their physiologically tolerable salts.

With regard to the dyes which can be used in the hair dyeing and tinting agents according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidationsfarbstoffvoφrodukte), published as Volume 7 of the "Dermatology" series (Ed .: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials" , published by the European Community, available in diskette form from the Federal Association of German Industrial and Commercial Enterprises for Medicinal Products, Health Products and Köφeφflegemittel eV, Mannheim.

To produce the colorants according to the invention, the oxidation dye precursors can be incorporated into a suitable water-containing carrier. Such carriers are for the purpose of coloring hair e.g. Creams, emulsions, gels or also foaming solutions containing surfactants, e.g. Shampoos, aerosols or other preparations that are suitable for use on the hair.

The colorants according to the invention can furthermore contain all active substances, additives and auxiliaries known for such preparations. In many cases, the colorants contain at least one surfactant, and in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps ),

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C- Atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _χ -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxy sulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

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

Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO - or -SO group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyl dimethylammonium glycinate, and 2 - Alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C _8- ι ₈ alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO H group and are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and C 12-1 o -acyl sarcosine.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example Addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,

C _12-22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

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

Adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,

- Addition products of ethylene oxide with sorbitan fatty acid esters

- Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) will), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} available under the name Tego Amid ^® S 18, are particularly notable for their good biodegradability. Quaternary ester compounds, so-called "esterquats", such as the methyl-hydroxyal- sold under the trademark Stepantex ^® , are also very readily biodegradable. kyldialkoyloxyalkylammonium methosulfates as well as the products sold under the trademark Dehyquart ^® such as Dehyquart ^® AU-46.

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

The compounds with alkyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

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

Furthermore, the hair treatment compositions according to the invention can preferably also contain a conditioning active ingredient selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils.

Cationic polymers can be preferred as conditioning agents. These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)), Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer) are examples of such cationic polymers. Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as, for example, vinyl pyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755. Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol and under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquatium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Cationic polymers of the first four groups are particularly preferred. Polyquaternium-2, polyquaternium-10 and polyquaternium-22 are very particularly preferred.

Also suitable as conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes, such as dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the products sold by Dow Coming under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 and the commercial products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethylsilylamodimethicone), Dow Coming ^® 929 emulsion (containing a hydroxylamino-modified silicone, which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® - Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, Quaternium-80).

Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents.

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

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate methacrylic copolymers and octyl methacrylate copolymers and lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobomylacrylate copolymers and acrylate copolymers, methyl acrylate copolymers, methyl acrylate copolymers /Ethylacrylat/N-tert.Butyl-acrylamid- Teφololymer,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants such as glucose and maleic acid, Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol. Glycerin and diethylene glycol,

Anti-dandruff agents such as piroctone olamine and zinc omadine, other substances for adjusting the pH value,

Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins, cholesterol, light stabilizers,

Consistency generators such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers like latex,

Pearlescent agents such as ethylene glycol mono- and distearate,

Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air as well as antioxidants.

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

In principle, the oxidative development of the coloring can take place with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. As an oxidation Persulfates, chlorites and in particular hydrogen peroxide or its adducts with urea, melamine and sodium borate are suitable. It is also possible to carry out the oxidation with the aid of enzymes. The enzymes can be used to transfer atmospheric oxygen to the developer component or to enhance the effect of small amounts of oxidizing agents present. An example of an enzymatic process is the procedure to increase the effect of small amounts (eg 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

The preparation of the oxidizing agent is expediently mixed with the preparation from the oxidation dye pre-products immediately before hair coloring. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can range between 15 and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.

A second object of this invention is the use of the aforementioned agents for dyeing keratin fibers.

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

Practical examples

example 1

Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Henkel)

Sodium salt of lauryl ether sulfate (approx. 27% active substance; INCI name: Sodium Laureth Sulfate) (Henkel)

Fatty acid amide with betaine structure (approx. 30% active substance; INCI name: Cocamidopropyl Betaine) (Henkel) hydroxyethyl cellulose (Hercules)

The coloring solution was diluted 1: 1 with a commercial 6% hydrogen peroxide preparation (market product Poly Color Brillance) and then applied to a strand of hair (Kerling, natural white). After an exposure time of 30 minutes at 32 ° C., the tress was rinsed, dried and the dyeing result obtained was determined visually according to the pocket dictionary of colors (2nd edition, Musterschmidt-Verlag Zürich-Göttingen, 1975). The result was a mandarin-orange color. In addition, the coloring cream was applied to a strand of hair (Kerling, natural white) in a second color without the addition of an oxidizing agent. After a contact time of 30 minutes at 32 ° C., the tress was rinsed, dried and the dyeing result obtained was determined as described above. The streak was colored carrot red.

Example 2

After the pH had been adjusted, the dyeing solution was diluted 1: 1 with a commercial 6% hydrogen peroxide preparation (market product Poly Color Brillance). The application preparation was applied to a strand of hair (Kerling, natural white). After a contact time of 30 minutes at 32 ° C., the strand of hair was rinsed, dried and the resulting dye result was determined visually as described above. The streak was colored birch gray.

After the pH had been adjusted, the dyeing solution was diluted 1: 1 with a commercial 6% hydrogen peroxide preparation (market product Poly Color Brillance). The application preparation was applied to a strand of hair (Kerling, natural white). After a contact time of 30 minutes at 32 ° C., the tress was rinsed, dried and the dyeing result obtained was determined visually as described above. The streak was colored leather brown. Example 4

5 2 - ((2-Amino-4-nitrophenyl) amino) ethanol

⁶ 4-amino-2-nitrodiphenylamine

After the pH had been adjusted, the dyeing solution was diluted 1: 1 with a commercial 6% hydrogen peroxide preparation (market product Poly Color Brillance). The application preparation was applied to a strand of hair (Kerling, natural white). After 30 minutes of exposure at 32 ° C, the lock was rinsed, dried and the resulting dye result was determined visually as described above. The streak was colored red-brown.

Example 5

After the pH had been adjusted, the dyeing solution was diluted 1: 1 with a commercial 6% hydrogen peroxide preparation (market product Poly Color Brillance). The application preparation was applied to a strand of hair (Kerling, natural white). After a contact time of 30 minutes at 32 ° C., the tress was rinsed, dried and the dyeing result obtained was determined visually as described above. The streak was colored burgundy.

Example 6

After the pH had been adjusted, the dyeing solution was diluted 1: 1 with a commercial 6% hydrogen peroxide preparation (market product Poly Color Brillance). The application preparation was applied to a strand of hair (Kerling, natural white). After a contact time of 30 minutes at 32 ° C., the tress was rinsed, dried and the dyeing result obtained was determined visually as described above. The streak was colored light ash gray.

Example 7

After the pH had been adjusted, the dyeing solution was diluted 1: 1 with a commercial 6% hydrogen peroxide preparation (market product Poly Color Brillance). The application preparation was applied to a strand of hair (Kerling, natural white). After a contact time of 30 minutes at 32 ° C., the tress was rinsed, dried and the dyeing result obtained was determined visually as described above. The streak was colored brown-red.

Claims

claims

1. Agent for dyeing keratin fibers, characterized in that it contains 4-amino-2- ((diethylamino) methyl) phenol as the developer component and 2-amino-3-hydroxypyridine as the coupler component.

2. Composition according to claim 1, characterized in that it further comprises at least one developer component selected from the group consisting of p-phenylenediamine, p-toluenediamine, p-aminophenol, l- (2'-hydroxyethyl) -2,5-diaminobenzene , 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 4,5-diamino-1 - (2-hydroxyethyl) pyrazole, 2-aminomethyl-4-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1 , 10-bis- (2,5-diaminophenyl) - 1, 4,7, 10-tetraoxadecane and o-aminophenol, contains.

3. Composition according to one of claims 1 to 2, characterized in that there is at least one further coupler component selected from the group formed by 1-naphthol, 1,5-, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, 3-amino-2-methylamino-6-methoxypyridine, resorcinol, 4-chlororesorcinol, 2-methylresorcinol, 2,5-dimethylresorcinol, m-aminophenol, o-aminophenol and 2-chlororesorcinol, contains.

4. Composition according to one of claims 1 to 3, characterized in that developer components in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, and coupler components in an amount of 0.005 to 20 wt. -%, preferably 0.1 to 5 wt .-%, each based on the entire oxidation colorant, are included.

5. Agent according to one of claims 1 to 4, characterized in that at least one substantive dye is included.

6. Composition according to one of claims 1 to 5, characterized in that at least one indole and / or at least one indoline derivative is included.

7. Use of agents according to one of claims 1 to 6 for dyeing keratin fibers.