DE4335625A1 - Ethandione for dyeing keratin fibers - Google Patents

Description

The invention relates to the use of ethanediones for dyeing ben of fibers containing keratin and those containing these compounds Colorants.

For dyeing keratin fibers, e.g. B. hair, wool or Furs generally come with either substantive dyes or oxidation dyes, which by oxidative coupling or several developer components with each other or with one or several coupler components are created for use. With Oxidati ons dyes can be intense dyeings with good fastness Achieve properties, the development of the color happens however under the influence of oxidizing agents such. B. H₂O₂ what often causes damage to the fiber. Direct color fabrics are applied under gentler conditions, after However, part of it is that the colors are often only inadequate proper authenticity properties.  

Coloring systems are based on the ethanediones described in more detail below Not yet known for dyeing fibers containing keratin.

Surprisingly, it has now been found that Ethandione can also be found in Absence of oxidizing agents excellent for coloring fibers containing keratin are suitable. The use of oxidizing agents However, it should by no means be excluded in principle.

As keratin fibers come e.g. B. wool, furs, skins and human hair into consideration. The ethane specified below In principle, diones can also be used to dye other natural fibers such as B. cotton, jute, sisal, linen or silk, modified Natural fibers, such as B. regenerated cellulose, nitro, alkyl or Hy droxyalkyl or acetyl cellulose and synthetic fibers, such as. B. Polyamide, polyacrylonitrile, polyurethane and polyester fibers ver be applied.

The invention relates to the use of ethanedions of the For mel I

wherein R¹ and R² independently of one another for straight-chain or ver branched alkyl radicals with 1 to 5 carbon atoms, for aryl radicals with C₁-C₄-alkyl-, C₁-C₄-alkoxy-, C₁-C₄-alkylamino-, C₁-C₄-dialkylamino-, Amino, hydroxyl, sulfo, carboxyl groups or halogen atoms substi can be tuiert for furyl, thienyl or pyridyl radicals with C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylamino, C₁-C₄ dialkylamino  groups or halogen atoms may be substituted, or R¹ and R² together with the two keto groups, optionally with one C₁-C₄ alkyl, oxo, sulfo or carboxyl substituted ali form cyclic non-quinoid 4-, 5-, 6- or 7-ring, which too can be bridged with a C₁-C₄ alkylene chain, or R¹ and R² ge together an optionally with C₁-C₄-alkyl, C₁-C₄-alkoxy, Ni tro, hydroxy, sulfo, carboxyl groups, halogen atoms or one fused 5- or 6-ring substituted 1,8-naphthylene or Can mean 1,1'-biphenylene for dyeing keratin-containing Fibers.

As examples of the 1,2-ethanediones to be used according to the invention can be named: diacetyl, pentane, hexane, heptane-2,3-dione, Hexane-3,4-dione, 4,4-dimethylpentane-2,3-dione, 1-phenyl-1,2-propane dione, 1-phenyl-1,2-butanedione, 1- (4-methoxy-, 1- (4-chlorophenyl) -1,2- Propanedione, 1-phenyl-3,3-dimethyl-1,2-butanedione, octane-4,5-dione, Benzil, anisil, salicil, 5,5'-dibromosalicil, 2,2'-furyl, 2,2'-thi enyl, 2,2'-, 4,4'-pyridil, 6,6'-dimethyl-4,4'-pyridil, 4-hydroxy-, 4-methoxy, 4-chloro, 4-methyl, 4-dimethylamino, 4,4'-dihydroxy, -Dimethyl-, -Dibromo-, -Dichlor-, -Bis-dimethylamino-, 2,4-dihydro xy-, 3,3'-dimethoxy-, 2'-chloro-3,4-dimethoxy-, 3,4,5,3 ', 4', 5'-hexa methoxy-benzil, cyclohexane hexaone, cyclohexane, cycloheptane, cyclo pentane, cyclobutane-1,2-dione, camphorquinone, 3-methylcyclopentane 1,3-dione, 8-bromo-2,3-bornandione, camphorquinone-10-sulfonic acid, 9,10-phenanthrenequinone, 2,7-dimethyl, 4,5-dimethyl, 2,7-dihydro xy-9,10-phenanthrenequinone, 11,12-dihydrochrysen-11,12-dione, Ace naphthenchinone, aceanthrenequinone. The substances are general available in the chemical trade.

The ethanediones of the formula I give shades in pale yellow to yellow Area. The wash resistance of the dyeings is surprisingly high. Particularly brilliant colors in yellow, brown, green and violet  area with good fastness properties (light fastness, wash fast fastness to rubbing) are achieved if the ethanediones of the formula I together with compounds with primary or secondary amino group, with a nitrogen-containing heterocyclic compound or an aromatic hydroxy compound can be used.

Another subject of the invention are therefore agents for dyeing fibers containing keratin, containing at least one ethanedione from For mel I and a compound with a primary or secondary amino group, a nitrogen-containing heterocycle or an aromatic Hydroxy compound and a water-containing carrier.

Suitable compounds with primary or secondary amino group are e.g. B. primary aromatic amines such as N- (2-hydroxyethyl) -N-ethyl, N, N-bis- (2-hydroxyethyl) -, N- (2-methoxyethyl-), 2,3-, 2,4-, 2,5-, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydro bromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,5-diami notoluene, phenol, anisole, phenethole, 2-chloro-p-phenylenediamine, 4-methylamino, 3-, 4-dimethylamino, 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-6- chloro, 2-methyl-5-amino-4-chloro, 2-methyl-5-amino-6-chloro, 5- (2-Hydroxyethylamino) -4-methoxy-2-methyl, 4-amino-2-aminomethyl phenol, 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-ben zoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzene sulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7- hydroxynaphthalene in 2-sulfonic acid, 7-amino-4-hydroxynaphthalene in 2-sul fonic 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-triaminophenol trihydrochloride, pentaaminobenzene pentahydro chloride, hexamaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzate catechol sulfate, 4,6-diaminopyro gallol dihydrochloride, 3,5-diamino-4-hydroxycatechol sulfate, aromatic anilines or phenols with another aromatic Rest such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene 2,2'-disulfonic acid, sodium salt, 4,4'-diaminodiphenylmethane, sulfide, -sulfoxide, -amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-di aminobenzophenone, 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-diaminophen oxy) -3,6-dioxaoctane-tetrahydrochloride, 1,3-bis- (4-aminophenyl amino) propane, -2-propanol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxy ethylamino] -2-propanol, bis- [2- (4-aminophenoxy) ethyl] methylamine trihydrochloride.

Suitable nitrogen-containing heterocycles are e.g. B. 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-di methylamino-5-amino-, 3-amino-2-methylamino-6-methoxy-, 2,3-diami no-6-methoxy-, 2,4,5-triamino-, 2,6-dihydroxy-3,4-dimethylpyridine, 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-meth oxy-6-methyl-pyrimidine, 3,5-diamino-pyrazole, -1,2,4-triazole, 3-ami no-, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-amino quinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 4-, 5-, 6-, 7-aminoindole, 5-, 6-aminoindazole, 5-, 7-aminobenzimidazole, -benzo thiazole, 2,5-dihydroxy-4-morpholinoaniline as well as indole and indoline derivatives, e.g. B. 5.6 dihydroxyindole, 5.6 dihydroxyindoline and 4 Hy droxyindoline, as well as those with preferably inorganic acids such as e.g. B. hydrochloric or sulfuric acid salts formed.

Suitable aromatic hydroxy compounds are e.g. B. 2-, 4-, 5-Me thylresorcinol, 3-dimethylaminophenol, resorcinol, 3-methoxyphenol,  Catechol, hydroquinone, pyrogallol, phloroglucin, hydroxyhy droquinone, 2-, 3-, 4-methoxy, 3-dimethylamino, 2- (2-hydroxy ethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -ace tophenone, 2-, 4-methyl-, 2-, 4-chlororesorcinol, 1-, 2-naphthol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphtha linsulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

Particularly suitable compounds with primary or secondary amino group are amino acids or oli composed of 2 to 9 amino acids gopeptide. Another subject of the invention are therefore means for Dyeing keratin-containing fibers containing at least one ethane dione of formula I and at least one amino acid or one of 2 to 9 amino acids built oligopeptide and a water-containing Carrier.

All naturally occurring and synthetic come as amino acids Amino acids in question, e.g. B. by hydrolysis from vegetable or animal proteins, e.g. B. collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein accessible amino acids. Both acidic and alkaline amino acids be used. Suitable oligopeptides are all natural occurring and synthetic amino acids built oligopeptides. The oligopeptides can be naturally occurring or synthetic oligopeptides, but also those in polypeptide or protein hydro lysates contained oligopeptides, provided that they have one for the Use sufficient in the colorants of the invention have solubility. As examples are e.g. B. glutathione or the in the hydrolyzates of collagen, keratin, casein, elastin, soy pro tein, wheat gluten or almond protein containing oligopeptides call.  

However, they are suitable for use in the colorants according to the invention especially those amino acids or oligopeptides that are selected are from the group tyrosine, histidine, lysine, phenylalanine, orni thin, DOPA, arginine and tryptophan.

In all colorants according to the invention, several ver different ethanediones of the formula I are used together; several different components from the groups can also be used of compounds with primary or secondary amino group, from nitrogen-containing heterocycles or aromatic hydroxyverbin can be used together.

The colorants according to the invention already result in physiological tolerable temperatures of below 45 ° C intense colorings. she are therefore particularly suitable for dyeing human hair. For use on human hair, the inventive Colorants incorporated into a water-based cosmetic carrier be tested. Suitable water-containing cosmetic carriers are e.g. B. Creams, emulsions, gels or even foaming solutions containing surfactants such as B. shampoos or other preparations suitable for use are suitable on the hair.

The water-containing cosmetic carrier usually contains wetting agents and Emulsifiers such as anionic, nonionic or ampholytic ten side, e.g. B. fatty alcohol sulfates, alkane sulfonates, o (-olefin sulfonates, Fatty alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide plant products on fatty alcohols, on fatty acids, on alkylphenols Sorbitan fatty acid esters, on fatty acid partial glycerides and fatty acid alkanolamides; Thickeners, e.g. B. fatty alcohols, fatty acids, Paraffin oils, fatty acid esters and other fat components in emulsified ter form; water-soluble polymeric thickeners such as natural ones Gums, e.g. B. gum arabic, karaya gum, guar gum, locust beans bread kernel flour, linseed gums and pectin, biosynthetic gums,  e.g. B. xanthan gum and dextrans, synthetic gums, e.g. B. Agar Agar and algin, starch fractions and derivatives such as amylose, amylo pectin and dextrins, modified cellulose molecules, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, clays such as B. bentonite or fully synthetic hydrocolloids, e.g. B. Poly vinyl alcohol or polyvinyl pyrrolidone, hair care additives, such as e.g. B. water-soluble cationic polymers, anionic polymers, nonionic polymers, amphoteric or zwitterionic polymers, Pantothenic acid, vitamins, plant extracts or cholesterol, pH adjusting agents, complexing agents and perfume oils as well as reducing agents Stabilization of the ingredients, e.g. B. ascorbic acid, finally can also use dyes to color the cosmetic preparations be included.

In addition, the addition of solubilizers such as ethylene, 1,3-propylene, 1,2-propylene, 1,2-butylene glycol, glycerin, ethanol, tert. Butanol, 2-propanol or phenethol in amounts of 2-50% to be useful.

The ethanediones of the formula I and the compounds with primary or secondary amino group, e.g. B. amino acids or from 2 to 9 amino acids ren constructed oligopeptides, the nitrogen-containing heterocycles or the aromatic hydroxy compounds are in an amount from 0.3 to 65 mmol, preferably 6 to 20 mmol, in each case to 100 g of the total colorant.

For the coloring result it can be advantageous to use the coloring agents Add ammonium or metal salts. Suitable metal salts are e.g. B. the formates, carbonates, halides, sulfates, butyrates, Va leriate, capronate, acetate, lactate, glycolate, tartrate, citrate, Gluconates, propionates, phosphates and phosphonates of potassium, Na triums, lithium, magnesium, calcium, strontium, barium, Manganese, iron, cobalt, copper, zinc; sodium is preferred  acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride Zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, -chloride and -acetate, which in the given case in an amount of 0.3 to 65, preferably 6 to 20 mmol, based on 100 g of the total Colorant are included.

The pH value of the ready-to-use coloring preparations is between 2 and 11, preferably between 5 and 9.

For dyeing hair, the colorants according to the invention are in the form of water-containing cosmetic carrier in an amount of 100 g hair applied, left there for about 30 minutes and then out rinses or washed out with a commercially available hair shampoo.

The two reactive components (ethanedione of the formula I and ami compound containing nitrogen groups, nitrogen-containing heterocycle or the aromatic hydroxy compound) can either be on simultaneously the hair can be applied or one after the other, taking it it doesn't matter which of the two components is applied first becomes; the ammonium or metal salts can be the first or second component can be added. Between applying the first and second components can take up to 30 minutes stood lying. Pretreatment of the hair with the saline solution is possible.

The two reactive components can be separated and separated the water-free or already stored in the finished formulation become. When stored separately, the reactive components only intimately mixed with one another immediately before use. There is a defined amount of warm when stored dry (50-80 ° C) water and add a homogeneous mixture to manufacture.  

The following examples are intended to explain the subject of the invention in more detail but without restricting it to this.

Examples Preparation of a coloring solution

A 10 mmole slurry of an ethanedione of formula was obtained I and 10 mmol of an amino group-containing compound, an aromatic the hydroxy compound or a nitrogen-containing heterocycle, 10 mmol sodium acetate and a drop of a 20% fatty alkyl ether prepares sulfate solution in 100 ml of water. The slurry was on Boiling temperature heated and filtered after cooling, the pH was then set to 6.

90% of this staining solution was grayed at 30 ° C for 30 minutes human hair that has not been pretreated. The respective Dyeing temperatures, dyeing times, shades and depths are the Tables 1 to 7.

The color depth was rated on the following scale:

-: no or very pale color
(+): weak intensity
+: medium intensity
+ (+): medium to strong intensity
++: strong intensity
++ (+): strong to very strong intensity
+++: very strong intensity

Claims (6)

1. Use of ethanediones of the formula I. where R¹ and R² independently of one another for straight-chain or branched alkyl radicals having 1 to 5 carbon atoms, for aryl radicals which are with C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino, C₁-C₄-dial kylamino, amino, hydroxy, sulfo, carboxyl or halo genatomen can be substituted for furyl, thienyl or pyridyl radicals with C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkyl amino, C₁-C₄ dialkylamino groups or halogen atoms may be substituted, or R¹ and R² together with the two keto groups may be an alicyclic, non-quinoidene 4 optionally substituted by C₁-C₄alkyl, oxo, sulfo or carboxyl groups -, 5-, 6- or 7-ring, which can also be bridged with a C₁-C₄-alkylene chain, or R¹ and R² together, optionally with a C₁-C₄-alkyl, C₁-C₄-alkoxy, nitro- , Hydro xy, sulfo, carboxyl groups, halogen atoms or an ankonden based 5- or 6-ring substituted 1,8-naphthylene or Can mean 1,1'-biphenylene for dyeing keratin-containing fibers. 2. Containing compositions for dyeing fibers containing keratin, in particular human hair

• at least one ethanedione of the formula I,
• - At least one compound with a primary or secondary amino group, a nitrogen-containing heterocycle or an aromatic hydroxy compound
• - And a water-based carrier.

3. Composition according to claim 2, containing at least one compound of formula I, at least one amino acid or one of 2 to 9 Amino acids built oligopeptide and a water-containing Carrier. 4. Composition according to claim 3, characterized in that the amino acid or the oligopeptide are selected from the group Tyro sin, histidine, lysine, phenylalanine, ornithine, DOPA, arginine and Tryptophan. 5. Means according to claim 2, characterized in that at least an ethanedione of the formula I in an amount of 0.3 to 65 preferably 6 to 20 mmol, and at least one containing amino groups Compound, a nitrogen-containing heterocycle, or aromatic hydroxy compound in an amount of 0.3 to 65, preferably 6 to 20 mmol, in each case based on 100 g of the total ten colorant are included. 6. Composition according to claim 3, characterized in that at least an ethanedione of the formula I in an amount of 0.3 to 65 preferably 6 to 20 mmol, and at least one amino acid or Oligopeptide composed of 2 to 9 amino acids in one quantity from 0.3 to 65, preferably 6 to 20 mmol, in each case based on 100 g of the total colorant are included.