DE4317850A1 - Agents for dyeing keratin-containing fibres - Google Patents

Abstract

The invention relates to the use of alloxan and isobarbituric acid and certain derivatives for dyeing keratin-containing fibres, especially human hair. The invention further relates to colorants which contain the abovementioned compounds in combination with compounds having primary or secondary amino groups or nitrogen-containing heterocyclic compounds.

Description

The invention relates to the use of alloxan and isobar bituric acid and its derivatives for dyeing keratin-containing Fa sern and colorants containing these compounds.

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 based on alloxan or isobarbituric acid and their So far, derivatives for dyeing keratin fibers have not been used known.

Surprisingly, it has now been found that Alloxan and Iso barbituric acid and certain derivatives even in the absence of oxi agents for dyeing keratin-containing Fa suitable. However, the use of oxidizing agents is intended by no means be excluded.

As keratin fibers come e.g. B. wool, furs, skins and human hair into consideration. The alloxane specified below and isobarbituric acid derivatives can in principle also be used for dyeing other natural fibers, such as. B. cotton, jute, sisal, linen or Silk, modified natural fibers, such as. B. regenerated cellulose, Ni tro, alkyl or hydroxyalkyl or acetyl cellulose and syntheti shear fibers such. B. polyamide, polyacrylonitrile, -, polyurethane and polyester fibers can be used.

The invention relates to the use of alloxan and isobar bituric acid and its derivatives of the formula I.

where R¹ and R² are independently hydrogen, C₁-C₄ alkyl, C₂-C₄-hydroxyalkyl, C₂-C₄ acyl, benzyl or phenyl groups represent and A for a methylene group CH₂ or a carbonyl group C = O stands for dyeing keratin fibers.  

The compounds of the formula I can also be in the hydrate form available.

Alloxanes are preferred for dyeing keratin-containing fibers used, that is to say those compounds of the formula I in which A is is a carbonyl group C = O. The reason is particularly suitable body Alloxan itself. This also by reductive dimerization of Alloxan resulting alloxan is suitable.

The compounds of formula I give shades in the yellow range. The Wash resistance of the dyeings is surprisingly high. Especially brilliant colors in the yellow, red and violet range with good Fastness properties (light fastness, wash fastness, fastness to rubbing) are achieved if the compounds of formula I together with Compounds with primary or secondary amino group or with one Nitrogen-containing heterocyclic compound - except Compounds of formula I themselves - are used.

Another subject of the invention are therefore agents for dyeing fibers containing keratin, containing at least one compound of Formula I and a compound with primary or secondary amino group pe or a nitrogen-containing heterocycle, except Ver bonds of formula I, and a water-containing carrier.

Suitable compounds with primary or secondary amino group are e.g. B. primary aromatic amines such as 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,5-diaminotoluene, phenol, anisole, phenethole, 2-chloro-p-phenylenediamine, 4-methylamino-, 3-, 4-dimethylamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4-methylamino-, 2-Me thyl-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-ami no-2-aminomethylphenol, 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-di sulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-amino isophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobes zol-tetrahydrochloride, 2,4,5-triaminophenol-trihydrochloride, penta aminobenzene pentahydrochloride, hexamaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzate catechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxy catechol sulfate, aromatic anilines or phenols with one further aromatic radical such as 4,4′-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, sodium salt, 4,4'-diaminodiphe nylmethane, sulfide, sulfoxide, amine, 4,4'-diaminobenzophenone, di phenyl ether, 3,3 ′, 4,4′-tetraaminodiphenyl tetrahydrochloride, 3,3 ', 4,4'-tetraamino-benzophenone, 1,3-bis (2,4-diaminophenoxy) -pro pan-tetrahydrochloride, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane tetrahydrochloride, 1,3-bis (4-aminophenylamino) propane, -2-propanol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -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 and indole and indoline derivatives, e.g. B. 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline.

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 fibers containing keratin, containing at least one ver bond of formula I and at least one amino acid or one of 2 Up 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 cysteine, methionine, proline, tyrosine, valine, gly cin, glutamic acid, histidine, aspartic acid, alanine, cystine, lysine, Hydroxyproline, leucine, isoleucine, phenylalanine, serine, ornithine, Threonine, DOPA, glutathione, but especially arginine and trypto phan.

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

The colorants according to the invention already result in physiological tolerable temperatures of below 45 ° C intense colorings. they 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, α-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.

The compounds of formula I and the compounds with primary or secondary amino group, e.g. B. amino acids or from 2 to 9 Amino acids built oligopeptides, or the nitrogen-containing Heterocycles are present in an amount of 0.3 to 65 in each case preferably 6 to 20 mmol, in each case based on 100 g of the total color preparation, included.

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 carbonates, halides, sulfates, nitrates, acetates, lactates, Glycolates, tartrates, citrates, gluconates, propionates, phosphates, sul fonates and phosphonates of potassium, sodium, lithium, magnesium,  Calcium, strontium, barium, manganese, iron, cobalt, copper, Zinc, lathans, ceres, neodymes and gadoliniums; Li are preferred thiumbromide, calcium bromide, calcium gluconate, strontium chloride, Strontium nitrate, aluminum chloride, aluminum lactate, zinc chloride, Zinc sulfate, magnesium chloride, magnesium sulfate, lanthanum nitrate, Am monium 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 entire colorant preparation are included.

The pH value of the ready-to-use coloring preparations is between 2 and 11, preferably between 5 and 8.

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 (compound of formula I and ami compound containing nitrogen groups or nitrogen-containing heterocycle, except compounds of formula I) can either be simultaneously can be applied to the hair or one after the other, whereby it doesn't matter which of the two components listed first will wear; between the application of the first and the second comm components can be up to 30 minutes apart.

Examples Preparation of a coloring solution

A 1 mmole slurry of a compound of Formula I was obtained and 1 mmol of a compound containing an amino group or a stick prepared heterocycle in 100 ml of water. Optional salts were added in an amount of 1 mmol each. The on slurry was heated to boiling temperature and after cooling filtered, the pH was then adjusted to 6.

90% of this staining solution was grayed at 35 ° C for 30 minutes human hair that has not been pretreated. The respective Dyeing temperatures, dyeing times, shades and depths are Ta see belle 1.

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 (8)

1. Use of alloxan and isobarbituric acid and their derivatives of the formula I. wherein R¹ and R² independently represent hydrogen, C₁-C₄-alkyl, C₂-C₄-hydroxyalkyl, C₂-C₄-acyl, benzyl or phenyl groups and A represents a methylene group CH₂ or a carbonyl group C = O , for dyeing keratin fibers. 2. Use according to claim 1, characterized in that the For mel I stands for an alloxan, in which A is a carbonyl group represents. 3. Use according to claim 2, characterized in that R¹ and R² are hydrogens. 4. Containing agents for dyeing keratin fibers, in particular human hair

• at least one compound of the formula I,
• at least one compound having a primary or secondary amino group or a nitrogen-containing heterocycle, with the exception of compounds of the formula I,
• - And a water-based carrier.

5. agent for dyeing keratin fibers according to claim 4, containing at least one compound of formula I, at least an amino acid or one composed of 2 to 9 amino acids Oligopeptide and an aqueous carrier. 6. Composition according to claim 5, characterized in that the amino acid or the oligopeptide are selected from the group cysts in, methionine, proline, tyrosine, valine, glycine, glutamic acid, Histidine, aspartic acid, alanine, cystine, lysine, hydroxyproline, Leucine, isoleucine, phenylalanine, serine, ornithine, threonine, DOPA, glutathione, but especially arginine and tryptophan. 7. Composition according to claim 4, characterized in that at least a compound of formula I in an amount of 0.3 to 65 preferably 6 to 20 mmol, and at least one containing amino groups Compound or a nitrogen-containing heterocycle take compounds of the formula I, 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 preparation are included. 8. Composition according to claim 5, characterized in that at least a compound of 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 entire colorant preparation are included.