DE4335627A1 - 1,3-propanedione for dyeing keratin fibers - Google Patents

Description

The invention relates to the use of 1,3-propanediones for Dyeing of keratin fibers as well as these compounds dyes.

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.  

Dyeing systems based on the 1,3-propanediones described in more detail below are not yet known for dyeing keratin fibers.

Surprisingly, it has now been found that 1,3-propanediones Excellent for dyeing even in the absence of oxidizing agents of keratin fibers. The use of oxidizing In principle, however, agents should not be excluded become.

As keratin fibers come e.g. B. wool, furs, skins and human hair into consideration. The 1,3-Pro specified below In principle, pandione can also be used to dye other naturfa sern, such as B. cotton, jute, sisal, linen or silk, modifi graced natural fibers, such as. B. regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers, such as B. polyamide, polyacrylonitrile, -, polyurethane and polyester fibers are used.

The invention relates to the use of 1,3-propanediones Formula I.

where R¹, R² and R⁵ independently of one another are hydrogen atoms, C₁-C₄- Alkyl-, C₂-C₄-hydroxyalkyl-, C₁-C₄-carboxyalkyl-, C₁-C₄-oxoalkyl- Furyl, thienyl, pyridyl or with C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁- C₄-alkylamino, amino, hydroxy, nitro, carboxy, sulfo or halogen are substituted phenyl, benzyl or benzoyl groups, and R¹  and R³ together also give a saturated or unsaturated optionally containing an O atom, optionally with C₁-C₄ alkyl, Phenyl, hydroxy or oxo groups substituted 5-, 6- or 7-ring can form, on which optionally an aromatic ring system is condensed and their acetals or ketals, for coloring fibers containing keratin.

As examples of the 1,3-propanediones to be used according to the invention can be named: acetylacetone, 3-methyl-2,4-pentanedione, 2,4- Dioxopentanoic acid, malondialdehyde (as tetrabutylammonium salt) 1,1,3,3-tetramethoxy, 1,1,3,3-tetraethoxypropane, 2,4-hexanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-nonanedione, 2,6-dimethyl-3,5-hep tandione, 2,4,6-heptane trione, 1-, 3-phenyl-acetylacetone, 1,3-diphenyl acetylacetone, dibenzoylmethane, dianisoylmethane, benzoylacetone, di benzoylacetone, 3-oxo-3-phenylpropionaldehyde, di-p-toluoylmethane, 2- (acetoacetyl) phenol, dianisoylmethane, 1,3-cyclopentanedione, 2-Me thyl-1,3-cyclopentanedione, 2-cyclopentene-2,4-dione, 4-hydroxy-5-me ethyl 2-cyclopentene-2,4-dione, 2-acetylcyclopentanone, 1,3-cyclohexane dione, 2-acetyltetralone, 2-acetyl-1,3-cyclohexanedione, 1,3-indanedione, 2-phenyl-1,3-indanedione, 2-acetyl-1,3-indanedione, 2-benzoyl-1,3-in danedione, 2-methyl-1,3-indanedione, 2- (4-dimethylaminophenyl-1,3-in dandione, curcumin, 3-methyl-1,2,4-cyclopentanedione, tribenzoylmethane, 2-thenoyl-, 2-furoyl-, nicotinoylacetone, dehydroacetic acid. The 1,3- Propandiones of the formula I can also be in the form of monovalent C₁-C₄ alcohols formed acetals are present. The substances are generally available in the chemical trade or according to the in "Weygand Hilgetag, organic chemical experimentation, 1970, Pages 289, 949, 994, 1001 "described synthesis methods bar.

The 1,3-propanediones of the formula I give shades in the pale yellow to Yellow area. The washability of the dyeings is surprising  high. Particularly brilliant colors in yellow, brown, green and vio lett area with good fastness properties (light fastness, washing fastness, fastness to rubbing) are achieved if the 1,3-propanediones of the Formula I together with compounds with primary or secondary Amino group, with a nitrogen-containing heterocyclic ver bond 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 1,3-propanedione Formula I and a compound with primary or secondary amino group pe, 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-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-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 and 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 1,3-propanedione of formula I and at least one amino acid or oligopeptide composed of 2 to 9 amino acids 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 1,3-propanediones 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, 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.

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 1,3-propanediones of the formula I and the compounds with primary or secondary amino group, e.g. B. amino acids or from 2 to 9 ami oligopeptides built up, or the nitrogen-containing He Terocycles 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 means 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 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 (1,3-propanedione of formula I and compound containing amino groups, nitrogen-containing heterocycle or aromatic hydroxy compound) can either simultaneously on the Hair can be applied or one after the other, there being none It matters which of the two components is applied first; the ammonium or metal salts can be the first or second Component are added. Between applying the first and the second component can be up to 30 minutes apart. Pretreatment of the hair with the saline solution is also 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 (50- 80 ° C) water and create a homogeneous mixture len.

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

There was a slurry of 10 mmoles of a 1,3-propanedione Formula I, 10 mmol of a compound containing amino groups, an aro Matic hydroxy compound or a nitrogen-containing heterocy clus, 10 mmol sodium acetate and a drop of a 20% Texa pon-N25 solution in 100 ml of water. Salts were optional in an amount of 10 mmol added. The slurry was heated to boiling temperature and filtered after cooling, the The pH was then adjusted 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 is the Table 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 (6)

1. Use of 1,3-propanediones of the formula I. where R¹, R² and R³ independently of one another hydrogen atoms, C₁-C₄-alkyl, C₂-C₄-hydroxyalkyl, C₁-C₄-carboxyalkyl-, C₁-C₄- oxoalkyl, furyl, thienyl, pyridyl or with C₁- C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino, amino, hydroxy, nitro, carboxy, sulfo or halogen substituted phenyl, benzyl or benzoyl groups, and R¹ and R³ together also a saturated or unsaturated, optionally an O atom containing, optionally with C₁-C₄-alkyl, phenyl, hydroxy or oxo groups substituted 5-, 6- or 7-ring can form, to which an aromatic ring system is optionally fused and their acetals or ketals , for dyeing fibers containing keratin. 2. Containing compositions for dyeing fibers containing keratin, in particular human hair

• at least one 1,3-propanedione 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 1,3-propanedione 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 a 1,3-propanedione of the formula I in an amount of 0.3 to 65, preferably 6 to 20 mmol, and at least one amino group neck term compound, a nitrogen-containing heterocycle or an 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 entire colorant are included. 6. Composition according to claim 3, characterized in that at least a 1,3-propanedione of the formula I in an amount of 0.3 to 65, preferably 6 to 20 mmol, and at least one amino acid or an oligopeptide composed of 2 to 9 amino acids in one Amount from 0.3 to 65, preferably 6 to 20 mmol, in each case bezo to 100 g of the total colorant.