WO1995011001A1

WO1995011001A1 - 1,3-propandiones for dyeing keratinic fibres

Info

Publication number: WO1995011001A1
Application number: PCT/EP1994/003327
Authority: WO
Inventors: Hinrich Möller; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1993-10-19
Filing date: 1994-10-10
Publication date: 1995-04-27
Also published as: DE4335627A1

Abstract

The use of 1,3-propandiones for dyeing keratinic fibres, in particular human hair, is disclosed, as well as dyes that contain these compounds, in particular combined with amines and aminoacids.

Description

"1,3-propanediones for dyeing keratin fibers"

The invention relates to the use of 1,3-propanediones for dyeing keratin-containing fibers and to colorants containing these compounds.

For dyeing keratin fibers, e.g. B. hair, wool or fur, generally either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with one another or with one or more coupler components, are used. With oxidation dyes intensive dyeings with good fastness properties can be achieved, but the development of the color takes place under the influence of oxidizing agents such as. B. H2O2, which often results in damage to the fiber. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties. Dyeing systems based on the 1,3-propanediones described in more detail below have not hitherto been known for dyeing fibers containing keratin.

Surprisingly, it has now been found that 1,3-propanediones are outstandingly suitable for dyeing keratin-containing fibers even in the absence of oxidizing agents. The use of oxidizing agents should in no way be excluded in principle.

As keratin fibers, e.g. Wool, furs, skins and human hair are considered. In principle, the 1,3-propanediones described below can also be used for dyeing other natural fibers, e.g. Cotton, jute, sisal, linen or silk, modified natural fibers, e.g. Regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as e.g. Polyamide, polyacrylonitrile, -, polyurethane and polyester fibers are used.

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

R ²

where R ¹ , R ^ and R3 independently of one another hydrogen atoms, C1-C4-alkyl, C2-C4-hydroxyalkyl, Cι-C4-carboxyalkyl, Cj-C4-0xoalkyl-, furyl, thienyl, pyridyl or with Cι-C4_Ai | _ζ yi _{f is} Q-C4-alkoxy, C - C4-alkylamino, amino, hydroxy, nitro, carboxy, sulfo or halogen-substituted phenyl, benzyl or benzoyl groups, and R ¹ and R3 together can also form a saturated or unsaturated, optionally containing an O atom, optionally substituted with C 1 -C 4 -alkyl, phenyl, hydroxyl or oxo groups, on the 5, 6 or 7 ring an aromatic ring system is condensed and its acetals or ketals for dyeing keratin fibers.

Examples of the 1,3-propanediones to be used according to the invention are: 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, 2,4-0ctanedione, 2,4-nonanedione, 2,6-dimethyl-3,5-heptanedione, 2, 4,6-heptane trione, 1-, 3-phenyl-acetylacetone, 1,3-diphenyl-acetylacetone, dibenzoylmethane, dianisoylmethane, benzoylacetone, di-benzoylacetone, 3-0xo-3-phenylpropionaldehyde, di-p-toluoylmethane, 2- ( Acetoacetyl) phenol, dianisoylmethane, 1,3-cyclopentanedione, 2-methyl-1, 3-cyclopentanedione, 2-cyclopentene-2,4-dione, 4-hydroxy-5-methyl-2-cyclopentene-2 , 4-dione, 2-acetylcyclopentanone, 1,3-cyclohexanedione, 2-acetyltetralone, 2-acetyl-l, 3-cyclohexanedione, 1,3-indanedione, 2-phenyl-l, 3-indanedione, 2-acetyl -l, 3-indanedione, 2-benzoyl-l, 3-indanedione, 2-methyl-l, 3-indanedione, 2- (4-dimethylaminophenyl-l, 3-indanedione, curcumin, 3-methyl- l, 2,4-cyclopentanedione, Tribenz oylmethane, 2-thenoyl, 2-furoyl, nicotinoylacetone, dehydroacetic acid. The 1,3-propanediones of the formula I can also be present in the form of with monohydric C _j-C4 alcohols formed acetals. The substances are generally available in the chemical trade or can be prepared by the synthesis methods described in "Weygand Hilgetag, Organochemical Experimental Art, 1970, pages 289, 949, 994, 1001".

The 1,3-propanediones of the formula I give shades in the pale yellow to yellow range. The washability of the dyeings is surprising high. Particularly brilliant colors in the yellow, brown, green and violet range with good fastness properties (light fastness, wash fastness, fastness to rubbing) are achieved if the 1,3-propanediones of the formula I together with compounds having a primary or secondary amino group, be used with a nitrogen-containing heterocyclic compound or an aromatic hydroxy compound.

A further subject of the invention are therefore agents for dyeing keratin-containing fibers containing at least one 1,3-propanedione of the formula I and a compound with primary or secondary amino group, a nitrogen-containing heterocycle or an aromatic hydroxy compound and a water-containing carrier.

Suitable compounds with a primary or secondary amino group are, for example, 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 dihydrobromide, 2-, 3-, 4-aminophenol, o-, m- , p-phenylenediamine, 2,5-diamino-toluene, -phenol, -anisole, -phenethol, 2-chloro-p-phenylenediamine, 4-methylamino-, 3-, 4-dimethylamino-, 3,4-methylenedioxyaniline, 3rd -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-hydroxyethy1a ino) -4-methoxy-2- methy1-, 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-hydroxybenzoic acid, 2-, 3-, 4- Aminobenzenesulfonic acid, 3-amino-4-hydroxybe azole-sulfonic acid, 4-amino-3-hydroxynaphthalene-l-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-triaminobenzo1, 1,2,4,5-tetraaminobenzo1-tetrahydrochloride, 2,4,5-triaminopheno1-trihydrochloride, pentaaminobenzo1-pentahydrochloride, hexamaminobenzo1-hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzate catechol sulfate, 4,6-diaminopyrogaHol-di ydroch oride, 3,5-diamino-4-hydroxybenzate catechol sulfate, aromatic anilines or phenols with a further aromatic radical such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, Na salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4 ^, diaminodiphenylamine-2-sulfonic acid, 4,4 '-Diaminobenzophenone, -diphenyl ether, 3,3', 4,4'-tetraaminodiphenyl-tetrahydrochloride, 3,3 ', 4,4'-tetraamino-benzophenone, 1,3-bis (2,4-diaminophenoxy) -propane-tetrahydrochloride, 1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane-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 tr ihydrochloride.

Suitable nitrogen-containing heterocycles are, for example, 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diarnino, 2,5-diamino, 2,3-diamino, 2-di- methylamino-5-amino-, 3-amino-2-methylamino-6-methoxy-, 2,3-diamino-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-methoxy-6-methyl-pyrimidine, 3,5-diamino-pyrazole, -1,2,4-triazole, 3-amino -, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquininaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 4-, 5-, 6-, 7-aminoindole, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives, for example 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, and their preferably inorganic acids such as. B. hydrochloric or sulfuric acid salts formed. Suitable aromatic hydroxy compounds are, for example, 2-, 4-, 5-methylresorcinol, 3-dimethylaminophenol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -acetophenone , 2-, 4-methyl-, 2-, 4-chlororesorcinol, 1-, 2-naphthol, 1,5-, 2,3-, 2,7-dihydroxynaphtha1in, 6-di eth 1 amino-4-hydroxy-2 -naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

Particularly suitable compounds with a primary or secondary amino group are amino acids or oligopeptides composed of 2 to 9 amino acids. A further subject of the invention is therefore agents for dyeing keratin-containing fibers containing at least one 1,3-propanedione of the formula I and at least one amino acid or an oligopeptide composed of 2 to 9 amino acids and a water-containing carrier.

Suitable amino acids are all naturally occurring and synthetic amino acids, for example the amino acids accessible by hydrolysis from vegetable or animal proteins, for example collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Both acidic and alkaline amino acids can be used. Suitable oligopeptides are all oligopeptides made up of naturally occurring and synthetic amino acids. The oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided they have sufficient water solubility for use in the colorants according to the invention. Examples include glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. However, those amino acids or oligopeptides selected from the group consisting of tyrosine, histidine, lysine, phenylalanine, ornithine, DOPA, arginine and tryptophan are particularly suitable for use in the colorants according to the invention.

Several different 1,3-propanediones of the formula I can also be used together in all of the colorants according to the invention; Likewise, several different components from the groups of compounds having a primary or secondary amino group, nitrogen-containing heterocycles or aromatic hydroxy compounds can also be used together.

The colorants according to the invention produce intensive colorations even at physiologically tolerable temperatures of below 45 ° C. They are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants according to the invention can be incorporated into a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are e.g. Creams, emulsions, gels or also surfactant-containing foaming solutions such as Shampoos or other preparations that are suitable for use on the hair.

The water-containing cosmetic carrier usually contains wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants, for example fatty alcohol sulfates, alkane sulfonates, α-olefin sulfonates, fatty alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide addition products, fatty alcohols, fatty acids, fatty acid sorbityl fatty acid, an alkylphenol acid fatty acid, and alkylphenol acid fatty acids, an alkylphenol acid fatty acid, anphenylglycerol fatty acid, anphenylglyceryl fatty acid, anphenylglyceryl fatty acid, anphenylglycerol fatty acid, anphenylglyceryl fatty acid, anphenylglycerol fatty acid, anylphenol fatty acid, and an alkylphenol fatty acid and fatty acid alkola ide; Thickeners, e.g. B. fatty alcohols, fatty acids, paraffin oils, fatty acid esters and other fat components in emulsified form; water-soluble polymeric thickeners such as natural gums, e.g. B. gum arabic, karaya-gum i, guar-gu mi, locust bean gum, linseed enguπβnen and pectin, biosynthetic gums, e.g. xanthan gum and dextrans, synthetic gums, e.g. B. agar-agar and algin, starch fractions and derivatives such as amylose, amylopectin and dextrins, modified cellulose molecules, eg. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, clays such as. B. bentonite or fully synthetic hydrocolloids, such as polyvinyl alcohol or polyvinylpyrrolidone, hair care additives such as 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 oil Reducing agents to stabilize the ingredients, e.g. As ascorbic acid, finally, dyes for coloring the cosmetic preparations can also be included.

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

The 1,3-propanediones of formula I as well as the compounds with primary or secondary amino group, e.g. Amino acids or oligopeptides made up of 2 to 9 amino acids, or the nitrogen-containing heterocycles, are in each case in an amount of 0.3 to 65, preferably 6 to 20 mmol, in each case based on 100 g of the total colorant , contain.

For the coloring result it can be advantageous to add ammonium or metal salts to the coloring agents. Suitable metal salts are, for example, the formates, carbonates, halides, sulfates, butyrates, variates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of potassium, sodium, lithium, magnesium, Calciu s, strontiums, bariums, manganese, iron, cobalt, copper, zinc; sodium are 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 of the ready-to-use coloring preparations is between 2 and 11, preferably between 5 and 9.

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

The two reactive components (1,3-propanedione of formula I and amino group-containing compound, nitrogen-containing heterocycle or aromatic hydroxy compound) can either be applied to the hair simultaneously or in succession, irrespective of which of the two components is applied first; the ammonium or metal salts can be added to the first or second component. There may be an interval of up to 30 minutes between the application of the first and the second component. Pretreatment of the hair with the saline solution is also possible.

The two reactive components can be stored separately and together either without water or already in the finished formulation. When stored separately, the reactive components are only intimately mixed with one another immediately before use. In the case of dry storage, a defined amount of warm (50-80 ° C.) water is to be added and a homogeneous mixture is to be produced.

The following examples are intended to explain the subject matter of the invention in more detail, but without restricting it thereto. Examples

Preparation of a coloring solution:

A slurry of 10 mmol of a 1,3-propanedione of the formula I, 10 mmol of a compound containing amino groups, an aromatic hydroxyl compound or a nitrogen-containing heterocycle, 10 mmol of sodium acetate and a drop of a 20% texapon- Prepare N25 solution in 100 ml of water. Salts were optionally added in an amount of 10 mmol each. The slurry was heated to boiling temperature and filtered after cooling, the pH was then adjusted to 6.

90% gray, untreated human hair was introduced into this coloring solution at 30 ° C. for 30 minutes. The respective dyeing temperatures, dyeing times, shades and depths of color can be found in 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 Table 1

Colourations with 1.3-indandion

Amino group-containing compound or nitrogen-containing heterocycle dye shade shade depth

- copper + (+) p-toluenediamine H2SO4 medium brown ++

2,4,5,6-tetraaminopyrimidine H2SO4 orange-yellow ^♦ ( ^♦ )

4-aminophenol HC1 medium brown + ( ^♦ )

2- (2,5-diaminophenyl) ethanol H2SO4 (Betoxol) medium brown ++ 1,8, bis (2,5-diaminophenoxy) -3,6-dioxaoctane 4HC1 gray ++

2-methylamino-3-amino-6-methoxypyridine 2HC1 dark brown ++ (+)

N-methyl-p-aminophenol H SO4 light brown ^♦ (+)

2-aminomethyl-4-aminophenol 2HC1 light brown + (+)

2,6-dihydroxy-3,4-dimethylpyridine red-brown ⁺ ( ⁺ ) l, 3-bis- (2,4-diaminophenoxy) propane 4HC1 gray-brown ++

4- (4-Amino-m-toluidino) phenol olive green +

Continuation of table 1

Ausfärbuπqen with 1.3-Indandion

A compound containing nitrogen groups or nitrogen-containing heterocycle dye shade shade depth

N, N-Dimethyl-p-phenylenediamine H SO4 red-brown ++

4,4'-diaminodiphenylamine H SO4 dark brown ^♦ + (+)

N- (4-methoxyphenyl) -p-phenylenediamine HCl tan + (+)

2,4-Dimethyl-3-ethylpyrrole dark copper ++

Pyrrole red-brown ++

Claims

claims

1. Use of 1,3-propanediones of the formula I.

where Rl, R2 and R3 independently of one another hydrogen atoms, -CC-alkyl, C2-C4-hydroxyalkyl, -C-C4-carboxyalkyl, C1-C4- oxoalkyl, furyl, thienyl, pyridyl or with Cι- C4_Aik i _f

C 1 -C 4 -alkoxy, C 1 -C 4 -alkylamino, amino, hydroxyl, nitro, carboxy, sulfo or halogen substituted phenyl, benzyl or benzoyl groups, and Rl and R3 together also represent a saturated or unsaturated, optionally an O- Atom-containing, optionally with C 1 -C 4 -alkyl, phenyl, hydroxyl or oxo groups substituted 5-, 6- or 7-ring, to which an aromatic ring system is optionally fused and their acetals or ketals, for dyeing keratin fibers.

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 an oligopeptide composed of 2 to 9 amino acids 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 tyrosine, histidine, lysine, phenylalanine, ornithine, DOPA, arginine and tryptophan.

5. Composition according to claim 2, characterized in that at least one 1,3-propanedione of formula I in an amount of 0.3 to 65, preferably 6 to 20 mmol, and at least one compound containing amino groups, a nitrogen-containing heterocycle or an aromatic hydroxy compound is contained in an amount of 0.3 to 65, preferably 6 to 20 mmol, in each case based on 100 g of the total colorant.

6. Composition according to claim 3, characterized in that at least one 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 an amount of 0.3 to 65, preferably 6 to 20 mmol, in each case based on 100 g of the total colorant.