WO1996022075A1

WO1996022075A1 - Diketo compounds for colouring keratin-containing fibres

Info

Publication number: WO1996022075A1
Application number: PCT/EP1996/000056
Authority: WO
Inventors: Hinrich Möller; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-01-18
Filing date: 1996-01-09
Publication date: 1996-07-25
Also published as: DE19501304A1

Abstract

The object of the invention is the use of diketo compounds of the formula (I) in which X is a saturated or unsaturated alkylene radical with 2 to 4 C atoms, which may be substituted by halogen, hydroxy, C1-C4 alkoxy, C1-C4 alkyl, C1-C4 hydroxyalkyl, C1-C4 alkoxy-(C1-C4)-alkyl, formyl, aryl, aryl-C1-C4 alkyl or formyl-C1-C4-alkyl radicals, and R?1 and R2¿ are mutually independently C¿1?-C4 alkyl groups or aryl groups which may be substitued by halogen atoms, hydroxy, C1-C4-alkyl-C1-C4-alkoxy, nitro, bis-C1-C4-alkylamino or carboxy groups, or are directly bonded together resulting in a cycloaliphatic ring, and the hydrates, semi-acetals or semi-ketals and acetals or ketals of the diketo compounds for formula (I) to colour keratin containing fibres, specially human hair.

Description

"Diketo compounds for dyeing keratin fibers"

The invention relates to the use of diketo compounds for dyeing fibers containing keratin, in particular human hair.

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 can be achieved with good fastness properties, but the development of the color happens under the influence of oxidizing agents such as. B. H ₂ O ₂ , 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.

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

The use of the diketo compounds described in more detail below for dyeing keratin fibers is not yet known.

As keratin fibers, e.g. Wool, furs, skins and human hair are considered. In principle, the diketo compounds 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 can be used.

The invention relates to the use of diketo compounds of the formula I.

wherein X represents a saturated or unsaturated alkylene radical having 2 to 4 carbon atoms, optionally by halogen, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl -, C ₁ -C ₄ alkoxy- (C ₁ -C ₄ ) alkyl-, formyl-, aryl-, aryl- (C ₁ -C ₄ ) alkylidene- or formyl- (C ₁ -C ₄ ) - alkyl radicals can be substituted,

and R * and R ² independently of one another for C ₁ -C ₄ alkyl groups or aryl groups, which are replaced by halogen atoms, hydroxy, C _1-4 alkyl-C _1-4 alkoxy, nitro, bis-C _1-4 alkylamino or carboxy groups can be substituted, or are directly connected to one another so that a cycloaliphatic ring results, as well as the hydrates, semiacetals or semiketals and acetals or ketals of diketo Compounds of formula (I) for dyeing keratin fibers, especially human hair.

Examples of the diketo compounds to be used according to the invention are: hexane-2,5-dione, 3-hexene-2,5-dione, 1,2-dibenzoylethylene, 1,2,4-triphenylbutane-1,4-dione , 1,2-dibenzoylethane, 1,2-dibenzoyl-1-chloroethane, 1,1,2,2-tetraacetylethane, cyclohexane-1,4-dione, 5,5-dimethyl-2-phenacylcyclohexane-1,3 -dione, 5-keto-D-fructose, octane-2,5-dione, 1-phenylpentane-1,4-dione, 1,1,4,4-tetraethoxycyclohexane, 4,4-diethoxycyclohexanone, 1,4-cyclohexanedione -monoethylene acetal, 2,6-heptanedione, 1,3-dibenzoyl propane.

1,2-Dibenzoylethylene, 1,4-cyclohexanedione, acetonylacetone, 1,3-dibenzoylpropane and 1,4-cyclohexanedione monoethylene acetal are preferably used.

These substances are generally known from the literature or available in the chemical trade.

The diketo compounds of the formula I alone dye keratin fibers only slightly yellow. Brilliant colorations in the orange, brown, red-brown, blue-black and black range with good fastness properties (light fastness, wash fastness, fastness to rubbing) are achieved if the diketo compounds of the formula I together with compounds having a primary or secondary amino group, for example aniline derivatives a nitrogen-containing heterocyclic compound, for example primary heteroaromatic amines, or an aromatic hydroxy compound. On the one hand, these are compounds that also only weakly dye hair on their own and only produce brilliant colorations together with the diketo compounds of the formula I. On the other hand, however, there are also compounds which are used as oxidation dye precursors and are suitable for dyeing hair alone; in the presence of the diketo compounds Formula I, however, produces even stronger, more brilliant shades with even better fastness properties.

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-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,5-diaminotoluene, -phenol, -anisole, -phenethol, 2-chloro-p-phenylenediamine, 4-methylamino-, 3-, 4-dimethylamino-, 3,4- Methylene dioxyaniline, 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- benzoic acid, 2-, 3-, 4-aminobenzene sulfonic 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-tetrahydrochloride, 2,4,5-triaminophenol-trihydrochloride, penta-aminobenzene-pentahydrochloride, hexamaminobenzene-hexahydrochloride, 2,4,6-triaminoresorcinol-trihydrochloride, 4,5-diaminobenzate catechol sulfate, 4,6-diaminopyrog dihydrochloride, 3,5-diamino-4-hydroxy-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'-Te traaminodiphenyl 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 , N, N-bis- [2- (4-aminophenoxy) ethyl] methylamine trihydrochloride.

Suitable nitrogen-containing heterocycles are e.g. 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino -, 3-amino-2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2,4,5-triamino-, 2, 6-dihydroxy-3,4-dimethylpyridine, 4,5,6-triamino-, 4-hydroxy-2,5,6-tri- amino-, 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-, 6th -, 7-aminoindole, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline as well as indole and indoline derivatives, e.g. 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, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, 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, 2-, 4-methyl-, 2-, 4-chlororesorcinol , 1-, 2-naphthol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid. Amino acids or oligopeptides composed of 2 to 9 amino acids are also suitable. All naturally occurring and synthetic amino acids are suitable as 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 that they have sufficient water solubility for use in the colorants according to the invention. Examples are e.g. Glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein.

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

The use of the isolated reaction products of diketo compounds of the formula I and compounds having a primary or secondary amino group, nitrogen-containing heterocycles, aromatic hydroxy compounds or amino acids as dyes also falls within the scope of the invention. The colorants produce intensive colorations even at physiologically tolerable temperatures of below 45 ° C. They are therefore particularly suitable for dyeing human hair. to When used on human hair, the colorants can be incorporated into a water-containing or even into an anhydrous cosmetic carrier. Examples of suitable anhydrous carriers are paraffin oil perliquidium or silicone oils of suitable viscosity. If necessary, anhydrous emulsifiers can be added to the oils. Suitable water-containing cosmetic carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions such as shampoos or other preparations which 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 on fatty alcohols, on fatty acids, on alkyl phenols, fatty acid sorbides, on fatty acid sorbides, on alkyl phenols, 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. Gum arabic, karaya gum, guar gum, locust bean gum, linseed gums and pectin, biosynthetic gums, for example 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, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, clays such as. B. bentonite or fully synthetic hydrocolloids, such as polyvinyl alcohol or polyvinyl pyrrolidone, 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 oils Stabilization of the ingredients, e.g. B. ascorbic acid, finally can also contain dyes for coloring the cosmetic preparations.

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 diketo compounds of the formula I and the compounds having a primary or secondary amino group, the amino acids or oligopeptides composed of 2 to 9 amino acids, the nitrogen-containing heterocycles or the aromatic hydroxy compounds are in each case in an amount of 0.3 to 65, preferably 6 up to 20 mmol, based in each case on 100 g of the total colorant.

For the coloring result it can be advantageous to add ammonium or metal salts to the coloring agents. Suitable metal salts are e.g. the formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of potassium, sodium, lithium, magnesium, calcium, strontiums, bariums, manganese , Iron, cobalt, copper, zinc; preferred are sodium 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 entire colorant are included.

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

For dyeing the hair, the colorants are in an aqueous or also an anhydrous cosmetic carrier in an amount of 50- 100 g applied to the hair, left there for about 30 minutes and then rinsed out or washed out with a commercially available hair shampoo. When using the water-free carrier, it is applied to damp hair.

The two reactive components can either be applied to the hair at the same time or else one after the other, regardless 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.

There is also the possibility of first mixing the two reactive components together and then applying the reaction product to the hair.

The two reactive components can be stored together, for example as a dry powder or in an anhydrous liquid formulation. With dry storage, a defined amount of warm (50 - 80 ° C) water must be added and a homogeneous mixture created. When using an anhydrous formulation, the hair must be moistened beforehand in order to achieve a sufficient coloring effect. When stored separately, the reactive components are only intimately mixed with one another immediately before use. Aqueous formulations are preferably used here. However, one of the reactive components can also be present as a powder or in an anhydrous liquid formulation. Examples

Preparation of a coloring solution:

A slurry of 10 mmoles of a diketo compound of formula I and 10 mmoles of a reactant, 10 mmoles of sodium acetate and a drop of a 20% fatty alkyl ether sulfate solution in 100 ml of water was prepared. 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 are the

Claims

Use of diketo compounds of formula I.

in which X represents a saturated or unsaturated alkylene radical having 2 to 4 carbon atoms, which is optionally substituted by halogen,

Hydroxy-, C ₁ -C ₄ -alkoxy-, C ₁ -C ₄ -alkyl-, C ₁ -C ₄ -hydroxyalkyl-, C ₁ -C ₄ -alkoxy- (C ₁ -C ₄ ) -alkyl-, formyl -, Aryl-, aryl- (C ₁ -C ₄ ) -alkyl or formyl- (C ₁ -C ₄ ) -alkyl radicals can be substituted, and R ¹ and R ² independently of one another for C ₁ -C ₄ - Alkyl groups or

Aryl groups, which are formed by halogen atoms, hydroxy, C _1-4 -alkyl-C _1-4 -

Alkoxy, nitro, bis-C _1-4 alkylamino or carboxy groups can be substituted,

or are directly connected to one another so that a cycloaliphatic ring results,

as well as the hydrates, half acetals or half ketals and acetals or

Ketals of the diketo compounds of the formula (I) for dyeing fibers containing keratin, in particular human hair. Use according to claim 1, characterized in that the dipeto compound of formula I or its hydrate, hemiacetal, halobetal, acetal or ketal is selected from the group 2,5-dimethoxytetrahydrofuran, 1,2-dibenzoylethylene , 1,4-cyclohexanedione, acetonylacetone, 1,3-dibenzoylpropane, 1,4-cyclohexanedione monoethylene acetal.