DE19501303A1 - Aryl ketones for dyeing keratin fibers - Google Patents

Abstract

The object of the invention is the use of aryl ketones of the formula (I) and for their ketals for colouring Keratin-containing fibres, especially human hair. In formula (I) R<1> is a C1-C4-alkyl group or an aryl group and R<1> may also be a C1-C4-alkylene group bonded with the aromatic radical of formula (I) or an isoelectronic, N, S or O-containing, possibly benzoannellised group and R<2>, R<3> and R<4> are mutually independently hydrogens, halogen atoms, hydroxy groups, C1-C4-alkoxy groups, C1-C4-alkyl groups, C2-C4-hydroxyalkyl groups, amino-(C1-C4)-alkyl groups, C1-C4-alkoxy-(C1-C4)-alkyl groups nitro, carboxy or sulpho groups or NR<5>R<6> groups, in which R<5> and R<6> are C1-C4-alkyl groups or C2-C4-hydroxyalkyl groups, and together with the N atom can represent a 5, 6 or 7 member ring or the aromatic system represents an usnic acid radical.

Description

The invention relates to the use of certain aryl keto nen for dyeing keratin fibers, especially human Hair.

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.

Surprisingly, it has now been found that certain aryls tone, even in the absence of oxidizing agents Suitable for dyeing keratin fibers. The use of oxidize the agents should not be excluded in principle will.  

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

As keratin fibers come e.g. B. wool, furs, skins and human hair into consideration. The aryls specified below In principle, clays 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 aryl ketones from For mel I

in which R¹ represents a C₁-C₄ alkyl group or an aryl group and R¹ is also a C₁- linked to the aromatic radical of formula I C₄-alkylene group or an isoelectronic N-, S- or O-hal term, optionally benzo-fused group, and R², R³ and R⁴ independently of one another for hydrogens, halogen atoms, Hydroxy groups, C₁-C₄ alkoxy groups, C₁-C₄ alkyl groups, C₂-C₄-Hy Droxyalkyl groups, amino (C₁-C₄) alkyl groups, C₁-C₄ alkoxy- (C₁-C₄) - alkyl groups, nitro, carboxy or sulfo groups or groups NR⁵R⁶ stand in which R⁵ and R⁶ are C₁-C₄-alkyl groups or C₂-C₄-hydroxyalkyl mean groups and together with the N atom also a 5-, 6- or  Can represent 7-membered ring and their ketals, for coloring of keratin fibers, especially human hair.

As examples of the aryl ketones or their ketals can be named: acetophenone, propiophenone, 2-, 3-, 4-hydroxyacetophenone, -propiophenone, -butyrophenone, 2,4-, 2,5-, 2,6-dihydroxyacetophenone, 2,3,4-, 3,4,5-, 2,4,6-trihydroxy-, 2,4,6-, 3,4,5-trimethoxy-acetophenone, 3,4,5-trimethoxy-acetophenone-diethyl ketal, 4-hydroxy-3-methoxy, 3,5-dimethoxy-4-hydroxy, 4-amino, 4-dimethylamino, 4-morpholino, 4-piperidino, 4-imidazolino, 2-hydroxy-5-bromo, 4-hydroxy-3-nitroacetophenone, acetophenone-2, -4-carboxylic acid, benzophenone, 4-hydroxy-, 2-amino-, 4,4'-, 2,4-dihy droxy-, 2,4,4'-, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-, 1-hydro xy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydro xy-, 3,5,7-, 4 ′, 5,7-, 5,6,7-trihydroxyflavon, quercetin, tannin, Rutin, Indanon, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-di hydroxyanthron.

Preferred uses are acetophenone, 2-hydroxyacetophenone, 4-hydroxyacetophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyaceto phenone, 2,6-dihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, and quercetin.

These substances are generally known in the literature or in chemicals del available.

The aryl ketones of formula I only dye keratin fibers only weak. Brilliant colors in orange, brown, reddish brown, blue black and black area with good fastness properties (light fastness, fastness to washing, fastness to rubbing) are achieved if the Aryl ketones of formula I together with compounds with primary or secondary amino group, e.g. B. aniline derivatives, with a nitrogen containing heterocyclic compound, e.g. B. primary hetero aroma  table amines, or an aromatic hydroxy compound used will. On the one hand, these are connections that stand alone Dye hair only weakly and only together with the aryl ketones of the formula I give brilliant colorations. On the other hand but also including compounds that are used as oxidation dye prepro Find products and suitable for hair dyeing alone are; in the presence of the aryl ketones of the formula I, however, are still stronger, more brilliant shades with even better authenticity properties achieved.

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-dichloro- p-phenylene diamine, 2-chloro-p-phenylene diamine, 2,5-dihydroxy-4-morpho lininoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylene diamine, 2,5-diaminotoluene, phenol, anisole, phenethole, 2-chloro-p- phenylenediamine, 4-methylamino, 3-, 4-dimethylamino, 3,4-methylene dioxyaniline, 3-amino-2,4-dichloro, 4-methylamino, 2-methyl-5-ami no-, 3-methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 2-Me thyl-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-ami nobenzoic acid, phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-di aminobenzoic 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, hexaaminobenzene 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'-diaminodiphenylamine-2- sulfonic acid, 4,4'-diaminobenzophenone, diphenyl ether, 3,3 ', 4,4'-Te traaminodiphenyl-tetrahydrochloride, 3,3 ', 4,4'-tetraamino-benzophe non, 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. 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, 3,5-diamino-2,6-dimethoxy, 2,4,5-triamino, 2,6-di hydroxy-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-amino-quinaldine, 2-, 6-aminonicotinic acid, 5-amino noisoquinoline, 4-, 5-, 6-, 7-aminoindole, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholino aniline and indole and indoline derivatives, e.g. B. 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, as well as their before preferably inorganic acids such. B. hydrochloric or sulfuric acid formed salts.

Suitable aromatic hydroxy compounds are e.g. B. 2-, 4-, 5-Me thylresorcinol, 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, acetophenone, 2-, 4-methyl-, 2-, 4-chlororesorcinol, 1-, 2-naphthol, 1,5-, 2,3-, 2,7-dihydroxynaph thalin, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-di hydroxy-2,7-naphthalenesulfonic acid.

Also amino acids or oligopeps composed of 2 to 9 amino acids tides are suitable. All occur naturally as amino acids menden and synthetic amino acids in question, e.g. B. by Hy Drolysis from vegetable or animal proteins, e.g. B. collagen, Keratin, casein, elastin, soy protein, wheat gluten or almond pro no accessible amino acids. It can be both acidic and alkaline amino acids are used. Suitable oli gopeptides are all naturally occurring and synthetic Amino acid 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.

Several different aryl ketones can also be used in all colorants Formula I are used together; also meh different components from the groups of compounds with primary or secondary amino group, of nitrogen-containing hetero cyclen, aromatic hydroxy compounds or amino acids together be used.  

The colorants already result in physiologically acceptable ones Temperatures below 45 ° C intense coloring. They are suitable therefore especially for coloring human hair. For use On human hair, the colorants can be immersed in water containing cosmetic carriers are incorporated. Suitable what cosmetic carriers containing ser are e.g. B. creams, emulsions, gels or also surfactant-containing foaming solutions such. B. shampoos or other preparations that are suitable for use on the hair are.

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 use of water-free carriers is also suitable if that substrate to be colored is moistened with water. As anhydrous Carriers are suitable for. B. combined with anhydrous emulsifiers Oils such as paraffin oils or silicone oils with low to medium viscosity sity.

The aryl ketones of formula I and the compounds with primary or secondary amino group, the amino acids or from 2 to 9 amino acids built-up oligopeptides, the nitrogen-containing heterocycles or the aromatic hydroxy compounds are in an amount of 0.3 to 65, preferably 6 to 20 mmol, each based on Contain 100 g of the entire 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 hair coloring, the colorants are in the form of the water-containing - or the anhydrous - cosmetic carrier in a quantity from 50-100 g applied to the hair, leave there for about 30 minutes and then rinsed out or with a commercially available hair shampoo washed out.

The two reactive components 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 escape together and separately the water-free or already stored in the finished formulation will. When stored separately, the reactive components only intimately mixed with one another immediately before use. The anhydrous storage can be either in powder form or in anhydrous gels or dispersions. When stored as a powder a defined amount of 50-80 ° C warm water is added to the mixture added and a homogeneous mixture made. Using of an anhydrous gel can be mixed with water or one direct application to damp hair.

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 aryl ketone of the formula became I and 10 mmol of a reactant, 10 mmol of sodium acetate and one Drop of a 20% fatty alkyl ether sulfate solution in 100 ml of water prepares. The slurry was heated to boiling temperature and filtered after cooling, the pH was then adjusted to 6 set.

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 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 (2)

1. Use of aryl ketones of the formula I. in which R¹ is a C₁-C₄-alkyl group or an aryl group and R¹ is also a C₁-C₄-alkylidene group or an isoelectronic N-, S- or O-containing, optionally benzo-fused group which is bonded to the aromatic radical of the formula I. can, and R², R³ and R⁴ independently of one another for hydrogen, halogen atoms, hydroxyl groups, C₁-C,-alkoxy groups, C₁-C₄-alkyl groups, C₂-C₄-hydroxyalkyl groups, amino (C₁-C₄) alkyl groups, C₁-C₄- Alkoxy- (C₁-C₄) -alkyl groups, nitro, carboxy or sulfo groups or NR⁵R⁶ groups, where R⁵ and R⁶ are C₁-C₄-alkyl groups or C₂-C₄-hydroxyalkyl groups and together with the N atom also a 5th -, 6- or 7-membered ring can represent and their ketals, for dyeing keratin-containing fibers, especially human hair. 2. Use according to claim 1, characterized in that the Aryl ketone of formula I is selected from acetophenone, 2-hydro xyacetophenone, 4-hydroxyacetophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,4,6-tri hydroxyacetophenone, 2,3,4-trihydroxyacetophenone, and quercetin.