WO1996022077A1

WO1996022077A1 - Aryl ketones for colouring keratin-containing fibres

Info

Publication number: WO1996022077A1
Application number: PCT/EP1996/000062
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: DE19501303A1

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) R1 is a C¿1?-C4-alkyl group or an aryl group and R?1¿ may also be a C¿1?-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, R3 and R4¿ are mutually independently hydrogens, halogen atoms, hydroxy groups, C¿1?-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?5R6¿ groups, in which R?5 and R6¿ are C¿1?-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

"Aryl ketones for dyeing keratin fibers"

The invention relates to the use of certain aryl ketones for dyeing keratin-containing fibers, in particular human hair.

For dyeing keratin fibers, e.g. B. hair, wool or furs, generally either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with each other 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. H2Ü2, 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 aryl ketones 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. The use of the aryl ketones described 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 aryl ketones described below can also be used to dye 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 aryl ketones of the formula I

in which R represents a C 1 -C 4 -alkyl group or an aryl group and R * also a C 1 -C 4 -alkylene group which is connected to the aromatic radical of the formula I or an N, S or O-containing isoelectronic group , optionally benzo-fused, and R ^, R and R ⁴ independently of one another for hydrogen, halogen atoms, hydroxy groups, -C-C _} - alkoxy groups, -C-C4-alkyl groups, C2 ~ C4-hydroxyalkyl groups, amino (-C-C4) alkyl groups, -C-C4-alkoxy- (Cι-C.4) - alkyl groups, nitro, carboxy or sulfo groups or groups NR5R6, where R5 and R & Cι-C4 ~ alkyl groups or C2 ~ C4- Hydroxyalkyl groups mean and together with the N atom can also represent a 5-, 6- or 7-membered ring or the aromatic system represents a usnic acid residue and their ketals for dyeing keratin fibers, in particular human hair.

Examples of the aryl ketones or their ketals to be used according to the invention are: acetophenone, propiophenone, 2-, 3-, 4-hydroxyacetophenone, -propiophenone, -butyrophenone, 2,4-, 2,5-, 2,6-dihydroxyacetophenone , 2,3,4-, 3,4,5-, 2,4,5-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 - Hydroxy-, 2,4,4'-, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1, 1-hydroxy-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 - hydroxyanthrone.

Acetophenone, 2-hydroxyacetophenone, 4-hydroxyacetophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,3,4-trihydroxyacetophenone and quercetin are preferably used and (+) - usnic acid.

These substances are generally Known from the literature or available in chemicals trade.

The aryl ketones of formula I alone only weakly stain keratin fibers. Brilliant colorations in the orange, brown, red-brown, blue-black and black range with good fastness properties (fastness to light, fastness to washing, fastness to rubbing) are achieved if the aryl ketones of the formula I together with compounds having a primary or secondary amino group, for example aniline derivatives , with a nitrogen-containing heterocytic compound, eg primary heteroaro a- table amines, or an aromatic hydroxy compound can be used. On the one hand, these are compounds which also only weakly dye hair on their own and only give brilliant colorations together with the aryl ketones of the formula I. On the other hand, however, there are also compounds which are used as oxidation dye precursors and which are suitable for dyeing hair on their own; in the presence of the aryl ketones of the formula I, however, even stronger, more brilliant shades with even better fastness properties are achieved.

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-phenylene diamine, 2-chloro-p-phenylene diamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4- Aminophenol, o-, m-, p-phenylene diamine, 2,5-diaminotoluene, phenol, anisole, phenethole, 2-chloro-p-phenylene diamine, 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, 5th - (2-Hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2- a inomethyl-phenol, l, 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-amino benzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic 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-triaminobenzene, 1,2,4 , 5-tetraaminobenzene tetrahydrochloride, 2,4,5-Tπ ^' aminophenol trihydrochloride, pentaaminobenzene pentahydrochloride, hexaaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzene catechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diaπrino-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'-diaminodiphenyl ethane, 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, 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-2,5-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-, 2nd -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 as well as indole and indoline derivatives, eg 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, as well as 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, 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-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, e.g. which by hydrolysis from vegetable or animal proteins, e.g. Collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein accessible amino acids. Both acidic and alkaline amino acids can be used. Suitable 01igopeptides 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 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 aryl ketones 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 colorants 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 can be incorporated into a water-containing cosmetic carrier. 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 apholytic surfactants, for example fatty alcohol sulfates, alkane sulfonates, α-olefin sulfonates, fatty alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide addition products with fatty alcohols, with fatty acids, with sorbitan fatty acids, with sorbitan fatty acids, with alkyl phenols 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 form; water-soluble polymeric thickeners such as natural gums, e.g. B. gum arabic, karaya gum, guar gum, locust bean gum, linseed gums and pectin, biosynthetic gums, such as xanthan gum and Dextraπe, synthetic gums, z. 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. 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 use of water-free carriers is also suitable if the substrate to be colored is moistened with water. Suitable water-free carriers are e.g. Oils combined with anhydrous emulsifiers such as paraffin oils or silicone oils of low to medium viscosity.

The aryl ketones 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 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, for example, 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; sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate are preferred, which in the given case are present in an amount of 0.3 to 65, preferably 6 to 20 mmol, based on 100 g of the total colorant, are contained. The pH of the ready-to-use coloring preparations is between 2 and 11, preferably between 5 and 9.

For hair dyeing, the colorants are applied to the hair in the form of the water-containing, or else the water-free, cosmetic carrier in an amount of 50-100 g, left there for about 30 minutes and then rinsed out or washed out with a commercially available hair shampoo.

The two reactive components 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 a time 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 together and separately 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. The water-free storage can take place either in powder form or in water-free gels or dispersions. When stored as a powder, a defined amount of 50-80 ° C warm water is added to the mixture and a homogeneous mixture is produced. If an anhydrous gel is used, it can be mixed with water or applied directly to damp hair.

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 mmoles of an aryl ketone 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 etched 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 are shown 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

Claims

claims

1. Use of aryl ketones of the formula I.

in which R 4 represents a C 1 -C 4 -alkyl group or an aryl group and R * also a C 1 -C 4 -alkylidene group or an isoelectronic N-, S- or O-containing, optionally connected to the aromatic radical of the formula I can be benzo-fused group, and R ^, R3 and R ⁴ independently of one another for hydrogen, halogen atoms, hydroxyl groups, C _j -C4-alkoxy groups, C _j -C4-alkyl groups, C2 ~ C4-hydroxyalkyl groups, amino ((-C-C4 ) -alkyl groups, -C-C4-alkoxy- (-C-C4) -alkyl groups, nitro, carboxy or sulfo groups or groups R ^ RÖ, where R5 and R ^ Cι-C4-alkyl groups or C2 ~ C4 -Hydroxyalkyl groups and together with the N atom can also represent a 5-, 6- or 7-membered ring or the aromatic system is a usnic acid residue and their ketals for dyeing keratin fibers, in particular human hair. Use according to claim 1, characterized in that the aryl ketone of formula I is selected from acetophenone, 2-hydroxyacetophenone, 4-hydroxyacetophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,4 , 6-tri-hydroxyacetophenone, 2,3,4-trihydroxyacetophenone, quercetin and (+) - usnic acid.