WO1995031959A1 - 2-oxyacetic acid derivatives for colouring keratin-containing fibres - Google Patents

Abstract

The object of the invention is the use of 2-oxyacetic acid derivatives for colouring keratin-containing fibres, especially human hair, and colorants containing said compounds, especially in combination with amines, amino acids and phenols.

Description

 "2-0xoic acid derivatives for dyeing eratin fibers"

The invention relates to the use of 2-0xoacetic acid derivatives for dyeing keratin fibers and dyes 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 happens 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.

Dyeing systems based on the 2-0xoacetic acid derivatives described in more detail below have so far not been known for dyeing keratin-containing fibers.

Surprisingly, it has now been found that 2-0xoacetic acid derivatives 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. For example, wool, furs, skins and human hair can be considered as fibers containing keratin. The 2-0xoacetic acid derivatives described in more detail below can in principle also be used for dyeing other natural fibers, such as cotton, jute, sisal, linen or silk, modified natural fibers, such as regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers , such as polyamide, polyacrylonitrile, -, polyurethane and polyester fibers can be used.

The invention relates to the use of 2-0xoacetic acid derivatives of the formula I.

eine Arenoylgruppe, eine C3-Cs-Alkenyl- gruppe, eine Mono- oder Dihydroxy-C2-Cö-alkylgruppe, eine Amino-Cι-C4- alkylgruppe, eine Sulfo-Cι-C4-alkylgruppe, eine Carboxy-Cj-C4-alkylgruppe, eine 2-Furylmethyl-, 2-Thienylmethyl-, 2-Pyridylmethyl-, 3-Pyridylmethyl- oder 4-Pyridylmethylgruppe oder für eine Gruppe der Formel II,

in which R ¹ and R ^ independently of one another for hydrogen, halogen atoms, C 1 -C 4 -alkyl groups, Ci-C / j-alkanoyl groups, Ci-Cj-alkoxy groups, nitro, hydroxyl, sulfo, carboxyl or NR ⁴ R ^ -Groups, where R ⁴ and R ^ independently of one another are hydrogen or Cj-C / j-alkyl groups, and R3 is hydrogen, a Ci-Cz ^ -alkyl group, an aryl group, a hydroxy group, one optionally with Ci-C / j-alkyl or aryl substituted amino group, a

an arenoyl group, a C3-Cs-alkenyl group, a mono- or dihydroxy-C2-Cö-alkyl group, an amino-Cι-C4-alkyl group, a sulfo-Cι-C4-alkyl group, a carboxy-Cj-C4-alkyl group , a 2-furylmethyl, 2-thienylmethyl, 2-pyridylmethyl, 3-pyridylmethyl or 4-pyridylmethyl group or for a group of the formula II,

stands in which R ^ and R? independently of one another, hydrogen, halogen atoms, hydroxyl groups, amino groups substituted with Cχ-C4-alkyl or aryl, Cι ~ C4-alkyl groups, Cι-C4-alkoxy groups, carboxy groups, sulfo groups mean, R ⁸ for hydrogen, a Cι-C4 alkyl group or a _2-C6-hydroxyalkyl group and n stands for 0, 1 or 2, and their alkali, alkaline earth or ammonium salts for dyeing keratin-containing fibers.

Preferred uses are 2-0xoacetic acid derivatives of the formula I in which R is a hydrogen atom or a sulfo group and R ^ and R ^ are hydrogen.

Examples of the 2-0xoacetic acid derivatives to be used according to the invention are: 2- (2-aminophenyl) -, 2- (2-amino-5-methylphenyl) -, 2- (2-amino-5-chlorophenyl) -, 2- (2-amino-5-nitrophenyl) -, 2- (2-amino-5-methoxyphenyl) -, 2- (2-hydroxylaminophenyl) -, 2- (2- (2-hydroxylethylamino) - phenyl) -, 2- (2-benzylaminophenyl) -, 2- (2- (2-sulfoethylamino) -phenyl) -, 2- (2- (3-sulfopropylamino) -phenyl) -, 2- (2- Allylaminophenyl) -, 2- (2-carboxymethylaminophenyl) -, 2- (2-amino-5-bromophenyl) -, 2- (2-amino-5,7-di-chlorophenyl) -, 2- (2-amino- 5-sulfophenyl) -, 2- (2-amino-5-carboxyphenyl) -, 2- (2-amino-4-carboxyphenyl) -, -2-oxoacetic acid and its sodium, potassium, ammonium and calcium salts .

Most of these substances are known from the literature and are prepared by alkaline hydrolysis of the corresponding isatin derivatives.

Some of the 2-0xoacetic acid derivatives of the formula I are new substances. For this reason, 2-0xoacetic acid derivatives of the formula I mel 1 I claimed, in which R ^ stands for hydrogen and R * represents a sulfo group located in the 5-position. A manufacturing method is given in the example section.

The 2-0xoacetic acid derivatives of the formula I give shades in the pale yellow to yellow range. The wash resistance of the dyeings is surprisingly high. Particularly brilliant colorations in the yellow, brown, green, violet and black range with good fastness properties (light fastness, wash fastness, fastness to rubbing) are achieved if the 2-0xoacetic acid derivatives of the formula I together with compounds having a primary or secondary amino group a nitrogen-containing heterocyclic compound or an aromatic hydroxy compound can be used. On the one hand, these are compounds which, on their own, also only weakly dye hair and only give brilliant dyeings together with the 2-0xoacetic acid derivatives 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 on their own; in the presence of the 2-0xoacetic acid derivatives of the formula I, however, even stronger, more brilliant shades with even better fastness properties are achieved.

Another subject of the invention is therefore agents for dyeing keratin-containing fibers containing at least one 2-0xoacetic acid derivative of the formula I and a compound having a 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-phenylene diamine, 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- Methylenedioxyan lin, 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-amino- methyl-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-aminobenzenesulfonic 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-hydroxy-naphthalene-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-tetraamino-benzene-tetrahydrochloride, 2, 4,5-triaminophenol-trihydrochloride, penta-aminobenzene-pentahydrochloride, hexamaminobenzene-hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzate catechol sulfate, 4,6-dia inopyrogallol dihydrochloride, 3,5-diamino -4-hydroxybrenzcatechin-sulfonic fat, aromatic Am ^* 1ine or phenols with a further aromatic radical, such as 4,4'-diaminostilbene-dihydr ochloride, 4.4 ^l -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 trihydrochloride.

Suitable nitrogen-containing heterocycles are, for example, 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethyl amino-5-amino-, 3-amino ^* -2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, S ^ -diamino-Σ.δ-dimethoxy-, 2,4,5- Triamino-, 2,6-dihydroxy-3,4-dimethyl-pyridine, 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 as well as indole and indoline derivatives, e.g. 5,6- Dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, as well as their with preferably inorganic acids such. B. hydrochloric or sulfuric acid salts formed.

Suitable aromatic hydroxy compounds are e.g. 2-, 4-, 5-methylresorcinol, 3-dimethylaminophenol, 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-tri-hydroxybenzoic acid, -acetophenone, 2-, 4th -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.

Particularly suitable compounds with a primary or secondary amino group are amino acids or oligopeptides composed of 2 to 9 amino acids. Another subject of the invention is therefore agents for dyeing keratin-containing fibers containing at least one 2-0xoacetic acid derivative 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.

All naturally occurring and synthetic amino acids are suitable as amino acids, e.g. which are obtained 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 oligopeptides are all oligopeptides composed 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 hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein.

However, those amino acids or oligopeptides that are selected from are particularly suitable for use in the colorants according to the invention the group tyrosine, histidine, lysine, phenylalanine, ornithine, DOPA, arginine and tryptophan.

Several different 2-0xoacetic acid derivatives 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, 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 fatty acids, 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. B. gum arabic, karaya gum, guar gumrni, locust bean gum, linseed gums and pectin, biosynthetic gums, eg xanthan gum i and dextrans, synthetic gums, e.g. B. agar and algin, starch fractions and derivatives such as amylose, amylopectin and dextrins, modified cellulose molecules, for. 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 as well as reducing agents for stabilizing the ingredients, e.g. B. 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 2-0xoacetic acid derivatives of the formula I and the compounds having a primary or secondary amino group, e.g. 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, in each case based on 100 g of the entire colorant, contain.

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; 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 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 (2-0xoacetic acid derivative of the formula I and amino group-containing compound, nitrogen-containing heterocycle or the aromatic hydroxy compound) can either be applied to the hair simultaneously or in succession, it being irrelevant 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 separately and together either anhydrous or already in the finished formulation. When stored separately, the reactive components are only intimately mixed with one another immediately before use. With dry storage, a defined amount of warm (50 - 80 ° C) water must be added and a homogeneous mixture created.

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

B e i s p i e l e

Manufacturing example:

2- (2-Arino-5-sulfophenyl) -2-oxoacetic acid, disodium salt

A solution of 50 g (0.164 mol) of 82% isatin-5-sulfonic acid, Na salt (contains 7% water and 11% sodium sulfate) in 500 ml of water was adjusted to pH 11.3 with 2N sodium hydroxide solution and 8 to 9 Heated to 40 ° C. until no more isatin-5-sulfonic acid, Na salt could be detected in the TLC. The mixture was then evaporated to 200 ml under reduced pressure and the solution thus obtained was used for colorations. The chemical structure of the evaporation residue was confirmed by H-NMR. The free acid was obtained by increasing the evaporation residue with a little water, adjusting the pH to 3, again evaporating under reduced pressure at a maximum of 30 ° C. and extracting the residue with a little warm ethanol after evaporating off the solvent under reduced pressure.

Preparation of a coloring solution:

There was a slurry of 10 mmol of a 2-0xoacetic acid derivative of the formula I and 10 mmol of a compound containing an amino group, an aromatic hydroxy compound or a nitrogen-containing heterocycle, 10 mmol of sodium acetate and a drop of a 20% fatty alkyl ether sulfate solution in 100 ml Prepares water. The slurry was heated to boiling temperature and filtered after cooling, the pH was then adjusted to 6.

90% gray, untreated human hair was placed in 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. Color depth was rated on the following scale:

no or a very pale color weak intensity

+ medium intensity

+ (+) medium to strong intensity

++ strong intensity

++ (+) strong to very strong intensity

+++ very strong intensity

Table 1

Colorings with 2- (2-A_rino-5-sulfopheπyl) -2-oxoessiqs5ure. Nβ2 salt

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

Continuation: Table 1

Color bit 2- (2-A_ino-5-sulfophenyl) -2-oxoessiqs_ure. Na2 salt

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

T a b e l l e 2

Colorings with 2-.2-A-rinophenyl) -2-oxoessiqs5ure

Amino group-containing compound or

Continued: T a b e l l e 2

Ausfärbunqen _rit 2- (2-A_ιinophenyl) -2-oxoessiqäure

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

Claims

Patent claims 1. Use of 2-0xoacetic acid derivatives of the formula I

in which R and R ^ independently of one another for hydrogen, halogen atoms, C 1 -C 4 -alkyl groups, C 1 -C 4 -alkanoyl groups, C 1 -C 4 -alkoxy groups, nitro, hydroxyl, sulfo, carboxyl or NR ⁴ R ⁵ - Groups are, where R ⁴ and R5 independently of one another are hydrogen or C 1 -C ⁴ -alkyl groups, and R ^{3 is} hydrogen, a C 1 -C 4 -alkyl group, an aryl group, a hydroxyl group, one optionally with C 4 -C 4 -alkyl or aryl substituted amino group, a C 1 -C 4 alkanoyl group, an arenoyl group, a C 3 -C 6 alkenyl group, a mono- or dihydroxy-C 2 -C 6 alkyl group, an amino C 1 -C 4 alkyl group, a sulfo C 1 -C 4 alkyl group alkyl group, a carboxy-C4-alkyl group, a 2-furyl, 2-thienyl, 2-pyridylmethyl, 3-pyridylmethyl or 4-pyridylmethyl group or for a group of formula II, (II),

stands in which R ^ and R? independently of one another, hydrogen atoms, halogen atoms, hydroxyl groups, amino groups substituted with C 1 -C 4 -alkyl or aryl, C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy groups ₍ carboxyl groups, sulfo groups, R ⁸ for hydrogen, a C 1 - C4-alkyl group or a C2-C5-hydroxyalkyl group and n stands for 0, 1 or 2, and their alkali metal, alkaline earth metal or ammonium salts for dyeing fibers containing keratin. 2. Use according to claim 1, characterized in that R ^{1 is} a hydrogen atom or a sulfo group and R ^ and R ^{3 are} hydrogen. 3. 2-0xoacetic acid derivatives of the formula I, where R ^ is hydrogen and R is a sulfo group in the 5-position. 4. Containing agents for dyeing fibers containing keratin, in particular human hair at least one 2-0xoacetic acid derivative 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. 5. Composition according to claim 4, containing at least one compound of formula I, at least one amino acid or an oligopeptide composed of 2 to 9 amino acids and a water-containing carrier. 6. Composition according to claim 5, characterized in that the amino acid or the oligopeptide are selected from the group tyrosine, histidine, lysine, phenylalanine, ornithine, DOPA, arginine and tryptophan. 7. Composition according to claim 4, characterized in that at least one 2-0xoacetic acid derivative of the formula I in an amount of 0.3 to 65, preferably 6 to 20 mmol, and at least one compound containing amino groups or a nitrogen-containing heterocycle in a quantity from 0.3 to 65, preferably 6 to 20 mmol, based in each case on 100 g of the total colorant, are present. 8. Composition according to claim 5, characterized in that at least one 2-0xoacetic acid derivative 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 of 0.3 to 65, preferably 6 to 20 mmol, based in each case on 100 g of the entire colorant, are present.