WO1999020597A1 - Novel aminophenol derivatives and the use thereof for dyeing keratin fibres - Google Patents

Abstract

The invention relates to novel aminophenol derivatives of general formula (I), wherein R<1> and R<2> represent (a) an alkyl group with 1 to 4 C-atoms or (b) an alkoxy group with 1 to 4 C-atoms on the condition that in each case, exactly one substituent from group (a) and exactly one substituent from group (b) is represented, and R<3> preferably represents hydrogen or a C1-C4 alkyl group. The invention also relates to the use of the novel aminophenol derivatives for dyeing keratin fibres and to dyes containing these compounds.

Description

NEW AMINOPHENOL DERIVATIVES AND THEIR USE FOR DYING KERANTINE FIBERS

The invention relates to new aminophenol derivatives, their use for dyeing keratin fibers and dyes containing these compounds.

For dyeing keratin fibers, especially human hair, the so-called oxidation colorants play a preferred role because of their intense colors and good fastness properties. Such colorants contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components.

Good oxidation dye precursors must first of all meet the following requirements: they must develop the desired color shades with sufficient intensity and authenticity in the oxidative coupling. They must also have a good ability to draw onto the fiber, whereby there must be no noticeable differences between stressed and freshly regrown hair, especially with human hair (leveling ability). They should be resistant to light, heat and the influence of chemical reducing agents, e.g. B. against perm fluids. After all, if they are used as a hair dye, they should not stain the scalp too much, and above all they should be harmless from a toxicological and dermatological point of view.

Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4- Aminopyrazolone derivatives and 2,4,5, 6-tetraaminopyrimidine and its derivatives are used.

Preferred developer components are p-phenylenediamine, p-toluenediamine, p-aminophenol, 1 - (β-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- ( 2,5-diaminophenoxy) ethanol, 4,5-diamino-1 - (2-hydroxyethyl) pyrazole, l-phenyl-3-carboxyamido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2 - On nomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-aminomethyl-4-aminophenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diammopyrrmidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-hydroxyethylaminomethyl-4-amino-phenol, 1,3-bis- [N- (2-hydroxyethyl) -N- (4-aminophenyl) amino] -2-propanol and 4,4'-diamino-diphenylamine.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components. 1-Naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomino methyl ether, m-phenylenediamine, l-phenyl are particularly suitable as coupler substances -3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, l, 3-bis (2,4-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro -6-methy 1-3 -aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol o-aminophenol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2 , 6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-bis (2-hydroxyethylamino) toluene, 2nd , 4-diaminophenoxyethanol and 2-an ino-4-hydroxyethylamino-anisole.

With a developer component or a special coupler / developer combination alone, it is usually not possible to obtain a color shade that looks natural on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. There is therefore a constant need for new, improved dye components. It was therefore the object of the present invention to find new coupler components which meet the requirements placed on oxidation dye precursors to a particular degree.

It has now been found that certain aminophenol derivatives meet the requirements imposed on coupler components to a high degree. Thus, using these coupler components with most known developer components, brilliant red to magenta color shades are obtained, which are extraordinarily lightfast and washable.

A first subject of the present invention are therefore aminophenol derivatives of the general formula (I)

in der R¹ und R² (a) für eine Alkylgruppe mit 1 bis 4 C-Atomen oder (b) für eine Alkoxygruppe mit 1 bis 4 C-Atomen stehen, mit der Maßgabe, daß jeweils genau ein Substituent aus der Gruppe (a) und genau ein Substituent aus der Gruppe (b) vertreten ist und R³ steht für

in which R ¹ and R ^{2 are} (a) an alkyl group with 1 to 4 carbon atoms or (b) an alkoxy group with 1 to 4 carbon atoms, with the proviso that in each case exactly one substituent from the group (a ) and exactly one substituent from group (b) is represented and R ³ stands for

- hydrogen,

a C _r to C ₄ alkyl group,

a C ^ -dihydroxyalkyl group,

a methyl group which carries 1 to 3 halogen atoms, in particular fluorine atoms, as substituents,

- A C - ^ - alkyl group with a maximum of 1 - 4 halogen atoms, especially fluorine atoms, as substituents

- a group - (CH ₂ ) _X -B, in which B stands for

- a hydroxy group,

- a group NR ⁵ R ⁶ or a group CO-NR ⁷ R ⁸ and x for a number from 1 to 4,

- a group -COOR ⁹ or

- A group -CO-NR ^{, 0} R ^π , where R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ^{11 are} independently hydrogen, a C _M alkyl group, a C hydroxy alkyl group and R ⁵ and R ⁶ , R ⁷ and R ⁸ as well as R ¹⁰ and R ¹¹ each together with the nitrogen atom carrying them can also be part of a morpholino, piperidino or pyrrolidino radical and R ^{5 can} also represent a group -SO ₂ -CH ₃ with the proviso that R ⁶ stands for hydrogen, and R ⁹ stands for hydrogen or a C _M alkyl group, and their water-soluble salts.

For the purposes of the present application, preference is given to aminophenol derivatives in which R ^{1 is} a substituent selected from group (a) and R ^{2 is} a substituent selected from group (b).

Aminophenol derivatives of the formula (I) in which R ^{3 represents} a C _r to C ₄ alkyl group, in particular hydrogen, are particularly preferred.

Also particularly preferred are aminophenol derivatives according to formula (I) in which R ^{1 represents} a methyl group and R ^{2 represents} a methoxy group.

Particularly preferred compounds for the purposes of the present invention are 6-methoxy-2-methyl-3-aminophenol and 6-methoxy-2-methyl-3- (β-hydroxyethylamino) phenol.

These compounds are prepared starting from the appropriately substituted nitrophenols (known from Eur. J. Med. Chem. (1995), 185) by hydrogenation and possibly subsequent alkylation or acylation. For details, reference is made to the synthesis example detailed in the example section. Since all of the substances according to the invention are amino compounds, the known acid addition salts can be prepared from them in a conventional manner. All statements in this document and accordingly the claimed scope of protection therefore relate both to the aminophenol derivatives of the formula (I) present in free form and to their water-soluble, physiologically tolerable salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates.

A second object of the present invention is the use of the aforementioned aminophenol derivatives as a coupler component in oxidation hair colorants.

Finally, a third object of the present invention are oxidation coloring agents for dyeing keratin fibers containing coupler components and developer components in a water-containing carrier, which contains one of the aforementioned aminophenol derivatives as the coupler component.

Keratin fibers in the sense of the present application are to be understood as furs, wool, feathers and in particular human hair. Although the oxidation colorants according to the invention are primarily suitable for dyeing keratin fibers, there is in principle nothing to prevent their use in other areas, particularly in color photography.

The oxidation colorants according to the invention can contain one or more developer components and, if desired, further coupler components in addition to the coupler components according to the invention. With regard to the further developer and coupler components, reference is made to the substances listed at the beginning of the description, which are preferred further dye components. Particularly preferred developer components are 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 1 - (β-hydroxyethyl) -2,5-diaminobenzene, p-phenylenediamine, p-toluenediamine, p-aminophenol, 3-methyl-p-aminophenol, 2- Hydroxy-methyl-p-aminophenol and 2-aminomethyl-p-aminophenol. According to the invention, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomino methyl ether, m-phenylenediamine, l-phenyl are particularly suitable as coupler components -3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, l, 3-bis (2,4-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro -6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol o-aminophenol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2, 6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-bis (2-hydroxyethylamino) toluene, 2,4-diaminophenoxyethanol and 2-amino-4-hydroxyethylamino-anisole are suitable. These further developer and coupler components are usually used in free form. For substances with amino groups, however, it can be preferred to use them in salt form, in particular in the form of the hydrochlorides and sulfates.

The hair colorants according to the invention preferably contain both the developer components and the coupler components in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, in each case based on the total oxidation colorant. Developer components and coupler components are generally used in approximately molar amounts to one another. If the molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components can be present in a molar ratio of 1: 0.5 to 1: 2.

In a preferred embodiment, the hair colorants according to the invention contain, in addition to the oxidation dye precursors, customary direct dyes, for example from the group of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, such as, for example, under the international names or trade names HC, in addition to the oxidation dye precursors Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds, as well as 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, 6-nitro-1 , 2,3, 4-tetrahydroquinoxaline, hydroxyethyl 1-2-nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol and 4-N-ethyl-1,4-bis (2'-hydroxyethylamino) - 2-nitrobenzene hydrochloride in an amount of 0.01 to 20% by weight, based on the entire oxidation hair dye. 4-.Amino-2-nitro-diphenyl.amin-2'-carboxylic acid, 6-nitro-l, 2,3,4-tetrahydroquinoxaline and HC Red BN are particularly preferred direct dyes according to the invention.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten bark, sage, blue wood, madder root, catechu, sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the optional direct dyes each represent uniform compounds. Rather, in the hair colorants according to the invention, due to the production processes for the individual dyes, further components may also be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.

With regard to the dyes which can be used in the hair colorants and tints according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European inventory of cosmetic raw materials ", published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicinal Products, Health Care Products and Personal Care Products, M-annheim. To produce the colorants according to the invention, the oxidation dye precursors are incorporated into a suitable water-containing carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, for example shampoos, aerosols or other preparations which are suitable for use on the hair.

Furthermore, the colorants according to the invention can contain all active ingredients, additives and auxiliaries known in such preparations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

linear fatty acids with 10 to 22 carbon atoms (soaps),

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,

Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,

Acyl taurides with 10 to 18 carbon atoms in the acyl group,

Acyl isethionates with 10 to 18 carbon atoms in the acyl group, Sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyls with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 12 to 18 carbon atoms, linear alpha Olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH-CH O) -SO H, in which R preferably a linear alkyl group with 10 to 18 C Atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO - or -SO group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyldimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C _g . _lg - alkyl or acyl group in the molecule contain at least one free amino group and at least one -COOH or -SO H group and

Are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylamino propionate and C -acylsarcosine.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

Addition products of 2 to 30 mol ethylene oxide and / or 0 to 5 mol propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group C _12.22 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol, C 1 alkyl mono- and oligoglycosides and their ethoxylated analogues,

8-22

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened

Castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, methyl l-alkylamidoemyl-2-alkylimidazolium -nium methosulfate and tricetylmethylammonium chloride. The quaternized protein hydrolysates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abü ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid ^® S 18, are characterized in particular by their good biodegradability.

Also very readily biodegradable quaternary Esterverbindungen, so-called "esterquats", such as those sold under the trademark Stepantex ^® are methyl hydroxyalkyldialkoyloxyalkyl-methosulfates. An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates. By contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Other common components of the preparations according to the invention can be:

Anionic, zwitterionic, amphoteric and non-ionic polymers such as, for example, vinyl acetate / crotonic acid copolymers, polydimethylsiloxanes, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid and anhydride polyesters, non-crosslinked polymers, non-copolymerized copolymers, non-copolymerized copolymers Acryl amidopropyl trimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl memacrylate / tert-butyl.arninoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, Vinylpyrrolidone / DimemylammoethylmemaciylatA ^ inylcaprolactam terpolymers and optionally derivatized cellulose ethers. Symmetrical and asymmetrical, linear and branched dialkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, for example di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether and di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether as well as di-tert -butyl ether, di-isopentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, isopentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether, defoamers such as silicones,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, gelatin, pectins, cellulose derivatives, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as. B. bentonite or fully synthetic hydrocolloids such as e.g. Polyvinyl alcohol and polyacrylamide structurants such as maleic acid, mono-, di- and oligosaccharides, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, dyes for coloring the agent,

Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol, other substances for adjusting the pH, animal and vegetable protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein, almond protein and wheat protein hydrolysates, and their fatty acid condensation products and quaternized derivatives,

Vitamins and vitamin precursors, such as panthenol, its derivatives and biotin, plant and honey extracts, such as in particular extracts from oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, linden flowers, almond, aloe vera, coconut, mango, apricot, lime, Wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, cuckoo flower, quendel, yarrow, hake, meristem, ginseng and ginger root, other active ingredients such as ceramides, allantoin, pyrrolidone carboxylic acids, and bisabolol, light stabilizers,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers, pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, complexing agents such as EDTA, NTA, ß-alanine diacetic acid and phosphonic acids, reducing agents and stabilizers such as e.g. Thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thio malic acid and α-mercaptoethanesulfonic acid, as well as ascorbic acid, sulfites and dithionites,

Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ , N ₂ and air as well

Antioxidants. With regard to further constituents and quantity ranges for the individual ingredients, reference is made to the manuals known to the person skilled in the art, e.g. K. Schrader, Fundamentals and Recipes for Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

The constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; For example, emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant. In principle, the oxidative development of the coloring can take place with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially when, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or their adducts with urea, melamine and potassium and sodium borate are suitable as oxidizing agents. It is also possible to carry out the oxidation with the aid of enzymes. The enzymes can be used to transfer atmospheric oxygen to the developer component or to enhance the effect of small amounts of oxidizing agents present. An example of an enzymatic process is the procedure to increase the effect of small amounts (eg 1% by weight and less, based on the total agent) of hydrogen peroxide by peroxidases.

The preparation of the oxidizing agent is expediently mixed with the preparation from the oxidation dye precursors immediately before hair coloring. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 10. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can range between 15 and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.

The following examples are intended to explain the subject of the invention in more detail.

Examples 1. Synthesis example

Synthesis of 6-methoxy-2-methyl-3-aminophenol

6 g (0.03 mol) of 6-methoxy-2-methyl-3-nitrophenol were hydrogenated in 100 ml of ethanol in the presence of 0.2 g of PdVC at a temperature of 20 ° C. and a pressure of 2x10 ⁵ Pa. After the hydrogen uptake had ended, the catalyst was filtered off, the filtrate was acidified with HC1 and then evaporated to dryness. Colorless crystals with a melting point of 230 ° C. were obtained as the product.

2. Colorings

First, a cream base of the following composition was produced [unless otherwise stated, all data are in g]:

Taig fatty alcohol 17.0

Lorol ^® techn. 4.0

Texapon ^® N 28 40.0

Dehyton ^® K ³ 25.0

Eumulgin ^® B 2 1.5 distilled water 12.5

C ₁₂ _ι ₈ fatty alcohol (HENKEL)

2

Sodium lauryl ether sulfate (approx. 28% by weight of active substance; CTFA name: Sodium Laureth Sulfate) (HENKEL)

Fatty acid amide derivative with betaine structure of the formula R-CONH (CH) N + (CH) CH COO "(approx. 30% by weight of active substance; CTFA name Cocoamidopropyl Betaine) (HENKEL)

-4

Cetylstearyl alcohol with approx. 20 mol EO (CTFA name: Ceteareth-20) (HENKEL)

The following hair color cream emulsion was then produced on the basis of this cream:

Cream base 50.0

Developer component 7.5 mmol Coupler component 7.5 mmol Na SO (inhibitor) 1.0

konz. Ammoniaklösung ad pH 10 Wasser ad 100

conc. Ammonia solution ad pH 10 water ad 100

The ingredients were mixed together in order. After the oxidation dye precursors and the inhibitor had been added, the pH of the emulsion was first adjusted to 10 using concentrated ammonia solution, and the mixture was then made up to 100 g with water.

The oxidative development of the color was carried out using 3% by weight hydrogen peroxide solution as the oxidation solution. For this purpose, 100 g of the emulsion were mixed with 50 g of hydrogen peroxide solution (3% by weight) and mixed.

The coloring cream was applied to approx. 5 cm long strands of standardized, 90% gray, but not specially pretreated human hair and left there at 32 ° C for 30 minutes. After the dyeing process was completed, the hair was rinsed, washed with a conventional shampoo and then dried. The following coupler and developer components were used for the coloring:

- Coupler component 6-methoxy-2-methyl-3-aminophenol (Kl)

- Developer components

2-ß-hydroxyethyl-p-phenylenediamine (El)

3-methyl-4-aminophenol (E2)

1 - (ß-hydroxyethyl) -2,5-diaminobenzene (E3) p-toluenediamine (E4)

Tetraaminopyrimidine (E5) p-aminophenol (E6)

The following colors were found:

Coupler developer nuance of colored hair

Kl El dark brown

Kl E2 red-brown

Kl E3 red black

Kl E4 photo brown

Kl E5 dark magenta

Kl E6 yellow-brown

Claims

claims Aminophenol derivatives of the general formula (I),

in which R ¹ and R ^{2 are} (a) an alkyl group with 1 to 4 carbon atoms or (b) an alkoxyl group with 1 to 4 carbon atoms, with the proviso that in each case exactly one substituent from the group (a ) and exactly one substituent from group (b) is represented and R ³ stands for - hydrogen, a C 1 -C ₄ -alkyl group, a C _3-4 dihydroxyalkyl group, - A methyl group which carries 1-3 halogen atoms, in particular fluorine atoms, as substituents, a C 1-4 alkyl group with a maximum of 1-4 halogen atoms, in particular fluorine atoms, as substituents - a group - (CH ₂ ) _X -B, in which B stands for - a hydroxy group, - a group NR ⁵ R ⁶ or a group CO-NR ⁷ R ⁸ and x for a number from 1 to 4, - a group -COOR ⁹ or - A group -CO-NR ¹⁰ R ", where R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ^u independently of one another represent hydrogen, a C -alkyl group, a C -hydroxy .alkyl group and R ⁵ and R ⁶ , R ⁷ and R ⁸ and R ¹⁰ and R ¹¹ each together with the nitrogen atom carrying them also form part of a morpholino, piperidino or pyrrolidino radical can and R ^{5 can} also represent a group -SO ₂ -CH ₃ with the proviso that R ⁶ then represents hydrogen, and R ⁹ represents hydrogen or a C - alkyl group, as well as their water-soluble salts. 2. Aminophenol derivatives according to claim 1, characterized in that R ^{1 stands} for a substituent selected from group (a) and R ^{2 stands} for a substituent selected from group (b). 3. aminophenol derivatives according to claim 1 or 2, characterized in that R ^{3 represents} a CI to C4 alkyl group or hydrogen. 4. aminophenol derivatives according to any one of claims 1 to 3, characterized in that R ^{1 represents} a methyl group. 5. aminophenol derivatives according to any one of claims 1 to 4, characterized in that R ^{2 represents} a methoxy group. 6. Use of aminophenol derivatives and their water-soluble salts according to any one of claims 1 to 5 as a coupler component in oxidation hair colorants. 7. Oxidation colorant for dyeing keratin fibers containing coupler components and developer components in a water-containing carrier, characterized in that it contains an aminophenol derivative as a coupler component according to one of claims 1 to 5. 8. oxidation colorant according to claim 7, characterized in that developer components in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, and coupler components in an amount of 0.01 to 20 wt .-% , preferably 0.5 to 5 wt .-%, each based on the total oxidation colorant, are included. 9. Oxidation colorant according to claim 7 or 8, characterized in that at least one developer component selected from 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, l- (β-hydroxyethyl ) -2,5-diamino-benzene, p-phenylenediamine, p-toluenediamine, p-aminophenol, 3-methyl-p-aminophenol and 2-aminomethyl-p-aminophenol. 10. Oxidation dye according to one of claims 7 to 9, characterized in that it also contains at least one substantive dye.