SK9152000A3 - Novel p-aminophenol derivatives, an oxidative colorant containing them and the use thereof - Google Patents

Abstract

Compounds of general formula (I), wherein A, B,C and D represent, independently from each other, an -OH- or -NHR- group, wherein R stands for a hydrogen atom or a C1-4 alkyl radical, with the proviso that A, B, C or D respectively stands for a hydroxy group, X stands for oxygen, sulphur, a sulfoxy or sulfoxyl group, R<1> and R<2> represent, independently from each other, hydrogen, fluorine, chlorine, a C1-4 alkyl or hydroxyalkyl group or a C2-4-dihydroxy-alkyl group, preferably a C2-dihydroxy alkyl group, and the physically acceptable salts of these compounds are highly suitable for use as developer components in oxidation coloring agents.

Description

Technical field

The present invention relates to novel p-aminophenol derivatives, to their use for dyeing keratin fibers, and to dye compositions containing these compounds.

BACKGROUND OF THE INVENTION

In dyeing keratin fibers, especially human hair, so-called oxidative dye compositions play an important role because of their intensive colors and good stability. Such dye preparations contain oxidation dye precursors, so-called developer components and coupling components. The developer components form dyes themselves under the influence of oxidizing agents or air oxygen, or by coupling with one or more of the coupling components.

In particular, good oxidation dye precursors must meet the following requirements: In the oxidative coupling reaction, they must produce desirable color shades with sufficient intensity and stability. In addition, they must have good pulling ability with respect to the fibers, and in particular, in human hair, no differences between worn and newly-grown hair (egalising ability) must be visible. They should be resistant to light, heat and the effects of chemical reducing agents, such as persistent fluids. Finally, when used in the form of a hair dye, they should not discolor the scalp too much and, in particular, should be toxicologically and logically sound.

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

Special representatives are, for example, p-phenylenediamine, p-toluylenediamine,

2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N, N '- (2-hydroxyethyl) -β-phenylenediamine,

2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4aminopyrazolone-5,4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-

4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N '- h / s - (2') hydroxyethyl) -N /, A / '- b / bis- (4'-aminophenyl) diamino-propan-2-ol.

As coupling components, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used. Particularly suitable coupling agents are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl- 3-Methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3- N - (2,4-diaminophenoxy) -propane, 2-chlororesorcin, 4-chlororesorcin, 2-chloro-6-methyl-3- aminophenol, 2-amino-4-hydroxypyridine, 2-methylresorcin, 5-methylresorcin and 2-methyl-4-chloro-5-aminophenol.

By using only the developmental component alone or a special coupling developmental combination, it is generally not possible to achieve a natural-looking color shade on the hair. In practice, therefore, combinations of different developer components and coupling components are usually used. In connection with this, there is still a demand for new, improved dye components.

It is therefore an object of the present invention to find novel developer components which substantially meet the requirements for oxidative dye precursors.

It has now been found that certain, hitherto unknown, p-aminophenol derivatives satisfy the conditions imposed on the developer components to a significantly high degree. By using these development components with most of the known coupling components, brilliant color shades are obtained, especially in the brown and red areas. The dyeings achieved are characterized by an exceptional light and wash-out stability.

SUMMARY OF THE INVENTION

The present invention provides p-aminophenol derivatives of formula (I)

(D

-3 in which

A, B, C and D independently represent a -OH- or -NHR- group, wherein R is a hydrogen atom or a C 1-4 -alkyl radical, provided that either A or B and C or D each represent a hydroxy group,

X represents an oxygen atom, a sulfur atom, a sulfoxy group or a sulfoxy group, and R ¹ and R ² independently of one another are hydrogen, fluorine, chlorine, C 1-4 -alkyl or C 1-4. ₄ -hydroxyalkylskupinu or _C2 ^ -dihydroxyalkylskupinu, preferably C 2 dihydroxyalkylskupinu.

These compounds can be prepared by known methods of organic synthesis. In detail, reference is made to the exemplary section where the synthesis example is illustrated in detail.

Since all of the compounds of the present invention are amino compounds, known acid addition salts can be prepared in conventional manner from these compounds. All statements in this specification, and hence the claimed area of protection, apply here both to the p-aminophenol derivatives of the general formula I present in free form and to their water-soluble, physiologically acceptable salts. Examples of such salts are hydrochlorides, hydrobromides, sulfates, phosphates, acetates, propionates, citrates and lactates.

Particularly suitable according to the invention have been the p-aminophenol derivatives of the formula I in which the group X represents an oxygen atom or a sulfur atom. A particularly preferred group X is oxygen.

Also preferred according to the invention are those p-aminophenol derivatives of the formula I in which those groups A, B, C and D, which are not -OH groups, are -NH ₂ groups.

Further, the radical of R ^{@ 1} and R @ ² in the p-aminophenol derivatives of the formula I have proved to be particularly preferred.

Finally, the present invention as particularly preferred p-aminophenol compound of the formula I have proven to be those in which the substituents R ¹ and R ^2, A and C and

B and D are always the same.

According to the invention, the most preferred material is 4-amino-2 - (((5-amino-2-hydroxyphenyl) methoxy) methyl) phenol.

The invention further relates to the use of said p-aminophenol derivatives as developmental components in oxidative dye preparations.

The invention also provides oxidative dye compositions for dyeing keratin fibers which contain coupling and development components in a water-containing carrier and which contain one of said paminophenol derivatives as a development component.

Keratin fibers are furs, wool, feathers and especially human hair. Although oxidative dye preparations are primarily suitable for dyeing keratin fibers, their use in other fields, in particular in color photography, is essentially not in the way.

The oxidation dye compositions of the present invention contain the developer components of the formula I as well as the coupling components, and may optionally contain further developer components as well as the coupling components.

Other preferred developmental components according to the invention are p-phenylenediamine, p-toluylenediamine, p-aminophenol, 2- (2,5-diaminophenyl) ethanol, N, N-N- (2-hydroxyethyl) p-phenylenediamine, p-phenylenediamine, p-phenylenediamine, -phenyl-3-carboxyamido-4-aminopyrazolone-5,4-amino-3-methylphenol, 4-amino-3-fluorophenol, 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-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-hydroxyethylaminomethyl-4-aminophenol as well as 4,4'-diaminodiphenylamine, 2-hydroxymethyl-4-aminophenol, b / s- (2-hydroxy-5) 1,4-N - (4-aminophenyl) diazacycloheptane, 1,3 (N, N '- b) s - (2'-hydroxyethyl) - N, N' - (b) -aminophenyl) methane; s- (4'-aminophenyl) diamino-1,3-propan-2-ol as well as 4,5-diaminopyrazole derivatives according to EP 0 740 931 and WO 94/08970, such as 4,5-diamino-1- (2'- hydroxyethyl) pyrazole are also developer components which may advantageously be combined with the developer components of the invention.

Particularly preferred further development components are p-phenylenediamine, 2,4,5,6-tetraaminopyrimidine, 4,5-diamino-1- (2'-hydroxyethyl) pyrazole, N, N-s- (2-hydroxyethyl) p. -phenylenediamine, bis- (2-hydroxy-5-aminophenyl) methane, 2- (2,5-diaminophenyl) ethanol, 3-methyl-4-aminophenol, 4-hydroxy-2,5,6-triaminopyrimidine, 2-aminomethyl -4-aminophenol and p-toluylenediamine.

Preferred coupling components according to the invention are 1-naphthol, pyrogalol, 1,5-,

2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol 1,3-bis- (2,4-diaminophenoxy) propane, 4-chlororesorcin, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcin, 5-methylresorcin, 2,5-dimethylresorcin, 2, 6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dihydroxy-3,4-diaminopyridine _I 2-methyl-4-chloro-5-aminophenol, 6-methyl-1,2,3, 4-tetrahydroquinoxaline, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluol, 2,6-bis- (2-hydroxyethylamino) toluol,

3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) anisole and 2,6-dimethyl-3-aminophenol.

Particularly preferred coupling components are 1-naphthol, m-aminophenol, 5-amino-2-methylphenol, 3-methylsulfonylamino-2-methylaniline, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dimethyl-3-aminophenol, , 4-diaminophenoxyethanol, 2,7-dihydroxynaphthalene, 6-methyl-1,2,3,4-tetrahydroquinoxaline, 1,7-dihydroxynaphthalene, 2-methyl-4-chloro-5-aminophenol, 3,4-methylenedioxyaniline, 2-methyl resorcinin 4-chlororesorcin, 3,4-methylenedioxyphenol, 2-amino-3-hydroxypyridine and 2-chloro-6-methyl-3-aminophenol.

These other developer and coupling components are generally used in free form. However, it may be advantageous for amino-containing substances to be used in the form of salts, in particular in the form of hydrochlorides and sulphates.

The hair colorants according to the invention contain both the developmental components and the coupling components preferably in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, based on the entire oxidative colorant. Generally, the developer components and the coupling components are added to each other in approximately molar amounts. Although the molar addition has proven expedient, a certain excess of the individual oxidant dye precursors is not a disadvantage so that the developer and coupling components can be contained in a molar ratio of 1: 0.5 to 1: 3, preferably 1: 1 to 1: 2 .

In a preferred embodiment, the hair colorants according to the invention contain, in addition to the oxidative dye precursors, additionally direct-acting dyes which are additionally customary in order to further modify the color shades. Directly acting dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct-acting dyes are compounds known under international designations or trade names

HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 58, Disperse Orange 3, HC

-6Red 3, HC Red BN, Basic Blue 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, as well as 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-

1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitrotoluidine, pycramic acid, 2 amino-6-chloro-4-nitrophenol and 4- N -ethyl-1,4-bis- (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride. The compositions of the invention contain in this embodiment directly acting substances preferably in an amount of 0.01. up to 20% by weight, based on the total colorant.

In addition, the preparations according to the invention may also contain naturally occurring dyes such as red hen, neutral hen, black hen, chamomile flower, sandalwood, black tea, bark of crustacean, sage, cichlid (blue wood), pickle root, catech, cedar and alkane root.

Further dye components included in the dye compositions of the invention may also be indoles and indolines, as well as physiologically acceptable salts thereof. Preferred examples are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole , 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Further preferred are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 6- hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

It is not necessary that the oxidant dye precursors or the direct-acting dyes always represent uniform compounds. In addition, other components may be present in subordinate amounts in the dye compositions of the invention, which is conditional upon the method of manufacture of the individual dyes, provided these do not adversely affect the dyeing result or if, for other reasons, e.g. Toxicological, may not be excluded.

In addition, with respect to the dyes used in the hair coloring and tinting compositions of the present invention, the monograph Ch. Animal, The Science of Hair Line, Chapter 7 (pages 248 to 250; direct-acting dyes) as well as Chapter

8, pages 264-267; oxidative dye pre-products), published as Volume 7 of the Dermatology series (edited by Ch. Culnan and H. Maibach), published by Marcel Dekker

Inc., New York, Basel, 1986, as well as the "European Inventory of Cosmetic Raw Materials", published by the European Union, which is available in diskette form from the Federal Union

-7 German industrial and commercial enterprises for the manufacture of pharmaceuticals, environmental goods and body care products e.V., Mannheim.

In the manufacture of the coloring compositions of the invention, the oxidation dye precursors are incorporated into a suitable water-containing carrier. For the purpose of coloring hair, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, for example shampoos, foam aerosols or other preparations suitable for use in the hair.

The coloring preparations according to the invention may further comprise all active, auxiliary and auxiliary substances known for such preparations. In many cases, the coloring compositions contain at least one surfactant, with essentially both anionic and amphoteric, ampholytic, nonionic and cationic surfactants. However, in many cases it has proven advantageous to select surfactants from anionic, amphoteric or nonionic surfactants.

Suitable anionic surfactants in the compositions of the invention are all anionic surfactants suitable for use on the human body. These are characterized by an anionic group giving rise to solubility in water, such as, for example, a carboxylate, sulfate, sulfonate or phosphate group, as well as a lipophilic alkyl group of about 10 to 22 carbon atoms. Additionally, the molecule may contain glycol or polyglycol ether groups, ester, ether and amido groups as well as hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of sodium, potassium and ammonium salts, as well as mono-, dia-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 formula RO- (CH 2 -CH 2 O) _X -CH 2 -COOH, wherein R is a linear alkyl group of 10 to 22 carbon atoms and x = 0 or 1 to 16,

- acyl sarcosides of 10 to 18 carbon atoms in the acyl group,

- acyltaurides having 10 to 18 carbon atoms in the acyl group,

- acyl isethionates having 10 to 18 carbon atoms in the acyl group,

- mono- and dialkyl esters of sulfosuccinic acid having from 8 to 18 carbon atoms in the alkyl group and monoalkylpolyoxyethyl esters of sulfosuccinic acid having from 8 to 18 carbon atoms in the alkyl group and from 1 to 6 oxyethyl groups,

- linear C 12 -C 18 alkanesulfonates,

- linear alpha-olefin sulfonates of 12 to 18 carbon atoms,

- S-fatty acid alpha-methyl esters of C 12 -C 18 fatty acids,

- alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _X -SO 3 H, wherein R is preferably a linear alkyl group having 10 to 18 carbon atoms and x = 0 or 1 to 12,

mixtures of surfactant hydroxysulfonates according to DE-A-37 25 030.

- sulphated hydroxyalkylpolyethylene- and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,

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

esters of tartaric acid and citric acid with alcohols, which are addition products of approximately 2 to 15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.

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

Zwitterionic surfactants refer to those surface-active compounds having in the molecule at least one quaternary ammonium group and at least one -COO ^(_), or -SO 3 ^0th Particularly preferred amphoteric surfactants are the so-called betaines such as N-alkyl- N, N -dimethylammonium glycinates, for example cocosalkyldimethylammonium glycinate, N-acylaminopropyl- N, N -dimethylammonium glycinates, for example cocoylaminopropyl-3-methyl-3-carboxymethyl-3-carboxymethyl-3-carboxymethyl hydroxyethyl imidazoline having from 8 to 18 carbon atoms in each alkyl or acyl group, as well as cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred amphoteric surfactant is the fatty acid amide derivative known under the INCI designation Cocamidopropyl Betaine.

Ampholytic surfactants are to be understood as meaning those surfactants which contain at least one free amino group and at least one -COOH group in addition to one C 1-8 -alkyl or C 1-8 -acyl group in the molecule.

-9 or -SO 3 H, 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-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids having in each case about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N / -kokosalkylaminopropionát, cocoacylaminoethylaminopropionate and C ₂ -i8 acyl sarcosine.

Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group, or a combination of a polyol and a polyglycol ether group as the hydrophilic group. Such compounds are, for example;

- addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols having 8 to 22 carbon atoms, fatty acids having 12 to 22 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group,

- mono- and diesters of C 22-22 fatty acids addition products from 1 to 30 moles of ethylene oxide with glycerine,

- C ₈ -22 alkyl monoglycosides and _{C-eighth 2} 2-alkyloligoglycosides and their ethoxylated analogues,

- 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,

- ethylene oxide addition products with fatty acid alkanolamides.

In particular, quaternary ammonium compounds are examples of cationic surfactants useful in the hair care compositions of the invention. Preferred are ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride triethylammonium chloride, lauryldimethylammonium chloride, triethyldimethylammonium chloride, triethyldimethylammonium chloride, lauryldimethylammonium chloride, triethyldimethylammonium chloride. Other cationic surfactants useful herein are quaternized protein hydrolysates.

Cationic silicone oils, such as those commercially available Q2-7224 (manufacturer: Dow Corning; stabilized;

-10-trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing hydroxylamine-modified silicone, also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) as well as Abil®-Quat 3270 and 3272 (manufacturer) : Th. Goldschmidt; diquaternary polydimethylsiloxane, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines, such as commercially available stearylamidopropyldimethylamine under the designation Tego Amid (R) 18, are characterized by a particularly good biodegradability in addition to a good conditioning effect.

Quaternary ester compounds, so-called "esterquats", such as methylhydroxyalkyldialkoyloxyalkylammonium methosulfates distributed under the trade name Stepantex® as well as products such as Dehyquart AU-46, are also very biodegradable.

An example of a quaternized sugar derivative useful as a cationic surfactant is the commercial product Glucquat®100, according to the INCI nomenclature it is "laurylmethylglucet-10-hydroxypropyldimonium chloride".

Compounds with alkyl groups which are used as surfactants may be uniform substances. As a rule, however, it is preferable to start with the production of these substances from natural vegetable or animal raw materials so as to obtain mixtures of substances with different alkyl chain-dependent lengths.

For surfactants which are ethylene oxide and / or propylene oxide fatty alcohol adducts or derivatives of these adduct products, both "normal" homologous distribution and thickened homologous distribution can be used. By "normal homologous distribution" is meant mixtures of homologues which are formed by the reaction of a fatty alcohol and an alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Concentrated homologous distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, oxides, hydroxides or alcoholates of alkaline earth metals are used as catalysts. The use of thickened homologous distribution products may be advantageous.

Other active ingredients, excipients and additives are, for example:

-11 nonionic polymers, for example vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes having quaternary groups, dimetyldialylamóniumchloridové polymers of dimethyl-acrylamide copolymers, quaternized with diethyl sulfate-dimethylaminoethyl vinyl pyrrolidone copolymers, copolymers vinylpyrolidónimidazoliniummetochlorid and quaternized polyvinyl alcohol, amphionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octyl acrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polyacrylic acids such as anionic polyacrylic acids such as anionic polyacrylic acids copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymer methyl vinyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N / ether. butylacrylamide terpolymers, thickeners such as agar-agar, guar gum, alginates, xanthan gum, acacia, caraya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives such as methylcellulose, hydroxyalkylcellulose, and starch glycellulose and carboxymethylmethylcellulose amylose, amylopectin adextrins, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants such as glucose and maleic acid, hair conditioning compounds such as phospholipids such as soy lecithin, egg lecithin and cephalins, as well as silicone oils, elastin hydrolysates, protein hydrolysates , collagen, keratin, milk-protein, soya-protein and wheat-protein hydrolysates, their condensation products with fatty acids as well as quaternized protein hydrolysates, perfume oils, dimethylisosorbide and cyclodextrins, solubilizers and o ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, anti-dandruff agents such as Piroctone Olamine and Zink Omadine,

- other pH-adjusting substances,

- active substances such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins,

- cholesterol,

- light-protection preparations (light antioxidants),

- consistency-forming substances such as sugar esters, polyol esters or polyol alkyl ethers,

- fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,

- fatty acid alkanolamides,

- complexing agents such as EDTA, NTA and phosphonic acids,

- swelling and penetrating substances such as glycerin, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, urea as well as primary, secondary and tertiary phosphates,

- opacifiers such as latex,

- pearlescent substances such as ethylene glycol monostearate and ethylene glycol distearate,

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

- antioxidants.

In the manufacture of the coloring compositions of the invention, the components of the water-containing carrier are added in conventional amounts intended for this purpose: for example, the emulsifier is used in concentrations of 0.5 to 30% by weight and the thickening agent in concentrations of 0.1 to 25% by weight of the total coloring composition.

The oxidative induction of dyeing can essentially be accomplished by the action of atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially when, in addition to dyeing, it is desirable to achieve a lightening effect on human hair. Possible oxidizing agents are persulphates, chlorites and in particular hydrogen peroxide or their addition products with urea, melamine or sodium borate. Furthermore, it is also possible to carry out oxidation by enzymes. The enzymes may serve to transfer the air oxygen to the developer component or to enhance the oxidizing agents present in small amounts. An example

The 13-enzymatic process is a process in which the effect of small amounts (e.g., 1% or less, based on the entire formulation) of hydrogen peroxide is enhanced by peroxidases.

Suitably, the oxidizing agent composition is admixed immediately prior to coloring the hair with a composition containing oxidative dye precursors. This results in a ready-to-use hair dye composition whose pH should preferably be in the range of 6 to 10. The use of hair dye compositions in a weakly alkaline environment is particularly preferred. Temperatures in use may range between 15 and 40 ° C. After a treatment time of approximately 30 minutes, the hair colorant is removed from the colored hair by rinsing. Subsequent shampooing is omitted when a high surfactant carrier such as a coloring shampoo is used.

The following examples are intended to illustrate the invention in more detail.

DETAILED DESCRIPTION OF THE INVENTION

Synthesis of 4-amino-2 - (((5-amino-2-hydroxyphenyl) methoxy) methyl) phenol

Diazonium solution (solution A):

The solution, consisting of 26 g (0.15 mol) of sulfanilic acid and 75 ml (0.15 mol) of 2N sodium hydroxide, was at +5 ° C together with 10.35 g (0.15 mol) of sodium nitrite diluted with 125 ml of water. Under cooling (+ 5 ° C), 131 ml (0.38 mol) of 10% hydrochloric acid was added dropwise over 30 minutes.

Solution A was added dropwise to the ice-cooled solution formed

17.25 g (0.075 mol) of cis- (2-hydroxybenzyl) ether in 120 ml (0.3 mol) of 10% sodium hydroxide solution. After the addition was complete, it was stirred at 20 ° C for 1.5 hours.

Then 69 g (0.4 mol) of sodium dithionite was added over 2 minutes. After 20 minutes at 75 ° C, the product was aspirated and washed with water. The product was obtained as colorless crystals, m.p. 175 DEG C. (decomposition).

2. Coloring

First, a cream base having the following composition was produced (all data are in g unless otherwise stated):

tallow fatty alcohol 17.0 Lorol®techn. ¹ 4.0 Texapon®N 28 ² 40.0 Dehyton®K ³ 25.0 Eumulgin® B 2 ⁴ 1.5 distilled water 12.5

¹ C12-ie-fatty alcohol (HENKEL) ² sodium lauryl ether sulphate (approximately 28% of active substance; INCI-designation:

Sodium Laureth Sulfate) (HENKEL) ³ fatty acid amide derivative with betaine structure of formula

R-CONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ COO · (approximately 30% of active substance; INCI-designation:

Cocoamidopropyl Betaine (HENKEL) ⁴ cetylstearyl alcohol with 20 moles EO (INCI designation: Ceteareth-20) (HENKEL)

The following cream hair dye emulsion was then made based on this cream:

cream base 50.0 developer component 7,5 mmoľ coupling component 7,5 mmoľ Na ₂ SO3 (inhibitor) 1.0 (NH ₄ ) ₂ SO ₄ 1.0 horses, ammonia solution to pH 10 Water to 100 * unless otherwise stated

The ingredients were mixed together in order. Alternatively, the direct-acting dyes were added with a corresponding reduction in the water content. After addition of oxidation dye precursors and inhibitor, the pH of the emulsion was first adjusted to 10 with a concentrated ammonia solution and then made up to 100 g with water.

The oxidation dye development reaction was carried out with a 3% hydrogen peroxide solution as the oxidation solution. To this end, 100 g of emulsion was combined and mixed with 50 g of hydrogen peroxide solution (9%).

The dye cream was applied to approximately 5 cm long strands of human hair that had been standardized to 90% greyish, but which had not previously been specially treated. The treatment time was 30 minutes at 32 ° C. After the dyeing process was completed, the hair was rinsed, washed with a conventional hair wash, and then dried.

The following coupling and development components, or direct acting dyes, were used for staining:

Development Components • 4-amino-2 - (((5-amino-2-hydroxyphenyl) methoxy) methyl) phenol (E1) • 2,4,5,6-tetraaminopyrimidine (E2) • 4,5-diamino-1- (2-hydroxyethyl) pyrazole (E3) • p-phenylenediamine (E4) • N, Nb / s- (2-hydroxyethyl) -p-phenylenediamine (E5) • 4-hydroxy-2,5,6-triaminopyrimidine ( E6) • p-toluylenediamine (E7) • 2- (2,5-diaminophenyl) ethanol (E8) • 2-aminomethyl-4-aminophenol (E9) • 4-amino-3-methylphenol (E10) • b / s- (2-hydroxy-5-aminophenyl) methane (E 11)

Coupling Components • 1-Naphthol (K1) • 2-Methyl-5-aminophenol (K2) • 2-Chloro-6-methyl-3-aminophenol (K3) • 2-Amino-3-hydroxypyridine (K4) • 2.6 -dimethyl-3-aminophenol (K5) • m-aminophenol (K6) • 2,7-dihydroxynaphthalene (K7) • 4-chlororesorcinin (K8) • 2-methyl-4-chloro-5-aminophenol (K9) • e- methyl-1,4-SAtetrahydroquinoxaline (K10) • 2-methyl resorcinin (K11) • 3-amino-2-methylamino-6-methoxypyridine (K12) • 2,4-diaminophenoxyethanol (K13) • 3-methylsulfonylamino-2-methylaniline (K14) ) • 1,7-dihydroxynaphthalene (K15) • 3,4-methylenedioxyphenol (K16) • 3,4-methylenedioxyaniline (K17) • m-phenylenediamine (K18)

Direct-acting dyes • 6-nitro-1,2,3,4-tetrahydroquinoxaline (D 1) • 2-nitro-4-aminodiphenylamine-2'-carboxylic acid (D2) • 2-amino-6-chloro-4-nitrophenol (D3) 2-nitro-1-amino-4-bis- (2-hydroxyethyl) aminobenzene (D4) 2-nitro-1- (2-hydroxyethyl) amino-4-methylbenzene (D5) 2- (2'-hydroxyethylamino) -4,6-dinitrobenzene (D6) • 1- (2'-hydroxyethyl) amino-2-nitro-4-bis- (2-hydroxyethyl) aminobenzene (D7) • 1- (2 -hydroxyethyl) amino-2-nitro-4-aminobenzene (D8) • 4- (2-nitrophenyl) aminophenol (D9)

The following colors were detected:

Developer component Coupling component Directly acting dye Shade of colored hair E1 K1 gray-red E1 K2 sivooranžová E1 K3 hnedočervená E1 K4 svetlooranžová E1 K5 gray-red E1 K6 • topasovožltá E1 + E3 ^a K1 + K3 ^a old pink E1 + E2 ^a K2 + K7 ^a matte purple E1 + E6 ^a K8 + K9 ^a gray-red E1 + E7 ^a K10 + K11 ³ champagne E1 + E4 ^a K12 black E1 + E5 ^a K5 + K13 ^a blackish E1 + E8 ^a K12 + K14 ^a - blue gray E1 + E9 ^ä K15 + K16 ³ 0.1% by weight D1 brownish orange E1 + E10 ^á K17 0.3% by weight of D2 matte red E1 + E11 ^ä K18 0.1% by weight of D3 vlasovohnedý E1 K3 0.1 wt. % D4 + 0.1 wt. D5 copper E1 K3 0.1 wt. % D6 + 0.1 wt. D7 rajčinovočervený E1 K9 0.1 wt. % D8 + 0.1 wt. D9 lakovočervený

^and 0.375 mmol each

Claims (13)

P-Aminophenol derivatives of the general formula I (I) in which A, B, C and D are each independently -OH- or -NHR-, wherein R is hydrogen or C 1-6 -alkyl, provided that either A or B and C or D are each hydroxy, X is an oxygen atom, a sulfur atom, a sulfoxy group or a sulfoxy group, R ¹ and R ² are independently H, F, Cl, Ci-4-alkyl or Ci.4-hydroxy, or C 2-4 dihydroxyalkylskupinu, preferably C ₂ -dihydroxyalkylskupinu, and the physiologically acceptable salts thereof. P-Aminophenol derivatives according to claim 1, in which the group X represents an oxygen or sulfur atom, preferably an oxygen atom. P-Aminophenol derivatives according to claim 1 or 2, in which the groups A, B, C and D, which are not -OH-groups, are -NH ₂ -groups. P-Aminophenol derivatives according to one of claims 1 to 3, in which R ¹ and R ² are hydrogen. P-Aminophenol derivatives according to one of Claims 1 to 4, in which the groups R ¹ and R ² and AaCaBaD are in each case the same. The p-aminophenol derivative according to claim 1 which is 4-amino-2 - (((5-amino-2-hydroxyphenyl) methoxy) methyl) phenol. Oxidative dye preparations for dyeing keratin fibers, comprising coupling and development components in a water-containing carrier, characterized in that they contain at least one paminophenol derivative according to one of claims 1 to 6 as a development component. 8. Oxidative coloring agents according to claim 7, characterized in that they contain at least one coupling component selected from the group consisting of: 1-naphthol, m-aminophenol, 5-amino-2-methylphenol, 3-methylsulfonylamino-2-methylaniline, 3 amino-2-methylamino-6-methoxy-pyridine, 2,6-dimethyl-3-aminophenol, 2,4-diamino- phenoxyethanol, 2,7-dihydroxynaphthalene, 6-methyl-1,2,3,4-tetrahydroquinoxaline, 1,7-dihydroxynaphthalene, 2-methyl-4-chloro-5-aminophenol, 3,4-methylenedioxyaniline, 2-methyl- resorcinol, 4-chlororesorcin, 3,4-methylenedioxyphenol, 2-amino-3-hydroxypyridine and 2-chloro-6-methyl-3aminophenol. Oxidative dye preparations according to claim 7 or 8, characterized in that they contain at least one further development component in addition to the p-aminophenol derivatives according to one of claims 1 to 6. 10. The oxidative dye composition of claim 9, wherein the further developer is selected from the group consisting of 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 4,5-diamino. -1- (2-hydroxyethyl) pyrazole, p-toluylenediamine, 2-aminomethyl-4-aminophenol, N, Nb / s- (2-hydroxyethyl) -p-phenylenediamine, penylenediamine, 2- (2,5-diaminophenyl) ethanol, 3-methyl-p-aminophenol and cis- (2-hydroxy-5-aminophenyl) methane. Oxidative dye preparations according to one of claims 7 to 10, characterized in that the developer components are present in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, and the coupling components are They are present in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, based on the total oxidative colorant. Oxidative dye preparations according to one of Claims 7 to 10, characterized in that they contain at least one direct-acting dye. Use of p-aminophenol derivatives according to one of Claims 1 to 6 and their physiologically acceptable salts as development components in oxidative dye preparations.