GB2337530A - Direct hair-colouring compositions based on phenalenone derivatives - Google Patents

Abstract

Compositions for dyeing and tinting keratinic fibres, in particular human hair, comprise, as a direct dyestuff, at least one compound corresponding to the general formula (I): [wherein R<SP>1</SP>-R<SP>8</SP> independently represent hydrogen, a C 1 -C 4 alkyl group, an allyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 monohydroxyalkyl group, a C 2 -C 4 dihydroxyalkyl group, a hydroxyl group, a halogen atom, a nitro group, a cyano group or an NR<SP>9</SP>R<SP>10</SP> group, wherein R<SP>9</SP> and R<SP>10</SP> independently represent hydrogen, a C 1 -C 4 alkyl group, an allyl group, a C 1 -C 4 hydroxyalkyl group or a C 2 -C 4 dihydroxyalkyl group; at least five of the substituents R<SP>2</SP> to R<SP>3</SP> being hydrogen] or physiologically-acceptable salts thereof. These compounds are distinguished in particular by an improved affinity of the dyestuff molecules for hair and/or an improved shine of the coloured hair.

Description

"Direct hair-colouring compositions and the use thereof" This invention

relates to compositions for dyeing and tinting keratinic fibres, in particular human hair, using specific direct dyestuffs and to the use thereof.

Formulations for tinting and dyeing hair are an important type of cosmetic composition. They may be used to give a lighter or deeper shade to the natural hair colour according to the wishes of an individual, to achieve a completely different hair colour or to cover undesirable colour shades, such as grey shades. Conventional haircolouring compositions are formulated either on the basis of oxidation dyestuffs or on the basis of direct dyestuffs, depending on the desired colour or permanence of the dyeing. Combinations of oxidation dyestuffs and direct dyestuffs are also often employed to achieve specific shades.

Good dyestuffs are distinguished by a high tinctorial strength. Good fastness to 0 0 0 perspiration, washing and light are furthermore desired. They should, moreover, be acceptable from the toxicological and dermatological aspect. It is also advantageous 0 0 if the substances have a high solubility in various base formulations.

Colouring compositions based on oxidation dyestuffs lead to brilliant and permanent 0 colour shades. However, they require the use of potent oxidizing agents, such as 0 hydrogen peroxide solutions. This may damage the hair to be dyed. This damage must then be counteracted using appropriate care products. Furthermore, contact -2between the skin and these colouring compositions may lead to undesirable reactions in particularly sensitive persons.

Colouring compositions based on direct dyestuffs manage without oxidizing agents 0 0 and may be formulated at pH values about neutral. A considerable disadvantage of colouring compositions based on direct dyestuffs is the low fastness to washing of the dyeings achieved. The affinity of the dyestuff molecules for hair and the shine of the coloured hair are also not completely satisfactory in many cases.

There therefore continues to be a need for colouring compositions based on direct dyestuffs which are distinguished by an improved affinity of the dyestuff molecules for hair andlor an improved shine of the coloured hair.

It has now been found, surprisingly, that the requirements imposed on direct dyestuffs are met to a high degree by specific phenalenone derivatives.

0 The present invention therefore provides compositions for dyeing and tinting keratinic fibres, in particular human hair, which comprise, as a direct dyestuff, at least one compound corresponding to the general formula (I):

0 1 15 R FR:k7- R R3 4 R R F' (1) wherein R' to R' independently represent hydrogen, aCCC4 alkyl group, an allyl group, a C,-C, alkoxy group, a C,-C, monohydroxyalkyl group, aC2-C4 dihydroxyalkyl group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, or an -NWRIO group, wherein R9 and R independently represent hydrogen, - aCI-C4alkyl group, - an allyl group, - aCl-C4 hydroxyalkyl group, or - aC2-C4dihydroxyalkyl group; at least five of the substituents R' to RB representing hydrogen.

According to the present invention, keratinic fibres are to be understood to be furs, wool, feathers and, in particular, human hair. Although the present colouring compositions are primarily suitable for dyeing keratinic fibres, there is in principle nothing against use in other fields.

-4Compounds corresponding to general formula (I) may be prepared by conventional syntheses. Phenalen-l-one and derivatives thereof are sometimes also called perinaphthenones in the literature.

i 20 1 In general formula M, the substituents R' to W' represent a C,-C, alkyl group, for example methyl, ethyl, propyl, isopropyl or butyl. Ethyl and methyl are preferred alkyl groups. R' to R may also represent an allyl group or aCI-C4 alkoxy group, for example a methoxy or an ethoxy group. R' to R may also represent aCCC4 hydroxyalkyl group, for example a hydroxymethyl, a 2-hydroxyethyl, a 3hydroxypropyl or a 4-hydroxybutyl group, or a C2-Cs dihydroxyalkyl group, e.g. a 2,3-dihydroxypropyl group. The substituents R' to R' may also represent a halogen atom, for example a F, a Cl or a Br atom.

Compounds corresponding to general formula (I) which are preferred according to the present invention are those wherein at least six of the substituents R' to R' represent hydrogen.

Compounds corresponding to creneral formula (I) which are also preferred according j= 0 to the present invention are those wherein at least six of the substituents R' to R8 represent hydrogen and the other two substituents independently represent hydrogen, a methyl group, a methoxy group, a hydroxyl group, a chlorine atom, an amino group, - a nitro group or a cyano group.

Specific compounds corresponding to general formula (I) in the context of the present invention are: phenalen-l-one, 6-hydroxyphenalenone, 3methylphenalenone, 9methylphenalenone, 2-hydroxyphenalenone, 3hydroxyphenalenone, 2-chloro-3hydro xyp henaleno n e, 2-chlorophenalenone, 6-methoxyphenalenone, 4hydroxyphenalenone, 4-methoxyphenalenone, aminophenalenone and 3-aminophenalenone.

2-nitrophenalenone, 2-nitro-3- Compounds corresponding to general formula (I) which have proved to be particularly outstanding in respect of the properties thereof are phenalen-l-one and 6hydroxyphenalenone.

The compositions according to the present invention usually contain a compound corresponding to general formula (I) in amounts of from 0.05 to 5.0 wt. %, based on 0 the colouring composition, in the case of oxidation dyestuffs without the oxidizing agent formulation. Amounts of from 0. 1 to 3 wt. % are preferred.

There are, in principle, no limitations on the usability of the compounds corresponding to general formula (I) in compositions for dyeing and tinting keratinic fibres.

is According to a first preferred embodiment of the present invention, these are compositions which are intended to effect only temporary dyeing of the fibres. Such compositions are often called tinting compositions. This embodiment also comprises, for example, those hair treatment compositions with which the hair not only is to be dyed temporarily but also is to be styled to a certain hairstyle. Tinting setting lotions are referred to in this case.

Since such compositions are usually formulated without the aid of oxidizing components, in particular hydrogen peroxide, the present compositions in this embodiment are free from oxidation dyestuff precursors.

Although the compounds corresponding to general formula (I) may also be employed as the sole dyestuff component, the compositions according to this embodiment preferably also comprise at least one further dyestuff of the direct type. Direct dyestuffs are conventionally nitrophenylenediamines, nitroaminophenols, azo dyestuffs, anthraquinones or indophenols. Preferred direct dyestuffs are the compounds known by the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, FIC Blue 12, 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, and 4-amino-2-nitrodiphenylamine-2'carboxylic acid, 6-nitro- 1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, 4ethylamino-3-nitrobenzoic acid and 2-chloro-6ethylamino- 1 -hydroxy-4nitrobenzene.

According to the present invention, direct dyestuffs are also to be understood to be natural dyestuffs, such as henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, alder buckthorn bark, sage, logwood, madder root, catechu, cedrela and alkanet root.

The compositions according to the present invention preferably contain the further direct dyestuffs in amounts of, in each case, from 0. 0 1 to 20 wt. %, based on the total composition.

According to a second preferred embodiment, the present compositions are haircolouring compositions for permanent dyeing of hair. These compositions comprise at least one oxidation dyestuff precursor of the developer type. These compounds, which as a rule are colourless, react with themselves under the action of oxidizing agents or atmospheric oxygen, optionally with the aid of specific enzymes or metal ions as a catalyst, to form the desired dyestuffs. However, as a rule, combinations of several developer components are employed, in particular to form natural hair colour shades. So-called couplers which react with the developer components under the influence of oxidizing agents, leading to new colours or a shading of the colour, are generally additionally employed. According to the present invention, it is possible to employ either one coupler component or several coupler components in combination with one or more developer components.

Developer components which are usually employed are primary aromatic amines having further free or substituted hydroxyl or amino groups in the para- or ortho- - 8 position, diaminopyridine derivatives, heterocyclic hydrazones, 4- arninopyrazolone derivatives and 2,4,5,6-tet-aaminopyrimidine and derivatives thereof.

Specific representatives are, for example, p-phenylenediamine, ptoluylenediamine, 12-aminophenol, o-aminophenol, 1-(2'-hydroxyethyl)-2,5diaminobenzene, N,N-bis(2-hydroxy-ethyl)-2-phenylenediamine, 2-(2,5diaminophenoxy)-ethanol, 1-phenyl-3carboxamido-4-amino-pyrazol-5-one, 4amino-3-methylphenol,. 2,4,5,6tetraaminopyrimidine, 2-hydroxy-4,5,6triaminopyrimidine, 4-hydroxy-2,5,6triaminopyrimidine, 2,4-dihydroxy-5,6diaminopyrimidine, 2-dimethylamino-4,5,6triaminopyrimidine, 2 -h ydroxyeth ylamino methyl -4 -am ino-ph enol, 4,4,diaminodiphenylarnine, 4amino-3-fluorophenol, 2-aminomethyl-4-amino-phenol, 2hydroxymethyl-4-a. minophenol, bis-(2-hydroxy-5-aminophenyl)-methane, 1,4-bis-(4aminophenyl)diazacycloheptane, 1,3-bis-(N-(2-hydroxyethyl)-N-(4aminophenylamino))-2propanol, 4-amino-2-(2-hydroxyethoxy)-phenol and 4,5diaminopyrazole derivatives according to EP 740 741 or WO 94108970, such as 4,5diamino- 1(2'-hydroxyethyl)-pyrazole.

Particularly preferred developers in the context of the present invention are paminophenol, 1-(2'-hydroxyethyl)-2,5-diaminobenzene, 2,4,5, 6tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5, 6triaminopyrimidine, 4,5-diamino- 1-(2-hydroxyethyl)-pyrazole, ptoluylenediamine, 2aminomethyl-4-amino-phenol, N,N-bis-(2-hydroxy-ethyl)p-phenylenediamine, pphenylenediamine, 3-methyl-p--arninophenol and bis(2-hydroxy-5-aminophenyl)methane.

Coupler components which are, as a rule, used are -m-phenylenediamine derivatives, naphthols, resorcinol and derivatives thereof, pyrazolones and -m-aminophenol derivatives. Particularly suitable coupler substances are I-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, qaminophenol, 5-amino-2-methylphenol, Maminophenol, resorcinol, resorcinolmonornethyl ether, ni-phenylenediamine, lphenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4diaminophenoxy)-propane, 4chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2methylresorcinol, 5methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dihydroxy-3, 4diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-bis(2hydroxyethylamino) -toluene, 2,4-diaminophenoxyethanol, 1-methoxy-2amino-4-(2hydroxyethylamino)-benzene, 2-methyl-4-chloro-5-amino-phenol, 6methyl-1,2,3,4tetrahydro-quinoxaline, 3,4-methylenedioxyphenol, 3,4methylenedioxyaniline, 2,6dimethyl-3-arnino-phenol, 3-arriino-6-methoxy-2methylarninophenol, 2-hydroxy-4aminophenoxyethanol, 2-methyl-S-(2hydro'xyethylamino)-phenol and 2,6-dihydroxy3,4-dimethylpyridine.

Particularly preferred coupler components are l-naphthol, 1,5-, 2,7- and 1,7dihydroxynaphthalene, resorcinol, 2,5-dimethylresorcinol, 2,6dihydroxy-3,4diaminopyridine, m-aminophenol, 5-amino-2-methylphenol, 3methylsulfonyl-amino-2methyl-aniline, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dimethyl-3-aminophenol, 2,4-diamino-phenoxyethanol, 6methyl-1,2,3,4-tetrahydro-quinoxalize, 2methyl-4-chloro-5-amino-phenol, 3, 4-methylenedioxyaniline, 2-methylresorcinol, 5methylresorcinol, 4chlororesorcinol, 3,4-methylenedioxyphenol, 2-amino-3- - 10hydroxypyridine and 2-chloro-6-methyl-3-aminophenol.

Those developer and coupling components which require no oxidizing agent apart from atmospheric oxygen for formation of the dyeing may be preferred according to the present invention.

The hair-colouring compositions according to the present invention may preferably contain both the developer components and the coupler components in an amount of from 0.005 to 20 wt. %, in each case based on the colouring composition without the oxidizing agent formulation. Developer components and coupler components are in general employed here in approximately molar amounts with respect to one another. Although use in molar amounts has proved expedient, a certain excess of individual oxidation dyestuff precursors is not a disadvantage, so that the developer components and coupler components may be present in a molar ratio of from 1:03 to L2.

If desired, the present compositions according to this embodiment may also comprise further direct dyestuffs for shading, in addition to the compounds corresponding to general formula (I), the developer and, optionally, coupler components. Reference is made at this point to the. list given above.

According to a third embodiment of the present invention, in addition to the 0 compounds corresponding to general formula (I), the colouring compositions may also comprise one or more compounds of a aroUp (a). The group (a) includes compounds having a primary or secondary amino group or hydroxyl group, which are selected from primary or secondary aliphatic or aromatic amines, nitrogen- containing heterocyclic compounds, a- to w-amino acids, oligopeptides comprising from 2 to 9 amino acids and aromatic hydroxy compounds, and/or a CH-active compound.

1 The present invention also encompasses the use of those substances which are reaction products of compounds corresponding to general formula (I) with 0 those of group (a).

Suitable compounds having a primary or secondary amino group are, e.g., primary aromatic amines, such as N,N-dimethyP, N,N-diethyP, N-(2hydroxyethyl)-N-ethyl-, N,N-bis-(2-hydroxyethyl)-, N-(2-methoxyethyl)-, 2, 3-, 2,4- and 2,5-dichloro-pphenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3- and 4aminophenol, 2-aminomethyl-4-aminophenol, 2hydroxymethyl-4-aminophenol, o_ and p-phenylenediamine, Q-toluylenediamine, 2,5diaminotoluene, -phenol and -phenetole, 4-amino-3-methylphenol, 2-(2,5diaminophenyl)-ethanol, 2,4dian-dnophenoxyethanol, 2-(2,5-diaminophenoxy)-ethanol, 4-methylamino-, 3amino-4-(2'-hydroxyethoxy)-, 3,4-methylenediamino and 3, 4methylenedioxyaniline, 3-amino-2,4-dichloro-, 4-methylamino-, 2-methyl-5amino-, 3-methyl-4-amino-,2-methyl-5-(2-hydroxyethylamino)-,6-methy1-3amino-2-chl oro-, 2-methyl-5-amino-4-chloro-, 3,4-methylenedioxy-, 5-(2hydroxyethylamino)-4methoxy-2-methyl-, and 4-amino-2-hydroxymethylphenol, 1,3-diamino-2,4dimethoxybenzene, 2-, 3- and 4-aminobenzoic acid and phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4- and 3,5-diaminobenzoic acid, 4and 5-aminosalicylic acid, 3-amino-4hydroxy- and 4-amino-3-hydroxybenzoic acid, 2-, 3- and 4-aminobenzenesulfonic acid, 3-amino-4hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-l- sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4hydroxynaphthalene- 2-sulfonic acid, 4-aniino-5-hydroxynaphthal ene-2,7-disuifonic acid, 3- amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5and 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5- triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6- triaminoresorcinol, 4,5diaminopyrocatechol, 4,6-diaminopyrogallol, 3, 5- diamino-4-hydroxypyrocatechol and aromatic anilines and phenols having a further aromatic radical, such as correspond to general formula (M:

14 R R - R 13 R11 6 (11) wherein R represents a hydroxyl or an amino group, which may be substituted by Cl-C4 alkYll Cl-C4 hydroxyalkyl or Cl-C, alkoxy-CI-C, alkyl, R 12, R 13, R 14, R's and R represent hydrogen, a hydroxyl or an amino group, which may be substituted by aCI-C4alkyl, Cl-C4hydroxyakI, Cl- C4aminoalkyl orCI-C4 alkoxy-CI-C4alkyl group, or represent a carboxylic acid or sulfonic acid group, and Z represents a direct bond, a saturated or unsaturated carbon chain which is optionally substituted by hydroxyl groups and has from 1 to 4 carbon atoms, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom or a group corresponding to general formula (III):

Q-(CHz-P-CHz.:Q)q (M) wherein P represents a direct bond or a CH2 or CHOH group, Q and Q' independently represent an oxygen atom, an Np17 group, wherein R 17 represents hydrogen or a CCC4 alkyl or hydroxy-C,-C4 alkyl group, or the group: 0-(CH2)p-NH or NH-(CH2)p-0, wherein p and p' represent 2 or 3, and o represents an integer of from 1 to 4; for example, 4,4-diaminostilbene, 4,4'-diaminostilbene-2,2'-disulfonic acid monoor di-Na salt, 4-amino-4'-dimethylaminostilbene, 4,4'- diaminodiphenyl methane, sulfide, -sulfoxide or -amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'diaminobenzophenone, diphenyl ether, 3,31,4,4-tetraaminodiphenyl, 3, 3',4,4'tetraamino-benzophenone, 1,3-bis-(2,4-diaminophenoxy)-propane, 1,8bis-(2,5diaminophenoxy)-3,6-dioxaoctane, 1, 3-bis- (4-aminophenylamino) propane and -2propanol, 1,3-bis-[N-(4-aminophenyl)-2-hydroxyethylamino]-2propanol, N,N-bis[2-(4-a.minophenoxy)-ethyll-methylamine and N-phenyl-1,4phenylenediamine.

The above-mentioned compounds may be employed both in the free form and in the form of the physiologically-acceptable salts thereof, in particular as salts of inorganic 0 acids, such as hydrochloric or sulfuric acid.

Suitable nitrogen-containing heterocyclic compounds are e.g. 2-, 3- and 4amino-, 2- a.mino-3-hydroxy-, 2,6-diamino-, 2,5-diamino-, 2,3-diamino-, 2dimethylamino-5- amino-, 2-methylamino-3-amino-6-methoxy-, 2,3-diamino-6-methoxy-, 2,6- dimethoxy-3,5-diamino-, 2,4,5-triamino- and 2,6-dihydroxy-3,4- dimethylpyridine, 2,4-dihydroxy-5,6-diamino-, 4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2hydroxy-4,5,6-triamino-, 2,4,5,6-tetraafnino-, 2-methylamino-4,5,6- triamino, 2,4and 4,5-diaminoand 2-amino-4methoxy-6-methyl-pyrimidine, 3, 5-diaminopyrazole and -1,2,4-triazole, 2-amino- and 3-amino-5- hydroxypyrazole, 2-, 3- and 8aminoquinoline, 4-amino-quinaldine, 2- and 6- aminonicotinic acid, 5arninoisoquinoline, 5- and 6-aminoindazole, 5- and 7-amino-benzimidazole and benzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives, such as 4-, 5-, 6- and 7-aminoindole, 5,6-dihydroxyindole, 5, 6-dihydroxyindoline and 4-hydroxyindoline. The above-mentioned compounds may be employed both in the free form and in the form of the physiologically-acceptable salts thereof, e.g. as salts of inorganic acids, such as hydrochloric or sulfuric acid.

C Preferred possible amino acids are all the naturally occurring and synthetic ot-amino acids, e.g. the amino acids accessible by hydrolysis from plant or animal proteins, e.g. collagen, keratin, casein, elastin, soya protein, wheat gluten or almond protein. Both acid and alkaline amino acids may be employed here. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan. However, other amino acids, such as 6aminocaproic acid, may also be employed.

The oligopeptides here may be naturally occurring or synthetic oligopeptides, and also the oliegopeptides contained in polypeptide or protein hydrolysis products, as long as they have a water-solubility sufficient for use in the colouring compositions according to the present invention. Examples which may be mentioned are, e.g., glutathione - 15 or the oligopeptides contained in the hydrolysis products of collagen, keratin, casein, clastin, soya protein, wheat gluten or almond protein. Plant-based oligopeptides are preferred for the present purposes.

Use together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds is furthermore preferred here.

Suitable aromatic hydroxy compounds are, e.g., 2-, 4- and 5methylresorcinol, 2,5dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3- and 4-methoxy-, 3dimethylamino-, 2-(2hydroxyethyl)- and 3,4-methylenedioxyphenol, 2,4- and 3,4dihydroxybenzoic acid and -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid and -acetophenone, 2- and 4-chlororesorcinol, l-naphthol, 1,5-, 2,3- and 2,7dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid and,6-dihydroxy-2,7-naphthalenesulfonic acid.

Examples of CH-active compounds which may be mentioned are 1,2,3,3tetramethyl3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium ptoluenesulfonate, 1,2,3,3tetmmethyl-'JH-indolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2methyleneindoline), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium 2-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl-2quinaldinium iodide, 1methyl-2-quinaldinium iodide, barbituric acid, thiobarbituric acid, 1,3dimethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3indoxyl acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

i i Further dyestuff components contained in the colouring compositions according to the present invention may also be indoles and indolines and physiologically-acceptable salts thereof. Preferred examples are 5,6dihydroxyindole, N-methyl-5,6dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, Nbutyl-5,6-dihydroxyindole, 6hydroxyindole, 6-aminoindole and 4-aminoindole. 5, 6dihydroxyindoline, Nmethyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 6-hydroxyindoline, 6aminoindoline and 4-aminoindoline are furthermore preferred.

In the case of substances havina amino aroups, it may be preferable to employ them 0 0 in the hair-colouring compositions according to the present invention in salt form, in particular in the form of the hydrochlorides and sulfates.

It is not necessary for the dyestuffs and dyestuff precursors in each case to be uniform compounds. Rather, the hair-colouring compositions according to the present invention may also comprise further components in minor amounts, as a result of the preparation for the individual dyestuffs, as long as these do not adversely influence the dyeing result or do not have to be excluded for other reasons, e.g. toxicological reasons.

With regard to the dyestuffs which may be employed in the hair-dyeing and -tinting compositions according to the present invention, reference is furthermore made expressly to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyestuffs), and chapter 8, pages 264-267; oxidation dyestuff 0 precursors), published as volume 7 of the series "Dermatology" (Editors: Ch. Culnan and H. Maibach), Verlag Marcel Dekker Inc., New York, Basel, 1986, and the "Europlische Inventar der Kosmetik-Rohstoffe [European inventory of cosmetics raw materials]", published by the European Community, obtainable in diskette form from Bundesverband Deutscher Industrie- und Handelsunternehmen fur Arzneimittel, Reformwaren und K6rperpfiegemittel e.V., Mannhelm.

According to a preferred embodiment, the compositions according to the present invention furthermore comprise anionic, nonionic or, in particular, cationic polymers, especially if they should also have conditioning or hair-setting properties.

Cationic polymers which are suitable as conditioning active compounds contain cationic groups within the polymer skeleton. These groups may be part of the polymer chain, but they may also be in side-chains bonded to a main chain via intermediate members. Conventional cationic groups contain quaternary nitrogen or phosphorus atoms. Groups having quaternary nitrogen atoms are preferred here. The quaternary nitrogen atoms here may either carry four different or, in some cases, identical substituents, or be part of a ring system. Preferred cationic groups are ammonium and imidazolium groups.

0 Examples of such polymers are:

1 Quaternized cellulose derivatives, such as are commercially available under the (RTM) W11m) names Celquatojand Polymer IRY The compounds CelquatT H 100, Celquat L and Polymer TR0400 are preferred quaternized cellulose derivatives.

Quaternized guar derivatives, such as are commercially available under the names Cosmedia Guar and laguar Preferred guar derivatives are, for example, Cosmedia Guarl& C-261 and Jaguar40 C 13-S.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and -methacrylate, such as vinylpyrrolidoneldimethylaminoalkyl methacrylate copolymer quaternized with diethyl sulfate, and vinylpyrrolidonelmethacrylamidopropyltrimethylammonium chloride copolymer.

Such compounds are commercially available under the names Gafquat34, Wquat3755 and WquatOHS100.

Copolymers of vinylpyrrolidone with vinylimidazolium methochloride, such as are (cp.) available under the name LuviqualPolymeric dimethyIdiallylammonium. salts and copolymers thereof with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names MerquatO 00 (poly(dimethyldiallylammonium chloride)) and Merquat&SSO (dimethyldiallylammonium chloride/acrylamide copolymer) are examples of such cationic polymers. Cationically derivatized silicone oils, such as the commercially available products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethylsilylamodimethicone), Dow Cornin. 929 Emulsion (comprising a hydroxyl-amino- modified silicone, which is also called amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil Quat 3270 and 3272 (manufacturer:

Th. Goldschmidt; diquaternary polydirnethylsiloxanes, quaternium-80).

Chitosan and derivatives thereof.

The compositions according to the present invention preferably contain the cationic polymers in amounts of from 0. 1 to 5 wt.%, based on the total formulation.

Suitable nonionic polymers are, for example:

Vinylpyrrolidone/vinyl ester copolymers, such as are marketed, for example, under the trademark Luviskolc (BASF). Luvisko10 VA 64 and Luviskol's VA 73, in each case vinylpyrrolidonelvinyl acetate copolymers, are preferred nonionic polymers. Cellulose ethers, such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, such as are marketed, for example, under the Oem) trademarks Culmina13 and BenecelO (AQUALON).

Shellac Polyvinylpyrrolidones, such as are marketed, for example, under the name Luvisko10 (BASF).

Examples of suitable anionic polymers are:

Copolymers of acrylic acid and/or methacrylic acid or esters thereof withCIO-C30 alkyl acrylates, such as are marketed, for example, under the name Pemuleny- Q?Mi Polymers and copolymers of crotonic acid with esters and amides of acrylic and methacrylic acid, such as vinyl acetate/crotonic acid and vinyl acetate/vinyl propionatelcrotonic acid copolymers. Compounds of this type are commercially available under the brand names Resyn (NATIONAL STARCH), Luvisetl (BASF) and Gafset(GAF); the products LuviseCIOCA-66 and LuvisetOCAP may be preferred.

Vinylpyrrolidonelvinyl acrylate copolymers, obtainable, for example, under the trademark Luviflexe (BASF). A preferred polymer is the vinylpyrrolidone/acrylate terpolymer available under the name Luviflexo VBM-35 (BASF).

Acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers, which are marketed, for example, under the name UltraholdO 1 strong (BASF), and methacrylic acidlethyl acrylate/1-butyl acrylate terpolymers, which are marketed under the name Luvime OOP (BASF).

The use of anionic, nonionic or cationic polymers may be preferred inthose haircolouring compositions which are free from oxidation dyestuff precursors.

To prepare the colouring compositions according to the present invention, the direct 0 dyestuffs and, optionally, the oxidation dyestuff precursors are incorporated into a suitable water-containing carrier. For the purpose of dyeing hair, such carriers are, e.g., creams, emulsions, gels or also surfactant-containing foaming solutions, e.g.

W 0 shampoos, foam aerosols or other formulations which are suitable for use on the hair.

The colouring compositions according to the present invention may furthermore 0 0 comprise all the active compounds, additives and auxiliary substances known for such formulations. In many cases, the colouring compositions comprise at least one -21surfactant, both anionic and zwitter-ionic, ampholytic, nonionic and cationic surfactants being suitable in principle. However, it has proved advantageous in many cases to choose the surfactants from anionic, zwitter-ionic or nonionic surfactants.

Suitable anionic surfactants in formulations according to the present invention are all the anionic surface-active substances suitable for use on the human body. These are characterized by an anionic group which renders them water-soluble, such as a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having from about 10 to 22 carbon atoms. The molecule may additionally 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 salts, as well as the mono-, di- and trialkanolammonium salts having 2 or 3 carbon atoms in the alkanol group, linear fatty acids having from 10 to 22 carbon atoms (soaps), ether-carboxylic acids corresponding to the general formula: R-O-(CH2-CH2COOH, wherein R represents a linear alkyl group having from CH20)x 10 to 22 carbon atoms and x represents 0 or 1 to 16, acyl sarcosides having from 10 to 18 carbon atoms in the acyl group, acyl taurides having from 10 to 18 carbon atoms in the acyl group, acyl isethionates having from 10 to 18 carbon atoms in the acyl group, sulfosuccinic acid mono- and di-alkyl esters having from 8 to 18 carbon atoms in the aIkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl esters having 0 -22from 8 to 18 carbon atoms in the alkyl group and from 1 to 6 oxyethyl groups, linear alkanesulfonates having from 12 to 18 carbon atoms, linear alpha-olefinsulfonates having from 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having from 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether-sulfates corresponding to the general formula: R-O(CH2-CH.20),-SO3H, wherein R represents a preferably linear alkyl group having from 10 to 18 carbon atoms and x = 0 or 1 to 12, mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene glycol ethers andlor hydroxyalkylpolypropylene glycol ethers according to DE-A-37 23 354, sulfonates of unsaturated fatty acids having from 12 to 24 carbon atoms and from 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 from about 2 to 15 molecules of ethylene oxide andlor propylene oxide on fatty alcohols having from 8 to 22 carbon atoms.

0 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 0 to 12 glycol ether groups in the molecule, and, in particular, salts of saturated and, in particular, unsaturated C8-C22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO(-) or -S03(_) group in the molecule are termed zwitterionic surfactants. Particularly suitable zwitter-ionic surfactants are the so-called betaines, such as N-alkyl-N,Ndimethylammonium glycinates, fo r example coco-alkyl- C dimethylammonium glycinate, N-acyl-aminopropyl-N,N-dimethylarnmonium glycinates, for example coco-acylaminopropyl-dimethylammonium glycinate, and 2alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having in each case from 8 to 18 carbon atoms in the alkyI or acyl group, as well as coco- 0 acylaminoethylhydroxyethylcarboxymethyI glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name cocamidopropyl betaine.

Ampholytic surfactants are to be understood to be those surface-active compounds which contain at least one free amino group'and at least one COOH or -S03H group in the molecule, in addition to a C&-C,s- alkyl or acyl group, and are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkylalycines, N-alkylpropionic acids, Nalkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-Nalkylamidopropyl-lycines, N-alkyltaurines, N-alkylsarcosines, 2alkylaminopropionic acids and alkylaminoacetic acids having in each case from about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coco-alkylaminopropionate, cocoacylaminoethylaminopropionate andC12-C,s acylsarcosine.

-24Nonionic surfactants contain, as the hydrophilic group, e.g. a polyol group, a polyaBqlene glycol ether group or a combination of polyol and polyglycol ether group. Such compounds are, for example, j z 1 addition products of from 2 to 30 mol of ethylene oxide andlor from 0 to 5 mol of propylene oxide on linear fatty alcohols having from 8 to 22 carbon atoms, on fatty acids having from 12 to 22 carbon atoms and on aIkylphenols having from 8 to 15 carbon atoms in the alkyl group, C,2C22 fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide on glycerol, CS-C22 alkyl mono- and oligo-glycosides and ethoxylated analogues thereof, 0 0 addition products of from 5 to 60 mol of ethylene oxide on castor oil and hydrogenated castor oil, addition products of ethylene oxide on sorbitan fatty acid esters, addition products of ethylene oxide onfatty acid aflanolamides.

Examples of the cationic surfactants which may be used in the hair treatment compositions according to the present invention are, in particular, quaternary ammonium compounds. Ammonium halides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, c. g. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, are -25preferred. The quaternized protein hydrolysis products are further cationic surfactants which may be used according to the present invention.

'15 Alkylamidoamines, in particular fatty acid amidoamines, such as the (RTM) stearylamidopropyldimethylamine available under the name Tego AmidOS 18, are i distinguished specifically by the good biodegradability thereof, in addition to a good conditioning action.

Quaternary ester compounds, so-called "esterquats", such as the methylhydroxyalkyldialkoyloxyalkyl-ammonium methosulfates marketed under the trademark StepantexO and the products marketed under the trademark DehyquartO, such as Dehyquart AU-46, are also very readily biodegradable.

An example of a quaternary sugar derivative which may be employed as a cationic surfactant is the commercial product Glucqua 00, a "lauryl methyl gluceth- 10 tt 0 hydroxypropyl dimonium chloride" according to INCI nomenclature.

The compounds having alkyl groups employed as surfactants may in each case be uniform substances. However, it is as a rule preferable to use natural plant or animal raw materials as starting substances for the preparation of these substances, so that substance mixtures of varying alkyl chain lengths, depending on the particular raw material, are obtained.

is For the surfactants which are addition products of ethylene oxide andlor propylene oxide on fatty alcohols or derivatives of these addition products, both products having a "normal" homologue distribution and those having a narrowed homologue distribution may be used. "Normal" homologue distribution is to be understood to be mixtures of homologues which are obtained by reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homologue distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether-carboxylic acids or alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products of narrowed homologue distribution may be preferred.

The surfactants are preferably present in the compositions according to the present invention in amounts of from 1 to 20, in particular from about 6 to 10 wt. %, in each case based on the total composition, if the composition according to the present 0 invention is a colouring shampoo. For colouring lotions or colouring gels, on the 0 other hand, amounts of from 1 to 10, in particular from 2 to 4 wt.%, in each case based on the total composition, are preferred.

Further active substances, auxiliary substances and additives are, for example, thickeners, such as aggar-agar, guar gum, alainates, xanthan aun, gurn arabic, C 0 0 C 0 karaya gum, carob bean flour, linseed gums, dextrans, cellulose derivatives, e.g.

methylceflulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions -27and derivatives, such as amylose, arnylopectin and dextrins, clays, such as e.g. bentonite, or completely synthetic hydrocolloids, such as e. g. polyvinyl alcohol, structuring agents, such as glucose and maleic acid, hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and cephalins, as well, as silicone oils, protein hydrolysis products, in particular hydrolysis products of elastin, collagen, ceratin, milk protein, soya protein and wheat protein, condensation products thereof with fatty acids and quaternized protein hydrolysis products, perfume oil, dimethyl isosorbide and cyclodextrins, solubilizing agents, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, antidandruff active compounds, such as piroctone olamine and zinc omadine, further substances for adjusting the pFI, active compounds such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extracts and vitamins, cholesterol, light stabilizers, agents for imparting consistency, such as sugar esters, polyol esters or polyol alkyl 0 0 ethers, fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid aIkanolamides, complexing agents, such as EDTA, NTA and phosphonic acids, -28swelling and penetration substances, such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, clouding agents, such as latex,' pearlescent agents, such as ethylene glycol mono- and di-stearate, propellants, such as propanelbutane mixtures, N20, dimethyl ether, C02and air, and antioxidants.

To prepare the colouring compositions according to the present invention, the constituents of the water-containing carrier are employed in the conventional amounts for this purpose; e.g. emulsifying agents are employed in concentrations of from 0.5 to 30 wt.% and thickeners are employed in concentrations of from 0. 1 to 25 wt.% of the total colouring composition.

The present invention also provides the use of such a composition for dyeing and tinting keratinic fibres, in particular human hair.

It is possible, in principle, to formulate the compositions according to the present invention such that they either remain on the hair or are rinsed out of the hair again.

According to a preferred embodiment, the compositions according to the present invention are formulated such that they can remain on the hair. This is particularly -29the case with so-called tinting compositions, but also with compositions which are also to have a hair-setting function.

- The following Examples are intended further to illustrate the present invention.

Examples

All the amounts in the Examples are parts, by weight 1. Hair-colouring creams using direct dyestuff Part mixture A Cetearyl alcohol 1.00 Fatty alcohol mixture based on coconut oil 1.00 AkypoORLM 45Nt 1.10 Propyl p--hydroxybenzoate 0.05 Methyl p-hydroxybenzoate 0.15 Water 70.00 Lauryl alcohol having about 4.5 rnol ethylene oxidelacetic acid sodium salt (about 82% active substance; INCI name: sodium laureth-6 carboxylate) (KAO, Chern-Y) The substances were melted at 8WC, mixed with hot water at 80C and emulsified with vigorous stirring. Thereafter, the emulsion was cooled with slow stirring.

is Part mixture B Ammonium sulfate Direct dyestuff corresponding to general formula 0 (1) 1.00 1.00 Ammonia (25% solution) Water to pH = 9.0 10.00 The dyestuff was dissolved in hot water at SO'C, ammonium sulfate and ammonia being added.

The dyestuff solution (part mixture B) was added to the emulsion (part mixture A) and the mixture was adjusted to pH = 9 using ammonia and made up to 100 parts, by weight, with water. Stirring was continued until room temperature was reached.

0 0 The thus-obtained colouring creams were applied to strands of standardized human 0 hair 5 em Iona which had greyed to the extent of 80%, but had not been particularly 0 0 pretreated, and were left there at 32'C for 30 min. Thereafter, the hair was rinsed, washed with a conventional hair-washing composition and then dried.

0 The result of the dyeing experiments [nay be seen from Table 1.

0 Table 1

Direct dyestuff Shade of the dyed hair phenalen-l-one yellow 6-hydroxyphenalenone madder red 2. Hatr-colQurina. creams using dire,ct dyestuff and amines is Colourinc, cream 1 Colourine, cream 2 TexaponONSO, 20.00 20.00 Dehyton A K2 12.50 12.50 LorolO, technical grade--' 2.00 2.00 HydrenolOD' 8.50 9.50 1 0.75 0.75 EumulainOAB2' Ascorbic acid 0.10 0.10 Sodium sulfite 0.10 0.10 p-toltiylenediamine sulfate 4.41 - 2,4,5,6- 4.76 tetraaminopyrimidine sulfate Ammonia (25% solution) to pH=8.56 to pH=9.18 Water to 100 to 100 1 Lauryl ether-sulfate sodium salt (HENKEL) 2 N,N-dimethyl-N-(Cs-C,a coco-amidopropyl)ammoniurn- acetobetaine (about 30% active substance; INCI name: aqua (water), cocamidopropyl betaine) (HENKEL) 3 C,2-CM fatty alcohol (INCI name coconut alcohol) (HENKEL) 4 C16-Cts fatty alcohol (HENKEL) Cetylstearyl alcohol with about 20 mol of ethylene oxide (INCI name: ceteareth20) (HENKEL) Immediately before use, 0.005 mol (0.90 a) phenalen-l-one was incorporated into the C hair-colouring creams described above. The mixture was then applied to natural 0 white hair strands about 5 cm Iona (Kerling) weighing about 1 g (weight ratio of 0 0 0 colouring mixture: hair strands corresponds to 4: 1).

After a contact time of 30 min at 32C, the strands of hair were washed, first with water and then with shampoo. After drying, the strands showed the following dyeings:

0 Colourina cream 1 dark brown 0 Colouring cream 2 dark orange

Claims (1)

1. Clair-m-.

   1.

   A composition for dyeing and tinting keratinic fibres, in particular human hair, characterized in that it comprises, as a direct dyestuff, a compound corresponding to the general formula (I):

   0 0 R R R 3 7 R (1) wherein R' to R' independently represent - hydrogen, a C,-C, alkyl group, an allyl aroup, aCCC4 alkoxy group, a C,-C, monohydroxyalkyl group, a C,,-C, dihydroxyalkyl group, tP a hydroxyl group, 0 a halogen atom, a nitro group 0 a cyano group or is - a C,-C, alkyl croup, an allyl croup, - a C,-C, hydroxyalkyl group or - a C2-C, dihydroxyalkyl group; at least five of the substituents R' to R' representing hydrogen.

   2.

   is A composition as claimed in claim 1 wherein at least six of the subsfituents R' to R' represent hydrogen and the other two substituents independently represent hydrogen, a methyl group, a methoxy group, a hydroxyl croup, a chlorine atom, an amino group, a nitro croup or a cyano group.

   A composition as claimed in claim 1 or claim 2 wherein at least seven of the substituents R' to R8 represent hydrogen.

   4. -A composition as claimed in any of claims 1 to 3 wherein R' represents a hydroxyl group.

   A composition as claimed in any of claims 1 to 3 wherein R' to R' represent hydrogen.

   is 6. A composition as claimed in any of claims 1 to 5 wherein it is free from oxidation dyestuff precursors.

   7. A composition as claimed in claim 6 wherein it remains on the hair.

   8. A composition as claimed in claim 6 or claim 7 wherein it is a hairsetting composition.

   9. A composition as claimed in any of claims 1 to 5 wherein it comprises at least one developer component andlor at least one coupler component.

   10. A composition as claimed in claim 9 wherein the developer component is selected from p-aminophenol, 1-(2'-hydroxyethyl)-2,5-diaminobenzene, 2,4, 5,6-tetraam i nopyri midi ne, 2-hydroxy-4,5,6-triaminopyrimidine, 4hydroxy-2,5,6-triai-ninopyrimidine, 4,5-diamino-l-(2-hydroxyethyl)pyrazole, 2-toluylenediamine, 2-aininoiliethy]-4-amino-phenol, N,N-bis-(2hydroxyethyl)-2-phenylenediamine, 2-phenylenediamine, 3-methyl-paminophenol and b is- (2 -h ydroxy-5 -am i no-phen yl) -methane.

   11. -A composition as claimed in claim 9 or claim 10 wherein the coupler component is selected from 1 -naphthol, 1,5-, 2,7- and 1,7dihydroxynaphthalene, resorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3, 4- diaminopyridine, m-aminophenol, 5-amino-2-methylphenol, 3methyisuifonylamino-2-methyl-aniline, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dimethyl-3-aiTiino-pheiiol, 2,4-diamino-phenoxyethanol, 6methyl- 1,2,3,4-tetrahydro-quinoxaline, 2-methyl-4-chloro-5-amino-phenol, 3,4-methylenedioxyaniline, 2-methyl-resorcinol, 5-methylresorcinol, 4chlororesorcinol, 3,4-methyletiedioxyphenol, 2-amino-3-hydroxypyridine and 2-chlo ro-6- methyl -3-ami nophenol.

   12. A composition as claimed in any of claims 1 to 11 wherein it also comprises an anionic, nonionic or cationic polymer.

   13. The use of a composition as claimed in any of claims 1 to 12 for dyeing and tintina hair.

   0