WO2006103036A1

WO2006103036A1 - Agents for colouring fibres containing keratin

Info

Publication number: WO2006103036A1
Application number: PCT/EP2006/002757
Authority: WO
Inventors: Hinrich Möller; Horst Höffkes; Doris Oberkobusch
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2005-04-01
Filing date: 2006-03-25
Publication date: 2006-10-05
Also published as: DE102005015330A1

Abstract

The invention relates to agents for the oxidative colouring of fibres containing keratin, in particular human hair, said agents containing compounds of formula (I) as an oxidation colorant intermediate product, in which the groups R1, R2, X and Y are defined as cited in claim 1. The colorant intermediate products are suitable for atmospheric oxidation colouring or colouring in the presence of additional oxidation agents, such as e.g. hydrogen peroxide. The invention also relates to the use of the derivatives according to formula (I) for colouring fibres containing keratin and to a corresponding method for colouring fibres containing keratin, in particular human hair.

Description

Agent for dyeing keratinous fibers

The invention relates to agents for the oxidative dyeing of keratin-containing fibers, in particular human hair, containing specific N-heterocyclic compounds, the use of these compounds for dyeing keratin-containing fibers, and a corresponding method for dyeing keratin-containing fibers, in particular human hair.

For the dyeing of keratin-containing fibers, either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with one another or with one or more coupler components, are generally used. Coupler and developer components are also referred to as oxidation dye precursors.

The developer components are usually primary aromatic amines having 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 used.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4, 5,6-tetraminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2.5 - diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine are generally used. used derivatives. Suitable coupling agents are, in particular, α-naphthol, 1,5,7,7-di- or 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethyl ether, m-phenylenediamine, 2,4- Diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1, 3 Bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy- 2-methylaminopyridine and 3,5-diamino-2,6-dimethoxypyridine.

For other common dye components, reference is expressly made to the series "Dermatology" by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, pages 248-250 (Direct-Dye), and Chap. 8, pp. 264-267 (oxidation dyes), as well as the European Inventory of Cosmetic Raw Materials, 1996, published by the European Commission, available in floppy form from the Federal Association of German Industrial and Trade Companies for Pharmaceuticals, Reform Goods and Personal Care, Mannheim ,

With oxidation dyes, intensive colorations with good fastness properties can be achieved. Still problematic is the provision of oxidation hair dyeings with sufficient fastness properties, in particular with very good fastness to light, washing and rubbing.

Furthermore, p-phenylenediamine and its derivatives can cause allergic reactions in some people, the so-called para-allergic. It is therefore always an object to provide colorants, in particular for the coloring of keratin-containing fibers such as hair, which do not have an allergenic effect. Consequently, it is desirable to develop oxidative dyes which are not derived from p-phenylenediamine yet possess excellent dyeing properties.

Surprisingly, it has now been found that the compounds according to formula I dye keratin-containing fibers oxidatively and the resulting dyeings have excellent fastness properties. They give colorations with excellent brilliance and color depth and lead to shades in the blue to red area. The dyes obtained by oxidative coupling are also ideal for use in hair dyes.

A first subject of the invention are agents for dyeing keratin-containing fibers, in particular human hair, which contain in a cosmetic carrier at least one compound according to formula I and / or their physiologically acceptable salts,

in which

• R ¹ and R ² are independently a hydrogen atom, a halogen atom, a linear or branched Ci-C ₆ alkyl group, a cyano group, a hydroxy group, a -C ₆ monohydroxyalkyl, a C ₂ -C ₆ - polyhydroxyalkyl group, a Ci-C ₆ alkoxy group, a hydroxy (C _r _C6) - alkoxy group, a group R ¹ R ¹¹ N- (CH ₂₎ P, wherein R ¹ and R ¹¹ are independently a hydrogen atom, a Ci- Ce-alkyl group, a C _r C ₆ -Hydroxyalkylgruppe or an aryl-C _r C ₆ - alkyl group and n is an integer from 0 to 6, or together with the residual molecule form an aromatic, optionally substituted six-membered ring,

X is an oxygen atom or a sulfur atom,

Y is a carbonyl group, a thiocarbonyl group, a methylene group CR ³ R ⁴ , or a vinylene group -CR ⁵ = CR ⁶ -, in which R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another represent a hydrogen atom, a halogen atom, a linear or branched C 1 -C ₆ -alkyl group, a

Cyano group, a hydroxy group, a C _r C ₆ monohydroxyalkyl group, a

C ₂ -C ₆ polyhydroxyalkyl group, a CrCβ-alkoxy group, a hydroxy (C _r _C6) - alkoxy group, a group R ^aι R ^IV N- (CH ₂₎ _m - wherein R ^ll! and R ^ιv are independent of each other is a hydrogen atom, a Ci-C ₆ alkyl group, a C _r C ₆ hydroxyalkyl group or an aryl-C _r C ₆ alkyl group and m is an integer from 0 to 6, or a group NR ⁷ , wherein R ⁷ represents a linear or cyclic C _r C ₆ alkyl group, a C ₂ -C ₆ - alkenyl group, an optionally substituted aryl group, an aryl (Ci-C ₆₎ - alkyl group, a -C ₆ monohydroxyalkyl, a C ₂ - C ₆ - Polyhydroxyalkylgruppe, a CrC ₆ alkoxy (CrC ₆ ) alkyl group, a group R ^v R ^vl N- (CH ₂ ) _q -, wherein R ^v and R ^vι independently represent a hydrogen atom, a C _r C ₆ alkyl group, a C _r C ₆ -hydroxyalkyl group or an aryl (C _r C ₆ ) alkyl group, wherein R ^v and R ^vι together with the nitrogen atom, an optionally substituted, 5, 6 or 7-membered ring and q is an integer from 2 to 6.

It is inventively preferred that the substituents R ¹ and R ² form an aromatic, optionally substituted six-membered ring (Benzannelierung) together with the remainder of the molecule. This six-membered ring is again preferably substituted by two radicals R ⁸ and R ⁹ , which independently of one another represent a hydrogen atom, a halogen atom, a linear or branched C ₁ -C ₆ -alkyl group, a cyano group, a hydroxy group, a C _r C ₆ - Monohydroxyalkyl group, a C ₂ -C ₆ -

Polyhydroxyalkyl group, a Ci-C ₆ alkoxy, a hydroxy (CrC ₆ ) alkoxy group, a group R ^vll R ^vnι N- (CH ₂ ) _r -, wherein R ^v "and R ^vι " independently represent a hydrogen atom , a CrC alkyl ₆ alkyl group, a C _r C ₆ hydroxyalkyl group, or an aryl-C _r C _6, and r is a whole number from 0 to. 6

The compounds of the formulas I are preferably selected from at least one of the compounds according to formulas (II) and / or (III) and / or their physiologically tolerable salts

wherein R ⁷ represents a linear or cyclic C _r C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an aryl (d-Ce) alkyl group, a C _r C ₆ monohydroxyalkyl group, a C ₂ -C ₆ - polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy (CrC ₆₎ alkyl group, a group R ^v R ^vl N- _q (CH ₂₎ -, in which R ^V and R ^VI are each independently a Hydrogen atom, a C _r C ₆ alkyl group, a CrC ₆ -hydroxyalkyl group or an aryl (C _r C ₆ ) alkyl group, wherein R ^v and R ^vι together with the nitrogen atom, an optionally substituted, 5-, 6- or 7 -membered ring, and q is an integer from 2 to 6.

• R ⁸ and R ⁹ independently represent a hydrogen atom, a halogen atom, a linear or branched Ci-C ₆ alkyl group, a cyano group, a hydroxy group, a Ci-C ₆ monohydroxyalkyl, a C ₂ -C ₆ - polyhydroxyalkyl , a C _r C ₆ alkoxy group, a hydroxy (dC ₆ ) alkoxy group, a group R ^v "R ^vlll N- (CH ₂ ) r-, wherein R ^v " and R ^vι "independently represent a hydrogen atom , a C _r C ₆ alkyl group, a C _r C ₆ hydroxyalkyl group or an arylCroC ₆ alkyl group, and r is an integer of 0 to 6.

Preferably, the compounds according to formula I are selected from the group formed from 2-aminoindolin-3-one, 2-amino-1-methylindolin-3-one, 2-aminoindan-1, 3-dione and the physiologically acceptable Salts of these compounds.

If the compounds according to the invention are present as physiologically acceptable salts, they are preferably formed by reacting the compounds of the formula I with organic or inorganic acids. The counterion of these salts is preferably selected from the group of the anions halide, benzenesulfonate, p-toluenesulfonate, C ₁ -C ₄ -alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, (C _r C ₄ ) -alkyl sulfate, hydrogensulfate, tetrafluoroborate, hexafluorophosphate and tetrachlorozincate selected.

In the following, examples of the groups or radicals mentioned as substituents in the context of this application will be mentioned. Examples of linear and branched C 1 -C 6 -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl. Examples of corresponding cyclic alkyl groups are cyclopentyl and cyclohexyl.

Examples of preferred C ₂ -C ₆ -alkenyl radicals are vinyl and allyl.

C ₁ -C ₆ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group.

The methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-

Butoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl are examples of

C _r C ₄ alkoxycarbonyl groups; the methoxycarbonyl and ethoxycarbonyl groups are particularly preferred.

Furthermore, as preferred examples of a Ci-C ₆ -Monohydroxyalkylgruppe a

Hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a

4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group. A 2-hydroxyethyl group is particularly preferred.

Examples of a C ₂ -C ₆ -polyhydroxyalkyl group are the 2,3-dihydroxypropyl group,

3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group.

The methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and the

Methoxy hexy Ig group are examples of inventive C ₁ -C ₆ -Akoxy-CrC ₆ - alkyl groups.

A preferred hydroxyCrC ₆ alkoxy group is the 2-hydroxyethoxy group.

Preferred aryl groups are phenyl, naphthyl and biphenyl.

Examples of halogen atoms are F, Cl, Br or I atoms, with Cl and Br atoms being very particularly preferred.

Preferred arylCrC ₆ -alkyl groups are benzyl and 2-phenylethyl.

The amino, diethylamino, dimethylamino, di (2-hydroxyethyl) amino, (2

Hydroxyethyl) amino,. Aminomethyl-, 2-aminoethyl-, 3-aminopropyl-, 2-

Dimethylaminoethyl, diethylaminomethyl, dimethylaminomethyl, 2-methylaminoethyl,

2-dimethylaminoethyl, piperidinomethyl, pyrrolidinomethyl, morpholinomethyl are preferred radicals of the group R'R "N- (CH ₂ ) n-, where the diethylaminomethyl,

Piperidinomethyl, 2-dimethylaminoethyl, dimethylamino and the amino group are particularly preferred.

A preferred C- _M carboxyalkyl group is the 3-carboxypropyl group.

The groups 1-carboxypropylene and 1-carboxyethylene are preferred carboxy (C _r

C ₄ ) -alkylene groups. The other terms used are derived according to the invention from the definitions given here.

The compounds according to the invention can be prepared by methods known from the literature, e.g. according to N. Gamon et al., Liebigs Ann. Chem., 1980, 2072-2094.

Keratin fibers are wool, furs, feathers and especially human hair to understand. The colorants of the invention can in principle but also for dyeing other natural fibers such. As cotton, jute, sisal, linen or silk, modified natural fibers such. As regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose can be used.

When using the dye precursors according to the invention according to formula (I), a dye is already formed under air oxidation. The dye forms under oxidative coupling and ammonia elimination.

The reaction products of the above-described oxidative coupling of the compounds according to formula I are colored and can be used according to the invention as substantive dyes in colorants for keratin-containing fibers. Preferred reaction products as an ingredient of colorants for keratin-containing fibers, in particular human hair, are selected from compounds of the formulas (RP1) and (RP2),

(RP1)

wherein the radical R ^{7 is defined} as described under formula (I) and R ⁸ and R ^{9 are} independently a hydrogen atom, a halogen atom, a linear or branched C _r C ₆ alkyl group, a cyano group, a hydroxy group, a C ₁ -C ₆ - monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C _r C ₆ alkoxy group, a hydroxy (C _r C ₆ ) alkoxy group, a group R ^vll R ^VIII N- (CH ₂ ) r-, wherein R ^v "and R ^vl" are independently a hydrogen atom, a CrC ₆ alkyl group, a CrC alkyl ₆ hydroxyalkyl group, or an aryl-C _r C _6, and r is a whole number from 0 to. 6

The reaction products are preferably present in an amount of 0.01-10% by weight, preferably 0.1-3% by weight, based in each case on the ready-to-use colorant.

The reaction products can be used both in the presence of the compounds of formula (I) and in the absence of the compounds of formula (I) in the colorants application. The use of the dye precursors according to formula (I) in the colorants, however, offers advantages in terms of the color fastness of the obtained dyeings. Furthermore, there is the option to use these reactive dye precursors together with other reactants in the compositions of the invention. It may therefore be advantageous to use at least one compound of the formula (I) together with at least one reactive carbonyl compound and / or with at least one oxidation dye precursor of the developer and / or coupler type.

Dyeing with increased brilliance and improved fastness properties (light fastness, wash fastness, rubfastness) over a wide range of nuances are achieved if the compounds of formula I used according to the invention together with at least one substance having a reactive carbonyl group (hereinafter called reactive carbonyl compound) in the inventive compositions are. Reactive carbonyl compounds according to the invention have at least one carbonyl group as reactive group which reacts with the compound of formula I under condensation to form a Schiff base. Furthermore, according to the invention, those compounds which can be used as reactive carbonyl components in which the reactive carbonyl group is derivatized such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the compounds of the formula I are always present. These derivatives are preferably addition compounds a) of amines and their derivatives to form imines or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound c) when component B is derived from aldehydes, of water to form hydrates as addition compound to the carbon atom of the carbonyl group of the reactive carbonyl compound, these derivatives are preferably not themselves colored.

Preferably, these reactive carbonyl compounds are aldehydes or ketones.

The reactive carbonyl compounds are preferably selected from compounds according to formula VII,

in which

• AR is benzene, naphthalene, pyridine, pyrimidine, pyrazine, pyridazine, carbazole, pyrrole, pyrazole, furan, thiophene, 1, 2,3-triazine, 1,3,5-triazine, quinoline, isoquinoline, indole, indoline, Indolizine, indan, imidazole, 1,2,4-triazole, 1, 2,3-triazole, tetrazole, benzimidazole, 1,3-thiazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, quinolizine, cinnoline, acridine, julolidine, Acenaphthene, fluorene, biphenyl, Diphenylmethane, benzophenone, diphenyl ether, azobenzene, chromone, coumarin, diphenylamine, stilbene, where the N-heteroaromatics may also be quaternized,

R ^9a is a hydrogen atom, a C _r C ₆ alkyl, C ₂ -C ₆ acyl, C ₂ -C ₆ alkenyl, C ₁ -C ₄ perfluoroalkyl, an optionally substituted aryl or heteroaryl group,

• R ^10, R ¹¹ and R ¹² independently represent a hydrogen atom, a halogen atom, a CrC ₆ alkyl, C ₁ -C ₆ -AIkOXy-, Ci-C ₆ aminoalkyl, C ₁ -C ₆ - Hydroxyalkyl group, a C _t -C ₆ alkoxyC _r C ₆ alkyloxy group, a C ₂ -C ₆ acyl group, an acetyl, carboxyl, carboxylato, carbamoyl, sulfo, sulfato, sulfonamide, suifonamido , C ₂ -C ₆ alkenyl, an aryl, an arylC _r C ₆ alkyl group, a hydroxy, a nitro, a pyrrolidine, a morpholino, a piperidino, an amino or Ammonio or a 1-imidazole (in) io group, where the last three groups with one or more Ci-C ₆ alkyl, C _r C ₆ carboxyalkyl, C ₁ -C ₆ hydroxyalkyl, C ₂ -C _6- alkenyl, CrC ₆ alkoxy-C _r C ₆ alkyl, with optionally substituted benzyl groups, with sulfo (CrC ₄ ) alkyl or heterocycle (CrC ₄ ) alkyl groups may be substituted, wherein two the radicals from R ¹⁰ , R ¹¹ , R ¹² and -ZYR ^9a together with the remainder of a molecule optionally fused substituted 5-, 6- or 7-ring, which may also carry a fused aromatic ring, form, the system AR depending on the size of the ring can carry further substituents, which can stand independently for the same groups as R ¹⁰ , R ¹¹ and R ¹² ,

Z is a direct bond, a carbonyl, a carboxy (C ₁ -C ₄ ) -alkylene, an optionally substituted C ₂ -C ₆ -alkenylene, C ₄ -C ₆ -alkadienylene, furylene, thienylene, Arylene, vinylenarylene, vinylenfururylene, vinylenthienylene group, wherein Z together with the -YR ^9a group can also form an optionally substituted 5-, 6- or 7-membered ring,

Y is a group which is selected from carbonyl, a group according to formula VI.1 and a group according to formula IX,

in which R ¹³ represents a hydrogen atom, a hydroxy group, a C ₁ -C ₄ - alkoxy group, a C _r C ₆ alkyl group, a Ci-C ₆ hydroxyalkyl group, a C ₂ - C ₆ -Polyhydroxya kylgruppe, a CrC _6! - Alkoxy-C 1 -C 6 -alkyl group, R ¹⁴ and R ¹⁵ independently of one another represent a C 1 -C ₆ -alkyl group, an aryl group or form together with the structural element OC-0 of the formula IX a 5- or 6-membered ring.

The reactive carbonyl compound is more preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4- Hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6- Trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, A-aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, A-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-Dihydroxy-benzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone , 3-hydroxyflavone, 3,5,7-trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1 -andanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1, 8- Dihydroxyanthrone, vanillin, coniferylaldehyde, • 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, A-

Methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, A-

Ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4- Hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3, 5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxy- benzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5- Trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-

Trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4- Dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2, 5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, A-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2- morpholinobenzaldehyde, A- Piperidinobenzaldehyd ^', 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-napthaidehyd, 4-hydroxy-3-methoxy-1 naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphtha haldehyde, A-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino cinnamic aldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H, 5l-l benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene -1,3,3-trimethyl-disdoline (Fischer's aldehyde or tribasic aldehyde), 2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindo-3-aldehyde, 1-acetylindole-3-aldehyde, 3 Acetylindole, 1-methyl-3-acetylindole, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde , 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-alde hyd, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromone-3-aldehyde, 3- (5'-nitro-2'-furyl) -ειcrolein, 3- (2'-furyl) acrolein and imidazole-2 aldehyde, 1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) - acetophenone, 2- (2'-pyridoyl) acetophenone and 2- (3'-pyridoyl) acetophenone, benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylidene acetone, 4-morpholinobenzylideneacetone, 4-diethylaminobenzylideneacetone, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione , 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-benzylidenecyclohexanone, 2- (4'-hydroxybenzylidene) -cyclohexanone, 2- (4'-dimethylaminobenzylidene) -cyclohexanone, 2-benzylidene- 1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) -1,3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5, 5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl 1, 3-cyclohexanedione, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) -cyclopentanone, 2- (4'-dimethylaminobenzylidene) -cyclopentanone, 5- (4-dimethylaminophenyl) -penta-2,4-dienal, 5- (4-hydroxybenzylidene) cyclopentanone 4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4 Dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta- 2,4-dienal, 6- (4-dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl ) hexa-3,5-dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-diene -2-one, 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3,5-dien-2-one, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal , 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5 -nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde , 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2 Nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4 Nitrozime aldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-ace- tylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1, 4-dimethyl-3-carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde, 4-formyl-i-methylpyridinium , 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-i-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-i-benzylpyridinium, 4-formyl 1, 2-dimethylpyridinium, 4-formyl-1, 3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1-methylpyridinium, 2-acetyl-1 -methylpyridinium, 4-acetyl-1-methyl-quinolinium, 5-formyl-1-methyl-quinolinium, 6-formyl-1-methyl-quinolinium, 7-formyl-1-methyl-quinolinium, 8-formyl-1-methyl-quinolinium, 5- Methyl-1-ethyl-quinolinium, 6-formyl-1-ethylquinolinium, 7-formyl) -1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl 1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquinoline, 6-formyl-1-allylquinolinium, 7-formyl-1 allylchi nolinium and 8-formyl-1-allylquinolinium, 5-acetyl-1-methylquinolinium, 6-acetyl-1-methylquinolinium, 7-acetyl-1-methylquinolinium, 8-acetyl-1-methylquinolinium, 5-acetyl 1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6-acetyl-1 benzylchinolinium, 7-acetyl-1-benzylquinolinium, 8-acetyl-1-benzylquinolinium, 5-acetyl-1-allylquinolinium, 6-acetyl-1-allylquinolinium, 7-acetyl-1-allyl quinolinium and 8- Acetyl-i-allylquinolinium, 9-formyl-10-methylacridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1, 3-dimethyl-2- (4'-formylphenyl) benzimidazolium, 1 , 3-Dimethyl-2- (4'-formylphenyl) imidazolium, 2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2- 4'-formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl) -3- methylbenzothiazolium, 2- (5 ¹ -formyl-2'-thienyl) -3-methylbenzoth iazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium, 5-chloro-2- (4'-formylphenyl) -3- methylbenzothiazolium, 2- (4'-formylphenyl) -3,5-dimethylbenzothiazolium benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate , trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5 Sulfo-isatin, 5-carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures of the above compounds.

Benzaldehyde, cinnamic aldehyde and naphthaldehyde and their derivatives, in particular with one or more of these, are very particularly preferred in the agents according to the invention a plurality of hydroxy, alkoxy and amino substituents used as the reactive carbonyl compound. Again, the compounds according to formula X are preferred,

wherein

• R ^16, R ¹⁷ and R ¹⁸ independently represent a hydrogen atom, a halogen atom, a C _r C ₆ alkyl group, a hydroxy group, a C ₁ -C ₆ - alkoxy group, an amino group, a C _r C ₆ dialkylamino group, a di (C ₂ -C ₆ - hydroxyalkyl) amino group, a di (Ci-C ₆ -alkoxy-CrC ₆ alkyl) aminoguppe, a C ₁ - C ₆ -Hydroxyalkyloxygruppe, a sulfonyl group, a carboxyl group, a sulfonic acid group, a sulfonamido group , a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ acyl group, an acetyl group or a nitro group,

Z 'is a direct bond or a vinylene group,

R ¹⁹ and R ²⁰ represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

Very particularly preferred compounds of the reactive carbonyl compounds are selected from the group consisting of vanillin, coniferyl aldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3- dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4- Hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde 3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4- methoxy-benzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxy-benzaldehyde, 4-ethoxy-2-hydroxy-benzaldehyde, 4-ethoxy-3-hydroxy benzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3, 5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-

Trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4 Dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2 , 5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2 Morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphtha-dehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy -1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-n aphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) benzaldehyde and piperonal.

According to the invention, it is desirable to dispense as much as possible with the presence of p-phenylenediamine and its derivatives. However, it is possible to combine the novel oxidation dye precursors of the formula I with conventional developer components and coupler components of the oxidative dyeing.

It may therefore nevertheless be advantageous to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as the developer component in the compositions according to the invention. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which

G ¹ is a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

Monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) -

AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -

Alkyl radical containing a nitrogen-containing group, a phenyl or a 4 ¹ -

Aminophenylrest is substituted;

G ² is a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

AIkOXy- (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or

Fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a

C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to

C ₄ -acetylaminoalkoxy, C ₁ - to C ₄ -mesylaminoalkoxy or C ₁ - to C ₄ -carbamoylaminoalkoxy;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino 3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2- methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroanine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2- Fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2 - (.beta.-hydroxyethyloxy) -p-phenylenediamine, 2- (.beta.-acetylaminoethyloxy) -p-phenylenediamine, N- (.beta.-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable Salt.

Very particularly preferred according to the invention p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) -p-pheny! Endiamin and N , N-bis (.beta.-hydroxyethyl) -p-phenylenediamine.

It may further be preferred according to the invention to use as developer component compounds in the compositions according to the invention which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or the where appropriate, is part of a bridging ring system; the bridge Y represents an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which may be one or more nitrogen-containing groups and / or one or more

Heteroatoms such as oxygen, sulfur or nitrogen atoms may be interrupted or terminated and possibly by one or more hydroxyl or C ₁ -

C ₈ alkoxy may be substituted, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -

Polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ to C ₄ alkyl radical, with the provisos that

the compounds of the formula (E2) contain only one bridge Y per molecule and

- The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

The substituents used in formula (E2) are defined according to the invention analogously to the above statements.

Preferred dinuclear developing agents of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol, N , N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis ( β-hydroxyethyl) -N, N'-bis (4-arninophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N ₁ N ¹ -diethyl-N, N'-bis - (4-amino-3-methylphenyl) -ethylenediamine, bis (2-hydroxy-5-aminophenyl) -methane, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, N, N ' Bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis- (2,5-diaminophenyl) -1,4,7,10- tetraoxadecane and its physiologically acceptable salts.

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (.beta.-hydroxyethyl) -N, N ^l bis (4'-aminophenyl) -1, 3-diamino-propan-2-ol, bis- (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of their physiologically acceptable salts.

Furthermore, it may be preferred according to the invention to use as the developer component in the compositions according to the invention a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (E3)

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a

(C ₁ - to C ₄₎ alkoxy (C _r to C ₄₎ alkyl group a C ₁ - to C ₄ aminoalkyl radical, a

Hydroxy (C _r to C ₄ ) -alkylamino, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - to C ₄ -hydroxyalkyl (C _r to C ₄ ) aminoalkyl or a (di-C ₁ - bis C ₄ alkylamino) -

(C ₁ - to C ₄ ) -alkyl radical, and

G ¹⁴ represents a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a

C _r to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy alkyl (C _r to C ₄₎ a C ₁ - to C ₄ aminoalkyl, or a C ₁ to C ₄ cyanoalkyl radical,

G ¹⁵ is hydrogen, a C _r to C ₄ -alkyl radical, a C ₁ - to C ₄ -

Monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ is hydrogen or a halogen atom.

The substituents used in formula (E3) are defined according to the invention analogously to the above statements. Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino 2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino 2- (diethylaminomethyl) -phenol.

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component may preferably be selected from heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.

Preferred pyridine derivatives are, in particular, the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4-methoxyphenyl) -amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-

Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open specification JP 02019576 A2 or in published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- triaminopyrimidine. Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5 Diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5- Diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4, 5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole , 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3 -methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) -amino-1,3-dimethylpyrazole, 3, 4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) -amino-1 methylpyrazole.

The coupler components optionally additionally present in the agents according to the invention are preferably selected from

- M-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl 3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2-hydroxyethyl) -amino 2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3 aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4-

Diaminophenoxyethanol, 1, 3-bis (2,4-diaminophenoxy) -propane, 1-methoxy-2-amino

4- (2-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis ( 2-hydroxyethyl) aminobenzene,

- o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as 2,6-dihydroxypyridine , 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy 4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as For example, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyhmidine, 2-amino-4-hydroxy 6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or

Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly preferred coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

Indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, can furthermore be used as precursors of naturally-analogous dyes in the compositions according to the invention. These groups can carry further substituents, for. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group.

Particularly suitable precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindoline of the formula Xa,

in the independently of each other

G ²¹ is hydrogen, a C _r C ₄ -alkyl group or a C _r C ₄ -hydroxy-alkyl group,

G ²² is hydrogen or a -COOH group, where the -COOH group may also be in the form of a salt with a physiologically compatible cation,

G ²³ is hydrogen or a C 1 -C ₄ -alkyl group,

G ²⁴ is hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-G ²⁶ in which G ²⁶ is a C 1 -C ₄ -alkyl group, and

- G ²⁵ is one of the groups mentioned under G ²⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin. Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula Xb,

(Xb)

G ²⁷

in the independently of each other

G ²⁷ is hydrogen, a C _r C ₄ -alkyl group or a C _r C ₄ -hydroxyalkyl group,

G ²⁸ is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

- G ²⁹ is hydrogen or an alkyl group ₄ C _r C,

G ³⁰ is hydrogen, a C _r C ₄ alkyl group or a group -CO-G ³² in which G ³² is a C _r C ₄ alkyl group, and

- G ³¹ is one of the groups mentioned under G ³⁰ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants of the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for. As the hydrochlorides, the sulfates and hydrobromides, are used. The indole or indoline derivatives are usually in these Amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-% included.

In a further embodiment, the colorants according to the invention for further modifying the color shades in addition to the compounds according to the invention additionally contain conventional substantive dyes, such as nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (.beta.-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (.beta.-hydroxyethyl) -aminophenol, 2 (2-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro 2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine 2'-carbo acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Furthermore, the agents according to the invention may preferably contain a cationic substantive dye. Particularly preferred are

(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

(c) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as described, for example, in EP-A2-998 908, here is explicitly referred to in the claims 6 to 11.

Preferred cationic substantive dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

(DZ1) (Basic Yellow 87)

Cl ^"

(DZ2)

(DZ3) (Basic Orange 31)

(DZ4)

(DZ5) (Basic Red 51)

(DZ9) The compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic substantive dyes of group (c). The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention particularly preferred substantive dyes.

The compositions according to the invention according to this embodiment contain the substantive dyes preferably in an amount of 0.01 to 20 wt .-%, preferably from 0.01 to 10 wt .-%, each based on the total colorant.

Furthermore, the preparations of the invention may also naturally occurring dyes, such as those contained in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkanel.

It is not necessary that the oxidation dye precursors present in the agents according to the invention or the substantive dyes optionally contained in each case represent uniform compounds. Rather, in the colorants according to the invention, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, eg. As toxicological, must be excluded.

To obtain further and more intense colorations, the compositions according to the invention may additionally contain color enhancers. The color enhancers are preferably selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, Arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine, their derivatives and their physiologically acceptable salts. The color intensifiers mentioned above can be used in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the total colorant.

The agent according to the invention already gives intensive dyeings under air oxidation. Consequently, the presence of additional oxidizing agents can be dispensed with. However, it may u. It may be desirable to add hydrogen peroxide or other oxidizing agents to the compositions of the present invention for achieving the hues that are brighter than the keratin-containing fiber to be dyed. Oxidizing agents are usually used in an amount of 0.01 to 6 wt .-%, based on the application solution. An oxidizing agent preferred for human hair is H ₂ O ₂ . Mixtures of several oxidizing agents, such as a combination of hydrogen peroxide and peroxodisulfates of the alkali and alkaline earth metals or from iodide ion sources, such as alkali metal iodides and hydrogen peroxide or the aforementioned peroxodisulfates, can be used. The Oxidationsmittei or the oxidizing agent combination can be used according to the invention in conjunction with oxidation catalysts in the hair dye for use. Oxidation catalysts are, for example, metal salts, metal chelate complexes or metal oxides, which allow a slight change between two oxidation states of the metal ions. Examples are salts, chelate complexes or oxides of iron, ruthenium, manganese and copper.

Further possible oxidation catalysts are enzymes especially in the presence of classical developer systems of the p-phenylenediamine or p-aminophenol type. Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.

Pyranose oxidase and eg D-glucose or galactose, Glucose oxidase and D-glucose,

- glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts,

Alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and their salts,

Tyrosinase oxidase and tyrosine,

Uricase and uric acid or their salts,

- choline oxidase and choline,

- amino acid oxidase and amino acids.

The colorants according to the invention give intensive dyeings even at physiologically compatible temperatures of below 45 ^° C. They are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants can usually be incorporated into an aqueous cosmetic carrier. Suitable hydrous cosmetic carriers are for. As creams, emulsions, gels or surfactant-containing foaming solutions such. As shampoos or other preparations which are suitable for use on the keratin fibers. If necessary, it is also possible to incorporate the colorants in anhydrous carrier.

The compositions according to the invention for the oxidative dyeing of keratinic fibers preferably contain at least one derivative of the general formula (I) in an amount of 0.01 to 10% by weight, particularly preferably 0.1 to 3% by weight, based on the finished composition ,

The agent for coloring keratinous fibers can be selected from any suitable agents that are particularly suitable for dyeing human hair. A cosmetically acceptable carrier used is in particular an otherwise customary carrier of agents for dyeing human hair. Apart from the derivatives of the general formula (i), the colorants according to the invention can be composed according to known colorants or contain the usual ingredients for these.

The agents according to the invention preferably contain the dye precursors in one suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. But it is also conceivable to integrate the dye precursors in a pulverfömnige or tablet-shaped formulation.

Aqueous-alcoholic solutions of the present invention are aqueous solutions containing, to understand 3 to 70 wt .-% of a C _r C ₄ -alcohol, in particular ethanol or isopropanol in a sense. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.

A general composition is given below:

Developer, also according to formula (I) 0.05 - 5%

Coupler 0.05 - 5%

Direct dyes, also 0.01 - 10%

Reaction products of the oxidative coupling of the compounds according to formula (I)

Surfactants, emulsifiers 0.1 - 20%

Fatty alcohols and other emulsifiers 0.5 - 20%

Complexing agent 0.05 - 10%

Buffering agent 0.1 - 1, 0%

Solubilizer + solvent 0.5 - 15% pH adjuster as needed

Perfume oils 0.1 - 0.6%

Polymers 0.1 - 5%

Water 50 - 98%

Suitable colorant compositions are described, for example, in DE-U1-299 11 819, DE-A-101 25 451, DE-U1-201 11 036, Kosmetik, ed. W. Umbach, 2nd ed. 1995, G. Thieme Verlag Stuttgart, New York.

Examples of further suitable and inventively preferred ingredients, active ingredients, additives and auxiliaries are given below.

Furthermore, the colorants of the invention may contain all known in such preparations. In many cases, the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 C atoms (Soap),

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 16,

Acylsarcosides having 10 to 18 C atoms in the acyl group,

Acyltaurides having 10 to 18 C atoms in the acyl group,

Acyl isethionates having 10 to 18 C atoms in the acyl group,

Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the

Alkyl group and sulfosuccinic acid mono-alkylpolyoxyethylester with 8 bis

18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 C atoms, linear α-olefin sulfonates having 12 to 18 C atoms, Alpha sulfo fatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 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 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 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 having 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C 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.

Nonionic surfactants contain as hydrophilic group z. For example, a polyol group, a polyalkylene glycol ether or a combination of polyol and Polyglykolether- 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 to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs and

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil. Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These connections are identified by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

Particular preference is given to those alkyl polyglycosides in which R ¹ consists essentially of C ₈ and C ₁₀ alkyl groups, essentially of C ₁₂ and C ₁₄ alkyl groups, essentially of C ₈ to C ₁₆ alkyl groups or essentially of C ₁₂ - to C ₁₆ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

The alkyl glycosides can also serve, in addition to their surfactant effect, the fixation to improve fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further constituent of the preparations according to the invention in the event that an effect of the perfume oil on the hair which exceeds the duration of the hair treatment is desired.

The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ^W or -SC ^ group. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the cocoacylaminopropyldimethylammoniumglycinate, and 2-alkyl-3-carboxy-methyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl-hydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are understood as meaning surface-active compounds which, in addition to a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and for the formation of internal Salts are capable. 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 having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

According to the invention, the cationic surfactants used may in particular be those of the quaternary ammonium compounds, esterquats and amidoamines type become.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the brands Stepantex® ^®, ^® and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-ethyl Palmitoyloxy-) dimethylammoniurnchlorid, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances that available under the brand Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine is.

Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

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

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

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

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, 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 narrow homolog distribution may be preferred.

Further active agents, auxiliaries and additives are, for example, nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / inylacetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl ammonium chloride copolymers, dimethylaminoethyl quaternized with diethyl sulfate methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacrylate / tert-butylaminoethylmethacrylate-hydroxypropyl methacrylate copolymers, anionic Polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / Maieinsäure- anhydrid copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpoly - mere,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabicum, karaya gum, locust bean gum, linseed gums, dextrans, celulose derivatives, eg. For example, methyl cellulose, hydroxyalkyl cellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolioids such. For example, polyvinyl alcohol,

Structureants such as glucose and maleic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, and silicone oils,

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,

Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine, other pH adjusters,

Active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins, cholesterol, light stabilizers,

Bodying agents 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,

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, opacifiers such as latex,

Pearlescing agents such as ethylene glycol mono- and distearate,

Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air and antioxidants.

For the dyeing result, it may be advantageous to add ammonium or metal salts to the colorants. Suitable metal salts are, for. As formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals such as potassium, sodium or lithium, alkaline earth metals such as magnesium, calcium, Strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, with sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate being preferred. These salts are preferably contained in an amount of 0.03 to 65 mmol, especially 1 to 40 mmol, based on 100 g of the total colorant.

The pH of the ready-to-use dyeing preparations is usually between 2 and 11, preferably between 5 and 10.

Examples

The dyeing creams according to Table 1 and the developer emulsion according to Table 2 were prepared by a known method.

All amounts are, unless otherwise indicated, wt .-% based on the total weight of the corresponding recipe.

The following raw materials were used for the production:

Table 1: Dyeing creams

Table 2: Developer emulsion

Each dyeing cream was mixed with the developer emulsion in a ratio of 1: 1 and dyed for each mixture on a natural white strand of hair (from Kerling) for 30 minutes at 32 ° C. The weight ratio of the application mixture to the hair was 4 to 1.

In the case of Formulation 1, a copper-colored nuance was created. In the case of Formulation 2 a color intensive red nuance.

Claims

Patent claims

1. means for dyeing keratin-containing fibers, in particular human hair, containing in a cosmetic carrier at least one compound according to formula I and / or physiologically acceptable salts thereof,

in which

• R ¹ and R ² are independently a hydrogen atom, a halogen atom, a linear or branched CRCE alkyl group, a cyano group, a hydroxy group, a Ci-C ₆ monohydroxyalkyl, a C ₂ -C ₆ polyhydroxyalkyl group, a C _r C ₆ alkoxy group, a hydroxy (C _r C ₆ ) alkoxy group, a group R ¹ R ¹¹ N- (CHa) _n -, in which R ¹ and R ¹¹ independently of one another represent a hydrogen atom, a C _r C ₆ - Alkyl group, a C _r C ₆ -hydroxyalkyl group or an aryl C _r C ₆ -alkyl group and n is an integer from 0 to 6, or together with the residual molecule form an aromatic, optionally substituted six-membered ring,

X is an oxygen atom or a sulfur atom,

Y represents a carbonyl group, a thiocarbonyl group, a methylene group CR ³ R ⁴ , a vinylene group -CR ⁵ = CR ⁶ -, wherein R ³ , R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, a halogen atom, a linear or branched C ₁ -C ₆ alkyl group, a cyano group, a hydroxy group, a C ₁ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy group, a hydroxy (C _r C ₆ ) alkoxy group, a group R ^l "R ^lv N- (CH ₂ ) _m -, wherein R ¹ " and R ^IV independently represent a hydrogen atom, a C _r C ₆ alkyl group, a C ₁ -C ₆ Hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group and m is an integer from 0 to 6, or a group NR ⁷ wherein R ⁷ is a linear or cyclic -C ₆ alkyl group, a C ₂ -C ₆ - alkenyl group, an optionally substituted aryl group, an aryl- (C _r _C6) alkyl group, a -C ₆ - Monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy (C ₁ -C ₆ ) alkyl group _l a group R ^v R ^vl N- (CH ₂ ) _q -, wherein R ^v and R ^vι independently represent a ^• hydrogen atom, a C _r C ₆ alkyl group, a C ₁ -C ₆ - hydroxyalkyl group or an aryl (Ci-C ₆₎ alkyl, wherein R ^v and R ^lr a together with the nitrogen atom, optionally substituted, 5-, 6- or 7-membered ring, and q is an integer of 2 to 6.

2. Composition according to claim 1, characterized in that in formula IR ¹ and R ² together with the residual molecule form a substituted with two radicals R ⁸ and R ⁹ benzannelation, wherein R ⁸ and R ⁹ are independently a hydrogen atom, a Halogen atom, a linear or branched C _r C ₆ alkyl group, a cyano group, a hydroxy group, a C _r C ₆ monohydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C _t -C e alkoxy group, a hydroxy (C _r C ₆₎ - alkoxy group, a group R ^VII R ^VIII N- (CH ₂₎ _r -, in which R ^v "and R ^VIII" are independently a hydrogen atom, a Ci-C ₆ alkyl group, a -C ₆ hydroxyalkyl group, or an arylCrC ₆ -alkyl group and r is an integer from 0 to 6.

3. Composition according to one of claims 1 or 2, characterized in that the compounds of formula (I) are selected from at least one of the compounds according to formulas (II) and / or (III) and / or their physiologically acceptable salts

wherein R ⁷ represents a linear or cyclic C _r C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an aryl (C _r C ₆ ) alkyl group, a C ₁ -C ₆ monohydroxyalkyl group, a C ₂ -C ₆ - polyhydroxyalkyl group, a C _r C ₆ alkoxy (CrC ₆₎ alkyl group, a group R ^v R ^vl N- (CH ₂₎ _q -, in which R ^V and R ^VI are each independently a hydrogen atom, a Ci-C ₆ alkyl group, a CrC ₆ -hydroxyalkyl group or an aryl (C _r C ₆ ) alkyl group, wherein R ^v and R ^vι together with the nitrogen atom, an optionally substituted, 5-, 6- or 7-membered Ring and q is an integer from 2 to 6.

• R ⁸ and R ⁹ independently represent a hydrogen atom, a halogen atom, a linear or branched C _r C ₆ alkyl group, a cyano group, a hydroxy group, a -C ₆ monohydroxyalkyl, a C ₂ -C ₆ polyhydroxyalkyl group, a -C ₆ alkoxy group, a hydroxy (C _r _C6) - alkoxy group, atom, a group R ^v "R ^VIII N- (CH ₂₎ _r, wherein R ^v" and R ^VIII "are independently a hydrogen, C _{R is} C ₆ alkyl group, a C _r C ₆ hydroxyalkyl group or an aryl C _r C ₆ alkyl group and r is an integer from 0 to 6.

4. Composition according to one of claims 1 to 4, characterized in that the compound according to formula (I) is selected from the group which is formed from 2-aminoindolin-3-one, 2-amino-1-methylindoline 3-one, 2-aminoindan-1, 3-dione and the physiologically acceptable salts of these compounds.

5. Composition according to one of claims 1 to 4, characterized in that it color amplifier selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3rd Hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine or any mixtures thereof.

6. Composition according to one of claims 1 to 7, characterized in that it additionally contains at least one reactive carbonyl compounds and / or at least one oxidation dye precursor of the developer and / or coupler type.

7. Composition according to one of claims 1 to 6, characterized in that it contains at least one substantive dye, preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant.

8. Composition according to one of claims 1 to 7, characterized in that ammonium or metal salts selected from the group of formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, Phosphates and phosphonates of alkali metals such as potassium, sodium or lithium, alkaline earth metals such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc.

9. Composition according to one of claims 1 to 8, characterized in that it contains onsmittel Oxidati-, in particular H ₂ O ₂ , in an amount of 0.01 to 6 wt .-%, based on the application solution.

10. Composition according to one of claims 1 to 9, characterized in that it contains anionic, cationic, zwitterionic or nonionic surfactants.

11. An agent for dyeing keratin-containing fibers, in particular human hair, comprising in a cosmetic carrier at least one reaction product of the oxidative coupling of the compounds according to formula I of claim 1.

12. Use of at least one agent according to one of claims 1 to 11 for dyeing keratin-containing fibers.

13. A method for dyeing keratin-containing fibers, in particular human hair, wherein a colorant, according to one of claims 1 to 11 applied to the keratin fibers, some time, usually about 15-30 minutes, left on the fiber and then rinsed again or with a shame poo is washed out.