WO2009103798A1

WO2009103798A1 - 9-[4-(amino) phenyl] acridinium salts as cationic direct dyes for coloring keratinous fibers

Info

Publication number: WO2009103798A1
Application number: PCT/EP2009/052060
Authority: WO
Inventors: Wibke Gross; Ralph Nemitz; Denise Fuhr; Anja Reichert; Astrid Kleen
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2008-02-22
Filing date: 2009-02-20
Publication date: 2009-08-27
Also published as: DE102009001039A1; EP2245013A1

Abstract

The application relates to cationic compounds of formula (Ia) where R1 to R9 and X- are defined as indicated in claim 1. Said compounds, some of which have not yet been described in the prior art, are suitable for coloring keratinous fibers, in particular human hair. In dyes of these compounds, extreme, intensive color nuances, in particular in the blue and violet range, are obtained with very good fastness properties. When simultaneously using oxidizing agents such as hydrogen peroxide or a mixture of hydrogen peroxide and peroxydisulfates, these direct dyes also provide illuminating nuances without reducing the color intensity and color brilliance.

Description

- [4- (AMINO) PHENYL] -ACRIDINIUM SALTS AS CATIONIC DIRECTORS FOR COLORING KERATIN-CONTAINING FIBERS.

The invention relates to novel cationic dyes and agents for dyeing and optionally simultaneous lightening of keratin-containing fibers, in particular human hair, which contain these dyes, the use of these cationic dyes for dyeing

Hair and a method for dyeing keratin fibers, in particular human

Hair.

For the dyeing of keratin-containing fibers are generally either substantive

Dyes or oxidation dyes obtained by oxidative coupling of one or more

Developer components with each other or with one or more coupler components arise, for use. Coupler and developer components are also referred to as oxidation dye precursors.

The developer components are usually primary aromatic amines having a further, in the para or ortho position free or substituted hydroxy or amino group,

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-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5 Diaminophenyl) ethanol, 2- (2,5-diamino phenoxy) ethanol, 1-phenyl-3-carboxamido-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, 2,5,6-triamino-4-hydroxy-pyrimidine and 4,5-diamino-1- (2-hydroxyethyl) pyrazole ,

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used.

Suitable coupler substances are in particular α-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl 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-methylamino pyridine and 3,5-diamino-2,6-dimethoxypyridine.

Although intensive dyeings having good fastness properties can be obtained with oxidation dyes, the development of the color generally takes place under the influence of oxidizing agents, such as, for example. H ₂ O ₂ , which in some cases may result in damage to the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes sensitize people with sensitive skin. Direct dyes are applied under gentler conditions, you Disadvantage lies in the fact that the dyeings often have only insufficient fastness properties.

The object of the present invention is to provide colorants for keratin-containing fibers, in particular human hair, which are at least equivalent in terms of color depth and fastness properties, such as light fastness, rubfastness and washfastness, as well as perspiration and cold wave fastness, to the usual oxidation hair colorants However, necessarily on oxidizing agents such. B. H ₂ O ₂ instructed to be. In the case of simultaneous use with oxidation dyes direct drawers should have sufficient stability against H ₂ O ₂ and not lose their positive fastness and dyeing properties. In addition, the colorants must have no or only a very low sensitizing potential and may under no circumstances be mutagenic. In addition, as bright and intense colors as possible should be achieved.

It has surprisingly been found that compounds of the general formula (Ia) are very suitable as direct drawers for hair coloring. In dyeings are obtained extremely intense shades, especially in the blue and violet range with very good fastness properties. The Direktzieher also provide with the simultaneous use of oxidizing agents such as hydrogen peroxide or a mixture of hydrogen peroxide and peroxydisulfates bright nuances without attenuation of color intensity and color brilliance. In this way, the simultaneous lightening and coloring of hair is possible, which also on dark hair, a bright color can be achieved.

Colorants containing compounds of the following formula (Ia) and some of the corresponding compounds themselves are not known.

The present invention relates, in a first embodiment, to agents for dyeing and, if appropriate, simultaneous lightening of keratin fibers, in particular human hair, comprising at least one cationic compound of the formula (Ia):

X (Ia) in the R ^1, R ^2, R ^3, R ⁴ independently represent a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C ₂ -C _e alkenyl group, a Ci-Cβ-hydroxyalkyl group, a C ₂ -C ₆ - Polyhydroxyalkyl group, a halogen atom, a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, an alkyloxycarbonyl group or a sulfonic acid group, wherein the two radicals R ¹ and R ² or R ³ and R ⁴ together form another fused, carbocyclic or heterocyclic ring may optionally bear a substituent R ¹² ,

R ⁵ is a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -

Hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - alkoxy-C _r C ₆ alkyl group, an amino-Ci-C ₆ alkyl group, a di-C ₁ -C ₆ - alkylamino-C ₂ C ₆ alkyl group, a cyano-dC ₆ alkyl group or a substituent of the formulas II to VII:

- (CH ₂ ) n -COOH _(||)

O

- (CH _? ) N - ^ - O- R11 v ² '(IV)

O (CH ₂ ) n - N - R1 1

FM θ ' _(V)

O R10 - (CH ") n - S-N-R10

⁰ (left)

O R10

- (CH ") n - ^ N-RIO

² (VII)

R ⁶ and R ⁷ independently represent a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C ₂ -C _e alkenyl group, a C- | -C _s hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a Halogen atom (chloride, bromide, iodide or fluoride), a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, an alkyloxycarbonyl group, a sulfonic acid group, a C ₁ -C ₆ - Alkoxy group, a hydroxy group, an amino group or a C ₁ -C ₆ dialkylamino group,

R ⁸ and R ⁹ independently of one another represent a substituent which is defined as R ⁵ or together form a 5-, 6- or 7-membered ring which may optionally carry further substituents or heteroatoms,

R ¹⁰ and R ¹¹ independently represent a hydrogen atom, a Ci-C ₆ - alkyl group, a Ci-C ₆ hydroxyalkyl group, a C ₂ -C ₆ - polyhydroxyalkyl group, a C ₂ -C ₆ alkenyl group, an aryl group or a heteroaryl

R ¹² is a hydrogen atom, a C _T -Cβ-alkyl group, a C ₂ -C ₆ -

Alkenyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a halogen atom, a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, an alkyloxycarbonyl group or a sulfonic acid group and

X- is a monovalent anion, preferably a halide (chloride, bromide, iodide or fluoride), hydrogen sulfate, V ₂ sulfate, V ₂ tetrachlorozincate, p- benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methane sulfate or methanesulfonate , 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. The term "dyeing of keratin fibers" used according to the invention encompasses any form of color change of the fibers. In particular, the color changes encompassed by the terms tinting, bleaching, oxidative dyeing, semi-permanent dyeing, permanent dyeing and temporary dyeing are included.

Examples of (C ₁ to C ₆ ) -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals. Examples of corresponding cyclic alkyl groups are cyclopentyl and cyclohexyl. Examples of preferred (C ₂ to C ₆ ) alkenyl radicals are vinyl and allyl.

Further, as preferred examples of a (C ₁ to C ₆ ) -Monohydroxyalkylgruppe a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxy propyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-Hydroxypentyl- and a 6-hydroxyethyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. Examples of a (C ₂ to C ₆ ) -polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-

Dihydroxybutyl group and the 2,4-dihydroxybutyl group.

Preferred (C ₁ to C ₆ ) alkoxy groups according to the invention are, for example, a methoxy or an ethoxy group.

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

Methoxyhexyl group are examples of inventive (C ₁ to C ₆ ) alkoxy (C ₂ to C ₆ ) - alkyl groups.

A preferred hydroxy (C 1 -C ₆ ) -alkoxy group is the 2-hydroxyethoxy group.

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

The aminomethyl, 2-aminoethyl, 3-aminopropyl, 2-dimethylaminoethyl, diethylaminomethyl,

Dimethylaminomethyl, 2-methylaminoethyl, dimethylamino, 1-piperidinomethyl, 1

Pyrrolidinomethyl, 4-morpholinomethyl, bis (2-hydroxyethyl) amino and the amino group

Examples of a group R ⁵ R ⁶ N- (CH ₂ ) _n -, where the diethylaminomethyl, 1-piperidinomethyl, 2-

Dimethylaminoethyl, dimethylamino and the amino group are particularly preferred.

Preferred aryl (C 1 -C 3) -alkyl groups are benzyl and 2-phenylethyl.

Substances of the general formula (Ia) in which the radicals R 1, R 2, R 3 and R 4 are identical to one

Are hydrogen, represent a preferred group of erfindungsgmäßen substances.

Furthermore, compounds are preferred in which the radical R5 is a dC ₆ alkyl group, a

C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, a C ₂ -C _β polyhydroxyalkyl group or a d-Ce-alkoxy-d-Ce-alkyl group. Compounds in which R5 is a methyl group, an allyl group or a 2-hydroxyethyl group are particularly preferred. Compounds in which R5 is a methyl group are very particularly preferred.

The radicals R6 and R7 independently of one another represent a hydrogen atom, a

Hydroxy group, a Halogenaotm (especially chloride or bromide) or an alkoxy group, so is still a preferred embodiment. It is particularly preferred according to the invention, when R6 and R7 are each a hydrogen atom.

In addition, a preferred embodiment exists when the radicals R8 and R9 are independently a dC ₆ alkyl group, a C ₂ -C _e alkenyl group or a C ₂ -C ₆ -

Hydroxyalkyl group or when R8 and R9 together form a 5-, 6- or 7-membered ring, which may optionally carry further substituents or heteroatoms. It is particularly preferred according to the invention, when R8 and R9 independently of one another for a

Methyl group, an allyl group or a 2-hydroxyethyl group. Furthermore, it is preferred according to the invention if R 8 and R 9 are identical substituents or together form a 5-, 6- or 7-membered ring, which may optionally be further

Can carry substituents or heteroatoms. It is very particularly preferred if both R 8 and R 9 are a 2-hydroxyethyl group. The direct dyes, it is in particular very particularly preferred in which represent R1, R2, R3 and R4 is a hydrogen atom, the radical R 5 is a _C-ι-C6 alkyl group or a C ₂ -C ₆ - represents alkenyl, it is at residues R6 and R7 independently is a hydrogen atom, a hydroxy group, a halogen atom (especially chloride or bromide) or an alkoxy group and the radicals R8 and R9 are independently a C ₁ -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, or a C ₂ -C ₆ hydroxyalkyl group, or when R 8 and R 9 together form a 5-, 6- or 7-membered ring which may optionally carry further substituents or heteroatoms.

Especially preferred are the direct drawers in which R1, R2, R3 and R4 represent a hydrogen atom, the radical R5 represents a methyl group or an allyl group, the radicals R6 and R7 independently of one another are a hydrogen atom, a hydroxy group Is halogen atom (in particular chloride or bromide) or a methoxy group and the radicals R 8 and R 9 are, independently of one another, a methyl group, an ethyl group, an allyl group or a 2-hydroxyethyl group, or together with the nitrogen atom which carries them, a piperidine ring, a morpholine ring, form a piperazine ring or a pyrrolidine ring.

Particularly preferred compositions according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers comprise at least one cationic compound from the group of

Salts of 9- [4- (dimethylamino) phenyl] -10-methylacridinium,

Salts of 9 - [(4-dimethylamino) phenyl] -10-ethylacridinium,

Salts of the 10-allyl-9- [4- (dimethylamino) phenyl] acrystalline,

Salts of 9 - [(4-dimethylamino) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (diethylamino) phenyl] -10-methylacridinium,

Salts of 9 - [(4-diethylamino) phenyl] -10-ethylacridinium,

Salts of the 10-allyl-9- [4- (diethylamino) phenyl] acridinium,

Salts of 9 - [(4-diethylamino) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (piperidin-1-yl) phenyl] -10-methylacridiniurn,

Salts of 9- [4- (piperidin-1-yl) phenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (piperidin-1-yl) phenyl] acridinium,

Salts of 9- [4- (piperidin-1-yl) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (morpholin-4-yl) phenyl] -10-methylacrylonine,

Salts of 9- [4- (morpholin-4-yl) phenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (morpholin-4-yl) phenyl] acridinium,

Salts of 9- [4- (morpholin-4-yl) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (piperazin-1-yl) phenyl] -10-methylacridinium,

Salts of 9- [4- (piperazin-1-yl) phenyl] -10-ethylacrylonine,

Salts of 10-allyl-9- [4- (piperazin-1-yl) phenyl] acridinium,

Salts of 9- [4- (piperazin-1-yl) phenyl] -10- (2-hydroxyethyl) acridinium, Salts of 9- [4- (4-methylpiperazin-1-yl) phenyl] -10-methylacridinium,

Salts of 9- [4- (4-methylpiperazin-1-yl) phenyl] -10-ethylacridinium,

Salts of the 10-allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium,

Salts of 9- [4- (4-methylpiperazin-1-yl) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (pyrrolidin-1-yl) phenyl] -10-methylacridinium,

Salts of 9- [4- (pyrrolidin-1-yl) phenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (pyrrolidin-1-yl) phenyl] acridinium,

Salts of 9- [4- (pyrrolidin-1-yl) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (diethylamino) -2-methoxyphenyl] -10-methylacridinium,

Salts of 9- [4- (diethylamino) -2-methoxyphenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (diethylamino) -2-methoxyphenyl] acridinium,

Salts of 9- [4- (diethylamino) -2-methoxyphenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium,

Salts of 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-ethylacridinium,

Salts of the 10-allyl-9- {4- [bis (2-hydroxyethyl) amino] phenyl} acridinium,

Salts of 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10- (2-ydroxyethyl) acridinium,

Salts of 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacrylonine,

Salts of 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-ethylacridinium,

Salts of 10-allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -acridinium,

Salts of 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (diethylamino) -2-hydroxyphenyl] -10-methylacridinium,

Salts of 9- [4- (diethylamino) -2-hydroxyphenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (diethylamino) -2-hydroxyphenyl] acridinium,

Salts of 9- [4- (diethylamino) -2-hydroxyphenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (dimethylamino) -3-bromophenyl] -10-methylacridinium,

Salts of 9- [4- (dimethylamino) -3-bromophenyl] -10-ethylacridiniums and / or

Salts of 10-allyl-9- [4- (dimethylamino) -3-bromophenyl] acridinium,

Salts of 9- [4- (dimethylamino) -3-bromophenyl] -10- (2-hydroxyethyl) acridinium.

Regarding the exact structure of these compounds, I would like to refer to the

Referred to in the accompanying priority document.

Particularly preferred compounds of formula (Ia) are

- 9- [4- (dimethylamino) phenyl] -10-methylacridinium p-toluenesulfonate

9- [4- (dimethylamino) phenyl] -10-methylacridinium p-benzenesulfonate 10-allyl-9- [4- (dimethylamino) phenyl] acridinium p-toluenesulfonate 10-allyl-9- [4- (dimethylamino) phenyl] acridinιum-p-benzenesulfonate

- 9- [4- (piperidin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate

- 9- [4- (piperidin-1-yl) phenyl] -10-methylacridinium p-benzenesulfonate 10-allyl-9- [4- (piperidin-1-yl) phenyl] acridinium p-toluenesulfonate 0-Allyl-9- [4- (piperidin-1-yl) phenyl] acridinium p-benzenesulfonate [4- (morpholin-4-yl) phenyl] -10-methylacridinium p-toluenesulfonate [4- (morpholine 4-yl] phenyl] -10-methylacridinium p-benzenesulfonate 0-allyl-9- [4- (morpholin-4-yl) phenyl] acridinium p-toluenesulfonate 0-allyl-9- [4- (morpholine) 4-yl) phenyl] acridinium p-benzenesulfonate [4- (piperazin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate [4- (piperazin-1-yl) phenyl] -10-methylacridinium p-Benzenesulfonate 0-allyl-9- [4- (piperazin-1-yl) phenyl] acridinium p-toluenesulfonate 0-Allyl-9- [4- (piperazin-1-yl) phenyl] acridinium p-benzenesulfonate - [4- (4-methylpiperazin-1-yl) phenyl] -10-methylacridinium-p-toluenesulfonate [4- (4-methylpiperazin-1-yl) phenyl] -10-methylacridinium-p-benzolsulfonat0-allyl-9- [4- (4-Methylpiperazin-1-yl) phenyl] acridinium p-toluenesulfonate 0-Allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium p-benzenesulfonate [4- (pyrrolidine 1-yl) ph8nyl] -10-methylacridinium p-toluenesulfonate - [4- (pyrrolidin-1-yl) phenyl] -10-methylacridinium p-benzenesulfonate 0 -Allyl-9- [4- (pyrrolidin-1-yl) phenyl] acridinium p-toluenesulfonate 0-Allyl-9- [4- (pyrrolidin-1-yl) phenyl] acridinium p-benzenesulfonate - [4- ( diethylamino) -2-methoxyphenyl] -10-methylacridinium-p-toluenesulfonate [4- (diethylamino) -2-methoxyphenyl] -10-methylacridinium-p-benzolsulfonat0-allyl-9- [4- (diethylamino) -2-methoxyphenyl ] acridinium-p-toluolsulfonat0-allyl-9- [4- (diethylamino) -2-methoxyphenyl] acridinium-p-benzenesulfonate {4- [Bιs (2-hydroxy8thyl) amino] phenyl} -10-methylacridinium-p- toluenesulfonate {4- [bis (2-hydroxy8thyl) amino] phenyl} -10-methylacridinium-p-benzolsulfonat0-allyl-9- {4- [bis- (2-hydroxyethyl) amino] phenyl} acridinium-p-toluolsulfonat0 allyl-9- {4- [bis- (2-hydroxyethyl) amino] phenyl} acridinium-p-benzenesulfonate {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacridinιum-p-toluenesulfonate {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacridinium-p-benzolsulfonat0-allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -acridinium-p-toluolsulfonat0-allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -acri dinium p-benzenesulfonate [4- (dimethylamino) ph8nyl] -10-methylacridinium bromide - [4- (dimethylamino) phenyl] -10-methylacridinium chloride 0-allyl-9- [4- (dimethylamino) phenyl] acridinium bromide 0-allyl- 9- [4- (Dimethylamino) phenyl] acridinium chloride - [4- (pyridin-1-yl) phenyl] -10-methylacridinium bromide - [4- (piperidin-1-yl) phenyl] -10-methylacridinium chloride 0-allyl-9 - [4- (piperidin-1-yl) phenyl] acridinium bromide 0-allyl-9- [4- (piperidin-1-yl) phenyl] acridinium chloride - 9- [4- (morpholin-4-yl] phenyl] -10-methylacridinium bromide

- 9- [4- (morpholin-4-yl] phenyl] -10-methylacridinium chloride 10-allyl-9- [4- (morpholin-4-yl) phenyl] acridinium bromide

- 10-allyl-9- [4- (morpholin-4-yl) phenyl] acridinium chloride

- 9- [4- (piperazin-1-yl) phenyl] -10-methylacridinium bromide

- 9- [4- (piperazin-1-yl) phenyl] -10-methylacridinium chloride 10-allyl-9- [4- (piperazin-1-yl) phenyl] acridinium bromide

- 10-allyl-9- [4- (piperazin-1-yl) phenyl] acridinium chloride

- 9- [4- (4-methylpiperazin-1-yl) phenyl] -10-methylacridinium bromide

- 9- [4- (4-Methylpiperazin-1-yl) phenyl] -10-methylacridinium chloride 10-Allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium bromide

- 10-allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium chloride

- 9- [4- (pyrrolidin-1-yl) phenyl] -10-methylacridinium bromide

- 9- [4- (pyrrolidin-1-yl) phenyl] -10-methylacridinium chloride 10-allyl-9- [4- (pyrrolidin-1-yl) phenyl] acridinium bromide

10-allyl-9- [4- (pyrrolidin-1-yl) phenyl] acridiniumchlorid

- 9- [4- (diethylamino) -2-methoxyphenyl] -10-methylacridinium bromide

- 9- [4- (Diethylamino) -2-methoxyphenyl] -10-methylacridinium chloride 10-Allyl-9- [4- (diethylamino) -2-methoxyphenyl] acridinium bromide 10-allyl-9- [4- (diethylamino) -2 methoxyphenyl] acridiniumchlorid

- 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium bromide

9- {4- [bis (2-hydroxyethyl) amino] -phenyl} -10-methylacromidinium chloride 10-allyl-9- {4- [bis (2-hydroxyethyl) amino] phenyl} acridinium bromide 10-allyl-9- {4- [bis- (2-hydroxyethyl) amino] phenyl} acridiniumchlorid

- 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacridinium bromide

- 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacridinium chloride

10-Allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -acridinium bromide and 10-allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -acridinium chloride. Very particularly preferred compounds of the formula (Ia) are

- 9- [4- (dimethylamino) phenyl] -10-methylacridinium p-toluenesulfonate

- 9- [4- (Dimethylamino) phenyl] -10-methylacridinium bromide 10-Allyl-9- [4- (dimethylamino) phenyl] acridinium p-toluenesulfonate 10-Allyl-9- [4- (dimethylamino) phenyl] acridinium bromide

- 9- [4- (piperidin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate

- 9- [4- (piperidin-1-yl) phenyl] -10-methylacridinium bromide 10-allyl-9- [4- (piperidin-1-yl) phenyl] acridinium p-toluenesulfonate 10-allyl-9- [4 - (piperidin-1-yl) phenyl] acridiniumbromid - 9- [4- (morpholin-4-yl] phenyl] -10-methylacridinium p-toluenesulfonate

- 9- [4- (morpholin-4-yl] phenyl] -10-methylacridinium bromide 10-allyl-9- [4- (morpholin-4-yl) phenyl] acridinium p-toluenesulfonate

- 10-allyl-9- [4- (morpholin-4-yl) phenyl] acridinium bromide

- 9- [4- (piperazin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate

- 9- [4- (piperazin-1-yl) phenyl] -10-methylacridinium bromide 10-allyl-9- [4- (piperazin-1-yl) phenyl] acridinium p-toluenesulfonate

- 10-allyl-9- [4- (piperazin-1-yl) phenyl] acridinium bromide

- 9- [4- (4-methylpiperazin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate

- 9- [4- (4-Methylpiperazin-1-yl) phenyl] -10-methylacridinium bromide 10-Allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium p-toluenesulfonate

10-allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium bromide

- 9- [4- (pyrrolidin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate

- 9- [4- (pyrrolidin-1-yl) phenyl] -10-methylacridinium bromide 10-allyl-9- [4- (pyrrolidin-1-yl) phenyl] acridinium p-toluenesulfonate 10-allyl-9- [4 - (pyrrolidin-1-yl) phenyl] acridiniumbromid

- 9- [4- (Diethylamino) -2-methoxyphenyl] -10-methylacridinium p-toluenesulfonate

- 9- [4- (Diethylamino) -2-methoxyphenyl] -10-methylacridinium bromide 10-allyl-9- [4- (diethylamino) -2-methoxyphenyl] acridinium p-toluenesulfonate 10-allyl-9- [4- (4-yl) diethylamino) -2-methoxyphenyl] acridiniumbromid

- 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium p-toluenesulfonate

9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium bromide 10-allyl-9- {4- [bis (2-hydroxyethyl) amino] phenyl} acridinium p-toluenesulfonate 10 allyl-9- {4- [bis- (2-hydroxyethyl) amino] phenyl} acridiniumbromid

- 9- {4 - [(2-Hydroxyethyl) methylamino] phenyl} -10-methylacridinium p-toluenesulfonate

- 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacridinium bromide

10-Allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -acridinium p-toluenesulfonate and 10-allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -acridinium bromide.

The salts of 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium, especially 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium-p -toluenesulfonate, the 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacrylonidinium bromide, the 9- {4- [bis (2-hydroxyethyl) amino] - phenyl} -10-methylacridinium chloride and the the 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium acetate are very particularly preferred direct drawers according to the invention. Further particularly preferred salts are listed explicitly below in the disclosure of the compounds per se. Compositions according to the invention containing the salts disclosed therein are also particularly preferred. The compositions according to the invention for dyeing and, if appropriate, simultaneous brightening of keratin fibers preferably contain the compound (s) of the formula (Ia) in amounts above 1 ppm and below 10% by weight, in each case based on the total agent. Preferred agents according to the invention for dyeing and optionally simultaneously lightening keratinic fibers are characterized in that they contain the compound (s) of the formula (Ia) in amounts of from 0.001 to 5% by weight, preferably from 0.0025 to 2.5% by weight. %, more preferably from 0.005 to 1, 5 wt .-% and in particular from 0.01 to 1 wt .-%, each based on the total agent.

The agents according to the invention serve to change the color of keratinic fibers, in particular human hair. The color change can be effected solely on the basis of the cationic compound (s) of the formula (Ia), but the agents according to the invention can also additionally contain further color-modifying substances, for example substantive dyes and / or oxidation dyes. Compositions according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers, which additionally contain, based on their weight, from 0.001 to 5% by weight of one or more oxidation dye precursors and / or direct dyes, are preferred.

For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components. The oxidation dyes are characterized by excellent, long-lasting dyeing results. For naturally acting dyeings but usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading. These further colorants are described below: The developer components are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5, 6- tetraaminopyrimidine and its derivatives used.

Very particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1, 3-diamino-propan-2-ol, 2-methoxymethyl-p-phenylenediamine, bis (2 -hydroxy-5-aminophenyl) -methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1 , 10-bis- (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- ( α, β-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (β- hydroxyethyl) pyrazole, 2,4,5,6-Tetraaminopyιϊmidin, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, and the physiologically acceptable salts of these compounds. Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components. Therefore, it is preferred according to the invention that at least one coupler component is additionally used when using at least one developer component. Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component. Couplers are preferably cyclic compounds which carry on cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. These groups are conjugated by a double bond system. When the cyclic compound is a six-membered ring, said groups are preferably in ortho position or meta position to each other.

Particularly preferred coupler components according to the invention are selected from m-aminophenol, 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, 2,4- Dichloro-3-aminophenol, 2- (2,4-diaminophenoxy) ethanol, 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, 2 - ({3 - [(2-hydroxyethyl) am ino ] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2 -Hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) ami no] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2 , 5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol, 1, 2,4-trihydroxybenzene, 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, 3 , 5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,4-diamino-pyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4 '-Methoxyphenyl) amino-3-aminopyridine, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 3-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7 Hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2- Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6- Dihydroxy-2-methylpyrimidine or mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

The coupler components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready oxidation dye.

In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1 2, can stand.

For temporary dyeings usually dyeing or tinting agents are used, which contain as coloring component so-called direct drawers. These are dye molecules that attach directly to the substrate and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more rapid undesirable change in shade or even a visible, homogeneous color loss occurs much faster.

Furthermore, the compositions according to the invention may contain at least one further substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably used in an amount of 0.001 to 20 wt .-%, based on the total application preparation. The total amount of substantive dyes is preferably at most 20% by weight.

Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes.

Preferred anionic substantive dyes are those under the international designations or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds. Preferred cationic substantive dyes are included

(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 mentioned for example in EP-A2-998 908, to which reference is explicitly made at this point in claims 6 to 11 are called.

The compounds known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic substantive dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^®, according to the invention are also very particularly preferred cationic direct dyes.

Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) ammophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5- chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic 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-4-nitrophenol.

It is not necessary that the substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, minor amounts of other components may be included, as far as these do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

Furthermore, as direct dyes also naturally occurring dyes may be used, as for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

Finally, another dyeing process has received much attention. In this method, precursors of the natural hair dye melanin are applied to the substrate, eg hair; These then form naturally-analogous dyes in the course of oxidative processes in the hair. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The dyeing can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agent must be used. In individuals with originally medium blond to brown hair, the indoline can be used as the sole dye precursor. For the On the other hand, satisfactory results can often only be achieved by using further dye components, in particular special oxidation dye precursors, for persons with originally red and, in particular, dark to black hair color. 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, N-methyl- 5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole, and especially the 5,6-dihydroxyindoline. Another possibility for color change is the use of colorants containing so-called Oxofarbstoffvorprodukte. A first class of oxo dye precursors are compounds having at least one reactive carbonyl group. This first class is called a component (Oxo1). A second class of oxo dye precursors form CH-acidic compounds and compounds having primary or secondary amino groups or hydroxy groups, which in turn are selected from compounds of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. This second class is called a component (Oxo2). The aforementioned components (oxo1) and (oxo2) are generally not themselves dyes, and therefore are not in themselves suitable for coloring keratin-containing fibers. In combination, they form dyes in a non-oxidative process of so-called oxo dyeing. The resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing

The Nuancenspektrum achievable with the gentle oxo staining is very broad and the color obtained often has an acceptable brilliance and color depth. However, it is also possible to use corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidizing agent in compounds of the component (oxo2). Thus, the oxo staining method can be readily combined with the oxidative staining system. As Oxofarbstoffvorprodukte is preferably a combination of at least one compound containing at least one reactive carbonyl group (component (oxo 1)) with at least one compound (component Oxo2)

Compounds selected from (oxo2a) CH-acl compounds and / or from

(Oxo2b) Compounds having primary or secondary amino group or hydroxy group selected from at least one compound of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. Reactive carbonyl compounds as component (oxo1) have in the context of the invention at least one carbonyl group as a reactive group which reacts with the component (oxo2) to form a covalent bond. Preferred reactive carbonyl compounds are selected from compounds which carry at least one formyl group and / or at least one keto group, in particular at least one formyl group. Furthermore, those compounds according to the invention are also suitable as component (Oxo1) in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the component (Oxo2) is 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) of water to form hydrates as addition compound (component (Oxo1) is derived in in this case c) from an aldehyde) to the carbon atom of the carbonyl group of the reactive carbonyl compound. Very particularly preferred reactive carbonyl compounds according to the invention are selected from 4-hydroxy-2-methoxybenzaldehyde, 2-chloro-3,4-dihydroxybenzaldehyde, 2-bromo-3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 2,3 Dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazole-4-carboxaldehyde and 2,4-dimethoxybenzaldehyde.

Very particularly preferred CH-acidic compounds according to the invention are selected from the physiologically acceptable salts of 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium and of 1,2-dihydro-1,3-one , 4,6-tetramethyl-2-oxo-pyrimidonium and 2- (cyanomethyl) -benzimidazole. Furthermore, as component (Oxo2b) at least one oxidation dye precursor having at least one primary or secondary amino group and / or at least one hydroxyl group can be used. Preferred suitable representatives are found under the execution of the oxidation dye precursors. However, it is preferred according to the invention if the compounds of the component (oxo2) are selected only among CH-acidic compounds. The above-mentioned compounds of component (Oxo1) and the component (Oxo2) are, when used, each preferably in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total Means, used. The agents according to the invention additionally preferably comprise hydrogen peroxide. Here, agents according to the invention for dyeing and, if appropriate, simultaneous lightening of keratinic fibers are particularly preferred, which contain 0.5 to 15% by weight, preferably 1 to 12.5% by weight, particularly preferably 2.5 to 10% by weight and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂₎ included.

The hydrogen peroxide may also be used in the form of its attachment compounds to solid supports, preferably hydrogen peroxide itself is used. The hydrogen peroxide is added as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as, for example, sodium perborate, Sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H ₂ O ₂ (Ii is a positive integer greater than 0), urea peroxide and melamine peroxide used. Very particularly preferred according to the invention are aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6 to 12 percent solutions in water are used.

For a color change by means of brightening or bleaching of the substrate, for example the hair, in addition to the oxidizing agents, at least one bleach booster is preferably used in the cosmetic compositions according to the invention. Bleach boosters are preferably used to increase the bleaching action of the oxidizing agent, in particular the hydrogen peroxide. Suitable bleach boosters are (BV-i) compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids and / or optionally substituted perbenzoic acid, and / or

(BV-ii) carbonate salts and / or bicarbonate salts, and / or

(BV-iii) organic carbonates, and / or

(BV-iv) carboxylic acids, and / or

(BV-v) Peroxo compounds.

Bleach boosters are preferably peroxo compounds, in particular inorganic peroxo compounds. Among the bleach-enhancing peroxy compounds according to the invention there are no addition products of hydrogen peroxide to other components and also not hydrogen peroxide itself. Moreover, the choice of peroxo compounds is subject to no restrictions. Preferred peroxy compounds are peroxydisulfate salts, persulfate salts, peroxydiphosphate salts (especially ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxydisulfate, ammonium persulfate, potassium persulfate, sodium persulfate, potassium peroxydiphosphate) and peroxides (such as barium peroxide and magnesium peroxide). Among these peroxo compounds which can also be used in combination, according to the invention, the peroxydisulfates, in particular ammonium peroxydisulfate, are preferred. Here, agents according to the invention for dyeing and optionally simultaneously lightening keratinic fibers are preferred which additionally contain 0.01 to 2% by weight of at least one solid peroxo compound selected from ammonium, alkali metal and alkaline earth metal persulphates, peroxomonosulphates and peroxydisulphates preferred agents include peroxydisulfates, which are preferably selected from sodium peroxydisulfate and / or potassium peroxodisulfate and / or ammonium peroxydisulfate and particularly preferred agents containing at least two different peroxydisulfates. Particular preference is furthermore given to persulfates, especially those known as Caro's salt

Mixture of potassium peroxosulphate, potassium bisulphate and potassium sulphate.

The bleach boosters are in the cosmetic compositions according to the invention preferably in amounts of 5 to 30 wt .-%, in particular in amounts of 8 to 20 wt .-%, each based on the

Weight of ready to use agent included.

Furthermore, it has proved to be advantageous if the colorant according to the invention contains at least one care substance. The representatives of the following ten groups of

Nursing materials not only allow an improved care condition of the fibers after the

Color change. Their presence is rather the cause of a more intense and above all more uniform coloring with improved fastness properties.

In the context of a first preferred embodiment, the color-modifying agent according to the invention contains as care substance at least one cationic surfactant. Preference according to the invention is given to cationic surfactants of the quaternary ammonium type, which

Esterquats and amidoamines. Preferred quaternary ammonium compounds are cetyltrimethylammonium chloride and stearyltrimethylammonium chloride

Preferred ester quats 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.

An inventively preferred alkylamidoamine presents under the name ^® S Tegoamid

18 is commercially available stearamidopropyl-dimethylamine

Further cationic surfactants suitable according to the invention are those under the INCI names

Linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride

Phosphates and stearamidopropyl PG-dimonium chlorides phosphates known substances.

The cationic surfactants are contained in the compositions according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total application preparation. Amounts of 0.1 to 5 wt .-% are particularly preferred.

In the context of a second preferred embodiment of the present invention, the color-modifying agents contain as care substance at least one nourishing polymer.

A first group of caring polymers are the cationic polymers. Cationic polymers are polymers according to the invention which have a group in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group independently of the pH of the agent These are generally polymers which contain a quaternary nitrogen atom, for example in the form of an ammonium group Preferred cationic groups are quaternary ammonium groups In particular, those polymers in which the quaternary ammonium group is bonded to a polymer main chain composed of acrylic acid, methacrylic acid or derivatives thereof via a C 1-4 hydrocarbon group have been found to be particularly suitable. Particularly suitable cationic polymers are the optionally crosslinked homopolymers and copolymers of methacryloyloxyethyltrimethylammonium chloride. The homopolymer bears the INCI name Polyquaternium-37. Corresponding copolymers preferably contain acrylamide, methacrylamide, acrylic acid as nonionogenic monomer units. _4- alkyl esters and methacrylic acid-C- _M- alkyl esters Among these non-ionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. Other preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^β 400 are preferred quaternized cellulose derivatives, cationic alkyl polyglycosides according to DE-PS 44 13 686, cationized honey, for example the commercial product Honeyquat ^® 50, cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia® ^® guar and Jaguar ^® products,

Polysiloxanes having quaternary groups, such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamide dimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and AbiP-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt), diquaternary polydimethylsiloxanes, quaternium-80), polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of Acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammoniurnchlorid)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially,

Vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as by the names of Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27, having quaternary Nitrogen atoms in the polymer backbone. Furthermore, cationized protein hydrolysates are to be counted among the cationic polymers, wherein the underlying protein hydrolyzate from the animal, for example from collagen, milk or

Keratin, from the plant, for example, from wheat, corn, rice, potatoes, soy or almonds, marine life forms, such as fish collagen or algae, or biotechnologically derived protein hydrolysates, may originate. Very particular preference is given to the cationic protein hydrolysates and derivatives based on plants.

Very particularly preferred amphoteric polymers are those under the INCI name

Acrylamidopropyltrimonium chlorides / acrylates copolymer known structures.

The color-modifying agents of the invention more preferably contain the cationic polymers

Way in an amount of 0.01 to 5 wt .-%, in particular in an amount of 0.1 to 2% by weight, each based on the total application preparation.

In the context of a third preferred embodiment, the color-modifying agents according to the invention comprise at least one UV filter.

Two preferred UV filters with cationic groups are those available as commercial products

Cinnamic acid compounds trimethylammonium chloride (lncroquat ^® UV-283) and dodecyl tosylate (Escalol ^® HP 610).

Of course, the teaching of the invention also includes the use of a combination of several UV filters. In the context of this embodiment, the combination of at least one water-insoluble UV filter with at least one UV filter with a cationic group is preferred.

The UV filters are contained in the compositions of the invention usually in amounts of 0.01-5 wt .-%, based on the total application preparation. Amounts of 0.1-2.5 wt .-% are preferred.

In the context of a fourth preferred embodiment, the color-modifying agents according to the invention contain as care substance at least one vitamin, one provitamin, one

Vitamin precursor and one of their derivatives.

The color-modifying agents according to the invention preferably contain vitamins, provitamins and

Vitamin precursors from groups A, B, C, E and H. The vitamin C may be very particularly preferred according to the invention. Panthenol, pantolactone, pyridoxine and its derivatives as well

Nicotinic acid amide and biotin are also particularly preferred.

In the context of a fifth preferred embodiment, the Ganz according to the invention particularly suitable are the extracts of Moringa Olifeira, green tea, almond, aloe vera,

Coconut, mango, apricot, lime, wheat, kiwi and melon.

The plant extracts can be used according to the invention both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80 wt .-% of active substance and used as solvent in their recovery

Extracting agent or extractant mixture. Furthermore, it may be preferred in the color-modifying agents according to the invention

Use mixtures of several, especially two, different plant extracts.

In the context of a sixth preferred embodiment, the color-modifying agents according to the invention contain as care substance at least one protein hydrolyzate and one of its

Derivatives.

Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein hydrolysates, which may also be present in the form of salts. Such products are, for example, under the trademarks Dehylan ^® (Cognis), Promois ^® (Interorgana) Collapuron ^®

(Cognis), Nutrilan® ^® (Cognis), Gelita-Sol ^® (German Gelatinefabriken Stoess & Co), Lexein ^®

(Inolex), Sericin sold (Pentapharm) and kerasol tm ^® (Croda).

Preferred according to the invention is the use of protein hydrolysates of plant origin, eg. B. soy, almond, pea, potato and wheat Such products are, for example, under the trademarks Gluadin ^® (Cognis), diamine ^® (Diamalt) ^® (Inolex),

Hydrosoy ^® (Croda), hydro Lupine ^® (Croda), hydro Sesame ^® (Croda), Hydro tritium ^® (Croda), and

Crotein ^® (Croda) available.

The protein hydrolysates are in the color-changing agents according to the invention in

Concentrations of 0.01% by weight up to 20% by weight, preferably from 0.05% by weight up to 15

Wt .-% and most preferably in amounts of 0.05 wt .-% up to 5 wt .-%, each based on the total application preparation included.

In a seventh preferred embodiment, the inventive

Preparations containing as care Ectoin or ectoine derivatives, allantoin, taurine and bisabolol.

The color-modifying agents according to the invention contain these active ingredients preferably in amounts of 0.001 to 2, in particular from 0.01 to 0.5 wt .-%, each based on the total

Application preparation.

In the context of an eighth preferred embodiment, the color-changing agents according to the invention contain as care substance at least one monosaccharide or oligosaccharide.

Furthermore, it has proved to be advantageous if the preparations according to the invention contain a heated, that is to say caramelized sugar, preferably caramelized, cane sugar.

The mono- or oligosaccharides are contained in the hair treatment compositions according to the invention preferably in an amount of 0.1 to 8 wt .-%, in particular 1 to 5 wt .-%, based on the total application preparation.

In a neuten embodiment, the inventive preparation contains (B) as

Care product at least one silicone oil and / or a silicone gum.

According to the invention suitable silicones or silicone gums are especially dialkyl and

Alkylarylsiloxanes, such as dimethylpolysiloxane and methylphenyl-polysiloxane, and their alkoxylated, quaternized or anionic derivatives.

Examples of such silicones are: Oligomeric polydimethylcyclosiloxanes (INCI name: Cyclomethicone), in particular the tetrameric and pentameric compounds sold as commercial products DC 344 and DC 345, respectively, by Dow Corning,

Hexamethyl disiloxane (INCI name: Hexamethyldisiloxane), z. B. the product sold under the name Abil ^® K 520,

Polydimethylsiloxane polymers (INCI name: Dimethicone), z. The products sold under the name DC 200 by Dow Corning, polyphenylmethylsiloxanes (INCI name ¹ phenyl trimethicone), for example the commercial product DC 556 fluid from Dow Corning,

Sihcon glycol copolymers (INCI name: Dimethicone Copolyol), z. The commercial products DC 190 and DC 193 from Dow Corning,

Esters and partial esters of silicone glycol copolymers, such as, for example, by the company Fanning under the trade name LIM Fancorsil ^® (INCI name: dimethicone copolyol Meadowfoamate) are distributed,

Hydroxy-terminated dimethylsiloxanes (INCI name: dimethiconol), e.g. Dow Corning's commercial products DC 1401 and Q2-1403, aminofunctional polydimethylsiloxanes and hydroxylamine-modified silicones (INCI name: Amodimethicone and Quaternium-80), such as the commercial products XF42-B1989 (manufactured by GE Toshiba Silicones) Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow ^Corning® 939 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker), and ABIP-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt), anionic silicone oils, such as the product Dow Corning ^® 1784 amino-modified organosilicones, such as the product Abil soft A843 (manufactured by Osi Specialties).

The preparations according to the invention preferably contain the silicones in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 5% by weight, based on the total application preparation. In the context of a tenth embodiment, the color change agents according to the invention contain at least one oil body and / or a wax as a care substance. The natural and synthetic cosmetic oil bodies include, for example: vegetable oils liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers having a total of between 12 and 36 carbon atoms,

Esteröle.

Dicarboxylic acid esters symmetrical, unsymmetrical or cyclic esters of carbonic acid with fatty alcohols,

Trifatty acid esters of saturated and / or unsaturated linear and / or branched

Fatty acids with glycerine, Fatty acid partial glycerides, which are monoglycerides, diglycerides and their technical

Mixtures.

The amount used of the natural and synthetic cosmetic oil bodies in the color-modifying agents according to the invention is usually 0.1-30% by weight, based on the total application preparation, preferably 0.1-20% by weight, and in particular 0.1-15% by weight. -%. In a tenth preferred embodiment of the present invention, the preparation further contains at least one flavonoid. Very particularly preferred flavonoids according to the invention

Tiliroside ([(2R, 3R, 4S, 5R, 6S) -6- [5,7-dihydroxy-2- (4-hydroxyphenyl) -4-oxo-chromen-3-yl] oxy-3,4,5 -trihydroxy-oxan-2-yl] methyl (E) -3- (4-hydroxyphenyl) prop-2-enoate; INCI name: Tiliroside, CAS No. 20316-62-5),

Rutin sulfate (3,3 ', 4', 4,7-pentahydroxyflavone-3-rhamnoglucoside, INCI name Disodium Rutinyl Disulfate),

Troxerutin (2- [3,4-bis (2-hydroxyethoxy) phenyl] -5-hydroxy-7- (2-hydroxyethoxy) -3- [3, 4,5-trihydroxy-6 - [(3,4, 5-trihydroxy-6-methyl-oxan-2-yl) oxymethyl] oxan-2-yl] oxy-chromen-4-one; INCI name: troxerutin, CAS No. 96304-71-1) and

isoquercetin (2- (3,4-dihydroxyphenyl) -5,7-dihydroxy-3 [(2S, 3R, 4S, 5R, 6R) -3,4,5-trihydroxy-6- (hydroxymethyl) oxan-2-one yl] oxy-chromen-4-one; CAS No. 482-35-9).

A very particularly preferred flavonoid according to the invention is tiliroside.

The flavonoids of the formula (I) are preferably present in the preparations according to the invention in an amount of from 0.0001 to 5% by weight, in particular from 0.002 to 1% by weight, based in each case on the pure active compound and the entire ready-to-use agent.

Although each of the care substances mentioned in the various embodiments alone already gives a satisfactory result, in the context of the present invention, all embodiments are included in which the color-changing agents also contain a plurality of care substances from different groups.

Particularly preferred care substances in the context of the present invention are, in particular, vitamin C, ubiquinones, panthenol and its derivatives, ectoin, chamomile extract, bisabolol, olive oil, royal jelly, mung bean extract and Moringa Olifeira extract

Furthermore, it has proved to be advantageous if the dyeing and / or brightening agents according to the invention contain nonionic surfactants.

Particularly preferred classes of nonionic surfactants are the alkoxylated fatty alcohols, the alkoxylated fatty acids and the alkylphenols and alkylphenol alkoxylates.

Agents according to the invention which contain non-ionic surface-active substances in amounts of 1 to 5% by weight have proved to be particularly advantageous. Furthermore, the dyeing and / or brightening agents according to the invention may contain all known in such preparations active ingredients, additives and excipients. In many cases, the agents contain at least one surfactant, 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, cationic or nonionic surfactants. Anionic surfactants may be very particularly preferred. Preferred anionic surfactants are alkyl sulfates, ether carboxylic acid salts having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule such as C ₁₂ H ₂₅ - (C ₂ H ₄ O) ₆ -CH ₂ -COONa and in particular salts of saturated and especially unsaturated C8-C22 carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

These anionic surfactants should preferably be present in solid, in particular powder form. Very particular preference is given to solid soaps, especially sodium stearate, at room temperature. These are preferably present in amounts of 5 to 20 wt .-%, in particular 10 to 15 wt .-%, before. Particularly suitable nonionic surfactants are C ₈ -C ₂₂ -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds have been found to be particularly suitable.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Alkylamidoamines, in particular fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability. Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as the Distearoylethylhydroxyethylammoniurnmethosulfat available in a blend with Cetearylalkohle under the name Dehyquart® ^® F 75 miles.

The compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.

As a further constituent, the compositions according to the invention may contain at least one ammonium compound from the group of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate in an amount of from 0.5 to 10, preferably 1 to 5 wt .-%, based on the total composition of the composition.

The compositions of the invention may contain the ingredients in a 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 possible to provide a powdered or tablet-shaped formulation, which is preferred for dyeing and / or brightening agents. For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C ₁ -C ₄ -alkoxy, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain further organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents. Preferred agents according to the invention are characterized in that they additionally contain a nonaqueous solvent, particularly preferred compositions according to the invention the solvent in a concentration of 0.1 to 30 weight percent, preferably in a concentration of 1 to 20 weight percent, most preferably in a concentration of 2 - 10 weight percent, each based on the agent included.

In further preferred agents according to the invention, the solvent is selected from ethanol, n-propanol, isoropanol, n-butanol, propylene glycol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, phenoxyethanol and benzyl alcohol and their mixtures.

The pH of the compositions according to the invention can be adjusted within a wide range by suitable ingredients such as acidifying agent or alkalizing agent. Oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen in the presence of oxidation dye precursors. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. This lightening effect may be desired regardless of the staining method. Accordingly, the presence of oxidation dye precursors is not a mandatory requirement for the use of oxidizing agents in the compositions according to the invention. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate.

However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

When using oxidants, the actual colorant is expediently immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the compounds of the formula I and, if appropriate, dye precursors, produced. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can be in a range between 15 and 40 ⁰ C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.

For the application of the compositions of the invention on the hair dyeing and / or brightening agents are mixed immediately before application with a hydrogen peroxide solution. The concentration of this hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; As a rule, 6-12% solutions in water are used. The proportions of dyeing and / or lightening agent and hydrogen peroxide solution are usually in the range 1: 1 to 1: 2, with an excess of hydrogen peroxide solution is particularly selected when no too pronounced Blondierwirkung is desired.

Also preferred according to the invention is the use of so-called complexing agents. Complex images are substances that can complex metal ions. Preferred complexing agents are so-called chelate complexing agents, ie substances which form cyclic compounds with metal ions, a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.

Particularly preferred in the context of the present invention is the use of one or more chelating agents from the groups of (i) polycarboxylic acids in which the sum of the carboxyl and optionally

Hydroxyl groups is at least 5, (ii) nitrogen-containing mono- or polycarboxylic acids, (iii) geminal diphosphonic acids, (iv) aminophosphonic acids, (v) phosphonopolycarboxylic acids, (vi) cyclodextrins.

A preferred class of substances with complex-forming properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene pentamine methylene phosphonate (DTPMP) and their higher homologs. They are preferably used in the form of the neutrally reacting sodium salts, eg. B. as hexasodium salt of EDTMP or as hepta- and octa Sodium salt of DTPMP. The complexing agent used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. These substances will be described below.

Compounds which are preferred according to the invention are phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylene phosphonate (EDTMP) or its hexasodium salt and / or diethylene triamine pentamethylene phosphonate (DTPMP ) or its hepta- or octasodium salt.

Particularly preferred agents according to the invention contain one or more substances from the group

(a) nitrilotriacetic acid (NTA),

(b) diethylenetriaminepentaacetic acid (DTPA),

(c) ethylenediamine disuccinic acid (EDDS),

(d) ethylenediamine-diglutaric acid (EDGA),

(e) 2-hydroxypropylenediamine disuccinic acid (HPDS),

(f) glycinamide-N, N'-disuccinic acid (GADS),

(g) ethylenediamine-N-N'-diglutaric acid (EDDG),

(h) 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS),

(i) ethylenediaminetetraacetic acid (EDTA),

(j) ethylene dicysteic acid (EDC),

(k) diaminoalkyldi (sulfosuccinic acid) (DDS),

(I) ethylenediamine-N-N'-bis (ortho-hydroxyphenylacetic acid (EDDHA),

(m) N-2-hydroxyethyl-N, N-diacetic acid,

(n) glyceryliminodiacetic acid,

(o) lminodiacetic acid N-2-hydroxypropylsulfonic acid,

(p) aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid,

(q) 8-alanine-N, N'-diacetic acid,

(r) aspartic acid-N, N'-diacetic acid,

(s) aspartic acid N-monoacetic acid,

(t) dipicolinic acid,

(u) and their salts and / or derivatives

A second subject of the present invention is a process for dyeing and possibly simultaneously brightening keratin fibers, in particular human hair, in which, if desired, a pretreatment agent M1 is applied to the fiber, then an agent M2 on the fiber is used, if desired the agent M2 the application is added a further agent M3, this agent M2 is rinsed off the fiber after a period of 5-30 minutes and after the treatment optionally an aftertreatment agent M4 is applied to the fiber and rinsed off after a contact time of a few minutes, wherein at least one of the agents M1, M2 or M3 a means according to the invention. The agents according to the invention can accordingly be formulated as single-component agents (dyeing and whitening agents M2 or aftertreatment agents M4), as two-component agents (M2 + M3) or as three-component agents (M2 + M3 + M4) and used accordingly. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or feared; the agent to be used in such systems is manufactured by the consumer just prior to use by mixing the component.

A dyeing and whitening process in which the whitening cream and the oxidizing agent are initially separate is preferred. A further subject of the present invention is therefore a process for dyeing and lightening human hair, in which an aqueous-based composition containing hydrogen peroxide is mixed with an agent according to the invention to form a homogeneous composition and applied to the hair.

In preferred processes of this type according to the invention, the aqueous-based composition contains 1 to 20% by weight, preferably 2 to 10% by weight and in particular 3 to 6% by weight of hydrogen peroxide, calculated as 100% H _2, by weight O ₂ . Further preferred processes according to the invention of this type are characterized in that the aqueous-based composition containing hydrogen peroxide with an agent according to the invention in a weight ratio of 1: 5 to 10: 1, preferably 1.2 to 5: 1 and especially 1: 2 to 2: 1 a homogeneous composition, and this is applied to the hair.

Alternatively, as mentioned above, a three-component system may also be used. A further subject of the present invention is therefore a process for dyeing and lightening human hair which comprises an aqueous-based composition containing hydrogen peroxide with a further agent containing preferably at least one alkalinity donor and / or substantive hair dye and / or at least one oxidation dye precursor, and a composition according to the invention mixed to a homogeneous composition, and this is applied to the hair.

With regard to further preferred embodiments of the method according to the invention, mutatis mutandis the statements made concerning the agents according to the invention apply.

A further subject of the present invention is therefore the use of cationic compounds of the formula (Ia):

X (Ia) in the

R ^1, R ^2, R ^3, R ⁴ independently represent a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, a C- | -C ₆ hydroxyalkyl group, a C ₂ - C ₆ polyhydroxyalkyl group, a halogen atom, a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, an alkyloxycarbonyl group or a sulfonic acid group, wherein the two radicals R ¹ and R ² or R ³ and R ⁴ together form a further fused, carbocyclic or heterocyclic ring optionally bearing a substituent R ¹² ,

R ⁵ stands for a C | _-C6 alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ -

Hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - alkoxy-CrC ₆ alkyl group, an amino-Ci-C ₆ alkyl group, a di-C ₁ -C ₆ - alkylamino-C ₂ -C _6- alkyl group, a cyano-d-Cβ-alkyl group or a substituent of the formulas II to VII. ¹

- (CH ₂ ) π - COOH _{(| |)}

O

- (CHJn - N-S-R1 1 2 / II

^R1 ° ° <ιι »

O

- (CH ₂ ) n - "- - O - RR1111

(IV)

_(V) O R10 II I (CH ₉ ) n - SN-R10

^2l Il

⁰ (VI)

O R10

- (CH,) n - ^ N-RIO

² (VII)

R ⁶ and R ⁷ independently represent a hydrogen atom, a Ci-C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, a Ci-C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a halogen atom (chloride , bromide, iodide or fluoride), a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, a Alkyloxycarbonylguppe, a sulfonic acid group, a Ci-C ₆ - alkoxy group, a hydroxy group, an amino group or a C ₁ -C ₆ - dialkylamino

R ¹⁰ and R ¹¹ independently represent a hydrogen atom, a CrC ₆ - alkyl group, a C-ι-C ₆ hydroxyalkyl group, a C ₂ -C ₆ - polyhydroxyalkyl group, a C ₂ -C _e alkenyl group, an aryl group or a heteroaryl

R ¹² represents a hydrogen atom, a dC ₆ alkyl group, a C ₂ -C ₆ -

X is a monovalent anion, preferably halide (chloride,

Bromide, iodide or fluoride), hydrogen sulfate, ^Λ / i sulfate, ^Λ / i tetrachlorozincate, p-benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methane sulfate or methanesulfonate. in agents for dyeing and, if appropriate, simultaneous lightening of keratinic fibers. Particularly preferably, the use of the compounds serves to achieve certain advantageous effects. Preferred according to the invention are uses for Increasing the fastness properties of the dyeings and / or

Increase color brilliance and / or

Increase the skin compatibility of dye or lightening agents.

With regard to further preferred uses according to the invention, the mutated mutandis applies to the preferred agents.

Some of the cationic compounds contained in the agents according to the invention are not yet known. Another object of the present invention are therefore cationic compounds of the formula (Ib):

^X (Ib) in the either

R ₁ ', R ₂ ', R ₃ ', R ₄ stand for a hydrogen atom

R ₅ 'represents allyl group or a 2-hydroxyethyl group

R ₆ 'and R _7' are each independently a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C ₂ -Cβ alkenyl group, a Ci-Cβ-hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a halogen atom ( Chloride, bromide, iodide or fluoride), carboxyl group, nitrile group, carbamoyl group, sulfonamido group, carboxamido group, alkyloxycarbonyl group, sulfonic acid group, C ₁ -C ₆ alkoxy group, hydroxy group, amino group or C ₁ -C ₆ - dialkylamino group,

R ₈ 'and R ₉ ' independently of one another represent a substituent which is defined as R ⁵ or together form a 5-, 6- or 7-membered ring which may optionally carry further substituents or heteroatoms,

X ^" is a monovalent anion, preferably halide (chloride,

Bromide, iodide or fluoride), hydrogensulfate, 14 sulphate, V2 tetrachlorozincate, p-benzenesulphonate, p-toluenesulphonate, acetate, tetrafluoroborate, Trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or methanesulfonate, or

R ₁ ', R _2', R ₃ ', R ₄ independently represent a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, a Ci-C ₆ hydroxyalkyl group, a C ₂ C ₆ polyhydroxyalkyl group, a halogen atom, a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, an alkyloxycarbonyl group or a sulfonic acid group, where the two radicals R ¹ and R ² or R ³ and R ⁴ together form a further fused, may form a carbocyclic or heterocyclic ring optionally bearing a substituent R ₁₀ ',

R ₅ 'represents a -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ -

Hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - alkoxy-CrC ₆ alkyl group, an amino-Ci-C ₆ alkyl group, a di-C ₁ -C ₆ - alkylamino-C ₂ -C _6- alkyl group, a cyano-d-Cβ-alkyl group

R ₆ 'and R _7' are each independently a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, a dC ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a halogen atom ( Chloride, bromide, iodide or fluoride), carboxyl group, nitrile group, carbamoyl group, sulfonamido group, carboxamido group, alkyloxycarbonyl group, sulfonic acid group, C ₁ -C ₆ alkoxy group, hydroxy group, amino group or C ₁ -C ₆ - dialkylamino group,

R ₈ 'and R ₉ ' together form a 5-, 6- or 7-membered ring which may optionally carry further substituents or heteroatoms,

R ₁₀ 'stands for a hydrogen atom, a dC ₆ alkyl group, a C ₂ -C ₆ -

X ^" is a monovalent anion, preferably halide (chloride,

Bromide, iodide or fluoride), hydrogensulfate, 14 sulfate, V ₂ tetrachlorozincate, p-benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, Trifluoromethanesulfonate, hexafluorophosphate, methanesulfate or

Methanesulfonate.

Furthermore, the following compounds are not known from the literature and subject of the present invention

- 9- [4- (Diethylamino) -2-hydroxyphenyl] -10-methylacridinium p-toluenesulfonate

- 9- [4- (dimethylamino) -3-bromophenyl] -10-methylacridinium p-toluenesulfonate

Particularly preferred cationic compounds according to the invention are selected from the group of

- Salts of 10-allyl-9- [4- (dimethylamino) phenyl] acridiniums

Salts of 10-allyl-9- [4- (diethylamino) phenyl] acridinium

Salts of 9- [4- (piperidin-1-yl) phenyl] -10-methylacridinium

Salts of 9- [4- (piperidin-1-yl) phenyl] -10-ethylacridinium

- Salts of 10-allyl-9- [4- (pιperidιn-1-yl) phenyl] acrιdiniums

Salts of 9- [4- (morpholin-4-yl) phenyl] -10-methylacridinium

Salts of 10-allyl-9- [4- (morpholin-4-yl) phenyl] acridinium

Salts of 9- [4- (piperazin-1-yl) phenyl] -10-methylacridinium

- Salts of 10-allyl-9- [4- (pιperazin-1-yl) phenyl] acridiniums

Salts of 9- [4- (4-methylpiperazin-1-yl) phenyl] -10-methylacridinium

Salts of 10-allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium

Salts of 9- [4- (pyrrolidin-1-yl) phenyl] -10-methylacridinium

- Salts of 10-allyl-9- [4- (pyrrolιdin-1-yl) phenyl] acridiniums

Salts of 9- [4- (diethylamino) -2-methoxyphenyl] -10-methylacridinium

Salts of 10-allyl-9- [4- (diethylamino) -2-methoxyphenyl] acridinium

Salts of 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium

- Salts 10-allyl-9- {4- [bis (2-hydroxyethyl) amino] phenyl} acridiniums

- Salts of 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacridinium

Salts of the 10-allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} acridinium

Salts of 9- [4- (diethylamino) -2-hydroxyphenyl] -10-methylacridinium

Salts of 10-allyl-9- [4- (diethylamino) -2-hydroxyphenyl] acridinium

Salts of 9- [4- (dimethylamino) -3-bromophenyl] -10-methylacridinium

Salts of 10-allyl-9- [4- (dimethylamino) -3-bromophenyl] acridinium.

Also at this point, reference should be made explicitly to the corresponding disclosure in the corresponding priority document with regard to the exact structures. Particularly preferred cationic compounds according to the invention are 10-allyl-9- [4- (dimethylamino) phenyl] acridinium bromide, 10-allyl-9- [4-

(diethylamino) phenyl] acridinium bromide, 9- [4- (piperidin-1-yl) phenyl] -10-methylacridinium bromide, 9- [4- (piperidin-1-yl) phenyl] -10-ethylacridinium bromide, 10-allyl-9 - [4- (piperidin-1-yl) phenyl] acridinium bromide, 9- [4- (morpholin-4-yl] phenyl] -10-methylacridinium bromide, 10-allyl-9- [4- (morpholin-4-yl) phenyl] acridinium bromide, 9- [4- (piperazin-1-yl) phenyl] -10-methylacridinium bromide, 10-allyl-9- [4- (piperazin-1-yl) phenyl] acridinium bromide, 9- [4- (4 -Methylpiperazin-1-yl) phenyl] -10-methylacridinium bromide, 10-allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium bromide, 9- [4- (pyrrolidin-1-yl) phenyl] 10-methylacridinium bromide, 10-allyl-9- [4- (pyrrolidin-1-yl) phenyl] acridinium bromide, 9- [4- (diethylamino) -2-methoxyphenyl] -10-methylacridinium bromide, 10-allyl-9- [ 4- (diethylamino) -2-methoxyphenyl] acridinium bromide, 9- {4- [bis (2-hydroxyethyl) amino] -phenyl} -10-methylacridinium bromide, 10-allyl-9- {4- [bis (2-hydroxyethyl ) amino] phenyl} acridinium bromide, 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacridinium bromide omide, 10-allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} acridinium bromide, 9- [4- (diethylamino) -2-hydroxyphenyl] -10-methylacridinium bromide, 10-allyl-9- [4 - (diethylamino) -2-hydroxyphenyl] acridinium bromide, 9- [4- (dimethylamino) -3-bromophenyl] -10-m8-thylacridinium bromide, 10-allyl-9- [4- (dimethylamino) -3-bromophenyl] acridinium bromide. Allyl 9- [4- (dimethylamino) phenyl] acridinium p-toluenesulfonate, 10-allyl-9- [4- (diethylamino) phenyl] acridinium p-toluenesulfonate, 9- [4- (piperidin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate, 9- [4- (Pipe-rid-in-1-yl) phenyl] -10-ethylacridinium p-toluenesulfonate, 10-allyl-9- [4- (piperidine-1-yl) yl) phenyl] acridinium p-toluenesulfonate, 9- [4- (morpholin-4-yl] phenyl] -10-methylacridinium p-toluenesulfonate, 10-allyl-9- [4- (morpholin-4-yl) phenyl ] acridinium p-toluenesulfonate, 9- [4- (piperazin-1-yl) phenyl] -10-methylacinedinium p-toluenesulfonate, 10-allyl-9- [4- (piperazin-1-yl) phenyl] acrystalline p-toluenesulfonate, 9- [4- (4-methyl-piperazin-1-yl) -phenyl] -10-methylacridinium-p-toluenesulf Fonate, 10-allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium p-toluenesulfonate, 9- [4- (pyrrolidin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate , 10-Allyl-9- [4- (pyrrolidin-1-yl) phenyl] acridinium p-toluenesulfonate, 9- [4- (diethylamino) -2-methoxyphenyl] -10-methylacridinium p-toluenesulfonate, 10-allyl -9- [4- (dimethylamino) -2-methoxyphenyl] acridinium p-toluenesulfonate, 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium p-toluenesulfonate, 10-allyl- 9- {4- [bis (2-hydroxyethyl) amino] phenyl} acridinium p-toluenesulfonate, 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacridinium p-toluenesulfonate, 10-allyl -9- {4 - [(2-hydroxyethyl) methylamino] phenyl} acridinium p-toluenesulfonate, 9- [4- (Diethylamino) -2-hydroxyphenyl] -10-methylacridinium p-toluenesulfonate, 10-allyl-9 [4- (diethylamino) -2-hydroxyphenyl] acridinium p-toluenesulfonate, 9- [4- (dimethylamino) -3-bromophenyl] -10-methylacridinium p-toluenesulfonate and 10-allyl-9- dimethylamino) -3-bromophenyl] acridinium-p-toluenesulfonate. Very particularly preferred cationic compounds are 10-allyl-9- [4-

(dimethylamino) phenyl] acridinium bromide, 10-allyl-9- [4- (diethylamino) phenyl] acridinium bromide, 9- [4- (piperidin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate, 9- [4 - (pyrperidin-1-yl) phenyl] -10-ethylacridinium p-toluenesulfonate, 10-allyl-9- [4- (piperidin-1-yl) phenyl] acridinium bromide, 9- [4- (morpholin-4-yl ] phenyl] -10-methylacridinium p-toluenesulfonate, 10-allyl-9- [4- (morpholine-4- yl) phenyl] acridinium bromide, 9- [4- (piperazin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate, 10-allyl-9- [4- (piperrazinyl-1-yl) phenyl] acridinium bromide, 9 - [4- (4-methylpiperazin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate, 10-allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium bromide, 9- [4 - (pyrrolidin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate, 10-allyl-9- [4- (pyrrolidin-1-yl) phenyl] acridinium bromide, 9- [4- (diethylamino) -] 2-methoxyphenyl] -10-methylacridinium p-toluenesulfonate, 10-allyl-9- [4- (diethylamino) -2-methoxyphenyl] acridinium bromide, 9- {4- [bis (2-hydroxyethyl) amino] phenyl} - 10-methylacridinium p-toluenesulfonate, 10-allyl-9- {4- [bis (2-hydroxyethyl) amino] phenyl} acridinium bromide, 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacridinium -p-toluenesulfonate, 10-allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} acridinium bromide, 9- [4- (di-sylamino) -2-hydroxyphenyl] -10-methylacridinium p-toluenesulfonate, 10 Allyl 9- [4- (diethylamino) -2-hydroxyphenyl] acridinium bromide, 9- [4- (Dim ethylamino) -3-bromophenyl] - 10-methylacridinium p-toluenesulfonate and 10-allyl-9- [4- (dimethylamino) -3-bromophenyl] acridinium bromide.

The 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium p-toluenesulfonate, the, 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium bromide, the 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium chloride and the 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacrιdinium Acetate are very particularly preferred according to the invention.

B e i s p e e l e

1 Synthesis Examples:

1.1 Synthesis Example 1: Preparation of 9- [4- (dimethylamino) -phenyl-10-methylacridinium p-toluenesulfonate

toluene

1.1 1 Synthesis of 10-methylacridinium p-toluenesulfonate

There was added 50.0 g (0.28 mol) of acridine along with 59.8 g (0.31 mol) of p-

Toluolsulfonsäuremethylester heated in 200 ml of toluene for six hours under reflux. After this

Cooling, the precipitated solid was filtered off and washed with toluene.

Yield: 92.4 g (90.6%)

1.1.2 Synthesis of 9- [4- (dimethylamino) phenyl] -10-methylacridinium p-toluenesulfonate 35.7 g (0.10 mol) of 10-methylacridinium p-toluenesulfonate were added together with 12.1 g (0, 10 mol) of N, N-dimethylaniline and 26.0 g (0.10 mol) of iodine dissolved in 500 ml of dimethylformamide and heated to 100 ⁰ C for 3 hours. After cooling, 1000 ml of diethyl ether was added to the reaction mixture, whereupon a dark oil separated. The oil was separated from the rest of the reaction and dissolved in 500 ml of dichloromethane. The organic phase was washed with water until the water phase was only slightly colored. Then the organic phase was dried with magnesium sulfate and concentrated in a rotary evaporator to give a dark blue powder.

Yield: 41.9 g (99.2%) 1.2 Synthesis Example 2: Preparation of 9- [4- (morpholin-4-yl) -phenyl-10-methylacridinium p-toluenesulfonate

1.2.1 Synthesis of 10-methylacridinium p-toluenesulfonate: cf. Synthesis Example 1, Level 1 (Point 1.1.1)

1.2 2 Synthesis of 9- [4- (morpholin-4-yl) phenyl] -10-methylacridinium p-toluenesulfonate

17.9 g (0.05 mol) of 10-methylacridinium p-toluenesulfonate were dissolved in 250 ml of dimethylformamide together with 8.2 g (0.05 mol) of N-phenylmorpholine and 13.0 g (0.05 mol) of iodine and heated to 100 ⁰ C for 3 hours. After cooling, 500 ml of diethyl ether was added to the reaction mixture, whereupon a dark solid parted. The solid was filtered off and washed with diethyl ether

Yield: 6.2 g (24.0%)

1.3 Synthesis Example 3: Preparation of 9- [4- (piperazin-1-yl) -phenyl-10-methylacridinium p-toluenesulfonate

1.3.1 Synthesis of 10-methylacridinium p-toluenesulfonate: cf. Synthesis Example 1, Step 1 (Item 1.1.1) 1.3 2 Synthesis of 9- [4- (piperazin-1-yl) phenyl] -10-methylacridinium p-toluenesulfonate

17.9 g (0.05 mol) of 10-methylacridinium p-toluenesulfonate were dissolved in 250 ml of dimethylformamide together with 8.1 g (0.05 mol) of N-phenylpiperazine and 13.0 g (0.05 mol) of iodine and heated to 100 ⁰ C for 3 hours. After cooling, the batch was concentrated in vacuo on a rotary evaporator. The remaining residue was taken up in 250 ml of dichloromethane. The dark, organic phase was washed twice with water, dried over sodium sulfate and concentrated on a rotary evaporator. Yield: 6.4 g (21.4%)

1.4 Synthesis Example 4: Preparation of 9- [2-hydroxy-4- (diethylamino) -phenyl-10-methylacridinium p-toluenesulfonate

1.4.1 Synthesis of 10-methylacridinium p-toluenesulfonate: cf. Synthesis Example 1, Level 1 (Point 1.1.1)

1.4.2 Synthesis of 9- [2-hydroxy-4- (dimethylamino) phenyl] -10-methylacridinium p-toluenesulfonate

17.9 g (0.05 mol) of 10-methylacridinium p-toluenesulfonate were dissolved in 250 ml of dimethylformamide together with 8.3 g (0.05 mol) of N-phenylpiperazine and 13.0 g (0.05 mol) of iodine and heated to 100 ⁰ C for 3 hours. After cooling, the batch was concentrated in vacuo on a rotary evaporator. The remaining residue was taken up in 250 ml of dichloromethane. The dark, organic phase was washed twice with water, dried over sodium sulfate and concentrated on a rotary evaporator. Yield 16.2 g (62.5%)

1.5 Synthesis Example 5: Preparation of 9- (4-f (2-hydroxyethyl) (ethyl) aminol-2-methylphenyll-10-methylacidinium p-toluenesulfonate

1.5.1 Synthesis of 10-methylacridinium p-toluenesulfonate: cf. Synthesis Example 1, Step 1

1.5.2 Synthesis of 9- {4 - [(2-hydroxyethyl) (ethyl) amino] -2-methylphenyl} -10-methylacridinium p-toluenesulfonate

20.0 g (0.064 mol) of 10-methylacridinium p-toluenesulfonate were added together with 11.5 g (0.064 mol) of N-ethyl-N- (2-hydroxyethyl) -m-toluidine in 180 ml of dimethylformamide for 1.5 hours heated to 105 ⁰ C. During the reaction, compressed air was bubbled through the reaction mixture through a gas inlet tube. After completion of the reaction, the cooled solution with 1800 ml of methyl terf-butyl ether was added and stored for 24 hours at -5 ⁰ C. The oil separated after this period was separated, washed with methyl tert-butyl ether and dried.

Yield: 16.9 g (56.9%)

1.6 Synthesis Example 6: Preparation of 10-methyl-9- [4- (pyrrolidin-1-yl) phenyl lacridinium p-toluenesulfonate (DZ 6)

1.6.1 Synthesis of 10-methylacridinium p-toluenesulfonate: cf. Synthesis Example 1, Step 1

1.6.2 Synthesis of 10-methyl-9- [4- (pyrrolidin-1-yl) phenyl] acridinium p-toluenesulfonate

20.0 g (0.064 mol) of 10-methylacridinium p-toluenesulfonate were together with 9.4 g (0.064 mol) of N-phenylpyrrolidine in 180 ml of dimethylformamide for 1.5 hours at 105 ⁰ C heated. During the Reaction was bubbled through the reaction mixture through a gas inlet tube of compressed air. After completion of the reaction, the cooled solution with 1800 ml of methyl-ferf-butyl ether was added and stored for 24 hours at -5 ⁰ C. The oil separated after this period was separated, washed with methyl-fer-butyl ether and dried.

Yield: 12.4 g (44.4%)

1.7. Synthesis Example 7: Preparation of 9- [4- (diethylamino) -2-methylphenyl-10-methylacridinium p-toluenesulfonate

1.7.1 Synthesis of 10-methylacridinium p-toluenesulfonate: cf. Synthesis Example 1, Step 1

1.7.2 Synthesis of 9- [4- (diethylamino) -2-methylphenyl] -10-methylacridinium p-toluenesulfonate

20.0 g (0.064 mol) of 10-methylacridinium p-toluenesulfonate were together with 10.4 g (0.064 mol) of N, N-diethyl-m-toluidine in 180 ml of dimethylformamide for 1.5 hours at 105 ⁰ C heated. During the reaction, compressed air was bubbled through the reaction mixture through a gas inlet tube. After completion of the reaction, the cooled solution with 1800 ml of methyl-ferf-butyl ether was added and stored for 24 hours at -5 ⁰ C. The oil separated after this period was separated, washed with methyl-fer-butyl ether and dried.

Yield: 10.0 g (34.6%)

SYNTHESIS EXAMPLE 8 Preparation of 9- (4-rBis (2-hydroxypropylaminophenyl) -10-methyl-acridinium p-toluenesulfonate (DZ 8)

1.8 1 Synthesis of 10-methylacridinium p-toluenesulfonate: cf. Synthesis Example 1, Step 1 1.8.2 Synthesis of 9- {4- [bis (2-acetoxyethyl) amino] phenyl} -10-methylacridinium p-toluenesulfonate

20.0 g (0.064 mol) of 10-methylacridinium p-toluenesulfonate were together with 17.0 g (0.064 mol) of N, N-bis (2-acetoxyethyl) aniline in 180 ml of dimethylformamide for 1.5 hours at 105 ⁰ C. heated. During the reaction, compressed air was bubbled through the reaction mixture through a gas inlet tube. After completion of the reaction, the cooled solution with 1800 ml of methyl tert-butyl ether was added and stored overnight at 0 ⁰ C. The precipitated after this period of solids was filtered off and recrystallized twice from water.

Yield: 11.4 g (33.1%)

1.8.3 Synthesis of 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methyl-acridinium p-toluenesulfonate

14.8 g (0.024 mol) of 9- {4- [bis (2-acetoxyethyl) amino] phenyl} -10-methylacridinium p-toluenesulfonate were refluxed in 150 ml of a 5% aqueous hydrochloric acid solution for 8 hours. After completion of the reaction, the reaction mixture was concentrated on a rotary evaporator completely in vacuo. The residual yellow-brown oil was redissolved in 200 ml of water and sodium hydroxide solution was added to a pH of 7, whereby the aqueous solution turned deep blue. The solution was again completely concentrated on a rotary evaporator in vacuo. This resulted in a dark blue solid. Yield: 9.8 g (76.6%) 2 coloration examples:

2.1 Preparation of the coloring creams

The following coloring creams were produced:

2.1.1 Nonionic Dyeing Cream

Hydrenol ^® D 6.0 g

Lorol® ^® (techn.) 6.0 g

Eumulgin ^® RH 40 1, 0 g

Eumulgin ^® B1 3.0 g

Eumulgin ^® B2 3.0 g

PHB methyl ester 0.3 g

PHB propyl ester 0.2 g

Phenoxyethanol 1, 0 g

Polydiol ^® 400 5.0 g

Direct puller DZI 1, 0 g

Ammonium sulfate 1, 0 g (in 30.0 g of water)

Natrosol ^® 250 HR 1, 0 g (in 15.0 g water)

NaOH 0.1% pH adjustment

Water ad 100 g

The first nine components were melted together at 80 ^° C., after which the dye was added. This mixture was emulsified with a solution of the ammonium sulfate in 30 g of water. Subsequently, a swelling of 1, 0 g Natrosol ^® 250 HR in 15.0 g of water was added. The pH stated in Table 2 was adjusted with 0.1% sodium hydroxide solution, then made up to 100 g with water.

2.1.2 Cationic Dyeing Cream

Stenol 16/18 ^® 4.0 g

Eumulgin ^® B1 1, 0 g

Dehyquart ^® A-CA 2.0 g

Ammonium sulfate 1, 0 g (in 30.0 g of water)

Direct puller DZ 1, 0 g

Water at 100 g

The Stenol ^® 16/18 was melted together with Eumulgin ^® B1 and Dehyquart ^® A-CA, the melt was then emulsified with hot water. Then, the dye and the aqueous ammonium sulfate solution were added. The pH was with ammonia bwz. Citric acid was adjusted to the value given in the table, then it was made up to 100 g with water. 2.1 .3 Anionic coloring cream

Hydrenol ^® D 1, 0 g

Lorol® ^® techn. 1, 0 g

Akypo RLM Soft ^® 45N 1, 1 g

PHB propyl ester 0.1 g

PHB methyl ester 0.1 g

Ammonium sulfate 1, 0 g (in 30.0 g of water)

Direct puller DZ 1, 0 g

Water at 100g

The first five components were melted together. This melt was emulsified with hot water, then it was predissolved in water or predispersed

Dye is added and the ammonium sulfate solution added. The pH value given in the table was adjusted with ammonia or citric acid, after which was added

Water made up to 100 g.

2.1 .4 Anionic coloring cream

Texapon.RTM ^® NSO UP 15.3 g

Hydrenol D ^® 2.5 g

Lorol® ^® (techn.) 4.5 g

Polychol 5 ^® 0.4 g

Dow ^Corning® 345 Fluid 0.1g

Eumulgin O 5 ^® 2.0 g

PHB methyl ester 0.2 g

PHB propyl ester 0.2 g

Polyethylene glycol MG 400 5.0 g

Direct puller DZ 1, 0 g

Ascorbic acid 0.2 g

Sodium bicarbonate 0.5 g

Water ad 100 g

The first 9 components were melted together at 80 ⁰ C, then the Direktzieher invention was added. Ascorbic acid and sodium bicarbonate were dissolved in water while stirring. It was then made up to about 95 g with water while stirring. The pH stated in the table was adjusted with 0.1% sodium hydroxide solution, then made up to 100 g with water.

2.1.5 Anionic dye cream

Texapon ^® NSU-UP 10.0 g

Lorol ^® (techn.) 5.0 g

Emulgade® ^® 1000 Nl 3.0 g Cetiol ^® HE 2.0 g

Dow ^Corning® 580 Wax 1, 0 g

ELFACOS ^® ST 37 2.0 g

PHB methyl ester 0.4 g

PHB propyl ester 0.3 g

1, 2-propanediol 7.5 g

Direct puller DZ 1, 0 g

Carbopol ^® Ultrez 10 1, 0 g

AMP 1, 0 g

Sodium silicate 40/42 5.0 g

Water ad 100 g

The first 8 components were melted together at 80 ⁰ C, then 1, 2-propanediol and the Direktzieher were added with stirring. The following 3 components were dissolved or suspended in one part of the water and also added to the base. With water was made up to about 95 g, the pH stated in the table was adjusted with citric acid or 0.1 percent sodium hydroxide solution. It was then made up to 100 g with stirring with stirring.

2.2 List of raw materials used

Akypo RLM 45 NV ^® lauryl alcohol 4.5 EO acetic acid sodium salt (at least 22% active ingredient content, INCI name: sodium laureth-5 carboxylate) (Chem-Y)

Carbopol ^® Ultrez 10 polyacrylate (INCI name: Carbomer) (Lubrizol) Cetiol ^® HE Coconut monoglyceride with approx. 7.3 EO units (INCI name: PEG-7 Glyceryl Cocoate) (Cognis)

Dehyquart ^® A-CA trimethyl hexadecyl ammonium chloride (approximately 24 -26% active substance; INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis) Dow Corning ^® 345 fluid decamethylcyclopentasiloxane (INCI name: Cyclomethicone) (Dow Corning) Dow Corning ^® 580 Wax mixture of stearoxytrimethylsilane and stearyl alcohol (about 40% stearyl alcohol, INCI name: stearoxytrimethylsilane, stearyl alcohol) (Dow Corning)

Elfacos ^® ST 37 INCI name: PEG-22 / Dodecyl Glycol Copolymer (Akzo) Emulgade ^® 1000 Nl INCI name: (Cetearylalcohol, ceteareth-20) Cognis) Eumulgin ^® B 1 cetylstearyl alcohol with about 12 EO units (INCI -Ceteareth-12) (Cognis)

Eumulgin ^® B2 Cetylstearylalkohol with about 20 EO units (INCI name: Ceteareth-20): ((Cognis) Eumulgin ^® 05 oleyl-cetyl alcohol with about 5 EO units from plants (oleth-5 INCI name) Cognis) Eumulgin ^® RH 40 hardened castor oil with approx. 40 EO units (INCI name: PEG-40 Hydrogenated Castor OiI) (Cognis)

Hydrenol ^® DC ₁₆ -i ₈ fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis) Lorol (techn.f C _12-i ₈ fatty alcohol (INCI name: Coconut Alcohol) (Cognis) Natrosol ^® 250 HR hydroxyethyl cellulose (INCI Designation: hydroxyethylcellulose) (Hercules)

Polychol ^® 5 ethoxylated lanolin alcohol with approx. 5 EO units (INCI name: Laneth-5) (Croda)

Polydiol ^® polyethylene glycol 400 (INCI name: PEG-8) (Cognis) Stenol 1618 ^® C _16-i ₈ fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis) Texapon ^® NSO-UP lauryl ether sulfate, sodium salt (ca. 27 5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)

2.3 dyeing

1, 8 g of the staining cream were applied to a ca. 6 cm long strand of human hair (Kerling

Euronaturhaar, blond) and left there for 30 minutes at 30 ⁰ C. After completion of the

Exposure time, the hair was rinsed, washed with a conventional shampoo and then dried. The hair tresses were dyed in the shades indicated in Table 2.

The number of the coloring cream refers in each case to the corresponding subchapter of paragraph 2.1:

Table 2:

Claims

Patent claims

1. An agent for dyeing and optionally simultaneously lightening keratin fibers, in particular human hair, containing at least one cationic compound of the formula (Ia) ¹

X (Ia) in the

R ^1, R ^2, R ^3, R ⁴ independently represent a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, a Ci-C ₆ hydroxyalkyl group, a C ₂ -C ₆ Polyhydroxyalkyl group, a halogen atom, a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, an alkyloxycarbonyl group or a sulfonic acid group, wherein the two radicals R ¹ and R ² or R ³ and R ⁴ together form another fused, carbocyclic or heterocyclic May form a ring optionally bearing a substituent R ¹² ,

R ⁵ stands for a -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ -

Hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - alkoxy-CrC ₆ alkyl group, an amino -C ₆ alkyl group, a di-C ₁ -C ₆ - alkylamino-C ₂ -C _6- alkyl group, a cyano-CrCe-alkyl group or a substituent of the formulas II to VII ¹ (CHL) n - COOH

^{V 2l} (H)

O

- (CHJn - N-S-R11 2 / II

^R1 ° ° (M) O

- (ChL) n - ^ - O-R11 v ² '(IV)

O R10 Il I - (CH ₂ ) n - SN-R10

⁰ (VI)

O R10 - (ChUn - ^ N-RIO

² (VIl)

R ⁶ and R ⁷ independently represent a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, a C r C ₆ hydroxyalkyl group, a C ₂ -C _e polyhydroxyalkyl group, a halogen atom ( Chloride, bromide, iodide or fluoride), carboxyl group, nitrile group, carbamoyl group, sulfonamido group, carboxamido group, alkyloxycarbonyl group, sulfonic acid group, C ₁ -C ₆ alkoxy group, hydroxy group, amino group or C ₁ -C ₆ - dialkylamino group,

R ¹⁰ and R ¹¹ independently represent a hydrogen atom, a C ₁ -C ₆ - alkyl group, a Ci-C ₆ hydroxyalkyl group, a C ₂ -C ₆ - polyhydroxyalkyl group, a C ₂ -C ₆ alkenyl group, an aryl group or a heteroaryl group,

R ¹² is a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -

Alkenyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a halogen atom, a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, an alkyloxycarbonyl group or a sulfonic acid group and X ^" is a monovalent anion, preferably halide (chloride,

Bromide, iodide or fluoride), hydrogen sulfate, sulfate ^Λ A, ^Λ A tetrachlorozincate, p-benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methane sulfate or methanesulfonate.

2. Means for dyeing and optionally simultaneous brightening of keratinic fibers according to claim 1, characterized in that it comprises at least one cationic compound from the group of

Salts of 9- [4- (dimethylamino) phenyl] -10-methylacridinium,

Salts of 9 - [(4-dimethylamino) phenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (dimethylamino) phenyl] acridinium,

Salts of 9 - [(4-dimethylamino) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (diethylamino) phenyl] -10-methylacridinium,

Salts of 9 - [(4-diethylamino) phenyl] -10-ethylacridinium,

Salts of the 10-allyl-9- [4- (diethylamino) phenyl] acridinium,

Salts of 9 - [(4-diethylamino) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (piperidin-1-yl) phenyl] -10-methylacrylonine,

Salts of 9- [4- (piperidin-1-yl) phenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (piperidin-1-yl) phenyl] acridinium,

Salts of 9- [4- (piperidin-1-yl) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (morpholin-4-yl) phenyl] -10-methylacridinium,

Salts of 9- [4- (morpholin-4-yl) phenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (morpholin-4-yl) phenyl] acridinium,

Salts of 9- [4- (morpholin-4-yl) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (piperazin-1-yl) phenyl] -10-methylacridinium,

Salts of 9- [4- (piperazin-1-yl) phenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (piperazin-1-yl) phenyl] acridinium,

Salts of 9- [4- (piperazin-1-yl) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (4-methylpiperazin-1-yl) phenyl] -10-methylacridinium,

Salts of 9- [4- (4-methylpiperazin-1-yl) phenyl] -10-ethylacridinium,

Salts of the 10-allyl-9- [4- (4-methylpiperazin-1-yl) phenyl] acridinium,

Salts of 9- [4- (pyrrolidin-1-yl) phenyl] -10-methylacridinium,

Salts of 9- [4- (pyrrolidin-1-yl) phenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (pyrrolidin-1-yl) phenyl] acridinium,

Salts of 9- [4- (pyrrolidin-1-yl) phenyl] -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (diethylamino) -2-methoxyphenyl] -10-methylacridinium,

Salts of 9- [4- (diethylamino) -2-methoxyphenyl] -10-ethylacridinium,

Salts of 10-allyl-9- [4- (diethylamino) -2-methoxyphenyl] acridinium, Salts of 9- [4- (diethylamino) -2-methoxyphenyl] -10- (2-hydroxyethyl) acridinium, salts of 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium, Salts of 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-ethylacridinium, salts of 10-allyl-9- {4- [bis (2-hydroxyethyl) amino] phenyl} acridinium, salts of 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10- (2-ydroxyethyl) acridinium, salts of 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-methylacridinium, Salts of 9- {4 - [(2-hydroxyethyl) methylamino] phenyl} -10-ethylacridinium, salts of 10-allyl-9- {4 - [(2-hydroxyethyl) methylamino] phenyl} acridinium, salts of 9 - {4 - [(2-hydroxyethyl) methylamino] phenyl} -10- (2-hydroxyethyl) acridinium,

Salts of 9- [4- (diethylamino) -2-hydroxyphenyl] -10-methylacridinium, salts of 9- [4- (diethylamino) -2-hydroxyphenyl] -10-ethylacridinium, salts of 10-allyl-9- [4 (diethylamino) -2-hydroxyphenyl] acridinium, salts of 9- [4- (diethylamino) -2-hydroxyphenyl] -10- (2-hydroxyethyl) acridinium, salts of 9- [4- (dimethylamino) -3- bromophenyl] -10-methylacridiniums, salts of 9- [4- (dimethylamino) -3-bromophenyl] -10-ethylacridinium, salts of 10-allyl-9- [4- (dimethylamino) -3-bromophenyl] acridinium and / or Salts of 9- [4- (dimethylamino) -3-bromophenyl] -10- (2-hydroxyethyl) acridiniums.

3. An agent for dyeing and optionally simultaneously brightening keratinic fibers according to any one of claims 1 to 2, characterized in that it contains the compound (s) of the formula (Ia) in amounts of 0.001 to 5 wt .-%, preferably of 0.0025 to 2.5 wt .-%, particularly preferably from 0.005 to 1, 5 wt .-% and in particular from 0.01 to 1 wt .-%, each based on the total agent contains.

4. Composition for dyeing and optionally simultaneous lightening of keratinic fibers according to any one of claims 1 to 3, characterized in that it additionally contains - based on its weight - from 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes.

5. An agent for dyeing and optionally simultaneous whitening of keratinic fibers according to any one of claims 1 to 4, characterized in that it is 0.5 to 15 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 2.5 to 10 wt .-% and in particular 3 to 6 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂ ).

6. A process for dyeing and optionally simultaneously lightening keratin fibers, in particular human hair, characterized in that, if desired, a pretreatment agent M1 is applied to the fiber, then a means M2 is applied to the fiber, wherein if desired the

Means M2 is added before use another agent M3, this agent M2 is rinsed from the fiber after a time of 5-30 minutes and, optionally after the treatment, an aftertreatment agent M4 is applied to the fiber and rinsed off again after a reaction time of a few minutes, at least one of the agents M1, M2 or M3 being an agent according to one of claims 1 to 5.

7. The method according to claim 6, characterized in that the application is supported by the action of heat and / or UV radiation during the contact time.

8. Use of cationic compounds of the formula (Ia):

X (Ia) in the

R ^1, R ^2, R ^3, R ⁴ independently represent a hydrogen atom, a Ci-C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, a CRCE-hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a Halogen atom, a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, an alkyloxycarbonyl group or a sulfonic acid group, where the two radicals R ¹ and R ² or R ³ and R ⁴ together can form a further fused, carbocyclic or heterocyclic ring, which optionally bears a substituent R ¹² ,

R ⁵ stands for a C- | -C _e alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ -

Hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - alkoxy-CrC ₆ alkyl group, an amino -C ₆ alkyl group, a di-CrC ₆ - alkylamino-C ₂ -C ₆ alkyl group, a Cyano-dC ₆ -alkyl group or for a substituent of the formulas II to VII. (CH ₉ ) π - COOH

^{V 2>} (H)

O (...)

- (CH,) n - ^ - O- R11 v ² '(IV)

O R10 II I (CH ₉ ) n - SN-R10

^2l Il

⁰ (VI)

O R10 - (CH ₉ ) n - ^ N-RIO

^{V 2} '(VIl)

R ⁶ and R ⁷ independently represent a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, a C r C ₆ hydroxyalkyl group, a C ₂ -C _e polyhydroxyalkyl group, a halogen atom ( chloride, bromide, iodide or fluoride), a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, a Alkyloxycarbonylguppe, a sulfonic acid group, a C ₁ -C ₆ - alkoxy group, a hydroxy group, an amino group or a C ₁ -C ₆ - dialkylamino group,

R ¹⁰ and R ¹¹ independently represent a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C- | -C ₆ hydroxyalkyl group, a C ₂ -C ₆ - polyhydroxyalkyl, C ₂ -C ₆ alkenyl group, a Aryl group or a heteroaryl group,

R ¹² is a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -

X is a monovalent anion, preferably halide (chloride,

Bromide, iodide or fluoride), hydrogen sulfate,> 2 sulfate ^1/2 tetrachlorozincate, p-benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methane sulfate or methanesulfonate. in agents for dyeing and, if appropriate, simultaneous lightening of keratinic fibers.

9. Use according to claim 8 for i. Increase the fastness properties of the dyeings and / or ii. Increase color brilliance and / or iii. Increase the skin compatibility of dye or lightening agents.

10. Cationic compounds of the formula (Ib):

X (Ib) in the either

R ₁ ', R ₂ ', R ₃ ', R ₄ stand for a hydrogen atom

R ₅ 'represents allyl group or a 2-hydroxyethyl group

R ₈ 'and R ₉ ' independently represent a substituent which is defined as R ⁵ or together form a 5-, 6- or 7-membered one Ring which may optionally carry further substituents or heteroatoms,

X ^" is a monovalent anion, preferably halide (chloride,

Bromide, iodide or fluoride), hydrogen sulfate,> 2 sulfate ^1/2 tetrachlorozincate, p-benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methane sulfate, or methanesulfonate, or

R ₁ ', R _2', R ₃ ', R ₄ independently represent a hydrogen atom, a C ₁ -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, a C r C ₆ hydroxyalkyl group, a C ₂ C ₆ polyhydroxyalkyl group, a halogen atom, a carboxyl group, a nitrile group, a carbamoyl group, a sulfonamido group, a carboxamido group, an alkyloxycarbonyl group or a sulfonic acid group, where the two radicals R ¹ and R ² or R ³ and R ⁴ together form a further fused, may form a carbocyclic or heterocyclic ring optionally bearing a substituent R ₁₀ ',

R ₅ 'represents a C-rC _e alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ -

Hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - alkoxy-d-Cβ-alkyl, _{amino-C-ι-C6} alkyl group, a di-C ₁ -C ₆ - alkylamino-C ₂ -C ₆ alkyl group, a cyano-Ci-C ₆ alkyl

R ₆ 'and R ₇ ' independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C _e alkenyl group, a C-rC ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group Halogen atom (chloride, bromide, iodide or fluoride), carboxyl group, nitrile group, carbamoyl group, sulfonamido group, carboxamido group, alkyloxycarbonyl group, sulfonic acid group, C ₁ -C ₆ alkoxy group, hydroxy group, amino group or C ₁ -C ₆ - dialkylamino group,

R ₁₀ 'stands for a hydrogen atom, a dC ₆ alkyl group, a C ₂ -C ₆ -

X ^" is a monovalent anion, preferably halide (chloride,

Bromide, iodide or fluoride), hydrogen sulfate,> 2 sulfate ^1/2 tetrachlorozincate, p-benzenesulfonate, p-toluenesulfonate, acetate, tetrafluoroborate, trifluoromethanesulfonate, hexafluorophosphate, methane sulfate or methanesulfonate.

11. 9- [4- (Diethylamino) -2-methoxyphenyl] -10-methylacridinium p-toluenesulfonate

12. 9- {4- [bis (2-hydroxyethyl) amino] phenyl} -10-methylacridinium p-toluenesulfonate

13. 9- {4 - [(2-Hydroxyethyl) methylamino] phenyl} -10-methylacridinium p-toluenesulfonate

14. 9- [4- (Diethylamino) -2-hydroxyphenyl] -10-methylacridinium p-toluenesulfonate

15. 9- [4- (Dimethylamino) -3-bromophenyl] -10-methylacridinium p-toluenesulfonate

Summary

The present application relates to cationic compounds of the formula (Ia):

X (Ia) with the definitions for R ¹ to R ⁹ and X ^" as in claim 1, which are suitable for coloring keratin fibers, in particular human hair, and are partly not yet described in the prior art itself.

In colorations of these compounds extremely intense shades, especially in the blue and violet area with very good fastness properties are obtained. These direct drawers also provide bright nuances without diminishing color intensity and color brilliance while using oxidants such as hydrogen peroxide or a mixture of hydrogen peroxide and peroxydisulfates.