EP2344113A2

EP2344113A2 - Means for treating keratin fibres containing cationic pyridinium derivatives

Info

Publication number: EP2344113A2
Application number: EP09747847A
Authority: EP
Inventors: Hartmut Manneck; Astrid Kleen; Wibke Gross
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2008-11-12
Filing date: 2009-11-05
Publication date: 2011-07-20
Also published as: WO2010054981A2; WO2010054981A3; DE102008057018A1

Abstract

The present invention relates to means for treating keratin fibers that contain, in a cosmetic carrier, a dying matting combination, which comprises at least one coloring component and is suitable for balancing yellowish and/or reddish color impressions remaining in the fiber in the lightening of the keratin fibers by a corresponding complementary dying, and at least one cationic pyridinium derivative. The invention further relates to such means for gently dying human hair blond, additionally containing at least one oxidant preparation and possibly a bleaching power enhancer preparation, to a method for the application thereof, and to the use of the means as gentle bleaching agents. Using the means according to the invention, it is also possible to avoid undesirable color shifts in yellowish and reddish nuances when dying hair blond.

Description

Combination of cationic bleach activators and dyes

The present application relates to combinations of additives for matting bleaches of keratinic fibers, in particular human hair, and also enhancers of the bleaching power of oxidizing agents for bleaching keratinic fibers, in particular human hair, based on specific, cationic pyridinium derivatives. Furthermore, gentle means for bleaching keratinic fibers are disclosed without undesirable color shift in yellow to reddish shades. In addition, a use for bleaching keratinic fibers without undesired color shift and a method for bleaching using the agent according to the invention are described.

Changing the shape and color of the hair is an important area of modern cosmetics. This allows the hair's appearance to be adapted to current fashion trends as well as to the individual wishes of the individual. In this case, permanent wave and other hair-changing methods can be used almost independently of the type of hair to be treated. In contrast, dyeing and in particular bleaching processes are limited to certain initial hair colors. So for lightening procedures, the so-called Blondierverfahren, essentially only dark blond or lighter hair. Especially for blondes of darker source hair colors, there is still a need for powerful methods. The basics of the Blondierverfahren are known in the art and in relevant monographs, eg. B. by K. Schrader, Foundations and formulations of cosmetics, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Limbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, described in summary.

In addition to coloring, brightening one's own hair color or bleaching is the very special wish of many consumers, as a blonde hair color is considered attractive and fashionable in terms of desirable. For this purpose, various Blondiermittel with different Blondierleistung are available in the market. In order to achieve a sufficient Blondierwirkung, such agents are usually adjusted strongly alkaline, the pH is between 9 and 10.5. Such high pH levels are required to ensure an opening of the outer cuticle (cuticle) and thus allow penetration of the active species, usually hydrogen peroxide, into the hair. The alkalizing agent used is usually ammonia, which however has the known disadvantage of unpleasant odor and possible irritation. In the past, alternative alkalizing agents were often used which, although admixed with ammonia, gave acceptable bleaching performance, but could not completely replace it. It therefore remained so far desire to reduce the ammonia concentration without sacrificing the

Blondierleistung the means to have to accept.

The oxidants contained in these products are able to lighten the hair fiber by the oxidative destruction of the hair dye melanin. For a moderate blonding effect, the use of hydrogen peroxide - optionally with the use of ammonia or other alkalizing agents - is sufficient as the oxidant alone. In order to achieve large color differences in the bleaching process, ie in particular to discolor dark or black hair, in addition to the already mentioned hydrogen peroxide preparations, in most cases additional bleach activators such as persalts are required as additional peroxide sources, and / or carbonates as additional alkalizing agents.

Therefore, the bleaching of dark-colored hair poses a particular challenge. The natural hair color is determined by melamine in the hair fiber cortex, the ratio of the two pigment classes, eumelanins with brownish-black tones and pheomelanins with reddish-orange tones, the actual hair color certainly. Usually, during the bleaching process, the natural melanin dyes are destroyed by oxidative action and thus a decolorization of the fibers is achieved. However, hairs are not uniformly decolorized due to different oxidative destruction rates of the various melanin pigment classes. In darker fibers with high melanin content usually a certain proportion of natural dyes remains, which is often reflected in yellowish to reddish nuances. Therefore, especially when bleaching darker hair, there is a color shift towards warm tones.

Color shifts in the direction of warm tones are usually undesirable for the users. Therefore, this color shift is usually counteracted by a coloring with the corresponding complementary color according to the theory of colors. The aim is a silvery-cool impression of the bleaching result. The expert speaks in this context of a matting. Depending on the initial hair color, a suitable matting colorant mixture must be used in order to compensate for redder color shifts due to greenish matting agents or yellowish color shifts due to rather violet matting agents.

Under the aggressive conditions (strong oxidizing agents, high pH) of the lightening preparation, the usually used, matting colorants are usually not sufficiently stable. Therefore, the bleaching step and the matting step are usually carried out sequentially. For reasons of ease of use, however, a single-stage bleaching, which already includes the matting color balance of the unwanted warm tones, is particularly advantageous.

In addition, the oxidative whitening is accompanied by damage to the hair, since not only the natural coloring components of the hair but also the other structural components of the hair are damaged. components of the hair are oxidatively damaged. Depending on the severity of the degree of damage, this ranges from rough, brittle and difficult to comb hair over a reduced resistance and tear resistance of the hair to hair breakage. The greater the amount of hydrogen peroxide used and, where appropriate, the peroxodisulfates, the greater the damage is usually caused on the keratin fiber. Brightening agents which show good brightening performance without simultaneously damaging the hair fiber are not yet known.

For bleaching human hair, solid or paste-like preparations with solid oxidizing agents are usually mixed with a dilute hydrogen peroxide solution immediately before use. This mixture is then applied to the hair and rinsed again after a certain exposure time. The exposure time on the hair to achieve a complete whitening lightening is between about 30 and 60 minutes.

Although bleaching agents hitherto on the market generally show good lightening performance, they can not be considered optimal due to hair damage, long application times and the possible skin irritation due to the high concentrations of oxidizing and alkalizing agents. There is therefore a need for bleaching agents which achieve a good color balance by the addition of stable matting components in the application preparation and at the same time cause the least possible damage to the hair.

In the course of its investigations, the Applicant has now surprisingly found that the mixture of a Mattierungskombination to compensate for the remaining with the lightening of keratinous fibers undesirable warm tones with special, cationic pyridinium derivatives excellent for matting Blondier- and / or lightening agents for keratinic fibers, especially human Hair, with little hair damage is suitable.

A first subject of the present invention is therefore an agent for the treatment of keratinic fibers which is characterized in that it comprises in a cosmetic carrier a) at least one coloring matting combination which comprises at least one coloring component and which is suitable for lightening the keratinic fiber to compensate for yellowish and / or reddish color impressions remaining in the fiber by a corresponding complementary coloring, b) and contains at least one cationic pyridinium derivative according to formula (I),

wherein L is a CH ₂ -CH ₂ or a C (R 5) = CH unit, in which R 5 is hydrogen, a C ₁ -C ₄ -alkyl group, a partially or completely halogenated C ₁ -C ₆ -alkyl group, C- | -C ₆ alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono- _(C-ι-C6 alkyl) amino group, a di- (C ₁ -C ₆ - alkyl) amino group, a C ₂ -C ₆ acylamino group, a halogen or an acyl group R'C (O), where R 'is a C ₁ -C ₄ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C ₁ -C _6- alkoxy-C ₂ -C ₆ -alkyl group,

R1 represents a _C-ι-C6 alkyl group, a partially or completely halogenated C ₁ -C ₆ -

Alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, a C-rC ₆ -alkoxy-C ₂ -C ₆ alkyl group, a carboxy-CrCβ-alkyl group, an aryl C-rC ₆ alkyl group, an amino C ₂ -C ₆ alkyl group, a mono (C 1 -C ₆ alkyl) amino C ₂ -C ₆ alkyl group, a di- (C 1 -C ₆ alkyl) aminoC C ₂ -C ₆ -alkyl group, a heteroarylCrC ₆ -alkyl group, a 3-oxobutyl group, a 2-oxopropyl group, an aryl group or a heteroaryl group,

R2 and R4 are each independently hydrogen, _C-ι-C4 alkyl group, a partially or completely halogenated C-ι-C ₆ alkyl, C ₁ -C ₆ -AIkOXy- group, a hydroxy group, a nitrile group, a Amino group, one a C _Σ -Ce-acylamino group, a halogen or an acyl group R'C (O), where R 'is a C ₁ -C ₄ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C 1 -C ₆ - Alkoxy-C ₂ -C ₆ alkyl group, and R 3 is hydrogen, a C ₁ -C ₄ alkyl group, a partially or fully halogenated C-ι-C ₆ alkyl group, C-ι-C ₆ alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono- _(C-ι-C6 alkyl) amino group, a di- (C.rC ₆ alkyl) amino group, a C ₂ -C ₆ acylamino group or a halogen with the proviso that at least one of R2, R4 or R5 is an acyl group R'C (O), wherein R 'is a C-ι-C ₄ alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C-ι-C ₆ -alkoxy-C ₂ -C ₆ alkyl group, or

And R2 together form a fused cyclus six membered aromatic carbocycle, R3 optionally additionally carries 1 to 3 substituents independently selected from C- | -C ₆ alkyl group, partially or completely halogenated C-ι-C ₆ alkyl , C ₂ -C ₆ alkenyl group, hydroxy group, amino group, mono- _(C-ι-C6 alkyl) amino group, di (C ₁ -C ₆ - alkyl) amino group, C ₁ -C ₆ -alkyl koxygruppe, Halogen, nitro group, nitrile group, carboxy group, optionally substituted aryl, or optionally substituted heteroaryl, and R _{4 is} hydrogen, a C 1 -C ₄ -alkyl group, a partially or completely halogenated C ₁ -C ₆ -alkyl group, C 1 -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono (C.rC ₆ alkyl) amino group, a Di- (C ₁ -C ₆ -alkyl) -amino group, a C ₂ -C ₆ -acylamino group, a halogen or an acyl group R'C (O) wherein R 'is a C 1 -C ₄ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C 1 -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, and the anion X ^"is a physiologically acceptable anion.

According to the invention, keratin-containing or keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair. Although the compositions according to the invention are suitable in the first place for dyeing and / or lightening keratin-containing fibers, in principle there is no obstacle to their use also in other fields.

The agents according to the invention contain the active ingredients in a cosmetic carrier. For the purposes of the invention, this cosmetic carrier is aqueous, alcoholic or aqueous-alcoholic. 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. For the purposes of the present invention, aqueous-alcoholic carriers are to be understood as meaning water-containing compositions containing from 3 to 70% by weight of a C 1 -C ₄ -alcohol, based on the total weight of the application mixture, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents, such as 4-methoxybutanol, ethyldiglycol, 1, 2-propylene glycol, n-propanol, n-butanol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, and diethylene glycol mono-n-butyl ether. Preference is given to all water-soluble organic solvents. For the purposes of the invention, an aqueous carrier contains at least 30% by weight, in particular at least 50% by weight, of water, based on the total weight of the application mixture.

As a mandatory ingredient comprises means, at least one coloring Mattierungskombination comprising at least one coloring component and which is adapted to compensate for the lightening of the keratin fiber in the fiber remaining yellowish and / or reddish color impressions by a corresponding complementary coloring.

As a rule, mixtures of different coloring components are particularly suitable for this, since in general the color balance can be precisely adjusted by small variations in the composition of the mixture.

For this purpose, it is crucial to match the amount and the ratio of the coloring components to each other precisely to achieve only a color balance to silvery cold tones, but not to achieve a coloration in the traditional sense of hair dyes.

Conventionally, therefore, significantly smaller amounts of coloring components are used, preferably less than 1.0% by weight, particularly preferably less than 0.5% by weight, of all colorants. giving components, each based on the total weight of the invention

Agent.

The coloring matting combination contains at least one color-changing component which is preferably selected (1) from at least one oxidation dye precursor and / or (2) from at least one substantive dye.

According to preferred means for mattifying lightening keratinischer fibers are therefore characterized in that they contain at least one oxidation dye precursor of the developer type and / or coupler type.

The mattifying brightening agents according to the invention comprise as oxidation dye precursors at least one coupler and at least one developer component. In addition, the mattifying brightening agents according to the invention may also contain substantive dyes as nuances.

Preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1, 2-dihydroxyethyl) -p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole-1 -yl) - propyl] amine, N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1, 3-diamino-propan-2-ol, 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- (1,2-dihydroxyethyl) phenol, 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4- Hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, and their physiologically acceptable salts. Particularly preferred developer components are p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H-imidazol-1-yl) propyl] amine, and / or 4,5-diamino-1- (2-hydroxyethyl) pyrazole and their physiologically acceptable salts. The developer components are preferably used in an amount of 0.0001 to 0.5 wt .-%, preferably 0.001 to 0.2 wt .-%, each based on the ready-to-use matting brightener.

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 developer component is additionally used when using at least one coupler component.

Preferred coupler components according to the invention are selected from 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5 Amino-4-chloro-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-amino-phenol, 2-aminophenol, 3-phenylenediamine, 2- (2,4 Diaminophenoxy) ethanol, 1, 3-bis (2,4-diamino phenoxy) 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) amino] -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) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2-hydroxyethyl) aminobenzene, resorcinol, 2 -Methylresorcinol, 4-chlororesorcinol, 1, 2,4-trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethyl-pyridine, 3 , 5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1, 5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1, 7-dihydroxynaphtha lin, 1, 8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or their physiologically acceptable salts. Particularly preferred is resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol, 3-aminophenol, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-methoxy -2- amino-4- (2'-hydroxyethylamino) benzene, 2-amino-3-hydroxypyridine and 1-naphthol and one of their physiologically acceptable salts. The coupler components are preferably used in an amount of 0.0001 to 0.5 wt .-%, preferably 0.001 to 0.2 wt .-%, each based on the ready-for-use matting brightener.

Furthermore, the agents according to the invention may contain at least one 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 0.0001 to 0.2 wt .-%, preferably from 0.001 to 0.1 wt .-%, each based on the total application preparation. The total amount of substantive dyes is preferably at most 0.1 wt .-%. Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes.

Particularly suitable anionic direct dyes are 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CI 15.985, Food Yellow No. 3, FD & C Yellow No. 6), 2,4-dinitro 1-naphthol-7-sulfonic acid disodium salt (Cl.10.316; Acid Yellow 1, Food Yellow No. 1), 2- (indan-1, 3-dion-2-yl) quinoline-x, x-sulfonic acid (mixture of Mono- and disulphonic acid) (Cl.47,005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 4 - ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid disodium salt ( CI 13,015, Acid Yellow 9), 5-hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (CI 19,140, Food Yellow No. 4 Acid Yellow 23), 3 - [(4-phenylamino) phenyl] azobenzenesulfonic acid, sodium salt (CI 13.065, Ki406, Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one (Cl.45, 350; Acid Yellow 73; D & C Yellow No. 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzenesulfonic acid, sodium salt (Cl.10, 385; Acid Orange 3), 4 - [(2, 4- Diy droxyphenyl) azo] benzenesulfonic acid sodium salt (CI 14,270, Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (CI 15,510, Acid Orange 7), 4 - [(2,4-dihydroxy-3 [(2,4-dimethylphenyl) azo] -phenyl) -azo] -benzenesulfonic acid, sodium salt (CI 20,170; Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo] -1- naphthalenesulfonic acid sodium salt (Cl 14.710; Acid Red 4), 4-hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid disodium salt (Cl 14.720; Acid Red No.14) , 6-Hydroxy-5 - [(4-sulfonaphth-1-yl) azo] -2,4-naphthalene-disulfonic acid trisodium salt (Cl 16,255, Ponceau 4R, Acid Red 18), 3-hydroxy-4 - [( 4-sulfonaphth-1-yl) azo] -2,7-naphthalenedisulfonic acid trisodium salt (Cl.16.185, Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalene disulfonic acid disodium salt (CI 17,200, Acid Red 33, Red 33), 5- (2-methylphenyl) azo] -2,7-naphthalenedisulfonic acid disodium salt (Cl Acid Red 35), 2- (3-hydroxy-2,4,5,7-tetraiodo-dibenzopyran-6-on-9-yl) -benzoic acid d Sodium salt (Cl. 45,430; Acid Red 51), N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthen-3-ylidene] -N-ethylethanammonium hydroxide, inner salt, sodium salt (CI 45, 100; Acid Red 52), 8 - [(4- (phenylazo) phenyl) azo] -7-naphthol-1,3-disulphonic acid disodium salt (CI 27,290; Acid Red 73), 2 ', 4', 5 ', 7'- Tetrabromo-3 ', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9' - [9H] xanthene] -3-one disodium salt (Cl.45, 380; Acid Red 87), 2 ', 4', 5 ', 7'-tetrabromo-4,5,6,7-tetrachloro-3', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9 '[9H] xanthene] -3-one disodium salt (CI 45.410; Acid Red 92), 3 ', 6'-dihydroxy-4', 5'-diiodospiro [isobenzofuran-1 (3H), 9 '(9H) -xanthen] -3-one disodium salt (CI 45425; Acid Red 95 ), 2-hydroxy-3 - ((2-hydroxy-naphth-1-yl) azo) -5-nitrobenzenesulfonic acid, sodium salt (Cl 15.655, Acid Red 184), 3-hydroxy-4- (3-methyl-5 oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylazo) -naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red 195), 3-hydroxy-4 - [(4- methyl-2-sulfonphenyl) azo] -2-naphthalenecarboxylic acid calcium salt (Cl 15.850: 1; P Pigment Red 57: 1), 3 - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt (Cl. 14,700; Food Red No. 1 ; Ponceau SX; FD & C Red No. 4), 1, 4-bis [(2-sulfo-4-methylphenyl) amino] -9,10-anthraquinone disodium salt (Cl. 61, 570; Acid Green 25), bis [4- (dimethylamino) phenyl] - (3,7-disulfo-2-hydroxynaphth-1-yl) - carbenium inner salt, sodium salt (CI 44,090, Food Green No. 4, Acid Green 50), bis [4- (diethylamino) -phenyl] (2 , 4-disulfophenyl) carbenium inner salt, sodium salt (2: 1) (CI 42.045, Food Blue No. 3, Acid Blue 1), bis [4- (diethylamino) phenyl] (5-hydroxy-2,4- disulfophenyl) - carbenium inner salt, calcium salt (2: 1) (CI 42,051, Acid Blue 3), N- [4 - [(2,4-disulfophenyl) [4- [ethyl (phenylmethyl) amino) phenyl] methylene ] -2,5-cyclohexadien-1-ylidene] -N-ethylbenzenemethanamine hydroxide, inner salt, sodium salt (CI 42.080, Acid Blue 7), (2-sulfophenyl) di [4- (ethyl- (4 betaine (CI 42.090, Acid Blue 9, FD & C Blue No. 1), 1-amino-4- (phenylamino) -9,10-anthraquinone-2-sulfonic acid ( Cl., 62, 555; Acid Blue 25), i-amino-cyclohexylamino, ^, -o-anthraquinone-sulfonic acid natri umsalz (Cl. 62045; Acid Blue 62), 2- (1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene) -2,3-dihydro-3-oxo-1H-indole-5-sulfonic acid disodium salt (CI 73.015, Acid Blue 74), 9- (2-carboxyphenyl) -3 - [(2-methylphenyl) -amino] -6 - [(2-methyl-4-sulfophenyl) amino] xanthylium inner salt. Sodium salt (Cl.45, 190; Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone, sodium salt (Cl.60,730; D & C Violet No. 2; Acid Violet 43), bis [3-nitro-4 - [(4-phenylamino) -3-sulfophenylamino] -phenyl] -sulfone (Cl 10.410, Acid Brown 13), 5-amino-4-hydroxy-6- [ (4-nitrophenyl) -azo] -3- (phenylazo) -2,7-naphthalenedisulfonic acid disodium salt (CI 20,470, Acid Black 1), 3-hydroxy-4- [^ -hydroxynaphth-i-y-azol -nitro-i-naphthalenesulfonic acid-chromium complex (3: 2) (Cl 15.711;

Acid Black 52), 4- (acetylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl) azo] -1-naphthalenedisulfonic acid tetrasodium salt (Cl Food Black No. 1), 3 ', 3 ", 5', 5" -tetrabromophenolsulfonphthalein (bromophenol blue), 3 ', 3 ", 4,5,5', 5", 6,7-octabromophenolsulfonephthalein (tetrabromophenol blue).

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 1 1 are called. The compounds which are also 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) aminophenol, 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 e and 2-chloro-6-ethylamino-4-nitro-phenol. 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 they do not adversely affect the staining or other reasons, such as toxicological, must be excluded.

Furthermore, as direct dyes also naturally occurring dyes can be used, as for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, brownwood, mallow, madder root, catechu and alkano root are included.

In a preferred embodiment of the present invention, the composition of the invention comprises a coloring matting combination comprising a combination of at least one blue direct dye and one red direct dye, wherein the weight ratio between the sum of all blue substantive dyes and the sum of all red substantive dyes is one of greater than or equal to 1.

This makes it possible to avoid unwanted color shifts towards pink / rose nuances.

Agents preferred according to the invention are characterized in that the total weight of all blue direct dyes is greater than the total weight of all red substantive dyes. Preferred agents are therefore characterized in that the weight ratio between the sum of all blue direct dyes and the sum of all red direct dyes has a value of 1 to 100, preferably from 1, 5 to 10 and particularly preferably from 2 to 4.

In principle, there are no limits to the choice of substantive dyes. However, it is particularly advantageous according to the invention if the substantive dyes have a sufficient stability to the conditions of the bleaching process. Preferably, the agent in the coloring matting combination contains as blue direct-dyeing dye at least one anionic substantive dye.

In a preferred embodiment, the agent contains at least one compound according to formula (I) and / or one of its physiologically tolerable salts as a blue direct-acting dye wherein

R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 are each independently hydrogen, fluoro,

Chlorine, bromine, iodine, a hydroxy group or a nitro group.

Depending on the pH of the agent, the compound according to formula (II) is in deprotonated form as one of its physiologically acceptable salts. Physiologically acceptable salts are alkali metal, alkaline earth metal or ammonium salts, it being possible to use both ammonium itself and also primary, secondary, tertiary or quaternary ammonium salts. These include, for example, the salts of the cations 2-hydroxyethylammonium, di (2-hydroxyethyl) ammonium, tri (2-hydroxyethyl) ammonium, triethylammonium and tetraethylammonium. Preferred salts of the compound according to formula (II) are sodium, potassium, magnesium, calcium and ammonium salts.

Furthermore, compounds of the formula (I) are pH-dependent in tautomeric equilibrium with their cyclized form of the formula (IIa) and / or one of their physiologically tolerable salts.

(II) (IIa)

Both structural formulas (II) and (IIa) therefore represent the same compound according to the invention.

Preferred agents contain as blue direct dye a compound according to formula (II) and / or one of its physiologically acceptable salts, wherein at least one of the substituents R 1, R 2, R 3 and / or R 4 is fluorine, chlorine, bromine or iodine.

Particularly preferred agents are characterized in that the agent contains as blue direct-dye at least one compound which is selected from the A group which is formed from compounds of the formula (II) and / or one of their physiologically tolerable salts in which a) R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 are bromine, b) R 1, R 4, R 5 , R6, R7 and R8 are bromine and R2 and R3 are hydrogen, c) R1 and R4 are hydrogen and R2, R3, R5, R6, R7 and R8 are bromine, d) R1, R2, R3 and R4 are fluorine and R5, R6, R7 and R8 are bromo, e) R1, R2, R3 and R4 are chlorine and R5, R6, R7 and R8 are bromine, f) R1, R2, R3 and R4 are iodine and R5, R6 , R7 and R8 are bromine, g) R1, R2, R3, R4, R5, R6, R7 and R8 are chlorine, h) R1, R2, R3 and R4 are bromine and R5, R6, R7 and R8 are chlorine i) R 1 and R 4 are hydrogen, R 5, R 6, R 7 and R 8 are chlorine, R 1 and R 4 are hydrogen, R 2 and R 3 are bromine and R 5, R 6, R 7 and R 8 are chlorine k) R1, R2, R3 and R4 are iodine and R5, R6, R7 and R8 are chlorine,

I) R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 are iodine, m) R 1, R 2, R 3 and R 4 are fluorine and R 5, R 6, R 7 and R 8 are iodine, n) R 1, R 2, R3 and R4 are chlorine and R5, R6, R7 and R8 are iodine or o) R1, R2, R3 and R4 are bromine and R5, R6, R7 and R8 are iodine.

It is very particularly preferred if the agent contains a compound according to formula (II) and / or one of its physiologically tolerable salts in which the radicals R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 are bromine. This compound is also known by the names 3 ', 3 ", 4, 5, 5', 5", 6,7-octabromophenolsulfonephthalein or tetrabromophenol blue.

Preferably, the agent contains at least one anionic substantive dye as red direct-acting dye, preferably from the group of fluorescein dyes.

In a preferred embodiment, the agent contains as red substantive dye at least one compound according to formula (III) and / or one of its physiologically acceptable salts

wherein R9, R10, R11, R12, R13, R14, R15 and R16 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, a hydroxy group or a nitro group.

Depending on the pH of the agent, the compound of the formula (III) is present in deprotonated form as one of its physiologically tolerable salts. Physiologically acceptable salts are alkali metal metal, alkaline earth metal or ammonium salts, wherein both ammonium itself as well as primary, secondary, tertiary or quaternary substituted ammonium salts can be used. These include, for example, the salts of the cations 2-hydroxyethylammonium, di (2-hydroxyethyl) ammonium, tri (2-hydroxyethyl) ammonium, triethylammonium and tetraethylammonium. Preferred salts of the compound according to formula (I) are sodium, potassium, magnesium, calcium and ammonium salts.

Furthermore, compounds of the formula (III) are pH-dependent in tautomeric equilibrium with their cyclized form of the formula (IIIa) and / or one of their physiologically tolerable salts.

(IM)

Both structural formulas (IM) and (IMa) therefore represent the same compound according to the invention.

Preferred agents contain as red substantive dye, a compound according to formula (III) and / or one of its physiologically acceptable salts, wherein at least one of the substituents R9, R10, R1 and / or R12 is hydrogen, chlorine, bromine or iodine.

Particularly preferred agents are characterized in that the agent contains as red direct substantive dye at least one compound which is selected from the group which is formed from compounds of the formula (III) and / or one of their physiologically tolerable salts, in which a) R9, R10, R11 and R12 are chlorine and R13, R14, R15 and R16 are bromine (known as Acid Red 92), b) R9 and R12 are chlorine, R11 and R12 are hydrogen and R13, R14, R15 and R16 are bromine (known as Acid Red 98), c) R9, R10, R11 and R12 are chlorine and R13, R14, R15 and R16 are iodine (known as Acid Red 94), d) R9, R10, R11 and R12 are hydrogen and R13, R14, R15 and R16 are bromo (known as Acid Red 87), or e) R9, R10, R11 and R12 are hydrogen and R13, R14, R15 and R16 are iodine (known as Acid Red 51).

It is very particularly preferred if the agent contains a compound of the formula (III) and / or one of its physiologically tolerable salts in which the radicals R 9, R 10, R 1 and R 12 are Chlorine and R13, R14, R15 and R16 for bromine (known as Acid Red 92). This compound is also known under the name D & C RED no. 28 or phloxin B known.

Dye combinations preferred according to the invention are those which contain at least the combination of tetrabromophenol blue and Acid Red 92; Tetrabromophenol blue and Acid Red 98, tetrabromophenol blue and Acid Red 94; Tetrabromphenol Blue and Acid Red 87 or Tetrabromphenol Blue and Acid Red 51. Very particularly preferred is a dye combination comprising at least one combination of a compound according to formula (II) in which R1, R2, R3, R4, R5, R6, R7 and R8 is bromine, and a compound of formula (IM) wherein R 9, R 10, R 11 and R 12 is chloro and R 13, R 14, R 15 and R 16 is bromo (tetrabromophenol blue and Acid Red 92).

It may further be preferred according to the invention if the agent contains further substantive dyes. The agent particularly preferably contains, as further substantive dye, a yellow and / or orange dye.

This is particularly advantageous if undesirable reddish color shifts occur during the bleaching process.

Preferably, the yellow dyes are selected from suitable yellow nitro dyes, such as 1, 2-diamino-4-nitrobenzene (CI. 76,020), 1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow 2), 1- (2 -Hydroxyethoxy) -2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 4), 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 5), 4- [(2,3-Dihydroxypropyl) amino] -3-nitro-1-trifluoromethylbenzene (HC Yellow 6), 2- [di (2-hydroxyethyl) amino] -5-nitrophenol, 2 - [(2-hydroxy ethyl) amino] -1-methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, 2-amino-4-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2-hydroxyethoxy) - 3-methylamino-4-nitrobenzene, 2,3- (dihydroxypropoxy) -3-methylamino-4-nitrobenzene, 3 - [(2-aminoethyl) amino] -1-methoxy-4-nitrobenzene hydrochloride (HC Yellow 9), 1-Chloro-2,4-bis [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow 10), 2 - [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow 11), 1 - [(2'-Ureidoethyl) amino] -4-nitrobenzene, 1-amino-4 - [(2-aminoethyl) amino] -5-methyl-2-nitrobenzene, 4 - [(2-hydroxy ethyl) amino] -3-nitro-1-methylbenzene, 1-chloro-4 - [(2-hydroxyethyl) amino] -3-nitrobenzene (HC Yellow 12), 4 - [(2-hydroxyethyl) amino] -3- nitro-1-trifluoromethylbenzene (HC Yellow 13), 4 - [(2-hydroxyethyl) amino] -3-nitrobenzonitrile (HC Yellow 14), 4 - [(2-hydroxyethyl) amino] -3-nitro benzamide (HC Yellow 15) 3 - [(2-hydroxyethyl) amino] -4-methyl-1-nitrobenzene, 4-chloro-3 - [(2-hydroxyethyl) amino] -1-nitrobenzene. Suitable yellow or orange quinone dyes are in particular 2 - [(2-aminoethyl) amino] -9,10-anthraquinone (HC Orange 5) and 2-hydroxy-1,4-naphthoquinone (CI 75,480, Natural Orange 6). Neutral, yellow or orange azo dyes can also advantageously be used according to the invention, in particular 4 - [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] -3-methylbenzene (HC Yellow 7), 2,6- Diamino-3 - [(pyridin-3-yl) azo] pyridine, 2 - {[4- (acetylamino) phenyl] azo} -4-methylphenol (CI 11855, Disperse Yellow 3), 4 - [(4-nitrophenyl ) azo] -aniline (CI 11, 005; Disperse Orange 3). As yellow or orange, anionic substantive dyes are in particular 6-hydroxy-5 [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (Cl 15.9855, Food Yellow No. 3, FD & C

Yellow No. 6), 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (Cl 10,316, Acid Yellow 1, Food Yellow No. 1), 2- (indan-1, 3-dion-2-yl) quinoline -x, x-sulfonic acid (mixture of mono- and disulfonic acid) (Cl 47,005, D & C Yellow No. 10, Food Yellow No. 13, Acid Yellow 3, Yellow 10), 4 - ((4-amino-3-sulfophenyl azo) benzenesulfonic acid disodium salt (CI 13,015, Acid Yellow 9), 5-hydroxy-1- (4-sulfophenyl) -4 - [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt (Cl.

19,140; Food Yellow No. 4; Acid Yellow 23), 3 - [(4-phenylamino) phenyl] azobenzenesulfonic acid sodium salt (CI 13.065, Ki406, Acid Yellow 36), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthene-3-one (J. Cl.45, 350; Acid Yellow 73; D & C Yellow No. 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzenesulfonic acid, sodium salt (Cl.10, 385; Acid Orange 3), 4 - [(2 , 4-Dihydroxyphenyl) azo] benzenesulfonic acid, sodium salt (CI 14,270, Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (CI 15, 510, Acid Orange 7), 4 - [(2,4-Dihydroxy-3 - [(2,4-dimethylphenyl) azo] -phenyl) azo] benzenesulfonic acid, sodium salt (CI 20,170; Acid Orange 24). Suitable cationic substantive dyes are in particular 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzenaminium chloride (CI 12,605, Basic Orange 69), di [4- (dimethyl) amino) phenyl] iminomethane hydrochloride (CI 41, 000; Basic Yellow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indole 1-ium chloride (Cl 48.055, Basic Yellow 11), 3-methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (Cl 12.719; Basic Yellow 57). Preferred yellow or orange, cationic substantive dyes are Basic Yellow 87 and Basic Orange 31.

Particularly preferred yellow or orange, 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 Yellow 13, HC Orange 1 and Disperse Orange 3, especially HC Yellow 13.

As a further obligatory component, the agents according to the invention comprise at least one cationic pyridinium derivative according to formula (I),

wherein

L is a CH ₂ -CH ₂ or a C (R 5) = CH unit, in which R 5 is hydrogen, a C 1 -C 4 -alkyl group, a partially or completely halogenated C ₁ -C ₆ -alkyl group, C-rC ₆ - Alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono (CC ₆ alkyl) amino group, a di (C ₁ -C ₆ alkyl) amino group, a C ₂ -C ₆ acylamino group, a halogen or an acyl group R'C (O), where R 'is a C ₁ -C ₄ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ - alkyl group is, R 1 is a C ₁ -C ₆ -alkyl group, a partially or completely halogenated CrC ₆ -

Alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkyl hydroxyalkyl group, a -C ₆ -alkoxy-C ₂ -C _6, a carboxy-CrCβ-alkyl group, an aryl Ci-Cβ alkyl group, an amino C ₂ -C ₆ alkyl group, a mono- (-C ₆ alkyl) - amino-C ₂ -C ₆ alkyl group, a di- (C-ι-C ₆ alkyl) amino-C ₂ -C ₆ -alkyl group, a heteroaryl-CrCβ-alkyl group, a 3-oxobutyl group, a 2-oxopropyl group, an aryl group or a heteroaryl group,

R2 and R4 are each independently hydrogen, a dC ^ alkyl group, a partially or fully halogenated -C ₆ alkyl group, C ₁ -C ₆ -AIkOXy- group, a hydroxy group, a nitrile group, an amino group, a mono- (CrC ₆ - Alkyl) -amino group, a di- (C 1 -C ₆ -alkyl) -amino group, a C _Σ -Ce -acylamino group, a halogen or an acyl group R'C (O), where R 'is a C 1 -C ₄ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, and R 3 is hydrogen, a C ₁ -C ₄ -alkyl group, a partially or completely halogenated C ₁ -C ₆ -alkyl group C ₁ -C ₆ alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono (C 1 -C ₆ alkyl) amino group, a di- (C 1 -C ₆ alkyl) amino group, a C ₂ -C ₆ acylamino group or a halogen, with the proviso that at least one of the radicals R ₂ , R 4 or R 5 is an acyl group R'C (O), where R 'is a C ₁ -C ₄ alkyl group, a C ₂ - C ₆ - hydroxyalkyl kylgruppe or a C-ι-C ₆ alkoxy-C ₂ -C ₆ alkyl group, or

R 2 and R 3 together form a fused six-membered aromatic carbocycle optionally additionally having 1 to 3 substituents which are selected independently of one another from C 1 -C ₆ -alkyl group, partially or completely halogenated C ₁ -C ₆ -alkyl group, C ₂ - C ₆ alkenyl group, hydroxy group, amino group, mono- (Ci-C ₆ alkyl) amino, di- (CrC ₆ - alkyl) amino, Ci-C ₆ alkoxy, halogen, nitro group, nitrile group, carboxyl group, optionally substituted aryl , or optionally substituted heteroaryl, and R4 is hydrogen, a C 1 -C ₄ -alkyl group, a partially or fully halogenated C 1 -C ₆ -alkyl group, C 1 -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group , a mono- (C ₁ -C ₆ -alkyl) -amino group, a di- (C ₁ -C ₆ -alkyl) -amino group, a C _Σ -Ce-acylamino group, a halogen or an acyl group R'C (O), in which R 'is a C ₁ -C ₄ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, and the anion X ^"is a physiologically acceptable anion.

This is able to significantly increase the bleaching effect in the brightening agents as bleaching power boosters, without causing increased hair damage. Alternatively, at the Use of such cationic pyridinium derivatives to the addition of further bleach booster partially or completely dispensed or the amount of oxidant can be reduced without having to accept losses in the whitening effect. This leads to a reduction of the hair damage with constant brightening performance.

In the following, examples of the radicals mentioned as substituents of the compounds of the formula (I) are listed:

Examples of C 1 -C ₄ -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ ,

-CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ .

Examples of C _r C ₆ -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ ,

-CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , - (CH ₂ ) ₄ CH ₃ , - ( CH ₂ ) ₅ CH ₃ .

Particularly preferred alkyl radicals are methyl and ethyl.

Examples of partially or completely halogenated C ₁ -C ₆ -alkyl radicals are the groups -CH ₂ F,

-CH ₂ Cl, -CF ₃ , -CH ₂ CF ₃ , -CF ₂ CF ₃ or -CH (CF ₃ ) ₂ , in particular -CF ₃ .

Examples of a C ₂ -C ₆ alkenyl group are a prop-2-enyl group (allyl group), a 2-methyl-prop-2-enyl group, a but-3-enyl group, a but-2-enyl group, a pent-4 -enyl group or a pent-3-enyl group. The prop-2-enyl group is particularly preferred in this context.

Examples of a d-Ce-alkoxy group are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ or

OC (CH ₃ ) ₃ , with the methoxy group (-OCH ₃ ) being preferred.

Examples of a d-Ce-alkoxycarbonyl group are -C (O) OCH ₃ , -C (O) OCH ₂ CH ₃ ,

-C (O) OCH ₂ CH ₂ CH ₃ , -C (O) OCH (CH ₃ ) ₂ or -C (O) OC (CH ₃ ) ₃ , wherein the methoxycarbonyl group

(-C (O) OCH ₃ ) is preferred.

Examples of a halogen are fluorine, chlorine, bromine or iodine, in particular fluorine and chlorine.

Furthermore, as preferred examples of a C ₂ -C ₆ -hydroxyalkyl group -CH ₂ CH ₂ OH,

-CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, where the group

-CH ₂ CH ₂ OH is preferred.

Examples of C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl groups are the groups -CH ₂ CH ₂ OCH ₃ ,

- (- / H ₂ (_ / H ₂ (- / H ₂ O (- / H _3, - (- / H ₂ (- / H ₂ OCΗ ₂ (- / H _3, - (_ / H ₂ (_ / H ₂ (- / H ₂ O (- / H ₂ (- / H ₃ , - (- / H ₂ (- / H ₂ OCΗ ((- / H ₃ ) ₂ ,

-CH ₂ CH ₂ CH ₂ OCH (CH ₃ ) ₂ .

Examples of a carboxy-C ₁ -C ₆ -alkyl group are the carboxymethyl group, the 2-carboxyethyl group or the 3-carboxypropyl group.

Examples of aryl-C 1 -C ₆ -alkyl groups are the benzyl group and the 2-phenylethyl group.

Examples of a heteroaryl-C 1 -C 6 -alkyl group are the pyridin-2-ylmethyl group, the pyridin-3-ylmethyl group, the pyridin-4-ylmethyl group, the pyrimidin-2-ylmethyl group, the pyrrol-1-ylmethyl group, the pyrrole 1-ylethyl group, the pyrazol-1-ylmethyl group or the pyrazol-1-yl-ethyl group.

Examples of a mono- or di- (C ₁ -C ₆ -alkyl) aminoC ₂ -C ₆ -alkyl group are the 2-methylaminoethyl group, 2-ethylaminoethyl group, 2-dimethylaminoethyl group, 2-diethylaminoethyl group,

3-methylaminopropyl group, 3-dimethylaminopropyl group, 2- (piperidin-1-yl) ethyl group, 2-

(Pyrrolidin-1-yl) ethyl group, 2- (morpholin-1-yl) ethyl group and 2-bis (2-hydroxyethyl) aminoethyl group wherein the 2-dimethylaminoethyl group and the 2-Diethylaminoethyl group are particularly preferred.

An example of an aryl group is the phenyl group, the 1-naphthyl group or the 2-naphthyl group.

Examples of a heteroaryl group are the pyridin-2-yl group, the pyridin-3-yl group, the

Pyridin-4-yl group, the pyrimidin-2-yl group, the pyrrol-1-yl group, the pyrrol-2-yl group, the

Pyrazol-1-yl group, the pyrazol-3-yl group or the pyrazol-2-yl group.

It is preferred if the anion X ^" according to formula (I) is selected from halide, in particular chloride, bromide and iodide, benzenesulfonate, p-toluenesulfonate, C-rC ₄ -alkyl sulfonate, trifluoromethanesulfonate, acetate, trifluoroacetate, perchlorate, Vi sulfate, hydrogen sulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. According to the invention is particularly favored it when the physiologically acceptable anion X ^'is a halide (particularly chloride or bromide), hydrogen sulfate, ¹ ^ sulfate, p-toluenesulfonate, benzenesulfonate and acetate is.

The compositions of the invention contain the cationic pyridinium derivatives of general structure (I) preferably in an amount of 0.01 to 25 wt .-%, in particular from 0.1 to 10% by weight, each based on the total weight of the ready-to-use agent.

A preferred embodiment of the present invention are agents containing at least one cationic pyridinium derivative according to formula (I) wherein

L is a C (R 5) = CH unit, where R 5 is hydrogen, a C ₁ -C ₄ -

Alkyl group, C-rC ₆ alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-Ci-Cβ-alkyl-amino group, a di- (C ₁ -C ₆ -alkyl) -amino group, a C ₂ -C ₆ -Acylamino group, a halogen or an acyl group R'C (O), wherein R 'is a C ₁ -C ₄ alkyl group, a C ₂ -C ₆ - hydroxyalkyl group or a C-ι-C ₆ alkoxy-C C ₂ -C ₆ alkyl group,

R1 represents a _C-ι-C6 alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkyl group hydroxy, a C-ι-C ₆ -alkoxy-C ₂ -C ₆ alkyl group, a carboxy _C-ι-C6 alkyl group, an aryl C-ι-C ₆ alkyl, amino-alkyl group, a C ₂ -C _6, a _(C-ι-C6 alkyl) amino C ₂ -C ₆ alkyl group, a di- (C "rC ₆ alkyl) amino-C ₂ -C ₆ alkyl group, a _{heteroaryl-C-ι-C6} alkyl group, a 3-oxobutyl group, a 2 Oxopropyl group, an aryl group or a heteroaryl group,

R 2 and R _{4 are} each independently of one another hydrogen, a C ₁ -C ₄ -alkyl group, C ₁ -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-C ₁ -C ₆ -alkylamino group, a dialkyl (C ₁ -C ₆ -alkyl) -amino group, a C _Σ -Ce-acylamino group, a halogen or an acyl group R'C (O), where R 'is a C 1 -C ₄ -alkyl group, a C C ₂ -C ₆ -hydroxyalkyl group or a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, and R 3 is hydrogen, a C ₁ -C ₄ -alkyl group, C ₁ -C ₆ -alkoxy group, a hydroxy group , a nitrile group, an amino group, a mono-C 1 -C ₆ -alkyl-amino- group, a di- (C ₁ -C ₆ -alkyl) -amino group, a C ₂ -C ₆ -acylamino group or a halogen, with the proviso that at least one of the radicals R _2, R 4 or R 5 represents an acyl group R'C ( O) wherein R 'represents a dC ^ alkyl group, a C ₂ -C ₆ alkyl group or a hydroxy C-ι-C ₆ -alkoxy-C ₂ -C ₆ alkyl group is.

Preferred agents contain as cationic pyridinium derivative at least one compound according to formula (I) wherein

L is a C (R5) = CH unit, wherein R5 is hydrogen or a

Acyl group R'C (O), where R 'is a C 1 -C ₄ alkyl group,

R1 is a Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkyl group hydroxy, a Ci-C ₆ -alkoxy-C ₂ -C ₆ alkyl group, an aryl-C C ₆ alkyl group or a 2-oxopropyl group, R 2 and R 4 each independently represent hydrogen or an acyl group

R'C (O), where R 'is a Ci-C ₄ alkyl group, and R3 is hydrogen, with the proviso that at least one of the radicals R2, R4 or R5 for an acyl group R'C (O) in which R 'represents a dC ^ alkyl group, a C ₂ -C ₆ alkyl group or a hydroxy C-ι-C ₆ -alkoxy-C ₂ -C ₆ alkyl group.

Preferred compounds of the formula (I) are those in which the radical R 1 has the general structure (I) for a C ₁ -C ₆ -alkyl group, for a C ₂ -C ₆ -alkenyl group or for a C ₂ -C ₆ -hydroxyalkyl group stands. In particular, it is preferred if the radical R _{1 of} the formula (I) is a C 1 -C ₆ -alkyl group, more preferably methyl.

Depending on the choice of the substituent L, regioisomers are encompassed in which the substituent R5 is either in the 6-position (ie in the ortho position relative to the nitrogen atom of the pyridine ring) or in the 5-position (ie in the meta position relative to the nitrogen atom). Atom of the pyridine ring) sits.

Preferred cationic pyridinium derivatives are characterized in that the substituent R5 is in the 6-position, and are therefore represented by compounds according to (IV):

The above definitions apply to the substituents R1, R2, R3, R4 and R5.

Particularly preferred cationic pyridinium derivatives according to the invention are characterized in that at least one of the radicals R 2 or R 4 represents an acyl group R'C (O), wherein R 'is a Ci-C ₄ alkyl group, a C ₂ -C ₆ hydroxyalkyl group or a CrC ₆ -Akoxy-C ₂ - C ₆ alkyl group. Such compounds are 4-acyl-pyridinium derivatives and 2-acylpyridinium derivatives according to formulas (V) and (VI):

wherein the substituents R1, R2, R3, R4, R5 and R 'are as defined above.

Particularly advantageous compounds are those acyl-pyridinium derivatives according to the formulas (V) or (IV) in which R3 is hydrogen, R2, R4 and R5 are each independently hydrogen or an acyl group R'C (O) and R 'is a methyl group stands.

Particularly preferred cationic acyl-pyridinium derivatives of the general formulas (V) and (VI) are

wherein X ^{'takes on} the meaning of the aforementioned preferred embodiments.

In particular, agents according to the invention are preferred which contain as cationic pyridinium derivative of general structure (I) at least one compound from the group formed from 2-acetyl-1-methylpyridinium p-toluenesulfonate, 2-acetyl-1-methylpyridinium benzene sulfonate, 2-acetyl-1-methylpyridinium bromide, 2-acetyl-1-methylpyridinium chloride, 2-acetyl-1-methylpyridinium hydrogensulfate, 2-acetyl-1-methylpyridinium acetate, 2-acetyl-1-allylpyridinium p-toluenesulfonate, 2 Acetyl-1-allylpyridinium benzenesulfonate, 2-acetyl-1-allylpyridinium bromide, 2-acetyl-1-allylpyridinium chloride, 2-acetyl-1-allylpyridinium hydrogensulfate, 2-acetyl-1-allylpyridinium acetate, 2-acetyl-1- (2-hydroxyethyl ) pyridinium p-toluenesulfonate, 2-acetyl-1- (2-hydroxyethyl) pyridinium benzene sulfonate, 2-acetyl-1- (2-hydroxyethyl) pyridinium bromide, 2-acetyl-1- (2-hydroxyethyl) pyridinium chloride, 2-acetyl-1- (2-hydroxyethyl) pyridinium hydrogen sulfate, 2-acetyl-1- (2-hydroxyethyl) pyridine dinium acetate, 2-acetyl-1- (2-oxopropyl) pyridinium p-toluenesulfonate, 2-acetyl-1 - (2-oxopropyl) pyridinium benzene sulfonate, 2-acetyl-1- (2-oxopropyl) pyridinium bromide, 2-acetyl 1- (2-oxopropyl) pyridinium chloride, 2-acetyl-1- (2-oxopropyl) pyridinium hydrogensulfate, 2-acetyl-1- (2-oxopropyl) pyridinium acetate, 2-acetyl-1-ethylpyridinium-p- Toluenesulphonate, 2-acetyl-1-ethylpyridinium benzene sulphonate, 2-acetyl-1-ethylpyridinium bromide, 2-acetyl-1-ethylpyridinium chloride, 2-acetyl-1-ethylpyridinium hydrogensulfate, 2-acetyl-1-ethylpyridinium acetate, 2-acetyl- 1- (2-methylprop-2-enyl) pyridinium p-toluenesulfonate, 2-acetyl-1- (2-methyl-prop-2-enyl) pyridinium benzene sulfonate, 2-acetyl-1- (2-methyl -prop-2-enyl) pyridinium bromide, 2-acetyl-1- (2-methyl-prop-2-enyl) pyridinium chloride, 2-acetyl-1- (2-methyl-prop-2-enyl) pyridinium hydrogen sulfate, 2-acetyl -1- (2-methyl-prop-2-enyl) pyridinium acetate, 2-acetyl-1-benzylpyridinium p-toluenesulfonate, 2-acetyl-1-benzylpyridinium benzenesulfonate, 2-acetyl-1-benzylpyridinium bromide id, 2-acetyl-1-benzylpyridinium chloride, 2-acetyl-1-benzylpyridinium hydrogensulfate, 2-acetyl-1-benzylpyridinium acetate, 2-acetyl-1- (2-methoxyethyl) -pyridinium p-toluenesulfonate, 2-acetyl- 1- (2-methoxyethyl) pyridinium benzene sulfonate, 2-acetyl-1- (2-methoxyethyl) pyridinium bromide, 2-acetyl-1- (2-methoxyethyl) pyridinium chloride, 2-acetyl-1- (2-methoxyethyl) pyridinium hydrogen sulfate, 2- Acetyl-1- (2-methoxyethyl) pyridinium acetate, 2,4-diacetyl-1-methylpyridinium p-toluenesulfonate, 2,4-diacetyl-1-methylpyridinium benzene sulfonate, 2,4-diacetyl-1-methylpyridinium bromide, 2 , 4-Diacetyl-1-methylpyridinium chloride, 2,4-diacetyl-1-methylpyridinium hydrogensulfate, 2,4-diacetyl-1-methylpyridinium acetate, 2,6-diacetyl-1-methylpyridinium p-toluenesulfonate, 2,6-diacetyl 1-methylpyridinium benzenesulfonate, 2,6-diacetyl-1-methylpyridinium bromide, 2,6-diacetyl-1-methylpyridinium chloride, 2,6-diacetyl-1-methylpyridinium hydrogensulfate, 2,6-diacetyl-1-methylpyridinium acetate, 2.6 diacetyl-1- (2-hydroxyethyl) pyridinium-pt oluenesulfonate, 2,6-diacetyl-1- (2-hydroxyethyl) pyridinium benzene sulfonate, 2,6-diacetyl-1- (2-hydroxyethyl) pyridinium bromide, 2,6-diacetyl-1- (2-hydroxyethyl) pyridinium chloride, 2 , 6-diacetyl-1- (2-hydroxyethyl) -pyridinium hydrogensulfate, 2,6-diacetyl-1- (2-hydroxyethyl) pyridinium acetate, 4-acetyl-1-methylpyridinium p-toluenesulfonate, 4-acetyl-1 methylpyridinium benzene sulphonate, 4-acetyl-1-methylpyridinium bromide, 4-acetyl-1-methylpyridinium hydrogen sulphate, 4-acetyl-1-allylpyridinium p-toluene sulphonate, A-acetyl-1-allylpyridinium benzene sulphonate, 4-acetyl-1-allylpyridinium bromide, 4- Acetyl-1-allyl pyridinium hydrogensulfate, 4-acetyl-1- (2-hydroxyethyl) pyridinium p-toluenesulfonate, 4-acetyl-1- (2-hydroxyethyl) pyridinium benzene sulfonate, 4-acetyl-1- (2-hydroxyethyl) pyridinium bromide , 4-acetyl-1- (2-hydroxyethyl) pyridinium hydrogensulfate, 4-acetyl-1- (2-oxopropyl) pyridinium p-toluenesulfonate, A-acetyl-1- (2-oxopropyl) pyridinium benzene sulfonate, 4-acetyl-1 (2-oxopropyl) pyridinium bromide, A-acetyl-1- (2-oxopropyl) py ridinium hydrogensulfate, 4-acetyl-1-ethylpyridinium p-toluenesulfonate, A-acetyl-1-ethylpyridinium benzenesulfonate, 4-acetyl-1-ethylpyridinium bromide, 4-acetyl-1-ethylpyridinium hydrogensulfate, 4-acetyl-1- (2-methyl -prop-2-enyl) pyridinium p-toluenesulfonate, 4-acetyl-1- (2-methyl-prop-2-enyl) pyridinium benzene sulfonate, 4-acetyl-1- (2-methyl-prop-2-enyl) pyridinium bromide , 4-acetyl-1- (2-methylprop-2-enyl) pyridinium hydrogensulfate, 4-acetyl-1-benzylpyridinium p-toluenesulfonate, 4-acetyl-1-benzylpyridinium benzene sulfonate, 4-acetyl-1-benzylpyridinium bromide, 4-acetyl-1-benzylpyridinium hydrogensulfate, 4-acetyl-1- (2-methoxyethyl) pyridinium p-toluenesulfonate, A-acetyl-1- (2-methoxyethyl) pyridinium benzene sulfonate, 4-acetyl-1- (2-methoxyethyl) pyridinium bromide and 4-acetyl-1 - (2-methoxyethyl) pyridinium hydrogensulfate. From this group, the following acyl-pyridinium derivatives are explicitly explicitly preferred

2-acetyl-1-methylpyridinium p-toluenesulfonate, 2-acetyl-1-methylpyridinium benzenesulfonate, 2-acetyl-1-methylpyridinium bromide, 2-acetyl-1-methylpyridinium chloride, 2-acetyl-1-methylpyridinium hydrogensulfate, 2-acetyl- 1-methylpyridinium acetate, 2,6-diacetyl-1-methylpyridinium p-toluenesulfonate, 2,6-diacetyl-1-methylpyridinium benzene sulfonate, 2,6-diacetyl-1-methylpyridinium bromide, 2,6-diacetyl-1-methylpyridinium chloride, 2,6-diacetyl-1-methylpyridinium hydrogensulfate, 2,6-diacetyl-1-methylpyridinium acetate, 4-acetyl-1-methylpyridinium p-toluenesulfonate, 4-acetyl-1-methylpyridiniumbenzenesulfonate, 4-acetyl-1-methylpyridinium bromide, 4-acetyl-1-methylpyridinium hydrogensulfate, 4-acetyl-1-allylpyridinium p-toluosulfonate, 4-acetyl-1-allylpyridinium benzene sulfonate, A-acetyl-1-allylpyridinium bromide, 4-acetyl-1-allylpyridinium hydrogensulfate, 4-acetyl- 1- (2-hydroxyethyl) pyridinium p-toluene sulfonate, 4-acetyl-1- (2-hydroxyethyl) pyridinium benzene sulfonate, 4-acetyl-1- (2-hydroxyethyl) pyridinium bromide and 4 Acetyl-1- (2-hydroxyethyl) pyridinium hydrogen sulfate. Particularly preferred are 2-acetyl-1-methylpyridinium p-toluenesulfonate and 4-acetyl-1-methylpyridinium p-toluenesulfonate.

A further preferred embodiment of the agent according to the invention is characterized in that the agent contains as cationic pyridinium derivative at least one compound according to formula (I), wherein L is a CH ₂ -CH ₂ group,

R 1 is a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, a carboxy- Ci-Cβ alkyl group, an aryl Ci-Cβ alkyl group, an amino C ₂ -C ₆ alkyl group, a (C-ι-C ₆ alkyl) amino C ₂ -C ₆ alkyl group, a di- (C-ι-C ₆ alkyl) amino-C ₂ -C ₆ alkyl group, a heteroaryl-Cr C ₆ alkyl group, a 3-oxobutyl group, a 2-oxopropyl group, an aryl group or a heteroaryl group,

R2 and R3 together form a fused six membered aromatic carbocycle, which may optionally additionally carries 1 to 3 substituents independently selected from Ci-C ₆ alkyl, C ₂ -C ₆ alkenyl group, hydroxy group, amino group, mono- C ₁ -C ₆ -alkylamino group, di- (C ₁ -C ₆ -alkyl) amino group, C ₁ -C ₆ -alkoxy group, halogen, nitro group, nitrile group, carboxy group, optionally substituted aryl radical, or optionally substituted heteroaryl radical, and R 4 is Hydrogen, a Ci-C ₄ alkyl group, Ci-C ₆ alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-C- | -C ₆ alkyl-amino group, a di- (C-ι-C ₆ Alkyl) amino group, a C ₂ -C ₆ acylamino group or a halogen.

Particularly preferred cationic pyridinium derivatives according to formula (I) are cationic 3,4-dihydroisoquinolinium derivatives according to formula (VII),

wherein R1 is a Ci-C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, a

C- | -C ₆ -alkoxy-C ₂ -C ₆ alkyl group, a carboxy-C | -C ₆ alkyl group, an aryl-C- | -C ₆ - alkyl group, an amino-C ₂ -C ₆ - alkyl group, a (C- | -C ₆ alkyl) amino-C ₂ -C ₆ alkyl group, a di- (C-ι-C ₆ alkyl) amino-C ₂ -C ₆ alkyl group, a heteroaryl-C -Cβ-alkyl group, a 3-oxobutyl group, a 2-oxopropyl group, an aryl group or a heteroaryl group, and the anion X ^"is a physiologically acceptable anion as defined above.

Very particularly advantageous compositions contain as cationic pyridinium derivative according to formula (I) a compound selected from

wherein X ^'in each case the meanings according to structure (I), or the meaning of the aforementioned preferred embodiments, assumes.

In particular, those agents are particularly preferred which are characterized in that at least one 3,4-dihydroisoquinolinium derivative according to formula (VII) is selected from compounds of the group which is formed from N-methyl-3,4-dihydroisoquinolinium-p- toluene sulfonate, N-methyl-3,4-dihydroisoquinolinobenzenesulfonate, N-methyl-3,4-dihydroisoquinolinium bromide, N-methyl-3,4-dihydroisoquinolinium hydrogensulfate, N-methyl-3,4-dihydroisoquinolinium acetate, N- Allyl-3,4-dihydroisoquinolinium p-toluenesulfonate, N-allyl-3,4-dihydroisoquinolinium benzene sulfonate, N-allyl-3,4-dihydroisoquinolinium bromide, N-allyl-3,4-dihydroisoquinolinium hydrogensulfate, N-allyl- 3,4-dihydroisoquinolinium acetate, 3,4-dihydro-2- (3-hydroxypropyl) isoquinolinium p-toluenesulfonate, 3,4-dihydro-2- (3-hydroxypropyl) isoquinolinium benzenesulfonate, 3,4-dihydro-2- (3 - hydroxypropyl) isoquinolinium bromide, 3,4-dihydro-2- (3-hydroxypropyl) isoquinolinium hydrogensulfate, 3,4-dihydro-2- (3-hydroxypropyl) isoquinolinium acetate 3,4-dihydro-2- (2-hydroxyethyl) isoquinolinium p-toluenesulfonate, 3,4-dihydro-2- (2-hydroxyethyl) isoquinolinium benzene sulfonate, 3,4-dihydro-2- (2 -hydroxyethyl) isoquinolinium bromide, 3,4-dihydro-2- (2-hydroxyethyl) isoquinolinium hydrogensulfate or 3,4-dihydro-2- (2-hydroxyethyl) isoquinolinium acetate.

In a particularly preferred embodiment, the inventive compositions contain as cationic pyridinium derivative of the formula (I) N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate.

The compositions according to the invention comprising at least one coloring matting combination which comprises at least one coloring component and which is suitable for compensating yellowish and / or reddish color impressions remaining in the fiber when the keratinic fiber is lightened by a corresponding complementary coloring, and at least one cationic pyridinium Derivatives according to formula (I) can be used particularly advantageously in lightening agents for keratinic fibers, in particular for human hair.

Usually, such brightening agents contain oxidizing agents for the oxidative destruction of natural and / or artificial hair dyes. Common oxidizing agent is in particular hydrogen peroxide.

Another object of the present invention is a means for whitening and / or bleaching keratinischer fibers, which is characterized in that it comprises mixing at least one oxidizing agent preparation (B) containing at least one oxidizing agent selected from hydrogen peroxide and its addition compounds to solid Carrier, and at least one preparation (A) is prepared, wherein the preparation (A) in a cosmetic carrier a) at least one coloring Mattierungskombination comprising at least one coloring component and which is suitable for lightening the keratin fiber to compensate for yellowish and / or reddish color impressions remaining in the fiber by a corresponding complementary coloring, b) and contains at least one cationic pyridinium derivative according to formula (I),

wherein

L stands for C CHHo ₂ --CCH ₂ - or a C (R 5) = CH unit in which R 5 is hydrogen, a C ₁ -C ₄ -alkyl group, C ₁ -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-C ₁ -C ₆ -alkylamino group, a di- (C ₁ -C ₆ -alkyl) -amino group, a C _Σ -C -acylamino group, a halogen or an acyl group R ' C (O) wherein R 'represents a -C ₄ alkyl group, a C ₂ -C ₆ hydroxyalkyl group or a C-ι-C ₆ -alkoxy-C ₂ -C ₆ alkyl group,

R1 alkyl group for a d-Cβ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, a C-ι-C ₆ -alkoxy-C ₂ -C _6, a carboxy Ci-Cβ-alkyl group, an aryl-C-rC ₆ -alkyl group, an amino-C ₂ -C ₆ -alkyl group, a (CrC ₆ -alkyl) amino-C ₂ -C ₆ - alkyl group, a di- (CrC ₆ alkyl) amino-C ₂ -C ₆ alkyl group, a heteroaryl-CrC ₆ - alkyl group, a 3-oxobutyl group, a 2-oxopropyl group, an aryl group or a heteroaryl group,

R2 and R4 are each independently hydrogen, a Ci-C ₄ alkyl, -C ₆ - (alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono- Ci-C ₆ alkyl-amino group, a di- Ci-C ₆ alkyl) amino group, a C ₂ -C ₆ acylamino group, a halogen or an acyl group R'C (O), in which R 'represents a -C ₄ - alkyl group, a C ₂ -C ₆ hydroxyalkyl group, or a -C ₆ -alkoxy-C ₂ -C ₆ represents alkyl group,

R 3 is hydrogen, a C 1 -C ₄ -alkyl group, C 1 -C 6 -alkoxy group, a hydroxy group, a nitrile group, an amino group, a monoCrCβ-alkylamino group, a di (C 1 -C ₆ -alkyl) -amino group, a C _Σ -Ce- Acylamino group or a halogen, with the proviso that at least one of R ₂ , R ₄ or R 5 is an acyl group R'C (O), where R 'is a C ₁ -C ₄ -alkyl group, a C ₂ -C ₆ -hydroxy alkyl group or a -C ₆ -alkoxy-C ₂ -C ₆ is alkyl, or

R2 and R3 together form a fused six membered aromatic carbocycle which optionally additionally carries 1 to 3 substituents which are independently selected from -C ₆ alkyl, C ₂ -C ₆ alkenyl group, hydroxy group, amino group, mono-CrC ₆ alkyl amino group, di- (C 1 -C ₆ -alkyl) amino group, C 1 -C ₆ -alkoxy group, halogen, nitro group, nitrile group, carboxy group, optionally substituted aryl, or optionally substituted heteroaryl, and R4 represents hydrogen, a Ci-C ₄ alkyl group, Ci-C ₆ alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-C | -C ₆ alkyl-amino group, a di- (C- | -C ₆ alkyl) amino group, a C ₂ -C ₆ acylamino group or a halogen, and the anion X ^"is a physiologically acceptable anion.

By using the cationic pyridinium derivative, the bleaching power of the oxidation agent of the preparation (B) is significantly increased, so that a stronger lightening can be achieved. The addition of the coloring Mattierungskombination is suitable to compensate for the lightening of the keratinic fiber in the fiber remaining yellowish and / or reddish color impressions by a corresponding complementary coloring

Particularly preferred agents for whitening and / or bleaching keratinic fibers are obtained by mixing at least one oxidizing agent preparation (B) comprising at least one oxidizing agent selected from hydrogen peroxide and its addition compounds to solid carriers, and at least one preparation (A) which is in a cosmetic Carrier at least one coloring matting combination and at least one cationic pyridinium derivative according to formula (I) prepared, wherein the preparation (A) is characterized in that the coloring matting combination as a coloring component, a combination of at least one blue direct dye and a red substantive Contains dye, wherein the weight ratio between the sum of all blue direct dyes and the sum of all red direct dyes has a value of greater than or equal to 1, and the total amount of substantive dyes 0.0 001 to 0.2 wt .-%, based on the total weight of the ready-to-use agent is.

For the other, preferred embodiments of this subject invention apply mutatis mutandis the foregoing.

It has been found to be particularly favorable according to the invention to provide the bleaching agents initially separately for the oxidizing agent preparation (B) and preparation (A) containing the dyes responsible for the matting effect and the cationic pyridinium derivatives, in order to prevent potential instabilities.

The keratin fiber bleaching compositions according to the invention comprise at least one oxidizing agent preparation (B). This contains at least one oxidizing agent selected from hydrogen peroxide and its attachment compounds to solid supports. Hydrogen peroxide is used as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidinone n H ₂ O ₂ (n 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, 3% to 12% by weight solutions in water are used. The agents according to the invention particularly preferably comprise hydrogen peroxide. Here, particular preference is given to compositions according to the invention for bleaching keratinic fibers which contain 0.5 to 18% by weight, preferably 1 to 15% by weight, particularly preferably 2.5 to 12% by weight and in particular 3 to 9% by weight. % Hydrogen peroxide (calculated as 100% H ₂ O ₂ ).

Oxidizing agent preparations (A) according to the invention are preferably aqueous, flowable oxidizing agent preparations. In this case, preferred preparations are characterized in that the flowable oxidizing agent preparation - based on their weight - 40 to 98 wt .-%, preferably 60 to 97.5 wt .-%, particularly preferably 70 to 97 wt .-%, more preferably 75 to 96 wt .-% and in particular 80 to 95 wt .-% water.

Furthermore, it has proven to be advantageous if the oxidizing agent preparations contain at least one stabilizer or complexing agent. Particularly preferred stabilizers are phenacetin, alkali benzoates (sodium benzoate) and salicylic acid. 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". The number of bound ligands depends on the coordination number of the central ion. Customary and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts. Complex-forming polymers, ie polymers which carry functional groups either in the main chain themselves or in the side thereof, which can act as ligands and generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds. Preferred complexing agents according to the invention are nitrogen-containing polycarboxylic acids, in particular EDTA, and phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and, in particular, 1-hydroxyethane-1,1-di-phosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediaminetetra methylenephosphonate (EDTMP or its hexasodium salt and / or diethylenetriaminepentamethylenephosphonate (DTPMP) or its hepta or octasodium salt.

The oxidizing agent preparation (B) contains, in addition to the actual oxidizing agent and optionally complexing agent further auxiliaries and additives. So it has according to the invention as preferably proved, when the oxidizing agent preparation contains at least one thickener. With regard to these thickeners, there are no fundamental restrictions. Both organic and purely inorganic thickening agents can be used.

The ready-to-use bleaching agents of preparation (A) and oxidizing agent preparation (B) should preferably have a pH in the range from 6 to 12. Particularly preferred is the application in an alkaline medium. Another preferred embodiment of the present invention is that the ready-to-use agent has a pH of between 7.0 and 12.0, preferably between 8.0 and 11.0. The pH values for the purposes of the present invention are pH values which were measured at a temperature of 22 ^° C.

Usually, the pH is adjusted with pH adjusters. In order to adjust the pH, those skilled in the art are familiar with common acidifying and alkalizing agents. The alkalizing agents which can be used for adjusting the pH are typically selected from inorganic salts, in particular the alkali metals and alkaline earth metals, organic alkalizing agents, in particular amines, basic amino acids and alkanolamines, and ammonia. Acidifying agents which are preferred according to the invention are pleasure acids, such as citric acid, acetic acid, malic acid or tartaric acid, and also dilute mineral acids.

Organic alkalizing agents which can be used according to the invention are preferably selected from alkanolamines of primary, secondary or tertiary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Very particularly preferred alkanolamines according to the invention are selected from the group consisting of monoethanolamine, 2-amino-2-methylpropan-1-ol and 2-amino-2-methylpropane-1,3-diol; in particular monoethanolamine. However, it has been found in the context of the investigations of the present invention that preferred according to the invention are characterized in that they additionally contain an inorganic alkalizing agent. The inorganic alkalizing agent of the present invention is preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, sodium carbonate and potassium carbonate. The compositions according to the invention preferably contain the alkalizing agents in amounts of from 0.2 to 25% by weight, in particular from 0.5 to 10% by weight.

A particularly preferred dosage form of the agent of the second subject of the invention is a kit of parts, which in separately prepared containers at least one oxidizing agent preparation (B) containing at least one oxidizing agent selected from hydrogen peroxide and its attachment compounds to solid support, and at least a preparation (A) is prepared, wherein the preparation (A) in a cosmetic carrier a) at least one coloring matting combination which comprises at least one coloring component and which is suitable for lightening the keratinic fiber in the fiber remaining yellowish and / or reddish color impressions by a corresponding complementary coloring to compensate, b) and at least one cationic pyridinium derivative according to formula (I).

Furthermore, it may be particularly advantageous according to the invention if said kit of parts contains at least one further hair treatment agent in a separate container, in particular a conditioning agent. In addition, the packaging unit may comprise application aids, such as combs, brushes or brushes, personal protective clothing, in particular one-way gloves, and, if appropriate, instructions for use.

With regard to the preferred embodiments of the preparation (A) and the oxidizing agent preparation (B), the above statements of the preceding subject of the invention apply.

By using the cationic pyridinium derivative, the lightening power of the compositions according to the invention is markedly increased, so that it may be possible to dispense with the addition of further bleach boosters, which leads to a reduced hair damage. However, it may be necessary to incorporate additional bleaching power enhancers into the composition for particularly high lightening, especially for very dark, highly pigmented, starting hair colors. If such a strong lightening is desired, it is preferred according to the invention if, in addition, a bleaching preparation (C) comprising at least one bleaching power enhancer is added to the mixture of oxidizing agent preparation (B) and the preparation (A). It may be irrelevant whether first a mixture (A) and (B) is prepared, and then the Blondierzubereitung (C) is mixed, or whether a different order of mixing of the individual components is used. It is preferred to mix the individual preparations in the earliest possible chronological order and preferably to apply the ready-to-use agent promptly to the keratinic fibers.

A further embodiment of the present application is therefore an agent for bleaching keratinic fibers, which comprises mixing at least one oxidizing agent preparation (B) containing at least one oxidizing agent selected from hydrogen peroxide and its addition compounds onto solid carriers, at least one bleaching preparation (C ), containing at least one bleaching power booster, and at least one preparation (A) is prepared, wherein the preparation (A) in a cosmetic carrier a) at least one coloring matting combination which comprises at least one coloring component and which is suitable for lightening the keratinic To compensate for fiber remaining in the fiber yellowish and / or reddish color impressions by a corresponding complementary coloring, b) and at least one cationic pyridinium derivative according to formula (I). It is particularly advantageous according to the invention if, in the ready-to-use agent for bleaching keratinic fibers, the total amount of coloring components of the coloring matting combination is 0.0001 to 0.2% by weight, based on the total weight of the ready-to-use agent.

As additional bleaching power amplifiers of the bleaching preparation (C) it is possible in the context of this invention to use peroxo compounds, furthermore compounds which give aliphatic peroxycarboxylic acids and / or substituted perbenzoic acid under perhydrolysis conditions, carbonic acid derivatives, alkyl carbonates, carbamates, silyl carbonates and carbamates. The bleaching force enhancer is preferably selected from ammonium peroxodisulfate, alkali metal peroxodisulfates, ammonium peroxomonosulfate, alkali metal hydrogen peroxomonosulfates, alkali metal peroxodiphosphates and alkaline earth metal peroxides. Particularly preferred bleach boosters are ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate, potassium hydrogen peroxomonosulfate, potassium peroxodiphosphate, magnesium peroxide and barium peroxide. Particularly preferred according to the invention are agents which contain at least one inorganic salt selected from peroxymonosulphates and / or peroxodisulphates in the bleaching formulation (C) as bleaching force enhancers. Furthermore, it has proved to be particularly preferred in the work of the present invention, when the compositions of the invention contain at least two different peroxodisulfates. Preferred peroxodisulfate salts are combinations of ammonium peroxodisulfate and potassium peroxodisulfate and / or sodium peroxodisulfate. The peroxo compounds are contained in an amount of 0.1 to 25 wt .-%, in particular in an amount of 0.5 to 15 wt .-%, based on the total weight of the ready-to-use agent. The use of persulfate salts or peroxodisulfate salts is generally carried out in the form of an optionally dedusted powder, paste or molded molding.

The anhydrous compositions according to the invention instead of and / or in addition to the solid peroxo compounds contain a further bleaching power amplifier.

As bleach amplifiers, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylene diamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or i-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran. As bleach booster of the type of carbonic acid derivatives may be preferred according to the invention

Carbonate salts or bicarbonate salts are used. These are preferably selected from the group of the ammonium, alkali metal (in particular sodium and potassium) and alkaline earth metal (in particular magnesium and calcium), carbonate salts or bicarbonate salts. Particularly preferred carbonate or bicarbonate salts are ammonium hydrogencarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, magnesium carbonate and calcium carbonate. These particularly preferred salts can be used alone or in their mixtures of at least two representatives as bleaching amplifiers.

Bleach enhancers of the alkyl carbonates and carbamates type as well as silyl carbonates and silicon carbamates can be used as bleach boosters in the anhydrous compositions and are characterized by compounds of the formula (BV) wherein

R 1 represents a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle,

X is a group O or NR 3, wherein R 3 is a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted silyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle, and

R 2 is a hydrogen atom, an alkali metal atom, in particular sodium, or a group SiR ₃ in which the radicals R independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or for a trialkylsilyl group, preferably one Trimethylsilylgruppe or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy or amino group.

Compositions particularly preferably used according to the invention are characterized in that the radical R1 in formula (BV) is selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl and also hydroxymethyl and hydroxyethyl.

Preferred radicals R 2 and R 3 in the formula (BV) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, t-butyl and trimethylsilyl radicals. Preferred radicals R in the formula (BV) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred compositions according to the invention are characterized in that the radicals R in formula (BV) are selected from methyl, ethyl, n-propyl, i-propyl, n- Butyl, i-butyl, t-butyl and hydroxymethyl and hydroxyethyl.

As further additional bleach boosters, in the compositions according to the invention preferably at least one compound selected from acetic acid, lactic acid, tartaric acid, citric acid, salicylic acid and ortho-phthalic acid may be contained.

The bleach boosters used in addition to or instead of peroxo compounds are preferred in amounts of from 0.05 to 10% by weight, in particular in amounts of from 0.2 to 5% by weight, in each case based on the total weight of the ready-to-use cosmetic agents By means of, included.

Although in principle there are no restrictions with regard to the formulation of the blonding preparation (C), it has proved to be preferred according to the invention if the preparation (C) is formulated anhydrous.

Anhydrous in the sense of the present invention means a water content based on the preparation (C) of less than 5 wt .-%, in particular of less than 2 wt .-%. Blondierzubereitungen containing less than 0.1 wt .-% water, according to the invention may be very particularly preferred.

The preparation (C) is preferably formulated as a powder or as an anhydrous paste. In the case of formulation as an anhydrous paste, it has proved to be particularly preferred if the preparation (C) at least one non-hydroxylated fatty acid ester having a melting point of at most 50 ⁰ C, in particular of at most 30 ⁰ C, and / or at least one Ci _O - C ₃₀ fatty acid with at least one additional hydroxyl group and / or a derivative thereof. Particular preference is given according to the invention to isopropyl myristate, C 16-18 alkyl ester, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, cetyl oleate, coconut fatty alcohol caprinate / caprylate, n-butyl stearate, oleyl erucate, isopropyl palmitate, oleyl oleate, hexyl laurate, myristyl myristate, cetearyl isononanoate, oleic acid decyl ester ,

With regard to the preferred embodiments of the preparation (A) and the oxidizing agent preparation (B), the above statements of the first and second subject invention apply.

A particularly preferred dosage form of the agent is furthermore a packaging unit (kit-of-parts), which in separately packaged containers contains at least one oxidizing agent preparation (B) containing at least one oxidizing agent selected from Hydrogen peroxide and its attachment compounds to solid supports, at least one

Bleaching preparation (C) containing at least one bleaching power enhancer and at least one preparation (A), wherein the preparation (A) in a cosmetic carrier a) at least one coloring matting combination which comprises at least one coloring component and which is suitable for whitening To compensate for the yellowish and / or reddish color impressions remaining in the fiber of the keratinic fiber by a corresponding complementary coloring, b) and contains at least one cationic pyridinium derivative according to formula (I).

With regard to the preferred embodiments of the preparation (A) and the oxidizing agent preparation (B) and the bleaching preparation (C), the above statements apply.

The mixture of the preparations (A) and (B) or, where appropriate, of the preparations (A), (B) and (C) before use leads to an application mixture according to the invention.

It has been found to be particularly advantageous according to the invention if the composition according to the invention additionally contains at least one nonionic component having an HLB value of less than or equal to 8.0. In the case of agents prepared by mixing different preparations, namely preparation (A) containing a coloring matting combination and a cationic pyridinium derivative, and the oxidizing agent preparation (B) and optionally a bleaching preparation (C), it may be immaterial in which of the preparations the nonionic component with an HLB value of less than or equal to 8.0 is contained. In particular, due to the advantageous stability of the preparations, the nonionic component having an HLB value of less than or equal to 8.0 is preferably incorporated into the preparation (A) containing a coloring matting combination and at least one cationic pyridinium derivative according to formula (I) ,

Nonionic in the sense of the invention means that the component does not form any ions in aqueous solution. The HLB value is a measure of the water or oil solubility of compounds introduced by Griffin (1950), with compounds having low HLB values having more hydrophobic properties than compounds having high HLB values. For the definition of the HLB value, reference is explicitly made to the statements in Hugo Janistyn, Handbuch der Kosmetika und Riechstoffe, IM. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Heidelberg, 1973, pages 68-78 and Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Publishing Company m.b.H. Stuttgart, 1974, pages 466-474, as well as the original works cited therein.

Nonionic components with an HLB value of less than or equal to 8.0 can be used for the purposes of the invention fats, oils, waxes or nonionic emulsifiers. For the purposes of the invention, fats and oils are understood as meaning solid, semi-solid or liquid, more or less viscous products of the plant or animal body, which consist essentially chemically of mixed triglycerides of higher fatty acids. Preferred vegetable oils are macadamia nut oil, kukui nut oil, palm oil, amaranth seed oil, peach kernel oil, avocado oil, olive oil, coconut oil, rapeseed oil, sesame oil, jojoba oil, soybean oil, peanut oil, evening primrose oil and tea tree oil. Mineral oils, in particular paraffin oils or waxes, can also be used according to the invention.

It is likewise possible to use waxes, in particular esters of long-chain C ₂₄ -C ₃₆ fatty acids (wax acids) with long-chain alcohols (fatty alcohols), triterpene or steroid alcohols (for example Ambrein, betulin), which are widespread in plants and animals. These include, for example, natural recent waxes such as bee or carnauba wax, which also contain free carboxy and hydroxy groups, which cause the emulsifying capacity of so-called wax soaps, and further natural fossil waxes, for example from lignite or petroleum, as well as waxes from the fisherman -Tropsch synthesis or polyethylene waxes mainly from straight-chain hydrocarbons; Depending on their provenance, however, fossil waxes may also contain branched or cycloaliphatic hydrocarbons.

In a preferred embodiment, the composition according to the invention contains a nonionic emulsifier having an HLB value of less than or equal to 8.0. Nonionic emulsifiers are, after all, surface-active substances which do not form ions in aqueous solution. The carrier of the surface-active action is therefore the total molecule. The hydrophilicity of such nonionic emulsifiers is achieved by the proportion of polar groups in the molecule. The nonionic emulsifiers include fatty alcohols, polymerization products of ethylene oxide and propylene oxide with saturated or unsaturated fatty alcohols, fatty acid esters of polyhydric alcohols with saturated or unsaturated fatty acids, alkyl esters of saturated or unsaturated fatty acids or alkylphenols and their alkoxylates.

Preferred nonionic components are fatty alcohols bearing 6 to 30 carbon atoms in their alkyl chain. The alkyl chain may contain one or more branches as well as cis and / or trans-configured double bonds. Examples thereof are hexyl alcohol (caproic alcohol), heptyl alcohol (oenanthalcohol), octyl alcohol (capryl alcohol), nonyl alcohol (pelargonyl alcohol), undecyl alcohol, undec-10-en-1-ol, dodecyl alcohol (lauryl alcohol), 2,6,8-trimethyl 4-nonanol (isolauryl alcohol), tridecyl alcohol, tetradecyl alcohol (myristyl alcohol), pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol or palmityl alcohol), heptadecyl alcohol, octadecyl alcohol (stearyl alcohol), isostearyl alcohol, (9Z) octadec-9-en-1-ol (Oleyl alcohol), (9E) octadec-9-en-1-ol (elaidyl alcohol), (9Z, 12Z) octadeca-9,12-dien-1-ol (linoleyl alcohol), (9Z, 12Z, 15Z ) - octadeca-9,12,15-trien-1-ol (linolenyl alcohol), nonadecan-1-ol (nonadecyl alcohol), eicosan-1-ol (eicosyl alcohol / arachyl alcohol), (9Z) -eicos-9-ene-1 -ol (gadoleyl alcohol), (5Z, 8Z, 11Z, 14Z) - eicosa-5,8,11,14-tetraen-1-ol (arachidonic alcohol), heneicosyl alcohol, docosyl alcohol (behenyl alcohol), (13Z) -docos- 13-en-1-ol (erucyl alcohol) or (13E) -docosen-1-ol (brassidyl alcohol). It According to the invention, it is likewise possible to use mixtures of fatty alcohols which are obtained by specific mixing or by extraction processes as such. Examples include coconut oil (mixture of C ₈ -C ₁₈ fatty alcohols) or cetearyl alcohol (1: 1 mixture of C ₁₆ - and Ci ₈ fatty alcohols).

Further preferred nonionic components with an HLB value of less than or equal to 8.0 are ethylene glycol ethers with fatty alcohols. In principle, ethylene glycol ethers of the abovementioned fatty alcohols can be used. In order to achieve an HLB value in the range according to the invention, it is preferred to use ethylene glycol ethers with fatty alcohols with a low degree of ethoxylation if possible. By degree of ethoxylation is meant the molar amount of ethylene oxide used per mole of fatty alcohol. Preference is given to ethylene glycol ethers having a degree of ethoxylation of 1 (fatty alcohol monoethylene glycol ether), 2 (fatty alcohol diethylene glycol ether) or 3 (fatty alcohol triethylene glycol ether). Preferred ethylene glycol ethers according to the invention are, for example, laureth-1, laureth-2, laureth-3, isolaureth-1, isolaureth-2, isolaureth-3, trideceth-1, trideceth-2, trideceth-3, myreth-1, myreth-2, myreth 3, ceteth-1, ceteth-2, ceteth-3, steareth-1, steareth-2, steareth-3, oleth-1, oleth-2, oleth-3, ceteareth-1, ceteareth-2, ceteareth-3 , Coceth-1, Coceth-2, Cocoeth-3, Pareth-1, Pareth-2 and Pareth-3. Particularly preferred are ceteth-1, laureth-2, ceteth-2, steareth-2, oleth-2, laureth-3, isolaureth-3, trideceth-3, ceteareth-3 and oleth-3.

Further preferred nonionic components with an HLB value of less than or equal to 8.0 are addition products of fatty alcohols with propylene oxide. In principle, propylene glycol ethers of the abovementioned fatty alcohols can be used, with propylene glycol ethers being preferred with fatty alcohols having a low degree of propylenation. The degree of propylenation is understood to mean the molar amount of propylene oxide used per mole of fatty alcohol. Preferred ethylene glycol ethers according to the invention are, for example, PPG-1 lauryl ether, PPG-2 lauryl ether, PPG-3 lauryl ether, PPG-1 isolauryl ether, PPG-2 isolauryl ether, PPG-3 isolauryl ether, PPG-1 tridecyl - ethers, PPG-2 tridecyl ethers, PPG-3 tridecyl ethers, PPG-2 myristyl ethers, PPG-3 myristyl ethers, PPG-1 cetyl ethers, PPG-2 cetyl ethers, PPG-3 cetyl ethers, PPG-1 stearyl ethers, PPG-2 stearyl ethers, PPG 3 stearyl ethers, PPG-1 oleyl ethers, PPG-2 oleyl ethers, PPG-3 oleyl ethers, PPG-1 cetearyl ethers, PPG-2 cetearyl ethers, PPG-3 cetearyl ethers, PPG-1 cocoyl ethers, PPG-2 cocoyl ethers and PPG-3 cocoyl ethers. Especially preferred is PPG-3 myristyl ether.

It is also possible to use mixed ethylene and propylene glycol ethers with fatty alcohols as nonionic components with an HLB value of less than or equal to 8.0.

As preferred nonionic emulsifiers, fatty acid esters of polyhydric alcohols with saturated or unsaturated fatty acids having 8 to 22, in particular 10 to 18, carbon atoms in the fatty acid group are likewise usable according to the invention, provided they meet the criterion according to the invention of an HLB value of less than or equal to 8.0. When Polyhydric alcohols are preferably ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitan or sugar and homo- or hetero-oligomers thereof.

Esters of ethylene glycol or propylene glycol according to the invention are both the monofatty acid esters and the difatty acid esters with (poly) ethylene and / or propylene glycols. Preferred fatty acids are, for example, lauric, myristic, palmitic, stearic, isostearic and oleic acids. Preferred compounds include ethylene glycol monofatty acid esters, propylene glycol monofatty acid esters, ethylene glycol difatty acid esters, polyethylene glycol monofatty acid esters and polyethylene glycol difatty acid esters. Particularly preferred compounds according to the invention are ethylene glycol distearate, ethylene glycol monostearate, propylene glycol monostearate, diethylene glycol monostearate, polyethylene glycol (100) monostearate, polyethylene glycol (200) monostearate, diethylene glycol monolaurate, polyethylene glycol (200) dilaurate, polyethylene glycol (100) monolaurate, polyethylene glycol (100) monooleate , Polyethylene glycol (200) dioleate or polyethylene glycol (400) dioleate.

Likewise preferred are mono-, di- or triflic acid esters of glycerol, its oligomers or its addition products with ethylene oxide and / or propylene oxide. In particular, glycerol monofatty acid esters, glycerol difatty acid esters and glycerol triflic acid esters are preferred. Exemplary compounds of this type are glyceryl trilaurate, glyceryl trimyristate, glyceryl tripalmitate, glyceryl tristearate, glyceryl triisostearate, glyceryl trioleate, Glyceryltricocoat, glyceryl dilaurate, Glyceryldimyristat, Glyceryldipalmitat, glyceryl distearate, glyceryl diisostearate, glyceryl dioleate, Glyceryldicocoat, glyceryl monolaurate, glyceryl monomyristate, glyceryl monopalmitate, glyceryl monostearate, glyceryl monoisostearate, glyceryl monooleate and glyceryl. Furthermore, mono- or poly fatty acid esters of polyglycerides can also be used according to the invention nonionic components. Decaglycerol decaoleate, decaglycerol octaoleate, decaglycerol decastearate, triglyceryl diisostearate or diglycerol monostearate are mentioned by way of example.

It is also possible to use triglycerides of hydroxyl-bearing fatty acids, in particular castor oil, which can be used cured or uncured. Ethoxylated castor oil is particularly preferred.

Likewise preferred nonionic components according to the invention are fatty acid esters of pentaerythritol, in particular pentaerythritol monofatty acid esters. Examples of these compounds are pentaerythritol monolaurate, pentaerythritol monomyristate, pentaerythritol monopalmitate, pentaerythritol monostearate and pentaerythritol monooleate.

Likewise preferred nonionic components according to the invention are fatty acid esters of sorbitan as the polyhydric alcohol, in particular sorbitan monofatty acid esters, sorbitan aldehyde esters and sorbitan trifatty acid esters. Examples of these compounds are sorbitan trioleate, sorbitan tristearate, sorbitan tripalmitate, sorbitan trimyristate, sorbitan triisostearate, sorbitan trilaurate, sorbitan dioleate, sorbitan distearate, sorbitan dipalmitate, sorbitane myristate, sorbitane disostearate, Sorbitan dilaurate, sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, sorbitan mono- myristate, sorbitan monoisostearate and sorbitan monolaurate.

It is further preferred according to the invention to use fatty acid diesters or polyesters with sugars, in particular sucrose, as their addition products with propylene oxide and / or ethylene oxide as nonionic components, provided that these compounds have an HLB value of less than or equal to 8.0. Examples of such compounds include sucrose dilaurate, sucrose dimyristate, sucrose dipalmitate, sucrose distearate, sucrose dioleate, sucrose tristearate, and polypropylene glycol sucrose tetrapalmitate.

Esters of branched non-hydroxylated C ₆ -C ₃₀ -Alkylmonocarbonäuren with optionally, C ₁ - C ₃₀ mono-alcohols are suitable according to the invention preferred as alkyl esters of saturated or unsaturated fatty acids. The monoesters of the fatty acids with monoalcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid components used in the esters are caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitoleic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic Behenic acid and erucic acid and their technical mixtures which are obtained, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids. Examples of the fatty alcohol moieties in the esters are isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Particularly preferred according to the invention are isopropyl myristate, cetearyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl sterearate, cetyl oleate, cocoyl caprinate / caprylate, n-butyl stearate, oleyl erucate, isopropyl palmitate, oleyl oleate, hexyl laurate, myristyl myristate, cetearyl isononanoate or decyl oleate.

Finally, alkoxylated fatty acid alkyl esters of the formula RC (O) - (OCH ₂ CH ₂ ) _W OR 'in which R is C (O) - for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R' is linear or branched alkyl radicals having 1 to 4 carbon atoms and w is a number from 1 to 20, are used as nonionic components, if they have an HLB value of 8.0 or smaller.

Another preferred class of nonionic components according to the invention having an HLB value of less than or equal to 8.0 is alkylphenols and their addition products of ethylene oxide and / or propylene oxide. Preferred compounds carry 6 to 21, in particular 6 to 15, carbon atoms in the alkyl chain. Preferred representatives of these compounds are octylphenol and nonylphenol, optionally alkoxylated with 1 to 3 moles of ethylene oxide and / or propylene oxide. Particularly suitable examples are octoxynol-1, octoxynol-2, octoxynol-3, nonoxynol-1, nonoxynol-2 and nonoxynol-3.

A preferred embodiment of the present invention is given when the nonionic component having an HLB value of less than or equal to 8.0 is selected from the group consisting of fatty alcohols, fatty alcohol monoethylene glycol ethers, fatty alcohol ethylene glycol ethers, fatty alcohol triethylene glycol ethers, glycerol monofatty acid esters, glycerol fatty acid esters, glycerol triflic acid esters, sorbitan monofatty acid esters, sorbitan dibutyl esters, sorbitan trifatty acid esters, pentaerythritol monofatty acid esters, ethylene glycol monofatty acid esters, ethylene glycol difatty acid esters, polyethylene glycol monofatty acid esters, polyethylene glycol difatty acid esters, sucrose diesters, propylene glycol monofatty esters and fatty acid alkyl esters.

Agents which are particularly preferred according to the invention are characterized in that they contain at least one fatty alcohol as nonionic component with an HLB value of less than or equal to 8.0. In particular, fatty alcohols having 12, 14, 16 or 18 carbon atoms in the alkyl chain are preferred.

It is preferred if the nonionic component having an HLB value of less than or equal to 8.0 to 1, 0 wt .-% to 50 wt .-%, in particular to 2.0 wt .-% to 25 wt. % and most preferably at 3.0 wt .-% to 15 wt .-%, in each case based on the total weight of the ready-to-use agent, present in the composition according to the invention.

The oxidizing agent preparation (B) and / or the preparation (A) containing the matting dyes are preferably formulated as flowable preparations.

Preferably, an emulsifier or a surfactant is added to the flowable preparations (A) and / or (B), surface-active substances being referred to as surfactants or as emulsifiers, depending on the field of application, and anionic, cationic, zwitterionic, amphoteric and nonionic surfactants and emulsifiers are selected. These substances will be described in detail below. Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. Preferred anionic surfactants are alkyl sulfates, alkyl ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate, sulfonate or sulfate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, N-acylaminopropyl-N, N-dimethylammonium glycinates and 2-alkyl-3-carboxymethyl-3-hydroxyethylimide. azolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group, and the cocoacylamino-ethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine. Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkyl aminopropionate the, cocoacylaminoethyl aminopropionate and C ₂ -C ₁₈ acyl sarcosine. Furthermore, it has proved to be advantageous if the hair treatment compositions according to the invention contain other nonionic surfactants which they do not fall under the above-described nonionic components having an HLB value of 8.0 or smaller. Suitable nonionic surfactants are, in particular, C ₈ -C ₂₂ -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds have been found to be particularly suitable. Further preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants. The anionic, nonionic, zwitterionic or amphoteric surfactants are used in amounts of from 0.1 to 45% by weight, preferably from 1 to 30% by weight and very particularly preferably from 1 to 15% by weight, based on the total amount of the ready-to-use agent ,

Also preferred according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates. The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines (eg stearamidopropyldimethylamine). Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^®, ^® and Dehyquart® Armocare® ^®. 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 agent. Amounts of 0.1 to 5 wt .-% are particularly preferred. In a preferred embodiment, nonionic, zwitterionic and / or amphoteric

Surfactants and mixtures thereof are preferred.

The compositions according to the invention may preferably contain at least one nonionic emulsifier or surfactant having an HLB value of 8 to 18, according to the methods described in the Römpp Lexikon Chemie (Hrg. J. Falbe, M. Regitz), 10th edition, Georg Thieme Verlag Stuttgart, New York, (1997), page 1764, listed definitions. Nonionic emulsifiers or surfactants having an HLB value of 10-15 may be particularly preferred according to the invention.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers (such as vinylpyrrolidinone / vinyl acrylate copolymers, polyvinylpyrrolidinone and vinylpyrrolidinone / vinyl acetate copolymers and polysiloxanes), zwitterionic and amphoteric polymers (such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate tert-butyl aminoethyl methacrylate-hydroxypropyl methacrylate copolymers), anionic polymers (such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidine / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers), thickening agents (such as agar-agar, guar gum, alginates, xanthan gum, gum arabicum, karaya gum, locust bean gum, Linseed gums, dextrans, cellulose derivatives, e.g., methylcellulose, hydroxyalkylcellulose, and carboxymethylcellulo se, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol), structurants (such as maleic acid and lactic acid), protein hydrolysates (especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates), perfume oils, Cyclodextrins, defoamers such as silicones, dyes for coloring the agent, antidandruff agents (such as Piroctone Olamine, zinc omadine and climazole), light stabilizers (in particular derivatized benzophenones, cinnamic acid derivatives and triazines), active substances (such as allantoin, pyrrolidonecarboxylic acids and their salts and bisabolol ), Cholesterol, bodying agents (such as sugar esters, polyol esters or polyol alkyl ethers), other fats and waxes such as beeswax, montan wax and paraffins, swelling and penetrating substances (such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary re phosphates), opacifying agents (such as latex, styrene / PVP and styrene / acrylamide copolymers), pearlizers (such as ethylene glycol mono- and distearate and PEG-3 distearate), pigments, blowing agents (such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air) and antioxidants.

The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents. With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced. A further subject of the present invention is a process for bleaching keratin fibers, in particular human hair, wherein an agent is obtained by mixing at least one oxidizing agent preparation (B) containing at least one oxidizing agent selected from hydrogen peroxide and its adducts to solid carriers, at least one bleaching preparation ( C), containing at least one bleaching power booster, and at least one preparation (A) is prepared, wherein the preparation (A) in a cosmetic carrier at least one coloring Mattierungskombination comprising at least one coloring component and which is suitable for whitening the keratinic fiber contained in the fiber yellowish and / or reddish color impressions by an appropriate complementary coloring, and at least one cationic pyridinium derivative according to formula (I) containing the agent for a period of 2 to 60 minutes , preferably 5 to 45 minutes is left in the hair, and the hair is then rinsed with water and / or a commercial shampoo. In the context of this article of the present invention, mutatis mutandis, the above statements apply analogously.

Another object of the present application is finally the use of an agent according to one of the aforementioned subject matter for matting during the whitening and / or bleaching keratinischer fibers, in particular human hair. In the context of this article of the present invention, mutatis mutandis, the above statements apply analogously.

The following examples are intended to illustrate the subject matter of the present invention without limiting it in any way.

B e i s p e e l e

1. Bleaching preparations with 4-acetyl-1-methylpyridinium p-toluenesulfonate:

HvdrenoT D INCI name: Cetearyl alcohol (Cognis) Lorol® ^® tech. INCI name: Coconut alcohol (Cognis) Eumulgin ^® B1 INCI Description of product: Ceteareth-12 (Cognis) Eumulgin ^® B2 INCI Description of product: Ceteareth-20 (Cognis) Akypo ^® Soft 45 NV INCI name: Sodium Laureth-5 carboxylate ( KAO Chemicals) Plantacare ^® 1200 UP INCI name: lauryl Glucoside (Cognis) Texapon ^® K 14 S 70 C INCI name: Sodium Myreth Sulfate (Cognis) Turpinal ^® SL INCI name: Etidronic Acid, Aqua (Water) (Solutia) Sodium silicate 40/42 Sodium water glass Disponil ^® FES 77 INCI name: Sodium Coceth-30 Sulfate (Cognis)

Hydrenol D, Lorol, Eumulgin B1, Eumulgin B2, Akypo Soft 45 NV, Plantacare 1200 UP and Texapon K 14 S 70 C were melted together at 80 ⁰ C and dispersed with a portion of the amount of water. Subsequently, the remaining recipe ingredients were incorporated with stirring in order. It was then made up to 100% by weight with water and the formulation was stirred cold.

Each bleaching cream was blended in a ratio of 1: 1 with a developer dispersion composed as follows. The pH of the finished application mixture was between 9 and 10.2.

Texapon NSO INCI name: Sodium Laureth Sulfate (Cognis)

Aculyn ^® 33 INCI name: Acrylates random copolymer (Rohm & Haas)

Dow Corning ^® DB 110 A INCI name: dimethicone (Dow Corning)

For the bleaching process, 4 times the amount of the finished application mixture was applied to strands of medium-blond hair of about 0.7 g weight. After the strands were bleached for 30 minutes at 32 ⁰ C, they were washed with a commercial shampoo and dried with a hair dryer.

2. Bleaching preparations with N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate:

Dehyton K INCI name: Cocoamidopropyl betaine (Cognis)

Each bleaching cream was mixed in a ratio of 1: 1 with the developer dispersion described under 1. The pH of the finished application mixture was between 9 and 10.2. For the Blondierprozess 4 times the amount of the finished application mixture was applied to strands of medium blond hair of about 0.7 g weight. After the strands were bleached for 30 minutes at 32 ⁰ C, they were washed with a commercial shampoo and dried with a hair dryer.

3. Bleaching preparations with 2-acetyl-1-methylpyridinium p-toluenesulfonate:

Each Blondiercreme was mixed in the ratio 1: 1 with the following developer dispersion. The pH of the finished application mixture was between 9 and 10.2.

Genamin STAC INCI name: Steartrimonioum Chloride (Clariant)

Claims

PATENT APPLICATIONS

1. A composition for the treatment of keratinic fibers, characterized in that it comprises in a cosmetic carrier a) at least one coloring matting combination comprising at least one coloring component and which is suitable for lightening the keratin fiber in the fiber remaining yellowish and / or reddish B) and at least one cationic pyridinium derivative according to formula (I), b) containing color impressions by a corresponding complementary coloring,

wherein

L is a CH ₂ -CH ₂ or a C (R 5) = CH unit, in which R 5 is hydrogen, a C ₁ -C ₄ -alkyl group, a partially or completely halogenated C ₁ -C ₆ -alkyl group, C-rC ₆ alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono- _(C-ι-C6 alkyl) amino group, a di- (C ₁ -C ₆ - alkyl) amino group, a C _Σ -Ce-acylamino group, a halogen or an acyl group R'C (O), wherein R 'is a C ₁ -C ₄ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C "rC ₆ -alkoxy-C C ₂ -C ₆ alkyl group,

R1 represents a C-rC ₆ alkyl group, a partially or completely halogenated C ₁ -C ₆ -

Alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, a C-ι-C ₆ -alkoxy-C ₂ -C ₆ alkyl group, a carboxy-Ci-Ce alkyl group, an aryl C-ι-C ₆ alkyl group, an amino-C ₂ -C ₆ alkyl group, a mono- _(C-ι-C6 alkyl) - amino-C ₂ -C ₆ alkyl group, a di- (C ι-C ₆ -alkyl) amino-C ₂ -C ₆ -alkyl group, a heteroaryl-C ₁ -C ₆ -alkyl group, a 3-oxobutyl group, a 2-oxopropyl group, an aryl group or a heteroaryl group,

R2 and R4 are each independently hydrogen, _C-ι-C4 alkyl group, a partially or fully halogenated C- | -C ₆ alkyl, C ₁ -C ₆ -AIkOXy- group, a hydroxy group, a nitrile group, a Amino group, a mono- (C ₁ -C ₆ -alkyl) -amino group, a di- (C ₁ -C ₆ -alkyl) -amino group, a C _Σ -Ce-acylamino group, a halogen or an acyl group R'C stand (O) wherein R 'is a _C-ι-C4 alkyl group, a C ₂ -C ₆ hydroxyalkyl group or a C "rC ₆ -alkoxy-C ₂ -C ₆ alkyl group, and R3 is hydrogen, a C 1 -C ₄ -alkyl group, a partially or completely halogenated C ₁ -C ₆ -alkyl group, C ₁ -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono- (C 1 -C ₆ -Alkyl) -amino group, a di- (C.rC ₆ -alkyl) -amino group, a C ₂ -C ₆ -acylamino group or a halogen, with the proviso that at least one of R2, R4 or R5 for a

Acyl group R'C (O), wherein R 'is a C- | -C ₄ alkyl group, a C ₂ -C ₆ - hydroxyalkyl group or a C- | -C ₆ alkoxy-C ₂ -C ₆ alkyl group , or

R 2 and R 3 together form a fused six-membered aromatic carbo-cyclus which optionally carries in addition 1 to 3 substituents which are selected independently from C 1 -C ₆ -alkyl group, partially or completely halogenated C 1 -C ₆ -alkyl group, C ₂ - C ₆ alkenyl group, hydroxy group, amino group, mono- (C ₁ -C ₆ -alkyl) -amino group, di- (C ₁ -C ₆ -alkyl) amino group, C ₁ -C ₆ -alkoxy group, halogen, nitro group, nitrile group, carboxyl group, optionally substituted aryl, or optionally substituted heteroaryl, and R4 is hydrogen, a _C-ι-C4 alkyl group, a partially or fully halogenated halo- C-ι-C ₆ alkyl group, C-ι-C ₆ Alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono (C ₁ -C ₆ -alkyl) -amino group, a di- (C ₁ -C ₆ -alkyl) -amino group, a C _Σ -Ce-acylamino group, a halogen or an acyl group R'C (O) wherein R 'is a C 1 -C ₄ alkyl group, a C ₂ -C ₆ hydroxyalkyl group ppe or a C 1 -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, and the anion X ^"is a physiologically acceptable anion.

2. Composition according to claim 1, characterized in that the coloring Mattierungskombination comprises a combination of at least one blue direct dye and a red direct dye, wherein the weight ratio between the sum of all blue direct dyes and the sum of all red direct dyes a value of greater or equal to 1.

3. Composition according to claim 2, characterized in that the weight ratio between the sum of all blue substantive dyes and the sum of all red substantive dyes has a value of 1 to 100, preferably from 1, 5 to 10 and particularly preferably from 2 to 4.

4. Composition according to one of claims 2 and 3, characterized in that the agent as a blue direct dye a compound according to formula (II) and / or one of its physiologically acceptable salts

wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each independently hydrogen,

Fluorine, chlorine, bromine, iodine, a hydroxy group or a nitro group contains.

5. A composition according to claim 4, characterized in that the agent contains as a blue direct dye at least one compound which is selected from the group consisting of compounds of formula (II) and / or one of its physiologically acceptable salts, wherein a ) R1, R2, R3, R4, R5, R6, R7 and R8 are bromine, b) R1, R4, R5, R6, R7 and R8 are bromine and R2 and R3 are hydrogen, c) R1 and R4 are hydrogen and R 2, R 3, R 5, R 6, R 7 and R 8 are bromo, d) R 1, R 2, R 3 and R 4 are fluorine and R 5, R 6, R 7 and R 8 are bromo, e) R 1, R 2, R 3 and R 4 are chlorine and R5, R6, R7 and R8 are bromo, f) R1, R2, R3 and R4 are iodine and R5, R6, R7 and R8 are bromine, g) R1, R2, R3, R4, R5, R6, R7 and R8 is chlorine, h) R1, R2, R3 and R4 are bromine and R5, R6, R7 and R8 are chlorine, i) R1 and R4 are bromine, R2 and R3 are hydrogen and R5, R6, R7 and R8 are chlorine, j) R1 and R4 are hydrogen, R2 and R3 are bromine and and R1, R2, R3 and R4 are iodine and R5, R6, R7 and R8 are chlorine, I) R1, R2, R3, R4, R5, R6, R7 and R8 is iodine, m) R1, R2, R3 and R4 are fluorine and R5, R6, R7 and R8 are iodine, n) R1, R2, R3 and R4 are chlorine and R5, R6, R7 and R8 are iodine or o) R1, R2, R3 and R4 are bromine and R5, R6, R7 and R8 are iodine.

6. Composition according to one of claims 2 to 5, characterized in that the agent as red substantive dye, a compound according to formula (III) and / or one of its physiologically acceptable salts

7. Composition according to claim 6, characterized in that the agent as red substantive

Dye comprises at least one compound which is selected from the group formed from compounds of formula (III) and / or one of its physiologically acceptable salts, wherein a) R9, R10, R11 and R12 are chlorine and R13, R14, R15 and R16 is bromine, b) R9 and R12 are chlorine, R1 and R12 are hydrogen and R13, R14, R15 and R16 are bromine, c) R9, R10, R11 and R12 are chlorine and R13, R14, R15 and R16 is iodine, d) R9, R10, R11 and R12 are hydrogen and R13, R14, R15 and R16 are bromine, or e) R9, R10, R11 and R12 are hydrogen and R13, R14, R15 and R16 are iodine stand.

8. Composition according to one of claims 1 to 7, characterized in that the agent contains as cationic pyridinium derivative at least one compound according to formula (I), wherein

L is a C (R 5) = CH unit, in which R 5 is hydrogen, a C 1 -C ₄ -

Alkyl group, C 1 -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-C ₁ -C ₆ -alkylamino group, a di- (C ₁ -C ₆ -alkyl) -amino group, a C ₂ - C ₆ acylamino group, a halogen or an acyl group R'C (O), where R 'is a C ₁ -C ₄ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C ₁ -C ₆ -alkoxy-C ₂ - C ₆ alkyl group stands,

R1 represents a _C-ι-C6 alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkyl group hydroxy, a C-ι-C ₆ -alkoxy-C ₂ -C ₆ alkyl group, a carboxy _C-ι-C6 alkyl group, an aryl C-ι-C ₆ alkyl group, an amino C ₂ -C ₆ alkyl group, a (C-rC ₆ alkyl) amino-C ₂ -C ₆ alkyl group, a di- (CrC ₆ alkyl) amino-C ₂ -C ₆ alkyl group, a heteroaryl-CrC ₆ alkyl group, a 3-oxobutyl group, a 2- oxopropyl group, an aryl group or a heteroaryl group is,

R 2 and R _{4 are} each independently of one another hydrogen, a C 1 -C ₄ -alkyl group, C ₁ -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-C ₁ -C ₆ -alkylamino group, a di (C -C ₆ alkyl) amino group, a C _Σ -Cε-acylamino group, a halogen or an acyl group R'C (O), where R 'is a Ci-C ₄ alkyl group, a C ₂ -C ₆ hydroxyalkyl group or a C- | -C ₆ -alkoxy-C ₂ -C ₆ alkyl group, and R3 represents hydrogen, a _C-ι-C4 alkyl group, Ci-Cβ alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-C ₁ -C ₆ -alkyl-amino group, a di- (C ₁ -C ₆ -alkyl) -amino group, a C _Σ -Ce-acylamino group or a halogen, with the proviso that at least one of the radicals R ₂ , R ₄ or R 5 is an acyl group R'C (O), where R 'is a C ₁ -C ₄ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C 1 -C ₆ -alkoxy-C ₂ -C ₆ alkyl group.

9. Composition according to one of claims 1 to 8, characterized in that the agent contains as cationic pyridinium derivative at least one compound according to formula (I), wherein

L is a C (R5) = CH unit, wherein R5 is hydrogen or a

Acyl group R'C (O), wherein R 'is a R 1 is a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, a Aryl-Ci-Cβ-alkyl group or a 2-oxopropyl group, R2 and R4 are each independently hydrogen or an acyl group

R'C (O), wherein R 'is a C-rC ₄ alkyl group, and R3 is hydrogen, with the proviso that at least one of R2, R4 or R5 is an acyl group

R'C (O), where R 'is a Ci-C ₄ alkyl group, a C ₂ -C ₆ hydroxyalkyl group or a Ci-C ₆ alkoxy-C ₂ -C ₆ alkyl group.

10. Composition according to one of claims 1 to 7, characterized in that the agent contains as cationic pyridinium derivative at least one compound according to formula (I), wherein

L is a CH ₂ -CH ₂ group,

R 1 is a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl group, a carboxy- Ci-Cβ alkyl group, an aryl Ci-Cβ alkyl group, an amino C ₂ -C ₆ alkyl group, a (C-ι-C ₆ alkyl) amino-C ₂ -C ₆ alkyl group, a Di- (C ₁ -C ₆ -alkyl) aminoC ₂ -C ₆ -alkyl group, a heteroaryl-C ₁ -C ₆ -alkyl group, a 3-oxobutyl group, a 2-oxopropyl group, an aryl group or a heteroaryl group,

And R2 together form a fused cyclus six membered aromatic carbocycle, R3 optionally additionally carries 1 to 3 substituents independently selected from Ci-C ₆ alkyl, C ₂ -C ₆ - alkenyl group, hydroxy group, amino group, mono- _CrC-6 alkyl amino group, di- (Ci-C ₆ alkyl) amino group, Ci-C ₆ alkoxy, halogen, nitro group, nitrile group, carboxyl group, optionally substituted aryl, or optionally substituted heteroaryl, and R4 is Hydrogen, a C 1 -C ₄ -alkyl group, C ₁ -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-C 1 -C ₆ -alkylamino group, a di (C 1 -C ₄₎ alkyl group; C ₆ alkyl) amino group, a C _Σ -Ce acylamino group or a halogen.

11. Composition for lightening and / or bleaching keratinic fibers, characterized in that it is prepared by mixing at least one oxidizing agent preparation (B) containing at least one oxidizing agent selected from hydrogen peroxide and its addition compounds to solid carriers, and at least one preparation (A) wherein the preparation (A) is in a cosmetic carrier a) at least one coloring matting combination containing at least one coloring

Component and which is suitable for compensating yellowish and / or reddish color impressions remaining in the fiber when the keratinic fiber is lightened by a corresponding complementary coloring, b) and contains at least one cationic pyridinium derivative according to formula (I),

wherein

L is a CH ₂ -CH ₂ - or a C (R ₅ ) = CH unit, in which R _{5 is} hydrogen, a C 1 -C ₄ -alkyl group, C 1 -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono- C 1 -C ₆ -alkylamino group, a di (C 1 -C ₆ -alkyl) amino group, a C _Σ -Ce -acylamino group, a halogen or an acyl group R'C (O), where R 'is a C 1 -C 4 -alkyl group, a C ₂ -C ₆ hydroxyalkyl group or a C-ι-C ₆ -alkoxy-C ₂ -C ₆ alkyl group

R1 represents a C-rC ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkyl group hydroxy, a C-rC ₆ -alkoxy-C ₂ -C ₆ alkyl group, a carboxy-dC ₆ alkyl group, an aryl Ci-C ₆ alkyl group, an amino-C ₂ -C ₆ alkyl group, a (Ci-C ₆ alkyl) amino-C ₂ -C ₆ alkyl group, a di- ( Ci-C ₆ alkyl) amino-C ₂ -C ₆ alkyl group, a heteroaryl-Ci-C ₆ alkyl group, a 3-oxobutyl group, a 2- oxopropyl group, an aryl group or a heteroaryl group,

R 2 and R _{4 are} each independently of one another hydrogen, a C 1 -C ₄ -alkyl group, C ₁ -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-C ₁ -C ₆ -alkylamino group, a di (C 1 -C ₄ ) alkyl group; C ₁ -C ₆ -alkyl) -amino group, a C ₂ -C ₆ -acylamino group, a halogen or an acyl group R'C (O), where R 'is a dd-alkyl group, a C ₂ -C ₆ -hydroxyalkyl group or a C-ι-C ₆ -alkoxy-C ₂ -C ₆ alkyl group represents,

R3 is hydrogen, a dd-alkyl group, C ₁ -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-C ₁ -C ₆ -alkylamino group, a di- (C ₁ -C ₆ -alkyl) -amino group, a C ₂ -C ₆ acylamino group or a halogen, with the proviso that at least one of the radicals R 2, R ₄ or R 5 is an acyl group R'C (O), where R 'is a Ci-C ₄ alkyl group, a C ₂ -C ₆ - hydroxyalkyl group or a Ci-C ₆ -alkoxy-C ₂ -C ₆ alkyl group, or

And R2 together form a fused cyclus six membered aromatic carbocycle, R3 optionally additionally carries 1 to 3 substituents independently selected from Ci-C ₆ alkyl, C ₂ -C ₆ - alkenyl group, hydroxy group, amino group, mono- dC ₆ alkyl amino group, di- (C- | -C ₆ alkyl) amino, C | -C ₆ alkoxy, halogen, nitro group, nitrile group, carboxy group, optionally substituted aryl, or optionally substituted heteroaryl, and R _{4 is} hydrogen, a C ₁ -C ₄ -alkyl group, C ₁ -C ₆ -alkoxy group, a hydroxy group, a nitrile group, an amino group, a mono-Ci-Ce-alkyl-amino group, a di- _(C-ι-C6 alkyl) amino group, a C ₂ -C ₆ acylamino group or a halogen, and the anion X ^"is a physiologically compatible anion is available.

12. Composition according to claim 11, characterized in that the coloring matting combination as a coloring component comprises a combination of at least one blue direct dye and a red direct dye, wherein the weight ratio between the sum of all blue direct dyes and the sum of all red substantive Dyes has a value of greater than or equal to 1, and the total amount of substantive dyes from 0.0001 to 0.2 wt .-%, based on the total weight of the ready-to-use agent is.

13. Composition according to one of claims 1 1 to 12, characterized in that it is prepared by mixing with additionally at least one Blondierzubereitung (C), containing as Blleichkraftverstärker at least one inorganic salt selected from Peroxomonosulfaten and / or Peroxodisulfaten.

14. Method in which an agent according to any one of claims 1 to 13 is applied to human hair, the agent is left in the hair for a period of 2 to 60 minutes, preferably 5 to 45 minutes, and then the hair with water and / or a commercial shampoo.

15. Use of a composition according to any one of claims 1 to 13 for matting during the whitening and / or bleaching keratinischer fibers, in particular human hair.