EP2488155A2

EP2488155A2 - Lightening agent having cationic acylpyridinium derivatives and certain ammonium compounds

Info

Publication number: EP2488155A2
Application number: EP10752845A
Authority: EP
Inventors: Wibke Gross; Ralph Nemitz; Astrid Kroos; Georg KNÜBEL
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2009-10-13
Filing date: 2010-09-17
Publication date: 2012-08-22
Also published as: DE102009045629A1; WO2011045142A3; JP2013507411A; US8277516B2; WO2011045142A2; US20120192890A1

Abstract

The invention relates to a means for lightening keratinous fibers, wherein a cosmetic carrier comprises (i) at least one oxidation agent, (ii) at least one acylpyridinium derivative of the formula (I) and (iii) at least one ammonium compound comprising hydroxyl groups of the formula (II).

Description

"Brightening Agents with Cationic Acylpyridinium Derivatives and Certain Ammonium Compounds"

The present invention relates to compositions for use on keratin fibers, in particular human hair, and in particular compositions for brightening keratinischer fibers, containing cationic Acylpyridiniumderivate, a hydroxyl-containing ammonium compound and an oxidizing agent and a corresponding method.

Brightening one's own hair color has always been the desire 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. 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 - as the oxidizing agent alone, for the achievement of a stronger Blondiereffektes usually a mixture of hydrogen peroxide and Peroxodisulfatsalzen and / or Peroxomonosulfatsalten is used. However, the lightening is also accompanied by damage to the hair, as not only the dyes of the hair, but also the other structural 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. Hair dyeing or whitening agents which show good lightening performance without simultaneously damaging the hair fiber are not yet known.

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.

The object of this invention is therefore to provide novel means for whitening or bleaching of hair, which are comparable or superior in their Aufhellleistung the usual on the market funds, but at the same time do not have the aforementioned disadvantages and in particular cause a reduced hair damage.

It has been disclosed in DE 102007047685 A1 that certain cationic 4-acetylpyridinium derivatives and certain imidazole derivatives are capable of being added to hydrogen peroxide as activator act and thereby achieve on hair compared to an application of the oxidizing agent alone a stronger whitening effect. A co-activator in this connection was a derivative of the imidazole, in particular imidazole itself. For toxicological reasons, the use of imidazole is no longer indicated and the search for a powerful substitute another central task of this invention.

The use of cationic acylpyridinium derivatives in hair dyeing is known, for example, from the publications DE 10148845 A1 or DE 10261656 A1. In both documents, however, these derivatives are described together with at least one second coloring component as a coloring agent and thus to increase the color intensity of the hair. From the state of the art, it has hitherto not been apparent that these 4-acylpyridinium derivatives can be used for the lightening of hair with a very good decolorizing power.

It has now been found, in a completely unpredictable manner, that a specific combination of the inventive pyridinium derivatives of the general structure (I), a hydroxyl-containing ammonium compound as a specific co-activator and an oxidizing agent exhibits a bleaching action which is comparable or superior to the prior art and lighten the hair much more than would be possible by using a comparable amount of hydrogen peroxide alone.

Due to the improved bleaching performance when using the composition according to the invention, the amount of oxidizing agent used can be reduced and hair damage can be minimized as a result. A shortening of the exposure time while achieving a whitening effect according to the prior art is possible in this way.

The agents of the invention discolor the natural dye melanin by oxidation. The active compound combination according to the invention forms no dye in the keratin-containing fiber without the presence of additional dyes / dye precursors. Also previously on or in the keratin-containing fiber synthetic dyes can be bleached using the means of the invention.

A first object of the present invention is therefore an agent for the treatment of keratinic fibers, in particular human hair, which is characterized in that the agent in a cosmetic carrier

(i) at least one oxidizing agent,

(ii) at least one acylpyridinium derivative of the formula (I) (I), in which

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-C ₂ -C ₆ - alkyl group, an aryl-C 1 -C 6 -alkyl group, a heteroaryl-C 1 -C 6 -alkyl group, an aryl group or a heteroaryl group,

R 2, R 3 and R 4 are each independently hydrogen, a C 1 -C ₆ alkyl group, a halogen atom or a C 1 -C ₆ acyl group, with the proviso that at least one of R 2, R 3 and R 4 is a Ci-C6-acyl group stands,

and X ^"is a physiologically acceptable anion, and

(iii) at least one hydroxyl-containing ammonium compound of the formula (II)

is either a carboxylate group (CO ₂ ^~ ), or one of the groups selected from a carboxylic acid group (CO ₂ H), an alkali metal carboxylate group (CO ₂ M) or a carboxylic acid-C 1 -C 6 -alkyl ester group Group, in which case the compound of the formula (II) for balancing the positive charge in each case comprises a physiologically acceptable anion.

Under keratinic fibers or keratin fibers are furs, wool, feathers and especially human hair to understand. Although the compositions according to the invention are primarily suitable for dyeing and / or whitening keratin fibers, in principle, there is nothing to prevent their use in other fields as well.

The agents according to the invention contain the active ingredients in a cosmetic carrier. The cosmetic carrier is preferably aqueous, alcoholic or aqueous-alcoholic. For the purpose of hair bleaching 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. However, it is also possible to provide for storage a powdery or tablet-shaped formulation, which is preferred for lightening agents. This is then before application in a solvent such as water or with organic solvents or with mixtures of water and organic solvents Received the application mixture mixed. For the purposes of the invention, an aqueous carrier contains at least 40% by weight, in particular at least 50% by weight, of water. For the purposes of the present invention, aqueous-alcoholic carriers are to be understood as meaning water-containing compositions containing 3 to 70% by weight of a C 1 -C ₄ -alcohol, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents such as 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. Preferred agents according to the invention are characterized in that they additionally contain a non-aqueous solvent, with particularly preferred agents according to the invention containing the solvent in a concentration of 0.1 to 30% by weight, preferably in a concentration of 1 to 20% by weight. , very particularly preferably in a concentration of 2 to 10 wt .-%, each based on the agent included.

As the first essential component, the agent according to the invention contains at least one oxidizing agent. As oxidizing agent all common oxidizing agents are conceivable. Hydrogen peroxide and suitable alkali metal, alkaline earth metal, iron, aluminum or zinc salts of perborates, peroxides, persulfates, percarbonates or organic peracids can be used. An embodiment of the present invention is characterized in that the agent contains, as the oxidizing agent, at least one compound selected from the group consisting of hydrogen peroxide, alkali metal peroxides and / or alkali metal perborates. These include sodium peroxide, potassium peroxide, sodium perborate and potassium perborate. Preferably, hydrogen peroxide itself is used as the aqueous solution. However, hydrogen peroxide can also be used in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as sodium percarbamide, polyvinylpyrrolidinone nH ₂ 0 ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide. Preferred oxidizing agents are selected from hydrogen peroxide, sodium peroxide and sodium perborate, in particular from hydrogen peroxide.

The oxidizing agents are in the mixture preferably from 0.01 to 25 wt .-%, particularly preferably from 0.1 to 15 wt .-% and particularly preferably from 0.5 to 8 wt .-%, each based on the total weight of ready to use agent, included.

In one embodiment of the present invention are those compounds of formula (I) are preferred in which the radical R1 of the general structure (I) is a C-C _ö alkyl group, a C ₂ -C ₆ alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group. It is preferred according to the invention if the radical R 1 is a C ₁ -C ₆ -alkyl group, preferably methyl, ethyl, n-propyl or isopropyl and particularly preferably methyl. It has been found that the acylpyridinium derivatives according to formula (I) according to the invention have particularly advantageous properties when they carry the acyl group either in the 2- or 4-position on the pyridine ring. Preferred compounds of formula (I) are additionally those compounds in which either the radical R 2 or the radical R4 is a C- | -C ₆ acyl group, preferably an acetyl group, is. It is further preferred if one of the radicals R 2 or R 4 is an acetyl group, while the other of these radicals and the radical R 3 are each hydrogen. A further embodiment of the present invention is therefore characterized in that the agent contains as acylpyridinium derivative according to formula (I) at least one 2-acetylpyridinium derivative and / or 4-acetylpyridinium derivative.

Suitable acetylpyridinium derivatives are the physiologically tolerable salts which contain, as cation, an acetylpyridinium derivative selected from 4-acetyl-1-methylpyridinium, 4-acetyl-1-allylpyridinium, 4-acetyl-1- (2-hydroxyethyl) pyridinium, 2- Acetyl-1-methylpyridinium, 2-acetyl-1-allylpyridinium and 2-acetyl-1- (2-hydroxyethyl) pyridinium.

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 1 -C 4 -alkyl sulfonate, trifluoromethanesulfonate, acetate, trifluoroacetate, perchlorate, sulfate, Hydrogen sulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate According to the invention, it is particularly advantageous if the anion X ^"is hydrogen sulfate, p-toluenesulfonate, benzenesulfonate or acetate.

In particular, those agents are preferred according to the invention which are characterized in that the acylpyridinium derivative of the formula (I) is selected from the group formed from 4-acetyl-1-methylpyridinium p-toluenesulfonate, 4-acetyl-1-methylpyridinium Benzenesulfonate, 4-acetyl-1-methylpyridinium hydrogensulfate, 4-acetyl-1-methylpyridinium acetate, 4-acetyl-1-allylpyridinium p-toluenesulfonate, 4-acetyl-1-allylpyridinium-benzenesulfonate, 4-acetyl-1-allylpyridinium hydrogen sulfate, 4-acetyl-1-allylpyridinium acetate, 2-acetyl-1-methylpyridinium p-toluenesulfonate, 2-acetyl-1-methylpyridinium-benzenesulfonate, 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 hydrogensulfate and 2-acetyl-1-allylpyridinium acetate.

Particularly preferred agents according to the invention are characterized in that they contain, as the acylpyridinium derivative of the formula (I), a compound selected from 4-acetyl-1-methylpyridinium p-toluenesulfonate and / or 2-acetyl-1-methylpyridinium p-toluenesulfonate , in particular 4-acetyl-1-methylpyridinium p-toluenesulfonate.

Such agents have been found to be preferred, which are characterized in that they contain one or more acylpyridinium derivatives of the formula (I) in a total amount of 0.001 to 15 Wt .-%, preferably from 0.01 to 10 wt .-% and particularly preferably from 0.1 to 5 wt .-%, each based on the total weight of the ready mixture mixture.

As a third essential ingredient, the agent according to the invention comprises at least one hydroxyl-containing ammonium compound of the formula (II),

Y is either a carboxylate group (C0 ₂ ^~ ),

or for one of the groups selected from a carboxylic acid group (C0 ₂ H), an alkali metal or ammonium carboxylate group (CO ₂ M) or a carboxylic acid C 1 -C 6 -alkyl ester group (C0 ₂ -C 1 -C 6) Alkyl), in which case the compound of the formula (II) for balancing the positive charge in each case comprises a physiologically acceptable anion.

It is preferred that the radical Y is a carboxylate group (C0 ₂ ^~ ), so that the compound according to formula (II) results in a betainic zwitterionic compound. This compound is known as carnitine.

In a further embodiment, the radical Y is selected from a carboxylic acid group (CO ₂ H), an alkali metal carboxylate group (CO ₂ M) or a carboxylic acid C 1 -C ₆ -alkyl ester group (CO ₂ -Ci-C6 alkyl). The resulting ammonium compound then comprises at least one physiologically acceptable anion to balance the charge.

The physiologically tolerable anion is preferably p-toluenesulfonate, benzenesulfonate, acetate, chloride, bromide, hydrogensulfate, sulfate, citrate, lactate, succinate, malonate or tartrate, preferably chloride or tartrate. The anion is used according to its valence and stoichiometry.

Preferred examples of an alkali metal or ammonium carboxylate group (CO ₂ M) are a sodium carboxylate group (CO ₂ Na), a potassium carboxylate group (CO ₂ K) and an ammonium carboxylate group (CO ₂ NH ₄ ). Preferred examples of a carboxylic acid C 1 -C 6 -alkyl ester group (C0 ₂ -C 1 -C 6 -alkyl) are a carboxylic acid methyl ester group (C0 ₂ Me), a carboxylic acid ethyl ester group (C0 ₂ Et), an isopropyl ester carboxylic acid group (C0 ₂ / Pr) and a carboxylic acid tert-butyl ester group (C0 ₂ f Bu). Particularly preferred are the methyl and ethyl ester groups.

The hydroxyl-containing ammonium compounds of the formula (II) contain an asymmetric carbon atom. For the designation of enantiomers, the absolute Configuration of these chiral centers using the Cahn-Ingold-Prelog rules determined and described using the stereo descriptors R and S. For historical reasons, the D / L convention for describing stereochemistry is also possible. In the context of the present invention, both possible enantiomers can be used equally as a specific compound or else mixtures thereof, in particular as racemates. In the present invention both enantiomers are encompassed by the invention, both the R-enantiomers and the S-enantiomers of each substance are according to the invention. In addition, it is possible to use both an equimolar mixture of both enantiomers (racemate) in hair whitening agents as well as any other conceivable molar ratio of R to S enantiomer. However, it is particularly advantageous to use the naturally preferred isomeric form, the L-configuration.

A further embodiment of the use according to the invention is characterized in that the agent as hydroxyl-containing ammonium compound of the formula (II) at least one compound selected from the group consisting of L-carnitine ((3R) -carnitine), D - Carnitine ((3S) carnitine), L / D-carnitine ((3R / S) carnitine) and their physiologically acceptable salts.

Particularly preferred as hydroxyl-containing ammonium compound of the formula (II) is a compound which is selected from the group formed from L-carnitine ((3R) -carnitine), D-carnitine ((3S) -carnitin) , L / D-carnitine (3R S) -carnitine, L-carnitine hydrochloride ((3R) - carnitine hydrochloride), D-carnitine hydrochloride ((3S) -carnitine hydrochloride), L / D-carnitine hydrochloride ((3R / S ) Carnitine hydrochloride), L-carnitine tartrate ((3R) carnitine tartrate), D-carnitine tartrate ((3S) carnitine tartrate) and L / D carnitine ((3R S) carnitine tartrate).

A further embodiment is characterized in that the agent comprises one or more hydroxyl-containing ammonium compound of the formula (II) in a total weight of 0.01 to 10 wt .-%, in particular from 0.01 wt .-% to 5 wt .-%, based on the total weight of the ready-to-use agent contains.

In consideration of the above-mentioned preferred embodiments, it represents a very specific and expressly preferred embodiment, when the means for lightening keratinic fibers in a cosmetic carrier in addition to hydrogen peroxide as the first component as a second component at least one compound selected from the group formed 4-acetyl-1-methylpyridinium p-toluenesulfonate, 4-acetyl-1-methylpyridinium benzenesulfonate, 4-acetyl-1-methylpyridinium bromide, 4-acetyl-1-methylpyridinium hydrogensulfate, 4-acetyl-1-allylpyridinium p-toluosulfonate, 4-Acetyl-1-allyl pyridinium benzene sulfonate, 4-acetyl-1-allyl pyridinium bromide, 4-acetyl-1-allyl pyridinium hydrogen sulfate, 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 hydrogensulfate and 4-acetyl-1-methylpyridinium p-toluenesulfonate and from 2-acetyl-1-methylpyridinium benzene sulfonate, 2-acetyl-1-methylpyridinium bromide, 2-acetyl- 1-methylpyridinium hydrogensulfate, 2-acetyl-1-allylpyridinium p-toluenesulfonate, 2-acetyl-1-allylpyridinium benzenesulfonate, 2-acetyl-1-allylpyridinium bromide, 2-acetyl-1-allylpyridinium hydrogensulfate, 2-acetyl-1 - (2-hydroxyethyl ) pyridinium p-toluenesulfonate, 2-acetyl-1- (2-hydroxyethyl) pyridinium benzenesulfonate, 2-acetyl-1- (2-hydroxyethyl) pyridinium bromide and 2-acetyl-1- (2-hydroxyethyl) pyridinium hydrogensulfate, and as third component at least one compound selected from the group consisting of L-carnitine ((3R) carnitine), D-carnitine ((3S) carnitine), L / D carnitine ((3R / S) carnitine ) and their physiologically acceptable salts in the already described preferred proportions.

Finally, very particular preference is given to compositions which contain one of the following combinations, wherein the weight data in turn relate to the total weight of the ready-to-use agent:

Combination (a):

0.1 to 4.0% by weight of 4-acetyl-1-methylpyridinium p-toluenesulfonate, 0.1 to 3.0% by weight of L-carnitine and 0.1 to 12.0% by weight of hydrogen peroxide ,

Combination (b):

0.1 to 4.0% by weight of 4-acetyl-1-methylpyridinium p-toluenesulfonate, 0.1 to 3.0% by weight of D- / L-carnitine and 0.1 to 12.0% by weight. -% hydrogen peroxide.

Combination (c):

0.1 to 4.0% by weight of 2-acetyl-1-methylpyridinium p-toluenesulfonate, 0.1 to 3.0% by weight of L-carnitine and 0.1 to 12.0% by weight of hydrogen peroxide ,

Combination (d):

0.1 to 4.0% by weight of 2-acetyl-1-methylpyridinium p-toluenesulfonate, 0.1 to 3.0% by weight of D- / L-carnitine and 0.1 to 12.0% by weight. -% hydrogen peroxide.

Bleaching processes on keratin fibers usually take place in an alkaline medium. However, in order to protect the keratin fibers as well as the skin as much as possible, it is not desirable to set too high a pH. Therefore, it is preferred that the pH of the ready-to-use agent is between 7 and 11, more preferably between 8 and 10.5. For the purposes of the present invention, the pH values are pH values which were measured at a temperature of 22 ° C.

To adjust the pH, common acidification and alkalizing agents are known to the person skilled in the art. The alkalizing agents which can be used for adjusting the pH are typically selected from ammonia, inorganic salts, in particular the alkali metals and alkaline earth metals, organic alkalizing agents, in particular amines and basic amino acids. Acidifying agents which are preferred according to the invention are pleasure acids, such as, for example, citric acid, acetic acid, malic acid or tartaric acid, and also dilute mineral acids. Inorganic alkalizing agents which can be used according to the invention are preferably selected from the group formed from sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, sodium carbonate and potassium carbonate. Particularly preferred are sodium hydroxide and / or potassium hydroxide. The basic amino acids are preferably selected from the group which is formed from L-arginine, D-arginine, D / L-arginine, L-lysine, D-lysine, D / L-lysine, particularly preferably L-arginine, D- Arginine and D / L-arginine. Preference is given to using additional acidifying agents and alkalizing agents in each case in an amount of from 0.05 to 15% by weight, in particular from 0.5 to 10% by weight, based on the total weight of the ready-to-use agent.

For the strong lightening of very dark hair, the sole use of hydrogen peroxide or its addition products to organic or inorganic compounds is often not sufficient. In these cases, a combination of hydrogen peroxide and persulfates or peroxodisulfates is usually used. It has been found that the addition of the acylpyridinium derivatives according to the invention of the general structure (I) and hydroxyl-containing ammonium compound of the formula (II) results not only in hydrogen peroxide alone but also in a combination of hydrogen peroxide and peroxodisulfate salts in an increase in the whitening power ,

Therefore, should the consumer feel the desire for a very strong bleaching, in a further embodiment it may be preferred if in addition to the cationic acylpyridinium compound of general structure (I), hydroxyl-containing ammonium compound of formula (II) and hydrogen peroxide additionally at least an inorganic persulfate salt or peroxodisulfate salt is contained in the agent for lightening the keratinic fibers. Preferred peroxodisulfate salts are ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate. The peroxodisulfate salts may be present in an amount of from 0.1 to 25% by weight, more preferably in an amount of from 0.5 to 15% by weight, based on the total weight of the ready-to-use agent.

The compositions according to the invention can be prepared directly before use from two or more separately packaged preparations. This is particularly useful for the separation of incompatible ingredients to avoid premature reaction.

A common way is therefore to use a first agent which contains at least one cationic acylpyridinium derivative of the general formula (I) and at least one hydroxyl-containing ammonium compound of the formula (II), directly before use with a second agent in which the oxidizing agent (s) according to the invention are contained. Another object of the present invention is therefore an agent for whitening keratinic fibers, in particular human hair, which immediately before application to the hair of a flowable preparation (A), which at least one cationic acylpyridinium derivatives of the general formula (I) and at least a hydroxyl group-containing ammonium compound of the formula (II), and an oxidizing agent preparation (B) containing at least one oxidizing agent selected from hydrogen peroxide and / or its addition compounds to organic or inorganic compounds is obtained.

The oxidizing agent preparation (B) is preferably an aqueous, flowable oxidizing agent preparation. Preferred agents for lightening keratinic fibers according to the invention are characterized in that the flowable oxidizing agent preparation (B) - based on its weight - 40 to 90 wt .-%, preferably 50 to 85 wt .-%, particularly preferably 55 to 80 wt. %, more preferably 60 to 77.5 wt .-% and in particular 65 to 75 wt .-% water.

The use of peroxodisulfate salts is generally carried out in the form of an optionally dedusted powder or a molding pressed into the mold. In order to avoid premature degradation of the acylpyridinium derivatives according to the invention by contact with the persulfates or peroxodisulfates, it is preferred according to the invention to provide the persulfates or peroxodisulfates as separately packaged component (C).

In this connection, a 3-component human hair whitening agent is another object of the present invention. This agent is applied to the hair immediately prior to application by thoroughly mixing a flowable preparation (A) containing at least one cationic acylpyridinium derivative of the general formula (I) and at least one hydroxyl-containing ammonium compound of the formula (II), an oxidizing agent preparation ( B) containing at least one oxidizing agent selected from hydrogen peroxide and / or its addition compounds to organic or inorganic compounds and additionally a third, present in powder form preparation (C), which contains at least one inorganic peroxodisulfate salt prepared.

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, which is an inventive agent with the three compulsory ingredients.

To further increase the performance of the oxidizing agent preparation, at least one optionally hydrated SiO ₂ compound may additionally be added to the composition according to the invention. It may be preferred according to the invention, the optionally hydrated Si0 ₂ compounds in amounts of 0.05 wt .-% to 15 wt .-%, particularly preferred zugt in amounts of 0, 15 wt .-% to 10 wt .-% and most preferably in amounts of 0.2 wt .-% to 5 wt .-%, each based on the anhydrous composition of the invention to use. The quantities given in each case the content of Si0 ₂ compounds (without their water content) in the funds again.

With regard to the optionally hydrated Si0 ₂ compounds, the present invention is in principle not limited. Preference is given to silicic acids, their oligomers and polymers, and salts thereof. Preferred salts are the alkali metal salts, especially their potassium and sodium salts. The optionally hydrated Si0 ₂ compounds can be present in various forms. According to the invention, the Si0 ₂ compounds are preferably used in the form of silica gels (silica gel) or as water glass. Particularly preferred according to the invention are water glasses.

In a preferred embodiment, the brightening agents according to the invention also contain at least one color-modifying component. The color-modifying component is selected from at least one oxidation dye precursor and / or substantive dye.

In one embodiment of the present invention, the color-modifying component agent comprises at least one oxidation dye precursor and / or direct dye. In a preferred embodiment of the use according to the invention, the dyeing preparation contains as color-modifying component at least one oxidation dye precursor.

As oxidation dye precursors, the dyeing formulations contain at least one developer component and optionally at least one coupler component. The developer components can form the actual dyes with one another, but preferably with coupler components. Preferably, therefore, the colorants of the present invention contain at least one developer type oxidation dye precursor and at least one coupler type oxidation dye precursor. The developer and coupler components are usually used in free form. In the case of substances having amino groups, however, it may be preferable to use them in salt form, in particular in the form of the hydrochlorides and hydrobromides or the sulfates.

In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components can be present in a molar ratio of 1: 0.5 to 1: 2. 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) -1,4J, 10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (1, 2 -dihydroxyethyl) phenol and 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. Very particularly preferred developer components are p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-) 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 10 wt .-%, preferably 0.001 to 5 wt .-%, each based on the ready-to-use agent.

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-methyl- phenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-methoxy

2-amino-4- (2-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) 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-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3 -methylpyrazol-5-one, 1-naphthol, 1, 5-dihydroxynaphthalene, 2J-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 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 are resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol, 3-aminophenol, 2- (2,4-diamino-phenoxy) 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 physiological compatible salts. The coupler components are preferably used in an amount of 0.0001 to 10 wt .-%, preferably 0.001 to 5 wt .-%, each based on the ready-to-use agent.

Furthermore, the agents for use 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. Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes. The substantive dyes are each preferably used in an amount of 0.001 to 20 wt .-%, in particular from 0.05 to 5 wt .-%, each based on the total application preparation. The total amount of substantive dyes is preferably at most 20% by weight.

Preferred anionic substantive dyes are those referred to as 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, Acid Black 52 and tetrabromophenol blue known compounds.

Preferred cationic substantive dyes are cationic triphenylmethane dyes, such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, aromatic systems which are substituted by a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17 and HC Blue 16, as well as Basic Yellow 87, Basic Orange 31 and Basic Red 51.

Preferred nonionic substantive dyes are 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 Red 10, HC Red 1 1. HC Red 13, HC Red BN, HC Blue 2, HC Blue 1 1, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, and 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 and 2-chloro-6-ethylamino-4-nitrophenol.

It is not necessary that the optionally contained substantive dyes each represent uniform compounds. On the contrary, due to the production processes for the individual dyes, minor amounts may contain further components. far these do not adversely affect the staining result or for other reasons, such as toxicological, must be excluded.

Furthermore, as direct dyes also occurring in nature dyes are used, as for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, walnut, buckthorn bark, sage, bluewood, madder root, catechu and alkano root are included.

In accordance with the invention, an oxidative brightener may also be applied to the hair along with a catalyst which promotes oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are z. For example, certain enzymes, iodides, quinones or metal ions.

Furthermore, it has proven to be advantageous if the brightening agents contain at least one stabilizer or complexing agent. Customary and preferred chelating agents in the context of the present invention are, for example, polycarboxylic acids, nitrogen-containing mono- or polycarboxylic acids, especially ethylenediaminetetraacetic acid (EDTA), ethylenediamine disuccinic acid (EDDS) and nitrilotriacetic acid (NTA), geminal diphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) (EDTMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP), phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and cyclodextrins, alkali stannates (sodium stannate), alkali pyrophosphates (tetrasodium pyrophosphate , Disodium pyrophosphate), alkali phosphates (sodium phosphate), and phosphoric acid. According to the invention, the agents preferably contain complexing agents of from 0.01 to 3% by weight, preferably from 0.05 to 1% by weight, based in each case on the total weight of the composition according to the invention.

The agents which can be used according to the invention are preferably formulated as flowable preparations. These include in particular emulsions, suspensions and gels, more preferably emulsions. The flowable preparations preferably additionally comprise as surface-active substance an emulsifier or a surfactant, surface-active substances depending on the field of use being referred to as surfactants or as emulsifiers and being selected from anionic, cationic, amphoteric, zwitterionic and nonionic surfactants.

The anionic, nonionic, amphoteric or zwitterionic surfactants are used in total amounts of from 0.1 to 45% by weight, preferably from 1 to 30% by weight and more preferably from 1 to 15% by weight, based on the total amount of the ready-to-use agent. The cationic surfactants are contained in the agents used according to the invention preferably in amounts of 0.05 to 10 wt .-%, particularly preferably 0.1 to 5 wt .-%, based on the total agent. Furthermore, the agents according to the invention may contain further active ingredients, auxiliaries and additives, such as, for example, cationic polymers, nonionic polymers; zwitterionic and amphoteric polymers; anionic polymers; Thickening agents (agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, eg methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose , Amylopectin and dextrins, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol); Hair conditioning compounds; Protein hydrolysates of vegetable or animal origin; Perfume oils, dimethylisosorbide and cyclodextrins; fiber structure-improving agents; defoamers; dyes; Anti-dandruff agents; Light stabilizers; agents; Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H; Plant extracts of vegetable oils; Cholesterol; Bodying agents; Fats and waxes (fatty alcohols, beeswax, montan wax and paraffins); Swelling and penetrating substances; Opacifiers blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, C0 ₂ and air; Antioxidants.

The selection of these further substances will be made by the person skilled in the art according to the desired properties of the preparations. The preparations used according to the invention contain the further active ingredients, auxiliaries and additives preferably in amounts of from 0.01 to 25% by weight, in particular from 0.05 to 15% by weight, based on the total amount of the ready-to-use agent.

The ready-for-use lightening agent is applied to the keratinic fibers and left for a certain exposure time on the fiber, especially in the hair. The application of the preparation is usually done by hand by the user. Personal protective clothing is preferably worn, in particular suitable protective gloves, for example made of plastic or latex (disposable gloves). But it is also possible to apply the preparation with an application aid on the keratinic fibers. The application and the contact temperature of the preparation is room temperature up to 45 ° C. Optionally, the effect of the preparation may be enhanced by external heat input, such as by means of a heat hood. The preferred exposure time of the preparation to the keratinic fiber is 10 to 60 minutes, preferably 15 to 45 minutes. After completion of the exposure time, the remaining agent is washed out of the keratinic fibers with the aid of a cleaning preparation or water. After washing, the keratinic fibers are optionally dried with a towel or a hot air blower. Washing with a shampoo is unnecessary if a carrier with high surfactant was used.

A second subject of the present invention is a multi-component packaging unit (kit-of-parts), which is characterized in that it comprises at least a first container (C1) with a preparation (A), contained in a cosmetic carrier

a) at least one acylpyridinium derivative of the formula (I) (I), in which

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-C ₂ -C ₆ -alkyl group, an aryl-C ₁ -C ₆ -alkyl group, a heteroaryl-C ₁ -C ₆ -alkyl group, an aryl group or a Heteroaryl group stands,

R 2, R 3 and R _{4 are} each independently of one another hydrogen, a C ₁ -C ₆ -alkyl group, a halogen atom or a C ₁ -C ₆ -acyl group, with the proviso that at least one of the radicals R 2, R 3 and R 4 represents a C6 acyl group stands,

and X ^"is a physiologically acceptable anion, and b) at least one hydroxyl-containing ammonium compound of the formula (II),

' ^OH (II), in which

Y is either a carboxylate group (C0 ₂ ^~ ),

or for one of the groups selected from a carboxylic acid group (C0 ₂ H), an alkali metal or ammonium carboxylate group (CO ₂ M) or a carboxylic acid C 1 -C 6 -alkyl ester group (C0 ₂ -C 1 -C 6) Alkyl), in which case the compound of the formula (II) for balancing the positive charge comprises a physiologically acceptable anion,

and at least one second container (C2) with a preparation (B) comprising at least one oxidizing agent in a cosmetic carrier.

The term "container" hereby signifies a picking possibility, irrespective of its shape, material or closure, which includes the possibility of containing substances or mixtures of substances The term "container" therefore includes, but is not limited to, the interior of a tube, a tube Bag or bag, a canister, a can, a tub, a bottle, a jar or a package, a box, a box, an envelope or other container. The components of the whitening composition may be contained in a single container, but it is also possible, and optionally preferred, to divide them into different containers and to guide the consumer to mix them together before use. In a particularly preferred embodiment, the packaging unit is characterized in that it contains at least one additional component selected from personal protective clothing, such as disposable gloves, apron, application aid, such as comb, brush, brush or applicette, and instructions for use. The instructions for use contain in particular information and instructions for the consumer (m / f) for the application of the means from the containers of the packaging unit in a method according to the first subject of the invention. An applicette is understood to be a broad brush, on the end of which there is a tip which allows and simplifies the division of bundles of fibers from the total amount of fibers.

The ready-for-use lightening agent is prepared by mixing preparation (A) with oxidation preparation (B) of the multi-component packaging unit.

The preferred embodiments of the first subject of the invention apply mutatis mutandis for the inventive multi-component packaging unit of the second subject of the invention.

A third object of the invention is the use of a composition according to the first subject of the invention for improving the brightening performance of whitening and / or coloring agents for keratinic fibers, in particular human hair.

Finally, another object of the present invention is a method which is characterized in that an agent of the first subject of the invention is obtained by mixing a preparation (A) contained in a cosmetic carrier

a) at least one acylpyridinium derivative of the formula (I)

(I), in which

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-C ₂ -C ₆ - is an alkyl group, an aryl-C 1 -C ₆ -alkyl group, a heteroaryl-C 1 -C ₆ -alkyl group, an aryl group or a heteroaryl group,

R 2, R 3 and R 4 each independently represent hydrogen, a C 1 -C 6 alkyl group, a halogen atom or a C 1 -C 6 acyl group, with the proviso that at least one of R 2, R 3 and R 4 is a C 1 -C 6 acyl group stands, and X ^"is a physiologically acceptable anion, and at least one hydroxyl-containing ammonium compound of the formula (II),

Y is either a carboxylate group (C0 ₂ ^~ ),

- or for one of the groups selected from a carboxylic acid group (C0 ₂ H), an alkali metal or ammonium carboxylate group (C0 ₂ M) or a carboxylic acid Ci-C _ö -alkyl ester group (C0 ₂ -Ci-C6 Alkyl), in which case the compound of the formula (II) for balancing the positive charge comprises a physiologically acceptable anion,

and at least one preparation (B) containing at least one oxidizing agent in a cosmetic carrier is prepared, this agent is applied immediately to human hair, the agent is left on the fiber for a time and then the remaining agent is rinsed from the hair ,

The duration of use of the agent in the process according to the invention is 10 to 60 minutes, preferably 15 to 45 minutes, during which the agent is left on the fiber. The application and the contact temperature of the preparation is room temperature up to 45 ° C. In particular, the temperature is between 10 ° C and 45 ° C, in particular between 20 ° C and 38 ° C. Optionally, the effect of the preparation may be enhanced by external heat input, such as by means of a heat hood.

After completion of the exposure time, the remaining agent is washed out of the keratinic fibers with the aid of a cleaning preparation or water. After washing, the keratinic fibers are optionally dried with a towel or a hot air blower. Washing with a shampoo is unnecessary if a carrier with high surfactant was used.

With regard to further preferred embodiments of the method according to the invention or the use according to the invention, what has been said about the agents according to the invention applies mutatis mutandis.

The following examples are intended to illustrate preferred embodiments of the invention without, however, limiting it. Examples

1st Synthesis Example

1.1 Synthesis of 4-acetyl-1-methylpryidinium p-toluenesulfonate

30.0 g (0.25 mol) of 4-acetylpyridine and 55.8 g (0.30 mol) of methyl p-toluenesulfonate were refluxed in 500 ml of ethanol for 5 hours. The solvent was removed in vacuo on a rotary evaporator and the residue digested with ether. After separating the ether phase, the product gradually crystallized out. The product was dried in vacuo. Yield: 59.9 g (82.5%); H-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 2.26 (s, 3H); 2.72 (s, 3H); 3.39 (s, 3H); 7, 1 1 (d, 2H); 7.49 (d, 2H); 8.42 (d, 2H); 9.20 (d, 2H); ³ C-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 20.8; 26.4; 48, 1; 124.8; 125.3; 127.7; 138.9; 145,2; 146.5; 148.3; 195.8.

2. Examples of bleaching

2.1 Preparation of a Blondiercreme

From the ingredients listed, bleaching creams were prepared as follows:

Hydrenol D (INCI name: Cetearyl alcohol (Cognis)); Lorol tech. (INCI name: Coconut alcohol (Cognis)); Eumulgin ^® B1 (INCI name: Ceteareth-12 (Cognis)); Eumulgin ^® B2 (INCI name: Ceteareth-20 (Cognis)); Akypo Soft 45 NV ^® (INCI name: Sodium Laureth-5 carboxylate (KAO Chemicals)); Plantacare® ^® 1200 UP (INCI name: lauryl glucosides (Cognis)); Texapon ^® K 14 S 70 C (ca. 70% active substance; INCI name: Sodium Myreth Sulfate (Cognis)); Turpinal ^® SL (about 60% active ingredient content, INCI name: Etidronic Acid, Aqua (Solutia)); Sodium silicate 40/42 (soda waterglass). The fat components were melted together at 80 ° 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% with water and the formulation was stirred cold. The formulation V1 is the non-inventive bleaching formulation without any activator addition. Formulation V2 represents a comparative formulation which is also not according to the invention and which contains only one cationic 4-acetylpyridinium deriva. The recipe E is a recipe according to the invention.

2.2 Mixing with the developer dispersion

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 (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate (Cognis)); Aculyn ^® 33 (about 28% solids in water; INCI name: Acrylates Copolymer (Rohm &Haas)); Dow ^Corning® DB 1 10 A (INCI name: dimethicone (Dow Corning)).

For the Blondierprozess 4 times the amount of the finished application mixture was applied to strands of dark brown hair (code: Kerling 2/0) of about 0.7 g weight. After the strands were bleached for 30 minutes at 32 ° C, they were washed with a commercial shampoo and dried with a hair dryer.

2.3 Evaluation of the brightening power

Each strand of hair was measured colorimetrically before and after the bleaching process. As a measure of the whitening power of the respective formulation, the AL value was used according to the following formula:

^- L _nac HHer ^- L _ago ago

Lafter = brightness of the strand after bleaching

orher = brightness of the strand before bleaching Twelve-fold was determined for each recipe; the average was calculated from the individual values. The larger the AL value, the better the brightening performance of the respective recipe.

Brightening performance with dark brown strands (Kerling 2/0)

2.4 Interpretation of the results

An estimation of the bleaching effects of the different formulations can be made by comparing the dL values. It is clear that with the combination according to the invention significantly larger dl_ values - and thus better brightening - could be achieved than was possible by the use of hydrogen peroxide alone or in combination with the acylpyridinium derivative. By using this special combination of three components, a substantial improvement could therefore be achieved compared to the existing state of the art.

Claims

P a n t a n s p r e c h e

1 . Agent for the treatment of keratinic fibers, in particular human hair, characterized in that the agent in a cosmetic carrier

(i) at least one oxidizing agent,

(ii) at least one acylpyridinium derivative of the formula (I)

(I), in which

R2, R3 and R4 are each independently hydrogen, a C- | -C ₆ - alkyl group, a halogen atom or a C- _| C ₆ acyl group, with the proviso that at least one of R 2, R 3 and R 4 is a C ₁ -C ₆ acyl group,

and X ^"is a physiologically acceptable anion, and

(iii) at least one hydroxyl-containing ammonium compound of the formula (II)

^OH (II), in which

Y is either a carboxylate group (C0 ₂ ^~ ),

or for one of the groups selected from a carboxylic acid group (C0 ₂ H), an alkali metal carboxylate group (C0 ₂ M) or a carboxylic acid Ci-C6-alkyl ester group, in which case the compound of formula (II) for the compensation each positive charge comprises a physiologically acceptable anion,

contains.

Composition according to claim 1, characterized in that the agent contains as Acylpyridiniumderivat of formula (I) at least one compound in which either R2 or R4 is a Ci-C6-acyl group, preferably an acetyl group.

3. Composition according to one of claims 1 and 2, characterized in that it contains as acylpyridinium derivative of the formula (I) at least one compound which is selected from the group formed from 4-acetyl-1-methylpyridinium p-toluenesulfonate, 4-acetyl-1-methylpyridinium-benzenesulfonate, 4-acetyl-1-methylpyridinium hydrogensulfate, 4-acetyl-1-methylpyridinium acetate, 4-acetyl 1-allylpyridinium p-toluenesulfonate, 4-acetyl-1-allylpyridinium benzenesulfonate, 4-acetyl-1-allylpyridinium hydrogensulfate, 4-acetyl-1-allylpyridinium acetate, 2-acetyl-1-methylpyridinium p-toluenesulfonate, 2- Acetyl-1-methylpyridinium-benzenesulfonate, 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 hydrogensulfate and 2-acetyl-1-allylpyridinium acetate, especially 4-acetyl-1-methylpyridinium p-toluenesulfonate.

Agent according to one of claims 1 to 3, characterized in that it contains one or more acylpyridinium derivatives of the formula (I) in a total amount of 0.001 to 15 wt .-%, preferably from 0.01 to 10 wt .-% and particularly preferably from 0, 1 to 5% by weight, based in each case on the total weight of the ready-to-use agents.

Composition according to one of claims 1 to 4, characterized in that the agent contains as oxidizing agent at least one compound which is selected from the group consisting of hydrogen peroxide, alkali metal peroxides and / or alkali metal perborates, in particular hydrogen peroxide.

Agent according to one of claims 1 to 5, characterized in that the agent as hydroxyl-containing ammonium compound of formula (II) a compound selected from the group consisting of L-carnitine, D-carnitine, L / D Carnitine, L-carnitine hydrochloride, D-carnitine hydrochloride, L / D-carnitine hydrochloride, L-carnitine tartrate, D-carnitine tartrate, and / or L / D-carnitine tartrate.

Agent according to one of claims 1 to 6, characterized in that the agent comprises one or more hydroxyl-containing ammonium compounds of the formula (II) in a total weight of 0.01 to 10 wt .-%, in particular of 0.01 wt. % to 5% by weight, based on the total weight of the ready-to-use agent.

Multi-component packaging unit (kit-of-parts),

comprising at least one first container (C1) with a preparation (A),

containing in a cosmetic carrier

a) at least one acylpyridinium derivative of the formula (I) (I), in which

and X ^"is a physiologically acceptable anion, and

at least one hydroxyl-containing ammonium compound of the formula (II),

Y is either a carboxylate group (C0 ₂ ^~ ),

and at least one second container (C2) with a preparation (B) containing at least one oxidizing agent in a cosmetic carrier.

Use of a composition according to any one of claims 1 to 7 for improving the whitening performance of whitening and / or coloring agents for keratinic fibers, in particular human hair.

A method, characterized in that the agent according to any one of claims 1 to 7 by mixing a preparation (A), comprising in a cosmetic carrier

a) at least one acylpyridinium derivative of the formula (I)

(I), in which 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-C ₂ -C ₆ -alkyl group, an aryl-C 1 -C ₆ -alkyl group, a heteroarylC- | -C ₆ - alkyl group, an aryl group or a heteroaryl group,

R 2, R 3 and R 4 each independently represent hydrogen, a C 1 -C 6 alkyl group, a halogen atom or a C 1 -C 6 acyl group, with the proviso that at least one of R 2, R 3 and R 4 represents a C 1 -C 6 acyl group stands,

and X ^"is a physiologically acceptable anion, and

b) at least one hydroxyl-containing ammonium compound of the formula (II)

' ^OH (II), in which

Y is either a carboxylate group (C0 ₂ ^~ ),