DE102007047688A1 - Brightening agent with cationic 3,4-Dihydroisochinoliniumderivaten and hydrogen peroxide - Google Patents

Abstract

The invention relates to a composition for whitening keratinic fibers, characterized in that it comprises, in a cosmetic carrier, at least one cationic 3,4-dihydroisoquinolinium derivative of the following general structure (I), 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 group C 1 -C 6 -alkyl group, a C 1 -C 6 -dialkylaminoC 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 ,. R 2, R 3 and R 4 are each independently hydrogen, hydroxy, amino, di (C 1 -C 6) alkylamino, C 1 -C 6 alkoxy, nitro, carboxy, nitrile, optionally substituted aryl, C 1 -C6-alkenyl group, may represent an optionally substituted heteroaryl group or R2 and R3 may together form another fused carbocyclic or heterocyclic ring which may be saturated or unsaturated and may optionally be substituted by up to three substituents ,. the anion X- represents a physiologically acceptable anion and contains hydrogen peroxide, the use of this hair-lightening agent and a corresponding method.

Description

The The present invention relates to agents for brightening keratinischer Fibers, d. H. Agent for use on keratin fibers, in particular human hair containing cationic 3,4-dihydroisoquinolinium derivatives and hydrogen peroxide, the use of this combination of cationic 3,4-dihydroisoquinolinium derivatives and hydrogen peroxide for lightening of hair as well as a corresponding procedure.

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 bleaching processes are limited to certain initial hair colors. The basics of the Blondierverfahren are known in the art and can be found in relevant monographs, eg. B. from Kh. Schrader, Basics and Formulations of Cosmetics, 2nd edition, 1989 . Dr. Alfred Hüthig Verlag, Heidelberg, or W. Umbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York , be read.

conventional Hair dyes usually consist of at least one Developer and at least one coupler substance and contain possibly still direct dyes as Nuanceure. Coupler and developer components are also referred to as oxidation dye precursors.

Next the coloring is the lightening of the own hair color resp. bleaching the very special desire of many consumers, since a blonde hair color considered attractive and desirable in terms of fashion becomes. For this purpose are in the market different Blondiermittel available with different bleaching performance. The oxidants contained in these products are able to by the oxidative destruction of the hair's own dye Melanin to lighten the hair fiber. For a moderate Bleaching effect is sufficient the use of hydrogen peroxide - if necessary using ammonia or other alkalizing agents - as Oxidizer alone, for achieving a stronger Bleaching effect is usually a mixture of hydrogen peroxide and Peroxidisulfatsalzen and / or Peroxymonosulfatsalten used. With the brightening, however, also a damage of the Hair is not just natural coloring Components of the hair, but also the remaining structural components of the hair are oxidatively damaged. Depending on the severity the degree of damage ranges from rough, brittle and difficult combed hair over a diminished Resistance and tear resistance of the hair to hair breakage. The larger the amount of used hydrogen peroxide and optionally the Peroxidisulfate is, the stronger damage will be in the Usually caused on the keratin fiber. Hair dyeing or Lightening agents, which show a good lightening performance, without simultaneously damaging the hair fiber are not yet known.

In front their application to human hair, hair dyeing and / or brightening agents in solid or pasty form with dilute aqueous hydrogen peroxide solution mixed. This mixture is then applied to the hair and rinsed out again after a certain exposure time. The Duration of exposure to the hair to achieve a complete Coloring or whitening is between about 30 and 40 Minutes. It is obvious that among users of these hair colors or Blondiermittel a need exists, this exposure time to reduce.

Blondierprozesse on keratinic fibers usually run in alkaline pH values, in particular between 9.0 and 10.5. These pH values are necessary to an opening of the outer To ensure cuticle (cuticle) and a penetration the active species (dye precursors and / or hydrogen peroxide) to allow in the hair. As an alkalizing agent is usually Ammonia used, however, for the users Disadvantage of intense smell and possible irritation.

Also if the Blondiermittel so far in the market in the Usually show good brightening, so they can due from hair damage, long usage times and the due high concentrations of oxidizing and alkalizing agents possible skin irritation can not be considered optimal.

The use of bleach activators to optimize stain removal and wash performance is well known in the detergent and cleaner art. In US 2005159327 A1 . WO 2000061713 A1 or WO 9846718 A1 For example, corresponding methods for cleaning systems are described. In the laundry bleach, however, usually elevated temperatures of 40-60 ° C are necessary. That with selected bleach activators even at much lower temperatures under physiologically acceptable conditions of use in a cosmetic formulation good brightening results on the substrate hair can be achieved, the skilled person so far not to refer to the prior art.

The Definition Bleach activator also comes from the detergent area and includes substances that lower the washing temperature enable. The bleach added to the detergents, usually peroxides, are often only from a temperature of 60 ° C active. The addition of bleach activators activates these peroxides even at temperatures of less than 60 ° C. Tetraacetylenediamine (TAED) is the largest activator economic importance in Europe.

It It is the object of this invention to provide novel bleach activator agents to provide lightening or bleaching of hair which in their Aufhellleistung the usual on the market Means are comparable or superior, at the same time however, have a reduced hair damage.

In unpredictable way could now be found that the Use of a combination of cationic 3,4-dihydroisoquinolinium compounds the general structure (I) and hydrogen peroxide, in particular even at low application temperatures of between 10 ° C and 40 ° C, which brightens hair much stronger than it by using a comparable amount of hydrogen peroxide alone would be possible.

conditioned by the improved Blondierleistung when using the inventive By means of the amount of oxidant used can be reduced and hair damage is thereby minimized. Also a shortening of the exposure time while achieving a The prior art whitening effect is this way possible.

worin

• • der Rest R1 für eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine Carboxy-C₁-C₆-alkylgruppe, eine Aryl-C₁-C₆-alkylgruppe, eine C₁-C₆-Dialkylamino-C₂-C₆-alkylgruppe, eine Heteroaryl-C₁-C₆-alkylgruppe, eine 3-Oxobutylgruppe, eine 2-Oxopropylgruppe, eine Arylgruppe oder eine Heteroarylgruppe steht,
• • die Reste R2, R3 und R4 unabhängig voneinander ein Wasserstoffatom, eine Hydroxygruppe, eine Aminogruppe, eine Di(C₁-C₆)alkylaminogruppe, eine C₁-C₆-Alkoxygruppe, Halogen, eine Nitrogruppe, eine Carboxygruppe, eine Nitrilgruppe, eine gegebenenfalls substituierte Arylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe darstellen können oder R2 und R3 zusammen einen weiteren ankondensierten carbozyklischen oder heterozyklischen Ring bilden können, welcher gesättigt oder ungesättigt sein kann und gegebenenfalls durch bis zu drei Substituenten substituiert sein kann,
• • das Anion X^– für ein physiologisch verträgliches Anion steht.

A first subject of the invention is therefore an agent for lightening keratinic fibers, characterized in that it contains in a cosmetic carrier hydrogen peroxide and at least one cationic 3,4-dihydroisoquinolinium derivative of the following general structure (I),

wherein

• • the radical 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 ₁ -C ₆ -alkyl group, an aryl-C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -dialkylamino-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,
• The radicals R 2, R 3 and R 4 independently of one another represent a hydrogen atom, a hydroxy group, an amino group, a di (C ₁ -C ₆ ) -alkylamino group, a C ₁ -C ₆ -alkoxy group, halogen, a nitro group, a carboxy group, a nitrile group, an optionally substituted aryl group, a C ₂ -C ₆ alkenyl group, an optionally substituted heteroaryl group, or R 2 and R 3 may together form another fused carbocyclic or heterocyclic ring which may be saturated or unsaturated and optionally substituted by up to three substituents can
• • the anion X ^{- stands} for a physiologically compatible anion.

Under Keratin fibers are furs, wool, feathers and especially human ones To understand hair. Although the inventive Means primarily for coloring and / or lightening Keratin fibers are suitable, is in principle a use also in other areas nothing contrary.

The following are examples of the radicals mentioned as substituents of the compounds of the formula (I): Examples of (C ₁ to 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 .

Examples of (C ₁ to C ₆ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a metho xy or an ethoxy group.

Furthermore, as preferred examples of a (C ₂ to C ₆ ) -hydroxyalkyl group, -CH ₂ CH ₂ OH, -H ₂ CH ₂ CH ₂ OH, -CHCH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH where the group -CH ₂ CH ₂ OH is preferred.

Examples for halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ), -CH ₂ CH ₂ CH ₂ -O- CH (CH ₃ ).

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

Examples of a carboxy-C ₂ -C ₆ -alkyl group are the carboxymethyl group, the 2-carboxyethyl group or the 3-carboxypropyl 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 1H-pyrrol-1-ylmethyl group, the 1H-pyrool-1-ylethyl group, the 1H-pyrazol-1-ylmethyl group or the 1H-pyrazol-1-ylethyl group.

One Example of aryl groups is the phenyl group.

Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

The agents according to the invention contain at least two essential ingredients: at least one cationic 3,4-dihydroisoquinolinium derivative of the formula (I) and hydrogen peroxide. invention Means may also be "application mixtures" d. H. Means that (although for reasons of stability) packed separately, but before use with each other mixed into an application mixture and then applied.

It is preferred if the radical R _{1 of} the general structure (I) is a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group.

Of Furthermore, it is favored according to the invention, if the radicals R 2, R 3 and R 4 of the general structure (I) represent a hydrogen atom represent.

It is preferred that X- of formula (I) is selected from halide (chloride, bromide, iodide), benzenesulfonate, p-toluenesulfonate, C ₁ -C ₄ -alkanesulfonate, trifluoromethanesulfonate, acetate, trifluoroacetate, perchlorate, ½ sulfate, hydrogensulfate , Tetrafluoroborate, hexafluorophosphate, hexafluorozincate or tetrafluorozincate.

According to the invention, it is particularly advantageous if the physiologically tolerable anion X ^{- is} a halide ion (in particular chloride or bromide), hydrogensulfate, ½ sulfate, p-toluenesulfonate, benzol sulfonate or acetate.

worin X^– jeweils die Bedeutungen gemäß Struktur (I), bzw. die Bedeutung der vorgenannten bevorzugten Ausführungsformen, annimmt.Particularly preferred cationic 3,4-dihydroisoquinolinium derivatives of general formula (I) are

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

In summary, agents according to the invention are very particularly preferred, which as cationic 3,4-dihydroisoquinolinium derivative of the general structure (I) at least one compound from the group
N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate,
N-methyl-3,4-dihydroisochinoliniumbenzolsulfonat
N-methyl-3,4-dihydroisochinoliniumhydrogensulfat
N-allyl-3,4-dihydroisoquinolinium p-toluene sulfonate
N-allyl-3,4-dihydroisochinoliniumbenzolsulfonat
N-allyl-3,4-dihydroisochinoliniumbromid
N-allyl-3,4-dihydroisochinoliniumacetat
3,4-dihydro-2- (3-hydroxypropyl) isoquinolinium p-toluene sulfonate
3,4-dihydro-2- (3-hydroxypropyl) isoquinolinium benzenesulfonate
3,4-dihydro-2- (3-hydroxypropyl) isochinoliniumbromid
3,4-dihydro-2- (3-hydroxypropyl) isochinoliniumacetat
3,4-Dihydro-2- (2-hydroxyethyl) isoquinolinium p-toluene sulfonate
3,4-Dihydro-2- (2-hydroxyethyl) isoquinolinium benzenesulfonate
3,4-dihydro-2- (2-hydroxyethyl) isoquinolinium bromide or
3,4-Dihydro-2- (2-hydroxyethyl) isochinoliniumacetat
contain.

So far not explicitly stated otherwise, refer to the following Quantities in each case on the weight of the ready-to-use agent.

When first essential ingredient contain the inventive The cationic 3,4-dihydroisoquinolinium derivatives of the general Structure (I) preferably in an amount of 0.03 to 65.00 mmol, in particular from 1.00 to 40.00 mmol, in each case based on 100 g of ready for use Agent.

The second essential ingredient is hydrogen peroxide in the composition according to the invention. Preferably, hydrogen peroxide itself is used as the aqueous solution. The hydrogen peroxide may also be 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, polyvinylpyrrolidone · H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide, be used.

Very particularly preferred according to the invention are aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6-12% solutions in water are used. Agents preferred according to the invention are characterized in that they contain, based on their weight, 0.5 to 12% by weight, preferably 2 to 10% by weight, particularly preferably 3 to 6% by weight of hydrogen peroxide (calculated as 100% pure H ₂ O ₂ ).

Blondierprozesse on keratin fibers usually run in an alkaline environment from. To the keratin fibers and also the skin as much as possible to spare, the setting of a too high pH value is not desirable. Therefore, it is preferable if the pH of the ready-to-use agent between 7 and 11, in particular between 8 and 10.5.

at The pH values for the purposes of the present invention are to pH values measured at a temperature of 22 ° C were.

The for adjusting the preferred pH value according to the invention Alkalizing agents can be selected from the group that formed is made from ammonia, basic amino acids, alkali hydroxides, Alkanolamines, alkali metal metasilicates, alkali phosphates and alkali hydrogen phosphates to be selected.

When Alkali metal ions are preferably lithium, sodium, potassium, in particular Sodium or potassium.

The usable as alkalizing agent according to the invention basic amino acids are preferably selected from the group formed from L-arginine, D-arginine, D, L-arginine, L-lysine, D-lysine, D, L-lysine, more preferably L-arginine, D-arginine, D, L-arginine as an alkalizing agent according to the invention used.

The alkali metal hydroxides which can be used as the alkalizing agent according to the invention are preferably made selected from the group consisting of sodium hydroxide and potassium hydroxide.

The alkanolamines which can be used as alkalizing agents according to the invention are preferably selected from primary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1 -Aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol , 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol. Very particularly preferred alkanolamines according to the invention are selected from the group consisting of 2-aminoethane-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methylpropane-1,3-diol.

In surprising Way could be found that the use of an imidazole compound together with a cationic 3,4-dihydroisoquinolinium derivative of the general formula (I) and hydrogen peroxide (or its adducts) the whitening result even further improved.

in der
R5 steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe oder eine (C₁-C₆)-Alkylgruppe,
R6 steht für ein Wasserstoffatom, eine Carboxaldehydgruppe, eine (C₁-C₆)-Alkylgruppe oder eine Nitrogruppe,
R7 steht für ein Wasserstoffatom, eine Carboxy-(C₁-C₆)-alkylgruppe, eine Amino-(C₁-C₆)-alkylgruppe, eine Carboxylgruppe, eine Carboxaldehydgruppe, eine (C₁-C₆)-Alkylgruppe, eine Nitrogruppe, eine 2-Amino-3-hydroxypropylgruppe oder eine Gruppe -CH₂-CH(NH₂)-COOH und
R8 steht für ein Wasserstoffatom, eine Carboxaldehydgruppe oder eine Carboxylgruppe.In a particular embodiment, it is therefore very particularly preferred if the agent according to the invention additionally contains at least one imidazole compound of the formula (II) and / or its physiologically tolerated salt,

in the
R5 represents a hydrogen atom, an optionally substituted aryl group or a (C ₁ -C ₆ ) -alkyl group,
R _{6 represents} a hydrogen atom, a carboxaldehyde group, a (C ₁ -C ₆ ) -alkyl group or a nitro group,
R7 represents a hydrogen atom, a carboxy (C ₁ -C ₆ ) alkyl group, an amino (C ₁ -C ₆ ) alkyl group, a carboxyl group, a carboxaldehyde group, a (C ₁ -C ₆ ) alkyl group, a Nitro group, a 2-amino-3-hydroxypropyl group or a group -CH ₂ -CH (NH ₂ ) -COOH and
R 8 represents a hydrogen atom, a carboxaldehyde group or a carboxyl group.

Prefers the imidazole compounds of the formula (II) selected from at least one member of a group, which is formed from histamine, D-histidine, L-histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole, imidazole-4-acetic acid, Imidazole-4-carboxylic acid, imidazole-4,5-dicarboxylic acid, Imidazole-2-carboxaldehyde, imidazole-4-carboxaldehyde, imidazole-5-carboxaldehyde, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole-5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, 4-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl) -imidazole, as well as the physiological acceptable salts of the aforementioned compounds. Particularly according to the invention Imidazole (R5 = R6 = R7 = R8 = H) is preferably used.

Preferably the imidazole compound (s) of the formula (II) become / become within certain quantity ranges used. Here are inventive Preferred agents which, based on 100 g of ready for use By means of, 0.03 to 65.00 mmol and especially 1.00 to 40.00 mmol at least one imidazole derivative of the formula (II).

For The strong lightening of very dark hair is the use of hydrogen peroxide or its addition products to organic or inorganic Connections often insufficient. In these cases is usually a combination of hydrogen peroxide and persulfates used. It has been found that the admixture of the invention 3,4-Dihydroisoquinolinium compounds of the general formula (I) not only with hydrogen peroxide alone, but also with one Combination of hydrogen peroxide and persulfate salts in one Increase in the whitening power results.

Therefore It may, the consumer should desire a very strong Feeling bleaching, in another embodiment be preferred when in addition to the cationic 3,4-dihydroisoquinolinium the general structure (I) and hydrogen peroxide in addition at least one inorganic persulfate salt in the brightening agent containing keratinic fibers.

The Persulfate salts can be used in an amount of 0.1 to 25 g, in particular in an amount of 1 to 15 g, based on 100 g of the ready to use agent, be included.

preferred Persulfate salts are ammonium peroxydisulfate, potassium peroxodisulfate, Sodium peroxydisulfate, ammonium persulfate, potassium persulfate and sodium persulfate.

Based on the previously mentioned preferred embodiments It may also be favored according to the invention be, a cosmetic carrier, which at least one cationic 3,4-dihydroisoquinolinium derivative of the general formula (I) and hydrogen peroxide, both at least one Imidazole derivative of general formula (II) and / or its physiological compatible salt and at least one inorganic persulfate add. These two additional components can contained side by side in the already mentioned proportions be.

As already mentioned, the inventive Means also separated directly before the application of two or more packaged preparations are produced. This is particularly suitable to separate incompatible ingredients to a premature one To avoid reaction.

A common one The way is therefore a first, the cationic 3,4-Dihydroisoquinolinium compounds of the general formula (I) and optionally an imidazole derivative of the general formula (II) contains, just before use with a second means, in which the or the inventive oxidizing agent are included, to mix.

One Another object of the present invention is therefore an agent for lightening keratinous fibers, especially human hair, which immediately before applying to the hair from a flowable Preparation A containing the cationic 3,4-dihydroisoquinolinium compounds of general formula (I) and optionally an imidazole derivative of the general formula (II) and an oxidizing agent preparation B, containing at least one oxidizing agent selected from hydrogen peroxide and / or its addition compounds organic or inorganic compounds.

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

Of the Use of persulfate salts is usually in the form of an optional dedusted powder or molded molding in shape. To premature degradation of the invention 3,4-dihydroisoquinolinium derivatives by contact with the persulfates it is preferred according to the invention to avoid the persulfates are available as separately packaged component C. to deliver.

In In this context is a 3-component means for lightening human hair another object of the present invention. This agent will be applied immediately before application on the hair by carefully mixing a flowable Preparation A containing the cationic 3,4-dihydroisoquinolinium compounds of general formula (I) and optionally an imidazole derivative of of general formula (II), an oxidizing agent preparation B, containing at least one oxidizing agent selected from hydrogen peroxide and / or its addition compounds organic or inorganic compounds and additionally a third, in powder form Preparation C, which at least containing an inorganic persulfate salt.

The Mixture of preparations A and B or, where appropriate, of the preparations A, B and C before application leads to an application mixture, the one inventive agent with the two mandatory ingredients.

Preferably is the flowable preparations A and / or B an emulsifier or a surfactant added, wherein surface-active Substances depending on the field of application as surfactants or as emulsifiers and anionic, cationic, zwitterionic, ampholytic and nonionic surfactants and emulsifiers selected are. These substances are described in detail below.

Furthermore, it has proved to be advantageous if the dyeing and / or brightening agents according to the invention contain nonionic surfactants. Such surfactants are the egg nen HLB value of 5.0 and greater, preferably. For the definition of the HLB value, express reference is made to the remarks in Hugo Janistyn, Handbook of Cosmetics and Fragrances, III. 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 Verlagsgesellschaft mbH Stuttgart, 1974, pages 466-474 , as well as the original works cited therein.

Especially Preferred nonionic surfactants are because of the ease of processing substances that commercially as solids or liquids in pure Form are available. The definition for purity does not refer to chemically pure compounds in this context. Rather, especially when it comes to products on a natural basis, mixtures of different Homologs are used, for example, with different alkyl chain lengths, as with products based on natural fats and oils to be obtained. Even with alkoxylated products are usually Mixtures of different degrees of alkoxylation. The term Purity in this context refers rather to the fact that the selected substances are preferably free from Solvents, adjusters and other impurities should be.

• – alkoxylierte Fettalkohole mit 8 bis 22, insbesondere 10 bis 16, Kohlenstoffatomen in der Fettalkylgruppe und 1 bis 30, insbesondere 1 bis 15, Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Fettalkylgruppen sind beispielsweise Lauryl-, Myristyl-, Cetyl-, aber auch Stearyl-, Isostearyl- und Oleylgruppen. Besonders bevorzugte Verbindungen dieser Klasse sind beispielsweise Laurylalkohol mit 2 bis 4 Ethylenoxid-Einheiten, Oleyl- und Cetylalkohol mit jeweils 5 bis 10 Ethylenoxideinheiten, Cetyl- und Stearylalkohol sowie deren Mischungen mit 10 bis 30 Ethylenoxideinheiten sowie das Handelsprodukt Aethoxal^®B (Henkel), ein Laurylalkohol mit jeweils 5 Ethylenoxid- und Propylenoxideinheiten. Neben den üblichen alkoxylierten Fettalkoholen können auch sogenannte „endgruppenverschlossene" Verbindungen erfindungsgemäß eingesetzt werden. Bei diesen Verbindungen weist die Alkoxygruppe am Ende keine OH-Gruppe auf, sondern ist in Form eines Ethers, insbesondere eines C1-C4-Alkyl-Ethers, „verschlossen". Ein Beispiel für eine solche Verbindung ist das Handelsprodukt Dehypon^®LT 054, ein C_12-18-Fettalkoholol + 4,5 Ethylenoxid-butylether.
• – alkoxylierte Fettsäuren mit 8 bis 22, insbesondere 10 bis 16, Kohlenstoffatomen in der Fettsäuregruppe und 1 bis 30, insbesondere 1 bis 15, Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Fettsäuren sind beispielsweise Laurin-, Myristin-, Palmitin-, Stearin-, Isostearin- und Ölsäure.
• – alkoxylierte, bevorzugt propoxylierte und insbesondere ethoxylierte, Mono-, Di- und Triglyceride. Beispiele für bevorzugte Verbindungen sind Glycerinmonolaurat + 20 Ethylenoxid und Glycerinmonostearat + 20 Ethylenoxid.
• – Polyglycerinester und alkoxylierte Polyglycerinester. Bevorzugte Verbindungen dieser Klasse sind beispielsweise Poly(3)glycerindiisostearat (Handelsprodukt: Lameform^®TGI (Henkel)) und Poly(2)glycerinpolyhydroxystearat (Handelsprodukt: Dehymuls^®PGPH (Henkel)).
• – Sorbitan-Fettsäureester und alkoxylierte Sorbitan-Fettsäureester wie beispielsweise Sorbitanmonolaurat und Sorbitanmonolaurat + 20 Ethylenoxid (EO).
• – Alkylphenole und Alkylphenolalkoxylate mit 6 bis 21, insbesondere 6 bis 15, Kohlenstoffatomen in der Alkylkette und 0 bis 30 Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Vertreter dieser Klasse sind beipielsweise Nonylphenol + 4 EO, Nonylphenol + 9 EO, Octylphenol + 3 EO und Octylphenol + 8 EO.

Preferred nonionic surfactants are

• - Alkoxylated fatty alcohols having 8 to 22, in particular 10 to 16, carbon atoms in the fatty alkyl group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty alkyl groups are, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl groups. Particularly preferred compounds of this class are, for example, lauryl alcohol with 2 to 4 ethylene oxide units, oleyl and cetyl alcohol with 5 to 10 ethylene oxide, cetyl alcohol and stearyl alcohol and mixtures thereof with 10 to 30 ethylene oxide units and the commercial product Aethoxal ^® B (Henkel), Lauryl alcohol with 5 ethylene oxide and 3 propylene oxide units. In addition to the usual alkoxylated fatty alcohols, it is also possible to use so-called "end-capped" compounds according to the invention In these compounds, the alkoxy group has no OH group at the end but is "closed" in the form of an ether, in particular a C 1 -C 4 -alkyl ether. , An example of such a compound is the commercially available product ^® Dehypon LT 054, a C _12-18 -Fettalkoholol + 4.5 ethylene oxide-butyl ether.
• - alkoxylated fatty acids having 8 to 22, in particular 10 to 16, carbon atoms in the fatty acid group and 1 to 30, in particular 1 to 15, ethylene oxide and / or propylene oxide units. Preferred fatty acids are, for example, lauric, myristic, palmitic, stearic, isostearic and oleic acids.
• - alkoxylated, preferably propoxylated and especially ethoxylated, mono-, di- and triglycerides. Examples of preferred compounds are glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide.
• Polyglycerol esters and alkoxylated polyglycerol esters. Preferred compounds of this class are for example poly (3) glycerol diisostearate (commercial product: Lameform ^® TGI (Henkel)) and poly (2) glycerinpolyhydroxystearat (commercial product: Dehymuls ^® PGPH (Henkel)).
• Sorbitan fatty acid esters and alkoxylated sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monolaurate + 20 ethylene oxide (EO).
• - Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15, carbon atoms in the alkyl chain and 0 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 4 EO, nonylphenol + 9 EO, octylphenol + 3 EO and octylphenol + 8 EO.

Especially preferred classes of nonionic surfactants Substances are the alkoxylated fatty alcohols that alkoxylated Fatty acids and the alkylphenols and alkylphenol alkoxylates represents.

When have particularly advantageous according to the invention Proved to be the non-ionic surfactants contained in amounts of 1-5 wt .-%.

Farther the dyeing and / or lightening agent all known in such preparations active, Additives and auxiliaries included. In many cases included the agents at least one surfactant, where in principle both anionic as well as zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven to be advantageous The surfactants from anionic, cationic or nonionic Select surfactants. Anionic surfactants can be particularly preferred.

Preferred anionic surfactants are alkyl sulfates, ether carboxylic acid salts having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule such as C ₁₂ H ₂₅ - (C ₂ H ₄ O) ₆ -CH ₂ -COONa and in particular salts of saturated and especially unsaturated C8-C22 carboxylic acids such as oleic acid, stearic acid, Isostearic acid and palmitic acid.

These anionic surfactants should preferably be in solid, in particular powder form available. Very particularly preferred are at room temperature solid soaps, in particular sodium stearate. These are preferred in amounts of 5 to 20 wt .-%, in particular 10 to 15 wt .-%, before.

When Nonionic surfactants are particularly suitable C8-C22 alkyl mono- and oligoglycosides and their ethoxylated analogs. Especially the non-ethoxylated compounds have been found to be particularly suitable.

Examples for in the hair lightening agents according to the invention Usable cationic surfactants are especially quaternary Ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, Dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, z. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic used according to the invention Surfactants are the quaternized protein hydrolysates.

Alkylamidoamines, in particular fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as the Distearoylethylhydroxyethylammoniummethosulfat available in a blend with Cetearylalkohle under the name Dehyquart® ^® F 75 miles.

at the compounds used as surfactants with alkyl groups each are uniform substances. However, it is usually preferred in the preparation of these substances of native to go out with vegetable or animal raw materials, so that one Substance mixtures with different, from the respective raw material receives dependent alkyl chain lengths.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether und andere, als Feststoff stabile bzw. im Handel erhältliche Verbindungen,
• – zwitterionische und amphotere Polymere, die als Feststoffe stabil bzw. bevorzugt als Handelsprodukte erhältlich sind,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren und Vinylacetat/Crotonsäure-Copolymere, sofern diese als Feststoffe stabil bzw. bevorzugt im Handel erhältlich sind,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• – Strukturanten wie Glucose, Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline, sowie Silikonöle
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Farbstoffe zum Einfärben der Zubereitungen,
• – Wirkstoffe wie Panthenol, Pantothensäure, Allantoin, Pyrrolidoncarbonsäuren und deren Salze,
• – Cholesterin,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs, Paraffine, Fettalkohole und Fettsäureester,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers and other solid-stable or commercially available compounds,
• Zwitterionic and amphoteric polymers, which are stable as solids or preferably available as commercial products,
• Anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids and vinyl acetate / crotonic acid copolymers, if these are stable or preferably commercially available as solids,
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as glucose, maleic acid and lactic acid,
• Hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, and silicone oils
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Dyes for coloring the preparations,
• - active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts,
• - cholesterol,
• Fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• Fatty acid alkanolamides,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - swelling and penetrating substances such as carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

The Selection of these other substances will be apparent to those skilled in the art according to desired properties of the agents meet.

When further ingredient may be inventive Compositions at least one ammonium compound from the group Ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate in an amount of 0.5 to 10, preferably 1 to 5 wt .-%, based on the total composition of the composition contain.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazolinium-methochlorid-Copolymere und quaternierter Polyvinylalkohol,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• – Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• – quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien,

enthaltenFurthermore, the dyeing and / or brightening agents according to the invention may contain further active ingredients, auxiliaries and additives, such as

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• Zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers, for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Fiber-structure-improving active substances, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• Quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers like silicones,
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• - active substances such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root,
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants,

contain

With regard to further optional components as well as 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 the cosmetics, 2nd edition, Hüthig book publishing house, Heidelberg, 1989 , referenced.

The agents according to the invention may contain the ingredients in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. 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. It is but also possible, a powdered or too Provide tablet-shaped formulation what for Dyeing and / or brightening agent is preferred.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C ₁ -C ₄ -alcohol, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain further organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

preferred Means according to the invention are characterized that they additionally a non-aqueous Solvent, with particularly preferred inventive Means the solvent in a concentration of 0.1-30 Percent by weight, preferably in a concentration of 1-20 Percent by weight, most preferably in one concentration from 2-10 weight percent, each based on the agent.

In further preferred inventive agents the solvent selected from ethanol, n-propanol, Isoropanol, n-butanol, propylene glycol, n-butylene glycol, glycerol, Diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, Phenoxyethanol and benzyl alcohol and their mixtures.

The agents according to the invention can additionally also contain dyes and / or dye precursors and thus be provided as a means of lightening and at the same time have a coloring effect. Such agents are hereinafter referred to as "colorants", as "lightening colorants" or as "dyeing and lightening agent ".

A oxidative staining of the fibers may be in the presence of oxidation dye precursors always done with atmospheric oxygen. It is preferred However, a chemical oxidizing agent used, especially then, if in addition to the coloring a whitening effect on human Hair is desired. This whitening effect can be independent be desired from the staining method. The presence Oxidation dye pretreatment is therefore not a mandatory requirement for use of oxidizing agents in the inventive Means. The oxidizing agents are persulfates, chlorites and in particular Hydrogen peroxide or its addition products to urea, Melamine and sodium borate in question.

According to the invention but also the oxidation dye along with one Catalyst can be applied to the hair, the oxidation of the Dye precursors, eg. B. by atmospheric oxygen activated. Such Catalysts are z. As metal ions, iodides, quinones or certain Enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

• – Pyranose-Oxidase und z. B. D-Glucose oder Galactose,
• – Glucose-Oxidase und D-Glucose,
• – Glycerin-Oxidase und Glycerin,
• – Pyruvat-Oxidase und Benztraubensäure oder deren Salze,
• – Alkohol-Oxidase und Alkohol (MeOH, EtOH),
• – Lactat-Oxidase und Milchsäure und deren Salze,
• – Tyrosinase-Oxidase und Tyrosin,
• – Uricase und Harnsäure oder deren Salze,
• – Cholinoxidase und Cholin,
• – Aminosäure-Oxidase und Aminosäuren.

Suitable enzymes are z. As peroxidases, which can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg. B.

• - pyranose oxidase and z. D-glucose or galactose,
• Glucose oxidase and D-glucose,
• - glycerol oxidase and glycerin,
• Pyruvate oxidase and pyruvic acid or its salts,
• Alcohol oxidase and alcohol (MeOH, EtOH),
• Lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or their salts,
• - choline oxidase and choline,
• - amino acid oxidase and amino acids.

at an application of oxidizing agents, the actual brightening and / or colorants expediently immediately before use by mixing the preparation of the Oxidizing agent with the preparation containing the compounds of the formula (I) and / or of the formula (II) and, if appropriate, dye precursors, produced. The resulting ready-to-use whitening and / or Hair dye preparation should preferably have a pH ranging from 6 to 12. Particularly preferred is the application of Brightening and / or hair dye in a weakly alkaline Milieu. The application temperatures can be in one range between 15 and 40 ° C lie. After an exposure time from 5 to 45 minutes, the hair dye is removed by rinsing removed from the hair to be dyed. The washing up with a shampoo is omitted if a carrier containing high levels of surfactant, z. As a dyeing shampoo was used.

Especially with hair that is difficult to dye, an inventive Agent optionally with additional dye precursors but also without prior mixing with the oxidation component be applied to the hair. After an exposure time of 20 up to 30 minutes then - possibly after an intermediate rinse - the Oxidation component applied. After another period of exposure from 10 to 20 minutes is then rinsed and if desired shampooed. In this embodiment, according to a first variant, in which the previous application of the dye precursors to effect a better penetration into the hair, the corresponding Medium adjusted to a pH of about 4 to 7. According to one second variant, first an air oxidation is sought, wherein the applied agent preferably has a pH of 7 to 10 has. In the subsequent accelerated post-oxidation may be the use of acidified peroxydisulfate solutions be preferred as the oxidizing agent.

additionally the agents according to the invention can be further Contain ingredients. A use of certain metal ions or For example, complexes may be preferred to provide intense colorations to obtain. Here are means according to the invention preferably, additionally Cu, Fe, Mn, Ru ions or Complexes of these ions contain.

Preferred agents according to the invention additionally contain Cu, Fe, Mn, Co, Ce, V, Ru ions or complexes of these ions, with particularly preferred agents being 0.0001 to 2.5% by weight, preferably 0.001 to 1 wt .-% of at least one compound from the group copper chloride (CuCl ₂ ), copper sulfate (CuSO ₄ ), iron (II) sulfate, manganese (II) sulfate, manganese (II) chloride, cobalt (II) chloride, cerium sulfate, cerium chloride , Vanadium sulfate, manganese dioxide (MnO ₂ ).

According to the invention preferred is also 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, wherein a single Ligand occupies more than one coordination site on a central atom, d. H. at least "bidentate". In this case, so normally stretched compounds by complex formation over closed an ion to rings. The number of bound ligands depends on the coordination number of the central ion.

common and in the context of the present invention, preferred chelate complex images For example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and hydroxyethanediphosphonic acids or their alkali metal salts. Also complexing polymers, ie polymers, either in the main chain itself or side by side to carry functional groups that can act as ligands and with suitable metal atoms usually under formation of Chelate complexes react, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can come from only one macromolecule or belong to different polymer chains. The latter leads to the networking of the material, provided that the complexing Polymers have not previously been crosslinked via covalent bonds were.

complexing Groups (ligands) of conventional complex-forming polymers are Iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, Dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and crown ether radicals with z. T. very specific. Activities towards ions different metals. Many base polymers are also commercially available important complexing polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethylenimines. Also natural polymers like cellulose, starch or chitin are complexing polymers. Furthermore these can be prepared by polymer-analogous transformations with others Ligand functionalities are provided.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine.

In the context of the present invention, it is particularly preferable to use one or more chelating agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di (β-hydroxyethyl) glycine, N- (1,2-dicarboxy 2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,
• d) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

When Polycarboxylic acids a) are used in this patent application Carboxylic acids - including monocarboxylic acids - understood, where the sum of carboxyl and contained in the molecule Hydroxyl groups is at least 5. Complexing agent the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the invention required alkaline pH values of the treatment solutions are these Chelating agents at least partially as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts become. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, especially sodium salts.

As well are further preferred complexing agents polymeric aminodicarboxylic acids, to mention their salts or their precursors. Especially Preference is given to polyaspartic acids or their salts and Derivatives, in addition to Cobuilder properties also a bleach-stabilizing Have effect.

Further suitable complexing agents are polyacetals, which by reaction of dialdehydes with polyolcarboxylic acids, which are 5 to 7 C atoms and at least 3 hydroxyl groups can be obtained. Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from Polyolcarbonsäuren such as gluconic acid and / or glucoheptonic acid.

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

According to the invention preferred Chelating agents are phosphonates, preferably hydroxyalkane or aminoalkanephosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its Di- or tetrasodium salt and / or ethylenediamine tetramethylene phosphonate (EDTMP) or its hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta- or octasodium salt.

• (a) Nitrilotriessigsäure (NTA),
• (b) Diethylenetriaminpentaesigsäure (DTPA),
• (c) Ethylendiamindibernsteinsäure (EDDS),
• (d) Ethylenediamindiglutarsäure (EDGA),
• (e) 2-Hydroxypropylendiamindibernsteinsäure (HPDS),
• (f) Glycinamid-N,N'-dibernsteinsäure (GADS),
• (g) Ethylendiamin-N-N'-diglutarsäure (EDDG),
• (h) 2-Hydroxypropylendiamin-N-N'-dibernsteinsäure (HPDDS),
• (i) Ethylendiamintetraessigsäure (EDTA),
• (j) Ethylendicysteinsäure (EDC),
• (k) Diaminoalkyldi(sulfobernsteinsäure) (DDS),
• (l) Ethylendiamine-N-N'-bis(ortho-hydroxyphenylesigsäure (EDDHA),
• (m) N-2-hydroxyethyl-N,N-diessigsäure,
• (n) Glyceryliminodiessigsäure,
• (o) Iminodiessigsäure-N-2-hydroxypropylsulfonsäure,
• (p) Asparaginsäure-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonsäure,
• (q) 8-Alanin-N,N'-diessigsäure,
• (r) Asparaginsäure-N,N'-diessigsäure,
• (s) Asparaginsäure-N-monoessigsäure,
• (t) Dipicolinsäure,
• (u) sowie deren Salze und/oder Derivate

From the above-mentioned groups of substances, some representatives are particularly preferred in the context of the present invention. Particularly preferred agents according to the invention contain one or more substances from the group

• (a) nitrilotriacetic acid (NTA),
• (b) diethylenetriaminepentaacetic acid (DTPA),
• (c) ethylenediamine disuccinic acid (EDDS),
• (d) ethylenediamine-diglutaric acid (EDGA),
• (e) 2-hydroxypropylenediamine disuccinic acid (HPDS),
• (f) glycinamide-N, N'-disuccinic acid (GADS),
• (g) ethylenediamine-N-N'-diglutaric acid (EDDG),
• (h) 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS),
• (i) ethylenediaminetetraacetic acid (EDTA),
• (j) ethylene dicysteic acid (EDC),
• (k) diaminoalkyldi (sulfosuccinic acid) (DDS),
• (l) ethylenediamine-N-N'-bis (ortho-hydroxyphenylacetic acid (EDDHA),
• (m) N-2-hydroxyethyl-N, N-diacetic acid,
• (n) glyceryliminodiacetic acid,
• (o) iminodiacetic acid N-2-hydroxypropylsulfonic acid,
• (p) aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid,
• (q) 8-alanine-N, N'-diacetic acid,
• (r) aspartic acid-N, N'-diacetic acid,
• (s) aspartic acid N-monoacetic acid,
• (t) dipicolinic acid,
• (u) and their salts and / or derivatives

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine

enthalten, wobei bevorzugte Mittel Phosphonate, vorzugsweise Hydroxyalkan- bzw. Aminoalkanphosphonate und insbesondere 1-Hydroxyethan-1,1-diphosphonat (HEDP) bzw. dessen Di- oder Tetranatriumsalz und/oder Ethylendiamintetramethylenphosphonat (EDTMP) bzw. dessen Hexanatriumsalz und/oder Diethylentriaminpentamethylenphosphonat (DTPMP) bzw. dessen Hepta- oder Octanatriumsalz, enthalten.Agents preferred according to the invention are characterized in that they additionally comprise one or more chelate complexing agents from the groups of

• (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
• (ii) nitrogen-containing mono- or polycarboxylic acids,
• (iii) geminal diphosphonic acids,
• (iv) aminophosphonic acids,
• (v) phosphonopolycarboxylic acids,
• (vi) cyclodextrins

Preferred agents include phosphonates, preferably hydroxyalkane or aminoalkanephosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and / or diethylenetriaminepentamethylenephosphonate ( DTPMP) or its hepta- or octasodium salt.

As already mentioned, the inventive Means not just pure lightening agents, d. H. as a so-called blonding agent, but also provided as a dyeing and whitening agent which, at the same time as the whitening, is also a coloring cause the keratin fibers. For this purpose, such inventive Means at least one dye precursor, preferably an oxidation dye precursor and / or at least one substantive dye.

In addition to their function as bleaching agents, the agents according to the invention of this embodiment are also colorants, ie agents for changing the color of keratinic fibers. Among these are in particular the so-called oxidation colorants are preferred. The oxidation colorants of the invention contain at least one coupler and at least one developer component. Coupler and developer components are also referred to as oxidation dye precursors. In addition, the oxidation colorants according to the invention may also contain substantive dyes as nuances.

According to the invention preferred Agent for dyeing and / or whitening keratinic fibers are therefore characterized in that they at least an oxidation dye precursor of the developer type and / or coupler type contain.

to Provision of color-changing cosmetic preparations, in particular for the skin or keratin fibers such as human hair, the expert knows the requirements of the Coloring various dyeing systems.

For permanent, intensive colorations with corresponding fastness properties so-called oxidation colorants are used. Such Colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or of Atmospheric oxygen with each other or under coupling with one or more Coupler components from the actual dyes. The oxidation colorants Although distinguished by excellent, long-lasting staining results out. For natural-looking dyeings but usually has a mixture of one larger number of oxidation dye precursors be used; in many cases will continue to be substantive Dyes used for shade.

When Developer components usually become primary aromatic amines with another, in para or ortho position free or substituted hydroxy or amino group, heterocyclic hydrazones, diaminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

Specific Representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-aminophenyl) -diaminopropan-2-ol.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, pyridine derivatives, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols used. Suitable coupler substances in particular 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, Resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 2-amino-3-hydroxypyridine, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

For temporary stains become common Dyeing or toning agents used as coloring Component so-called direct pullers included. This is it around dye molecules that are directly on the substrate raise and no oxidative process to form the Need color. Belongs to these dyes for example, that already from antiquity for coloring body and hair known henna. These dyes are much more sensitive to shampooing than the oxidative dyeings, so that then very much faster a much undesirable nuance shift or even a visible homogeneous color loss occurs.

After all another dyeing process has received a lot of attention found. In this process, precursors of the natural Hair Dye Melanin on the substrate, eg. As hair applied; These then form natural analogues in the course of oxidative processes in the hair Dyes off. At, in particular multiple, application of means With 5,6-dihydroxyindoline it is possible to give people with graying Hair to reproduce the natural hair color. The coloration can be done with atmospheric oxygen as the sole oxidant, so that resorted to no further oxidizing agents must become. In persons with originally mittelblondem to brown hair, indoline can be the sole dye precursor be used. For use with persons with original red and especially dark to black hair color can against it Satisfactory results often only through co-use further dye components, in particular special oxidation dye precursors, be achieved.

Another possibility for color change offers the use of colorants, which soge called Oxofarbstoffvorprodukte included. A first class of oxo dye precursors are compounds having at least one reactive carbonyl group. This first class is called a component (Oxo1). A second class of oxo dye precursors form CH-acidic compounds and compounds having primary or secondary amino groups or hydroxy groups, which in turn are selected from compounds of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. This second class is called a component (Oxo2). The aforementioned components (oxo1) and (oxo2) are generally not themselves dyes, and therefore are not in themselves suitable for coloring keratin-containing fibers. In combination, they form dyes in a non-oxidative process of so-called oxo dyeing. The resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing.

The Nuance spectrum achievable with gentle oxo staining is very wide and the obtained color often shows an acceptable brilliance and color depth. Under compounds of However, component (Oxo2) can also be corresponding Developing and / or coupling agent oxidation dye precursors with or use without the use of an oxidizing agent. Consequently the method of oxo dyeing can be used readily combine with the oxidative staining system.

Should Substrates are lightened or even bleached, which become the substrate coloring dyes usually oxidative using appropriate Oxidizing agents, such as hydrogen peroxide, decolorized.

• (1) aus mindestens einem Oxidationsfarbstoffvorprodukt vom Typ der Entwicklerkomponenten und gegebenenfalls zusätzlich mindestens einer Kupplerkomponente und/oder
• (2) aus Oxofarbstoffvorprodukten und/oder
• (3) aus mindestens einem direktziehenden Farbstoff und/oder
• (4) aus mindestens einer Vorstufe naturanaloger Farbstoffe.

In one embodiment of the color change, the object of the present invention can be combined with at least one color-changing component. The color-changing components in the context of the present invention are preferably selected

• (1) at least one oxidation dye precursor of the type of developer components and optionally additionally at least one coupler component and / or
• (2) from oxo dye precursors and / or
• (3) from at least one direct dye and / or
• (4) from at least one precursor of naturally-colored dyes.

wobei

• – G¹ steht für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen (C₁ bis C₄)-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• – G² steht für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest oder einen (C₁ bis C₄)-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• – G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, Iod- oder Fluoratom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Hydroxyalkoxyrest, einen (C₁ bis C₄)-Acetylaminoalkoxyrest, einen Mesylamino-(C₁ bis C₄)-alkoxyrest oder einen (C₁ bis C₄)-Carbamoylaminoalkoxyrest;
• – G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen (C₁ bis C₄)-Alkylrest oder
• – wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

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

in which

• G ¹ represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) - Alkoxy (C ₁ to C ₄ ) alkyl, 4'-aminophenyl or (C ₁ to C ₄ ) alkyl substituted with a nitrogen-containing group, a phenyl or a 4'-aminophenyl;
• G ² represents a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) - Alkoxy (C ₁ to C ₄ ) alkyl or (C ₁ to C ₄ ) alkyl substituted with a nitrogen-containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) -hydroxyalkoxy radical, a (C ₁ to C ₄ ) -acetylaminoalkoxy radical, a mesylamino (C ₁ to C ₄ ) -alkoxy radical or a (C ₁ to C ₄ ) -Carbamoylaminoalkoxyrest;
• G ⁴ represents a hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) -alkyl radical or
• When G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Particularly preferred p-phenylenediamines of formula (E1) are selected from one or more compounds of the group formed from p-phenylenediamine, p-toluenediamine, 2-chloro-p-pheny lendiamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p- phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl ) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β -Hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p- phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- ( β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine, 5 , 8-Diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

Completely according to the invention Particularly preferred p-phenylenediamine derivatives of the formula (E1) are selected from at least one compound of the group p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, as well as the physiologically acceptable salts of these compounds.

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

wobei:

• – Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen (C₁ bis C₄)-Alkylrest, durch einen (C₁ bis C₄)-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• – die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder (C₁ bis C₈)-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• – G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen (C1 bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• – G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen (C₁ bis C4)-Alkylrest,

mit der Maßgabe, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten.Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

• - Z ¹ and Z ² independently of one another are a hydroxyl or NH ₂ radical which is optionally substituted by a (C ₁ to C ₄ ) -alkyl radical, by a (C ₁ to C ₄ ) -hydroxyalkyl radical and / or by a bridge Y is substituted or which is optionally part of a bridging ring system,
• - The bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be substituted by one or more hydroxyl or (C ₁ to C ₈ ) alkoxy, or a direct bond,
• G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a (C ₁ -C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a C ₁ to C ₄ ) -aminoalkyl radical or a direct compound for bridging Y,
• G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a (C ₁ to C ₄ ) -alkyl radical,

with the proviso that the compounds of the formula (E2) contain only one bridge Y per molecule.

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

Preferred dinuclear developing agents of the formula (E2) are in particular selected from at least one of the following compounds: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino -propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4'-aminophenyl) - tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) tetramethylenediamine, N, N'-bis (4- (methylamino) phenyl) tetramethylenediamine, N , N'-diethyl-N, N'-bis- (4'-amino-3'-me thylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy 5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically acceptable salts.

All particularly preferred binuclear developer components of the formula (E2) are selected from N, N'-bis (β-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 or one of the physiologically acceptable salts of these compounds.

wobei:

• – G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest, einen Hydroxy-(C₁ bis C₄)-alkylaminorest, einen (C₁ bis C₄)-Hydroxyalkoxyrest, einen (C₁ bis C₄)-Hydroxyalkyl-(C₁ bis C₄)-aminoalkylrest oder einen (Di-[(C₁ bis C₄)-alkyl]amino)-(C₁ bis C₄)-alkylrest, und
• – G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest oder einen (C₁ bis C₄)-Cyanoalkylrest,
• – G¹⁵ steht für Wasserstoff, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• – G¹⁶ steht für Wasserstoff oder ein Halogenatom.

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

in which:

• G ¹³ represents a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl, (C ₁ to C ₄ ) aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, (C ₁ to C ₄ ) hydroxyalkoxy, a (C ₁ to C ₄ ) hydroxyalkyl (C ₁ to C ₄ ) aminoalkyl radical or a (di - [(C ₁ to C ₄ ) alkyl] amino) - (C ₁ to C ₄ ) alkyl radical, and
• G ¹⁴ is a hydrogen or halogen atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -aminoalkyl radical or a (C ₁ to C ₄ ) -cyanoalkyl radical,
• G ¹⁵ is hydrogen, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

The used in formula (E3) substituents are analogous to the invention defined to the above statements.

preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) -phenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and its physiological compatible salts.

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

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

Farther For example, the developer component may be selected from heterocyclic Developer components, such as pyrimidine derivatives, Pyrazole derivatives, pyrazolopyrimidine derivatives or their physiological compatible salts.

worin

• – G¹⁷, G¹⁸ und G¹⁹ unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁ bis C₄)-Alkoxygruppe oder eine Aminogruppe steht und
• – G²⁰ für eine Hydroxygruppe oder eine Gruppe -NG²¹G²² steht, worin G²¹ und G²² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe,

mit der Maßgabe, dass maximal zwei der Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ eine Hydroxygruppe bedeuten und höchstens zwei der Reste G¹⁷, G¹⁸ und G¹⁹ für ein Wasserstoffatom stehen. Dabei ist es wiederum bevorzugt, wenn gemäß Formel (E4) mindestens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Gruppe -NG²¹G²² stehen und höchstens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Hydroxygruppe stehen.Preferred pyrimidine derivatives are selected according to the invention from compounds of the formula (E4) or their physiologically tolerated salts,

wherein

• G ¹⁷ , G ¹⁸ and G ¹⁹ independently of one another represent a hydrogen atom, a hydroxy group, a (C ₁ to C ₄ ) alkoxy group or an amino group and
• G ^{20 is} a hydroxy group or a group -NG ²¹ G ²² in which G ²¹ and G ²² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group .

with the proviso that a maximum of two of the groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 is} a hydroxy group and at most two of the radicals G ¹⁷ , G ¹⁸ and G ^{19 are} a hydrogen atom. In this case, it is again preferred if, according to formula (E4), at least two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a group -NG ²¹ G ²² and at most two groups of G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a hydroxy group.

Especially preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

worin

• – G²³, G²⁴, G²⁵ stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte Aryl-(C₁ bis C₄)-alkylgruppe, mit der Maßgabe dass, wenn G²⁵ für ein Wasserstoffatom steht, G²⁶ neben den vorgenannten Gruppen zusätzlich für eine Gruppe -NH₂ stehen kann,
• – G²⁶ für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe oder eine (C₂ bis C₄)-Polyhydroxyalkylgruppe und
• – G²⁷ steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe, eine (C₁ bis C₄)-Alkylgruppe oder eine (C₁ bis C₄)-Monohydroxyalkylgruppe, insbesondere für ein Wasserstoffatom oder eine Methylgruppe.

Preferred pyrazole derivatives are selected according to the invention from compounds of the formula (E5),

wherein

• G ²³ , G ²⁴ , G ²⁵ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -monohydroxyalkyl group, a (C ₂ to C ₄ ) -polyhydroxyalkyl group, a optionally substituted aryl group or an optionally substituted aryl- (C ₁ to C ₄ ) -alkyl group, with the proviso that when G ^{25 is} a hydrogen atom, G ^{26 may} additionally be a group -NH _{2 in} addition to the abovementioned groups,
• G ^{26 represents} a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group or a (C ₂ to C ₄ ) polyhydroxyalkyl group and
• G ²⁷ represents a hydrogen atom, an optionally substituted aryl group, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -monohydroxyalkyl group, in particular a hydrogen atom or a methyl group.

Preferably in formula (E5) the radical -NG ²⁵ G ²⁶ binds to the 5 position and the radical G ²⁷ to the 3 position of the pyrazole cycle.

Especially preferred pyrazole derivatives are in particular the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3- methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) -pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-Amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, as well their physiologically acceptable salts.

wobei:

• – G²⁸, G²⁹ und G³⁰, G³¹ unabhängig voneinander stehen für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen Aryl-Rest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁ bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁ bis C₄)-alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C₁ bis C₄)-Monohydroxyalkyl- oder einen Di[(C₁ bis C₄)-Hydroxyalkyl]-(C₁ bis C4)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen Aryl-Rest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Aminoalkylrest, einen (C₁ bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁ bis C₄)alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C₁ bis C₄)-Hydroxyalkyl- oder einen Di-[(C₁ bis C₄)-hydroxyalkyl]amino-(C₁ bis C₄)-alkylrest, einen Aminorest, einen (C₁ bis C₄)-Alkyl- oder Di-[(C₁ bis C₄)-hydroxyalkyl]aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, dass
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG²⁸G²⁹ und NG³⁰G³¹ belegen die Positionen (2, 3); (5, 6); (6, 7); (3, 5) oder (3, 7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG²⁸G²⁹ (oder NG³⁰G³¹) und die Gruppe OH belegen die Positionen (2, 3); (5, 6); (6, 7); (3, 5) oder (3, 7);

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E6) and its tautomeric forms, if a tautomeric equilibrium exists:

in which:

• G ²⁸ , G ²⁹ and G ³⁰ , G ³¹ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, an aryl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical is a (C ₁ to C ₄ ) -alkoxy- (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -aminoalkyl radical which is optionally substituted by an acetyl-ureide or a sulfonyl radical Rest may be protected, a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) aminoalkyl where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a (C ₁ to C ₄ ) monohydroxyalkyl or a di [(C ₁ to C ₄ ) hydroxyalkyl] - (C ₁ to C ₄ ) aminoalkyl,
• The X radicals independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, an aryl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, a (C ₁ to C ₄ ) aminoalkyl radical, a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl radical, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) -aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a (C ₁ to C ₄ ) -hydroxyalkyl or a di - [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) alkyl, an amino, a (C ₁ to C ₄ ) alkyl or di - [(C ₁ to C ₄ ) hydroxyalkyl] amino, a halogen atom, a carboxylic acid group or a sulfonic acid group .
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1, with the proviso that
• The sum of p + q is not equal to 0,
• If p + q equals 2, n has the value 0, and the groups NG ²⁸ G ²⁹ and NG ³⁰ G ³¹ occupy the positions (2, 3); (5, 6); (6, 7); (3, 5) or (3, 7);
• If p + q is 1, n is 1, and the groups NG ²⁸ G ²⁹ (or NG ³⁰ G ³¹ ) and the group OH occupy the positions (2, 3); (5, 6); (6, 7); (3, 5) or (3, 7);

The used in formula (E7) substituents are analogous to the invention defined to the above statements.

When the pyrazolo [1,5-a] pyrimidine of the above formula (E6) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:

• – Pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – Pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-7-ol;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-5-ol;
• – 2-(3-Aminopyrazolo[1,5-a]pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazolo[1,5-a]pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazolo[1,5-a]pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.In particular, among the pyrazolo [1,5-a] pyrimidines of the above formula (E7):

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
• 3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
• 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine;

and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The Pyrazolo [1,5-a] pyrimidines of the above formula (E6) can as described in the literature by cyclization starting from an aminopyrazole or hydrazine.

All particularly preferred developer components are selected from at least one compound from the group that is formed p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H- imidazol-1-yl) propyl] amine, N, N'-bis (β-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- (α, β-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, and the physiologically acceptable salts of these compounds.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (E1) to (E6): Examples of (C ₁ to 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 ₁ to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group.

Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group, -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CHCH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, with the group -CH ₂ CH ₂ OH being preferred.

A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.

Examples for halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) -monoalkylamino groups, (C ₁ to C ₄ ) -dialkylamino groups, (C ₁ to C ₄ ) -trialkylammonium groups, (C ₁ to C ₄ ) -monohydroxyalkylamino groups, Imidazolinium and -NH ₃ ⁺ .

Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) trialkylammonium groups are -N ⁺ (CH ₃ ) ₃ , -N ⁺ (CH ₃ ) ₂ (CH ₂ CH ₃ ), -N ⁺ (CH ₃ ) (CH ₂ CH ₃ ) ₂ ,

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino radicals are -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ), -CH ₂ CH ₂ CH ₂ -O- CH (CH ₃ ).

Examples of hydroxy (C ₁ to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-CHCH (OH) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) -acetylaminoalkoxy radicals are -O-CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ NHC (O) CH ₃ , -O-CH ₂ CH ₂ CH ₂ NHC (O ) CH ₃ , -O-CH ₂ CH (NHC (O) CH ₃ ) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ NHC (O) CH ₃ .

Examples of (C ₁ to C ₄ ) -carbamoylaminoalkoxy radicals are -O-CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ .

Examples of (C ₁ to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH (NH ₂ ) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .

Examples of (C ₁ to C ₄ ) -cyanoalkyl radicals are -CH ₂ CN, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ CH ₂ CN.

Examples of (C ₁ to C ₄ ) -hydroxyalkylamino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH.

Examples of di [(C ₁ to C ₄ ) -hydroxyalkyl] amino (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N ( CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ .

One Example of aryl groups is the phenyl group.

Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

Kupplerkomponenten do not form a significant part of the oxidative staining alone Coloring, but always need the present of developer components. Therefore, it is preferred according to the invention that when using at least one developer component in addition at least one coupler component is used.

Kupplerkomponenten For the purposes of the invention, at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component out. Couplers are preferred cyclic compounds that participate in the cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups.

If the cyclic compound is a six-membered ring (preferably aromatic), so the said groups are preferably in the ortho position or meta-position to each other.

• – m-Aminophenol und/oder dessen Derivate,
• – m-Diaminobenzol und/oder dessen Derivate,
• – o-Diaminobenzol und/oder dessen Derivate,
• – o-Aminophenolderivate, wie beispielsweise o-Aminophenol,
• – Naphthalinderivate mit mindestens einer Hydroxygruppe,
• – Di- beziehungsweise Trihydroxybenzol und/oder deren Derivate,
• – Pyridinderivate,
• – Pyrimidinderivate,
• – Monohydroxyindol-Derivate und/oder Monoaminoindol-Derivate,
• – Monohydroxyindolin-Derivate und/oder Monoaminoindolin-Derivate,
• – Pyrazolonderivate, wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin oder 6-Amino-benzomorpholin,
• – Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,

Coupler components according to the invention are preferably selected as at least one compound from one of the following classes:

• M-aminophenol and / or its derivatives,
• M-diaminobenzene and / or its derivatives,
• O-diaminobenzene and / or its derivatives,
• O-aminophenol derivatives, such as o-aminophenol,
• Naphthalene derivatives having at least one hydroxy group,
• Di- or trihydroxybenzene and / or derivatives thereof,
• - pyridine derivatives,
• - pyrimidine derivatives,
• Monohydroxyindole derivatives and / or monoamine indole derivatives,
• Monohydroxyindoline derivatives and / or monoaminoindoline derivatives,
• Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Morpholine derivatives such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

mixtures of two or more compounds from one or more of these Classes are also within the scope of this embodiment according to the invention.

worin
G¹ und G² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine Amino-(C₁ bis C₆)-alkylgruppe, eine (C₁ bis C₆)-Dialkylamino-(C₁ bis C₆)-alkylgruppe oder eine (C1 bis C₆)-Alkoxy-(C₁ bis C₆)-alkylgruppe, wobei G¹ und G² gemeinsam mit dem Stickstoffatom einen fünfgliedrigen, sechsgliedrigen oder siebengliedrigen Ring bilden können,
G³ und G⁴ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine (C1 bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe, eine (C₁ bis C₆)-Alkyox-(C₂ bis C₆)-alkoxygruppe, eine Arylgruppe oder eine Heteroarylgruppe.The m-aminophenols or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K1) and / or from at least one physiologically tolerated salt of a compound of the formula (K1),

wherein
G ¹ and G ² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) -alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, an aryl (C ₁ to C ₆ ) alkyl group, an amino (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆₎ dialkylamino (C ₁ to C ₆₎ alkyl group or a (C1 to _C6) alkoxy (C ₁ to C ₆₎ alkyl group, wherein G ¹ and G ² together with the nitrogen atom can form a five-membered, six-membered or seven-membered ring,
G ³ and G ⁴ independently represent a hydrogen atom, a halogen atom, a (C1 to _C4) alkyl group, a (C ₁ to C ₄₎ alkoxy group, a hydroxy group, a (C ₁ to C ₄₎ -monohydroxyalkyl, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group, a (C ₁ to C ₆ ) alkoxy (C ₂ to C ₆ ) alkoxy group, an aryl group or a heteroaryl group ,

Especially preferred m-aminophenol coupler components are selected from at least one compound from the group that is formed from m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiological compatible salts of all the compounds mentioned above.

worin
G⁵, G⁶, G⁷ und G⁸ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Heteroaryl-(C₁ bis C₄)-alkylgruppe, eine (C2 bis C₄)-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterozyklus bilden
G⁹ und G¹⁰ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe, eine ω-(2,4-Diaminophenyl)-(C₁ bis C₄)- alkylgruppe, eine ω-(2,4-Diaminophenyloxy)-(C₁ bis C₄)-alkoxygruppe, eine (C₁ bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)-Alkoxy-(C₂ bis C₄)-alkoxygruppe, eine Arylgruppe, eine Heteroarylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe.The m-diaminobenzenes or derivatives thereof which can be used according to the invention are preferably selected from at least one compound of the formula (K2) and / or from at least one physiologically tolerated salt of a compound of the formula (K2),

wherein
G ⁵ , G ⁶ , G ⁷ and G ⁸ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) -alkenyl group , a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl group, an aryl (C ₁ to C ₄ ) alkyl group, a heteroaryl (C ₁ to C ₄ ) alkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G ⁹ and G ¹⁰ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group, an ω- (2,4-diaminophenyl) - (C ₁ to C ₄ ) -alkyl group, an ω- (2,4-diaminophenyloxy) - (C ₁ to C ₄ ) alkoxy group, a (C ₁ to C ₄ ) alkoxy group, a hydroxy group, a (C ₁ to C ₄ ) alkoxy (C ₂ to C ₄ ) alkoxy group, an aryl group, a heteroaryl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group.

Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group formed from m-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-hydroxyethylamino) -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 and the physiologically acceptable salts of all the above-mentioned compounds.

worin
G¹¹, G¹², G¹³ und G¹⁴ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Heteroaryl-(C₁ bis C₄)-alkylgruppe, eine (C₂ bis C₄)-Perfluoracylgruppe, oder gemeinsam mit dem Stickstoffatom einen fünfgliedrigen oder sechsgliedrigen Heterozyklus bilden
G¹⁵ und G¹⁶ unabhängig voneinander stehen für ein Wasserstoffatom, ein Halogenatom, eine Carboxylgruppe, eine (C₁ bis C₄)-Alkylgruppe, eine (C1 bis C₄)-Alkoxygruppe, eine Hydroxygruppe, eine (C₁ bis C₄)- Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Hydroxy-(C₁ bis C₄)-alkoxygruppe.The o-diaminobenzenes or their derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K3) and / or from at least one physiologically tolerated salt of a compound of the formula (K3),

wherein
G ¹¹ , G ¹² , G ¹³ and G ¹⁴ independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group , a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl group, an aryl (C ₁ to C ₄ ) alkyl group, a heteroaryl (C ₁ to C ₄ ) alkyl group, a (C ₂ to C ₄ ) perfluoroacyl group, or together with the nitrogen atom form a five-membered or six-membered heterocycle
G ¹⁵ and G ¹⁶ are independently a hydrogen atom, a halogen atom, a carboxyl group, a (C ₁ to C ₄₎ alkyl group, a (C1 to _C4) alkoxy group, a hydroxy group, a (C ₁ to C ₄₎ Monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a hydroxy (C ₁ to C ₄ ) alkoxy group.

Especially preferred o-diaminobenzene coupler components are selected from at least one compound from the group that is formed from 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all above mentioned compounds.

preferred Di- or trihydroxybenzenes and their derivatives selected from at least one compound of the group, which is formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, Pyrogallol and 1,2,4-trihydroxybenzene.

worin
G¹⁷ und G¹⁸ stehen unabhängig voneinander für eine Hydroxygruppe oder eine Gruppe -NG²¹G²²,
worin G²¹ und G²² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine Arylgruppe, eine (C₁ bis C4)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Heteroaryl-(C₁ bis C₄)-alkylgruppe,
G¹⁹ und G²⁰ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₄)-Alkylgruppe oder eine (C₁ bis C₄)-Alkoxygruppe.The pyridine derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K4) and / or from at least one physiologically tolerable salt of a compound of the formula (K4),

wherein
G ¹⁷ and G ¹⁸ independently of one another represent a hydroxyl group or a group -NG ²¹ G ²² ,
wherein G ²¹ and G ^{22 are} independently a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, an aryl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl group, an aryl (C ₁ to C ₄ ) alkyl group, a heteroaryl (C ₁ to C ₄ ) alkyl group,
G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -alkoxy group.

It is preferred if, according to formula (K4), the radicals G ¹⁷ and G ^{18 are} in the ortho position or in the meta position relative to one another.

Particularly preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino 6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2, 6-dimethoxypyridine, 3,4-diamino pyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically acceptable salts of the aforementioned compounds.

preferred Naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group that is formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

worin
G²³ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe,
G²⁴ steht für eine Hydroxygruppe oder eine Gruppe -NG²⁶G²⁷, worin G²⁶ und G²⁷ unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C4)-Polyhydroxyalkylgruppe,
G²⁵ Wasserstoffatom, ein Halogenatom oder eine (C₁ bis C4)-Alkylgruppe,
mit der Maßgabe, dass G²⁴ in meta-Position oder ortho-Position zum Strukturfragment NG²³ der Formel bindet.The indole derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K5) and / or from at least one physiologically tolerated salt of a compound of the formula (K5),

wherein
G ²³ represents a hydrogen atom, a C ₁ to C ₄ alkyl group, a C ₃ to C ₆ cycloalkyl group, a C ₂ to C ₄ alkenyl group, a C ₁ to C ₄ monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group, an aryl (C ₁ to C ₄ ) alkyl group,
G ²⁴ represents a hydroxy group or a group -NG ²⁶ G ²⁷ , in which G ²⁶ and G ²⁷ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ^{25 is a} hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) -alkyl group,
with the proviso that G ²⁴ binds in the meta position or ortho position to the structural fragment NG ^{23 of} the formula.

Especially Preferred indole derivatives are selected from at least a compound of the group formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable Salts of the aforementioned compounds.

worin
G²⁸ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe,
G²⁹ steht für eine Hydroxygruppe oder eine Gruppe -NG³¹G³², worin G³¹ und G³² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C4)-Polyhydroxyalkylgruppe,
G³⁰ Wasserstoffatom, ein Halogenatom oder eine (C₁ bis C4)-Alkylgruppe,
mit der Maßgabe, dass G²⁹ in meta-Position oder ortho-Position zum Strukturfragment NG²⁸ der Formel bindet.The indoline derivatives which can be used according to the invention are preferably selected from at least one compound of the formula (K6) and / or from at least one physiologically tolerable salt of a compound of the formula (K6),

wherein
G ²⁸ represents a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₃ to C ₆ ) cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group , a (C ₂ to C ₄ ) polyhydroxyalkyl group, an aryl (C ₁ to C ₄ ) alkyl group,
G ²⁹ represents a hydroxy group or a group -NG ³¹ G ³² , in which G ³¹ and G ³² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ to C ₄ ) alkenyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group,
G ^{30 is a} hydrogen atom, a halogen atom or a (C ₁ to C ₄ ) -alkyl group,
with the proviso that G ²⁹ binds in the meta position or ortho position to the structural fragment NG ^{28 of} the formula.

Especially preferred indoline derivatives are selected from at least a compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable Salts of the aforementioned compounds.

Preferred pyrimidine derivatives are selected from at least one compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2 -Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihy droxy-2-methylpyrimidine and the physiologically acceptable salts of the aforementioned compounds.

Particularly according to the invention preferred coupler components are selected from m-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-aminophenol, o-aminophenol, m-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-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxy-ethoxy) -5-methyl-phenylamine, 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, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures these compounds or the physiologically acceptable Salts of the aforementioned compounds.

The Coupler components are preferably present in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use oxidation colorants.

there become developer components and coupler components in general used in about molar amounts to each other. If also the molar use has proved to be useful, so is a certain excess of individual oxidation dye precursors not detrimental, leaving developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2, can stand.

The following are examples of the radicals mentioned as substituents of the compounds of the formulas (K1) to (K6): Examples of (C ₁ to 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 .

Inventive examples of (C ₃ to C ₈ ) -cycloalkyl groups are the cyclopropyl, the cyclopentyl and the cyclohexyl group.

Examples of (C ₁ to C ₄ ) -alkoxy radicals according to the invention are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group.

Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group, -CH ₂ OH, -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, with the group -CH ₂ CH ₂ OH being preferred.

A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.

Examples for halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.

Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) -monoalkylamino groups, (C ₁ to C ₄ ) -dialkylamino groups, (C ₁ to C ₄ ) -trialkylammonium groups, (C ₁ to C ₄ ) -monohydroxyalkylamino groups, Imidazolinium and -NH ₃ ⁺ .

Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ , -NHCH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) -dialkylamino group are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ -O -CH (CH ₃ ) ₂ .

Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkoxy groups are the groups -O-CH ₂ CH ₂ -O-CH ₃ , -O-CH ₂ CH ₂ CH ₂ -O-CH ₃ , -O-CH ₂ CH ₂ -O-CH ₂ CH ₃ , -O-CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -O-CH ₂ CH ₂ -O-CH (CH ₃ ) ₂ , -O-CH ₂ CH ₂ CH ₂ -O-CH (CH ₃ ) ₂ .

Examples of hydroxy (C ₁ to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH, -O-CH ₂ CH (OH) CH ₃ , -O-CH ₂ CH ₂ CH ₂ CH ₂ OH.

Examples of (C ₁ to C ₄ ) -aminoalkyl radicals are -CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH (NH ₂ ) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .

An example of aryl groups is the phenyl group, which may also be substituted. Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

Farther the agents according to the invention can be at least contain a direct dye. This is about Dyes that grow directly on the hair and no oxidative Need process for color training. Substantive Dyes are usually nitrophenylenediamines, nitroaminophenols, Azo dyes, anthraquinones or indophenols.

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

Substantive Dyes can be anionic, cationic and nonionic substantive dyes are subdivided.

Anionic 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 (CI 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 di-sodium Disulfonic acid) (CI 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 (CI 45, 350; Acid Yellow 73, D & C Yellow No 8), 5 - [(2,4-dinitrophenyl) amino] -2-phenylaminobenzenesulfonic acid, sodium salt (CI 10,385; Acid Orange 3), 4 - [(2,4-dihydroxyphenyl) az o] -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 (CI 14.710, Acid Red 4), 4 -Hydroxy-3 - [(4-sulfonaphth-1-yl) azo] -1-naphthalenesulfonic acid disodium salt (CI 14,720; Acid Red No. 14), 6-hydroxy-5 - [(4-sulfonaphth-1-) yl) azo] -2,4-naphthalenedisulfonic acid trisodium salt (CI 16,255; Ponceau 4R; Acid Red 18); 3-hydroxy-4 - [(4-sulfonaphth-1-yl) azo] -2,7-naphthalene disulfonic acid trisodium salt (CI 16.185; Acid Red 27), 8-amino-1-hydroxy-2- (phenylazo) -3,6-naphthalenedisulfonic acid disodium salt (CI 17, 400; Acid Red 33, Red 33); (Acetylamino) -4-hydroxy-3 - [(2-methylphenyl) azo] -2,7-naphthalenedisulfonic acid disodium salt (CI 18.065; Acid Red 35), 2- (3-hydroxy-2,4,5, 7-tetraiodo-dibenzopyran-6-on-9-yl) -benzoic acid disodium salt (CI 45,430; Acid Red 51), N- [6- (6,8 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-disulfonic 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 (CI 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-hydroxynaphth-1-yl) azo) -5-nitrobenzenesulfonic acid, sodium salt (CI 15,685; 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 (CI 15.850: 1; Pigment Red 57: 1), 3 - [(2,4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic acid disodium salt (CI 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 (CI 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-sulfophenyl) methyl) amino) phenyl] -carbenium disodium salt betaine (CI 42.090, Acid Blue 9, FD & C Blue No. 1), 1-amino-4- (phenylamino) -9, 10-anthraquinone-2-sulfonic acid (CI 62.055, Acid Blue 25), 1-amino-4- (cyclohexylamino) -9,10-anthraquinone-2-sulfonic acid, sodium salt (CI 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 S alz, sodium salt (CI 45.190; Acid Violet 9), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone sodium salt (CI 60,730, D & C Violet No. 2, Acid Violet 43), Bis [3 nitro-4 - [(4-phenylamino) -3-sulfophenylamino] -phenyl] -sulfone (CI 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 - [(2-hydroxynaphth-1-yl) azo] -7-nitro-1 naphthalene-sulfonic acid chromium complex (3: 2) (CI 15,711, Acid Black 52), 4- (acetylamino) -5-hydroxy-6 - [(7-sulfo-4 - [(4-sulfophenyl) azo] naphth-1-yl azo] -1,7-naphthalenedisulfonic acid tetrasodium salt (CI 28,440, Food Black No. 1), 3 ', 3 ", 5', 5" -tetrabromophenolsulfonephthalein (bromophenol blue).

preferred anionic substantive dyes are among the international ones 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.

Cationic direct dyes:

When cationic substantive dyes are in particular 9- (dimethylamino) benzo [a] phenoxazine-7-ium chloride (C.I. 51,175; Basic Blue 6), di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium chloride (C.I. 42,595; Basic Blue 7), di (4- (dimethylamino) phenyl) - (4- (methylphenylamino) -naphthalen-1-yl) carbenium chloride (C.I. 42,563, Basic Blue 8), 3,7-di (dimethylamino) -phenothiazine-5-ium chloride (C.I. 52.015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (C.I. 44.045; Basic Blue 26), 2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methylsulfate (C.I. 11,154; Basic Blue 41), 8-amino-2-bromo-5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (C.I. 56,059; Basic Blue No. 99), bis [4- (dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride (C.I. 42,535, Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium chloride (C.I. 42,520; Basic Violet 2), tri [4- (dimethylamino) -phenyl] carbenium chloride (C.I. 42,555; Basic Violet 3), 2- [3,6- (diethylamino) dibenzopyranium-9-yl] benzoic acid chloride (C.I., 45.170, Basic Violet 10), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (C.I. 42,510 Basic Violet 14), 1,3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (C.I. 21,010; Basic Brown 4), 1 - [(4-aminophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride (C.I. 12,250, Basic Brown 16), 1 - [(4-amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride, 1 - [(4-amino-3-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol-chloride (C.I. 12,251; Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzeneamine chloride (C.I. 12.605, Basic Orange 69), 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (C.I. 50,240, Basic Red 2), 1,4-dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1,2,4-triazolium chloride (C.I. 11,055; Basic Red 22), 2-hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) -naphthalene chloride (C.I. 12,245; Basic Red 76), di [4- (dimethylamino) phenyl] iminomethane hydrochloride (C.I. 41,000, Basic Yellow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indol-1-ium chloride (C.I., 48,055; Basic Yellow 11), 3-methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (C.I. 12.719; Basic Yellow 57), bis [4- (diethylamino) phenyl] phenylcarbenium hydrogensulfate (1: 1) (C.I., 42.040, Basic Green 1), di (4- (dimethylamino) phenyl) -phenylmethanol (C.I. 42,000, Basic Green 4), 1- (2-morpholiniumpropylamino) -4-hydroxy-9,10-anthraquinone methylsulfate, 1 - [(3- (dimethylpropylaminium) -propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride and direct dyes containing a heterocycle, the has at least one quaternary nitrogen atom.

• (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• (c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908 , auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

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) direct dyes containing a heterocycle containing at least one quaternary nitrogen atom, as shown for example in the EP-A2-998 908 to which reference is made at this point, are called in the claims 6 to 11.

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

The Compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also available under the terms 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.

Nonionic substantive dyes:

When Nonionic substantive dyes are particularly suitable nonionic nitro and quinone dyes and neutral azo dyes.

Suitable blue nitro dyes are in particular:
1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene (HC Blue 2), 1-Methylamino-4- [methyl- (2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Blue 6), 1 - [(2,3-dihydroxypropyl) amino] -4- [ethyl- (2- hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 9), 1 - [(2,3-dihydroxypropyl) amino] -4- [methyl (2-hydroxyethyl) amino] -2-nitrobenzene (HC Blue 10) , 4- [di (2-hydroxyethyl) amino] -1 - [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue 11), 4- [ethyl- (2-hydroxyethyl) amino] -1- [ (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue 12), 2 - ((4-amino-2-nitrophenyl) amino) -5-dimethylaminobenzoic acid (HC Blue 13), 1-amino-3 Methyl 4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet 1), 1- (3-hydroxypropylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet 2 ), 1- (2-aminoethylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene, 4- (di (2-hydroxyethyl) amino) -2-nitro-1-phenylaminobenzene.

Suitable red nitro dyes are in particular:
1-Amino-4 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 7), 2-amino-4,6-dinitrophenol (picramic acid) and its salts, 1,4-diamino-2-nitrobenzene ( CI 76,070), 4-amino-2-nitrodiphenylamine (HC Red 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red 13), 1-amino-4- [(2-hydroxyethyl) amino] -5-chloro-2-nitrobenzene, 4-amino-1 - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red 3), 4 - [(2-hydroxyethyl) methylamino] -1- (methylamino) -2-nitrobenzene, 1-amino-4 - [(2,3-dihydroxypropyl) amino] -5-methyl-2-nitrobenzene, 1-amino-4- (methylamino) -2- nitrobenzene, 4-amino-2-nitro-1 - [(prop-2-en-1-yl) amino] benzene, 4-amino-3-nitrophenol, 4 - [(2-hydroxyethyl) amino] - 3-nitrophenol, 4 - [(2-nitrophenyl) amino] phenol (HC Orange 1), 1 - [(2-Aminoethyl) amino] -4- (2-hydroxyethoxy) -2-nitrobenzene (HC Orange 2), 4- (2,3-dihydroxypropoxy) -1 - [(2-hydroxyethyl) amino] -2 -nitrobenzene (HC Orange 3), 1-amino-5-chloro-4 - [(2,3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red 10), 5-chloro-1,4- [di (2 , 3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red 11), 2 - [(2-hydroxyethyl) amino] -4,6-dinitrophenol, 4-ethylamino-3-nitrobenzoic acid, 2 - [(4-amino-) 2-nitrophenyl) amino] benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol (HC Red BN), 2,5-diamino-6-nitropyridine, 6-amino-3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 3-amino-6 - [(2-hydroxyethyl) amino] -2-nitropyridine , 3-amino-6- (ethylamino) -2-nitropyridine, 3 - [(2-hydroxyethyl) amino] -6- (methylamino) -2-nitropyridine, 3-amino-6- (methylamino) -2-nitropyridine, 6- (ethylamino) -3 - [(2-hydroxyethyl) amino] -2-nitropyridine, 1,2,3,4-tetrahydro-6-nitroquinoxaline, 7-amino-3,4-dihydro-6-nitro-2H -1,4-benzoxazine (HC Red 14).

Suitable yellow nitro dyes are in particular:
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-hydroxyethyl) 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-hydroxyethyl) 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-nitrobenzamide (HC Yellow 15) 3 - [(2-hydroxyethyl) amino] -4-methyl-1-nitrobenzene, 4-chloro-3 - [(2-hydroxyethyl) amino] - 1-nitrobenzene.

Suitable quinone dyes are in particular:
1,4-di [(2,3-dihydroxypropyl) amino] -9,10-anthraquinone, 1,4-di [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 61.545, Disperse Blue 23), 1 - [(2-hydroxyethyl) amino] -4-methylamino-9,10-anthraquinone (CI 61,505, Disperse Blue 3), 2 - [(2-aminoethyl) amino] -9,10-anthraquinone (HC Orange 5) , 1-amino-4-hydroxy-9,10-anthraquinone (CI 60.710, Disperse Red 15), 1-hydroxy-4 - [(4-methyl-2-sulfophenyl) amino] -9,10-anthraquinone, 7- Beta-D-glucopyranosyl-9,10-dihydro-1-methyl-9,10-dioxo-3,5,6,8-tetrahydroxy-2-anthracenecarboxylic acid (CI 75,470, Natural Red 4), 1 - [(3 Aminopropyl) amino] -4-methylamino-9,10-anthraquinone (HC Blue 8), 1 - [(3-aminopropyl) amino] -9,10-anthraquinone (HC Red 8), 1,4-diamino-2- methoxy-9,10-anthraquinone (CI 62.015, Disperse Red 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis [(2-hydroxyethyl) amino] -9,10-anthraquinone (CI 62.500 Disperse Blue 7, Solvent Blue No. 69), 1,4-diamino-9,10-anthraquinone (CI 61.100, Disperse Violet 1), 1-amino-4- (methylamino) -9,10-anthraquinone (CI 61.105 , Disperse Violet 4, Solvent Violet No. 12), 2-hydroxy-3-methoxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-hydroxy-3-methyl-1,4-naphthoquinone, N- {6 - [( 3-chloro-4- (methylamino) phenyl) imino] -4-methyl-3-oxo-1,4-cyclohexadien-1-yl} urea (HC Red 9), 2 - {{4- [di (2- hydroxyethyl) amino] phenyl} amino} -5 - [(2-hydroxyethyl) amino] -2,5-cyclohexadiene-1,4-dione (HC Green 1), 5-hydroxy-1,4-naphthoquinone (CI 75,500, Natural Brown 7), 2-hydroxy-1,4-naphthoquinone (CI 75,480, Natural Orange 6), 1,2-dihydro-2- (1,3-dihydro-3-oxo-2H-indol-2-ylidene) 3H-indol-3-one (CI 73,000), 4 - {{5 - [(2-hydroxyethyl) amino] -1-methyl-1H-pyrazol-4-yl} imino} -4,5-dihydro-5 - [(2-hydroxyethyl) -imino] -1-methyl-1H-pyrazole sulfate (1: 1), hydrate (1: 1).

Suitable neutral azo dyes are in particular:
1- [di (2-hydroxyethyl) amino] -3-methyl-4 - [(4-nitrophenyl) azo] benzene (CI 11.210, Disperse Red 17), 1- [di (2-hydroxyethyl) amino] -4 - [(4-nitrophenyl) azo] benzene (Disperse Black 9), 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).

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-Nit ro-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-nitro phenol.

It It is not necessary that the substantive dyes each represent uniform connections. Rather, conditioned by the manufacturing processes for the individual Dyes, in minor amounts still contain other components be, as far as they do not adversely affect the dyeing result or for other reasons, e.g. B. toxicological, excluded Need to become.

Farther can also be used as direct dyes in nature occurring dyes are used, as for example in henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and Alkana root are included.

• – mindestens einer Verbindung, die mindestens eine reaktive Carbonylgruppe enthält (Komponente (Oxo 1)) mit mindestens einer Verbindung (Komponente Oxo2)
• – Verbindungen, ausgewählt aus (Oxo2a) CH-aciden Verbindungen und/oder aus (Oxo2b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus mindestens einer Verbindung der Gruppe, die gebildet wird aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen

zum Einsatz.As Oxofarbstoffvorprodukte preferably a combination of

• - at least one compound containing at least one reactive carbonyl group (component (oxo 1)) with at least one compound (component oxo2)
• Compounds selected from (oxo2a) CH-acidic compounds and / or from (oxo2b) compounds having a primary or secondary amino group or hydroxy group selected from at least one compound of the group formed from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds

for use.

• a) von Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Additionsverbindung
• b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Additionsverbindung
• c) von Wasser unter Bildung von Hydraten als Additionsverbindung (Komponente (Oxo1) leitet sich in diesem Fall c) von einem Aldehyd ab)

an das Kohlenstoffatom der Carbonylgruppe der reaktiven Carbonylverbindung.Reactive carbonyl compounds as component (oxo1) have in the context of the invention at least one carbonyl group as a reactive group which reacts with the component (oxo2) to form a covalent bond. Preferred reactive carbonyl compounds are selected from compounds which carry at least one formyl group and / or at least one keto group, in particular at least one formyl group. Furthermore, those compounds according to the invention are also suitable as component (Oxo1) in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the component (Oxo2) is always present. These derivatives are preferably addition compounds

• a) amines and derivatives thereof to form imines or oximes as addition compound
• b) of alcohols to form acetals or ketals as addition compound
• c) of water with formation of hydrates as addition compound (component (oxo1) is derived in this case c) from an aldehyde)

to the carbon atom of the carbonyl group of the reactive carbonyl compound.

Preferred reactive carbonyl compounds of the component (oxo1) are selected from the group consisting of benzaldehyde and its derivatives, naphthaldehyde and its derivatives, cinnamaldehyde and its derivatives, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine -9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3 trimethylindoline (Fischer's aldehyde or tribasic aldehyde),
2-indolealdehyde, 3-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2 aldehyde, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, pyridoxal, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl trifluoro-acetone, chromone-3-aldehyde, 3- (5'-nitro-2 '-furyl) -acrolein, 3- (2'-furyl) -acrolein and imidazole-2-aldehyde, 5- (4-dimethylaminophenyl) -penta-2,4-dienal, 5- (4-diethylaminophenyl) -penta-2, 4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4 dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal,
9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-formyl-1 methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4- Formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methyl-quinolinium, 2-For 1-methyl-quinolinium, 5-formyl-1-methyl-quinolinium, 6-formyl-1-methyl-quinolinium, 7-formyl-1-methyl-quinolinium, 8-formyl-1-methyl-quinolinium, 5-formyl-1-ethyl-quinolinium , 6-Formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl-1 benzylchinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquinolinium, 6-formyl-1-allylquinolinium, 7-formyl-1-allylquinolinium and 8-formyl-1-allylquinolinium benzene sulphonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methyl-isatin, 1-allyl-isatin, 1 Hydroxymethylisatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures of the above compounds.

worin

• • R¹, R² und R³ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine Formylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine (C₁ bis C₆)-Dialkylaminogruppe, eine Di(C₂-C₆-hydroxyalkylaminogruppe, eine Di(C₁ bis C₆)-alkoxy-(C₁ bis C₆)-alkyl)aminoguppe, eine (C₁ bis C₆)-Hydroxyalkyloxygruppe, eine Sulfonylgruppe, eine Carboxylgruppe, eine Sulfonsäuregruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine (C₂ bis C₆)-Acylgruppe, eine Acetylgruppe oder eine Nitrogruppe,
• • Z' steht für eine direkte Bindung oder eine Vinylengruppe,
• • R⁴ und R⁵ stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring.

Benzaldehyde and / or cinnamaldehyde and / or naphthaldehyde and / or at least one derivative of these abovementioned aldehydes, which in particular carry one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl component in the oxo dyeing. In this case, preference is again given to the reactive carbonyl compound of the component (oxo1) selected from at least one compound of the formula (AC-1),

wherein

• R ¹ , R ² and R ³ are each independently hydrogen, halogen, (C ₁ to C ₆ ) alkyl, (C ₂ to C ₆ ) alkenyl, formyl, hydroxy, C ₁ C ₆ alkoxy group, a (C ₁ to C ₆ ) dialkylamino group, a di (C ₂ -C ₆ hydroxyalkylamino group, a di (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl) amino group, a (C ₁ to C ₆ ) -hydroxyalkyloxy group, a sulfonyl group, a carboxyl group, a sulfonic acid group, a sulfonamide group, a carbamoyl group, a (C ₂ to C ₆ ) -acyl group, an acetyl group or a nitro group,
• Z 'is a direct bond or a vinylene group,
• R ⁴ and R ⁵ represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

The derivatives of benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component (Oxo1) are preferably selected from at least one compound of the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy 1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3 Bromo-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino 2-methoxybenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxy benzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dim ethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5- Trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3- Dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy- 3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy-benzaldehyde, 2,5-dihydrox benzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3, 5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3 Chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo-5-methoxybenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4- Dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1 naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimeth ylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3 Carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3-carboxy-4-hydroxybenzaldehyde, 5-carboxyvanillin, 3-carboxy-4-hydroxy-5-methylbenzaldehyde, 3-carboxy-5-ethoxy-4-hydroxybenzaldehyde, 3-allyl 4-hydroxybenzaldehyde, 3-allyl-4-hydroxy-5-methoxybenzaldehyde, 3-allyl-4-hydroxy-5-methylbenzaldehyde, 3-allyl-5-bromo-4-hydroxybenzaldehyde, 3,5-diallyl-4-hydroxybenzaldehyde, 3-allyl-5-carboxy-4-hydroxybenzaldehyde (3-allyl-5-formyl-2-hydroxybenzoic acid), 3-allyl-4-hydroxy-5-formylbenzaldehyde (5-allyl-4-hydroxyisophthalaldehyde) and piperonal.

When CH-acidic compounds generally become such compounds which is bound to an aliphatic carbon atom Carrying hydrogen atom, due to electron-withdrawing Substituents an activation of the corresponding carbon-hydrogen bond is effected. In principle, the choice of CH-acidic compounds no limits, as long as after condensation with the reactive Carbonyl compounds of the component (Oxo1) one for the human eye visible colored compound is obtained. It deals according to the invention preferably to such CH-acid Compounds which have an aromatic and / or a heterocyclic Rest included. The heterocyclic radical may in turn be aliphatic or be aromatic. Most preferably, the CH-acidic compounds are selected from heterocyclic compounds, in particular cationic, heterocyclic Links.

worin

• • R⁶ steht für eine lineare oder cyclische (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine (C₁ bis C₆)-Alkoxy-(C₁ bis C₆)-alkylgruppe, eine Gruppe R^IR^II-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• • R⁷ steht für eine (C₁ bis C₆)-Alkylgruppe, insbesondere für eine Methylgruppe,
• • X^– steht für ein physiologisch verträgliches Anion,
• • der Zyklus der Formel (CH-1) repräsentiert alle Ringstrukturen, die zusätzlich weitere Heteroatome wie Stickstoff, Sauerstoff oder Schwefel enthalten können und ferner ankondensierte Ringstrukturen tragen können, wobei alle diese Ringsstrukturen zusätzliche Substituenten tragen können,
• • Het steht für einen gegebenenfalls substituierten Heteroaromaten,
• • X¹ steht für eine direkte Bindung oder eine Carbonylgruppe.

Very particular preference is given to using as component (oxo2a) at least one CH-acidic compound having an aromatic or aliphatic, heterocyclic basic body which is selected from cyclic onium compounds having the structural unit of the formula (CH-1) and / or compounds of the formula (CH-) 2)

wherein

• R ⁶ is a linear or cyclic (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) polyhydroxyalkyl group, a (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl group, a group R ^I R ^II - (CH ₂ ) _m -, wherein R ^I and R ^II independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) hydroxyalkyl group or an aryl (C ₁ to C ₆₎ alkyl group, wherein R ^I and R ^II together with the nitrogen atom form a 5-, 6-, or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• R ⁷ is a (C ₁ to C ₆ ) -alkyl group, in particular a methyl group,
• • X ^- is a physiologically acceptable anion,
• The cycle of the formula (CH-1) represents all ring structures which may additionally contain other heteroatoms such as nitrogen, oxygen or sulfur and may further carry fused ring structures, all of these ring structures being able to carry additional substituents,
• Het is an optionally substituted heteroaromatic,
• • X ¹ represents a direct bond or a carbonyl group.

preferred Ring structures bearing the structural unit of the formula (CH-1), are preferably selected according to the invention from 3H indolium, benzothiazolium, benzoxazolium, 1,2-dihydro-2-oxopyrimidinium, Quinolinium, quinoxaline or pyridinium.

According to the invention, compounds of the formula (CH-2) are particularly suitable for those in which the radical Het according to formula (CH-2) is derived from one of the heteroaromatic compounds furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine , Pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole, quinoline , Isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, phenazine, benzocinnoline, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, purine, pteridine or coumarin, the aforementioned heteroaromatics having at least one group selected from a halogen atom, a nitro group, a thio group, a thio (C ₁ to C ₆ ) alkyl group, a heteroaryl group, an aryl group, a (C ₁ to C ₆ ) alkyl group, a (C ₁ b is C ₆ ) -alkoxy, hydroxy, (C ₂ to C ₆ ) -hydroxyalkyl, (C ₂ to C ₆ ) -polyhydroxyalkyl, (C ₁ to C ₆ ) -alkoxy (C ₁ to C ₆ ) alkyl group, an aryl (C ₁ to C ₆ ) alkyl group, an amino group, a (C ₁ to C ₆ ) monoalkylamino group, a (C ₁ to C ₆ ) dialkylamino group, a dialkylaminoalkyl group - (CH ₂ ) _n - NR'R '', wherein n is an integer of 2 and 6 and R 'and R "independently represent a linear or branched alkyl group, which may optionally together form a ring, may be substituted.

Preferably the compounds according to formula (CH-2) are selected from at least one compound of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-methyl-2-trifluoromethyl-3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5-fluoro-2-thenoyl) -acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl) -acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- (2-methyl-indol-3-oyl) -acetonitrile, 8-cyanoacetyl-7-methoxy-4-methylcoumarin, 2- (2-Isopropyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (2-phenyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (quinoxalin-2-yl) -acetonitrile, 2- (cumarone-2-yl) -acetonitrile, 6,7-dichloro-5- (cyanoacetyl) -2,3-dihydro-1-benzofuran-2-carboxylic acid tert-butyl ester, 2- (6-Hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile and 2- (1-phenyl-1,4-dihydrothiochromeno [4,3-c] pyrazol-3-oyl) - acetonitrile.

worin

• • R⁸ und R⁹ stehen unabhängig voneinander für eine lineare oder cyclische (C₁ bis C₆)-Alkylgruppe, eine (C₂ bis C₆)-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-(C₁ bis C₆)-alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine (C₁ bis C₆)-Alkoxy-(C₁ bis C₆)-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₄)-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• • R¹⁰ und R¹² stehen unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe, wobei mindestens einer der Reste R¹⁰ und R¹² eine (C₁ bis C6)-Alkylgruppe bedeutet,
• • R¹¹ steht für ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe, eine (C₂ bis C₆)-Polyhydroxyalkylgruppe, eine (C₁ bis C₆)-Alkoxygruppe, eine (C₁ bis C₆)-Hydroxyalkoxygruppe, eine Gruppe R^IIIR^IVN-(CH₂)_q-, worin R^III und R^IV stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe und q steht für eine Zahl 1, 2, 3, 4, 5 oder 6, wobei der Rest R¹¹ zusammen mit einem der Reste R¹⁰ oder R¹² einen 5- oder 6-gliedrigen aromatischen Ring bilden kann, der gegebenenfalls mit einem Halogenatom, einer (C₁ bis C₆)-Alkylgruppe, einer (C₁ bis C6)-Hydroxyalkylgruppe, einer (C₂ bis C₆)-Polyhydroxyalkylgruppe, einer (C₁ bis C₆)-Alkoxygruppe, einer (C₁ bis C₆)-Hydroxyalkoxygruppe, einer Nitrogruppe, einer Hydroxygruppe, einer Gruppe R^VR^VIN-(CH₂)_s-, worin R^V und R^VI stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₆)-Alkylgruppe, eine (C₁ bis C₆)-Hydroxyalkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe und s steht für eine Zahl 0, 1, 2, 3, 4, 5 oder 6 substituiert sein kann,
• • Y steht für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NR^VII, worin R^VII steht für ein Wasserstoffatom, eine Arylgruppe, eine Heteroarylgruppe, eine (C₁ bis C6)-Alkylgruppe oder eine Aryl-(C₁ bis C₆)-alkylgruppe,
• • X^– steht für ein physiologisch verträgliches Anion.

The CH-acidic compounds of the oxo dye precursors of the component (oxo2a) are preferably selected from at least one compound of the formula (CH-3),

wherein

• R ⁸ and R ⁹ are each independently a linear or cyclic (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) polyhydroxyalkyl group, a (C ₁ to C ₆ ) alkoxy (C ₁ to C ₆ ) alkyl group , a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) hydroxyalkyl group or an aryl (C ₁ to C ₄ ) alkyl group, wherein R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• R ¹⁰ and R ¹² independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group, where at least one of the radicals R ¹⁰ and R ¹² denotes a (C ₁ to C ₆ ) -alkyl group,
• R ¹¹ represents a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group, a (C ₂ to C ₆ ) -polyhydroxyalkyl group, a (C ₁ to C ₆ ) - Alkoxy group, a (C ₁ to C ₆ ) -hydroxyalkoxy group, a group R ^III R ^IV N- (CH ₂ ) _q -, in which R ^III and R ^IV independently of one another represent a hydrogen atom, a (C ₁ to C ₆ ) - Alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group or an aryl (C ₁ to C ₆ ) alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ¹¹ together with one of R ¹⁰ or R ^{12 may form} a 5- or 6-membered aromatic ring optionally substituted with a halogen atom, a (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) -polyhydroxyalkyl group, a (C ₁ to C ₆ ) -alkoxy group, a (C ₁ to C ₆ ) -hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂ ) _s - wherein R ^V and R ^VI are independently f alkyl group and R is a hydrogen atom, a (C ₁ to C ₆₎ alkyl group, a (C ₁ to C ₆₎ hydroxyalkyl group, or an aryl (C ₁ to C ₆₎ s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,
• Y is an oxygen atom, a sulfur atom or a group NR ^VII , where R ^VII is a water atom, an aryl group, a heteroaryl group, a (C ₁ to C6) alkyl group or an aryl (C ₁ to C ₆₎ alkyl group,
• • X ^- stands for a physiologically compatible anion.

At least one group R ¹⁰ or R ¹² according to formula (CH-3) necessarily stands for a (C ₁ to C ₆ ) -alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its α-carbon atom. Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group. Most preferably, R ¹⁰ and R ¹² are each independently hydrogen or a methyl group, wherein at least one group R ¹⁰ or R ^{12 is} a methyl group.

In In a preferred embodiment, Y is of the formula (CH-3) for an oxygen or a sulfur atom, more preferred for an oxygen atom.

The radical R ^{8 of} the formula (CH-3) is preferably selected from a (C ₁ to C ₆ ) -alkyl group (particularly preferably a methyl group), a (C ₂ to C ₆ ) -alkenyl group (in particular an allyl group), a (C ₂ to C ₆ ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.

R ^{11 of} the formula (CH-3) is preferably a hydrogen atom.

Particularly preferred in formula (CH-3) are the radicals R ⁹ , R ¹⁰ and R ^{12 is} a methyl group, the radical R ^{11 is} a hydrogen atom, Y is an oxygen or sulfur atom and the radical R ⁸ is selected from a ( C ₁ to C ₆ ) alkyl group (particularly preferably a methyl group), a (C ₂ to C ₆ ) alkenyl group (especially an allyl group), a (C ₂ to C ₆ ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or a optionally substituted benzyl group.

Preferably, the compounds according to formula (CH-3) are selected from one or more compounds of the group of salts with physiologically acceptable counterion X ^- , which is formed from salts of
1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidiniums,
1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-1,3-diphenyl-4-methyl-2-thioxo-pyrimidiniums,
1,2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and
1,2-dihydro-3,4-dimethyl-2-thioxo-chinazoliniums.

Very particularly preferred compounds according to formula (CH-3) are selected from one or more compounds of the group of salts with physiologically acceptable counterion X ^- , which is formed from salts of
1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1,3,4-trimethyl-2-oxo-pyrimidiniums,
1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums,
1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium and
1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidiniums.

X ^- is in the formulas (CH-1) and (CH-3) and in the above lists preferably for halide, benzenesulfonate, p-toluenesulfonate, (C ₁ to C ₄ ) alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogen sulfate, Tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. The anions chloride, bromide, iodide, hydrogensulfate or p-toluenesulfonate are particularly preferably used as X ^- .

links of the formula (CH-3) according to the invention are particularly preferably used.

The CH-acidic compounds of the oxo dye precursors of the component (Oxo2a) are most preferably selected from at least one compound of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-methyl-2-trifluoromethyl-3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5-fluoro-2-thenoyl) -acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl) -acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- (2-methyl-indol-3-oyl) -acetonitrile, 8-cyanoacetyl-7-methoxy-4-methylcoumarin, 2- (2-Isopropyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (2-phenyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (quinoxalin-2-yl) -acetonitrile, 2- (cumarone-2-yl) -acetonitrile, 6,7-dichloro-5- (cyanoacetyl) -2,3-dihydro-1-benzofuran-2-carboxylic acid tert-butyl ester, 2- (6-Hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile, 2- (1-phenyl-1,4-dihydrothiochromeno [4,3-c] pyrazol-3-oyl) - acetonitrile, 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H-indolium methanesulfonate, 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, 3-ethyl-2-methylbenzoxazolium iodide, 3-ethyl-2-methyl-benzothiazolium iodide, 1-ethyl-4-methyl-quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3-trimethylquinoxalinium iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium-p-toluenesulfonate, 1-ethyl-2-methyl-quinolinium-p-toluenesulfonate, 1,2,3-trimethylquinoxaluminum p-toluenesulfonate, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium chloride, 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium hydrogensulphate, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium hydrogensulphate, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogensulphate, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium hydrogensulphate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium hydrogensulphate, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium hydrogensulphate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxo-pyrimidinium hydrogensulphate, 1,2-dihydro-1,3,4-trimethyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-thioxo-pyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium hydrogensulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium chloride and 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium hydrogen sulfate.

Of Furthermore, as component (Oxo2b) at least one oxidation dye precursor with at least one primary or secondary Amino group and / or at least one hydroxy group can be used. Preferred suitable representatives can be found under the execution the oxidation dye precursors. However, it is preferred according to the invention if the compounds of the component (Oxo2) only under CH-acidic Connections are selected.

The above-mentioned compounds of the component (Oxo1) and of the component (Oxo2), if they are used, respectively preferably in an amount of 0.03 to 65 mmol, in particular of 1 to 40 mmol, based on 100 g of the total agent used.

The dyestuff precursors of naturally-analogous dyes are preferably indoles and indolines which have at least two groups selected from hydroxy and / or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. B. in the form of a Etherification or esterification of the hydroxy group or alkylation of the amino group. In a further embodiment, the colorants contain at least one idol and / or indoline derivative. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (RN1),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,

and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially preferred derivatives of indoline are the 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid.

Especially noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and in particular the 5,6-dihydroxyindoline.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,
• – sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (RN2),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,
• - As well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Especially preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid.

Within of this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and especially the 5,6-dihydroxyindole.

One second subject of the present invention is a method for lightening keratin fibers, in particular human hair, characterized in that a means of the first subject of the invention Applied to the keratin fibers, 5 to 60 minutes leave the fiber and then rinsed out again or washed out with a shampoo.

Especially the temperature during the exposure time is from 5 to 60 minutes between 10 ° C and 40 ° C, in particular between 20 ° C and 38 ° C.

In the context of such a method, it may be preferable to characterize the method in that
if desired, a pretreatment agent M1 is applied to the fiber, then a means M2 is applied to the fiber, optionally adding a further agent M3 to the means M2 before use,
this agent M2 is rinsed off from the fiber after a time of 5-60 minutes and after the treatment optionally an aftertreatment agent M4 is applied to the fiber and rinsed off after a contact time of a few minutes,
wherein at least one of the means M1, M2 or M3 or the mixture of the means M2 and M3 is an inventive means of the first subject of the invention.

The Accordingly, agents according to the invention can be used as one-component agent (coloring and / or lightening agent M2), formulated as a two-component agent (M2 + M3) and correspondingly be applied. Separation into multicomponent systems offers especially where there are incompatibilities of the ingredients to be expected or feared; the one to be used Means is in such systems by the consumer directly before the Application made by mixing the component.

One Dyeing and / or lightening process in which the compounds the general structure (I) and the hydrogen peroxide first are present separately, is preferred. Another item The present invention is therefore a method of dyeing and lightening of human hair, in which a composition aqueous-based, containing hydrogen peroxide, with a composition containing at least one compound of the general structure (I) (vide supra) to a means of the first Invention article mixed, and this applied to the hair becomes.

A further embodiment of the invention Process for lightening and optionally coloring human hair, in which a composition on aqueous Base containing hydrogen peroxide with another agent containing preferably at least one alkalinity donor and / or substantive hair dye and / or at least one oxidation dye precursor, and an agent containing the compounds of the general structure (I) (vide supra) and optionally additionally the formula (II) (vide supra) mixed to a homogeneous composition, and this is applied to the hair.

One third object of the invention is the use of the means of first subject of the invention for lightening keratinhaltigen Fibers, in particular human hair.

In terms of further preferred embodiments of the invention Process or the use according to the invention applies mutatis mutandis to the invention Means said.

Examples

1.0 Synthesis Example

1.1. Synthesis of 3,4-dihydroisoquinoline

100.0 g (0.75 mol) of 1,2,3,4-tetrahydroisoquinoline were initially charged and, with cooling, 417 ml of a 12.5% strength aqueous sodium hypochlorite solution were added. The temperature was kept at 13 ° C. After completion of the addition, the reaction mixture was stirred for two hours at room temperature. Subsequently, 300.0 g of a 50% aqueous sodium hydroxide solution was added and stirred at 80 ° C for a further 8 hours. After cooling the reaction mixture, another 250 ml of water were added. The separating organic phase was separated from the aqueous phase and the crude product distilled (40 mbar / 115 ° C). The product precipitated as a clear, yellow liquid which was used in the second stage.
Yield: 69.0 g (70.1%)

1.2. Synthesis of N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate (A1)

69.0 g (0.53 mol) of the product from Step 1 were added to a solution of 98.6 g (0.53 mol) of p-toluenesulfonic acid methyl ester in 200 ml of toluene. The reaction which took place was exothermic and the temperature of the reaction mixture rose to 90.degree. After the reaction had ceased, the mixture was stirred for 3 hours at 60 ° C, whereby a light beige colored solid began to precipitate. This waxy solid was filtered off and dried in vacuo.
Yield: 148.1 g (88.7%)
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 2.25 (s, 3H); 3.18 (t, 2H); 3.72 (s, 3H); 4.01 (t, 3H); 7.09 (d, 2H); 7.20 (m, 2H); 7.52 (d, 2H); 7.58 (m, 1H); 7.79 (m, 1H); 9.23 (s, 1H)
¹³ C-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 24.2; 26.8; 50.0; 52.7; 126.0; 127.3; 130.6; 130.8; 132.3; 136.0; 139.1; 140.1; 140.7; 148.1; 169.1

2. Examples of bleaching

2.1. Bleaching with hydrogen peroxide and hydrogen peroxide / imidazole

2.1.1. Preparation of a Blondiercreme

Hydrenol^® D

C_16-18-Fettalkohol (INCI-Bezeichnung: Cetearyl alcohol) (Cognis)

Lorol^® tech.

C_12-18-Fettalkohol (INCI-Bezeichnung: Coconut alcohol) (Cognis)

Texapon^® NSO

Laurylethersulfat, Natriumsalz (ca. 27,5% Aktivsubstanz; INCI-Bezeichnung: Sodium Laureth Sulfate) (Cognis)

Stabylen^® 30

Acrylsäure/Vinylester-Copolymer (INCI-Bezeichnung: ACRYLATES/VINYL ISODECANOATE CROSSPOLYMER) (Coast Chemical)

Cetiol^® OE

Dioctylether (INCI-Bezeichnung: Dicaprylylether) (Cognis)

Turpinal^® SL

1-Hydroxyethan-1,1-diphosphonsäure (ca. 58–61% Aktivsubstanzgehalt; INCI-Bezeichnung: Etidronic Acid, Aqua (Water)) (Solutia)

Natriumsilikat 40/42

Natronwasserglas

Gluadin^® W40

Weizenproteinhydrolysat (mind. 40% Festkörper; INCI-Bezeichnung: Aqua (Water), Hydrolyzed Wheat Protein, Sodium Benzoate, Phenoxyethanol, Methylparaben, Propylparaben) (Cognis)

From the ingredients listed, bleaching creams were prepared as follows: raw material Wt .-% V1 V2 E1 E2 Hydrenol D 12.0 12.0 12.0 12.0 Lorol techn. 2.4 2.4 2.4 2.4 Texapon NSO 26.5 26.5 26.5 26.5 Stabylene 30 0.1 0.1 0.1 0.1 Cetiol OE 2.4 2.4 2.4 2.4 Turpinal SL 0.2 0.2 0.2 0.2 Sodium silicate 40/42 0.5 0.5 0.5 0.5 Gluadin W 40 0.35 0.35 0.35 0.35 ammonium sulfate 1.0 1.0 1.0 1.0 Ammonia 25% 7.6 7.6 7.6 7.6 imidazole - 2.0 - 2.0 N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate (A1) - - 2.0 2.0 water ad 100 ad 100 ad 100 ad 100

Hydrenol ^® D

C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

Lorol® ^® tech.

C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis)

Texapon.RTM ^® NSO

Lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)

Stabylen ^® 30

Acrylic acid / vinyl ester copolymer (INCI name: ACRYLATES / VINYL ISODECANOATE CROSSPOLYMER) (Coast Chemical)

Cetiol ^® OE

Dioctyl ether (INCI name: dicaprylyl ether) (Cognis)

Turpinal® ^® SL

1-hydroxyethane-1,1-diphosphonic acid (about 58-61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

Sodium silicate 40/42

Natronwasserglas

Gluadin® ^® W40

Wheat protein hydrolyzate (at least 40% solids, INCI name: Aqua (Water), Hydrolyzed Wheat Protein, Sodium Benzoate, Phenoxyethanol, Methylparaben, Propylparaben) (Cognis)

Stabylen ^® 30 and Cetiol ^® OE were pre-dispersed at room temperature. Subsequently, the other components were incorporated with stirring in order, then made up to 100% with water.

at the formulations V1 and V2 are not according to the invention Comparative formulations without bleach activator, the formulations E1 and E2 are examples according to the invention with bleach activator (E1) or with bleach activator and imidazole (E2).

2.1.2. Mixing with the developer dispersion

Turpinal^® SL

1-Hydroxyethan-1,1-diphosphonsäure (ca. 58–61% Aktivsubstanzgehalt; INCI-Bezeichnung: Etidronic Acid, Aqua (Water)) (Solutia)

Texapon^® NSO

Laurylethersulfat, Natriumsalz (ca. 27,5% Aktivsubstanz; INCI-Bezeichnung: Sodium Laureth Sulfate) (Cognis)

Aculyn^® 33

Acrylpolymer (ca. 28% Festkörper in Wasser; INCI-Bezeichnung: Acrylates Copolymer)

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. raw material Wt .-% Ammonia 25% 0.62 dipicolinic 0.10 disodiumpyrophosphate 0.03 Turpinal SL 1.50 Texapon NSO 2.00 Dow Corning DB 110 A (non-ionic silicone emulsion) 0.07 Aculyn 33A (acrylic polymer) 12,00 Hydrogen peroxide 50% 22.40 water ad 100

Turpinal® ^® SL

1-hydroxyethane-1,1-diphosphonic acid (about 58-61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

Texapon.RTM ^® NSO

Lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)

Aculyn ^® 33

Acrylic polymer (about 28% solids in water, INCI name: acrylates copolymer)

For the Blondierprozeß was dark blond on strands, light brown and dark brown hair (codes: Kerling 7/0, Fischbach & Miller 6923 and Kerling 2/0) of about 0.7 g weight 4 times the amount of finished Application mixture applied. After the strands for Bleached for 30 minutes at 32 ° C, they were treated with a commercial shampoo and with a hair dryer dried.

2.1.3. Evaluation of the whitening performance

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 dL value was used according to the following formula: dL = L later - L previously L _afterwards = brightness of the strand after bleaching
L = lightness _before the strand before bleaching

For each recipe and each hair type was twelve times, from the individual values, the average value was formed. The larger the dL value, the better the brightening performance of the respective recipe. Whitening with dark blond strands (Kerling 7/0) No. dL (recipe V1) dL (recipe V2) dL (recipe E1) dL (recipe E2) 1 12.08 11.98 12.33 14.04 2 11,70 10.54 11.44 14.79 3 11.53 10.22 15.57 14.24 4 10.19 11.15 12.66 13.11 5 10.86 9.79 13.52 14.22 6 12.04 13.83 13,90 15.51 7 11.21 10.97 12.38 14.35 8th 10.97 12,11 15.89 13.18 9 7.63 11.65 13.97 16.20 10 11.19 13.24 14.38 11.21 11 9.56 10.21 12.40 13.03 12 10.45 11.2 12.24 13.25 ∅ 10.8 11.4 13.4 13.9 Whitening performance with light brown strands (Fischbach & Miller 6923) No. dL (recipe V1) dL (recipe V2) dL (recipe E1) dL (recipe E2) 1 14.76 11.48 14,74 14.91 2 11,60 11.48 12.42 16.76 3 12.36 10.66 13.23 15.46 4 13.54 11.02 17.66 14.04 5 11.14 11.2 15.16 14.95 6 11.10 11.56 13.92 15,60 7 13,45 10.83 13.42 15.53 8th 10.77 12.1 13.50 14.46 9 11.96 11.04 13.54 14.46 10 12.77 11.57 11.89 15.16 11 10.24 10.88 14.06 14.12 12 10.93 12.43 11.64 13.67 ∅ 12.1 11.4 13.8 14.9 Whitening power with dark brown strands (Kerling 2/0) No. dL (recipe V1) dL (recipe V2) dL (recipe E1) dL (recipe E2) 1 5.93 4.72 6.61 8.91 2 4.40 5.10 8.66 7.86 3 4.10 6.26 8.75 9.77 4 4.88 4.29 9.44 7.96 5 4.35 5.8 7.83 7.85 6 6.41 6.35 7.47 8.45 7 6.38 7.03 8.02 8.89 8th 5.20 7.56 7.90 7.51 9 6.09 6.03 8.49 8.40 10 4.66 6.2 7.48 9.12 11 6.31 5.58 6.97 9.63 12 4.80 6.54 7.32 8.51 ∅ 5.3 6.0 7.9 8.6

2. Blondings with hydrogen peroxide and persulfates

2.1. Preparation of a Blondiercreme

Hydrenol^® D

C_16-18-Fettalkohol (INCI-Bezeichnung: Cetearyl alcohol) (Cognis)

Eumulgin^® B2

Cetylstearylalkohol mit ca. 20 EO-Einheiten (INCI-Bezeichnung: Ceteareth-20) (Cognis)

Lorol^® tech.

C_12-18-Fettalkohol (INCI-Bezeichnung: Coconut alcohol) (Cognis)

Texapon^® NSO

Laurylethersulfat, Natriumsalz (ca. 27,5% Aktivsubstanz; INCI-Bezeichnung: Sodium Laureth Sulfate) (Cognis)

Dehyton^® K

N,N-Dimethyl-N-(C8-18-kokosamidopropyl)ammoniumaceto-betain (ca. 30% Aktivsubstanz; INCI-Bezeichnung: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

Turpinal^® SL

1-Hydroxyethan-1,1-diphosphonsäure (ca. 58–61% Aktivsubstanzgehalt; INCI-Bezeichnung: Etidronic Acid, Aqua (Water)) (Solutia)

Natriumsilikat 40/42

Natronwasserglas

From the ingredients listed, bleaching creams were prepared as follows: raw material Wt .-% V3 E3 Hydrenol D 8.00 8.00 Eumulgin B2 0.45 0.45 Lorol®. techn. 3.00 3.00 Texapon NSO 16.00 16.00 Dehyton K. 10.00 10.00 Monoethanolamine 8.00 8.00 L-arginine 1.00 1.00 Turpinal SL 0.20 0.20 Sodium silicate 40/42 0.50 0.50 N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate (A1) - 2.00 water ad 100 ad 100

Hydrenol ^® D

C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

Eumulgin ^® B2

Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

Lorol® ^® tech.

C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis)

Texapon.RTM ^® NSO

Lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)

Dehyton ^® K

N, N-dimethyl-N- (C8-18-cocoamidopropyl) ammonium aceto-betaine (about 30% active ingredient; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

Turpinal® ^® SL

1-hydroxyethane-1,1-diphosphonic acid (about 58-61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

Sodium silicate 40/42

Natronwasserglas

First Hydrenol ^® D ^® Eumulgin B2, Lorol® were. ^® techn., Texapon ^® NSO and Dehyton ^® K are melted together at 80 ° C. This melt was mixed with a portion of the amount of water and the Mixture vigorously stirred. With continued stirring, then the indicated amounts of the remaining ingredients were added and allowed to cool the recipe to room temperature. Formulation V3 is the comparative formulation not according to the invention without 3,4-dihydroisoquinolinium compounds; Formulation E3 is the example according to the invention with 3,4-dihydroisoquinolinium derivative as the hydrogen peroxide activator.

2.2.2. Mixing with the developer dispersion

Turpinal^® SL

1-Hydroxyethan-1,1-diphosphonsäure (ca. 58–61% Aktivsubstanzgehalt; INCI-Bezeichnung: Etidronic Acid, Aqua (Water)) (Solutia)

Texapon^® NSO

Laurylethersulfat, Natriumsalz (ca. 27,5% Aktivsubstanz; INCI-Bezeichnung: Sodium Laureth Sulfate) (Cognis)

Acrysol^® 33

Acrylpolymer (ca. 28% Festkörper in Wasser; INCI-Bezeichnung: Acrylates Copolymer)

The Blondiercremes were mixed in each case in the ratio 1: 1 with a developer dispersion composed as follows. raw material Wt .-% Sodium hydroxide 45% 0.73 dipicolinic 0.10 disodiumpyrophosphate 0.03 Turpinal SL 1.50 Texapon NSO 2.00 Dow Corning DB 110 A (non-ionic silicone emulsion) 0.07 Aculyn 33A (acrylic polymer) 15.00 Hydrogen peroxide 50% 22.40 water ad 100

Turpinal® ^® SL

1-hydroxyethane-1,1-diphosphonic acid (about 58-61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

Texapon.RTM ^® NSO

Lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)

Acrysol ^® 33

Acrylic polymer (about 28% solids in water, INCI name: acrylates copolymer)

2.2.3. Addition of persulfate

Subsequently were 100 g of the under 2.2. obtained mixture still with 8.33 g Potassium peroxydisulfate mixed. The pH of this finished application mixture was between 9 and 10.2.

For the Blondierprozeß was dark blond on strands, light brown and dark brown hair (codes: Kerling 7/0, Fischbach & Miller 6923 and Kerling 2/0) of about 0.7 g weight 4 times the amount of finished Application mixture applied. After the strands for Bleached for 30 minutes at 32 ° C, they were treated with a commercial shampoo and with a hair dryer dried.

2.2.4. Evaluation of the whitening performance

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 dL value was used according to the following formula: d L = L later - L previously L _afterwards = brightness of the strand after bleaching
L _before = brightness of the strand before bleaching

For each recipe and each hair type was a double determination, from the individual values in each case the mean value was formed. The larger the dL value, the better the brightening performance of the respective recipe. Whitening with dark blond strands (Kerling 7/0) No. dL (recipe V3) dL (recipe E3) 1 19.17 22.34 2 19,00 20.66 ∅ 19.09 21,50 Whitening performance with light brown strands (Fischbach & Miller 6923) No. dL (recipe V3) dL (recipe E3) 1 19,88 25.64 2 20.37 23.97 ∅ 20.13 24.81 Whitening power with dark brown strands (Kerling 2/0) No. dL (recipe V3) dL (recipe E3) 1 13,09 15.78 2 12.45 14,92 ∅ 12.77 15.35

3. Interpretation of the results

A Estimation of the bleaching effects of the different formulations can be made by comparing the dL values. It is clearly evident that with a combination from hydrogen peroxide and the invention cationic isoquinolinium derivative significantly larger dL values could be achieved than by using the same Amount of hydrogen peroxide alone was possible. By the Use of imidazole could add the bleaching effect be further improved.

Also showed bleaching tests with a combination of hydrogen peroxide, Peroxidisulfatsalzen and the inventive cationic isoquinolinium derivative gives better brightening performance, when using a comparable Blondierrezeptur without the Activator could be achieved. By the use of the invention Bleach activators in bleaching formulations could therefore face the existing state of the art a significant improvement be achieved.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• US 2005159327 A1 [0008]
• - WO 2000061713 A1 [0008]
• - WO 9846718 A1 [0008]
• - EP 998908 A2 [0207]

Cited non-patent literature

• - Kh. Schrader, Basics and Formulations of Cosmetics, 2nd edition, 1989 [0002]
• - Dr. Alfred Hüthig Verlag, Heidelberg, or W. Umbach (ed.), Kosmetik, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York [0002]
• - Hugo Janistyn, Handbook of Cosmetics and Fragrances, III. Volume: The personal care products, 2nd edition, Dr. med. Alfred Hüthig Verlag Heidelberg, 1973, pages 68-78 [0061]
• - Hugo Janistyn, Paperback of modern perfumery and cosmetics, 4th edition, Scientific Verlagsgesellschaft mbH Stuttgart, 1974, pages 466-474 [0061]
• - Kh. Schrader, Basics and Formulations of Cosmetics, 2nd Edition, Hüthig Buch Verlag, Heidelberg, 1989 [0078]

Claims (16)

A composition for lightening keratinic fibers, characterized in that it contains in a cosmetic carrier hydrogen peroxide and at least one cationic 3,4-dihydroisoquinolinium derivative of the following general structure (I),

wherein the 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-C ₁ -C ₆ -alkyl group, an aryl-C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -dialkylamino-C ₂ -C ₆ -alkyl group, a heteroaryl-C ₁ -C ₆ -alkyl group, a 3-Oxobutylgruppe, a 2-oxopropyl group, an aryl group or a heteroaryl group, the radicals R2, R3 and R4 are independently a hydrogen atom, a hydroxy group, an amino group, a di (C ₁ -C ₆ ) alkylamino group, a C ₁ -C ₆ alkoxy group, halogen, a nitro group, a carboxy group, a nitrile group, an optionally substituted aryl group, a C ₂ -C ₆ alkenyl group, an optionally substituted heteroaryl group, or R 2 and R 3 may together form another fused carbocyclic or heterocyclic ring, which may be saturated or unsaturated and optionally substituted by up to three S Substituents may be substituted, the anion X ^{- is} a physiologically acceptable anion. Composition according to claim 1, characterized in that the radical R _{1 of} the general structure (I) is a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₂ -C ₆ -hydroxyalkyl group. Agent according to claims 1 and 2, characterized in that the radicals R 2, R 3 and R 4 are of the general structure (I) represent a hydrogen atom. Composition according to one of claims 1 to 3, characterized in that the physiologically acceptable anion X ^{- represents} a halide ion (in particular chloride or bromide), hydrogen sulfate, ½ sulfate, p-toluenesulfonate, Benzolfulfonat or acetate. Agent according to one of claims 1 to 4, characterized in that at least one cationic compound of the general structure (I) selected from compounds the group formed from N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate, N-methyl-3,4-dihydroisochinoliniumbenzolsulfonat N-methyl-3,4-dihydroisochinoliniumhydrogensulfat N-allyl-3,4-dihydroisoquinolinium p-toluene sulfonate N-allyl-3,4-dihydroisochinoliniumbenzolsulfonat N-allyl-3,4-dihydroisochinoliniumbromid N-allyl-3,4-dihydroisochinoliniumacetat 3,4-dihydro-2- (3-hydroxypropyl) isoquinolinium p-toluene sulfonate 3,4-dihydro-2- (3-hydroxypropyl) isoquinolinium benzenesulfonate 3,4-dihydro-2- (3-hydroxypropyl) isochinoliniumbromid 3,4-dihydro-2- (3-hydroxypropyl) isochinoliniumacetat 3,4-Dihydro-2- (2-hydroxyethyl) isoquinolinium p-toluene sulfonate 3,4-Dihydro-2- (2-hydroxyethyl) isoquinolinium benzenesulfonate 3,4-Dihydro-2- (2-hydroxyethyl) isochinoliniumbromid or 3,4-Dihydro-2- (2-hydroxyethyl) isochinoliniumacetat contain is. Agent according to one of claims 1 to 5, characterized in that the cationic 3,4-dihydroisocholinium derivatives the general structure (I) in an amount of 0.03 to 65.00 mmol, in particular 1.00 to 40.00 mmol, in each case based on 100 g of ready to use agent, are included. Composition according to one of claims 1 to 6, characterized in that it - based on its weight - 0.5 to 12 wt .-%, preferably 2 to 10 wt .-% and particularly preferably 3 to 6 wt .-% hydrogen peroxide ( calculated as 100% H ₂ O ₂ ). Agent according to one of claims 1 to 7, characterized in that the pH of the ready for use Application mixture between 7 and 11, especially between 8 and 10.5, is. Agent according to one of claims 1 to 8, characterized in that additionally at least one imidazole compound according to formula (II) and / or its physiologically acceptable salt is contained,

in which R5 represents a hydrogen atom, an optionally substituted aryl group or a (C ₁ -C ₆ ) -alkyl group, R _{6 represents} a hydrogen atom, a carboxaldehyde group, a (C ₁ -C ₆ ) -alkyl group or a nitro group, R 7 represents a hydrogen atom, a carboxy (C ₁ -C ₆ ) alkyl group, an amino (C ₁ -C ₆ ) alkyl group, a carboxyl group, a carboxaldehyde group, a (C ₁ -C ₆ ) alkyl group, a nitro group, a 2-amino-3-hydroxypropyl group or a group -CH ₂ -CH (NH ₂ ) -COOH and R 8 represents a hydrogen atom, a carboxaldehyde group or a carboxyl group. Agent according to claim 9, characterized that the additional imidazole compound according to formula (II) is selected from at least one compound the group formed from histamine, D-histidine, L-histidine, DL-histidine, D-histidinol, L-histidinol, DL-histidinol, imidazole, Imidazole-4-acetic acid, imidazole-4-carboxylic acid, Imidazole-4,5-dicarboxylic acid, imidazole-2-carboxaldehyde, imidazole-4-carboxaldehyde, Imidazole-5-carboxaldehyde, 2-nitroimidazole, 4-nitroimidazole, 4-methylimidazole-5-carboxaldehyde, N-methylimidazole-2-carboxaldehyde, 4-methylimidazole, 2-methylimidazole, N-methylimidazole, N- (4-aminophenyl) -imidazole and the physiological acceptable salts of the aforementioned compounds. Agent according to one of claims 9 or 10, characterized in that the imidazole compound according to formula (II) and / or their physiologically acceptable salt in an amount of 0.03 to 65.00 mmol, especially 1.00 to 40.00 mmol, based on 100 g of the ready-to-use agent, is present. Agent according to one of claims 1 to 11, characterized in that additionally at least one inorganic Persulfate salt is included. Agent according to claim 12, characterized in that that the inorganic persulfate salts contained in an amount from 0.1 to 25 g, in particular in an amount of 1 to 15 g, based to 100 g of the ready-to-use agent. Composition according to one of claims 12 or 13, characterized in that the inorganic Persulfatsalze be selected from at least one compound from the Group consisting of ammonium peroxydisulfate, potassium peroxodisulfate and sodium peroxydisulfate. Method of lightening keratinic fibers, characterized in that an agent according to any one of claims 1 to 14 applied to the keratin fibers, 5 to 60 minutes left on the fiber and then rinsed out again or washed out with a shampoo. Cosmetic use of an agent after one of claims 1 to 14 for lightening keratinhalten Fibers, in particular human hair.