DE102008061857A1 - Colorants based on CH-acidic compounds - Google Patents

Abstract

The present application relates to agents for coloring keratinic fibers, in particular human hair, containing at least one CH-acidic compound and at least one reactive carbonyl compound, wherein these further comprise at least one solubilizer which is selected from (a) the compounds containing at least one C4 C22 alkyl chain carrying at least one hydroxy group etherified with ethylene oxide and / or propylene oxide units, wherein the total number of ethylene oxide and propylene oxide units in the molecule is greater than 20, and (b) the cyclic organic carbonates ,

Description

The The present invention relates to agents for coloring keratinic Fibers based on CH-acidic compounds and reactive carbonyl compounds, which contain a special solubilizer, different Kits for finishing this staining system and staining procedures using this staining system.

To the Dyeing hair is the expert in various dyeing systems known, which vary in the durability of the coloring the hair and the degree of damage the hair has during of the hair dyeing process can vary greatly.

For permanent, intensive colorations with corresponding fastness properties so-called oxidation dyes 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 atmospheric oxygen with each other or under coupling with one or more coupler components the actual dyes. The oxidation colorants Although distinguished by excellent, long-lasting staining results out. For natural-looking dyeings but usually it has to be a mixture of a larger one Number of oxidation dye precursors are used; in many Traps will continue to be substantive dyes for shading used.

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-di-chloro-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 Direktzieher 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.

A offers further possibility for color change the use of colorants, which are so-called oxo dye precursors contain. A first class of oxo dye precursors are compounds with at least one reactive carbonyl group. This first class will referred to as component (Oxo1). A second class of oxo dye precursors form CH-acidic compounds and compounds with primary or secondary amino group or hydroxy group, which in turn are selected from compounds of the group that formed is made from primary or secondary aromatic Amines, nitrogen-containing heterocyclic compounds and aromatic Hydroxy compounds. This second class is called Component (Oxo2) designated. The aforementioned components (Oxo1) and (Oxo2) are generally themselves no dyes, and are therefore suitable for each taken alone, not for coloring keratin-containing Fibers. In combination, they form in a non-oxidative process of the so-called oxo dyeing dyes. The resulting Dyeings have partial color fastness on the keratin-containing Fiber comparable to those of oxidation staining are.

The nuance spectrum achievable with gentle oxo staining is very broad and the resulting dye often has acceptable brilliance and color depth. However, it is also possible to use corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidizing agent in compounds of the component (oxo2). Thus, the method of oxo staining can be readily combined with the oxidative staining system.

There in the oxo dyeing without the use of oxidizing agents such as hydrogen peroxide bright colors with good Durability on the hair can be achieved, this is Dyeing method with little damage to the hair connected and against this background for the consumer of special interest.

From the packaging and packaging of the dye over The sale to the consumer application can be time periods from several months to even a few years. Uses the Consumers a hair dye, which these long storage periods but he still wants a brilliant one and intense color result. The provision of the coloring agent Stable storage is therefore one of the key challenges in the packaging.

In In the past, therefore, the CH-acidic compounds were proposed and formulate the reactive carbonyl compound in powder form and only immediately before use with a liquid preparation, containing the remaining ingredients, such as the alkalizing agent to mix. However, at one such a high solubility requirements to provide the Oxofarbstoffvorprodukte. An uneven Mixing of the components, for example by the consumer leads to spotty, uneven colorations, which often do not meet the customer requirements.

But also in the incorporation of Oxofarbstoffvorprodukte on the part of Manufacturer plays the sufficient solubility essential Role, because this is the only way to avoid the Oxofarbstoffevorprodukte settle later during storage. If Such settlements occur, the danger is great that this leads to an uneven distribution of the Oxofarbstoffvorprodukte in the application mixture and thus to uneven Dyeing leads.

task Therefore, in the context of oxo dyeing, it is the object of the present invention a system for coloring keratinic fibers, and in particular human hair, that's how it is is optimized that the components of the final application mix ensure a homogeneous distribution of Oxofarbstoffvorprodukte and thus even after long storage periods dyeings of high color intensity can be obtained.

Surprisingly could now be found that incorporating a special Solubilizer in the application preparation, for example by incorporation of the solubilizer in one or several of the separately manufactured subcomponents, the storage stability of the colorant is greatly increased in an unpredictable manner.

• (a) den Verbindungen, die mindestens eine C₄-C₂₂-Alkylkette aufweisen, die mindestens eine Hydroxygruppe trägt, die mit Ethylenoxid- und/oder Propylenoxid-Einheiten verethert ist, wobei die Gesamtzahl an Ethylenoxid- und Propylenoxid-Einheiten im Molekül größer als 20 ist, und
• (b) den cyclischen organischen Carbonaten.

A first subject of the present invention are therefore agents for coloring keratinic fibers, in particular human hair, containing at least one CH-acidic compound and at least one reactive carbonyl compound, wherein they further contain at least one solubilizer which is selected from

• (A) the compounds having at least one C ₄ -C ₂₂ alkyl chain which carries at least one hydroxyl group etherified with ethylene oxide and / or propylene oxide units, wherein the total number of ethylene oxide and propylene oxide units in the molecule larger than 20, and
• (b) the cyclic organic carbonates.

Under Keratin fibers are wool, furs, feathers and in particular to understand human hair. The invention Dyes can in principle but also for dyeing other natural fibers, such. As cotton, jute, sisal, linen or Silk, modified natural fibers, such. Regenerated cellulose, nitro, Alkyl or hydroxyalkyl or acetyl cellulose and synthetic Fibers, such as As polyamide, polyacrylonitrile, Polyurtehan and polyester fibers be used.

Particularly good storage stabilities could be found if the ready-to-use agents as solubilizers at least one compound having at least one C ₄ -C ₂₂ alkyl chain carrying at least one hydroxyl group which is etherified with ethylene oxide and / or propylene oxide units, wherein the Total number of ethylene oxide and propylene oxide units in the molecule is greater than 20, and contain at least one cyclic organic carbonate.

• (a1) den Anlagerungsprodukten von 21 bis 100 Ethylenoxid-Einheiten an gegebenenfalls gehärtete Mono-, Di- und Triglyceride von C_8-22-Fettsäuren,
• (a2) den Anlagerungsprodukten von 21 bis 60 Ethylenoxid-Einheiten an C_8-22-Fettalkohole,
• (a3) den Anlagerungsprodukten von 2 bis 50 Ethylenoxid-Einheiten und 2 bis 35 Propylenoxid-Einheiten an C₄-C₂₂-Alkanole.

Preferred solubilizers from the group of compounds which have at least one C ₄ -C ₂₂ -alkyl chain which carries at least one hydroxyl group which is etherified with ethylene oxide and / or propylene oxide units, wherein the total number of ethylene oxide and propylene oxide units in Molecule greater than 20 is selected from

• (a1) the addition products of 21 to 100 ethylene oxide units to optionally cured mono-, di- and triglycerides of C _8-22 fatty acids,
• (a2) the addition products of 21 to 60 ethylene oxide units of C _8-22 fatty alcohols,
• (a3) the addition products of 2 to 50 ethylene oxide units and 2 to 35 propylene oxide units of C ₄ -C ₂₂ alkanols.

From the group (a1) of the addition products of 21 to 100 ethylene oxide units of optionally cured mono-, di- and triglycerides of C _8-22 fatty acids, the compounds have from 25 to 90, especially from 30 to 80, especially with 35 to 60 ethylene oxide units proved to be particularly advantageous.

Farther Advantageous representatives of this group are selected from ethoxylated castor oil, olive oil ethoxylate, almond oil ethoxylate, Mink oil ethoxylate, polyoxyethylene glycol caprylic / capric acid glycerides, Polyoxyethylene glycerol monolaurate and polyoxyethylene glycol coconut fatty acid glycerides.

All Particularly preferred compounds of this class according to the invention are PEG-40 Hydrogenated Castor Oil, PEG-25 Hydrogenated Castor Oil, PEG-54 Hydrogenated Castor Oil and PEG-60 Hydrogenated Castor Oil. PEG-40 Hydrogenated Castor Oil is a completely according to the invention particularly preferred solubilizers of this group.

Out the group (a2) of the adducts of 21 to 60 ethylene oxide units have connections with 25 to 55, especially 26 to 50, completely especially 30 to 45 ethylene oxide units proved to be preferred.

advantageous In particular, it has had an impact on storage stability for Laureth-23, Ceteareth-30, Ceteareth-50, Steareth-30 and steareth-40.

From the group (a3) of the adducts of 2 to 50 ethylene oxide units and 2 to 35 propylene oxide units of C ₄ -C ₂₀ alkanols, compounds having 5 to 33 propylene oxide units and 16 to 35 ethylene oxide units have been found.

According to the invention, particularly advantageous C ₄ -C ₂₀ -alkanols are 1-butanol, 2-butanol, isobutanol and 1-pentanol, 2-pentanol, amyl alcohol and the C ₁₂ - to C ₂₀ -fatty alcohols, in particular lauryl alcohol, myristyl alcohol, cetyl alcohol, Stearyl alcohol and mixtures thereof proved.

Particularly according to the invention preferred representatives are selected from PPG-28-buteth-35, PPG-26-buteth-26, PPG-25-buteth-25, PPG-5-buteth-20, PPG-33-buteth-45, PPG-20-buteth-30, PPG-12-buteth-16, PPG-5-Ceteth-20, PPG-10-Ceteareth-20, PPG-1-Ceteth-20, PPG-2-Ceteth-20, PPG-4-Ceteth-20, PPG-5-ceteth-20, PPG-8-ceteth-20, PPG-25-laureth-25 and PPG-23-steareth-34.

Completely according to the invention particularly preferred representatives of this group are PPG-26-buteth-26, PPG-4-ceteth-20, PPG-8-ceteth-20 and PPG-5-ceteth-20. PPG-5-ceteth-20 and PPG-26-buteth-26 are very particularly preferred according to the invention.

The inventively preferred compounds (a) having at least one C ₄ -C ₂₂ alkyl chain carrying at least one hydroxyl group which is etherified with ethylene oxide and / or propylene oxide units, wherein the total number of ethylene oxide and propylene oxide units in Molecule greater than 20, can also be used in combination with each other or with other excipients.

Thus, for example, a mixture of a compound of group (a1) with a compound of formula (a2) has proven to be particularly advantageous. Such preferred combinations are, for example, PPG-28-buteth-35 + PEG-40 Hydrogenated Castor Oil, PPG-26-buteth-26 + PEG-40 Hydrogenated Castor Oil, PPG-25-buteth-25 + PEG-40 Hydrogenated Castor Oil, PPG-5-Buteth-20 + PEG-40 Hydrogenated Castor Oil, PPG-33-Buteth-45 + PEG-40 Hydrogenated Castor Oil, PPG-20-Buteth-30 + PEG-40 Hydrogenated Castor Oil, PPG-12-Buteth -16 + PEG-40 Hydrogenated Castor Oil, PPG-5-Ceteth-20 + PEG-40 Hydrogenated Castor Oil, PPG-10-Ceteareth-20 + PEG-40 Hydrogenated Castor Oil, PPG-1-Ceteth-20 + PEG- 40 hydroge nated Castor Oil, PPG-2-Ceteth-20 + PEG-40 Hydrogenated Castor Oil, PPG-4-Ceteth-20 + PEG-40 Hydrogenated Castor Oil, PPG-5-Ceteth-20 + PEG-40 Hydrogenated Castor Oil, PPG -8-Ceteth-20 + PEG-40 Hydrogenated Castor Oil, PPG-25-Laureth-25 + PEG-40 Hydrogenated Castor Oil, PPG-23-Steareth-34 + PEG-40 Hydrogenated Castor Oil, PPG-28-Buteth -35 + PEG-25 Hydrogenated Castor Oil, PPG-26-Buteth-26 + PEG-25 Hydrogenated Castor Oil, PPG-25-Buteth-25 + PEG-25 Hydrogenated Castor Oil, PPG-S-Buteth-20 + PEG- 25 Hydrogenated Castor Oil, PPG-33-Buteth-45 + PEG-25 Hydrogenated Castor Oil, PPG-20-Buteth-30 + PEG-25 Hydrogenated Castor Oil, PPG-12-Buteth-16 + PEG-25 Hydrogenated Castor Oil, PPG-S-Ceteth-20 + PEG-25 Hydrogenated Castor Oil, PPG-10-Ceteareth-20 + PEG-25 Hydrogenated Castor Oil, PPG-1-Ceteth-20 + PEG-25 Hydrogenated Castor Oil, PPG-2-Ceteth -20 + PEG-25 Hydrogenated Castor Oil, PPG-4-Ceteth-20 + PEG-25 Hydrogenated Castor Oil, PPG-S-Ceteth-20 + PEG-25 Hydrogenated Castor Oil, PPG-B-Ceteth-20 + PEG-25 Hydrogenated Castor Oil, PPG-25-Laureth-25 + PEG-25 Hydrogenated Castor Oil, PPG-23-Steareth-34 + PEG-25 Hydrogenated Castor Oil, PPG-28-Buteth-35, PPG-26 Buteth-26, PPG-25-Buteth-25, PPG-S-Buteth-20 + PEG-54 Hydrogenated Castor Oil, PPG-33-Buteth-45 + PEG-54 Hydrogenated Castor Oil, PPG-20-Buteth-30 + PEG-54 Hydrogenated Castor Oil, PPG-12-Buteth-16 + PEG-54 Hydrogenated Castor Oil, PPG-S-Ceteth-20 + PEG-54 Hydrogenated Castor Oil, PPG-10-Ceteareth-20 + PEG-54 Hydrogenated Castor Oil, PPG-1-Ceteth-20 + PEG-54 Hydrogenated Castor Oil, PPG-2-Ceteth-20 + PEG-54 Hydrogenated Castor Oil, PPG-4-Ceteth-20 + PEG-54 Hydrogenated Castor Oil, PPG S-Ceteth-20 + PEG-54 Hydrogenated Castor Oil, PPG-B-Ceteth-20 + PEG-54 Hydrogenated Castor Oil, PPG-25-Laureth-25 + PEG-54 Hydrogenated Castor Oil, PPG-23-Steareth-34 + PEG-54 Hydrogenated Castor Oil, PPG-28-Buteth-35 + PEG-60 Hydrogenated Castor Oil, PPG-26-Buteth-26 + PEG-60 Hydrogenated Castor Oil, PPG-25-Buteth-25 + PEG-60 Hydrogenated C Astor Oil, PPG-S-Buteth-20 + PEG-60 Hydrogenated Castor Oil, PPG-33-Buteth-45 + PEG-60 Hydrogenated Castor Oil, PPG-20-Buteth-30 + PEG-60 Hydrogenated Castor Oil, PPG 12-Buteth-16 + PEG-60 Hydrogenated Castor Oil, PPG-S-Ceteth-20 + PEG-60 Hydrogenated Castor Oil, PPG-10-Ceteareth-20 + PEG-60 Hydrogenated Castor Oil, PPG-1-Ceteth-20 + PEG-60 Hydrogenated Castor Oil, PPG-2-Ceteth-20 + PEG-60 Hydrogenated Castor Oil, PPG-4-Ceteth-20 + PEG-60 Hydrogenated Castor Oil, PPG-S-Ceteth-20 + PEG-60 Hydrogenated Castor Oil, PPG-B-Ceteth-20 + PEG-60 Hydrogenated Castor Oil, PPG-25-Laureth-25 + PEG-60 Hydrogenated Castor Oil and PPG-23-Steareth-34 + PEG-60 Hydrogenated Castor Oil.

The combination of PEG-40 hydrogenated castor oil with PPG-S-ceteth-20 and / or PPG-26-buteth-26 is particularly preferred according to the invention. Such a product is, for example, from the company Sensient Cosmetic Technologies under the trade name Solubilisant ^® LRI commercially available (INCI name PPG-26-Buteth-26, PEG-40 Hydrogenated Castor Oil).

Farther have mixtures of the compounds of group (a) with ethoxylated Polysorbates and / or ethoxylated alkylphenols as vorteihaft within the meaning of the present invention.

Polysorbates having a degree of ethoxylation of from 20 to 80 have proven to be advantageous. Such products are available with different degrees of ethoxylation, for example, under the trade name Tween ^® commercially commercially.

When Alkylphenols are especially nonylphenols and octylphenols as advantageous in terms of improving the storage stability and an improvement in the uniformity of resulting staining proved. As further advantageous it has been found that the alkylphenols 1 to 100, preferably 1 to 70, more preferably 1 to 20 ethylene oxide units.

A product comprising such a combination, for example, under the trade designation Solubilisant ^® Gamma 2428 Gattefosse commercially available (INCI name: PEG-40 Hydrogenated Castor Oil, Polysorbate-20, octoxynol-11).

worin die Reste R¹, R², R³ und R⁴ unabhängig voneinander für ein Wasserstoffatom oder organische Reste, insbesondere Alkyl-, Alkenyl- oder Alkylaryl, stehen, die zusätzlich mit weiteren Gruppen, insbesondere Hydroxygruppen, substituiert sein können.As cyclic organic carbonate (b) according to the invention preferably at least one cyclic carbonic acid ester is suitable. These cyclic esters of carbonic acid are derived from 1,3-dioxolan-2-one and can be described by the following basic structure of the formula (I-1):

wherein the radicals R ¹ , R ² , R ³ and R ⁴ independently of one another are a hydrogen atom or organic radicals, in particular alkyl, alkenyl or alkylaryl, which may additionally be substituted by further groups, in particular hydroxyl groups.

In the main body, the 1,3-dioxolan-2-one, the radicals R ¹ , R ² , R ³ and R ^{4 of} the formula (I-1) are each a hydrogen atom. Furthermore, preferably suitable cyclic carbonic esters relate to derivatives of this basic body, where at least one of the radicals R ¹ , R ² , R ³ and R ^{4 of} the formula (I-1) is different from a hydrogen atom. There are no limits to the structural diversity, so that mono-, di-, tri- and tetra-substituted 1,3-dioxolan-2-ones of the formula (I-1) are suitable for use in the context of the present invention.

in der R¹ für einen substituierten oder unsubstituierten Alkyl-, Alkenyl- oder Alkylarylrest steht.Particularly preferred are in addition to the unsubstituted 1,3-dioxolan-2-one itself, in particular the monosubstituted in the 4-position derivatives of the following formula (I-2)

in which R ^{1 is} a substituted or unsubstituted alkyl, alkenyl or alkylaryl radical.

Preferred radicals R ¹ according to formula (I-2) are methyl, ethyl, n-propyl, iso-propyl and hydroxymethyl, 1-hydroxyethyl and 2-hydroxyethyl radicals.

Particularly preferred agents according to the invention are therefore characterized in that they contain as 1,3-dioxolan-2-one derivative at least one compound of the above formula (I-2) in which R ^{1 is} a substituted or unsubstituted alkyl, alkenyl or alkylaryl radical, wherein in further preferred agents of the invention the radical R ¹ in formula (I-2) is selected from methyl, ethyl, n-propyl, isopropyl and hydroxymethyl, 1-hydroxyethyl and 2- hydroxyethyl radicals.

Particularly preferred 1,3-dioxolan-2-ones of the formula (I-1) are selected from the group consisting of ethylene carbonate (R ¹ , R ² , R ³ and R ⁴ = H), propylene carbonate (R ¹ = CH ₃ and R ² , R ³ and R ⁴ = H) and glycerol carbonate (R ¹ = CH ₂ OH and R ² , R ³ and R ⁴ = H). Very particular preference is given to propylene carbonate.

Completely according to the invention Particularly preferred is the use of at least one solubilizer of Group (a) and at least one solubilizer of the group (B).

Farther it is inventively preferred if the ready for use Means at least two solubilizers of the group (a) and at least one solubilizer of group (b). It is particularly preferred according to the invention if the agent is a solubilizer of the group (a1), a Solubilizer group (a3) and a solubilizer the group (b) contains.

• – PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Propylencarbonat,
• – PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Propylencarbonat,
• – PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Glycerincarbonat,
• – PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Glycerincarbonat,
• – PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Ethylencarbonat sowie
• – PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Ethylencarbonat.

Particularly preferred combinations are in particular

• PEG-40 Hydrogenated Castor Oil + PPG-S-ceteth-20 + propylene carbonate,
• PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + propylene carbonate,
• PEG-40 Hydrogenated Castor Oil + PPG-S-ceteth-20 + glycerin carbonate,
• PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Glycerol Carbonate,
• - PEG-40 Hydrogenated Castor Oil + PPG-S-ceteth-20 + ethylene carbonate as well
• PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + ethylene carbonate.

The Combinations PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Propylene carbonate and PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 Glycerol carbonate are very particular according to the invention prefers.

• – PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Propylencarbonat + Polysorbate-20,
• – PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Propylencarbonat + Polysorbate-20,
• – PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Glycerincarbonat + Polysorbate-20,
• – PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Glycerincarbonat + Polysorbate-20,
• – PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Ethylencarbonat + Polysorbate-20,
• – PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Ethylencarbonat + Polysorbate-20,
• – PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Propylencarbonat + Polysorbate-40,
• – PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Propylencarbonat + Polysorbate-40,
• – PEG-40 Hydrogenated Castor Oil + PPG-5-Ceteth-20 + Glycerincarbonat + Polysorbate-40,
• – PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Glycerincarbonat + Polysorbate-40,
• – PEG-40 Hydrogenated Castor Oil + PPG-5-Ceteth-20 + Ethylencarbonat + Polysorbate-40 sowie
• – PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Ethylencarbonat + Polysorbate-40.

It is further preferred if, in addition to these mixtures, an ethoxylated derivative of the polysorbate is present, for example polysorbate-20 or polysorbate-40:

• PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Propylene Carbonate + Polysorbate-20
• PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Propylene carbonate + Polysorbate-20,
• - PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Glycerol Carbonate + Polysorbate-20,
• - PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Glycerol Carbonate + Polysorbate-20,
• PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Ethylene Carbonate + Polysorbate-20
• PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Ethylene Carbonate + Polysorbate-20
• PEG-40 Hydrogenated Castor Oil + PPG-S-Ceteth-20 + Propylene Carbonate + Polysorbate-40,
• - PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Propylene Carbonate + Polysorbate-40,
• - PEG-40 Hydrogenated Castor Oil + PPG-5-Ceteth-20 + Glycerol Carbonate + Polysorbate-40,
• - PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Glycerol Carbonate + Polysorbate-40,
• - PEG-40 Hydrogenated Castor Oil + PPG-5-Ceteth-20 + Ethylene Carbonate + Polysorbate-40 as well
• - PEG-40 Hydrogenated Castor Oil + PPG-26-Ceteth-26 + Ethylene Carbonate + Polysorbate-40.

The solubilizers according to the invention in the ready-to-use agents preferably in an amount of 0.5 to 20% by weight, in particular from 1 to 10% by weight, very particularly from 3 to 6 wt .-%, each based on the weight of the total Preparation, used.

When another component essential to the invention contains the ready-to-use Means at least one reactive carbonyl compound.

• 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 have in the context of the invention at least one carbonyl group as a reactive group which reacts with the CH-acidic component 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.

Under the reactive carbonyl compounds of the agent A are compounds selected from compounds of the following group preferred: Benzaldehyde and its derivatives, naphthaldehyde and its derivatives, Cinnamaldehyde and its derivatives, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde), 2-indolealdehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 2- (1 ', 3', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, pyridoxal, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, chromon-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, piperonal, 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-formyl-1-methyl-quinolinium, 5-formyl-1-methyl-quinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl-1-benzyl-quinolinium, 8-formyl-1-benzyl-quinolinium, 5-formyl-1-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7-formyl-1-allyl-quinolinium and 8-formyl-1-allyl-quinolinium-benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures of the above compounds.

It is particularly preferred if, as the reactive carbonyl compound of the agent A, a compound selected from at least one of the compounds 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-dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxybenzaldehyde 2,5-dimethylbenzaldehyde, 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- hydroxy-benzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimeth oxybenzaldehyde, 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- methyl-benzaldehyde, 2,4-dihydroxy-6-methyl-benzaldehyde, 2,4-dihydroxy-3-methoxybenzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy benzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxybenzaldehyde 6-methylbenzaldehyde, 3,4-dihydroxy-2-methoxy-benzaldehyde, 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-dimethylaminobenzaldeh yd, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodo benzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3,4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 2-chloro-3,4- dihydroxybenzaldehyde, 2-bromo-3,4-dihydroxybenzaldehyde, 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-dimethylaminobenzaldehyde hyd, 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) and 3-allyl-4-hydroxy-5-formylbenzaldehyde or (5-allyl-4-hydroxyisophthalaldehyde).

Completely according to the invention particularly preferred reactive carbonyl compounds are selected from 4-hydroxy-2-methoxybenzaldehyde, 2-chloro-3,4-dihydroxybenzaldehyde, 2-bromo-3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazole-4-carboxaldehyde and 2,4-dimethoxy-benzaldehyde.

The reactive carbonyl compounds are preferably present in an amount from 0.03 to 65.00 mmol, based on 100 g of ready for use Composition, used. The use of 0.50 to 30.00 mmol, based on 100 g of the ready-to-use composition, in particular prefers.

When other components essential to the invention contain the ready-to-use Means at least one CH-acidic compound.

When CH-acidic compounds generally become such compounds which is bound to an aliphatic carbon atom Carry hydrogen atom, due to electron-withdrawing substituents an activation of the corresponding carbon-hydrogen bond is effected. Said hydrogen atom can with the help of a base to be abstracted.

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^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 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.

The ready-to-use agent preferably comprises at least one CH-acidic compound selected from at least one compound of the formula (CH-1) and / or from at least one compound 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 is} N- (CH ₂ ) _m -, in which R ^I and R ^II independently of one another 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 can 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.

The compounds of formula (CH-1) and (CH-2) are CH-acidic compounds. From the cationic compounds of the formula (CH-1), it is possible by targeted addition of a base which effects the cleavage of a proton to represent the corresponding uncharged enamine form. As an example for compounds of the formula (CH-1), the illustration of the enamine form is illustrated below by means of the formulas (CH-1-A) and (CH-1-B) with R ⁷ = CH ₃ . The corresponding enamine forms of the CH-acidic compounds according to formula (CH-1) are also according to the invention.

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^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 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.

It is particularly preferred according to the invention to select the compounds of the formula (CH-1) 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 represent a hydrogen atom or a C ₁ -C ₆ alkyl group, wherein at least one of R ¹⁰ and R ^{12 is} 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 the radicals R ¹⁰ or R ^{12 may form} a 5- or 6-membered aromatic ring optionally substituted by 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 ^IV are independently represents 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 s represents 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 hydrogen atom, an aryl group, a heteroaryl group, a (C ₁ to C ₆ ) 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 ^{6 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 ⁶ 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.

Very particularly brilliant hair colorations can be obtained if the CH-acidic compound of the formula (CH-1) and / or the formula (CH-2) is a compound selected from at least one compound of the group consisting of 2- (2-furoyl) - acetonitrile, 2- (5-bromo-2-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-benzimidazole-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, 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile and the salts with physiologically compatible counterion X ^- des
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
is used. Therefore, the compounds of this group are particularly preferred.

Completely according to the invention particularly preferred CH-acidic compounds are selected from the physiologically acceptable salts of 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium and 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium and 2- (cyanomethyl) benzimidazole.

The CH-acidic compounds of the formula (CH-1) and / or of the formula (CH-2) are preferably in an amount of 0.03 to 65.00 mmol, based to 100 g of the ready-to-use agent. The use from 1.00 to 30.00 mmol, based on 100 g of ready for use By means of is particularly preferred.

In In another embodiment, the inventive Means additionally at least one developer component and optionally at least one coupler component as oxidation dye precursors contain. However, it is preferred that the invention Formulate agent free of oxidation dye precursors, especially if the allergy risk for para-allergic should be minimized. Thus, a preferred invention Means by being free of oxidation dye precursors are of the developer type.

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 the formula (E1) are selected from one or more p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6- Diethyl p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino 3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-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, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, 5,8-diaminobenzoyl 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 to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) -polyhydroxyalkyl radical, - (C1 to _C4) aminoalkyl radical or a direct bond to the bridge 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) -tetrame ethylenediamine, N, N'-bis- (4- (methylamino) phenyl) tetramethylenediamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, bis- (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine , N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and 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 -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 steht 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 with 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 radical,
• 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 especially -NH _2, (C ₁ to C ₄₎ monoalkylamino, (C 1 -C ₄₎ -dialkylamino, (C ₁ to C ₄₎ -Trialkylammoniumgruppen, (C ₁ to C ₄₎ -Monohydroxyalkylaminogruppen, 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 ) ₂ (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 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 (C ₁ to C ₆ ) 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 of one another represent a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) 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, a (C ₁ to C ₆ ) - Alkyoxy (C ₂ to C ₆ ) alkoxy group, an aryl lgruppe 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.

Especially preferred m-diaminobenzene coupler components are selected from at least one compound from the group that is 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-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 and the physiological compatible salts of all the compounds mentioned above.

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 independently of one another represent a hydrogen atom, a halogen atom, a carboxyl group, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -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 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 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.

Especially preferred pyridine derivatives are selected from at least a 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-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiological 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 formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1.3 Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydro xynaphthalene, 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-dihydroxy-2-methylpyrimidine and the physiologically acceptable Salts of the aforementioned compounds.

Particularly preferred coupler components according to the invention are selected from m-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-amino-phenoxyethanol, 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-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis - (2'-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2, 6-Dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7 -Hydroxyindoline or mixtures of these compounds or 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 mixture of agent A, agent B and optionally Medium C, used.

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.

In the following, examples of the substituents as the compounds of formulas (K1) to (K6) said radicals are enumerated: Examples of (C ₁ to C ₄₎ -alkyl, 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 ₃ to C ₆ ) cycloalkyl groups according to the invention are cyclopropyl, cyclopentyl and cyclohexyl.

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 .

One Example of aryl groups is the phenyl group, which also may be substituted.

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

It may be preferred according to the invention, the inventive Agent as a further dye precursor a natural analog dye add.

When Dye precursors of naturally-analogous dyes are preferably those Indoles and indolines were used, which selected at least two groups from hydroxy and / or or amino groups, preferably as a substituent at the six-ring, exhibit. These groups may have additional substituents wear, z. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. In a further embodiment the colorants contain at least one indole and / or Indoline. Compositions according to the invention, contain the precursors of natural dyes, are preferred used as air-oxidative coloring agents. In this embodiment Therefore, the said compositions will not be associated with an additional Oxidizing agent added.

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
• – R⁶ 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 ⁶ represents 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 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.

The Indoline or the indole derivatives can both as free bases as well as in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. B. the hydrochlorides, sulfates and hydrobromides.

Farther may additionally in the agent according to the invention at least one substantive dye may be included. It acts dyes which are applied directly to the hair and none need oxidative process to form the paint. Direct 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 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 ) azo] -benzenesulfonic acid sodium salt (CI 14,270; Acid Orange 6), 4 - [(2-hydroxynaphth-1-yl) azo] -benzenesulfonic acid, sodium salt (CI 15.510, Acid Orange 7), 4 - [(2,4-dihydroxy-3 - [(2,4-) dimethylphenyl) azo] -phenyl) azo] -benzenesulfonic acid, sodium salt (CI 20,170; Acid Orange 24), 4-hydroxy-3 - [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid, sodium salt (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-sulfonaphthalene) 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), 5- (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 - (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- [isobenzo furan-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) -xanthene] -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-methylphenynamino] -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-ethylbenzenemethanaminium 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-methylphenynamino] -6 - [(2-methyl-4-sulfophenyl) amino] xanthylium inner salt, sodium salt (CI 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:

Particularly suitable cationic direct dyes are 9- (dimethylamino) benzo [a] phenoxazine-7-ium chloride (CI 51.175; Basic Blue 6), di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl]. carbenium chloride (CI 42,595; Basic Blue 7), di (4- (dimethylamino) phenyl) - (4- (methylphenylamino) -naphthalen-1-yl) carbenium chloride (CI 42,563, Basic Blue 8), 3,7-Di (dimethylamino) phenothiazine-5-ium chloride (CI 52.015 Basic Blue 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (CI 44.045, Basic Blue 26 ), 2 - [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methylsulfate (CI 11.154, Basic Blue 41), 8-amino-2-bromo 5-hydroxy-4-imino-6 - [(3- (trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone chloride (CI 56.059; Basic Blue No. 99), bis [4- (dimethylamino) phenyl] - [4- (methylamino) phenyl] carbenium chloride (CI 42,535, Basic Violet 1), tri (4-amino-3-methylphenyl) carbenium chloride (CI 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 (CI 45,170, Basic Violet 10), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (CI 42.510 Basic Violet 14), 1,3-bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI 21.010, Basic Brown 4), 1 - [(4-aminophenyl) azo] -7 - (trimethylammonio) -2-naphthol chloride (CI 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 (CI 12.251, Basic Brown 17), 3 - [(4-amino-2,5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzolaminium chloride (CI 12,605, Basic Orange 69), 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (CI 50.240, Basic Red 2), 1,4-dimethyl-5 - [(4- (dimethylamino) phenyl) azo] -1,2,4-triazolium chloride (CI 11.055, Basic Red 22), 2-hydroxy-1 - [(2-methoxyphenyl) azo] -7- (trimethylammonio) -naphthalene chloride (CI 12.245, Basic Red 76), di [4- (dimethylamino) phenyl] iminomethane hydrochloride (CI 41,000, Basic Yell ow 2), 2- [2 - ((2,4-dimethoxyphenyl) amino) ethenyl] -1,3,3-trimethyl-3H-indol-1-ium chloride (CI 48,055; Basic Yellow 11), 3-methyl-1-phenyl-4 - [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (CI 12.719; Basic Yellow 57), bis [4- (diethylamino) phenyl] phenylcarbenium hydrogensulfate (1: 1) (CI 42.040, Basic Green 1), di (4- (dimethylamino) phenyl) phenylmethanol (CI 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 substantive dyes containing a heterocycle having 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 having at least one quaternary nitrogen atom, as described 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-nitro-diphenylamine (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-nitrobe nzol (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-hydroxyethylamino] -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-aminoethynamino) -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-cyclohexadiene 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-indole -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 direct dyes are among the international ones 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 Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds, and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, Picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

It 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.

• – Weiterhin kann der erfindungsgemäße Kit auch in der Natur vorkommende Farbstoffe, wie sie beispielsweise in Henna rot, Henna neutral, Henna schwarz, Kamillenblüte, Sandelholz, schwarzen Tee, Faulbaumrinde, Salbei, Blauholz, Krappwurzel, Catechu, Sedre und Alkannawurzel enthalten sind, enthalten.

The agents according to the invention may contain the optionally contained developers, couplers and / or direct drawers in an amount of from 0.01 to 20.00% by weight, based on the kit according to the invention and thus based on a mixture of agent A and agent B and optionally additionally Medium C included.

• Furthermore, the kit according to the invention may also contain naturally occurring dyes, such as those found in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, sedre and alkano root ,

to Obtaining further and more intense colorations the inventive Agent additionally color enhancers included. The Color enhancers are preferably selected from the group consisting of piperidine, piperidine-2-carboxylic acid, Piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, Pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, Pyrazole, 1,2,4-triazole, piperazidine, their derivatives and their physiologically acceptable salts.

The above standing color amplifier can in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the finished application mixture, be used.

• – -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.

On the presence of oxidizing agents, for. B. H ₂ O ₂ , can, in particular if the erfindungsge Moderate agent contains no oxidation dye precursors can be dispensed with. If the agent according to the invention contains air-oxidizable oxidation dye precursors or indole or indoline derivatives, oxidizing agent can be dispensed with without problems in such a case. However, it may be desirable to add hydrogen peroxide or other oxidizing agents to the kit of the present invention to achieve the nuances brighter than the keratin-containing fiber to be dyed. Oxidizing agents are generally used in an amount of 0.01 to 6 wt .-%, based on the finished application mixture. A preferred oxidizing agent for human hair is H ₂ O ₂ . Also, mixtures of several oxidizing agents, such as a combination of hydrogen peroxide and peroxodisulfates of the alkali and alkaline earth metals or iodide ion sources, such as. As alkali metal iodides and hydrogen peroxide or the aforementioned peroxodisulfates can be used. The oxidizing agent or the oxidizing agent combination can be used according to the invention in conjunction with oxidation catalysts in the hair dye. Oxidation catalysts are, for example, metal salts, metal chelate complexes or metal oxides, which allow a slight change between two oxidation states of the metal ions. Examples are salts, chelate complexes or oxides of iron, ruthenium, manganese and copper. Other possible oxidation catalysts are enzymes. Suitable enzymes are, for. 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, for. 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.

Farther the kit according to the invention can all be used in such Preparations known active ingredients, additives and excipients.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – 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.-Butylacrylamid-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 Glucose und Maleinsäure,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Antischuppenwirkstoffe wie Piroctone Olamine und Zink Omadine,
• – Wirkstoffe wie Panthenol, Pantothensäure, Allantoin, Pyrrolidoncarbonsäuren und deren Salze, Pflanzenextrakte und Vitamine,
• – Cholesterin,
• – Lichtschutzmittel,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs, Paraffine, Fettalkohole und Fettsäureester,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate, Imidazole, Tannine, Pyrrol,
• – Trübungsmittel wie Latex,
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft sowie Antioxidantien.

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,
• Anionic polymers such as, 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-butylacrylamide 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 glucose and maleic acid,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine,
• - active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - sunscreen,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• Fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• Fatty acid alkanolamides,
• - complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole,
• Opacifiers such as latex,
• Pearlescing agents such as ethylene glycol mono- and distearate,
• - Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air and antioxidants.

The Components of the cosmetic carrier are used for the production of the agent according to the invention in Uses customary amounts for this purpose; z. B. become emulsifiers in concentrations of 0.5 to 30 wt .-% and thickener in Concentrations of 0.1 to 25 wt .-% based on the respective Used funds.

There the invention essential components of the application preparation to undergo chemical reactions with each other and accordingly together are not readily storable, must they are packaged in several separate formulations.

Especially The Oxofarbstoffvorprodukte are reactive and must be accordingly be carefully prepared.

In a first embodiment of the present invention become the reactive carbonyl compounds and the CH-acidic compounds made up in two separate means.

there The agents can be used in one suitable aqueous, alcoholic or aqueous-alcoholic Carrier included. For the purpose of hair coloring are such carriers, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as Shampoos, foam aerosols or other preparations intended for the application on the hair are suitable. But it is also conceivable the Oxofarbstoffvorprodukte in a powdery or also to integrate tablet-like formulation.

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.

For the case that the Oxofarbstoffvorprodukte in an aqueous, alcoholic or aqueous-alcoholic carrier incorporated, it has proved to be advantageous if the preparations are adjusted to an acidic pH.

It it was found that the assembly of reactive carbonyl compounds in an aqueous, alcoholic or aqueous-alcoholic cosmetic carrier, wherein the pH of this agent between 2.5 and 5 (mean B), the storage stability of the carbonyl compounds increased considerably.

Also the incorporation of the special CH-acidic compounds into one aqueous, alcoholic or aqueous-alcoholic cosmetic carrier, wherein the pH of this agent between 0.5 and 2.5 (mean A) increases stability the formulation to the extent that it is also in storage over for several months to no significant degradation of the content of CH-acidic Connection is coming.

Especially Store-stable formulations can be obtained if the agent B has a pH between 3.2 and 4.5, therefore this pH range is preferred.

Furthermore it is preferred if the agent A has a pH of 1 to 2 and particularly preferably has a pH of 1.1 to 1.9.

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

The Adjustment of the pH in the agents A and / or B can help an organic or inorganic acid such as Hydrochloric acid, sulfuric acid, hydrobromic acid, Phosphoric acid, acetic acid, tartaric acid, Citric acid, lactic acid, malic acid or glycolic acid.

In In this context, the setting of the invention pH values with the aid of sulfuric acid, hydrochloric acid, Tartaric acid, citric acid, malic acid or lactic acid is particularly preferred.

For the application must have the agents A and B just before application be intimately mixed with each other on the hair fiber. To further However, it may be advantageous to improve the staining result Be the staining even in an alkaline pH range perform.

Therefore it may be preferable in a particular embodiment if in addition a third agent C is added, which in a cosmetic carrier at least one alkalizing agent contains and has a pH of 7 to 11.

Becomes the staining is carried out in an alkaline pH range, For example, before application to the hair fiber, the Carefully mix components A, B and C together.

at that contained in agent C in a cosmetic carrier Alkalizing agents may preferably be alkalizing agents selected from the group formed from ammonia, basic amino acids, alkali hydroxides, alkanolamines, Alkali metal metasilicates, urea, morpholine, N-methylglucamine, Imidazole, alkali phosphates and alkali hydrogen phosphates. As alkali metal ions are preferably lithium, sodium, potassium, especially 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-histidine, D-histidine, D, L-histidine, L-lysine, D-lysine, D, L-lysine, particularly preferably L-arginine, D-arginine, D, L-arginine as an alkalizing agent used in the context of the invention.

The usable as alkalizing agent according to the invention Alkali hydroxides are preferably selected from the group which is formed from 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.

Especially Preferably, the alkalizing agent is selected from at least one compound from the group that is formed from Ammonia, 2-aminoethanol, 2-amino-2-methylpropan-1-ol, 2-amino-2-methyl-propane-1,3-diol, Potassium hydroxide, sodium hydroxide, L-arginine, D-arginine, DL-arginine, N-methylglucamine, morpholine, imidazole and urea.

Furthermore can also grow to a pH greater as used by 7 to 11 buffer systems in means C. become.

When pH buffer system according to the invention chemical compounds or a combination of chemical compounds viewed in a solution that cause the pH of the solution with the addition of a small amount of acid or lye changes only slightly to a volume of the cosmetic carrier. This change is less pronounced than this with the addition of the same amount of acid or alkali to an equal volume of the cosmetic carrier without pH buffer system is the case.

Such pH buffer systems are preferably selected from among at least one member selected from bicarbonate, organic acid (especially citric acid) / monohydrogen phosphate, malic acid (especially citric acid) / dihydrogen phosphate, tris (hydroxymethyl) aminomethane / maleic acid / NaOH, Tris (hydroxymethyl) aminomethane / maleic acid / KOH, tris (hydroxymethyl) aminomethane / HCl, monohydrogenphosphate / dihydrogenphosphate, dihydrogenphosphate / NaOH, dihydrogenphosphate / KOH, H ₃ BO ₃ / KCl / NaOH, H ₃ BO ₃ / KCl / KOH, borate / HCl , Borate / halide (especially chloride such as potassium chloride) / NaOH, borate / halide (especially chloride such as potassium chloride) / KOH, Theorell and Stenhagen buffer system, McIlvine buffer system, glycine / NaOH and glycine / KOH. Particularly preferred pH buffer systems are selected from at least one member of the group formed from tris (hydroxymethyl) aminomethane / maleic acid / NaOH, tris (hydroxymethyl) aminomethane / maleic acid / KOH, tris (hydroxymethyl) aminomethane / HCl, borate / HCl and H ₃ BO ₃ / KCl / NaOH.

The slashed pH buffer systems from the above list, mixtures of these by the slash The compounds listed in the list are anionic Compounds are in the form of their salts with a corresponding monovalent or polyvalent cation used. Preferred cations are Alkali metal cations (especially sodium or potassium) and ammonium ions.

According to the invention are the edible acids which can be used in the buffer systems For example, citric acid, tartaric acid or malic acid or mixtures thereof.

The pH buffer system is preferably in an amount of 0.1 to 10.0 wt .-%, particularly preferably from 0.3 to 5.0% by weight, very particularly preferably from 0.5 to 3.0 wt .-%, each based on the weight of the application mixture from agent A, agent B and agent C, in the ready-to-use colorant contain.

In In this context, the pH of the final application mixture, which is prepared by mixing the agents A, B and C, between 7 and 11 are. Is the pH of the final application mixture in a range of 7.5 to 9.0, it is preferred.

• – ein Mittel (A), enthaltend mindestens eine CH-acide Verbindung,
• – ein Mittel (B), enthaltend mindestens eine reaktive Carbonylverbindung, sowie
• – ein Mittel (C), enthaltend mindestens ein Alkalisierungsmittel, wobei mindestens eines der Mittel (A), (B) oder (C) mindestens einen Lösungsvermittler, ausgewählt aus (a1) den Verbindungen, die mindestens eine C₄-C₂₂-Alkylkette aufweisen, die mindestens eine Hydroxygruppe trägt, die mit Ethylenoxid- und/oder Propylenoxid-Einheiten verethert ist, wobei die Gesamtzahl an Ethylenoxid- und Propylenoxid-Einheiten im Molekül größer als 20 ist, und (a2) den cyclischen organischen Carbonaten. enthält.

A second subject of the present invention is therefore a kit for coloring keratinic fibers comprising at least

• An agent (A) containing at least one CH-acidic compound,
• An agent (B) containing at least one reactive carbonyl compound, and
• - an agent (C) containing at least one alkalizing agent, wherein at least one of the agents (A), (B) or (C) at least one solubilizer selected from (a1) the compounds containing at least one C ₄ -C ₂₂ alkyl chain having at least one hydroxy group etherified with ethylene oxide and / or propylene oxide units, the total number of ethylene oxide and propylene oxide units in the molecule being greater than 20, and (a2) the cyclic organic carbonates. contains.

Regarding the CH-acidic compounds, the reactive carbonyl compounds as well of the solubilizer is explicit at this point the above statements referenced.

in the This object may be of various forms give. The agents (A) and (B) are preferably powdery, creamy, gel or formulated as Oxofarbstoffvorproduktkonzentrat.

Under an oxo dye precursor concentrate is one according to the invention Oxofarbstoffmenge to understand that in a small amount of solubilizer has been recorded. For example, it is preferred that the or the Oxofarbstoffvorprodukte of one type (reactive carbonyl compounds or CH-acidic compounds) in an amount of 1 to 10 ml of a To formulate solver. Such formulations can in principle contain further constituents, but are preferred limited to these two components. For this Embodiment, the cyclic carbonates have as particularly preferred solubilizers.

Under Pulverfömiger confection is inventively a Formulation having a preferred average particle size from 0.0001 to 500 μm, in particular from 0.001 to 500 μm, especially understood from 0.05 to 300 microns.

Next The oxo dye precursors of one type contain the invention powdery formulations preferably a suitable Filler.

In addition to usual inorganic, finely divided pigments, such as titanium dioxide and silica (for example in the form of fumed silica), have also water-soluble fillers as proved suitable. Examples of such fillers are the disaccharides, such as cellobiose, maltose (malt sugar), Lactose (milk sugar), sucrose (cane sugar), gentobiose, melibiose, Trehalose and Turanose. Lactose is particular to the invention prefers.

According to the invention suitable Fillers are also polyethylene glycols and polypropylene glycols. A polyethylene glycol is particularly preferred.

Silica, in particular fumed silica, according to the invention is a very particular zugter filler for powdered formulations.

For the case that both the agent (A) and the agent (B) in an aqueous, alcoholic or aqueous-alcoholic Carrier incorporated, this can be immediate mixed before use with the agent (C) and the resulting Mixture can be applied directly. In this case, the agent (C) as an aqueous solution of the invention essential Alkalizing agent may be formulated. Even if in principle the Addition of other ingredients is not required, this should be but not be excluded in general.

For the case where one of the agents (A) or (B) is in an aqueous, alcoholic or aqueous-alcoholic carrier is incorporated and the other of the means (A) or (B) in solid form or as an oxo dye concentrate these also immediately before use with the agent (C) mixed and the resulting mixture applied immediately become. In this case, the agent (C) as aqueous Solution of the alkalizing agent essential to the invention be formulated. Although in principle the addition of other ingredients is not required, but this is not generally excluded be.

For the case where one of the agents (A) or (B) is in solid form and the other of the two agents (A) or (B) also in solid Or is present as an oxo dye precursor concentrate proved to be advantageous when the agent (C), the immediate is added before use, the alkalizing agent in an aqueous, alcoholic or aqueous-alcoholic Carrier with other ingredients, such as surfactants and / or thickening agents. especially in the Traps in which one of the agents (A) or (B) is formulated as a powder is, it has proved to be particularly advantageous when the mixture a additional preparation (E) is added which is a novel Contains solubilizer.

In a second embodiment of the present invention become the reactive carbonyl compounds and the CH-acidic compounds compounded together in an agent that in powder form, granulated or as a solid.

One powdery agent has a preferred average Particle size from 0.0001 to 50 microns, in particular from 0.05 to 30 μm.

When Granules according to the invention are granular Particles understood. These granular particles are flowable.

granules can by wet granulation, by dry granulation or compaction and produced by melt solidification granulation become. The most common granulation technique is wet granulation, because this technique is subject to the least restrictions is and safest to granules with favorable properties leads. The wet granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably used in mixers, fluidized beds or spray towers, wherein said mixer, for example, with stirring and kneading tools can be equipped. For the granulation but are also combinations of fluidized bed (s) and mixer (s), or combinations of different mixers used. The granulation occurs under the action of low to high shear forces.

If the agent is present as a shaped body, then can these shaped bodies according to the invention any geometric Shape, such as concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder-segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral To shape. Also completely irregular bases like arrow or animal shapes, trees, clouds etc. will be realized. The training as a blackboard, the bar or bar form, Cube, cuboid and corresponding room elements with levels Side surfaces and in particular cylindrical Embodiments with a circular or oval cross-section and moldings of spherical geometry preferred according to the invention. Especially preferred are shaped bodies in the form of spherical geometry.

The cylindrical embodiment detects the presentation form from the tablet to compact cylinder pieces with one Ratio of height to diameter larger 1. If the base molding corners and edges, so are These are preferably rounded. As an additional optical Differentiation is a rounded embodiment Corners and beveled ("touched") Edges preferred.

The spherical design comprises not only a spherical shape but also a hybrid of spherical and cylindrical shape, wherein each base of the cylinder is capped with a hemisphere. The half ku Rules preferably have a radius of about 4 mm and the entire molded body of this embodiment has a length of 12-14 mm.

An inventive shaped body with a spherical configuration can be produced by the known methods. It is possible to produce the moldings by extrusion of a premix with subsequent shaping, as for example in the WO-A-91/02047 is made in detail, which is expressly incorporated herein by reference.

In Another preferred embodiment will therefore almost spherical moldings, in particular by Extrusion and subsequent rounding for shaping, produced.

In In another embodiment, the portioned Pressings in each case as separate individual elements be formed that the predetermined dosage of CH-acidic Compounds or reactive carbonyl compounds equivalent. However, it is also possible to form pellets, which connect a plurality of such mass units in a compact, in particular by predetermined predetermined breaking points, the light Separability portioned smaller units is provided. The formation of the portioned pellets as tablets in cylindrical or cuboid shape may be appropriate, with a Diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, Eccentric or rotary presses are suitable devices in particular for the production of such compacts.

A another possible spatial form of the invention Shaped body has a rectangular base on, wherein the height of the molded body is smaller as the smaller rectangle side of the base. rounded Corners are preferred in this form of supply.

One Another molding that can be made has one plate-like or tabular structure with alternately thick long ones and thin short segments, so that individual segments from this "bar" at the predetermined breaking points, the represent the short thin segments, broken off and can be used in such portions. This Principle of the "bar-shaped" shaped body can also be in other geometric shapes, such as vertical standing triangles that are alongside each other only on one side connected, be realized.

Contain the shaped body according to the invention in addition the coupler component at least one other component, it can be advantageous in a further embodiment, the different components not exclusive to one to press uniform tablet. When tableting obtained in this embodiment moldings, which have several layers, ie at least two layers. It is also possible that these different Layers have different dissolution rates. From this can have advantageous application properties the shaped body result. For example, if components contained in the moldings, which are mutually negatively affect, so it is possible the one component to integrate in the faster soluble layer and the to incorporate another component into a slower soluble layer, so that the components are not already during the Dissolution process react with each other.

Of the Layer structure of the molded body can be both stacked take place, whereby a dissolution process of the inner layer (s) already takes place at the edges of the shaped body when the outer layers are not yet complete are solved. In the stacked arrangement the stacking axis can be arranged arbitrarily to the tablet axis. The stacking axis can thus, for example, in a cylindrical Tablet parallel or perpendicular to the height of the cylinder lie.

It but also according to another embodiment be preferred if a complete enclosure the inner layer (s) through the respectively further outward lying (s) layer (s) is achieved, resulting in a prevention the early solution of components of the inner layer (s) leads. Preference is given to moldings, in which the layers with the different active ingredients wrap themselves. For example, be a layer (A) completely from the Layer (B) and this in turn completely from the layer (C) wrapped. Similarly, shaped bodies be preferred in which z. B. the layer (C) completely from layer (B) and these in turn completely from the layer (A) is wrapped.

Similar effects can also be achieved by coating ("coating") individual components of the composition to be pressed or of the entire molding. For this purpose, the bodies to be coated, for example, be sprayed with aqueous solutions or emulsions, or over the Method of melt coating obtained a coating. For example, the use of a coating of hydroxypropyl methylcellulose, cellulose, PEG stearates and colored pigments is suitable as being suitable according to the invention.

The (Moldings) moldings produced according to the invention can - as described above - completely or partially provided with a coating. Method, in which a post-treatment in the application of a coating layer on the mold surface (s) in which / which the filled well (s) are located or in applying a Coating layer is composed on the entire molded body preferred according to the invention.

A molded article according to the invention has a preferred breaking hardness of 30-100 N, particularly preferably 40-80 N, very particularly preferably 50-60 N (measured according to European Pharmacopoeia 1997, 3rd edition, ISBN 3-7692-2186-9, "2.9.8 breaking strength of tablets"; Page 143-144 with a Schleuniger 6D tablet hardness tester ).

Of further can moldings according to the invention from one described by the term "base molding", per se by known Tablettiervorgänge produced Moldings are made, which has a trough. preferred In this embodiment, the basic shaped body becomes first produced and the further pressed part in another Operation on or in this base molding or introduced. The resulting product is described below referred to the generic term "tray molding" or "depression tablet".

Of the Basic shaped body according to the invention in principle assume all realizable spatial forms. Particularly preferred the spatial forms already mentioned above. The shape of the trough can be free be selected, according to the invention moldings are preferred in which at least one trough a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five, seven and octagonal prismatic as well as rhombohedral form. Even completely irregular trough shapes such as arrow or animal forms, trees, clouds, etc. can be realized become. As with the basic moldings are wells with rounded corners and edges or with rounded corners and touched Edges preferred.

The Size of the trough compared to the entire molded body depends on the intended use of the Moldings. Depending on whether in the second compressed part a lower or greater amount of active substance The size of the trough can be included vary. Regardless of the intended use are molded bodies preferred in which the weight ratio of base molding to fill wells ranging from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, more preferably from 3: 1 to 50: 1 and especially from 4: 1 to 30: 1.

Similar Statements can be made to the surface portions, that of the basic shaped body or the trough filling make out at the total surface of the molding. Here, moldings are preferred in which the surface the pressed-in cavity filling 1 to 25%, preferably 2 to 20%, more preferably 3 to 15% and especially 4 to 10% of the total surface area of the filled base tablet accounts.

If, for example, the overall shaped body has dimensions of 20 × 20 × 40 mm and thus a total surface area of 40 cm ² , well fillings are preferred which have a surface area of 0.4 to 10 cm ² , preferably 0.8 to 8 cm ² , more preferably of 1.2 to 6 cm ² and in particular from 1.6 to 4 cm ² .

The Trough filling and the base molding are preferably optically distinguishable colored. In addition to the optical Differentiation, well-tolerated tablets have technical advantages on the one hand by different solubilities of the different Ranges on the other hand, but also by the separate storage of Active ingredients in the various molding body areas.

Moldings, where the pressed-in bowl filling slower dissolves as the basic shaped body, are preferred according to the invention. By incorporating certain ingredients, on the one hand the Solubility of the well filling specifically varies On the other hand, the release of certain ingredients from the trough filling to advantages in the dyeing process to lead. Ingredients that are preferred at least proportionally are located in the trough filling, for example described in the paragraph "other components" conditioning agents, oils, vitamins and plant active ingredients.

It may be preferred according to the invention, individual Active ingredients before their incorporation into the molding separately to encapsulate; so it is conceivable, for example, particularly reactive Components or the fragrances to use in encapsulated form.

The Production of the shaped bodies according to the invention takes place first by the dry mixing of the ingredients, which may be pre-granulated in whole or in part, and subsequent informing, in particular pressing too Tablets, resorting to known methods can be. For the preparation of the invention Shaped body is the premix in a so-called template compressed between two stamps to a fixed compressed. This Process, hereinafter referred to as tabletting, is divided into four sections: dosage, compaction (elastic Deformation), plastic deformation and ejection.

First the premix is introduced into the die, the filling amount and thus the weight and shape of the resulting molding by the position of the lower punch and the shape of the pressing tool be determined. The consistent dosage even at high molding throughputs is preferably via a volumetric dosage of the premix reached. In the course of tabletting touched the upper stamp the pre-mix and lower in the direction of of the lower punch. In this compression, the particles become of the premix pressed closer to each other, where the void volume within the filling between the Stamping decreases continuously. From a certain position of the Upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding. Depending on the physical properties of the premix will also be a part the premix particle is crushed, and it still comes on higher pressures to sinter the premix. With increasing pressing speed, ie high throughput rates, the phase of elastic deformation is shortened so that the resulting moldings are more or less large May have cavities. In the last step the tableting is the finished molded body by the Lower punch pushed out of the die and by subsequent Transportation transported away. At this time is only the weight of the molding final determined because the compacts due to physical processes (rear expansion, crystallographic effects, cooling etc.) their shape and size can still change.

The Tableting is carried out in commercially available tablet presses, which are basically equipped with single or double punches could be. In the latter case, not only the upper punch used for pressure build-up, also the lower punch moves while the pressing process on the upper punch to, while the upper punch pushes down. For small production quantities Eccentric tablet presses are preferably used in which the or the stamps are attached to an eccentric, the in turn on an axis with a certain rotational speed is mounted. The movement of these punches is the way of working of a standard four-stroke engine comparable. The compression can be done with a top and bottom stamp, it can but also several stamps attached to an eccentric disc, wherein the number of die holes is extended accordingly. The throughputs of eccentric presses vary according to type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs are chosen Rotary tablet presses, in which on a so-called die table a larger number of matrices circular is arranged. The number of matrices varies depending on the model 6 and 55, with larger matrices commercially are available. Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure active only by the upper or lower stamp, but also by both Stamp can be built. The die table and the stamp move around a common perpendicular axis, where the punches with the help of rail-like curved tracks during circulation into the positions for filling, compression, plastic deformation and ejection are brought. To the Areas where a particularly serious increase or decrease the stamp is required (filling, compaction, ejection), these curved paths are replaced by additional low-pressure pieces, Pull-down rails and lifting tracks supported. The filling the die takes place via a rigidly arranged feed device, the so-called filling shoe, which comes with a storage container for the premix is connected. The pressure on the Premix is on the pressing paths for upper and Lower punch individually adjustable, whereby the pressure build-up by the forward movement of the stamp shank heads on adjustable Pressure rollers happens.

Concentric presses can be provided to increase the throughput with two filling shoes, which only a semicircle must be run through to produce a tablet. To produce two-layered and multi-layered shaped bodies, several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling. By suitable process management are in this way, coat and point tablets produced, which have a onion-like structure, in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible. Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 holes and an inner circle with 35 holes are used simultaneously for pressing. The throughputs of modern rotary tablet presses amount to over one million moldings per hour.

• – Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• – Geringe Umdrehungszahl des Rotors
• – Große Füllschuhe
• – Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• – Füllschuh mit konstanter Pulverhöhe
• – Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Small variations in weight can be achieved in the following ways:

• - Use of plastic inserts with small thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching of the Füllschuhflügeldrehzahl on the speed of the rotor
• - filling shoe with constant powder height
• - Decoupling of filling shoe and powder template

to Reduction of Stempelanbackungen offer all Non-stick coatings known in the art. Especially advantageous are plastic coatings, plastic inserts or plastic stamps. Rotary stamps have proved to be advantageous, wherein if possible upper and lower punches rotatable should be. With rotating punches can on a plastic insert usually be waived. Here should be the stamp surfaces be electropolished.

It It was also shown that long press times are advantageous. These can be with pressure rails, several pressure rollers or low rotor speeds are set. Because the hardness fluctuations the tablet caused by the fluctuations of the pressing forces should be used systems that limit the pressing force. Here can elastic punches, pneumatic compensators or resilient elements are used in the force path. Also can the pressure roller are made resilient.

in the According to the present invention suitable tabletting machines are available, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Fann Instruments Company, Houston, Texas (USA), Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Presses AG, Berlin, as well as Romaco GmbH, Worms. Other providers include Dr. med. Herbert Pete, Vienna (AT), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) as well as Mediopharm Kamnik (SI). Particularly suitable is, for example, the Hydraulic double pressure press HPF 630 from LAEIS, D. Tableting tools are for example from the company Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber % Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Further Providers are z. Senss AG, Reinach (CH) and the Medicopharm, Kamnik (SI).

The However, a method for producing the shaped body is not limited to the fact that only a particulate Premix is pressed into a molding. Much more can the procedure also be extended to the effect that in a manner known per se, multilayer moldings by preparing two or more premixes, the be pressed together. Here, the first filled Pre-mix slightly pre-pressed to a smooth and parallel to the To get moldings floor running top, and after filling the second premix to the finished molding finally pressed. For three- or multi-layered moldings another pre-compression takes place after each premix addition, before after addition of the last premix of the molding is squeezed.

The compression of the particulate composition in the trough can be carried out analogously to the preparation of the base tablets on tablet presses. Preference is given to a procedure in which only the basic shaped bodies are produced with a depression, then filled and subsequently pressed again. This can be done by ejecting the base tablets from a first tablet press, filling and transport in a second tablet press, in which the final compression takes place. Alternatively, the final compression can also take place by means of pressure rollers which roll over the shaped bodies located on a conveyor belt. But it is also possible to provide a rotary tablet press with different sets of stamps, so that a first set of dies depressions pressed into the moldings and the second set of stamps after filling by Nach Pressing ensures a flat molding surface.

• – ein Mittel (F), das in Pulverform, granuliert oder als Festkörper vorliegt, enthaltend mindestens eine CH-acide Verbindung sowie mindestens eine reaktive Carbonylverbindung, sowie
• – ein flüssiges Mittel (G), enthaltend mindestens ein Alkalisierungsmittel sowie mindestens einen Lösungsvermittler, ausgewählt aus (a1) den Verbindungen, die mindestens eine C₄-C₂₂-Alkylkette aufweisen, die mindestens eine Hydroxygruppe trägt, die mit Ethylenoxid- und/oder Propylenoxid-Einheiten verethert ist, wobei die Gesamtzahl an Ethylenoxid- und Propylenoxid-Einheiten im Molekül größer als 20 ist, und (a2) den cyclischen organischen Carbonaten.

A third object of the present invention is therefore a kit for coloring keratinous fibers, comprising at least

• - An agent (F), which is in powder form, granulated or solid state, containing at least one CH-acidic compound and at least one reactive carbonyl compound, and
• - A liquid agent (G) containing at least one alkalizing agent and at least one solubilizer selected from (a1) the compounds having at least one C ₄ -C ₂₂ alkyl chain carrying at least one hydroxy group, which with ethylene oxide and / or Etherified with propylene oxide units, wherein the total number of ethylene oxide and propylene oxide units in the molecule is greater than 20, and (a2) the cyclic organic carbonates.

Also in the context of this article is to the above statements explicitly referred to the components essential to the invention.

One third subject of the present invention is a method for dyeing keratin-containing fibers, in particular human Hair, characterized in that one of the invention ready-to-use agent applied to the keratin-containing fiber, Leave on the fiber for 5 to 60 minutes and pour rinsed out again or washed out with a shampoo.

One Fourth object of the present invention is a method for dyeing keratin-containing fibers, in particular human Hair, in which the components of an inventive Kits are mixed together just prior to use, and the resulting application preparation to the keratin-containing Applied fiber, left on the fiber for 5 to 60 minutes and then anschießend rinsed out again or washed out with a shampoo.

Has according to the invention it proved to be advantageous if the preparation based on the fibers are applied has a pH of 7 to 10.

Also with regard to further embodiments of the invention Method applies the above mutatis mutandis.

Examples

1 Preparation of the preparations

The quantities are in grams, unless otherwise stated. 1.1 Preparation of the preparations (A) containing at least one CH-acidic compound component A1 A2 A3 A4 A5 A6 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium bromide 9 mmol 15 mmol 10 mmol - 12 mmol - 2- (cyanomethyl) benzimidazole 6 mmol - - - - - 1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogensulfonat - - - 10 mmol - 12 mmol Aerosil ^® 200 0.13 0.16 0.10 - 0.12 0.12 propylene carbonate - - - 7.5 - - component A7 A8 A9 A10 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium bromide 7 mmol 6 mmol 7 mmol 6 mmol 2- (cyanomethyl) benzimidazole 3 mmol 4 mmol 3 mmol 4 mmol 1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogensulfonat - - - - Hydrenol ^® D - 3.0 - 3.4 Lorol® ^®, tech. - 0.4 - 0.6 Eumulgin ^® B2 - 1.2 - 1.7 Texapon.RTM ^® NSO 2.0 - 1.5 - Dehyton ^® K 1.5 2.0 2.5 5.0 Plantacare ^® 2000 UP - 2.0 - - Sident 22 S ^® 1.2 - 2.1 - Antil 171 ^® 0.8 - - 0.3 Aerosil ^® 200 - - - - Solubilisant ^® LRI 1.0 4.0 1.0 2.5 Tween ^® 80 - 1.0 - - Tween ^® 20 - - - 1.0 propylene carbonate 2.0 1.5 1.5 3.0 glycerol - - - - Sulfuric acid / monoethanolamine ad pH 1.8 ad pH 1.7 ad pH 1.1 ad pH 1.9 water ad 100 g ad 100 g ad 100 g ad 100 g component A11 A12 A13 A14 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium bromide 15 mmol 4 mmol 10 mmol - 2- (cyanomethyl) benzimidazole - 6 mmol - - 1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogensulfonat - - - 10 mmol Hydrenol ^® D - 1.5 3.0 - Lorol® ^® tech. - 1.0 0.8 - Eumulgin ^® B2 - 2.0 1.0 - Texapon.RTM ^® NSO - 3.0 - 2.0 Dehyton ^® K 3.0 - - - Plantacare ^® 2000 UP 1.2 - 4.5 2.5 Sident 22 S ^® - 0.3 - 1.1 Antil 171 ^® 1.8 0.4 - 0.7 Aerosil ^® 200 - - - - Solubilisant ^® LRI 0.75 2.0 1.5 2.5 Tween ^® 20 - - 2.5 - propylene carbonate 2.0 2.5 1.0 0.9 glycerol - - - - Sulfuric acid / monoethanolamine ad pH 1.5 ad pH 1.2 ad pH 1.8 ad pH 1.0 water ad 100 g ad 100 g ad 100 g ad 100 g component A15 A16 A17 A18 A19 A20 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium bromide 15 mmol 11 mmol 12 mmol 9 mmol 10 mmol - 2- (cyanomethyl) benzimidazole - 4 mmol - 3 mmol - - 1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogensulfonat - - - - - 10 mmol Plantacare ^® 2000 UP - - - - - 3.8 Sident 22 S ^® - - - - - 1.1 Antil 171 ^® - - - - - 0.7 Aerosil ^® 200 0.20 0.14 - - 0.80 - Solubilisant ^® LRI - - - - - 1.3 Tween ^® 20 - - - - - - propylene carbonate - - 8.0 - - 4.3 glycerol - - - 8.5 - - Sulfuric acid / monoethanolamine - - - - - ad pH 1.7 water - - - - - ad 100 g

1.1.1 Preparation of the cream formulations A8, A10, A12 and A13

Lorol ^®, Eumulgin ^® B2 and / or Hydrenol D ^® were melted together at 80 ° C. In this melt, the necessary for the individual formulations proportions of the components Texapon ^® NSO, Dehyton ^® K and / or Plantacare ^® 2000 UP were incorporated.

1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfonate and / or 2- (Cyanomethyl) benzimidazole were dissolved in propylene carbonate and / or glycerin carbonate and 80 to 90 ° C hot water and added with stirring. After cooling, the remaining formulation ingredients, such as Solubilisant ^® LRI, Tween ^® 20 and / or Tween ^® 80 were added. Then ident ^® were given 22 S and / or Antil ^® 171 added. The source process was awaited. By adding sulfuric acid or monoethanolamine, the pH stated for the particular formulation was set. Finally, it was made up to 100 g with warm water.

1.1.2 Preparation of gel formulations A7, A9, A11, A14 and A20

1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfonate and / or 2- (Cyanomethyl) benzimidazole were dissolved in 70 g of water, propylene carbonate and / or glycerin carbonate with stirring. Then, the necessary for the individual formulations proportions of the components Texapon ^® NSO, Dehyton ^® K and / or Plantacare ^® 2000 UP were added. During the cooling, the previously pre-swollen means ^® Sident 22 S and / or Antil ^® 171 was added with continued stirring. The source process was awaited. Finally, by adding sulfuric acid or monoethanolamine, the pH stated for the particular formulation was established and made up to 100 g with cold water. 1.2 Preparation of the agent B containing at least one reactive carbonyl compound component B1 B2 B3 B4 B5 B6 4-hydroxy-2-methoxybenzaldehyde 6 mmol 3 mmol 1 mmol 2 mmol 4 mmol 1 mmol 3,4-dihydroxy-5-methoxybenzaldehyde 9 mmol 6 mmol 6.5 mmol 6 mmol 6 mmol 5 mmol 1,2-dihydro-1,5-dimethyl-4-formyl-2-phenyl-3H-pyrazol-2-one - 6 mmol 5.5 mmol - - 4 mmol 2,4-dimethoxy-benzaldehyde - - - 2 mmol - - Hydrenol ^® D 3.0 2.5 - 1.5 2.0 - Lorol® ^® tech. 0.4 0.6 - - 1.5 - Eumulgin ^® B2 1.8 0.5 - 1.0 - - Texapon.RTM ^® NSO 1.5 - 1.0 2.0 4.5 1.5 Dehyton ^® K 2.0 2.5 - - - 1.5 Plantacare ^® 2000 UP - 1.0 3.0 2.0 - - Sident 22 S ^® - - 2.0 0.4 - 1.5 Antil 171 ^® - - - 0.3 - - Aerosil ^® 200 - - - - - - Solubilisant ^® LRI 2.5 1.6 1.4 2.0 3.0 1.8 Tween ^® 20 - 3.0 - 1.0 0.5 - propylene carbonate 4.0 1.5 5.0 3.0 1.0 6.0 Phosphoric acid / monoethanolamine ad pH 3.5 ad pH 3.8 ad pH 4.2 ad pH 3.9 ad pH 3.6 ad pH 4.1 water ad 100 g ad 100 g ad 100 g ad 100 g ad 100 g ad 100 g component B7 B8 B9 B10 4-hydroxy-2-methoxybenzaldehyde 9.5 mmol 10 mmol 3 mmol 2 mmol 3,4-dihydroxy-5-methoxybenzaldehyde 0.5 mmol - - - 1,2-dihydro-1,5-dimethyl-4-formyl-2-phenyl-3H-pyrazol-2-one - - 7 mmol - 2,4-dimethoxy-benzaldehyde - - - 8 mmol Aerosil ^® 200 0.06 0.09 0.08 - glycerol - - - 7.0 component B11 B12 B13 4-hydroxy-2-methoxybenzaldehyde 2.25 mmol 1.75 mmol 15 mmol 3,4-dihydroxy-5-methoxybenzaldehyde 0.25 mmol 0.25 mmol - 1,2-dihydro-1,5-dimethyl-4-formyl-2-phenyl-3H-pyrazol-2-one 7.5 mmol - - 2,4-dimethoxy-benzaldehyde - 8 mmol - Hydrenol ^® D - 1.6 2.8 Lorol® ^® tech. - 1.7 - Eumulgin ^® B2 - 0.5 1.6 Texapon.RTM ^® NSO 1.5 - 2.0 Dehyton ^® K 1.0 2.0 - Plantacare ^® 2000 UP - 1.0 2.0 Sident 22 S ^® 2.4 - 0.5 Antil 171 ^® - 0.5 - Aerosil ^® 200 - - - Solubilisant ^® LRI 1.9 2.5 1.2 Tween ^® 80 - - 2.5 propylene carbonate 3.5 1.5 4.0 glycerol - - - Phosphoric acid / monoethanolamine ad pH 4.3 ad pH 3.7 ad pH 4.0 water ad 100 g ad 100 g ad 100 g component B14 B15 B16 B17 B18 B19 B20 4-hydroxy-2-methoxybenzaldehyde - - 0.5 mmol 1 mmol 2 mmol 3.8 mmol 2 mmol 3,4-dihydroxy-5-methoxybenzaldehyde 15 mmol 10 mmol 9.5 mmol 12 mmol 8 mmol 11.2 mmol 10 mmol 1,2-dihydro-1,5-dimethyl-4-formyl-2-phenyl-3H-pyrazol-2-one - - - 2 mmol - - - 2,4-dimethoxy-benzaldehyde - - - - 2 mmol - - Hydrenol ^® D - 4.0 - - - - - Lorol® ^® tech. - 0.2 - - - - - Eumulgin ^® B2 - 3.1 - - - - - Texapon.RTM ^® NSO - 3.5 - - - - - Dehyton ^® K - - 4.8 - - - - Plantacare ^® 2000 UP - - - - - - - Sident 22 S ^® - - 2.3 - - - - Aerosil ^® 200 0.10 - - 0.11 - 0.12 0.08 Solubilisant ^® LRI - 7.0 1.1 - - - - propylene carbonate - - 5.0 - 11 - - Phosphoric acid / monoethanolamine - ad pH 4.2 ad pH 3.5 - - - - water - ad 100 g ad 100 g - - - -

1.2.1 Preparation of the cream formulations B1, B2, B4, B5, B12, B13 and B15

Lorol ^®, Eumulgin ^® B2 and / or Hydrenol D ^® were melted together at 80 ° C. In this melt, the necessary for the individual formulations proportions of the components Texapon ^® NSO, Dehyton ^® K and / or Plantacare ^® 2000 UP were incorporated.

4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 1,2-dihydro-1,5-dimethyl-4-formyl-2-phenyl-3H-pyrazol-2-one and / or 2, 4-Dimethoxybenzaldehyde were dissolved in propylene carbonate and / or glycerin carbonate with 80 to 90 ° C hot water and added with stirring. After cooling, the remaining formulation ingredients, such as Solubilisant ^® LRI, Tween ^® 20 and / or Tween ^® 80 were added. Then ident ^® were given 22 S and / or Antil ^® 171 with further stirring slowly added. The Quelivorgang was awaited. By adding phosphoric acid or monoethanolamine, the pH stated for the particular formulation was set. Finally, it was filled with warm water to 100 g.

1.2.2 Preparation of gel formulations B3, B6, B11 and B16

4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 1,2-dihydro-1,5-dimethyl-4-formyl-2-phenyl-3H-pyrazol-2-one and / or 2, 4-Dimethoxybenzaldehyde were dissolved in 70 g of 80 to 90 ° C hot water, propylene carbonate and / or glycerol carbonate with stirring, then the necessary for the individual formulations proportions of the components Texapon ^® NSO, Dehyton ^® K and / or Plantacare ^® 2000 UP were added. During the cooling, the previously pre-swollen means ^® Sident 22 S and / or Antil ^® 171 was added with continued stirring. The source process was awaited. Finally, by adding phosphoric acid or monoethanolamine, the pH stated for the particular formulation was established and made up to 100 g with cold water. 1.2.3 Preparation of the agent C containing an alkalizing agent medium component C1 20% monoethanolamine solution C2 Concentrated ammonia solution in water C3 10% sodium hydroxide solution C4 10% arginine solution C5 10% potassium hydroxide solution component C6 C7 C8 Hydrenol ^® D 3.4 1.8 - Lorol® ^® tech. 0.8 0.3 - Eumulgin ^® B2 1.6 0.9 - Texapon.RTM ^® NSO 1.9 1.2 - Dehyton ^® K 2.4 - 1.8 Plantacare® ^® 2000 - 4.2 3.7 Sident 22 S ^® - 0.5 0.8 Antil 171 ^® - 0.7 2.0 Solubilisant ^® LRI 2.6 4.5 3.8 Tween ^® 20 1.2 - - Monoethanolamine ad pH 9.4 ad pH 8.7 ad pH 10.2 water ad 100 ad 100 ad 100

1.2.4 Preparation of alkaline cream formulations C6 and C7

Lorol ^®, Eumulgin ^® B2 and / or Hydrenol D ^® were melted together at 80 ° C. In this melt, the necessary for the individual formulations proportions of components Texapon ^® NSO, Dehyton ^® K and / or Plantacare® ^® 2000 UP incorporated. After cooling, the remaining formulation ingredients Solubilisant ^® LRI and / or Tween ^® 20 were added. Then ident ^® were given 22 S and / or Antil ^® 171 with further stirring slowly added. The source process was awaited. By adding monoethanolamine, the pH stated for the particular formulation was set. Finally, it was filled with warm water to 100 g.

1.2.5 Preparation of the alkaline gel formulation C8

Texapon ^® NSO, Dehyton ^® K and / or Plantacare ^® 2000 UP, Solubilisant ^® LRI were gellst in 70 g of 80 to 90 ° C hot water while stirring. During the cooling, the previously pre-swollen means ^® Sident 22 S and / or Antil ^® 171 was added with continued stirring. The Quelivorgang was awaited. Finally, the pH was adjusted by adding monoethanolamine and made up to 100 g with warm water. 1.3 Composition of funds E component E1 E2 E3 E4 propylene carbonate 5.0 - 10 - glycerol - 5.0 - 10

1.4 List of used commercial products

• Aerosil ^® 200 silica (INCI name: Silica) (Degussa)
• Antil ^® 171 polyol fatty acid ester (INCI name: PEG-18 Glyceryl Oleate / Cocoate) (Goldschmidt)
• Dehyton ^® CN, N-dimethyl-N- (C8-18-cocamidopropyl) ammoniumaceto betaine (30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)
• Eumulgin ^® B2 Cetylstearylalkohol with about 20 EO units (INCI name: Ceteareth-20) (Cognis)
• Hydrenol ^® DC _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)
• Lorol® ^® tech. C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis)
• Plantacare ^® 2000 UP C _8-16 Alkylglucoside (about 51-55% active ingredient content in water, INCI name: Decyl Glucoside, Aqua (Water)) (Cognis)
• Sident ^® 22 S hydrated silicic acid (INCI name: Hydrated Silica) (Evonik)
• Solubilisant ^® LRI about 9.5 to 10.5 wt .-% water content; INCI name: PPG-26-Buteth-26, PEG-40 Hydrogenated Castor Oil (Sensient Cosmetic Technologies)
• Texapon ^® NSO lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)
• Tween ^® 20 ethoxylated sorbitan monolaurate (about 2.5-3 wt .-% water content; INCI name: Polysorbate-20) (Croda)
• Tween ^® 80 sorbitan monooleate with about 20 EO units (max 3 wt .-% of water; INCI name:. Polysorbate 80) (Croda)

2 colorations

to Production of the ready-to-use staining mixture of the shades 7-9, 12, 25-31, 43 and 44 were the means (A) and (B) intimately mixed in a weight ratio of 1: 1. Directly then, as much of the preparation (C) was added, until the u. G. Nuance table indicated pH of the mixture was achieved.

to Production of the ready-to-use staining mixture of the shades 1-5, 10, 38 and 39 became the agent (A), present in Powder form and / or powder compressed as a ball, to the middle (B) quantitatively converted to the agent (E) if necessary additionally added and afterwards intimately mixed. Immediately after that, so much of the Preparation (C) added until the u. G. nuances table specified pH of the mixture was reached.

to Production of the ready-to-use staining mixture of the shades 13-21 and 42 became the agent (B), present in powder form and / or powder pressed together as a sphere, converted quantitatively into the mean (A), the agent (E) was optionally added in addition, and then intimately mixed. Immediately afterwards So much of the preparation (C) was added until the in the u. G. Nuance table specified pH of the mixture achieved has been.

to Production of the ready-to-use dye mixture, the nuances 6 and 11, were the agent (A), present as a liquid drop, quantitatively converted to the agent (B) and then intimately mixed. Immediately after that, so much of the Preparation (C) added until the u. G. nuances table specified pH of the mixture was reached.

to Production of the ready-to-use dye mixture, the nuances 22-24, were the agent (B), present as a drop of liquid, quantitatively converted to the agent (A) and then intimately mixed. Immediately after that, so much of the Preparation (C) added until the u. G. nuances table specified pH of the mixture was reached.

to Production of the ready-to-use dye mixture, the nuances 32-34, 37 and 40, were the agent (A), present in Powdered and / or compressed as a ball powder together with the agent (B), also present in powder form and / or as a ball compressed powder, quantitatively converted to the middle (C) and then intimately mixed. Possibly. was added the remedy (E) was added. After intimate mixing provides the in the u. G. Nuance table indicated pH of the mixture one.

to Production of the ready-to-use staining mixture of the shades 35, 36 and 41 were the agent (A), present in powder form and / or as a liquid drop, together with the agent (B), too present in powder form and / or as liquid drops, quantitatively converted to the agent (C). After more intimate Mixing arises in the u. G. Table given pH the mixture.

All ready-to-use colorants were applied in a ratio of 3 g of color mixture to 1 g of hair (Kerling natural white). After a contact time of 30 minutes at 32 ° C, the strands were rinsed with lukewarm water and then dried in a warm air stream (30 to 40 ° C). The stains were visually assessed under a daylight lamp. 2.1 Combinations for the production of nuances (nuance table) Nuances no. combined formulation Ausfärbe pH colour Nuance 1 A1 + B1 + C1 7.5 medium brown Nuance 2 A2 + B2 + C3 + E1 8.2 dark brown Nuance 3 A5 + B3 + C2 9.0 black-brown Nuance 4 A6 + B3 + C4 + E2 7.9 dark brown Nuance 5 A3 + B4 + C5 8.5 black-brown Nuance 6 A4 + B4 + C2 9.2 dark brown Nuance 7 A7 + B4 + C1 7.4 medium brown Nuance 8 A7 + B5 + C4 8.8 medium brown Nuance 9 A8 + B5 + C3 7.7 tan Nuance 10 A3 + B6 + C5 8.0 black-brown Nuance 11 A4 + B6 + C4 8.4 medium brown Nuance 12 A7 + B6 + C1 7.8 tan Nuance 13 A13 + B7 + C2 7.6 dark wine red Nuance 14 A14 + B7 + C4 8.1 Dark red Nuance 15 A12 + B7 + C1 7.8 Red orange Nuance 16 A13 + B8 + C5 + E3 8.6 Dark red Nuance 17 A14 + B8 + C3 + E4 9.0 red Nuance 18 A10 + B8 + C4 + E1 7.5 Red orange Nuance 19 A13 + B9 + C2 8.3 Orange red Nuance 20 A14 + B9 + C5 7.9 copper Nuance 21 A9 + B9 + C1 7.4 copper Orange Nuance 22 A13 + B10 + C3 8.0 Orange red Nuance 23 A14 + B10 + C4 8.7 copper Nuance 24 A9 + B10 + C2 7.8 copper Orange Nuance 25 A13 + B11 + C5 8.2 red copper Nuance 26 A14 + B11 + C3 7.7 orange copper Nuance 27 A13 + B12 + C1 8.3 red copper Nuance 28 A14 + B12 + C4 7.0 orange copper Nuance 29 A13 + B13 + C2 8.1 Dark red Nuance 30 A10 + B13 + C5 9.0 Red orange Nuance 31 A11 + B13 + C1 8.4 dark wine red Nuance 32 A15 + B14 + C8 8.0 black Nuance 33 A15 + B17 + C6 7.5 black Nuance 34 A16 + B19 + C8 8.2 black Nuance 35 A17 + B18 + C7 7.8 black Nuance 36 A18 + B20 + C8 8.5 black Nuance 37 A19 + B14 + C6 7.6 black Nuance 38 A19 + B15 + C2 8.3 Black Blue Nuance 39 A19 + B16 + C5 7.4 violet Nuance 40 A19 + B17 + C8 + E2 8.6 black Nuance 41 A19 + B18 + C7 7.7 black Nuance 42 A20 + B14 + C1 8.1 black Nuance 43 A20 + B15 + C3 7.9 Black Blue Nuance 44 A20 + B16 + C4 8.4 violet

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

• - EP 998908 A2 [0165]
• WO 91/02047 A [0232]

Cited non-patent literature

• - European Pharmacopoeia 1997, 3rd edition, ISBN 3-7692-2186-9, "2.9.8 breaking strength of tablets"; Page 143-144 with a tablet hardness tester Schleuniger 6D [0242]

Claims (15)

Agent for coloring keratinic fibers, in particular human hair, containing at least one CH-acidic compound and at least one reactive carbonyl compound, characterized in that it also contains at least one solubilizer selected from (a) the compounds which have at least one C ₄ - C ₂₂ alkyl chain bearing at least one hydroxyl group etherified with ethylene oxide and / or propylene oxide units, wherein the total number of ethylene oxide and propylene oxide units in the molecule is greater than 20, and (b) the cyclic organic carbonates , Composition according to claim 1, characterized in that it comprises as solubilizer at least one compound which has at least one C ₄ -C ₂₂ -alkyl chain which carries at least one hydroxyl group which is etherified with ethylene oxide and / or propylene oxide units, the total number of ethylene oxide and propylene oxide units in the molecule is greater than 20, and contains at least one cyclic organic carbonate. Composition according to one of claims 1 or 2, characterized in that the at least one compound having at least one C ₄ -C ₂₂ alkyl chain carrying at least one hydroxyl group which is etherified with ethylene oxide and / or propylene oxide units, wherein the total number of ethylene oxide and propylene oxide units in the molecule is greater than 20, selected from (a1) the addition products of 21 to 100 ethylene oxide units to optionally cured mono-, di- and triglycerides of C _8-22 fatty acids, ( a2) the addition products of 21 to 60 ethylene oxide units of C _{8-22 fatty} alcohols, (a3) the addition products of 2 to 50 ethylene oxide units and 2 to 35 propylene oxide units of C ₄ -C ₂₂ alkanols. Composition according to Claim 3, characterized in that the adduct of 21 to 100 ethylene oxide units is optionally selected from monohydric mono-, di- and triglycerides of C _8-22 fatty acids selected from ethoxylated castor oil, olive oil ethoxylate, almond oil ethoxylate, mink oil ethoxylate, polyoxyethylene glycol caprylic / capric acid glycerides, polyoxyethylene glycerol monolaurate and polyoxyethylene glycol coconut fatty acid glycerides. Composition according to claim 3, characterized in that the adduct of 21 to 60 ethylene oxide units of C _8-22 fatty alcohols is selected from laureth-23, ceteareth-30, steareth-30 and steareth-40. Composition according to claim 3, characterized in that the adduct of 2 to 50 ethylene oxide units and 2 to 35 propylene oxide units of C ₄ -C ₂₀ alkanols is selected from PPG-28-buteth-35, PPG-26-buteth-26 , PPG-25-buteth-25, PPG-5-buteth-20, PPG-33-buteth-45, PPG-20-buteth-30 or PPG-12-buteth-16, PPG-5-ceteth-20. Agent according to one of claims 1 to 6, characterized in that the cyclic carbonate is selected is made of ethylene carbonate, propylene carbonate and glycerol carbonate. Agent according to one of claims 1 to 7, characterized in that the CH-acidic compound is selected from compounds of formula (CH-1) and / or compounds of formula (CH-2),

wherein - R ⁶ represents 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 is} N- (CH ₂ ) _m -, wherein R ^I and R ^II independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -Al kylgruppe, 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 can 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 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 which ring structures may carry additional substituents, - Het represents an optionally substituted heteroaromatic and - X ¹ represents a direct bond or a carbonyl group. Means according to claim 8, characterized in that the CH-acidic compound is selected from physiological compatible salts of 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium, of 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium and 2- (cyanomethyl) benzimidazole. Agent according to one of claims 1 to 9, characterized in that the reactive carbonyl compound is selected is from 4-hydroxy-2-methoxybenzaldehyde, 2-chloro-3,4-dihydroxybenzaldehyde, 2-bromo-3,4-dihydroxybenzaldehyde, 3,4-Dihydroxy-5-methoxybenzaldehyde, 2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazole-4-carboxaldehyde and 2,4-dimethoxybenzaldehyde. Kit for coloring keratinous fibers, comprising at least - an agent (A) containing at least one CH-acidic compound, - an agent (B) containing at least one reactive carbonyl compound, and - an agent (C) containing at least one alkalizing agent, wherein at least one of the agents (A), (B) or (C) at least one solubilizer selected from (a3) the compounds having at least one C ₄ -C ₂₂ alkyl chain carrying at least one hydroxy group, which with ethylene oxide and etherified or propylene oxide units, wherein the total number of ethylene oxide and propylene oxide units in the molecule is greater than 20, and (a4) the cyclic organic carbonates. contains. Kit for coloring keratinous fibers, comprising at least: - an agent (F) which is in powder form, granulated or solid state, containing at least one CH-acidic compound and at least one reactive carbonyl compound, and - a liquid agent (G) containing at least one Alkalizing agent and at least one solubilizer selected from (a1) the compounds having at least one C ₄ -C ₂₂ alkyl chain carrying at least one hydroxyl group etherified with ethylene oxide and / or propylene oxide units, wherein the total number of ethylene oxide and propylene oxide units in the molecule is greater than 20, and (a2) the cyclic organic carbonates. Process for dyeing keratin-containing Fibers, in particular human hair, characterized in that an agent according to one of claims 1 to 10 is applied to keratin-containing fiber applied, 5 to 60 minutes on the fiber left and then rinsed again or washed out with a shampoo. Process for dyeing keratin-containing Fibers, in particular human hair, characterized that the components of the kit according to one of the claims 11 or 12 are mixed together immediately before use, and the resulting application formulation to the keratin-containing fiber applied, left on the fiber for 5 to 60 minutes and then blasted rinsed out again or washed out with a shampoo. Method according to one of claims 13 or 14, characterized in that the preparation based on the fibers is applied, has a pH of 7 to 10.