DE10315421A1 - Powerful oxidative hair treatment agents with fiber structure stabilization through radical scavengers - Google Patents

Abstract

The present invention relates to agents for the oxidative treatment of keratin-containing fibers which contain hydrogen peroxide and at least one radical scavenger with a diffusion constant of less than 10 · -14 · m · 2 · / s, and to a process for the oxidative hair treatment of fibers containing keratin with this agent and the use thereof the corresponding means for stabilizing the fiber structure in oxidative processes.

Description

The present invention relates to agents for oxidative hair treatment of keratin-containing fibers which contain hydrogen peroxide and at least one radical scavenger with a diffusion constant of less than 10 ^-14 m ² / s, as well as a method for lightening or bleaching keratin-containing fibers with this agent and the use of the corresponding Means for stabilizing the fiber structure in oxidative processes.

Human Hair is becoming more diverse today Treated with hair cosmetic preparations. These include, for example cleaning the hair with shampoos, care and regeneration with douches and cures as well as bleaching, dyeing and shaping the hair with colorants, Tints, Corrugating agents and styling preparations. Thereby, means to change play or nuance of the color of the scalp hair plays a prominent role.

For permanent, intense colors So-called oxidation dyes are used with appropriate fastness properties 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 with each other or with coupling with one or more coupler components the actual dyes. The oxidation colorants are characterized by excellent, long-lasting dyeing results out.

Further become common lightening procedures, the so-called bleaching procedures. The basics of the bleaching process are known to the person skilled in the art and in relevant Monographs, e.g. by K. Schrader, basics and recipes of the Cosmetics, 2nd edition, 1989, Dr. Alfred Hüthig Verlag, Heidelberg, or W. Umbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, described in summary.

To the Lightening or bleaching of human hair - especially for highlighting - are usually solid or pasty Preparations with solid oxidizing agents immediately before use with a diluted one hydrogen peroxide solution mixed. This mixture is then applied to the hair and rinsed out after a certain exposure time.

All listed Unless otherwise stated, quantities refer exclusively to these Application mixtures.

It is known that during the Lightening or bleaching of cellulose fibers with hydrogen peroxide Free radicals for bleaching effects are responsible (W. Schlenker, Textile Chemist and Colorist, 1996, Vol. 29, No. 12, pages 23-28). This model let yourself easily transferred to keratin fibers. The conventional ready-to-use bleaching agent for keratin fibers in addition to hydrogen peroxide mostly peroxodisulfate compounds to increase the brightening power. As is known in the chemical reaction of peroxodisulfate compounds with hydrogen peroxide free radicals, for example the hydroperoxide radical or the Hydroxyl radical, generated (M.-S. Tsao, W. K. Wilmarth, Adv. Chem. Ser., 1962, 36, pages 113-122).

The Keratin-containing fiber, especially human hair from an outer covering (cuticle). This consists of an approximately six to ten-layer arrangement flaky and overlapping Cuticular cells together. The scales are by one another multi-component membrane complex, the so-called Cement, glue and protect the fiber interior effectively against environmental influences. Spindle-shaped cells the fiber interior is formed by a composite system of markrofibrils and cement (Cortex). The hair dye sits between this composite system Pigment granules containing melanin (from: K. Schrader, Fundamentals and formulations of cosmetics, 2nd verb. u. ext. Ed., Hüthig, Heidelberg, 1989).

There the natural Hair dye predominantly located in the cortex the bleaching agents for effective bleaching your effect inside the hair unfold. For this it is necessary to remove the bleaching active species through the To transport the cuticle into the cortex. The degeneration the fiber structure, in particular the structure of the cuticle but also promoted by the bleaching active species.

In the worst case, the keratin-containing fiber, in particular human hair, can partially lose the protective cuticle, as a result of which the exposed inner fiber structure is exposed to environmental influences, such as mechanical effects due to friction, for example when combing. These environmental influences can cause further degeneration of the fiber until fiber breakage or fiber tearing. The presence of free radicals in the cuticle is therefore undesirable. Since hydrogen peroxide is also used as an oxidizing agent for the oxidative dyeing of keratin fibers, the technical teaching can be transferred to this dyeing method.

task The present invention is therefore the degeneration of the fiber structure, especially the cuticle, while to minimize the bleaching process without the lightening power of the bleaching agent, especially in the cortex.

It has now surprisingly been found that during the oxidative hair treatment with agents containing hydrogen peroxide, the fiber structure, in particular in the region of the cuticle, is stabilized if the agent additionally contains at least one radical scavenger with a diffusion constant of less than 10 ^-14 m ² / s. Remarkably, the addition of these special radical scavengers does not restrict the brightening performance of the bleaching agent, or does not significantly limit it.

A first subject of the present invention is therefore an agent for the oxidative treatment of keratin fibers, in particular human hair, containing hydrogen peroxide and at least one radical scavenger with a diffusion constant of less than 10 ^-14 m ² / s, preferably less than 10 ^-15 m ² / s ,

Under Fibers, wool, feathers and especially understood human hair.

The bleaching agents according to the invention contain hydrogen peroxide as the first important component. According to the invention, the hydrogen peroxide is used as a solution or in the form of a solid addition compound of hydrogen peroxide onto inorganic or organic compounds, such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone.n H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine.

The Hydrogen peroxide or its addition products are preferred in 0.1-12% by weight, particularly preferably in 1-6% by weight, in each case based on the weight of the bleaching agent.

mit:
M_t= Absorbierte Menge zum Zeitpunkt t
M_∞= Absorbierte Menge im Gleichgewicht
r= Zylinderradius für das europäische Haar von 35 μm
berechnet.The diffusion constant of the radical scavengers is determined experimentally via the absorption (sorption) of the radical scavengers into the fiber. The diffusion constant D is preferably according to the invention from the experimentally determined data on the approximation of diffusion in cylindrical bodies (JP Forestier, International Journal of Cosmetic Science, 1982, 4, pages 153-174):

With:
M _t = amount absorbed at time t
M _∞ = absorbed amount in equilibrium
r = cylinder radius for European hair of 35 μm
calculated.

10 mL of a 0.01-0.1 molar solution of the substance to be examined (solvent: water / ethanol mixture in a volume ratio of 3: 1) are added to a strand of hair of 1 g weight in a 50 mL screw cap glass (time t = 0). The pH of the solution was previously adjusted to the required pH with ammonia or tartaric acid. The substance diffuses into the hair with constant gentle movement (100 running revolutions per minute) on a shaker (Retsch). At least 5 different time intervals, samples of 10 μL each are taken and, after appropriate dilution, the residual amount of substance M _{t is determined} at a suitable time using a suitable quantitative analysis method (for example HPLC or quantitative thin-layer chromatography). The amount absorbed in equilibrium M _∞ is determined after 10 hours. The plot of M _t / M _∞ against t ^1/2 provides the diffusion coefficient from the slope of the straight line after linear regression.

The Diffusion constant of the radical scavenger according to the invention preferably at the pH of the ready-to-use agent according to the invention determined at room temperature. This preferred pH is between pH 4.5 and 12, particularly preferably between pH 6.5 and 12, entirely particularly preferably between pH 7 and 12.

Ionian radical scavengers preferred according to the invention a molecular weight greater than 200 g / mol, nonionic radical scavenger on the other hand have a preferred molar mass of greater than 300 g / mol, particularly preferred larger than 400 g / mol.

The Molar mass of radical scavengers is generally preferably less than 1000 g / mol with the exception of Molar mass of radical scavengers protein-based. This is preferably less than 2000 g / mol.

The are radical scavengers according to the invention preferably hydroxyl radical scavenger.

The radical scavengers are in the agents according to the invention preferably in an amount of 0.05-10% by weight, particularly preferably in an amount of 0.5-5% by weight, each based on the weight of the agent according to the invention, contain.

The radical scavengers used in the agents according to the invention are preferably selected from oligopeptides, polypeptides, keratan sulfate, cellulose and derivatives thereof, chitosan and derivatives thereof, hyaluronic acid and derivatives thereof, heparin and derivatives thereof, starch and derivatives thereof, cationic compounds, aromatic compounds, sulfur-containing compounds , Vitamins, flavone derivatives, tannins, terpenes, DNA, C ₆ -C ₁₂ -α, ω-oligocarboxylic acids, C ₈ -C ₂₂ alkylphosphonic acids, ketones and aldehydes and the physiologically tolerable salts of the aforementioned compounds.

In a further embodiment of the agent according to the invention become the radical scavengers based on oligopeptides or polypeptides selected from Carnosine, anserine, alcohol dehydrogenase, aldolase, carboxypeptidase A, Rennin, GlycerylGlycerylGlycerylGlycin, Glycylphenylalanin, Lysine-Vasopressin, Lysozyme, phenylalanine, rennin, serum albumin, papain, typinogen, Ribonuclease, polyalanine, polyserine, gelatin, elastin, collagen, Keratin, milk protein, Soy protein, almond protein and wheat protein as well as the hydrolyzate of these proteins including their condensation products with fatty acids as well quaternized protein hydrolyzates as well as the physiologically acceptable ones Salts of the aforementioned compounds.

Preferred protein hydrolyzates are highly degraded keratin hydrolyzates (molecular weights in the range from 400 to 800). Furthermore, quaternized protein hydrolysates, such as those under the trade names Gluadin® ^® WQ are sold, according to the invention particularly preferably (INCI name: Laurdimonium hydroxypropyl hydrolyzed wheat protein) and crotein ^® Q (hydroxypropyltrimonium Hydrolyzed Collagen INCI name).

In a further embodiment of the agent according to the invention the cellulose derivatives are selected from cellulose, microcrystalline Cellulose, cellulose acetopropionate, cellulose acetobutyrate, cellulose acetate, Cellulose xanthate, (2-carboxyethyl) cellulose, carboxymethyl cellulose, (2-hydroxyethyl) cellulose, dextran and hexadecyl (2-hydroxyethyl) cellulose as well as the physiologically tolerable Salts of these compounds.

In a further embodiment of the agent according to the invention become the radical scavengers based on chitosan derivatives selected from succinylchitosan, chitosan-2-hydroxyethyl ether and chitosonium pyrrolidone carboxylate.

In a further embodiment of the agent according to the invention, the free radical scavengers are selected on the basis of starch derivatives from corn starch, hydrolyzed corn starch, rice starch, hydrolyzed rice starch, wheat starch, hydrolyzed wheat starch, potato starch, hydrolyzed potato starch, soybean starch, hydrolyzed soybean starch and the hydroxy-C ₂ -C ₄ - alkyl, 2-hydroxy-3-trimethylammonio-propyl, diethylaminoethyl ether, 2-hydroxy-3-dimethyllaurylammonio-propyl, carboxymethyl, C ₂ -C ₂₀ acyl derivatives of the aforementioned starch derivatives and the physiologically tolerable salts of these compounds ,

In a further embodiment of the agent according to the invention become the radical scavengers based on cationic compounds selected from cationic surfactants and cationic polymers.

In this embodiment, the cationic surfactants are preferably selected from cationic surfactants of the quaternary ammonium compound, esterquat and amidoamine type. Preferred quaternary ammonium compounds are am monium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• – polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Acrylsäure sowie Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)), Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) und Merquat^® 280 (Dimethyldiallylammoniumchlorid-Acrylsäure-Copolymer im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• – Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• – quaternierter Polyvinylalkohol sowie die unter den Bezeichnungen
• – Onamer^® M (Polyquaternium-1)
• – Mirapol^® A15 (Polyquaternium 2),
• – Polyquaternium 17,
• – Polyquaternium 18 und
• – Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

The cationic polymers are preferably selected from polymers which contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.
• - polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)), Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer commercially available products are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol and those under the names
• - Onamer ^® M (Polyquaternium-1)
• - Mirapol ^® A15 (Polyquaternium 2),
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

In a further embodiment of the agent according to the invention become the radical scavengers based on aromatic compounds selected from acetophenone and its Derivatives, benzophenone and its derivatives, benzoquinone and its Derivatives, biphenyl and its derivatives, p-aminobenzoic acid and their Derivatives, anthranilic acid and their derivatives, aniline derivatives, N, N-dimethylacetamine, anisole derivatives, benzoic acid and their derivatives, terephthalic acid and their derivatives, salicilic acid and their derivatives, salicylaldehyde, methyl gallate, propyl gallate, Octyl gallate, dodecyl gallate, 1,2,4-trimethoxybenzene, 1,3,5-trimethoxybenzene, 3,4-dihydroxy-cinnamic acid and their derivatives, p-toluenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, sulfanilic acid, 4,5-dihydroxy-2,7-naphthalenedisulfonic acid, 1-naphthylacetic acid, 1-naphthylcarboxylic acid, 2-naphthylcarboxylic acid, luminol, 3-indoleacetic acid, 5-indolylacetic acid, 3-indolylpropionic acid, 1-methylindole, 2-methylindole, 3-methylindole, 2,2-dimethyl-1-phenyl-1-propanol, 2-methyl-1-phenyl-1-propanol, 2-methyl-1-phenyl-2-propanol, 3-pyridine caboxamide, 4-pyridinecarboxamide, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, 2,4,6-trimethyl-3-hydroxypyridine, 4-ethyl-5-hydroxy-2-methylpyridine, nicotinamide, pyridoxine, rhodamine B, xylenol orange, hemoglobin, hemin, Diphenylamine and its derivatives, diphenyl acetate, eosin, fluorescin, 1- (2-hydroxyethyl) -2-methyl-5-nitroimidazole, 1- (2-hydroxyethyl-3-methoxypropyl) -2-nitroimidazole, urocanic acid, phenylacetic acid and their derivatives, phenylacetamide, purine, adenine, adenosine, and the physiologically acceptable Salts of these compounds.

In a further embodiment of the agent according to the invention, the radical scavengers based on sulfur-containing compounds are selected from penicillin derivatives, glutathione in the oxidized form, cystamine in the oxidized form, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, hepta-thionine sulfoxi min, dilauryl thiodipropionate, distearyl thiodipropionate, di-tert-butyl disulfide, and the ester, ether, sugar, peptide, lipid derivatives and the physiologically acceptable salts of all these compounds.

In a further embodiment of the agent according to the invention become the radical scavengers based on aldehydes or ketones selected from uracil, dihydrouracil, Thymine, thymidine, guanine, 5,6-dihydroguanine, guanylic acid, guanosine, Cytidine, cytosine, xanthine and their dinucleotides, oligonucleotides or polynucleotides, polyvinylpyrrolidone, folic acid and its derivatives, rutinic acid and their derivatives, bilirubin, biliverdin, plastcquinone, ubiquinone, Bovinon, Helveticon, 9,10-anthraquinone, 9,10-anthraquinone-1-sulfonic acid, 9,10-anthraquinone-2-sulfonic acid, as well the physiologically tolerable Salts of these compounds.

In a further embodiment of the agent according to the invention become the radical scavengers selected based on vitamins from retinol, retinal, 3,4-didehydroretinal, Vitamin B1, vitamin B2, vitamin B6, vitamin B9, biotin, pantothenic acid, vitamin D1, vitamin D3, α-tocopherol and its esters, vitamin K1, vitamin K2 and vitamin K3.

Examples of the C ₆ -C ₁₂ -α, ω-oligocarboxylic acids which can be used in the agent according to the invention are polylactic acid, poly-tartaric acid, azelaic acid and sebacic acid and the physiologically tolerable salts of the abovementioned compounds.

Examples of the C ₈ -C ₂₂ -alkylphosphonic acids which can be used in the agent according to the invention are the n-octylphosphonic acid and the n-decylphosphonic acid and the physiologically tolerable salts of the abovementioned compounds.

The The bleaching effect can be increased by so-called "bleach boosters". These are in the As a rule, solid peroxo compounds that do not form addition products Represent hydrogen peroxide on other components. The selection of those in the agents according to the invention Peroxo compounds contained are in principle not subject to any restrictions; usual, Peroxo compounds known to the person skilled in the art are, for example, ammonium peroxydisulfate, Potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, Potassium persulfate, sodium persulfate, potassium peroxide phosphate and peroxides like magnesium and barium peroxide. Among these peroxo compounds, According to the invention, the inorganic ones can also be used in combination Connections preferred. The peroxidisulfates are particularly preferred, especially ammonium peroxydisulfate.

The Peroxo compounds are preferred in the bleaching agents according to the invention in amounts of 1-40% by weight, in particular in amounts of 2-30% by weight, contain.

The agents according to the invention preferably contain additional at least one alkalizing agent. According to the the specialist for Bleaching agents known, usual Alkalizing agents such as ammonium, alkali metal and alkaline earth metal hydroxides, -carbonates, -hydrogencarbonates, -hydroxycarbonates, -carbamides, -silicates especially alkali metal silicates, and alkali phosphates used become.

Alkalizing agents which are very particularly preferred according to the invention are silicates which are formed from an aqueous solution of a silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ O) _p , where n stands for a positive rational number and m and p independently of one another for a positive rational number or for 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1.

Next the components described by the molecular formula can glasses of water other additives in small amounts, such as Phosphates or magnesium salts.

According to the invention particularly preferred water glasses are sold by the company. Henkel sold under the names Ferrosil® ^® 119, soda water glass 40/42, Portil ^® A, Portil ^® AW and Portil ^® W and by Akzo under the name Britesil® ^® C20.

The bleaching agents according to the invention contain alkalizing agents preferably in amounts of 0.5-25% by weight, in particular 1-10% by weight.

The agents according to the invention can additionally contain at least one surfactant, with both anionic and zwitterionic, ampholytic and nonionic being suitable in principle. In many cases, however, it has proven advantageous to use anionic, zwitterionic or nonionic surfactants Select surfactants.

• – lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030 ,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354 ,
• – Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344 ,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

Suitable anionic surfactants in agents according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Monosulfonic acid and dialkyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates with 12 to 18 carbon atoms,
• Linear alpha olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,
• - Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030 .
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23 354 .
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344 .
• - Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid ,

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(-) - or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl -3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C _8-18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C _{12- 18} acyl sarcosine.

• – Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C_12-22-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – C_8-22-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

• Addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,
• C _12-22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,
• C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,
• - adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,
• - Addition products of ethylene oxide with sorbitan fatty acid esters
• - Adducts of ethylene oxide with fatty acid alkanolamides.

at the compounds with alkyl groups used as surfactants they are all uniform substances. However, it is usually preferred in the manufacture of these substances from native vegetable or animal raw materials, so that one mixes substances with different alkyl chain lengths depending on the respective raw material.

at the surfactants, the adducts of ethylene and / or propylene oxide of fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood as mixtures of homologues that are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. On the other hand, narrow homolog distributions are obtained if, for example Hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates can be used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Farther can the agents according to the invention additionally a conditioning agent selected from the group of paraffin oils, vegetable oils and synthetic oils is formed.

Suitable conditioning agents are silicone oils, especially dialkyl and alkylarylsiloxanes, such as dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the products sold by Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 as well as the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxyl-amino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt ; diquaternary polydimethylsiloxanes, Quaternium-80).

Likewise Paraffin oils, synthetic, can be used as conditioning agents manufactured oligomeric alkenes as well as vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil.

Likewise suitable hair conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephaline.

The agents according to the invention can still contain plant extracts. Usually these extracts made by extracting the whole plant. But it can in individual cases also be preferred, the extracts exclusively from flowers and / or Scroll of the plant.

Regarding the usable according to the invention Plant extracts are particularly referred to the extracts, in the on page 44 of the 3rd edition of the guide to the ingredient declaration cosmetic products, published by the industry association and Detergent e.V. (IKW), Frankfurt.

According to the invention all the extracts from oak bark, nettle, witch hazel, hops, Chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, Aloe vera, spruce needles, horse chestnut, sandalwood, Juniper, coconut, Mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, Sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, Thyme, lemon balm, hake, coltsfoot, marshmallow, meristem, green tea, Ginseng and ginger root preferred.

Especially the extracts from oak bark, nettle, witch hazel, Hops, chamomile, burdock root, horsetail, linden flowers, almond, Aloe vera, coconut, Mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, Sage, rosemary, birch, cuckoo flower, quendel, yarrow, hake, Meristem, green Tea, ginseng and ginger root.

The extracts from almond, aloe vera, Coconut, mango, apricot, lime, wheat, kiwi, melon and green tea.

As Extracting agent for the production of the plant extracts mentioned can Water, alcohols and mixtures thereof can be used. Under the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as the sole extractant and as a mixture with Water, preferred. Plant extracts based on water / propylene glycol in relation to 1:10 to 10: 1 have proven to be particularly suitable.

The Plant extracts can according to the invention both in pure as well as in diluted Form are used. If they are used in diluted form, usually contain them approx. 2 - 80 % By weight of active substance and as a solvent the extractant or mixture of extractants used in their extraction.

Farther it may be preferred to use mixtures of the agents according to the invention several, in particular from two, different plant extracts use.

Likewise honey extracts are according to the invention. These extracts are analogous to the plant extracts won and usually contain 1 - 10 % By weight, in particular 3-5 % By weight, active substance. Water / propylene glycol mixtures can also preferred extractants here.

The agents according to the invention can additionally Mono-, di- and oligosaccharides such as glucose, inositol, Galactose, fructose, fructose, sucrose, cellobiose and lactose contain. Can continue also derivatives of these pentoses and hexoses, such as the corresponding ones On and uronic acids (Sugar acids) Sugar alcohols, sugar amines, such as N-glucosamine, N-acetylglucosamine, 2-amino-2-deoxy-D-galactose, β-benzylglucoside and glycosides, used according to the invention become. The sugar acids can according to the invention in free Form, in the form of their salts, preference is given to calcium, magnesium and zinc salts, and used in the form of their esters or lactones. preferred sugar acids are the gluconic acid, Gluconic acid-γ-lactone, lactobionic acid, the glucuronic and their mono- or dilactones, the pangamic acid, the Sugar acid, the mannosugaric acid and their mono respectively Dilactone as well as the mucic acid and their mono- or dilactones. Preferred sugar alcohols are sorbitol, mannitol and dulcitol.

Farther can α-hydroxycarboxylic acids and their salts in the agents according to the invention be used. Preferred according to the invention acids are lactic acid, malic acid, tartaric acid, glyceric acid and Maleic acid. lactic acid is particularly preferred.

Farther can lipid-soluble Ester alcohols or ester polyols in the agents according to the invention be included. As lipid soluble they can be viewed when 5% by weight of these products are in cetyl alcohol at 80 ° C dissolve clearly.

The more suitable according to the invention. Ester alcohols or ester polyols can be obtained by reacting one epoxyfatty with water or mono- or polyhydric alcohols with 1 - 10 carbon atoms under opening of the epoxy ring and formation of a vicinal dihydroxyethyl or Hydroxy-alkoxy-ethyl. The epoxy fatty acid ester can also be a Epoxidation product from a technical fatty acid ester with proportions of saturated fatty acids his. However, the epoxy oxygen content should be at least 3% by weight, preferably 5-10% by weight.

The epoxy fatty are either epoxidized fatty acid esters of monohydric alcohols, e.g. e.g. epoxidized oleic acid methyl ester, linoleic acid methyl ester, ricinoleic or epoxidized fatty acid esters polyhydric alcohols, e.g. Glycerol monooleate or propylene glycol monooleate or epoxidized fatty acid triglycerides, e.g. oleic acid triglyceride or unsaturated oils such as Olive oil, Soybean oil, Sunflower oil, linseed oil, rape oil.

Technically Unsaturated fatty acid methyl ester epoxides from unsaturated are particularly interesting Vegetable fatty acids. The ester polyol is the reaction product of a vegetable oil fatty acid methyl ester epoxidate with a polyol with 2-6 C atoms and 2 - 6 Hydroxyl groups are particularly preferred. Can be used as polyols e.g. Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butanediol, Pentanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol or Diglycerin may be included.

The conversion is particularly suitable for the bleaching agents according to the invention as the ester polyol Zung product of a Pflanzenfettsäuremethylester epoxidate with trimethylol propane with a hydroxyl number of 350 - 450. One such product based on Sojaölfettsäuremethylester epoxide and trimethylol propane is commercially available under the trade designation Sovermol ^® 760th

In a preferred embodiment of the present invention, the agents further contain a magnesium compound. The agents according to the invention can be further optimized with regard to their structure-preserving properties by adding the Mg ²⁺ cations. Preferred magnesium compounds are inorganic and organic Mg ²⁺ salts, such as, for example, the halides, the carbonates and hydrogen carbonates, the acetate and the citrate.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere und Polysiloxane,
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyltrimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• – Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z.B. Polyvinylalkohol,
• – Strukturanten wie Maleinsäure und Milchsäure,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsmittel und -vermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• – Entschäumer wie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• – Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Pigmente,
• – Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien.

Other active ingredients, auxiliaries and additives are, for example

• Non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers and polysiloxanes,
• - zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• - anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert.butyl acrylamide terpolymers,
• - Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, clays such as. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• - Quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• - defoamers like silicones,
• Dyes for coloring the agent,
• - anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol,
• Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,
• - cholesterol,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as walrus, beeswax, montan wax and paraffins,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• - opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,
• - pigments,
• - stabilizing agents for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

Regarding others optional components and the amounts of these components used expressly to the relevant manuals known to those skilled in the art, e.g. B. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

The bleaching agents according to the invention are preferred shortly before use on the fiber by mixing made of at least two components. For this purpose a component A containing at least one peroxo compound, with a hydrogen peroxide solution mixed as component B, at least one of the composition A or B, preferably composition A, contains the radical scavenger according to the invention.

The concentration of the hydrogen peroxide solution of component B is determined on the one hand by the legal requirements and on the other hand by the desired effect; usually 6- to 12-pro percent solutions used in water. The quantitative ratios of component A and component B are usually in the range from 1: 1 to 1: 2, an excess of component B being chosen in particular when no excessive bleaching effect is desired.

• – mindestens einen direktziehenden Farbstoff und/oder
• – mindestens ein Oxidationsfarbstoffvorprodukt vom Entwicklertyp (Entwicklerkomponente) sowie gegebenenfalls mindestens ein Oxidationsfarbstoffvorprodukt vom Kupplertyp (Kupplerkomponente).

If the bleaching agent according to the invention is used as a lightening colorant, it contains

• - at least one substantive dye and / or
• - At least one oxidation dye precursor of the developer type (developer component) and optionally at least one oxidation dye precursor of the coupler type (coupler component).

As Suitable direct dyes have been nitro dyes proved. According to the invention are under Nitro dyes the coloring Understand components that have at least one aromatic ring system, that carries at least one nitro group.

Especially preferred nitro dyes are HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, HC Violet 1 and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis- (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) -aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, picramic and their salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Next The nitro dyes are also the azo dyes, anthraquinones or synthetic naphthoquinones preferred according to the invention Dyes. Preferred substantive dyes of this type are for example Disperse Orange 3 Disperse Blue 3, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52 and 2-hydroxy-1,4-naphthoquinone.

• (i) kationische Triphenylmethanfarbstoffe,
• (ii) aromatische Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, und
• (iii) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist.

Furthermore, it can be preferred according to the invention if the synthetic direct dye carries a cationic group. Are particularly preferred

• (i) cationic triphenylmethane dyes,
• (ii) aromatic systems substituted with a quaternary nitrogen group, and
• (iii) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom.

Examples for dyes Class (i) are in particular Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14.

Examples for dyes Class (ii) are in particular Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17.

Examples of dyes of class (iii) are particularly in the EP-A2-998 908 , to which reference is expressly made at this point, is disclosed in claims 6 to 11.

Preferred cationic direct dyes of group (üi) are in particular the following compounds:

The Compounds of the formulas (DZ1), (DZ3) and (DZ5) are very special preferred cationic direct dyes of group (iii).

Farther can the agents according to the invention dyes occurring in nature, such as for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, Sedre and alkanna root are included.

The agents according to the invention contain the substantive dyes preferably in an amount from 0.01 to 20% by weight.

As Developer components are commonly used primary aromatic amines with another, in para or ortho position located, free or substituted hydroxyl or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

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 C₁- bis C₄-Mesylaminoalkoxyrest 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 can be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

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 radical (C ₁ to C ₄ ) alkyl, a 4'-aminophenyl group or a C ₁ to C ₄ alkyl group which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl group;
• 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 radical (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by 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, a C ₁ to C ₄ hydroxyalkoxy, a C ₁ to C ₄ acetylaminoalkoxy, a C ₁ to C ₄ mesylaminoalkoxy or a C ₁ to C ₄ carbamoylaminoalkoxy;
• - G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
• - If G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo group, such as an ethylenedioxy group.

Examples of the C ₁ to C ₄ alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C ₁ to C ₄ hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ -polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the amino groups, 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 ammonium.

Especially preferred p-phenylenediamines of the formula (E1) are selected from 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- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane as well as their physiologically compatible Salt.

According to the invention very particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

It can continue according to the invention be preferred to use compounds as developer components, that contain at least two aromatic nuclei that are 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 den Maßgaben, dass
• – die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• – die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

Among the binuclear developer components which can be used in the agents according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:

in which:

• Z ¹ and Z ² independently of one another represent 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 bridging Y. is or is possibly part of a bridging ring system,
• - The bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms and may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, 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, a C ₁ to C ₄ aminoalkyl radical or a direct connection 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 provisos that
• - The compounds of formula (E2) contain only one bridging Y per molecule and
• - The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-diethyl-N, N'-bis (4'-amino-3'-methylphenyl) ethylene diamine, 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 tolerable Salts.

All particularly preferred binuclear developer components of the formula (E2) are N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis- (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of their physiologically acceptable salts.

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-Alkylamino)-(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 can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as developer component. P-Aminophenol derivatives of the formula (E3) are particularly preferred

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 -monohy hydroxyalkyl 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, a hydroxy- (C ₁ - to C ₄ ) -alkylamino, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - to C ₄ -hydroxyalkyl- (C _{1 to} C ₄ ) -aminoalkyl or a (di-C ₁ to C ₄ -Alkylamino) - (C ₁ - to C ₄ ) -alkyl radical, and
• - G ¹⁴ represents a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C2 to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) Alkoxy (C ₁ to C ₄ ) alkyl, a C ₁ to C ₄ aminoalkyl or a C ₁ to C ₄ cyanoalkyl,
• G ¹⁵ represents 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 represents hydrogen or a halogen atom.

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

preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (☐-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 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- (diethylaminomethyl) phenol as well as their physiologically tolerable 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- (diethyl-aminomethyl) phenol.

Further 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 the developer component can be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, Pyrazole, pyrazole-pyrimidine derivatives and their physiologically tolerable Salt.

Preferred pyridine derivatives are especially the compounds described in the patents GB 1 026 978 and GB 1 153 196 are described, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-methoxyethyl) amino -3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are in particular the compounds described in the German patent DE 2 359 399 , the Japanese laid-open patent JP 02019576 A2 or in published patent application WO 96/15765, such as 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.

Preferred pyrazole derivatives are in particular the compounds described in the patents DE 3 843 892 . DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988 are described, such as 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- (☐-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4, 5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

wobei:

• – G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, 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-Hydroxyalkyl- 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-Hydroxyalkylrest, 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)-aminoalkylrest, 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 NG¹⁷G¹⁸ und NG¹⁹G²⁰ 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 NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) 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 pyrazolo [1,5-a] pyrimidine of the following formula (E4) and its tautomeric forms, provided there is a tautomeric equilibrium:

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -Polyhydroxyalkylrest a (C ₁ - to C ₄ ) -alkoxy- (C ₁ - to C ₄ ) -alkyl residue, a C ₁ - to C ₄ -aminoalkyl residue, optionally protected by an acetyl-ureide or a sulfonyl residue can be 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 with 5 or 6 chain links, a C ₁ - to C ₄ -hydroxyalkyl- 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 -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical , an amino radical, a C ₁ to C ₄ alkyl or di (C ₁ to C ₄ hydroxyalkyl) amino radical, 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 is 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);
• - if p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2,3); (5,6); (6,7); (3.5) or (3.7);

The Substituents used in formula (E4) are analogous according to the invention to the above statements Are defined.

If the pyrazolo [1,5-a] pyrimidine of the above formula (E4) contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, 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-Amino-pyrazolo[1,5-a]pyrimidin-7-ol;
• – 3-Amino-pyrazolo[1,5-a]pyrimidin-5-ol;
• – 2-(3-Amino-pyrazolo[1,5-a]pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Amino-pyrazolo[1,5-a]pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Amino-pyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 2-[(7-Amino-pyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• – 5,6-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,6-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethyl-pyrazolo[1,5-a]pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.Among the pyrazolo [1,5-a] pyrimidines of the above formula (E4) one can mention in particular:

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - 2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• - 2,7-dimethyl-pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• - 3-amino-pyrazolo [1,5-a] pyrimidin-7-ol;
• - 3-amino-pyrazolo [1,5-a] pyrimidin-5-ol;
• - 2- (3-amino-pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-amino-pyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;
• - 2 - [(7-Amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) 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-dimethyl-pyrazolo [1,5-a] pyrimidine;

as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.

The Pyrazolo [1,5-a] pyrimidines of the above formula (E4) can be as described in the literature by cyclization starting from one Aminopyrazole or be made by hydrazine.

As Such indoles are preferred as precursors of nature-analogous dyes and indolines are used which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring. These groups can carry further substituents, e.g. B. in the form of etherification or Esterification of the hydroxyl group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

in der unabhängig voneinander

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

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Derivatives of 5,6-dihydroxyindoline of the formula (Ia) as developer component are particularly suitable as precursors of naturally analogous hair dyes,

in the independently of each other

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

as well as physiologically tolerable salts of these compounds with an organic or inorganic acid.

Especially preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid as well as the 6-hydroxyindoline, the 6-aminoindoline and the 4-aminoindoline.

Especially within this group, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 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.Derivatives of 5,6-dihydroxyindole of the formula (Ib) are also outstandingly suitable as precursors of nature-analogous hair dyes,

in the independently of each other

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

as well as physiologically tolerable 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, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

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 in particular 5,6-dihydroxyindole.

The Indoline and indole derivatives can in the agents according to the invention both as free bases and in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. B. the hydrochloride, of sulfates and hydrobromides. The indole or Indoline derivatives are common in these in amounts of 0.05-10 % By weight, preferably 0.2-5% by weight.

In a further embodiment it can be preferred according to the invention be the indoline or Indole derivative in combination with at least one amino acid or to use an oligopeptide. The amino acid is advantageous an α-amino acid; all are particularly preferred α-amino acids Arginine, ornithine, lysine, serine and histidine, especially arginine.

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

• – m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6-methylphenol, 5-Amino-4-chlor-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)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• – o-Aminophenol und dessen Derivate,
• – m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxyethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol und 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol,
• – o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• – Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• – Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• – Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• – Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Aminobenzomorpholin,
• – Chinaxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• – Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• – Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder
• – Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)-amino-3,4-methylendioxybenzol.

Coupler components preferred according to the invention are

• - m-Aminophenol and its derivatives such as 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 and 2,4-dichloro- 3-aminophenol,
• O-aminophenol and its derivatives,
• - m-Diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 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 and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,
• O-diamino benzene and its derivatives such as 3,4-diamino benzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as, for example, resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 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 and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinaxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• - Pyrimidine derivatives, such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diami no-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

According to the invention particularly preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

On The second subject of the present extension is a method for oxidative treatment of keratin fibers, in which the keratin fibers Fiber with one of those described in the first subject of the invention agents according to the invention treated and the agent after an exposure time of 30-45 minutes rinsed out again becomes.

On third object of the present invention is the use the agents according to the invention described in the first subject of the invention for structural stabilization of keratin fibers in oxidative Processes.

Claims (19)

Agent for the oxidative treatment of keratin fibers, in particular human hair, containing hydrogen peroxide, characterized in that it further contains at least one radical scavenger with a diffusion constant of less than 10 ^-14 m ² / s. Agent according to claim 1, characterized in that the radical scavengers are hydroxyl radical scavengers. Agent according to one of claims 1 or 2, characterized in that the radical scavengers are selected from oligopeptides, polypeptides, keratan sulfate, cellulose and derivatives thereof, chitosan and derivatives thereof, hyaluronic acid and derivatives thereof, heparin and derivatives thereof, starch and derivatives thereof, cationic Compounds, aromatic compounds, sulfur-containing compounds, vitamins, flavone derivatives, tannins, terpenes, DNA, C ₆ -C ₁₂ -α, ω-oligocarboxylic acids, C ₈ -C ₂₂ alkylphosphonic acids, ketones and aldehydes and the physiologically tolerable salts of the aforementioned compounds. Agent according to claim 3, characterized in that the oligopeptides or polypeptides are selected from carnosine, anserine, alcohol dehydrogenase, aldolase, carboxypeptidase A, Rennin, GlycerylGlycerylGlycerylGlycin, Glycylphenylalanin, Lysine-Vasopressin, Lysozyme, phenylalanine, rennin, serum albumin, papain, typinogen, Ribonuclease, polyalanine, polyserine, gelatin, elastin, collagen, Keratin, milk protein, Soy protein, almond protein and wheat protein as well as the hydrolyzate of these proteins including their condensation products with fatty acids as well quaternized protein hydrolyzates as well as the physiologically acceptable ones Salts of the aforementioned compounds. Agent according to claim 3, characterized in that the cellulose derivatives selected are made of cellulose, microcrystalline cellulose, cellulose acetopropionate, Cellulose acetate butyrate, cellulose acetate, cellulose xanthate, (2-carboxyethyl) cellulose, Carboxymethyl cellulose, (2-hydroxyethyl) cellulose, dextran and hexadecyl (2-hydroxyethyl) cellulose as well as the physiologically tolerable Salts of these compounds. Agent according to claim 3, characterized in that the chitosan derivatives selected are from succinylchitosan, chitosan-2-hydroxyethyl ether and chitosonium pyrrolidone carboxylate. Agent according to claim 3, characterized in that the starch derivatives are selected from corn starch, hydrolyzed corn starch, rice starch, hydrolyzed rice starch, wheat starch, hydrolyzed wheat starch, potato starch, hydrolyzed potato starch, soy starch, hydrolyzed soy starch and the hydroxy-C ₂ -C ₄ -alkyl- , 2-Hydroxy-3-trimethylammonio-propyl, diethylaminoethyl ether, 2-hydroxy-3-dimethyllaurylammonio-propyl, carboxymethyl, C ₂ -C ₂₀ acyl derivatives of the aforementioned starch derivatives and the physiologically tolerable salts of these compounds. Agent according to claim 3, characterized in that the cationic Connections selected are made of cationic surfactants and cationic polymers. Agent according to claim 3, characterized in that the aromatic Connections selected are made of acetophenone and its derivatives, benzophenone and its Derivatives, benzoquinone and its derivatives, biphenyl and its derivatives, p-aminobenzoic acid and their derivatives, anthranilic acid and their derivatives, aniline derivatives, N, N-dimethylacetamine, anisole derivatives, benzoic acid and their derivatives, terephthalic acid and their derivatives, salicilic acid and their derivatives, salicylaldehyde, methyl gallate, propyl gallate, Octyl gallate, dodecyl gallate, 1,2,4-trimethoxybenzene, 1,3,5-trimethoxybenzene, 3,4-dihydroxy-cinnamic acid and their derivatives, p-toluenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, sulfanilic acid, 4,5-dihydroxy-2,7-naphthalenedisulfonic acid, 1-naphthylacetic acid, 1-naphthylcarboxylic acid, 2-naphthylcarboxylic acid, luminol, 3-indoleacetic acid, 5-indolylacetic acid, 3-indolylpropionic acid, 1-methylindole, 2-methylindole, 3-methylindole, 2,2-dimethyl-1-phenyl-1-propanol, 2-methyl-1-phenyl-1-propanol, 2-methyl-1-phenyl-2-propanol, 3-pyridine caboxamide, 4-pyridine carboxamide, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, 2,4,6-trimethyl-3-hydroxypyridine, 4-ethyl-5-hydroxy-2-methylpyridine, nicotinamide, Pyridoxine, Rhodamine B, Xylenol Orange, Hemoglobin, Hemin, Diphenylamine and its Derivatives, diphenyl acetate, eosin, fluorescin, 1- (2-hydroxyethyl) -2-methyl-5-nitroimidazole, 1- (2-hydroxyethyl-3-methoxypropyl) -2-nitroimidazole, urocanic acid, phenylacetic acid and their derivatives, phenylacetamide, purine, adenine, adenosine, and the physiologically acceptable Salts of these compounds. Agent according to claim 3, characterized in that the sulfur-containing compounds are selected from penicillin derivatives, Glutathione of the oxidized form, cystamine of the oxidized form, homocysteine sulfoximine, Buthionine sulfones, penta-, hexa-, hepta-thionine sulfoximine, dilauryl thiodipropionate, Distearyl thiodipropionate, di-tert-butyl disulfide, and the ester, ether, sugar, peptide, lipid derivatives and physiologically acceptable Salting all of these compounds. Agent according to claim 3, characterized in that the Aldehydes or ketones selected are from uracil, dihydrouracil, thymine, thymidine, guanine, 5,6-dihydroguanine, guanylic acid, guanosine, Cytidine, cytosine, xanthine and their dinucleotides, oligonucleotides or polynucleotides, polyvinylpyrrolidone, folic acid and its derivatives, rutinic acid and their derivatives, bilirubin, biliverdin, plastoquinone, ubiquinone, Bovinon, Helveticon, 9,10-anthraquinone, 9,10-anthraquinone-1-sulfonic acid, 9,10-anthraquinone-2-sulfonic acid, as well the physiologically tolerable Salts of these compounds. Agent according to claim 3, characterized in that the Selected vitamins are from retinol, retinal, 3,4-didehydroretinal, vitamin B1, vitamin B2, vitamin B6, vitamin B9, biotin, pantothenic acid, vitamin D1, vitamin D3, α-tocopherol and its esters, vitamin K1, vitamin K2 and vitamin K3. Agent according to one of claims 1 to 12, characterized in that that it at least one additional Bleach booster selected from ammonium peroxydisulfate, potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, Potassium persulfate, sodium persulfate, potassium peroxide phosphate, magnesium percarbonate, magnesium peroxide and contains barium peroxide. Agent according to one of claims 1 to 13, characterized in that that it additionally contains at least one alkalizing agent. Agent according to one of claims 1 to 14, characterized in that that it a pH of 4.5 to 12. Agent according to one of claims 1 to 15, characterized in that that additionally a Surfactant selected from anionic, nonionic, zwitterionic and amphoteric Contains surfactants. Agent according to one of claims 1 to 16, characterized in that it at least one substantive dye and / or at least one Oxidation dye intermediate of the developer and / or coupler type contains. Process for the oxidative treatment of keratin Fibers, characterized in that the keratin-containing fiber with an agent according to a of claims 1 to 17 treated and the agent after an exposure time of Rinsed again for 30-45 minutes becomes. Use of the agent according to one of claims 1 to 17 for structural stabilization of keratin fibers in oxidative Processes.