AU2005284472A1 - Method for stylishly changing the color of keratinic fibers - Google Patents

Description

IN THE MATTER OF Australian patent application based on International patent application (PCT/EP2005/008949) In the name of Henkel Kommanditgesellschaft auf Aktien DECLARATION I, Pierre KIHN, 234 route d'Arlon, L-8010 STRASSEN, Grand-Duchy of Luxembourg, hereby declare: 1. That I am well acquainted with the German and English languages 2. That the attached document is, to the best of my knowledge and belief, a true and exact translation made by me from German into English of a document furnished to me as the authentic text of the International Patent Application identified above. Declared at Strassen, this 13.02.2007 Pierre HNdec-au-err dec-au-err PCT/EP2005/008949 H 06203 PCT RR/Tb METHOD FOR STYLISHLY CHANGING THE COLOR OF KERATINIC FIBERS [0002]The present invention relates to a method for dyeing keratinic fibers, especially human hair, in which some fibers are selectively bleached in a lightening step, whereupon the entire amount of keratinic fibers are dyed with a special colorant. In addition, a kit-of-parts, comprising a lightener and a colorant, as well as application aids and the use of this kit in the inventive dyeing method are the subject matter of the invention. [0003] Nowadays, human hair is treated in a variety of ways with hair cosmetic preparations. They include, for example, the cleaning of hair with shampoos, care and regeneration with rinses and cures as well as bleaching, dyeing and styling the hair with colorants, toners, permanent wave lotions and styling preparations. Among these, agents for changing or nuancing the color of hair play a prominent role. From the viewpoint of the lighteners, which produce an oxidative lightening of the hair by degrading the natural hair colorants, there exist essentially four important types of hair dyes in the field of hair dyeing. [0004]The so-called oxidation dyes are used for long-lasting, intensive colorations with corresponding authentic characteristics. Such dyes usually comprise oxidation dye precursors, "developer components" and "coupler components". Under the influence of oxidizing agents or from atmospheric oxygen, the developer components form the actual colorants among each other or by coupling with one or more coupler components. Indeed, the oxidation dyes are characterized by excellent, long lasting coloration results. However, for colorations with a natural appearance, normally a mixture of a large number of oxidation dye precursors must be employed; in many cases, further substantive dyes are used for shading/nuancing.

H 06203 PCT RR/Tb [0005] Normally, primary aromatic amines with an additional free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives as well as 2,4,5,6-tetraaminopyrimidine and derivatives thereof are employed as the developer components. [0006]Specific exemplary representatives are p-phenylenediamine, p toluylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N,N-bis(2 hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenyl)ethanol, 2-(2,5 diaminophenoxy)ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolone-5, 4 amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 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) diamino-propane-2-ol. [0007]m-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as the coupling components. Particularly suitable coupling substances are 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 1,7 dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3 methylpyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis(2',4' diaminophenoxy)propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6 methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4 chloro-5-aminophenol. [0008]For temporary colorations, usually colorants or toners are used that comprise "substantives" as the coloring component. These are dye molecules that are directly absorbed onto the hair and do not require any oxidative process to develop the color. These dyes include, for example, Henna that was already known in antiquity for dyeing skin and hair. In general, these dyes are significantly more sensitive to shampooing than are oxidative dyes, with the 2 H 06203 PCT RR/Tb result that many unwanted nuance shifts or even a visible "decolorization" occur. [0009]Finally, another dyeing method has attracted lots of interest. In this method, precursors of the natural hair dye melanin are applied onto the hair; in the course of oxidative processes they then form analogs to natural colorants in the hair. This type of product with 5,6-dihydroxyindoline as the dye precursor was described in EP-B1-530 229. By using, especially repeated use, of agents with 5,6-dihydroxyindoline it is possible to restore the natural hair color to people with gray hair. In this way the coloration can take place with atmospheric oxygen as the sole oxidizing agent, with the result that no recourse is needed to other oxidizing agents. The indoline can be employed as the sole dye precursor for people with naturally medium blond to brown hair. On the other hand, for use by people with naturally red and especially dark to black hair, satisfactory results can frequently only be obtained when additional dye components are used as well, in particular specific oxidation dyestuff precursors. [00010] A further possibility to dye keratinic fibers is by the use of colorants that comprise a combination of the components A compounds that comprise a reactive carbonyl group with components B compounds selected from (a) CH-acidic compounds, (b) compounds containing primary or secondary amino groups or hydroxyl groups, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) oligopeptides built of 2 to 9 amino acids. The corresponding dyeing method (hereinafter called oxo dyeing) is described for example in the publications WO-Al-99/18916, WO-A1-00/38638, WO-Al 01/34106 and WO-Al-01/47483. The resulting colorations exhibit to some extent genuine colors on the keratinic fibers, which are comparable with those made by oxidation dyeing. The nuance spectrum that is obtainable with the gentle oxo dyeing is very broad and the resulting color often exhibits an acceptable brilliance and depth of color. The previously mentioned components 3 H 06203 PCT RR/Tb A and B, hereinafter called oxo dye precursors are generally not dyes themselves, and therefore are not all suitable per se for dyeing keratinic fibers. In combination, they form dyes in a non-oxidative process. However, among the compounds of components B, suitable oxidation dye precursors of the developer type and/or coupler type also find use with or without added oxidizing agents. In this way the oxo dyeing method can be directly combined with the oxidative dye system. [00011] "Bleaching agents" are used for lightening keratinic fibers. They comprise oxidizing agents that oxidatively act on the natural hair coloration melanin and optionally on the synthetic dye present in the fiber and thereby produce a color change and ideally a lightening of the hair color. The principles of bleaching and oxidative dyeing processes are known to the person skilled in the art and are reviewed in the relevant monographs, for example K. Schrader, Grundlagen und Rezepturen der Kosmetika, 2 nd edition, 1989, Dr. Alfred Hcthig Verlag, Heidelberg, or W. Umbach (Editor), Kosmetik, 2 nd Edition, 1995, Georg Thieme Verlag, Stuttgart, New York. [00012] However, the selective oxidative lightening of keratinic fibers treated with colorants is not readily accomplished. Unwanted color shifts to e.g. orange or green tones often result from the oxidative lightening of such color modified fibers and must be absolutely prevented. In the context of lightening, the only wanted color effects are those that denote a lightening of the starting shade. Moreover, it is desirable to provide a uniform color tone to a well defined part of the hair, such as e.g. meshes and to distribute these well defined parts again as uniformly as possible over the whole of the hair. For shading/nuancing meshes, this means that a hair fiber must be uniformly shaded/nuanced from the hairline to the ends and these meshes should be distributed as evenly as possible in the hair on top and also in the hair regions below them. In this manner, uniform and naturally looking, light color reflexes are obtained. 4 H 06203 PCT RRfTb [00013] Accordingly, the object of the present invention is to provide a method that, in a primary dyeing of keratinic fibers with colorants, confers richly contrasting, uniform and naturally looking, light color reflexes over the whole area of the fiber bundles. [00014] It was surprisingly found that uniform color reflexes without unwanted color shifts can be achieved with oxidative lightening, if the oxidative lightening occurs first and is then followed by the coloration step, and a specific colorant and a lightener, in the following called shading composition, is used in this method. [00015] Accordingly, a first subject matter of the invention is a method for dyeing keratinic fibers, especially human hair, in which A a shading composition, comprising, in a cosmetic carrier, at least one thickener, hydrogen peroxide and at least one alkalizing agent, is applied on one part of the fibers and is rinsed off again after a contact time Z1, B the fibers are subsequently optionally dried and then C a dye is applied onto all of the fibers and rinsed off again after a contact time Z2, wherein the dye, as the coloring component, comprises (a) at least two oxidation dye precursors, wherein one oxidation dye precursor must be of the developer type or (b) at least two oxo dye precursors, wherein at least one oxo dye precursor must be a reactive carbonyl compound. [00016] In the context of this application, keratin-containing fibers are understood to mean furs, wool, feathers and particularly human hair. Although the dyes of the inventive method are primarily suitable for dyeing keratinic fibers, in principle, nothing prevents their use in other fields, especially in color photography. 5 H 06203 PCT RRITb [00017] A sharper contrast transition is effected between the hair regions dyed in step C and the oxidatively lightened hair regions from step A if the hair is dried prior to step A and the shading composition is applied onto the dried hair. [00018] The shading composition is applied to a part of all of the keratinic fibers being treated. This means that one or more subsets are selected as fiber bundles among all the fibers. In order to achieve uniformly dispersed color effects, these fiber bundles, in the case of human hair, should be selected not only from the hair on top but also from the hair regions lying underneath the hair on top. Moreover, the chosen fiber bundles are preferably selected as uniformly as possible over the surface of the whole head of hair. The chosen fiber bundles are either totally or partially treated with the shading composition. With a complete treatment, meshes are obtained with light color effects. With a partial treatment, the fiber ends, for example, or other chosen regions of the fiber bundle can be selectively shaded. [00019] In principle, the shading composition can be applied onto the selected strands of fiber by hand, using suitable protective gloves. However, the shading composition is preferably applied to the hair region to be shaded with an applicator, such as, for example a brush, a pencil or an applicette. An applicette is understood to mean a wide pencil whose shaft ends in a tip that facilitates and enables the fiber bundles or meshes to be separated from all the fibers. [00020] A round brush is preferably used as the applicator, in particular for shading short hair up to 20 cm long or for shading the hair ends. A round brush has a shaft and a head of bristles. In a round brush, the bristles of the head of bristles are arranged in the form of a cylinder around a central body of the round brush, wherein the totality of the attached bristles describes an essentially cylindrical exterior surface with one end of the bristles, while the other end of said surface is attached to the body of the head of bristles. The body of the head of bristles is again positioned at one end of the shaft of the 6 H 06203 PCT RRITb round brush or is a part of an end area of the shaft. Preferably, the round brush used in the inventive method has bristles that are maximum 2 cm in length and the diameter of the cylindrical head of bristles is maximum 2.5 cm. The cylinder of the head of bristles is maximum 4 cm in length. A mascara brush is eminently suitable for applying the shading composition. [00021] A particularly preferred way of achieving an improved uniform application of the shading composition for the application of color effects in the form of meshes over the head hair area while retaining sharp contrasts is to use a cap having a plurality of pre-formed holes or optionally markings for the placement of holes in the surface of the cap arranged in a grid-like pattern spread over the surface of the cap. In a preferred embodiment of the method, the preferably dry fibers are accordingly covered with such a cap. Using an aid in the form of a crochet hook, fiber bundles or hair strands are then pulled through holes in the cap. Subsequently, using suitable protective gloves, the shading composition according to step A is then distributed onto the selected areas of hair by hand as in the case of a shampoo or by using a brush. After a contact time Z1, the shading composition is rinsed off and the cap is removed. [00022] The cap is preferably made from at least one film that preferably consists of polyethylene or polyvinyl chloride. If the cap consists of one film layer, it is possible to prestamp or predraw the plurality of holes arranged in a grid-like pattern. In the case of a merely predrawn pattern, the film has no holes and has to be punctured at the selected predrawn place and the hair strands are then pulled through the hole thus formed. It is preferred according to the invention to make the cap from two superimposed film layers. These film layers preferably consist of polyethylene or polyvinyl chloride. The film on the inside of the cap preferably has no premade holes. In addition, the outer film bears the preferably already prepunched grid-like pattern. [00023] The holes in the hole grid and their predrawing preferably have a diameter of from 0.1 to 0.75 mm. The optionally only predrawn holes are preferably arranged such that they lie on the imaginary lines of a grid. The grid 7 H 06203 PCT RRITb preferably consists of squares. All optionally only predrawn holes are spaced at a uniform distance apart along the grid lines; this is preferably 0.5 to 2 cm. [00024] The cap is preferably in the shape of a boat or a helmet. Particular preference is given to the helmet form. Very particular preference is given to a cap as is depicted in Figs. 1 to 4. This cap consists primarily of two side sections (1) and (2) and a middle section (3) and a peaked section (4). These sections are joined together at their contact points preferably through a sealed and/or sewn seam (8) and (9). The seams and the outer edges of sections (1), (2), (3) and (4) are edged with a hem. The hem preferably consists of the material of the outer film. The sections (1), (2) and (3) of the cap consist of 2 superimposed films. The outer film has a prepunched hole grid, the inner film has no holes. The two superimposed films are joined together firstly by the joining seam of sections (1), (2) and (3), and secondly by the hem. When pulled over the head, the cap covers the back of the head and has an opening at the front for the face (see Fig. 2, the "front view"). The peaked section (4) is attached to the upper section of the face area. The edge of the peaked section and the outer edge of sections (1), (2) and (3) are edged as described above by a hem. The hem is extended in the lower region of the face area beyond the edge of the cap and forms the tapes (5) and (6) right and left, with which the cap can be secured on the head by tying the tapes under the chin. Fig. 2 and Fig. 4 show the piece of elastic (7), which is incorporated along the lower edge of the middle section (3). The piece of elastic ensures that the cap is close fitting. Using the piece of elastic, the cap can be adapted to different head sizes. [00025] The contact time Z1 is preferably 5 to 60 minutes, particularly preferably 20 to 45 minutes. [00026] In another embodiment of the method, the fiber bundles that have been separated off and treated with the shading composition are wrapped in a foil, preferably in aluminum foil, and left in this foil for the duration of the contact 8 H 06203 PCT RR/Tb time Z1. This embodiment can preferably be used for shorter contact times of up to 30 minutes. [00027] The shading compositions of the method according to the invention comprise hydrogen peroxide. The hydrogen peroxide is added to the shading composition as a solution or in the form of a solid addition compound of hydrogen peroxide onto inorganic or organic compounds, such as, for example, sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinyl pyrrolidone.nH 2 0 2 (n is a positive integer greater than 0), urea peroxide and melamine peroxide. Hydrogen peroxide is preferably present in the shading composition in an amount of from 0.5 to 6.0% by weight, based on the weight of the shading composition. [00028] The shading compositions of the method according to the invention preferably comprise additional peroxy compounds. These are understood as meaning those peroxy compounds that are neither hydrogen peroxide itself, nor addition products of hydrogen peroxide on other components. The selection of the peroxy compounds additionally present in the compositions according to the invention is not in principle subject to any limitations; customary peroxy 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 peroxydiphosphate and peroxides such as magnesium and barium peroxide. According to the invention, the inorganic compounds are preferred among these peroxide compounds and can also be employed in combination. The peroxysulfates, particularly ammonium peroxydisulfate, are particularly preferred. [00029] The peroxy compounds are comprised in the shading compositions according to the invention preferably in amounts of from 1 to 40% by weight, in particular, in amounts of from 2 to 30% by weight. 9 H 06203 PCT RR/Tb [00030] The pH of the inventive compositions is preferably in a pH range from pH 2.5 to 12.0, particularly preferably from pH 8.5 to 11.0. [00031] The shading compositions of the method according to the invention comprise, as the preferred alkalizing agent, at least one compound chosen from ammonium, alkali metal and alkaline earth metal hydroxides, carbonates, hydrogen carbonates, hydroxycarbonates and carbamides, and also alkali metal phosphates. [00032] In addition, the shading composition can additionally comprise at least one SiO 2 compound, which may optionally be hydrated. According to the invention, it may be preferred to use the optionally hydrated SiO 2 compounds in amounts of from 0.05% by weight to 15% by weight, particularly preferably in amounts of from 0.15% by weight to 10% by weight and quite particularly preferably in amounts of from 0.2% by weight to 5% by weight, in each case based on the total shading composition. The quantitative data here in each case give the content of the SiO 2 compounds (without their water fraction) in the compositions. [00033] With regard to the optionally hydrated SiO 2 compounds, the present invention is not in principle subject to any limitations. Preference is given to silicic acids, their oligomers and polymers, and their salts. Preferred salts are the alkali metal salts, in particular, the potassium and sodium salts. The sodium salts are quite particularly preferred. [00034] The optionally hydrated SiO 2 compounds can be present in various forms. According to the invention, the Si0 2 compounds are preferably used in the form of silica gels or particularly preferably as water-glass. Some of these SiO 2 compounds may be in the form of an aqueous solution. [00035] According to the invention, quite particular preference is given to water-glasses that are formed from a silicate of the formula (SiO2)n(Na20)m(K 2 0)p, where n is a positive rational number and m and p, 10 H 06203 PCT RR/Tb independently of one another, are a positive rational number or are 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. [00036] Besides the components described by the empirical formula, the water-glasses can also comprise, in small amounts, further additives, such as, for example, phosphates or magnesium salts. [00037] Particularly preferred water-glasses according to the invention are sold, inter alia, by Henkel under the names Ferrosil® 119, Natronwasserglas 40/42, Portil® A, Portil® AW, Portil® N and Portil® W and by Akzo under the name Britesil® C20. [00038] The preferred viscosity of the shading composition is from 5 000 to 100 000 mPa.s, particularly preferably from 30 000 to 80 000 mPa.s (Brookfield rotary viscometer, 25 OC., spindle #4, 20 rpm). [00039] The viscosity is adjusted by means of the thickener comprised in the shading composition. Polymers can increase the viscosity of aqueous and non-aqueous phases in cosmetic preparations. In aqueous phases, their propensity to increase the viscosity is based on their solubility in water or their hydrophilic nature. They are used both in surface-active and also in emulsion like systems. Some examples of preferred polymeric thickeners are listed below; these may be present in the shading composition of the inventive method: Acrylamides Copolymer, Acrylamide/Sodium Acrylate Copolymer, Acrylamide/Sodium Acryloyldimethyl Taurate Copolymer, Acrylates/Acetoacetoxyethyl Methacrylate Copolymer, Acrylates/Beheneth-25 Methacrylate Copolymer, Acrylates/C10-30 Alkyl Acrylate Crosspolymer, Acrylates/Ceteth-20 Itaconate Copolymer, Acrylates/Ceteth-20 Methacrylate Copolymer, Acrylates/Laureth-25 Methacrylate Copolymer, Acrylates/Palmeth 25 Acrylate Copolymer, Acrylates/Palmeth-25 Itaconate Copolymer, Acrylates/Steareth-50 Acrylate Copolymer, Acrylates/Steareth-20 Itaconate 11 H 06203 PCT RR/Tb Copolymer, Acrylates/Steareth-20 Methacrylate Copolymer, Acrylates/Stearyl Methacrylate Copolymer, AcrylatesNinyl Isodecanoate Crosspolymer, Acrylic Acid/Acrylonitrogens Copolymer, Agar, Agarose, Alcaligenes Polysaccharides, Algin, Alginic Acid, Ammonium Acrylates/Acrylonitrogens Copolymer, Ammonium Acrylates Copolymer, Ammonium AcryloyldimethyltaurateNinyl Formamide Copolymer, Ammonium AcryloyldimethyltaurateNP Copolymer, Ammonium Alginate, Ammonium Polyacryloyldimethyl Taurate, Amylopectin, Ascorbyl Methylsilanol Pectinate, Astragalus Gummifer Gum, Attapulgite, Avena Sativa (Oat) Kernel Flour, Bentonite, Butoxy Chitosan, Caesalpinia Spinosa Gum, Calcium Alginate, Calcium Carboxymethyl Cellulose, Calcium Carrageenan, Calcium Potassium Carbomer, Calcium Starch Octenylsuccinate, C20-40 Alkyl Stearate, Carbomer, Carboxybutyl Chitosan, Carboxymethyl Chitin, Carboxymethyl Chitosan, Carboxymethyl Dextran, Carboxymethyl Hydroxyethylcellulose, Carboxymethyl Hydroxypropyl Guar, Cellulose Acetate Propionate Carboxylate, Cellulose Gum, Ceratonia Siliqua Gum, Cetyl Hydroxyethylcellulose, Cholesterol/HDI/Pullulan Copolymer, Cholesteryl Hexyl Dicarbamate Pullulan, Cyamopsis Tetragonoloba (Guar) Gum, Diglycol/CHDM/Isophthalates/SIP Copolymer, Dihydrogenated Tallow Benzylmonium Hectorite, Dimethicone Crosspolymer-2, Dimethicone Propyl PG-Betaine, DMAPA Acrylates/Acrylic Acid/Acrylonitrogens Copolymer, Ethylene/Sodium Acrylate Copolymer, Gelatin, Gellan Gum, Glyceryl Alginate, Glycine Soja (Soybean) Flour, Guar Hydroxypropyltrimonium Chloride, Hectorite, Hydrated Silica, Hydrogenated Potato Starch, Hydroxybutyl Methylcellulose, Hydroxyethyl Acrylate/Sodium Acryloyldimethyl Taurate Copolymer, Hydroxyethylcellulose, Hydroxyethyl Chitosan, Hydroxyethyl Ethylcellulose, Hydroxypropylcellulose, Hydroxypropyl Chitosan, Hydroxypropyl Ethylenediamine Carbomer, Hydroxypropyl Guar, Hydroxypropyl Methylcellulose, Hydroxypropyl Methylcellulose Stearoxy Ether, Hydroxypropyl Starch, Hydroxypropyl Starch Phosphate, Hydroxypropyl Xanthan Gum, Hydroxystearamide MEA, Isobutylene/Sodium Maleate Copolymer, Lithium Magnesium Silicate, Lithium Magnesium Sodium Silicate, Macrocystis Pyrifera (Kelp), Magnesium Alginate, Magnesium Aluminum Silicate, Magnesium Silicate, Magnesium Trisilicate, Methoxy PEG-22/Dodecyl Glycol Copolymer, 12 H 06203 PCT RRITb Methylcellulose, Methyl Ethylcellulose, Methyl Hyd roxyethylcellulose, Microcrystalline Cellulose, Montmorillonite, Moroccan Lava Clay, Natto Gum, Nonoxynyl Hydroxyethylcellulose, Octadecene/MA Copolymer, Pectin, PEG 800, PEG-Crosspolymer, PEG-150/Decyl Alcohol/SMDI Copolymer, PEG-175 Diisostearate, PEG-190 Distearate, PEG-15 Glyceryl Tristearate, PEG-140 Glyceryl Tristearate, PEG-240/HDI Copolymer Bis-Decyltetradeceth-20 Ether, PEG-100/IPDI Copolymer, PEG-180/Laureth-50/TMMG Copolymer, PEG 10O/Lauryl Dimethicone Crosspolymer, PEG-15/Lauryl Dimethicone Crosspolymer, PEG-2M, PEG-5M, PEG-7M, PEG-9M, PEG-14M, PEG-20M, PEG-23M, PEG-25M, PEG-45M, PEG-65M, PEG-90M, PEG-115M, PEG 160M, PEG-120 Methyl Glucose Trioleate, PEG-180/Octoxynol-40/TMMG Copolymer, PEG-150 Pentaerythrityl Tetrastearate, PEG-4 Rapeseedamide, PEG-150/Stearyl Alcohol/SMDI Copolymer, Polyacrylate-3, Polyacrylic Acid, Polycyclopentadiene, Polyether-1, Polyethylene/Isopropyl Maleate/MA Copolyol, Polymethacrylic Acid, Polyquaternium-52, Polyvinyl Alcohol, Potassium Alginate, Potassium Aluminum Polyacrylate, Potassium Carbomer, Potassium Carrageenan, Potassium Polyacrylate, Potato Starch Modified, PPG-14 Laureth-60 Hexyl Dicarbamate, PPG-14 Laureth-60 Isophoryl Dicarbamate, PPG-14 Palmeth-60 Hexyl Dicarbamate, Propylene Glycol Alginate, PVP/Decene Copolymer, PVP Montmorillonite, Rhizobian Gum, Ricinoleic Acid/Adipic Acid/AEEA Copolymer, Scierotium Gum, Sodium Acrylate/Acryloyldimethyl Taurate Copolymer, Sodium Acrylates/Acrolein Copolymer, Sodium Acrylates/Acrylonitrogens Copolymer, Sodium Acrylates Copolymer, Sodium Acrylates/Vinyl Isodecanoate Crosspolymer, Sodium AcrylateNinyl Alcohol Copolymer, Sodium Carbomer, Sodium Carboxymethyl Chitin, Sodium Carboxymethyl Dextran, Sodium Carboxymethyl Beta-Glucan, Sodium Carboxymethyl Starch, Sodium Carrageenan, Sodium Cellulose Sulfate, Sodium Cyclodextrin Sulfate, Sodium Hydroxypropyl Starch Phosphate, Sodium Isooctylene/MA Copolymer, Sodium Magnesium Fluorosilicate, Sodium Polyacrylate, Sodium Polyacrylate Starch, Sodium Polyacryloyldimethyl Taurate, Sodium Polymethacrylate, Sodium Polystyrene Sulfonate, Sodium Silicoaluminate, Sodium Starch Octenylsuccinate, Sodium Stearoxy PG-Hydroxyethylcellulose Sulfonate, Sodium Styrene/Acrylates 13 H 06203 PCT RR/Tb Copolymer, Sodium Tauride Acrylates/Acrylic Acid/Acrylonitrogens Copolymer, Solanum Tuberosum (Potato) Starch, Starch/Acrylates/Acrylamide Copolymer, Starch Hydroxypropyltrimonium Chloride, Steareth-60 Cetyl Ether, Steareth 100/PEG-136/HDI Copolymer, Sterculia Urens Gum, Synthetic Fluorphlogopite, Tamarindus Indica Seed Gum, Tapioca Starch, TEA-Alginate, TEA-Carbomer, Triticum Vulgare (Wheat) Starch, Tromethamine Acrylates/Acrylonitrogens Copolymer, Tromethamine Magnesium Aluminum Silicate, Welan Gum, Xanthan Gum, Yeast Beta-Glucan, Yeast Polysaccharides, Zea Mays (Corn) Starch. [00040] When the dye of the inventive method is an oxidative dye then it comprises at least one developer component. Normally, primary aromatic amines with an additional free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4 aminopyrazolone derivatives as well as 2,4,5,6-tetraaminopyrimidine and derivatives thereof are employed as the developer components. [00041] According to the invention, it may be preferred to use a p phenylenediamine derivative or one of its physiologically compatible salts as the developer component. Particular preference is given to p-phenylenediamine derivatives of the formula (El)

NGG

2

:G

3 NGG G I (El)

NH

2 wherein - G 1 is a hydrogen atom, a Cl- to C 4 -alkyl group, a Cj- to C4-monohydroxyalkyl group, a C 2 - to C 4 -polyhydroxyalkyl group, a (Ci- to C 4 )-alkoxy(C 1 - to C 4 )-alkyl group, a 4' aminophenyl group or a Cl- to C 4 -alkyl group that is substituted by a nitrogen-containing group, a phenyl group or a 4'-aminophenyl group; 14 H 06203 PCT RRITb - G 2 is a hydrogen atom, a Cl- to C 4 -alkyl group, a Cl- to

C

4 -monohydroxyalkyl group, a C 2 - to C 4 -polyhydroxyalkyl group, a (Cl- to C 4 )-alkoxy(C 1 - to C 4 )-alkyl group or a C 1 to C 4 -alkyl group that is substituted by a nitrogen containing group; - G 3 is a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C 1 - to C 4 alkyl group, a C 1 - to C4-monohydroxyalkyl group, a C 2 - to

C

4 -polyhydroxyalkyl group, a (C 1 - to C4)-hydroxyalkoxy group, a Ci- to C 4 -acetylamino group, a Cl- to C 4 mesylamino alkoxy group or a C 1 - to C 4 carbamoylaminoalkoxy group; - G 4 stands for a hydrogen atom or a C 1 - to C 4 -alkyl group or - if G 3 und G 4 are in the ortho position relative to one another, they can together form a bridging a,w alkylenedioxo group, such as, for example, an ethylenedioxy group. [00042] Examples of the C 1 - to C 4 -alkyl groups specified as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl groups. Inventively preferred Cl- to C 4 -alkoxy groups are a methoxy or ethoxy group, for example. Furthermore, preferred examples of a C 1 - to C 4 -hydroxyalkyl group that may be mentioned 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 C4-polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. According to the invention, examples of halogen atoms are.F, Cl or Br atoms, Cl atoms being quite particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (El) are, in particular, the amino groups, C 1 - to C 4 -monoalkylamino groups, C 1 - to C 4 -dialkylamino groups, C 1 - to 15 H 06203 PCT RRFIb

C

4 -trialkylamino groups, C 1 - to C4-monohydroxyalkylamino groups, imidazolinium and ammonium. [00043] Particularly preferred p-phenylenediamines of the formula (El) are chosen from p-phenylenediamine, p-toluylenediamine, 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(P3-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis(P3 hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(3-hydroxyethyl)amino-2 chloroaniline, 2-(13-hydroxyethyl)-p-phenylenediamine, 2-(a,13-dihydroxyethyl)-p phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p phenylenediamine, N-(P-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N,N-(ethyl,P hydroxyethyl)-p-phenylenediamine, N-(3,y-dihydroxypropyl)-p phenylenediamine, N-(4'-aminophenyl)-p-phenylenediamine, N-phenyl-p phenylenediamine, 2-(P-hydroxyethyloxy)-p-phenylenediamine, 2-(13 acetylamino ethyloxy)-p-phenylenediamine, N-(P-methoxyethyl)-p phenylenediamine and 5,8-diaminobenzo-l1,4-dioxane, and their physiologically compatible salts. [00044] According to the invention, quite particularly preferred p phenylenediamine derivatives of Formula (El) are p-phenylenediamine, p toluylenediamine, 2 -(1-hydroxyethyl)-p-phenylenediamine, 2-(cx, P dihydroxyethyl)-p-phenylenediamine and N, N-bis-(P3-hydroxyethyl)-p phenylenediamine. [00045] According to the invention, it may also be preferred to use compounds as the developer component, which comprise at least two aromatic nuclei, that are substituted by amino and/or hydroxyl groups. 16 H 06203 PCT RR/Tb [00046] Among the binuclear developer components, which can be used in the dyes according to the invention, mention may be made in particular, of the compounds which conform to the following formula (E2), together with their physiologically compatible salts: zI z 2 G' S -- y-- G 6 (E2)

NG

9

G

0

NG

1 G12 wherein: - Z 1 and Z 2 , independently of one another, are a hydroxyl or NH 2 group, which is optionally substituted by a Cj- to

C

4 -alkyl group, by a Cl- to C 4 -hydroxyalkyl group and/or by a bridge Y 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, for example, a linear or branched alkylene chain or an alkylene ring, which can be 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 possibly be substituted by one or more hydroxyl or C 1 - to Cs-alkoxy groups, or is a direct bond, - G 5 und G 6 , independently of one another, are a hydrogen or halogen atom, a Cl- to C 4 -alkyl group, a Cl- to C 4 monohydroxyalkyl group, a C2- to C 4 -polyhydroxyalkyl group, a Cl- to C 4 -aminoalkyl group or a direct bond to the bridge Y, - G 7 , G 8 , G 9 , G 1 0 , G 1 " and G 12 , independently of one another, are a hydrogen atom, a direct bond to the bridge Y or a Cl- to C 4 -alkyl group, 17 H 06203 PCT RRITb with the provisos that the compounds of Formula (E2) comprise only one bridge Y per molecule and the compounds of Formula (E2) comprise at least one amino group that carries at least one hydrogen atom. [00047] According to the invention, the substituents in formula (E2) are defined analogously to the above statements. [00048] Preferred binuclear developer components of the formula (E2) are, in particular: N,N'-bis(P-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3 diaminopropan-2-ol, N,N'-bis(P-hydroxyethyl)-N,N'-bis(4' aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(P-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine,

N,N'

bis( 4 -methylaminophenyl)tetramethylenediamine, N,N'-diethyl-N,N'-bis(4' amino-3'-methylphenyl)ethylenediamine, bis(2-hydroxy-5 aminophenyl)methane, 1,3-bis(2,5-diaminophenoxy)propan-2-ol, 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 compatible salts. [00049] Quite particularly preferred binuclear developer components of the formula (E2) are N,N'-bis(P-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3 diaminopropan-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 and 1,10-bis(2',5'-diaminophenyl)-1,4,7,10-tetraoxadecane or one of their physiologically compatible salts. [00050] Moreover, according to the invention, it may be preferred to use a p-phenylenediamine derivative or one of its physiologically compatible salts as the developer component. p-Aminophenol derivates of the Formula (E3) are particularly preferred. 18 H 06203 PCT RRITb OH 16 13 G G 1 (E3)

G

1 4 G

NHG

15 wherein: - G 13 is a hydrogen atom, a halogen atom, a C 1 - to C 4 -alkyl group, a Cl- to C4-monohydroxyalkyl group, a C 2 - to C 4 polyhydroxyalkyl group, a (Ci- to C 4 )-alkoxy-(Cl- to C 4

)

alkyl group, a Cl- to C 4 -aminoalkyl group, a hydroxy-(Cl to C4)-alkylamino group, a Cl- to C4-hydroxyalkoxy group, a C 1 - to C4-hydroxyalkyl-(Cl-to

C

4 )-aminoalkyl group or a (di-C 1 - to C 4 -alkylamino)-(C 1 - to C 4 )-alkyl group, and - G 4 is a hydrogen or halogen atom, a C 1 - to C 4 -alkyl group, a C 1 - to C4-monohydroxyalkyl group, a C 2 - to C 4 polyhydroxyalkyl group, a (Cl- to C 4 )-alkoxy-(C 1 - to C 4

)

alkyl group, a C 1 - to C 4 -aminoalkyl group or a C 1 - to C 4 cyanoalkyl group, - G 1* 5 stands for hydrogen, a Cl- to C 4 -alkyl group, a Cj- to C4-monohydroxyalkyl group, a C 2 - to C4-polyhydroxyalkyl group, a phenyl group or a benzyl group, and - G 16 stands for hydrogen or a halogen atom. [00051] According to the invention, the substituents in formula (E3) are defined analogously to the above statements. [00052] Preferred p-aminophenols of the Formula (E3) are especially 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-(13-hydroxyethoxy)phenol, 4-amino-2 methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2 19 H 06203 PCT RRITb methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(B hydroxyethyl-aminomethyl)phenol, 4-amino-2-(c,p-dihydroxyethyl)phenol, 4 amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4 amino-2-(diethyl-aminomethyl)phenol together with their physiologically compatible salts. [00053] Quite particularly preferred compounds of the Formula (E3) are p aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4 amino-2-(ca,3-dihydroxyethyl)phenol and 4-amino-2 (diethylaminomethyl)phenol. [00054] Furthermore, the developer component can be selected from o aminophenol and its derivatives, such as, for example 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol. [00055] In addition, the developer component can be chosen from heterocyclic developer components, such as, for example, the pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and their physiologically compatible salts. [00056] Preferred pyridine derivatives are, in particular, the compounds which are described in the patents GB 1 026 978 and GB 1,153,196, such as 2,5-diaminopyridine, 2 -(4'-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino 6-methoxypyridine, 2 -(13-methoxyethyl)amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine. [00057] Preferred pyrimidine derivatives are, in particular, the compounds which are described in the German patent DE 2,359,399, the Japanese laid open specification JP 02019576 A2 or in the laid-open specification WO 96/15765, such as 2,4,5,6-tetraminopyrimidine, 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. 20 H 06203 PCT RRITb [00058] Preferred pyrazole derivatives are, in particular, the compounds which are 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, such as 4,5-diamino-l-methylpyrazole, 4,5-diamino-1l-(P13-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1l-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1,3 dimethylpyrazole, 4,5-diamino-3-methyl-1l-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-1l-methylpyrazole, 4,5 diamino-1 -tert-butyl-3-methylpyrazole, 4,5-diamino-1 -(P-hydroxyethyl)-3 methylpyrazole, 4,5-diamino-l-ethyl-3-methylpyrazole, 4,5-diamino-1l-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-l-isopropylpyrazole, 4-amino-5-(2 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-(P-hydroxyethyl)amino-1 -methylpyrazole. [00059] Preferred pyrazolo pyrimidine derivatives are, in particular, the derivatives of the pyrazolo[1,5-a]pyrimidine of the following formula (E4) and its tautomeric forms provided there is a tautomeric equilibrium: (X) 5- N 3 -- [NGI 7 G 1]p " 2 (E4) (HO)n- - 7 -N -[NG 19

G

20 ]q wherein: - G 17 , G 18 , G 19 and G 20 independently of one another stand for a hydrogen atom, a C 1 - bis C 4 -alkyl group, an aryl group, a C 1 - to C 4 -Hydroxyalkyl group, a C 2 - to C 4 Polyhydroxyalkyl group a (Ci- to C4)-alkoxy-(C1- to C 4

)

alkyl group, a Cl- to C 4 -aminoalkyl group, optionally protected by an acetyl-ureido or a sulfonyl group, a (Cl 21 H 06203 PCT RRITb to C 4 )-alkylamino-(C 1 - to C 4 )-alkyl group, a di-[(C 1 - to C 4

)

alkyl]-(Cl- to C 4 )-aminoalkyl group, wherein the dialkyl groups optionally form a carbocycle or a heterocycle with 5 or 6 chain members, a C 1 - to C 4 -hydroxyalkyl- or a di (Cl- to C4)-[hydroxyalkyl]-(C 1 - to C 4 )-aminoalkyl group, - the X-groups independently of one another stand for a hydrogen atom, a Cj- bis C 4 -alkyl group, an aryl-group, a Cl- to C 4 -hydroxyalkyl group, a C 2 - to C 4 polyhydroxyalkyl group a (C 1 - to C 4 )-alkoxy-(Cl- to C4) alkyl group, a Cl- to C 4 -aminoalkyl group, a (Cl- to C 4

)

alkylamino-(Cl- to C 4 )-alkyl group, a di-[(C 1 - to C 4 )-alkyl] (Cl- to C 4 )-aminoalkyl group, wherein the dialkyl groups optionally form a carbocycle or a heterocycle with 5 or 6 chain members, a Cl- to C4-hydroxyalkyl- or a di-(Ci- to C4)-[hydroxyalkyl]-(C 1 - to C 4 )-aminoalkyl group, an amino group, a C 1 - bis C 4 -alkyl- or a di-(C 1 - to C4) [hydroxyalkyl]-(Cl- to C 4 )amino group, 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 equal to 2, then n has the value 0, and the groups NG 17

G

18 and NG 19

G

20 occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7); - if p + q is equal to 1, then n has the value 1, and the groups NG 1 7

G

18 (or NG 19

G

20 ) and the group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7); [00060] According to the invention, the substituents in formula (E4) are defined analogously to the above statements. 22 H 06203 PCT RRITb [00061] If the pyrazolo[1,5-a]pyrimidine of the above formula (E4) comprises a hydroxy group in 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: NG17 G18 H NG G18 N N rN N- N OH 0 Among the pyrazolo[1,5-a]pyrimidines of the above formula (E4), mention may be made in particular, of: - 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-Aminopyrazolo[1, 5-a]pyrimidine-7-ol; - 3-Aminopyrazolo[1,5-a]pyrimidine-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 hydroxyethyl)am ino]ethanol; - 2-[(7-Aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2 hydroxyethyl)am ino]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 compatible salts and their tautomeric forms if a tautomeric equilibrium is present. 23 H 06203 PCT RR/Tb [00062] The pyrazolo[1,5-a]pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from an aminopyrazole or from hydrazine. [00063] The precursors of nature-analogous dyes that are used are preferably those indoles and indolines, which have at least one hydroxyl or amino group, preferably as the substituent on the six-membered ring. These groups can carry further substituents, e.g., in the form of an etherified or esterified hydroxyl group or an alkylated amino group. These indoles and indolines can be used as the developer component in oxidation hair colors. [00064] Of particularly good suitability as precursors of nature-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (la), 4 3 R - 0R3 s 5

O

] - R 2 0MN R I R (la) in which, independently of one another R' stands for hydrogen, a Cl-C 4 -alkyl group or a Cl 1

-C

4 -hydroxyalkyl group,

R

2 stands for hydrogen or a -COOH group, where the -COOH group may also be present as the salt with a physiologically compatible cation,

R

3 stands for hydrogen or a C 1

-C

4 -alkyl group,

R

4 stands for hydrogen, a Cl-C 4 -alkyl group or a -CO-R 6 group, in which

R

6 stands for a Ci-C 4 -alkyl group, and R 5 stands for one of the groups cited for R 4 , and physiologically compatible salts of these compounds with an organic or inorganic acid. [00065] Particularly 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 24 H 06203 PCT RRITb dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6 hydroxyindoline, 6-aminoindoline and 4-aminoindoline. [00066] Within this group, emphasis is placed particularly on N-methyl 5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6 dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and, in particular, 5,6 dihydroxyindoline. [00067] In addition, derivatives of 5,6-hydroxyindole of the formula (Ib) are exceptionally suitable as precursors of nature-analogous hair dyes, 43 R- R3 R O R R -0 : N

R

2 I R (Ib) in which, independently of one another

R

1 stands for hydrogen, a C 1

-C

4 -alkyl group or a C1-C 4 -hydroxyalkyl group,

R

2 stands for hydrogen or a -COOH group, where the -COOH group may also be present as the salt with a physiologically compatible cation,

R

3 stands for hydrogen or a C1 -C 4 -alkyl group,

R

4 stands for hydrogen, a C 1

-C

4 -alkyl group or a -CO-R 6 group, in which R 6 stands for a Cl-C4-alkyl group, and

R

s stands for one of the groups cited for R 4 , and physiologically compatible salts of these compounds with an organic or inorganic acid. [00068] Particularly 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 and 6-hydroxyindole, 6-aminoindole and 4-aminoindole. 25 H 06203 PCT RR/Tb [00069] Within this group, emphasis is given to 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. [00070] In the dyeing compositions used within the scope of the method according to the invention, the indoline and indole derivatives can be used either as free bases or else in the form of their physiologically compatible salts with inorganic or organic acids, e.g., the hydrochlorides, the sulfates and hydrobromides. The indole or indoline derivatives are present in these usually in amounts of from 0.05-10% by weight, preferably 0.2-5% by weight. [00071] In a further embodiment, it may be preferred according to the invention to use the indoline or indole derivative in hair dyeing compositions in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an a-amino acid; quite particularly preferred a-amino acids are arginine, ornithine, lysine, serine and histidine, in particular, arginine. [00072] In a further preferred embodiment, the dyeing compositions of the process according to the invention comprise at least one coupler component. [00073] In general, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives as well as heterocyclic compounds are generally used as the coupling components. [00074] According to the invention, preferred coupler components are m-aminophenol and derivatives thereof such as, for example, 5-amino-2 methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3 trfluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-(2'-hyd roxyethyl)amino-2-methylphenol, 3-(diethylamino)phenol, 1,3-dihydroxy-5-(methylamino)benzene, 3 (ethylamino)-4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and derivatives thereof, 26 H 06203 PCT RRITb m-diaminobenzene and derivatives thereof such as, for example, 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-diaminobenzene and derivatives thereof such as, for example, 3,4 diaminobenzoic acid and 2,3-diamino-1-methylbenzene, di- and trihydroxybenzene derivatives such as, for example, resorcinol, resorcinol monomethyl ether, 2-methyl resorcinol, 5-methyl resorcinol, 2,5 dimethyl resorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4 trihydroxybenzene, pyridine derivatives such as, for example, 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, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1 -naphthol, 2-hydroxyethyl-1 -naphthol, 1,5 dihydroxynaphthalene, 1,6-dihdroxynaphthalene, 1,7-dihdroxynaphthalene, 1,8 dihdroxynaphthalene, 2,7-dihdroxynaphthalene and 2,3-dihdroxynaphthalene, morpholine derivatives such as, for example, 6-hydroxybenzomorpholine and 6-aminobenzomorpholine, quinoxaline derivatives such as, for example, 6-methyl-1,2,3,4 tetrahydroquinoxaline, pyrazole derivatives such as, for example, 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as, for example, 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives, such as, for example 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, or 27 H 06203 PCT RR/JTb methylenedioxybenzene derivatives such as, for example, 1-hydroxy-3,4 methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1-(2' hydroxyethyl)-amino-3,4-methylenedioxybenzene. [00075] According to the invention, particularly preferred coupler components are 1 -naphthol, 1,5-dihydroxynaphthalene, 2,7 dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m aminophenol, resorcinol, m-phenylenediamine, 1-phenyl-3-methylpyrazol-5 one, 2,4-dichloro-3-aminophenol, 1,3-bis(2,4-diaminophenoxy)propane, 2 chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 3 amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6 dihydroxy-3,4-dimethylpyridine, 2-methylresorcinol, 5-methylresorcinol, 2 methyl-4-chloro-5-aminophenol and the physiologically compatible salts of the above-mentioned compounds. [00076] After carrying out the method according to the invention, color pairs are produced which are formed from the dyeing step C and the earlier lightening in step A of the method according to the invention. According to the invention, the base coloration is defined as the coloration of the fibers on fibers that had not been lightened. The coloration on the lightened fibers produces a lightened coloration in the base coloration tone of the base coloration. The formation of such color pairs according to the invention can be determined by colorimetry. [00077] It is particularly preferred to formulate the dyeing compositions in such a way that, after carrying out the method according to the invention, one of the 10 color pairs for the starting coloration and the oxidatively nuanced hair is produced according to Table 1: Table 1 No. Color of the base coloration Color of the lightened coloration 1 mid blonde blonde 2 dark blonde light blonde 28 H 06203 PCT RR/Tb 3 red orange-red 4 red light red 5 copper red light copper blonde 6 violet dark pink 7 golden brown golden blonde 8 mid brown brown blonde 9 dark brown light brown 10 black brown brown [00078] Surprisingly, it has been found that the following combinations of oxidation dye precursors are particularly well suited for preparing color pairs with the blonde starting coloration (color pair 1 and 2 according to Table 1): - at least one p-phenylenediamine derivative according to formula (El) - at least one p-aminophenol derivative according to formula (E3) - at least one pyridine derivative as the coupler - at least one compound chosen from m-aminophenol or its derivatives as the coupler. [00079] Surprisingly, it has been found that the following combinations of oxidation dye precursors are particularly well suited for preparing color pairs with red starting coloration (color pairs 3, 4 and 5 according to Table 1): - at least one heterocyclic developer chosen from pyrazole derivatives and pyrimidine derivatives - at least two compounds chosen from m-aminophenol and its derivatives as the coupler. [00080] Surprisingly, it has been found that the following combinations of oxidation dye precursors are particularly well suited for preparing color pairs with violet starting color (color pair 6 according to Table 1): - at least one pyrazole derivative as the developer - at least one pyridine derivative as the coupler 29 H 06203 PCT RR/Tb - at least one compound chosen from m-aminophenol or its derivatives as the coupler. [00081] Surprisingly, it has been found that the following combinations of oxidation dye precursors are particularly well suited for preparing color pairs with brown starting coloration (color pairs 7, 8 and 9 and 10 according to Table 1): - at least one p-phenylenediamine derivative according to formula (El) - at least one pyridine derivative as the coupler - at least one compound chosen from m-aminophenol or its derivatives as the coupler. [00082] For forming the color pairs, the above-mentioned preferred oxidation dye precursors are used in the above-mentioned combinations as preferred developers and couplers. [00083] The dyeing compositions of the method according to the invention comprise both the developer components and also the coupler components preferably in an amount of from 0.005 to 10% by weight, preferably from 0.1 to 5% by weight, in each case based on the total oxidation dyeing composition. [00084] Here, developer components and coupler components are generally used in approximately molar amounts relative to one another. Although the molar use has also proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, meaning that developer components and coupler components may be present in a molar ratio of from 1:0.5 to 1: 3, in particular, 1:1 to 1: 2. [00085] For the shading, the dyeing compositions of the method according to the invention can comprise one or a plurality of substantive dyes. Substantive dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyestuffs are the 30 H 06203 PCT RRfTb compounds known under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellowl2, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57:1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 as well as 1,4-bis(P-hydroxyethyl)amino-2 nitrobenzene, 3-nitro-4(p-hydroxyethyl)aminophenol, 2-(2'-hydroxyethyl)amino 4,6-dinitrophenol, 1-(2'-hydroxyethyl)amino-4-methyl-2-nitrobenzenel, 1-amino 4

-(

2 '-hydroxyethyl)amino-5-chlor-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, 2-hydroxy- 1,4-naphthoquinone, hydroxyethyl-2-nitrotoluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, 4 ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-l-hydroxy-4 nitrobenzene. [00086] In addition, the dye composition can comprise a cationic substantive dyestuff. Particular preference is given here to a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, b) aromatic systems which are substituted by a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and c) substantive dyes which comprise a heterocycle that has at least one quaternary nitrogen atom, as are specified, for example, in EP-A2 998,908 in the claims 6 to 11, which are explicitly incorporated here by reference. [00087] Preferred cationic substantive dyes of group (c) are, in particular, the following compounds: 31 H 06203 PCT RRTb H

CH

3 I

H

3 CN NN(DZI)

CH

3

SO

4 H CH 3 N N (DZ2)

H

3 C

OCH

3 cr

CH

3 H N N-- -N H+N N H (DZ3) CN I c CH 3

CH

3 H N N N CN+-N CH 3 (DZ4) I

CH

3 CI

CH

3 CH3 N N / \ N+-N

CH

3 (DZ5) N

CH

3 Cl 32 H 06203 PCT RR/Tb

CH

3 H N N N

N+

- N (DZ6) I hl

CH

3 CIf

NH

2 .N .OCH 3

H

3 CN " OC+H3 (DZ7) N 0

NH

2 + I

CH

3 CI

H

3 C N C H3 H3CHN aONH2+ (DZ8) I

CH

3 Cf

H

3 C N~C Cl- N 'CH 3 Cf ,H

H

3 C (DZ9) N [00088] The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known under the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are quite particularly preferred cationic substantive dyes of group (c). [00089] The cationic substantive dyes that are commercialized under the trade name Arianor@ are likewise quite particularly preferred cationic substantive dyes according to the invention. 33 H 06203 PCT RR/Tb [00090] The dyeing compositions can comprise the substantive dyes in an amount of from 0.1 to 5% by weight, based on the total dyeing composition. [00091] In addition, the dyeing compositions of the inventive method can also comprise naturally occurring dyestuffs contained in henna red, henna neutral, henna black, camomille leaves, sandalwood, black tea, alder buckthorn bark, sage, logwood, madder root, cashew, cedar and alkanet root. [00092] However, it is preferred according to the invention that the dyeing compositions used in the inventive method do not comprise substantive dyes. [00093] It is not required that each of the oxidation dyestuff precursors or the substantive dyestuffs be pure compounds. In fact, the inventive hair colorants, due to the manufacturing processes for the individual dyestuffs, may comprise minor quantities of even more components, in so far as they have no detrimental influence on the coloration result or that they must be excluded on other grounds, e.g. toxicological. [00094] In regard to the useable dyestuffs in the inventive hair colorants and hair tints, reference is expressly made to the monograph of Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; substantive dyes) and chapter 8, (pages 264-267; oxidation dyestuff precursors), published as volume 7 in the series "Dermatology" (Editor: Ch. Culnan and H. Maibach), Verlag Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the European Union, obtainable in disk form from the Bundesverband Deutscher Industrie und Handelsunternehmen fOr Arzneimittel, Reformwaren und Karperpflegemittel e.V., Mannheim. [00095] The dyeing composition of the inventive method can comprise, as the color-imparting component, at least one three-part combination, selected from the components A compounds that comprise a reactive carbonyl group with component 34 H 06203 PCT RRJTb B compounds selected from (a) CH-acidic compounds, (b) compounds containing primary or secondary amino groups or hydroxyl groups, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) oligopeptides built of 2 to 9 amino acids. wherein at least one representative of this combination has to be a compound with a reactive carbonyl group in accordance with component A. [00096] Compounds according to the invention with a reactive carbonyl group (also termed below reactive carbonyl compounds or component A) have at least one carbonyl group as the reactive group that reacts with the compounds of component B to form a chemical bond linking the two components. Moreover, according to the invention, such compounds are also applicable as component A, in which the reactive carbonyl group is protected or derivatized in such a manner that the carbon atom of the derivatized or protected carbonyl group always remains reactive towards the component B. These derivatives are preferably condensation compounds of reactive carbonyl compounds with a) amines and their derivatives, forming imines or oximes as the condensation compounds b) alcohols, forming acetals or ketals as the condensation compounds c) water, forming hydrates with aldehydes as the condensation compound. [00097] Component A is preferably chosen from the group which is formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3 hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3 hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3 hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4 trihydroxyacetophenone, 3,4,5-trihyd roxyacetophenone, 2,4,6 trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5 35 H 06203 PCT RRTb trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4 hydroxy-3-methoxyacetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4 aminoacetophenone, 4-dimethylaminoacetophenone, 4 morpholinoacetophenone, 4-piperidinoacetophenone, 4 imidazolinoacetophenone, 2-hydroxy-5-bromoacetophenone, 4-hydroxy-3 nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4 carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2 aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4 dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4 trihydroxybenzophenone, 2-hydroxy-1 -acetonaphthone, 1-hydroxy-2 acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3 hydroxyflavone, 3,5,7-trihydroxyflavone, 4',5,7-trihydroxyflavone, 5,6,7 trihydroxyflavone, quercetin, 1-indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone, vanillin, coniferyl aldehyde, 2 methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2 ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4 hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4 hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4 hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4 hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3 hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2 ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2 hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3 dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5 dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4 dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4 trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6 trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5 trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2 hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3 dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5 36 H 06203 POT RR/Tb dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4 dihydroxybenzaldehyde, 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-hydroxy-2 methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4 diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4 diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4 morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4 piperidinobenzaldehyde, 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-1l-naphthaldehyde, 4-hydroxy-1 naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2 methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3 methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxycinnamaldehyde, 4 dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4 dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4 diethylaminocinnamaldehyde, 4-dibutylaminobenzaldehyde, 4 diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4-(1 imidazolyl)benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1 H,5H benzo[ij]quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy- 1H,5H benzo[ij]quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2 formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribase aldehyde), 2-indole aldehyde, 3-indole aldehyde, 1-methylindole-3-aldehyde, 2 methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl 3-acetylindole, 2-(1 ',3',3'-trimethyl-2-indolinylidene)acetaldehyde, 1 methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2 pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine, 3 acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyltrifluoroacetone, chromone-3-aldehyde, 3-(5'-nitro-2'-furyl)acrolein, 3-(2'-furyl)acrolein and 37 H 06203 PCT RRITb imidazole-2-aldehyde, 1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5 triacetylbenzene, 2-benzoylacetophenone, 2-(4' methoxybenzoyl)acetophenone, 2-(2'-furoyl)acetophenone, 2-(2' pyridoyl)acetophenone and 2-(3'-pyridoyl)acetophenone, benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4 methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4 dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4 pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4 morpholinobenzylideneacetone, 4-diethylaminobenzylideneacetone, 3 benzylidene-2,4-pentanedione, 3-(4'-hydroxybenzylidene)-2,4-pentanedione, 3 (4'-dimethylaminobenzylidene)-2,4-pentanedione, 2 benzylidenecyclohexanone, 2-(4'-hydroxybenzylidene)cyclohexanone, 2-(4' dimethylaminobenzylidene)cyclohexanone, 2-benzylidene-1,3 cyclohexanedione, 2-(4'-hydroxybenzylidene)-1,3-cyclohexanedione,- 3-(4' dimethylaminobenzylidene)-1,3-cyclohexanedione, 2-benzylidene-5,5-dimethyl 1,3-cyclohexanedione, 2-(4'-hydroxybenzylidene)-5,5-dimethyl-1,3 cyclohexanedione, 2-(4'-hydroxy-3-methoxybenzylidene)-5,5-dimethyl-1,3 cyclohexanedione, 2-(4'-dimethylaminobenzylidene)-5,5-dimethyl-1,3 cyclohexanedione, 2-benzylidenecyclopentanone, 2'-(4 hyd roxybenzylidene)cyclopentanone, 2-(4' dimethylaminobenzylidene)cyclopentanone, 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, 6-(4-dimethylaminophenyl)hexa-3,5-dien-2-one, 6-(4 diethylaminophenyl)hexa-3,5-dien-2-one, 6-(4-methoxyphenyl)hexa-3,5-dien-2 one, 6-(3,4-dimethoxyphenyl)hexa-3,5-dien-2-one, 6-(2,4 dimethoxyphenyl)hexa-3,5-dien-2-one, 6-(4-piperidinophenyl)hexa-3,5-dien-2 one, 6-(4-morpholinophenyl)hexa-3,5-dien-2-one, 6-(4-pyrrolidinophenyl)hexa 3,5-dien-2-one, 5-(4-dimethylamino-1 -naphthyl)penta-3,5-dienal, 2 nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3 nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3 38 H 06203 PCT RRTb nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5 nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3 nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3 nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2 nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5 dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5 nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro 4-formylbenzene sulfonic acid, 4-nitro-1 -naphthaldehyde, 2 nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9 methyl-3-carbazole aldehyde, 9-ethyl-3-carbazole aldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4-dimethyl-3 carbazole aldehyde, 1,4,9-trimethyl-3-carbazole aldehyde, 4-formyl-1 methylpyridinium-, 2-formyl-l1-methylpyridinium-, 4-formyl-1l-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 -methylquinolinium-, 2-formyl-1 methylquinolinium-, 4-acetyl-1l-methylpyridinium-, 2-acetyl-1l-methylpyridinium-, 4-acetyl-1 -methylquinolinium-, 5-formyl-1 -methylquinolinium-, 6-formyl-1 methylquinolinium-, 7-formyl-1 -methylquinolinium-, 8-formyl-1 methylquinolinium-, 5-formyl-1l-ethylquinolinium-, 6-formyl-1l-ethylquinolinium-, 7-formyl-1l-ethylquinolinium-, 8-formyl-1l-ethylquinolinium, 5-formyl-1 benzylquinolinium-, 6-formyl-1 -benzylquinolinium-, 7-formyl-1 benzylquinolinium-, 8-formyl-1l-benzylquinolinium-, 5-formyl-1l-allylquinolinium-, 6-formyl-1 -allylquinolinium-, 7-formyl-1 -allylquinolinium- and 8-formyl-1 allylquinolinium-, 5-acetyl-1l-methylquinolinium-, 6-acetyl-1l-methylquinolinium-, 7-acetyl-1 -methylquinolinium-, 8-acetyl-1 -methylquinolinium-, 5-acetyl-1 ethylquinolinium-, 6-acetyl-1l-ethylquinolinium-, 7-acetyl-1l-ethylquinolinium-, 8 acetyl-1 -ethylquinolinium-, 5-acetyl-1 -benzylquinolinium-, 6-acetyl-1 benzylquinolinium-, 7-acetyl-1 -benzylquinolinium-, 8-acetyl-1 benzylquinolinium-, 5-acetyl-1l-allylquinolinium-, 6-acetyl-1l-allylquinolinium-, 7 acetyl-1 -allylquinolinium- and 8-acetyl-1 -allylquinolinium-, 9-formyl-10 methylacridinium-, 4-(2'-formylvinyl)-l-methylpyridinium-, 1,3-dimethyl-2-(4' 39 H 06203 PCT RRITb formylphenyl)benzimidazolium-, 1,3-dimethyl-2-(4'-formylphenyl)imidazolium-, 2-(4'-formylphenyl)-3-methylbenzothiazolium-, 2-(4'-acetylphenyl)-3 methylbenzothiazolium-, 2-(4'-formylphenyl)-3-methylbenzoxazolium-, 2-(5' formyl-2'-furyl)-3-methylbenzothiazolium-, 2-(5'-formyl-2'-furyl)-3 methylbenzothiazolium-, 2-(5'-formyl-2'-thienyl)-3-methylbenzothiazolium-, 2 (3'-formylphenyl)-3-methylbenzothiazolium-, 2-(4'-formyl-1 -naphthyl)-3 methylbenzothiazolium-, 5-chloro-2-(4'-formylphenyl)-3-methylbenzothiazolium , 2-(4'-formylphenyl)-3,5-dimethylbenzothiazolium benzenesulfonate, p toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methyl sulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methylisatin, 1-allylisatin, 1-hydroxymethylisatin, 5 chloroisatin, 5-methoxyisatin, 5-nitroisatin, 6-nitroisatin, 5-sulfoisatin, 5 carboxyisatin, quinisatin, 1-methylquinisatin, and any mixtures of the above compounds. [00098] In general, CH-acids are recognized as compounds that possess a hydrogen atom bonded to an aliphatic carbon atom, in which the carbon hydrogen bond is activated due to electron-withdrawing substituents. According to the invention, CH-acidic compounds also include enamines, which result from the alkaline treatment of quaternized N-heterocycles having a CH-acidic alkyl group that is conjugated with the quaternary nitrogen. [00099] The CH-acidic compounds of component B are preferably chosen from the group consisting of 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3 tetramethyl-3H-indolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methyleneindoline (Fischer's base), 2,3 dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p toluenesulfonate, 2,3-dimethylnaphtho[1,2-d]thiazolium p-toluenesulfonate, 3 ethyl-2-methylnaphtho[1,2-d]thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1,4-dimethylquinolinium iodide, 1,2 dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3 dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylacetate, 2-coumaranone, 5-hydroxy-2-coumaranone, 40 H 06203 PCT RRfTb 6-hyd roxy-2-coumaranone, 3-methyl-1 -phenylpyrazolin-5-one, indane-1,2 dione, indane-1,3-dione, indan-1 -one, benzoylacetonitrile, 3 dicyanomethyleneindan-1 -one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethylcyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2 methylbenzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl 4-methylquinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3 trimethylquinoxalinium iodide, 3-ethyl-2-methylbenzoxazolium p toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl 4-methylquinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p toluenesulfonate, and 1,2,3-trimethylquinoxalinium p-toluenesulfonate. [000100] Preferred primary or secondary aromatic amines of component B are chosen from N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p phenylenediamine, N-(2-hydroxyethyl)-N-ethyl-p-phenylenediamine, N,N-bis(2 hydroxyethyl)-p-phenylenediamine, N-(2-methoxyethyl)-p-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4-dichloro-p-phenylenediamine, 2,5 dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4 morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2 aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5 diaminotoluene, 2,5-diaminophenol, 2,5-diaminoanisole, 2,5-diaminophenethol, 4-amino-3-methylphenol, 2-(2,5-diaminophenyl)ethanol, 2,4 diaminophenoxyethanol, 2-(2,5-diaminophenoxy)ethanol, 3-amino-4-(2 hydroxyethyloxy)phenol, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3 methyl-4-aminophenol, 2-methyl-5-(2-hydroxyethylamino)phenol, 3-amino-2 chloro-6-methylphenol, 2-methyl-5-amino-4-chlorophenol, 5-(2 hydroxyethylamino)-4-methoxy-2-methylphenol, 4-amino-2 hydroxymethylphenol, 2-(diethylaminomethyl)-4-aminophenol, 4-amino-1 hydroxy-2-(2-hydroxyethylaminomethyl)benzene, 1-hydroxy-2-amino-5 methylbenzene, 1 -hyd roxy-2-amino-6-methylbenzene, 2-amino-5 acetamidophenol, 1,3-dimethyl-2,5-diaminobenzene, 5-(3 hydroxypropylamino)-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 41 H 06203 PCT RRITb N,N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 5-amino-4-fluoro 2-methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino-5-(2 hydroxyethoxy)toluene, 2,4-diamino-5-methylphenetol, 3,5-diamino-2-methoxy 1-methylbenzene, 2-amino-4-(2-hydroxyethylamino)anisole, 2,6-bis(2 hydroxyethylamine)-l-methylbenzene, 1,3-diamino-2,4-dimethoxybenzene, 3,5 diamino-2-methoxytoluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 aminobenzoic acid, 2-aminophenylacetic acid, 3-aminophenylacetic acid, 4 aminophenylacetic acid, 2,3-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4 aminosalicylic acid, 5-aminosalicylic acid, 3-amino-4-hydroxybenzoic acid, 4 amino-3-hydroxybenzoic acid, 2-aminobenzenesulfonic acid, 3 aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4 hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-l1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4 hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7 disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5 aminoisophthalic acid, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,4,5 tetraminobenzene, 2,4,5-triaminophenol, pentaminobenzene, hexaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminopyrocatechin, 4,6 diaminopyrogallol, 1-(2-hydroxy-5-aminobenzyl)-2-imidazolidinone, 4-amino-2

((

4 -[(5-amino-2-hydroxyphenyl)methyl]piperazinyl)methyl)phenol, 3,5-diamino 4-hydroxypyrocatechin, 1,4-bis(4-aminophenyl)-1,4-diazacycloheptane, aromatic nitriles, such as 2-amino-4-hydroxybenzonitrile, 4-amino-2 hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile, nitro group containing amino compounds, such as 3-amino-6-methylamino-2-nitropyridine, picramic acid, [8-[(4-amino-2-nitrophenyl)azo]-7-hydroxynaphth-2-yl]trimethyl ammonium chloride, [8-((4-amino-3-nitrophenyl)azo)-7-hydroxynaphth-2 yl]trimethyl ammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4,6 dinitrobenzene, 1-amino-2-nitro-4-[bis(2-hydroxyethyl)amino]benzene, 1-amino 2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5), 1-amino-2-nitro-4 [(2-hydroxyethyl)amino]benzene (HC Red No. 7), 2-chloro-5-nitro-N-2 hydroxyethyl-1,4-phenylenediamine, 1-[(2-hydroxyethyl)amino]-2-nitro-4 aminobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 42 H 06203 PCT RR/Tb 6-nitro-o-toluidine, 1-amino-3-methyl-4-[(2-hydroxyethyl)amino]-6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4-[(2,3-dihydroxypropyl)amino]-5 chlorobenzene (HC Red No. 10), 2-(4-amino-2-nitroanilino)benzoic acid, 6 nitro-2,5-diaminopyridine, 2-amino-6-chloro-4-nitrophenol, 1-amino-2-(3 nitrophenylazo)-7-phenylazo-8-naphthol-3,6-disulfonic acid disodium salt (Acid Blue No. 29), 1-amino-2-(2-hydroxy-4-nitrophenylazo)-8-naphthol-3,6-disulfonic acid disodium salt (Palatine chrome green), 1-amino-2-(3-chloro-2-hydroxy-5 nitrophenylazo)-8-naphthol-3,6-disulfonic acid disodium salt (Gallion), 4-amino 4'-nitrostilbene-2,2'-disulfonic acid disodium salt, 2,4-diamino-3',5'-dinitro-2' hydroxy-5-methylazobenzene (Mordant brown 4), 4'-amino-4 nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1-amino-4-nitro-2-(2-nitrobenzylideneamino)benzene, 2-[2 (diethylamino)ethylamino]-5-nitroaniline, 3-amino-4-hydroxy-5 nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4 nitroacenaphthene, 2-amino-1 -nitronaphthalene, 5-amino-6-nitrobenzo-1,3 dioxole, anilines, in particular, nitro group-containing anilines, such as 4 nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4 nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1 -(2-hydroxyethylamino)benzene, 2-nitro-1 -amino-4-[bis(2 hydroxyethyl)amino]benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 1-amino-5-chloro-4-(2-hydroxyethylamino)-2-nitrobenzene, aromatic anilines and phenols with a further aromatic group, as shown in the formula II

R

7 R 10 R9" P 1

R

1 R 9P R -1

R

12 (I R (ll) in which * R 7 stands for a hydroxyl or an amino group, which can be substituted with Cl 14 -alkyl, CI4-hydroxyalkyl, C14-alkoxy or C14-alkoxy-Cl4-alkyl groups, * R 8 , R 9 , R 10 , R 11 and R 12 independently of one another stand for a hydrogen atom, a hydroxyl or an amino group, which can be substituted with C- 43 H 06203 PCT RRITb alkyl, Cl4-hydroxyalkyl, Cl4-alkoxy, C14-aminoalkyl or Cl4-alkoxy-C 1 4-alkyl groups, and * P is a direct bond, an optionally hydroxyl group-substituted, saturated or unsaturated carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfoxy, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula III

-Q'-(CH

2

-Q-CH

2 -Q")o- (111) in which * Q means a direct bond, a CH 2 - or CHOH- group, * Q' and Q", independently of one another, stand for an oxygen atom, an

NR

13 group, in which R 13 is a hydrogen atom, a C 14 -alkyl or a hydroxy C1_4-alkyl group, it also being possible for the two groups, together with the remainder of the molecule, to form a 5-, 6- or 7-membered ring, the group O-(CH 2 )p-NH or NH-(CH 2 )p'-O, in which p and p' are 2 or 3, and * o is a number from 1 to 4, [000101] such as, for example, 4,4'-diaminostilbene and the hydrochloride thereof, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4-amino 4'-dimethylaminostilbene and hydrochloride thereof, 4,4' diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,3',4,4' tetraminodiphenyl, 3

,

3 ',4,4'-tetraminobenzophenone, 1,3-bis(2,4 diaminophenoxy)propane, 1, 8 -bis(2,5-diaminophenoxy)-3,6-dioxaoctane, 1,3 bis(4-aminophenylamino)propane, 1,3-bis(4-aminophenylamino)-2-propanol, 1,3-bis[N-(4-aminophenyl)-2-hydroxyethylamino]-2-propanol, N,N-bis[2-(4 aminophenoxy)ethyl]methylamine, N-phenyl-1,4-phenylenediamine and bis(5 amino-2-hydroxyphenyl)methane. 44 H 06203 PCT RR/Tb [000102] The above-mentioned compounds can be used either in the free form or in the form of their physiologically compatible salts, in particular, as salts of inorganic acids, such as hydrochloric acid or sulfuric acid. [000103] Suitable nitrogen-containing heterocyclic compounds are, for example, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3 hydroxypyridine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2 (aminoethylamino)-5-aminopyridine, 2,3-diaminopyridine, 2-dimethylamino-5 aminopyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,3-diamino-6 methoxypyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,4,5-triaminopyridine, 2,6-dihydroxy-3,4-dimethylpyridine, N-[2-(2,4-diaminophenyl)aminoethyl]-N-(5 amino-2-pyridyl)amine, N-[2-(4-aminophenyl)aminoethyl]-N-(5-amino-2 pyridyl)amine, 2,4-dihydroxy-5,6-diaminopyrimidine, 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4,5,6-tetraminopyrimidine, 2-methylamino-4,5,6-triaminopyrimidine, 2,4 diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy-6 methylpyrimidine, 3,5-diaminopyrazole, 3,5-diamino-1,2,4-triazole, 3 aminopyrazole, 3-amino-5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1 (2-hydroxyethyl)-4,5-diaminopyrazole, 1-phenyl-3-methyl-4,5-diaminopyrazole, 4-amino-2,3-dimethyl-1 -phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 1 phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8 aminoquinoline, 4-aminoquinaldine, 2-aminonicotinic acid, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5 aminobenzimidazole, 7-aminobenzimidazole, 5-aminobenzothiazole, 7 aminobenzothiazole, 2,5-dihydroxy-4-morpholinoaniline, and indole and indoline derivatives, such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7 aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. Further heterocyclic compounds, which can be used according to the invention, are the hydroxypyrimidines disclosed in DE-U1-299 08 573. The above mentioned compounds can be used either in the free form or in the form of their physiologically compatible salts, e.g., as salts of inorganic acids, such as hydrochloric acid or sulfuric acid. 45 H 06203 PCT RRJTb [000104] Suitable aromatic hydroxy compounds are, for example, 2 methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5 dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucine, hydroxyhydroquinone, 2-methoxyphenol, 3 methoxyphenol, 4-methoxyphenol, 3-dimethylaminophenol, 2-(2 hydroxyethyl)phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxyphenylacetic acid, 3,4 dihydroxyphenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, 2,4,6 trihydroxyacetophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7 dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid. [000105] The compounds of component A and the compounds of component B are preferably used in the compositions according to the invention in each case in an amount of from 0.03 to 65 mmol, in particular, from 1 to 40 mmol, based on 100 g of the overall dyeing composition. The molar ratio of the compound of component A and the compound of component B can be in the range from 0.5 to 2.0, preference being given to the use of equimolar quantities. If components A and B are stored separately, the actual dyeing composition is prepared directly prior to use by mixing. [000106] In principle, an oxidative coloration of the fibers can take place with atmospheric oxygen in the presence of oxidation dye precursors. However, it is preferred to use a chemical oxidizing agent, particularly when a lightening effect of the natural pigments of human hair besides the coloring is desired. This lightening effect may be desired independently of the dyeing method. The presence of oxidation dye precursors is accordingly not a necessary prerequisite for the use of oxidizing agents in the dyeing compositions of the method according to the invention. Suitable oxidizing agents are, in particular, hydrogen peroxide and its addition products onto urea, melamine and sodium borate. If the dye precursors and the oxidizing agent are stored separately, the actual dyeing composition is prepared directly prior to use by mixing. 46 H 06203 PCT RRTb [000107] According to the invention, it is preferred to formulate the dyeing compositions of the method according to the invention to be free from peroxy compounds. Peroxy compounds are defined as the compounds as are described below in the scope of the preferred embodiments of the nuancing agent. [000108] According to the invention, however, the oxidation dyeing composition can also be applied to the hair together with a catalyst that activates the oxidation of the dye precursors, e.g., by atmospheric oxygen. Such catalysts are, for example, metal ions, iodides, quinones or certain enzymes. [000109] Suitable metal ions are, for example, Zn 2+ , Cu 2 + , Fe2+, Fe 3 +, Mn2+, Mn 4 +, Li*, Mg 2 , Ca2+ and Al 3 +. Zn2+, Cu 2 + and Mn 2+ are particularly suitable here. In principle, the metal ions can be employed in the form of any physiologically compatible salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By use of these metal salts, both the formation of the coloration can be accelerated, and the color tint can be selectively influenced. [000110] Suitable enzymes are, for example, peroxidases, which can considerably enhance the effect of small amounts of hydrogen peroxide. Also of suitability according to the invention are those enzymes which directly oxidize the oxidation dye precursors with the help of atmospheric oxygen, such as, for example, the laccases, or produce in situ small amounts of hydrogen peroxide and in so doing 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 substrates specific therefor, e.g. pyranose-oxidase and e.g. D-glucose or galactose, glucose-oxidase and D-glucose, glycerine-oxidase and glycerine, 47 H 06203 PCT RR/Tb pyruvate-oxidase and pyruvic acid or its salts, alcohol-oxidase and alcohol (MeOH, EtOH), lactate-oxidase and lactic acid or its salts, tyrosinase-oxidase and tyrosine, uricase and uric acid or its salts, choline oxidase and choline, amino acid oxidase and amino acids. [000111] When using oxidizing agents, the actual dyeing composition is expediently prepared directly prior to use by mixing the preparation of the oxidizing agent with the preparation comprising the compounds of the formula I and optionally dye precursors. The resulting ready-for-use hair coloration preparation should preferably have a pH in the range 6 to 12. The hair dye is particularly preferably applied in a weakly alkaline milieu. The application temperatures can be in a range between 15 and 40 OC. After a contact time of 5 to 45 minutes, the hair dye is removed from the hair by rinsing. There is no need to wash the hair with a shampoo if a strong surfactant-containing carrier, e.g. a color enhancing shampoo, was used. [000112] Particularly in the case of hair that is difficult to dye, it is possible to apply a composition according to the invention to the hair, optionally with additional dye precursors, but also without prior mixing with the oxidizing component. After an application time of 20 to 30 minutes, and optionally after an intermediate rinse, the oxidation component is applied. After an application time of 10 to 20 minutes, the hair is then rinsed and if desired shampooed. In this embodiment, according to a first variant, in which the prior application of the dye precursors was intended to afford a better penetration into the hair, the agent is adjusted to a pH of about 4 to 7. According to a second variant, initially an air oxidation is aimed for, wherein the applied agent preferably has a pH from 7 to 10. In the subsequent accelerated post-oxidation, the use of acidically adjusted peroxydisulfate solutions can be preferred as the oxidizing agent. 48 H 06203 PCT RR/Tb [000113] The compositions of the method according to the invention comprise the inventive ingredients preferably in a suitable aqueous, alcoholic or aqueous-alcoholic cosmetic carrier. Such carriers are, for example, creams, emulsions, gels and also surfactant-containing foaming solutions, such as, for example, shampoos, foam aerosols or other preparations that are suitable for use on the hair. However, it is also conceivable to integrate the ingredients into a powdered or tablet-shaped formulation. [000114] For the purposes of the present invention, aqueous-alcoholic solutions are understood as meaning aqueous solutions comprising 3 to 70% by weight of a Cl-C 4 -alcohol, in particular, ethanol or isopropanol. The compositions according to the invention can additionally comprise further organic solvents, such as, for example, methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference here is given to all water-soluble organic solvents. [000115] The colorants and the shading compositions of the inventive method can furthermore comprise all active substances, additives and auxiliaries known for such preparations. [000116] In many cases the colorants and/or shading compositions comprise at least one surfactant, wherein, in principle, not only anionic, but also zwitterionic, ampholytic, non-ionic and cationic surfactants are suitable. However, in many cases it has proved advantageous to select the surfactants from among anionic, zwitterionic or non-ionic surfactants. [000117] Suitable anionic surfactants for the inventive preparations are all anionic surface-active materials that are suitable for use on the human body. They are characterized by a water solubilizing anionic group, such as e.g. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing about 10 to 22 carbon atoms. In addition, the molecule may contain glycol or polyglycol ether groups, ester, ether and amide groups as well as hydroxyl groups. Exemplary suitable anionic surfactants are, each in the form 49 H 06203 PCT RRITb of the sodium, potassium and ammonium as well as the mono-, di- and trialkanol ammonium salts with 2 or 3 carbon atoms in the alkanol group, - linear fatty acids containing 10 to 22 carbon atoms (soaps), - ether carboxylic acids of the formula R-O-(CH 2

-CH

2 0)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, - sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethylene groups, - linear alkane sulfonates with 12 to 18 carbon atoms, - linear alpha-olefin sulfonates with 12 to 18 carbon atoms - alpha-sulfo fatty acid methyl esters of fatty acids with 12 to 18 carbon atoms, - alkyl sulfates and alkyl polyglycol ether sulfates of formula R-(CH 2

-CH

2 0)x-SO 3 H, in which R is preferably a linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12, - Mixtures of surface-active hydroxy sulfonates according to DE-A-37 25 030, - sulfated hydroxyalkyl polyethylene- and/or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354, - sulfonated unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344, 50 H 06203 PCT RR/Tb - esters of tartaric acid and citric acid with alcohols that represent the addition products of about 2-15 molecules of ethylene oxide and/or propylene oxide on fatty alcohols with 8 to 22 carbon atoms, [000118] 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 especially salts of saturated and particularly unsaturated 08-022 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. [000119] Non-ionic surfactants comprise e.g. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Exemplary compounds of this type are - addition products of 2 to 30 moles ethylene oxide and/or 0 to 5 moles propylene oxide to linear fatty alcohols with 8 to 22 carbon atoms, to fatty acids with 12 to 22 carbon atoms and to alkyl phenols with 8 to 15 carbon atoms in the alkyl group, - 012-022 fatty acid mono and diesters of addition products of 1 to 30 moles ethylene oxide on glycerine; - 08-022 alkyl mono- and oligoglycosides and their ethoxylated analogs and - addition products of 5 to 60 moles ethylene oxide on castor oil and hydrogenated castor oil, [000120] Preferred non-ionic surfactants are alkyl polyglycosides of the general formula R' 1 0-(Z)x. These compounds are characterized by the following parameters. [000121] The alkyl group R 1 comprises 6 to 22 carbon atoms and may be both linear and also branched. Primary linear aliphatic groups and aliphatic groups, which are methyl-branched in the 2-position, are preferred. Such alkyl 51 H 06203 PCT RR/Tb groups are for example 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1 stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. On using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain preponderate. [000122] The alkyl polyglycosides used according to the invention may simply comprise for example a defined alkyl group R 1 . However normally, these compounds are manufactured from natural fats and oils or mineral oils. In which case, the alkyl groups R are present as mixtures corresponding to the starting compounds or to each of the compounds worked up. [000123] Such alkyl polyglycosides are particularly preferred in which R' consists - essentially of C8- and Clo0 alkyl groups, - essentially of C 1 2 - and C 1 4 alkyl groups, - essentially of C8- to C16 alkyl groups or - essentially of C12- to C16 alkyl groups. [000124] Any mono or oligosaccharide can be added as the sugar building block Z. Usually, sugars with 5 or 6 carbon atoms as well as the corresponding oligosaccharides are used. Such sugars are for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; glucose is particularly preferred. [000125] The alkyl polyglycosides used according to the invention comprise on average 1.1 to 5 sugar units. Alkyl polyglycosides with x-values of 1.1 to 1.6 are preferred. Alkyl polyglycosides with x-values of 1.1 to 1.4 are quite particularly preferred. [000126] Besides their surfactant effect, the alkyl glycosides also serve to improve the fixing of scent components on the hair. Thus, when it is desirable for the effect of the perfume oil on the hair to last beyond the hair treatment, the 52 H 06203 PCT RR/Tb person skilled in the art will preferably have recourse to this class of substances as a further ingredient of the inventive preparations. [000127] The alkoxylated homologs of the cited alkyl polyglycosides can also be used according to the invention. These homologs can comprise on average up to 10 ethylene oxide and/or propylene oxide units per alkyl glycoside unit. [000128] Moreover, zwitterionic surfactants can be used, particularly as co surfactants. Zwitterionic surfactants are designated as those surface-active compounds that carry at least one quaternary ammonium group and at least one -COO(-)or -SO3 ( -) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example the cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example the cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3 carboxymethyl-3-hydroxyethyl imidazolines with 8 to 18 carbon atoms in each of the alkyl or acyl groups, as well as cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative, known under the INCl name cocoamidopropyl betaine. [000129] Likewise suitable, in particular as co-surfactants, are ampholytic surfactants. The ampholytic surfactants are understood to include such surface-active compounds that apart from a C 8

-

18 alkyl or acyl group, comprise at least one free amino group and at least one COOH or SO 3 H group in the molecule, and are able to form internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylamino propionic acids, N-alkylamino butyric acids, N-alkylimino dipropionic acids, N-hydroxyethyl-N alkylamidopropylglycine, N-alkyltaurines, N-alkylsarcosines, 2 alkylaminopropionic acids and alkylamino acetic acids with about 8 to 18 carbon atoms in each alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylamino propionate, the cocoacylaminoethylamino propionate and the C 1 2 -1 8 acyl sarcosine. 53 H 06203 PCT RR/Tb [000130] According to the invention, surfactants of the type quaternary ammonium compounds, esterquats and the amido amines are particularly employed as the cationic surfactants. [000131] Preferred quaternary ammonium compounds are ammonium halides, particularly chlorides and bromides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chloride, e.g. cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride, as well as the imidazolium compounds known under the INCl designations Quaternium-27 and Quaternium-83. The long alkyl chains of the abovementioned surfactants have preferably 10 to 18 carbon atoms. [000132] Esterquats are known compounds, which both comprise at least one ester function and also a quaternary ammonium group as structural elements. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2 dihydroxypropyldialkylamines. Such products are marketed, for example, under the trade names Stepantex@, Dehyquart@ and Armocare®. The products Armocare® VGH-70, an N,N-bis(2-palmitoyloxyethyl)dimethyl ammonium chloride, as well as Dehyquart@ F-75, and Dehyquart@ AU-35 are examples of such esterquats. [000133] The alkylamido amines are normally manufactured by the amidation of natural or synthetic fatty acids and fatty acid fractions with dialkylaminoamines. According to the invention, a particularly suitable compound from this substance group is represented by stearamidopropyldimethylamine, commercially available under the designation Tegamid ® S 18. 54 H 06203 PCT RRITb [000134] The quatemized protein hydrolyzates illustrate further inventively usable cationic surfactants. [000135] Cationic silicone oils, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (comprising a hydroxylamino modified silicone, 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) are similarly suitable according to the invention. [000136] An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat®100, a "lauryl methyl gluceth-10 hydroxypropyl dimonium chloride" according to INCI nomenclature. [000137] For compounds with alkyl groups used as surfactants, they may each be pure substances. However, it is normally preferred to start with natural vegetal or animal raw materials for the manufacture of these materials, with the result that mixtures of substances are obtained, which have different alkyl chain lengths that depend on each raw material. [000138] For surfactants, which are represented by the addition products of ethylene oxide and/or propylene oxide to fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution as well as those with a narrow homolog distribution may be used. The term "normal" homolog distribution is understood to mean mixtures of homologs obtained from the reaction of fatty alcohols and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. On the other hand, narrow homolog distributions are obtained if e.g. hydrotalcite, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred. 55 H 06203 PCT RRITb [000139] In addition, the dyeing compositions and the shading compositions of the inventive method can comprise further active ingredients, auxiliaries and additives, such as, for example, non-ionic polymers, such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers and polysiloxanes, cationic polymers, such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide dimethyl diallyl ammonium chloride copolymers, dimethylaminoethyl methacrylate-vinyl pyrrolidone copolymers quaternized with diethyl sulfate, vinyl pyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers, such as, for example, acrylamidopropyl trimethyl ammonium chloride/acrylate copolymers and octylacrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, anionic polymers, such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/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, structurants such as maleic acid and lactic acid, hair conditioning compounds like phospholipids, for example soya lecithin, egg lecithin and cephalin, protein hydrolyzates, particularly those of elastin, collagen, keratin, milk protein, soya protein and wheat protein, their condensation products with fatty acids as well as quaternized protein hydrolyzates, perfume oils, dimethyl isosorbitol and cyclodextrins, solvents and solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerine and diethylene glycol, fiber structure improvers, particularly mono, di and oligosaccharides, such as, for example glucose, galactose, fructose, fruit sugar and lactose, 56 H 06203 PCT RRITb quaternized amines, such as methyl 1-alkylamidoethyl-2-alkylimidazolium methosulfate defoamers such as silicones, dyestuffs to color the composition, anti-dandruff active materials like piroctone olamine, zinc omadine and climbazole, photo protective agents, in particular derivatized benzophenones, cinnamic acid derivatives and triazines, substances for adjusting the pH, such as, for example, customary acids, in particular food acids and bases, active ingredients, such as allantoin, pyrrolidone carboxylic acids and salts thereof, and bisabolol, vitamins, provitamins and vitamin precursors, in particular those of groups A, B3, Bs, B 6 , C, E, F and H, plant extracts such as extracts from green tea, oak bark, stinging nettle, hamamelis, hops, henna, camomile, burdock root, field horsetail, hawthorn, linden flowers, almonds, aloe vera, spruce needles, horse chestnut, sandal wood, juniper, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, malva, lady's smock, common yarrow, thyme, lemon balm, rest-harrow, coltsfoot, marshmallow (althaea), meristem, ginseng and ginger, cholesterol, thickeners like sugar esters, polyol esters or polyol alkyl ethers, fats and waxes like spermaceti, beeswax, montan wax and paraffins, fatty acid alkanolamides, chelating agents like EDTA, NTA, P-alanine diacetic acid and phosphonic acids, swelling and penetration agents such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas, and primary, secondary and tertiary phosphates, opacifiers such as latex, styrene/PVP copolymers and styrene/acrylamide copolymers, 57 H 06203 PCT RR/Tb pearlizing agents such as ethylene glycol mono- and distearate as well as PEG-3-distearate, pigments, stabilizers for hydrogen peroxide and other oxidizing agents, blowing agents such as propane-butane mixtures, N 2 0, dimethyl ether, CO 2 and air, antioxidants [000140] With regard to further optional ingredients and their amounts used, reference is expressly made to the relevant handbooks known to the expert, for example the monograph by K. Schrader, Grundlagen und Rezepturen der Kosmetika, 2nd edition, HOthig Buch Verlag, Heidelberg, 1989. [000141] The application temperatures of the colorants can be in a range between 15 and 40 oC. After a contact time Z2 of preferably 2 to 60 minutes, particularly preferably 5 to 45 minutes, the hair dye is removed from the hair by rinsing. There is no need to wash the hair with a shampoo if a strong surfactant-containing carrier, e.g. a color enhancing shampoo, was used. [000142] It is essential to the invention to carry out the coloration step C of the inventive method directly after step A and/or step B. The time that is defined as directly afterwards for the purposes of the invention is at most 90 minutes. The preferred time interval between the completed procedure of step A of the method according to the invention and the start of the procedure of step C should be not longer than 60 minutes, particularly preferably not longer than 45 minutes, quite particularly preferably not longer than 20 minutes. [000143] A second subject matter of the present application is a kit, comprising * optionally an applicator, * a container Cl, comprising a dye, * a container C2a, comprising a hydrogen peroxide-containing composition and 58 H 06203 PCT RR/Tb * a container C2b, comprising a composition that comprises at least one thickener and at least one alkalizing agent. wherein the dye, as the coloring component, comprises (b) at least two oxidation dye precursors, wherein one oxidation dye precursor must be of the developer type or (c) at least two oxo dye precursors, wherein at least one oxo dye precursor must be a reactive carbonyl compound [000144] It is preferred that the shading composition resulting from mixing the contents of container C2a and C2b has a viscosity of from 5000 to 100 000 mPa s (Brookfield rotary viscometer, 25 'C, spindle #4, 20 rpm). [000145] The dyeing composition and the shading composition as a mixture of C2a and C2b have the preferred features as have been described in the first subject matter of the invention. Suitable applicators are the applicators specified in the first subject matter of the invention. Furthermore, it is preferred according to the invention to additionally include in the kit a cap with, optionally only predrawn hole grids and a crochet hook. The cap has the preferred features as already described in the first subject matter of the invention. [000146] Preferably, the kit contains the dyeing composition in two containers Cla and Clb. For an oxidative dyeing composition, container Cla contains the so-called dyeing cream that comprises the dye precursors, and a hydrogen peroxide-containing composition is kept in container lb. [000147] If it is an oxo dyeing composition, the compounds of component A can be stored in container Cla and, separately, the compounds of component B can be stored in container C1b. [000148] A third subject matter of the invention is the use of the kit according to the second subject matter of the invention in a method of the first subject matter of the invention. 59 H 06203 PCT RRTb Examples The following raw materials were used in the preparation of the formulation examples below: Hydrenolo D C 16

-C

18 fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis) Texapon® NSO sodium lauryl sulfate (INCI name: Sodium Lauryl Sulfate) (Cognis) Lorol® techn. C 1 2

-C

18 -fatty alcohol (INCI name: Coconut Alcohol) (Cognis) Lorol® C 16 cetyl alcohol (Cognis) Dehyton® K N,N-Dimethyl-N-(C8-C, la-cocoamidopropyl) ammonium acetobetaine (ca. 30 % active substance; INCl name: Aqua (Water), Cocamidopropyl Betaine) (Cognis) Aculyn® 33 (INCI name: Acrylates Copolymer) (Rohm & Haas) Turpinal® SL 1-hydroxyethane-1,1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water)) (Solutia) Soda water-glass 40/42 sodium silicate (Cognis) Idranal® Ill ethylenediaminetetraacetic acid disodium salt-2

H

2 0 (INCl name: Disodium EDTA) (manufacturer: Riedel De Haen) Britesil® C20 sodium silicate (INCI name: Sodium Silikate) (The PQ Corporation) Eumulgin® B2 cetylstearyl alcohol with ca. 20 EO units (INCl name: Ceteareth-20) 60 H 06203 PCT RRITb Lanette® E cetylstearyl alcohol sulfate, sodium salt (INCI name: Sodium Cetearyl Sulfate) (Cognis) Ceasit I C16-18 fatty acid, calcium salt (INCl name: Calcium Stearate) (Barlocher) Aerosil ® 200 Silicon dioxide (INCl name: Silica) (Degussa) 1. Formulations of the Oxidation Hair Dyeing Composition A dyeing cream is manufactured according to Table 2: Table 2: Dyeing cream Quantities in Raw material wt.% Hydrenol® D 8.0 Lorol® techn. 2.0 Texapon® NSO 16.0 Dehyton® K 10.0 Ascorbic acid 0.4 Sodium sulfite 0.5 Ammonium chloride 0.5 Turpinal® SL 0.2 Soda water-glass 40/42 0.5 m-Aminophenol 0.02 Resorcinol 0.13 p-Toluylenediamine 0.36 2,7-Dihydroxynaphthalene 0.10 2-Methylresorcinol 0.03 61 H 06203 PCT RR/Tb 3-Amino-2-methylamino-6-methoxypyridine 0.015 2-Amino-3-hydroxypyridine 0.001 3-Methyl-4-aminophenol 0.03 Perfume 0.2 Ammonia (25% aqueous solution) 0.6 Water ad 100 2. Formulations of the shading composition The following compositions in Tables 3 and 4 were manufactured: Table 3: Shading powder Raw material Quantities in wt.% Ammonium peroxydisulfate 21.5 Sodium phosphate 4.0 Aerosil 200 3.0 Potassium persulfate 33.0 Britesil® C20 22.0 Sodium stearate 8.0 Ceasit I 4.0 Magnesium oxide 2.0 Magnesium hydroxide 1.0 carbonate Lanette@ E 1.0 Idranal® III 0.5 62 H 06203 PCT RRITb Table 4: Hydrogen peroxide solution Raw material Quantity in wt.% Lorol C16 3.6 Eumulgin 0.9 Texapon@ NSO 2.25 Ammonia (25%) 0.65 Dipicolinic acid 0.1 Sodium pyrophosphate 0.03 Turpinal@ SL 1.5

H

2 0 2 6 Water ad 100 3. Assessment of the dyeing result of the inventive method 3.1 Carrying out Step A of the inventive method 25.0 g of the shading powder of Table 3 was mixed with 50 mL of the composition of Table 4 to afford the shading composition. Onto a separated fiber bundle consisting of about one third of the hair fibers of a human hair tress, 1 g of the shading composition was applied uniformly over the entire area of the fiber bundle by means of a mascara brush, left on the hair for a period of 10 minutes at 32 *C, and then rinsed off. The hair tress was dried with the hand towel and retained a residual dampness. 3.2 Carrying out Step C of the inventive method Shortly before use, a dyeing cream of Table 2 was mixed with the oxidizing agent preparation of Table 5 in the weight ratio 1: 1. Table 5: Oxidizing agent preparation Raw material Quantity in wt.% Hydrogen peroxide 6.00 63 H 06203 PCT RR/Tb Aculyn® 33 3.40 Texapon® NSO 2.00 Turpinal® SL 1.50 Sodium pyrophosphate 0.03 Dipicolinic acid 0.10 Ammonia (25% aqueous solution) 0.62 Water ad 100 2 g of the previously manufactured mixture were applied to the complete hair tress treated according to point 3.1, left on the hair for a period of 30 minutes at 32 °C, and then rinsed off. The hair tress was dried and the coloration result of the shaded hair was assessed. The hair acquired a blonde coloration with light blonde color reflections in the shaded area. 4. Use of a Cap with Hole Grid The dry head hair of a test subject with light blonde starting hair was covered with a cap with a hole grid. Using a crochet hook, individual hair strands were pulled through the holes in the cap, said holes being uniformly distributed over the surface of the cap. The hair strands that had been pulled through were combed. The shading composition was prepared by mixing 25.0 g of the shading powder of Table 3 and 50 mL of the composition according to Table 4 and applied to the hair strands using a brush. After a contact time of 30 minutes, the shading composition was rinsed off and the cap removed from the head and the hair was dried with a hand towel such that the hair retained a residual dampness (inventive step A). A hair dyeing composition was prepared by mixing the dyeing cream of Table 2 with the oxidizing agent preparation of Table 5 in a weight ratio of 1: 1. 64 H 06203 PCT RR/Tb This hair dyeing composition was applied to the entire head hair of the test subject and rinsed off again after a contact time of 30 minutes (step C of the inventive method). The hair acquired a basic blonde tone with light blonde meshes both in the hair on top and also in the underlying areas. The meshes are uniformly shaded from the hairline to the ends and form a sharp contrast to the non-shaded hair. 65

Claims (14)

1. Method for dyeing keratin-containing fibers, in particular human hair, in which A a shading composition, comprising, in a cosmetic carrier, at least one thickener, hydrogen peroxide and at least one alkalizing agent, is applied on one part of the fibers and is rinsed off again after a contact time Z1, B the fibers are subsequently optionally dried and then C a dye comprising coloring components is applied onto all the fibers and rinsed off again after a contact time Z2, wherein the dye, as the coloring component, comprises (a) at least two oxidation dye precursors, wherein at least one oxidation dye precursor must be of the developer type or (b) at least two oxo dye precursors, wherein at least one oxo dye precursor must be a reactive carbonyl compound.

2. Method according to claim 1, wherein the shading composition further comprises at least one peroxy compound.

3. Method according to one of claims 1 or 2, wherein the shading composition is applied onto a part of the previously dyed keratinic fibers by means of an applicator chosen from the group formed from brushes, pencils and applicettes.

4. Method according to one of claims 1 to 3, wherein the viscosity of the shading composition is 5000 to 100 000 mPa s (Brookfield rotation viscosimeter, 25 'C, spindle #4, 20rpm).

5. Method according to one of claims 1 to 4, wherein prior to Step A, the keratin-containing fibers are covered with a cap comprising an optionally 66 H 06203 PCT RR/Tb only premarked grid of holes, through which selected fiber bundles are pulled, then Step A is effected and then the cap is removed again.

6. Method according to one of claims 1 to 5, wherein the time between the completed Step A and the start of Step C is 60 minutes at most.

7. Method according to one of claims 1 to 6, wherein the dyeing composition is free of substantive dyes.

8. Method according to one of claims 1 to 7, wherein the oxidation dye precursors of the developer type are selected from the list formed by 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-(2-hydrbxyethoxy)phenol, 4-amino-2 methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2 methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(P hydroxyethylaminomethyl)phenol, 4-amino-2-(a,1-dihydroxyethyl)phenol, 4 amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6 dichlorophenol, 4-amino-2-(diethylaminomethyl)phenol, N,N'-bis(p hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropan-2-ol, N,N'-bis(p hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4 aminophenyl)tetramethylenediamine, N,N'-bis(P3-hydroxyethyl)-N,N'-bis(4 aminophenyl)tetramethylenediamine, N,N'-bis(4 methylaminophenyl)tetramethylenediamine, N,N'-diethyl-N,N'-bis(4'-amino 3'-methylphenyl)ethylenediamine, bis(2-hydroxy-5-aminophenyl)methane, 1,3-bis(2,5-diaminophenoxy)propan-2-ol, 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, p-phenylenediamine, p-toluylenediamine, 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 67 H 06203 PCT RRTb methyl-(N, N-diethyl)aniline, N,N-bis(P-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis(P-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(o hydroxyethyl)amino-2-chloroaniline, 2-(13-hydroxyethyl)-p phenylenediamine, 2-(a,0-dihydroxyethyl)-p-phenylenediamine, 2-fluoro-p phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(P-hydroxypropyl) p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl 3-methyl-p-phenylenediamine, N,N-(ethyl, 3-hydroxyethyl)-p phenylenediamine, N-(P,y-dihydroxypropyl)-p-phenylenediamine, N-(4' aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-(P hydroxyethyloxy)-p-phenylenediamine, 2-(P-acetylaminoethyloxy)-p phenylenediamine, N-p-methoxyethyl)-p-phenylenediamine and 5,8 diaminobenzo-1,4-dioxane, 4,5-diamino-1l-methylpyrazole, 4,5-diamino-1 (-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-l1-(4' chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3 methyl-l-phenylpyrazole, 4,5-diamino-l1-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-1l-(P3-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-1l-isopropylpyrazole, 4,5-diamino-3-methyl-1 isopropylpyrazole, 4-amino-5-(2-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1 methyl-4-methylaminopyrazole, 3,5-diamino-4-(P3-hydroxyethyl)amino-1 methylpyrazole, 2,4,5,6-tetraminopyrimidine, 4-hydroxy-2,5,6 triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino 4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6 triaminopyrimidine, 2,5-diaminopyridine, 2-(4'-methoxyphenyl)amino-3 aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(P-methoxyethyl)amino-3 amino-6-methoxypyridine and 3,4-diaminopyridine and their physiologically compatible salts. 68 H 06203 PCT RRITb

9. Method according to one of claims 1 to 8, wherein the oxidation dye precursors are selected from the list formed by 1-naphthol, 1,5 dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7 dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, m-phenylenediamine, 1-phenyl-3-methylpyrazol-5-one, 2,4 dichloro-3-aminophenol, 1, 3 -bis(2,4-diaminophenoxy)propane, 2 chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 3 amino-2-methylamino-6-methoxypyridine, 2-amino-3-hydroxypyridine, 2,6 dihydroxy-3,4-dimethylpyridine, 2-methylresorcinol, 5-methylresorcinol, 2 methyl-4-chloro-5-aminophenol and the physiologically compatible salts of the above-cited compounds.

10. Method according to one of claims 1 to 9, wherein the reactive carbonyl component is selected from the list formed by acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4 hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3 hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4 dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6 dihyd roxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5 trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6 trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5 trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxyacetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4 dimethylaminoacetophenone, 4-morpholinoacetophenone, 4 piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5 bromoacetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2 carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4 hydroxybenzophenone, 2-aminobenzophenone, 4,4' dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4' trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy- 1 acetonaphthone, 1-hydroxy-2-acetonaphthone, chromone, chromone-2 carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7-trihydroxyflavone, 4',5,7 69 H 06203 PCT RRITb trihyd roxyflavone, 5,6 ,7-trihydroxyflavone, quercetin, 1 -indlanone, 9 fluorenone, 3-hydroxyfluorenone, anthrone, 1 ,8-dihydroxyanthrone, vanillin, coniferyl aldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4 methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4 ethoxybenzaldehyde, 4-hyd roxy-2 ,3-dimethoxybenzaldehyde, 4-hydroxy 2, 5-d imethoxybenzaidehyde, 4-hyd roxy-2 ,6-d imethoxybenzaldehyde, 4 hyd roxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4 hyd roxy-2 ,3-d imethylbenzaldehyde, 4-hyd roxy-2 ,5-dimethylbenzaldehyde, 4-hyd roxy-2 ,6-dimethylbenzaldehyde, 4-hyd roxy-3, 5 dimethoxybenzaldehyde, 4-hydroxy-3 ,5-dimethylbenzaldehyde, 3,5 d iethoxy-4-hyd roxybenzaldehyde, 2 ,6-diethoxy-4-hydroxybenzaldehyde, 3 hyd roxy-4-methoxybenzaldehyde, 2-hyd roxy-4-methoxybenzaldehyde, 2 ethoxy-4-hyd roxybenzaldehyde, 3-ethoxy-4-hyd roxybenzaldehyde, 4 ethoxy-2-hyd roxybenzaldehyde, 4-ethoxy-3-hyd roxybenzaldehyde, 2,3 dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5 dimethoxybenzaldehyde, 2 ,6-dimethoxybenzaldehyde, 3,4 dimethoxybenzaldehyde, 3,5-dimethoxybenzaidehyde, 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 hyd roxybenzaldehyde, 3-hyd roxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5 dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4 dihydroxybenzaldehyde, 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-trihyd roxybenzaidehyde, 4-hydroxy-2 methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4 diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4 d iethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4 morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4 piperidinobenzaidehyde, 2-methoxy-1 -naphthaldehyde, 4-methoxy-1 naphthaldehyde, 2-hydroxy-1 -naphthaldehyde, 2,4-dihydroxy-1 70 H 06203 PCT RRITb naphthaldehyde, 4-hydroxy-3-methoxy-l-naphthaldehyde, 2-hydroxy-4 methoxy-1l-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4 dimethoxy-1 -naphthaldehyde, 3,4-dimethoxy-1 -naphthaldehyde, 4-hydroxy 1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2 methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3 methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxycinnamaldehyde, 4 dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4 dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4 diethylaminocinnamaldehyde, 4-dibutylaminobenzaldehyde, 4 diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4 (1 -imidazolyl)benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1 H,5H benzo[ij]quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1 H,5H benzo[ij]quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2 formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribase aldehyde), 2-indole aldehyde, 3-indole aldehyde, 1-methylindole-3 aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3 acetylindole, 1-methyl-3-acetylindole, 2-(l1',3',3'-trimethyl-2 indolinylidene)acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2 acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyltrifluoroacetone, chromone-3-aldehyde, 3-(5'-nitro 2'-furyl)acrolein, 3-(2'-furyl)acrolein and imidazole-2-aldehyde, 1,3 diacetylbenzene, 1,4-d iacetylbenzene, 1,3,5-triacetylbenzene, 2 benzoylacetophenone, 2-(4'-methoxybenzoyl)acetophenone, 2-(2' furoyl)acetophenone, 2-(2'-pyridoyl)acetophenone and 2-(3' pyridoyl)acetophenone, benzylideneacetone, 4 hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4 methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4 dimethylaminobenzylideneacetone, 3,4 methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4 piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4 diethylaminobenzylideneacetone, 3-benzylidene-2,4-pentanedione, 3-(4' 71 H 06203 PCT RRfTb hydroxybenzylidene)-2,4-pentanedione, 3-(4'-dimethylaminobenzylidene) 2,4-pentanedione, 2-benzylidenecyclohexanone, 2-(4' hydroxybenzylidene)cyclohexanone, 2-(4' dimethylaminobenzylidene)cyclohexanone, 2-benzylidene-1,3 cyclohexanedione, 2-(4'-hydroxybenzylidene)-1,3-cyclohexanedione, 3-(4' dimethylaminobenzylidene)-1,3-cyclohexanedione, 2-benzylidene-5,5 dimethyl-1,3-cyclohexanedione, 2-(4'-hyd roxybenzylidene)-5,5-dimethyl 1,3-cyclohexanedione, 2-(4'-hydroxy-3-methoxybenzylidene)-5,5-dimethyl 1,3-cyclohexanedione, 2-(4'-dimethylaminobenzylidene)-5,5-dimethyl-1,3 cyclohexanedione, 2-benzylidenecyclopentanone, 2'-(4 hydroxybenzylidene)cyclopentanone, 2-(4' dimethylaminobenzylidene)cyclopentanone, 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, 6-(4-dimethylaminophenyl)hexa-3,5-dien-2-one, 6-(4 diethylaminophenyl)hexa-3,5-dien-2-one, 6-(4-methoxyphenyl)hexa-3,5 dien-2-one, 6-(3,4-dimethoxyphenyl)hexa-3,5-dien-2-one, 6-(2,4 dimethoxyphenyl)hexa-3,5-dien-2-one, 6-(4-piperidinophenyl)hexa-3,5 dien-2-one, 6-(4-morpholinophenyl)hexa-3,5-dien-2-one, 6-(4 pyrrolidinophenyl)hexa-3,5-dien-2-one, 5-(4-dimethylamino-1 naphthyl)penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4 nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4 nitrobenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2 nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3 nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2 nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6 nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2 nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2 hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2 nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5 72 H 06203 PCT RRTb dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4 formylbenzenesulfonic acid, 4-nitro-l-naphthaldehyde, 2 nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9 methyl-3-carbazolealdehyde, 9-ethyl-3-carbazolealdehyde, 3 acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4-dimethyl-3-carbazole aldehyde, 1,4,9-trimethyl-3-carbazole aldehyde, 4-formyl-l1-methylpyridinium-, 2-formyl-l-methylpyridinium-, 4-formyl-1 ethylpyridinium-, 2-formyl-l-ethylpyridinium-, 4-formyl-l-benzylpyridinium-, 2-formyl-l-benzylpyridinium-, 4-formyl-1,2-dimethylpyridinium-, 4-formyl 1,3-dimethylpyridinium-, 4-formyl-1 -methylquinolinium-, 2-formyl-1 methylquinolinium-, 4-acetyl-1 -methylpyridinium-, 2-acetyl-1 methylpyridinium-, 4-acetyl-1 -methylquinolinium-, 5-formyl-1 methylquinolinium-, 6-formyl-1 -methylquinolinium-, 7-formyl-1 methylquinolinium-, 8-formyl-1 -methylquinolinium, 5-formyl-1 ethylquinolinium-, 6-formyl-1l-ethylquinolinium-, 7-formyl-1l-ethylquinolinium ,8-formyl-1l-ethylquinolinium, 5-formyl-1l-benzylquinolinium-, 6-formyl-1 benzylquinolinium-, 7-formyl-1 -benzylquinolinium-, 8-formyl-1 benzylquinolinium, 5-formyl-1l-allylquinolinium-, 6-formyl-1l-allylquinolinium-, 7-formyl-1l-allylquinolinium-and 8-formyl-1l-allylquinolinium-, 5-acetyl-1 methylquinolinium-, 6-acetyl-1 -methylquinolinium-, 7-acetyl-1 methylquinolinium-, 8-acetyl-1 -methylquinolinium-, 5-acetyl-1 ethylquinolinium-, 6-acetyl-1l-ethylquinolinium-, 7-acetyl-1l-ethylquinolinium-, 8-acetyl-1l-ethylquinolinium-, 5-acetyl-1 -benzylquinolinium-, 6-acetyl-1 benzylquinolinium-, 7-acetyl-1 -benzylquinolinium-, 8-acetyl-1 benzylquinolinium-, 5-acetyl-1l-allylquinolinium-, 6-acetyl-1l-allylquinolinium-, 7-acetyl-1l-allylquinolinium- and 8-acetyl-1l-allylquinolinium-, 9-formyl-10 methylacridinium-, 4-(2'-formylvinyl)-l-methylpyridinium-, 1,3-dimethyl-2 (4'-formylphenyl)benzimidazolium-, 1,3-dimethyl-2-(4' formylphenyl)imidazolium-, 2 -(4'-formylphenyl)-3-methylbenzothiazolium-, 2 -( 4 '-acetylphenyl)-3-methylbenzothiazolium-, 2-(4'-formylphenyl)-3 methylbenzoxazolium-, 2-(5'-formyl-2'-furyl)-3-methylbenzothiazolium-, 2 (5'-formyl-2'-furyl)-3-methylbenzothiazolium-, 2-(5'-formyl-2'-thienyl)-3 methylbenzothiazolium-, 2-(3'-formylphenyl)-3-methylbenzothiazolium-, 2 73 H 06203 PCT RPRJTb (4'-formyl-1 -naphthyl)-3-methylbenzothiazolium-, 5-chloro-2-(4' formylphenyl)-3-methylbenzothiazolium-, 2-(4'-formylphenyl)-3,5 dimethylbenzothiazolium benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methylisatin, 1-allylisatin, 1-hydroxymethylisatin, 5-chloroisatin, 5-methoxyisatin, 5-nitroisatin, 6-nitroisatin, 5-sulfoisatin, 5 carboxyisatin, quinisatin, 1-methylquinisatin as well as any mixtures of the above compounds.

11. Kit comprising * optionally an applicator, *a container C1, comprising a dye, Sa container C2a, comprising a hydrogen peroxide-containing composition and * a container C2b, comprising a composition that comprises at least one thickener and at least one alkalizing agent. wherein the dye, as the coloring component; comprises (a) at least two oxidation dye precursors, wherein at least one oxidation dye precursor must be of the developer type or (b) at least two oxo dye precursors, wherein at least one oxo dye precursor must be a reactive carbonyl compound.

12. Kit according to claim 11, wherein on mixing the contents of container C2a and C2b, the viscosity of the resulting shading composition is 5000 to 100 000 mPa s (Brookfield rotation viscosimeter, 25 °C, spindle #4, 20 rpm).

13. Kit according to claim 11 or 12, wherein the oxidation dye precursors and a hydrogen peroxide-containing composition are separately packaged in a container Cla and container Clb respectively.

14. Use of the kit according to one of the claims 11 to 13 in a method for dyeing keratin-containing fibers according to one of the claims 1 to 10. 74