AU5973399A - Method for dyeing fibres containing keratin using stable diazonium salts - Google Patents

Description

WO 00/15184 1 PCT/EP99/06526 Method for Dyeing Fibres Containing Keratin Using Stable Diazonium Salts This invention relates to a process for coloring keratin-containing fibers, more particularly human hair, in which stable diazonium salts are used as a coloring component. In general, keratin-containing fibers, for example hair, wool or pelts, 5 are dyed either with substantive dyes or with oxidation dyes which are formed by oxidative coupling of one or more primary intermediates with one another or with one or more secondary intermediates. Primary and secondary intermediates are also known as oxidation dye precursors. The primary intermediates normally used are primary aromatic 10 amines containing another free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6 tetraaminopyrimidine and derivatives thereof. Special representatives are, for example, p-phenylenediamine, p 15 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-5-pyrazolone, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl 4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6 20 diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine. The secondary intermediates used are generally m-phenylene diamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols. Particularly suitable secondary inter mediates are c-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5 25 amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 1 -phenyl-3- WO 00/15184 2 PCT/EP99/06526 methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4-diamino phenoxy)-propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6 methyl-3-aminophenol, 2-methyl resorcinol and 5-methyl resorcinol. With regard to other typical dye components, reference is 5 specifically made to the series entitled "Dermatology" (Editors: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York/Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; Substantive Dyes) and Chapter 8 (pages 264-267; Oxidation Dye Precursors) and to the "Europaische Inventar der Kosmetik-Rohstoffe" published by the 10 European Commission and available on floppy disk from the Bundesver band Deutscher Industrie- und Handelsunternehmen fOr Arzneimittel, Reformwaren und K6rperpflegemittel e.V., Mannheim, Germany. Although intensive colors with good fastness properties can be obtained with oxidation dyes, the color is generally developed under the 15 influence of oxidizing agents, such as H 2 0 2 for example, which in some cases can result in damage to the fibers. In addition, some oxidation dye precursors or certain mixtures of oxidation dye precursors can occasionally have a sensitizing effect in people with sensitive skin. Although substantive dyes are applied under more moderate conditions, their disadvantage is 20 that, in many cases, the colors obtained often have inadequate fastness properties. The use of diazonium salts for coloring keratin-containing fibers is known from the prior art and is described, for example, in CH-PS 630 254, DE 27 39 227, FR-PS 78 05441 and DE-OS 27 57 855. Nitrogen 25 containing heterocyclic compounds are used as secondary intermediates in CH-PS 630 254 and in DE-OS 27 39 227. In FR-PS 78 05441, the secondary intermediate is an arylamide derivative of acetaldehyde. Naphthyl compounds are known as secondary intermediates from DE-OS 27 57866. 30 In the documents cited above, the diazonium salts are used in the WO 00/15184 3 PCT/EP99/06526 presence of suitable secondary intermediates. The coloring process is carried out by first pretreating the keratin-containing fibers to be colored with the secondary intermediate by allowing the secondary intermediate to act on the fibers for a while. The diazonium salt is then applied in a second 5 step. The two-step process is labor-intensive and time-consuming. The problem addressed by the present invention was to provide colorants for keratin fibers, more especially human hair, which could be applied to the fibers in a few steps and which would be at least equivalent in quality to conventional oxidation hair dyes in regard to depth of color, 10 grey coverage and fastness properties, but which would not necessarily have to contain oxidizing agents, such as H 2 0 2 for example. In addition, the colorants according to the invention would have very little, if any, sensitizing potential. It has surprisingly been found that the stable diazonium salts 15 corresponding to formula (1) below can be used both as substantive dyes and in combination with secondary intermediates for coloring keratin containing fibers, even in one-step processes. They give colors with excellent brilliance and depth of color. The use of oxidizing agents is not necessary although, in principle, they may be present. 20 The present invention relates to a process for coloring keratin containing fibers, more particularly human hair, characterized in that A) at least one stable diazonium salt corresponding to formula 1: R4 oN$=N Y" R1 25 in which R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a (C14) alkyl group, a (C1.4 alkoxy kroup, a hydroxy-(C 1 4)-alkoxy group, a hydroxy group, a sulfo group, WO 00/15184 4 PCT/EP99/06526 a carboxy group, an amino group, which may be substituted by a (C1. 4) alkyl group, hydroxyalkyl group, a C 14 acyl group or by an optionally substituted benzene group or which may be part of a heterocycle, or a (C14) acyl group; two of the substituents may also form a fused 5 benzene ring and may be an optionally substituted phenyl group or, together with the N atom, form a heterocyclic ring, B) optionally in combination with a compound selected from compounds containing a primary or secondary amino group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic 10 compounds and/or aromatic hydroxy compounds and/or CH-active compounds, or a physiologically compatible salt of such a diazonium salt, is applied to the fibers in a one-step process. In the context of the invention, keratin-containing fibers are 15 understood to include wool, pelts, feathers and, in particular, human hair. In principle, however, the colorants according to the invention may also be used to color other natural fibers such as, for example, cotton, jute, sisal, linen or silk, modified natural fibers such as, for example, regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers 20 such as, for example, polyamide, polyacrylonitrile, polyurethane and polyester fibers. The stable diazonium salts of formula I used in accordance with the invention are preferably selected from the group consisting of 4 diazophenylamine sulfate (Variaminblausalz RT), 4-diazo-4' 25 methoxydiphenylamine chloride (Variaminblausalz B), 4-diazo-3,2' dimethylazobenzene sulfonate (Echtgranatsalz GBC), 2-methoxy-4 nitrobenzene diazonium naphthalene-1 ,5-disulfonate, 4-diazo-2,5 dimethoxy-4'-nitroazobenzene chloride/zinc chloride double salt (Echtschwarzsalz K), 2,5-dimethoxy-4-benzoyl aminophenyl diazonium 30 chloride (Echtblausalz RR), 2-methoxy-4-nitrobenzene diazonium-1,5- WO 00/15184 5 PCT/EP99/06526 naphthalene disulfonate (Echtrotsalz B), 4-chloro-2-nitrobenzene diazonium chloride/zinc chloride double salt (Echtrotsalz 3 GL), 5-chloro-2 methoxybenzene diazonium chloride/zinc chloride double salt (Echtrotsalz RC), 4-benzamido-2-methoxy-5-methylbenzene diazonium chloride/zinc 5 chloride double salt (Echtviolettsalz B), 2-diazo-1-naphthol-4-sulfonic acid, Na salt of 2-diazo-1-naphthol-5-sulfonic acid and mixtures thereof. These compounds are known from the literature or are commercially obtainable. The above-mentioned stable diazonium salts corresponding to 10 formula I are used in the process according to the invention in quantities of preferably 0.03 to 65 mmol and more preferably 1 to 40 mmol, based on 100 g of the colorant as a whole. If the stable diazonium salts corresponding to formula I are used as sole colorant in the process according to the invention, colors in the brown 15 range are obtained. Colors with even greater brilliance and improved fastness properties (fastness to light, washing, rubbing), above all in the yellow, orange, brown and black ranges, are obtained when the compounds corresponding to formula I are used together with the compounds referred to as component B. These are, on the one hand, 20 compounds which on their own color keratin-containing fibers very weakly and only produce brilliant colors in conjunction with the diazonium salts corresponding to formula I and, on the other hand, compounds which are already used as oxidation dye precursors. The compounds of component B may be used in a quantity of 0.03 25 to 65 mmol and more particularly 1 to 40 mmol, based on 100 g of the colorant as a whole. Several different stable diazonium salts corresponding to formula I may also be used together in the process according to the invention. Similarly, several different compounds of component B may also be used 30 together. This embodiment also encompasses the use of substances WO 00/15184 6 PCT/EP99/06526 which represent reaction products of stable diazonium salts corresponding to formula I with the above-mentioned compounds of component B. According to the invention, the compounds corresponding to formula I and the compounds of component B optionally used are applied to the fibers in 5 a one-step process. This means that the components are applied simultaneously with no need for the fibers to be pretreated with any one of the components. Suitable compounds containing a primary or secondary amino group for component B are, for example, primary aromatic amines, such as N,N 10 dimethyl-, N,N-diethyl-, N-(2-hydroxyethyl)-N-ethyl-, N,N-bis-(2-hydroxy ethyl)-, N-(2-methoxyethyl)-, 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2 chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydro bromide, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxy methyl-4-aminophenol, o-, p-phenylenediamine, o-toluylenediamine, 2,5 15 diaminotoluene, -phenol, -phenethol, 4-amino-3-methylphenol, 2-(2,5-di aminophenyl)-ethanol, 2,4-diaminophenoxyethanol, 2-(2,5-diamino phenoxy)-ethanol, 4-methylamino-, 3-amino-4-(2'-hydroxyethyloxy)-, 3,4 methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4 methylamino-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5-(2 20 hydroxyethylamino)-, 6-methyl-3-amino-2-chloro-, 2-methyl-5-amino-4 chloro-, 3,4-methylenedioxy-, 5-(2-hydroxyethylamino)-4-methoxy-2 methylphenol, 4-amino-2-hydroxymethylphenol, 1,3-diamino-2,4 dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, -phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino 25 4-hydroxy-, 4-amino-3-hydroxybenzoic acid, 2-, 3-, 4-aminobenzene sulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxy naphthalene-1 -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 30 aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, WO 00/15184 7 PCT/EP99/06526 1,2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, 2,4,6-triaminoresorcinol, 4,5-diaminopyrocatechol, 4,6-diaminopyrogallol, 3,5-diamino-4-hydroxy pyrocatechol, aromatic nitriles, anilines, more particularly anilines containing nitro groups, such 4-nitroaniline, 4-nitro-1,3-phenylenediamine, 5 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, 2-amino-6-chloro-4-nitrophenol, 1-amino-5-chloro-4-(2 hyd roxyethylamino)--2-nitrobenzene, aromatic anilines and phenols containing another aromatic radical corresponding to formula II: 10 R6 R5 R8 R RR7 R9 R7R R10 in which R 4 is a hydroxy group or an amino group which may be substituted by C1.4 alkyl, C 1

.

4 hydroxyalkyl, C 1

.

4 -alkoxy or C1.4-alkoxy-CI4-alkyl groups, 15 R 6 , R 7 , R 8 , R 9 and R 10 represent hydrogen, a hydroxy group or an amino group which may be substituted by C1.4 alkyl, C 1 .4 hydroxyalkyl, C 1 .4 alkoxy, C1.4 aminoalkyl or C 1

.

4 -alkoxy-C 1

.

4 -alkyl groups and X is a direct bond, a saturated or unsaturated, optionally hydroxy substituted carbon chain containing 1 to 4 carbon atoms, a carbonyl, 20 sulfonyl or imino group, an oxygen or sulfur atom or a group corresponding to formula Ill:

Z-(CH

2

-Y-CH

2 -Z')o (Ill) 25 in which Y is a direct bond, a CH 2 or CHOH group, Z and Z' independently of one another represent an oxygen atom, an NR 13 WO 00/15184 8 PCT/EP99/06526 group, where R 1 3 is hydrogen, a C14 alkyl or a hydroxy-C 1 4-alkyl group, the group O-(CH 2 )p-NH or NH-(CH 2 )p.-O, where p and p' = 2 or 3, and o is a number of 1 to 4, such as for example 4,4'-diaminostilbene, 4,4'-diaminostilbene-2,2'-disul 5 fonic acid monosodium or disodium salt, 4-amino-4'-dimethylaminostilbene, 4,4'-diaminodiphenyl methane, -sulfide, -sulfoxide, -amine, 4,4' diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, 3,3',4,4'-tetraaminodiphenyl, 3,3'4,4'-tetraaminobenzo phenone, 1,3-bis-(2,4-diaminophenoxy)-propane, 1,8-bis-(2,5-diamino 10 phenoxy)-3,6-dioxaoctane, 1,3-bis-(4-aminophenylamino)-propane, -2 propanol, 1,3-bis-[N-(4-aminophenyl)-2-hydroxyethylamino]-2-propanol, N,N-bis-[2-(4-aminophenoxy)-ethyl]-methylamine, N-phenyl-1,4-phenylene diamine. The compounds mentioned above may be used both in free form 1.5 and in the form of their physiologically compatible salts, more especially as salts of inorganic acids, such as hydrochloric acid or sulfuric acid. Suitable nitrogen-containing heterocyclic compounds are, for exam ple, 2-, 3-, 4-amino-, 2-amino-3-hydroxy-, 2,6-diamino-, 2,5-diamino-, 2,3 diamino-, 2-dimethylamino-5-amino-, 2-methylamino-3-amino-6-methoxy-, 20 2,3-diamino-6-methoxy-, 2,6-dimethoxy-3,5-diamino-, 2,4,5-triamino-, 2,6 dihydroxy-3,4-dimethyl pyridine, 2,4-dihydroxy-5,6-diamino-, 4,5,6-tri amino-, 4-hydroxy-2,5,6-triamino-, 2-hydroxy-4,5,6-triamino-, 2,4,5,6-tetra amino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4 methoxy-6-methyl pyrimidine, 3,5-diaminopyrazole, -1,2,4-triazole, 3 25 amino-, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-amino quinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-amino indazole, 5-, 7-aminobenzimidazole, -benzothiazole, 2,5-dihydroxy-4 morpholinoaniline and indole and indoline derivatives, such as 4-, 5-, 6-, 7 aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxy 30 indoline. The compounds mentioned above may be used both in free form WO 00/15184 9 PCT/EP99/06526 and in the form of their physiologically compatible salts, for example as salts of inorganic acids, such as hydrochloric acid or sulfuric acid. Suitable aromatic hydroxy compounds are, for example, 2-, 4-, 5 methyl resorcinol, 2,5-dimethyl resorcinol, resorcinol, 3-methoxyphenol, 5 pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydro quinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2-(2-hydroxyethyl)-, 3,4 methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -acetophenone, 2-, 4-chloro resorcinol, 1-naphthol, 1,5-, 1,6-, 1,7-, 2,3-, 2,6-, 2,7-dihydroxynaphthalene, 10 2-naphthol-3,6-disulfonic acid Na salt, 6-dimethylamino-4-hydroxy-2 naphthalene sulfonic acid, 3,6-dihydroxy-2,7-naphthalene sulfonic acid. Examples of CH-active compounds are 1,2,3,3-tetramethyl-3H indolium iodide, 1,2,3,3-tetraamethyl-3H-indolium-p-toluene sulfonate, 1,2,3,3-tetramethyl-3H-indolium methane sulfonate, Fischer's base (1,3,3 15 trimethyl-2-methyleneindoline), 2,3-dimethylbenzothiazolium iodide, 2,3 dimethylbenzothiazolium-p-toluene sulfonate, rhodanine, rhodanine-3 acetic acid, 1-ethyl-2-quinaldinium iodide, 1-methyl-2-quinaldinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethyl thiobarbituric acid, diethyl thiobarbituric acid, oxindole, 3-indoxyl acetate, coumaranone and 1-methyl 20 3-phenyl-2-pyrazolinone. In a particularly preferred embodiment, the compounds of component B are selected from the group consisting of N-(2-hydroxyethyl) N-ethyl-, 2-chloro-p-phenylenediamine, N,N-bis-(2-hydroxyethyl)-p phenylenediamine, 4-aminophenol, p-phenylenediamine, 2-(2,5 25 diaminophenyl)-ethanol, 2,5-diaminotoluene, 3,4-methylenedioxy aniline, 3 amino-2,4-dichloro-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5-(2 hydroxyethylamino)-, 2-methyl-5-amino-4-chloro-, 6-methyl-3-amino-2 chloro-, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2 amino-4-(2-hydroxyethylamino)-, 3,4-methylenedioxyphenol, 3,4-diamino 30 benzoic acid, 2,5-diamino-, 2-dimethylamino-5-amino-, 3-amino-2- WO 00/15184 10 PCT/EP99/06526 methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6 dimethoxy-, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2-methylamino-4,5,6-triaminopyrimidine, 3,5 diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole, 5,6 5 dihydroxyindoline, 1-naphthol, 1,5-, 1,6-, 1,7-, 2,3-, 2,6-, 2,7 dihydroxynaphthalene and 2-naphthol-3,6-disulfonic acid Na salt and physiologically compatible salts thereof formed with preferably inorganic acids. Oxidizing agents, for example H 2 0 2 , need not present. However, it 10 may be desirable in some cases to add hydrogen peroxide or other oxidizing agents in the process according to the invention to obtain shades which are lighter than the keratin-containing fibers to be colored. Oxidizing agents are generally used in a quantity of 0.01 to 6% by weight, based on the solution applied. A preferred oxidizing agent for human hair is H 2 0 2 . 15 In one preferred embodiment, typical substantive dyes, for example from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, are added in the process according to the invention, in addition to the compounds present in accordance with the invention, in order further to modify the color tones. Examples of suitable 20 substantive dyes are the compounds known under the International names or commercial names of HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 25 and also picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-amino-2 nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis-(2'-hyd roxyethylamino)-2-n itrobenzene hydrochloride and 1 -methyl-3-nitro-4-(2'-hydroxyethyl)-aminobenzene. In this embodiment, the substantive dyes are added in the process according to the invention in 30 a quantity of, preferably, 0.01 to 20% by weight, based on the colorant as a WO 00/15184 11 PCT/EP99/06526 whole. The oxidation dye precursors or the substantive dyes present, if any, do not have to be single compounds. Instead, by virtue of the processes used for producing the individual dyes, small quantities of other 5 components may be used in the process according to the invention providing they do not adversely affect the coloring result or have to be ruled out for other reasons, for example toxicological reasons. The processs according to the invention gives intensive colors even at physiologically compatible temperatures of <450C. Accordingly, it is 10 particularly suitable for coloring human hair. For application to human hair, the individual components are normally incorporated in a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are, for example, creams, emulsions, gels or even surfactant-containing foaming solutions, for example shampoos or other formulations suitable for 15 application to the keratin-containing fibers. If necessary, the components may even be incorporated in water-free carriers. In addition, any of the known active substances, additives and auxiliaries typical of coloring preparations may be used in the process according to the invention. In many cases, at least one surfactant is 20 present, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has been found to be of advantage to select the surfactants from anionic, zwitterionic or nonionic surfactants. Suitable anionic surfactants for the compositions according to the 25 invention are any anionic surface-active substances suitable for use on the human body. Such substances are characterized by a water-solubilizing anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing around 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether, 30 amide groups and hydroxyl groups may also be present in the molecule.

WO 00/15184 12 PCT/EP99/06526 The following are examples of suitable anionic surfactants - in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group: 5 - linear fatty acids containing 10 to 22 carbon atoms (soaps), - ether carboxylic acids corresponding to the formula R-O-(CH 2

-CH

2 0)x

CH

2 -COOH, in which R is a linear alkyl group containing 10 to 22 carbon atoms and x = 0 or 1 to 16, - acyl sarcosides containing 10 to 18 carbon atoms in the acyl group, 10 - acyl taurides containing 10 to 18 carbon atoms in the acyl group, - acyl isethionates containing 10 to 18 carbon atoms in the acyl group, - sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 15 oxyethyl groups, - linear alkane sulfonates containing 12 to 18 carbon atoms, - linear c-olefin sulfonates containing 12 to 18 carbon atoms, - a-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms, 20 - alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the formula R-O(CH 2

-CH

2 0)x-SO 3 H, in which R is a preferably linear alkyl group containing 10 to 18 carbon atoms and x = 0 or 1 to 12, - mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, 25 - sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354, - sulfonates of unsaturated fatty acids containing 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344, - esters of tartaric acid and citric acid with alcohols in the form of addition 30 products of around 2 to 15 molecules of ethylene oxide and/or WO 00/15184 13 PCT/EP99/06526 propylene oxide with fatty alcohols containing 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and, in 5 particular, salts of saturated and, more particularly, unsaturated C 8

-

2 2 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. In the context of the invention, zwitterionic surfactants are surface active compounds which contain at least one quaternary ammonium group 10 and at least one -C00(-) or -SO3() group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl am monium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2 15 alkyl-3-carboxymethyl-3-hydroxyethy imidazolines containing 8 to 18 car bon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name of Cocamidopropyl Betaine. Ampholytic surfactants are surface-active compounds which, in 20 addition to a C 8

-

18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N alkyl iminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines, 25 N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl amino propionate, cocoacyl aminoethyl aminopropionate and C 12

-

18 acyl sarcosine. 30 Nonionic surfactants contain, for example, a polyol group, a poly- WO 00/15184 14 PCT/EP99/06526 alkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are - products of the addition of 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide onto linear fatty alcohols containing 8 to 22 5 carbon atoms, onto fatty acids containing 12 to 22 carbon atoms and onto alkylphenols containing 8 to 15 carbon atoms in the alkyl group, - C12-22 fatty acid monoesters and diesters of products of the addition of 1 to 30 moles of ethylene oxide onto glycerol, - C8-22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof, 10 - products of the addition of 5 to 60 moles of ethylene oxide onto castor oil and hydrogenated castor oil, - products of the addition of ethylene oxide onto sorbitan fatty acid esters, - products of the addition of ethylene oxide onto fatty acid alkanolamides. Examples of cationic surfactants suitable for use in the hair 15 treatment formulations according to the invention are, in particular, quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, 20 stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride. Other cationic surfactants suitable for use in accordance with the invention are the quaternized protein hydrolyzates. 25 Also suitable for use in accordance with the invention are cationic silicone oils such as, for example, the commercially available products Q2 7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethi cone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: 30 General Electric), SLM-55067 (manufacturer: Wacker) and Abil@-Quat WO 00/15184 15 PCT/EP99/06526 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl siloxanes, quaternium-80). Alkyl amidoamines, particularly fatty acid amidoamines, such as the stearyl amidopropyl dimethyl amine obtainable as Tego Amid@S 18, are 5 distinguished not only by their favorable conditioning effect, but also and in particular by their ready biodegradability. Quaternary ester compounds, so-called "esterquats", such as the the methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the trade name of Stepantex@, are also readily 10 biodegradable. One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat@100 (CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride). 15 The compounds containing alkyl groups used as surfactants may be single compounds. In general, however, these compounds are produced from native vegetable or animal raw materials so that mixtures with different alkyl chain lengths dependent upon the particular raw material are obtained. 20 The surfactants representing addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products may be both products with a "normal" homolog distribution and products with a narrow homolog distribution. Products with a "normal" homolog distribution are mixtures of homologs which are obtained in the reaction of 25 fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with 30 a narrow homolog distribution can be of advantage.

WO 00/15184 16 PCT/EP99/06526 Other active substances, auxiliaries and additives are, for example, - nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers and polysiloxanes, 5 - cationic polymers, such as quaternized cellulose ethers, polysiloxanes containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyl diallyl ammonium chloride copolymers, dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymers quater nized with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride 10 copolymers and quaternized polyvinyl alcohol, - zwitterionic and amphoteric polymers such as, for example, acrylamido propyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2 hydroxypropyl methacrylate copolymers, 15 - 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/iso bornyl acrylate copolymers, methyl vinyl ether/maleic anhydride co polymers and acrylic acid/ethyl acrylate/N-tert.butyl acrylamide ter 20 polymers, - thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such as 25 amylose, amylopectin and dextrins, clays such as, for example, bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol, - structurants, such as glucose and maleic acid, - hair-conditioning compounds, such as phospholipids, for example soya 30 lecithin, egg lecithin and kephalins, and also silicone oils, WO 00/15184 17 PCT/EP99/06526 - protein hydrolyzates, more particularly elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolyzates, condensation products thereof with fatty acids and quaternized protein hydrolyzates, - perfume oils, dimethyl isosorbide and cyclodextrins, 5 - solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, - antidandruff agents, such as Piroctone Olamine and Zinc Omadine, - other substances for adjusting the pH value, - active substances, such as panthenol, pantothenic acid, allantoin, 10 pyrrolidone carboxylic acids and salts thereof, plant extracts and vitamins, - cholesterol, - UV filters, - consistency factors, such as sugar esters, polyol esters or polyol alkyl 15 ethers, - fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, - fatty acid alkanolamides, - complexing agents, such as EDTA, NTA and phosphonic acids, 20 - swelling and penetration agents, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, - opacifiers, such as latex, 25 - pearlizers, such as ethylene glycol mono- and distearate, - propellents, such as propane/butane mixtures, N 2 0, dimethyl ether,

CO

2 and air and - antioxidants. To produce the colorants used in the process according to the 30 invention, the constituents of the water-containing carrier are used in the WO 00/15184 18 PCT/EP99/06526 usual quantities for this purpose. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight while thickeners are used in concentrations of 0.1 to 25% by weight, based on the colorant as a whole. It can be of advantage to the coloring result to add ammonium or 5 metal salts to the colorants. Suitable metal salts are, for example, formates, carbonates, halides, sulfates, butyrates, valerates, caproates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or 10 barium, or of aluminium, manganese, iron, cobalt, copper or zinc, sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate being preferred. These salts are preferably present in a quantity of 0.03 to 65 mmol and more preferably in a 15 quantity of 1 to 40 mmol, based on 100 g of the colorant as a whole. The pH value of the ready-to-use coloring preparations is normally in the range from 2 to 11 and preferably in the range from 5 to 9. In the process according to the invention, the components and typical cosmetic ingredients are normally applied to the keratin-containing 20 fibers, left thereon for a certain time, normally about 30 minutes, and then rinsed out or washed out with a shampoo. According to the invention, the stable diazonium salts corresponding to formula I and the compounds of component B are applied to the hair in a single process step, i.e. the components are applied together or 25 successively, but without any pretreatment of the fibers by any one of the components. The ammonium or metal salts optionally present may be added to the first or to the second component. However, this does not mean that the fibers cannot be pretreated with the salt solution. The stable diazonium salts corresponding to formula I and the 30 compounds of component B may be stored either separately or together WO 00/15184 19 PCT/EP99/06526 either in a liquid or paste-form preparation (water-based or water-free) or as a dry powder. If the components are stored together in a liquid preparation, the preparation in question should be substantially water-free to reduce any reaction between the components. In the event of separate 5 storage, the reactive components are thoroughly mixed together just before application. In the event of dry storage, a certain quantity of warm (50 to 80 0 C) water is normally added and a homogeneous mixture prepared before application. 10 ExampLes Preparation of a coloring solution: A suspension of 10 mmol of a stable diazonium salt corresponding to formula I, 10 mmol of an oxidation dye precursor, 10 mmol of sodium 15 acetate and one drop of a 20% fatty alkyl ether sulfate solution in 100 ml of water was prepared. The suspension was briefly heated to around 80*C and, after cooling, was filtered and then adjusted to pH 6. A tress of 90% grey, non-pretreated human hair was placed in this coloring solution for 30 minutes at 300C. The tress was then rinsed for 30 20 seconds with luke-warm water, dried with warm air and then combed out. The particular shades and depths of color are shown in Table 1 below. The depth of color was evaluated on the following scale: - : very faint, if any, color 25 (+) : weak intensity + : medium intensity +(+) :medium to strong intensity ++ : strong intensity ++(+) :strong to very strong intensity ++ : very strong intensity WO 00/15184 20 PCT/EP99/06526 Table 1 Coloring with 2,5-dimethoxy-4-benzovlaminophenyl diazonium chloride (Echtblausalz RR) Reactant pH Color Intensity 6.0 Orange-brown ++ 2,5-Diaminotoluene x H 2

SO

4 6.0 Medium brown ++ 2,4,5,6-Tetraaminopyrimidine x H 2

SO

4 6.0 Yellow-orange +(+) 1,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctane x 4HCI 6.0 Grey-brown ++ 2-Methylamino-3-amino-6-methoxypyridine x 2HCI 6.0 Orange-brown ++ 2-(2,5-Diaminophenyl)-ethanol x H 2

SO

4 6.0 Medium brown ++ 2-Aminomethyl-4-aminophenol x 2HCI 6.0 Light brown + N,N-bis-(hydroxyethyl)-p-phenylenediamine x H 2

SO

4 6.0 Dark violet ++(+) 4,4'-Diaminodiphenylamine x H 2

SO

4 6.0 Grey-brown ++ 3,5-Diamino-2,6-dimethoxypyridine x 2HCI 6.0 Medium brown +(+) Table 2 Coloring with 2,5-dimethoxy-4-benzoylaminophenyl diazonium chloride (Echtblausalz RR) Reactant pH Color Intensity 9.0 Orange-brown ++(+) 2,5-Diaminotoluene x H 2

SO

4 9.0 Medium brown +(+) 1,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctane x 4HCI 9.0 Grey-brown ++ 2-Methylamino-3-amino-6-methoxypyridine x 2HCI 9.0 Orange-brown + 2-(2,5-Diaminophenyl)-ethanol x H2SO4 9.0 Medium brown +(+) N,N-Bis-(hydroxyethyl)-p-phenylenediamine x H 2

SO

4 9.0 Grey-brown +(+) 4,4'-Diaminodiphenylamine x H 2 SO4 9.0 Dark violet ++(+) WO 00/15184 21 PCT/EP99/06526 Table 3 Coloring with 4-diazodiphenylamine sulfate (Variaminblausalz RT) Reactant pH Color Intensity 4.0 Brown-yellow ++ 2,5-Diaminotoluene x H 2

SO

4 4.0 Dark brown ++(+) 2,4,5,6-Tetraaminopyrimidine x H 2

SO

4 4.0 Medium brown + 1,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctane x 4HCI 4.0 Dark brown +++ 2-Methylamino-3-amino-6-methoxypyridine x 2HCI 4.0 Dark brown +++ 2-(2,5-Diaminophenyl)-ethanol x H 2 SO4 4.0 Yellow-brown +(+) 2-Aminomethyl-4-aminophenol x 2HCI (Oxamitol) 1:1 4.0 Orange-brown +(+) N,N-bis-(hydroxyethyl)-p-phenylenediamine x H 2

SO

4 1:1 4.0 Dark brown ++(+) 4,4'-Diaminodiphenylamine x H 2 SO4 4.0 Medium brown ++ 3,5-Diamino-2,6-dimethoxypyridine x 2HCI 4.0 Brown black +++ Table 4 Coloring with 4-diazo-4'-methoxydiphenylamine chloride (Variaminblausalz B) Reactant pH Color Intensity 6.0 Orange-brown ++ 2,5-Diaminotoluene x H 2 SO4 6.0 Dark brown ++(+) 2,4,5,6-Tetraaminopyrimidine x H 2

SO

4 6.0 Dark orange-brown ++(+) 1,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctane x 4HCI 6.0 Dark grey +++ 2-Methylamino-3-amino-6-methoxypyridine x 2HCI 6.0 Black +++ 2-(2,5-Diaminophenyl)-ethanol x H 2

SO

4 6.0 Violet-dark grey ++(+) 2-Aminomethyl-4-aminophenol x 2HCI 6.0 Medium brown +(+) N,N-bis-(hydroxyethyl)-p-phenylenediamine x H 2

SO

4 6.0 Dark brown +++ 4,4'-Diaminodiphenylamine x H 2 SO4 6.0 Dark brown ++ 3,5-Diamino-2,6-dimethoxypyridine x 2HCI 6.0 Black +++ WO 00/15184 22 PCT/EP99/06526 Table 5 Coloring with 4-diazo-4'-methoxydiphenvlamine chloride (Variaminblausalz B) Reactant pH Color Intensity 9.0 Brown-yellow + 2,4-Diaminophenoxyethanol x 2HCI 9.0 Rust red + 1-Naphthol 9.0 Red-brown ++(+) 1,3-Bis-(2,4-diaminophenoxy)-propane 9.0 Light brown +(+) 2-Methylamino-3-amino-6-methoxypyridine x 2HCI 1:1 9.0 Grey-black ++ 5-Amino-2-methylphenol 9.0 Red brown ++ 1,5-Dihydroxynaphthalene 9.0 Dark violet ++(+) 2-Amino-4-(2-hydroxyethylamino)-anisole 9.0 Brown-red ++ 3-Amino-2-chloro-6-methylphenol 9.0 Dark brown-red +++ 3,5-Diamino-2,6-dimethoxypyridine x 2HCI 9.0 Black ++ Table 6 Coloring with 4-diazo-3,2'-dimethylazobenzene sulfate (Echtgranatsalz GBC) Reactant pH Color Intensity 6.0 Brown-orange ++ 2,4-Diaminophenoxyethanol x 2HCI 6.0 Light brown + 1,3-Bis-(2,4-diaminophenoxy)-propane 6.0 Brown-grey ++ 2-Methylamino-3-amino-6-methoxypyridine x 2HCI 6.0 Black-brown ++ 2-Amino-4-(2-hydroxyethylamino)-anisole 6.0 Violet-brown ++(+) 3-Amino-2-chloro-6-methylphenol 6.0 Yellow + 3,5-Diamino-2,6-dimethoxypyridine x 2HCI 6.0 Black +++ WO 00/15184 23 PCT/EP99/06526 Table 7 Coloring with 2-methoxy-4-nitrobenzene diazonium-1,5-naphthalene disulfonate (Echtrotsalz B) Reactant pH Color Intensity 6.0 Brown-orange ++ 2,5-Diaminotoluene x H 2 S0 4 6.0 Brown-yellow +(+) Lehmanns-Blau (2-amino-4-(2-hydroxyethylamino)-anisole) 6.0 Brown yellow +(+) 1,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctane x 4HCI 6.0 Olive-grey ++ 2-Methylamino-3-amino-6-methoxypyridine x 2HCI 6.0 Orange-brown ++ N,N-Bis-(2-hydroxyethyl)-p-phenylenediamine x H 2

SO

4 6.0 Medium brown (+)+ 3-Aminophenol hydrochloride 6.0 Brown-yellow ++ 3,5-Diamino-2,6-dimethoxypyridine x 2HCI 6.0 Dark green ++(+) Table 8 Coloring with 4-diazo-2,5-dimethoxy-4'-nitroazobenzene chloride/zinc chloride double salt (Echtschwarzsalz K) Reactant pH Color Intensity 2,5-Diaminotoluene x H 2

SO

4 6.0 Medium brown ++ 2,4,5,6-Tetraaminopyrimidine 6.0 Brown-orange +(+) 1,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctane x 4HCI 6.0 Dark grey ++(+) 2-Methylamino-3-amino-6-methoxypyridine x 2HCI 6.0 Dark brown +++ 2-(2,5-Diaminophenyl)-ethanol x H 2

SO

4 6.0 Medium brown +(+) 2-Aminomethyl-4-aminophenol x 2HCI 6.0 Yellow-brown +(+) N,N-bis-(hydroxyethyl)-p-phenylenediamine x H 2

SO

4 6.0 Brown grey +(+) 4,4'-Diaminodiphenylamine x H 2

SO

4 6.0 Dark grey ++(+) 3,5-Diamino-2,6-dimethoxypyridine x 2HCI 6.0 Black +++

Claims (10)

1. A process for coloring keratin-containing fibers, more particularly human hair, characterized in that A) at least one stable diazonium salt corresponding to formula I: 5 R4 R3 N=EN Y" R 4 R (I) in which R 1 , R 2 , R 3 and R 4 independently of one another represent a hydrogen atom, a halogen atom, a (C 14 ) alkyl group, a (C 1 . 4 alkoxy 10 kroup, a hydroxy-(C 1 .4)-alkoxy group, a hydroxy group, a sulfo group, a carboxy group, an amino group, which may be substituted by a (C1. 4) alkyl group, hydroxyalkyl group, a C 14 acyl group or by an optionally substituted benzene group or which may be part of a heterocycle, or a (C 1 . 4 ) acyl group; two of the substituents may also form a fused 15 benzene ring and may be an optionally substituted phenyl group or, together with the N atom, form a heterocyclic ring, B) optionally in combination with a compound selected from compounds containing a primary or secondary amino group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic 20 compounds and/or aromatic hydroxy compounds and/or CH-active compounds, or a physiologically compatible salt of such a diazonium salt, is applied to the fibers in a one-step process.

2. A process as claimed in claim 1, characterized in that the stable 25 diazonium salt corresponding to formula I is selected from 4 diazophenylamine sulfate (Variaminblausalz RT), 4-diazo-4' methoxydiphenylamine chloride (Variaminblausalz B), 4-diazo-3,2' dimethylazobenzene sulfonate (Echtgranatsalz GBC), 2-methoxy-4- WO 00/15184 25 PCT/EP99/06526 nitrobenzene diazonium naphthalene-1,5-disulfonate (Echtrotsalz B), 4 d iazo-2,5-dimethoxy-4'-nitroazobenzene chloride/zinc chloride double salt (Echtschwarzsalz K), 2,5-dimethoxy-4-benzoyl aminophenyl diazonium chloride (Echtblausalz RR), 2-methoxy-4-nitrobenzene diazonium-1,5 5 naphthalene disulfonate, 4-chloro-2-nitrobenzene diazonium chloride/zinc chloride double salt (Echtrotsalz 3 GL), 5-chloro-2-methoxybenzene diazonium chloride/zinc chloride double salt (Echtrotsalz RC), 4 benzamido-2-methoxy-5-methylbenzene diazonium chloride/zinc chloride double salt (Echtviolettsalz B), 2-diazo-1-naphthol-4-sulfonic acid, Na salt 10 of 2-diazo-1-naphthol-5-sulfonic acid and mixtures thereof.

3. A process as claimed in claim 1 or 2, characterized in that the stable diazonium salts corresponding to formula I are present in a quantity of 0.03 to 65 mmol and more particularly in a quantity of 1 to 40 mmol, based on 100 g of the colorant as a whole. 15 4. A process as claimed in any of claims 1 to 3, characterized in that component B is selected from primary or secondary amines from the group consisting of N-(2-hydroxyethyl)-N-ethyl-, N-(2-methoxyethyl)-, 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, N,N-bis (2-hydroxyethyl)-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline 20 dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,4 diaminophenoxyethanol, 2-(2,5-diaminophenyl)-ethanol, 2,5-diamino toluene, -phenol, -phenethol, 4-methylamino-, 3-amino-4-(2'-hydroxyethyl oxy)-, 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4 dichloro-, 4-methylamino-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl 25 5-(2-hydroxyethylamino)-, 2-methyl-5-amino-4-chloro-, 6-methyl-3-amino-2 chloro-, 5-(2-hydroxyethylamino)-4-methoxy-2-methyl-, 2-amino-4-(2 hydroxyethylamino)-, 4-amino-2-aminomethyl-, 4-amino-2-hydroxymethyl phenol, 1,3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, -phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5 30 aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxybenzoic acid, WO 00/15184 26 PCT/EP99/06526 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalenesulfonic acid, 6-amino-7-hydroxy naphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2 5 naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4 triaminobenzene, 1,2,4,5-tetraaminobenzene tetrahydrochloride, 2,4,5-tri aminophenol trihydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5 diaminopyrocatechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5 diamino-4-hydroxypyrocatechol sulfate, aromatic nitriles, anilines, more 10 particularly anilines containing nitro groups, such as 4-nitroaniline, 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-nitro diphenylamine-2'-carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino

5-chloro-4-(2-hydroxyethylamino)-2-nitrobenzene, aromatic anilines and 15 phenols containing another aromatic radical, such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid sodium salt, 4,4' diaminodiphenyl methane, -sulfide, -sulfoxide, -amine, 4,4' diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, 3,3',4,4'-tetraaminodiphenyl tetrahydrochloride, 3,3'4,4' 20 tetraaminobenzophenone, 1,3-bis-(2,4-diaminophenoxy)-propane tetra hydrochloride, 1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane tetrahydro chloride, 1,3-bis-(4-aminophenylamino)-propane, -2-propanol, 1,3-bis-[N (4-aminophenyl)-2-hydroxyethylamino]-2-propanol, N,N-bis-[2-(4-amino phenoxy)-ethyl]-methylamine trihydrochloride; 25 nitrogen-containing heterocyclic compounds selected from the group consisting of 2-, 3-, 4-amino-, 2-amino-3-hydroxy-, 2,6-diamino-, 2,5 diamino-, 2,3-diamino-, 2-dimethylamino-5-amino-, 3-amino-2 methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6 dimethoxy-, 2,4,5-triamino-, 2,6-dihydroxy-3,4-dimethyl pyridine, 4,5,6-tri 30 amino-, 2-hydroxy-4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2,4,5,6-tetra- WO 00/15184 27 PCT/EP99/06526 amino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4 methoxy-6-methyl pyrimidine, 2,3,4-trimethyl pyrrole, 2,4-dimethyl-3-ethyl pyrrole, 3,5-diaminopyrazole, -1,2,4-triazole, 3-amino-, 3-amino-5 hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquinaldine, 2-, 6 5 aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7 aminobenzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 4-, 5-, 6-, 7-hydroxyindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4 hydroxyindoline and physiologically compatible salts of these compounds 10 formed with preferably inorganic acids; aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methyl resorcinol, 2,5-dimethyl resorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydro quinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2-(2-hydroxyethyl)-, 3,4 15 methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -acetophenone, 2-, 4-chloro resorcinol, 1-naphthol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethyl amino-4-hydroxy-2-naphthalene sulfonic acid, 3,6-dihydroxy-2,7-naphtha lene sulfonic acid and 20 CH-active compounds selected from the group consisting of 1,2,3,3 tetramethyl-3H-indolium iodide, 1,2,3,5-tetraamethyl-3-indolium-p-toluene sulfonate, 1,2,3,5-tetramethyl indolium methane sulfonate, 2,3 dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium-p-toluene sulfonate, rhodanine, rhodanine-3-acetic acid, 1 -ethyl(methyl)-2 25 quinaldinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethyl(ethyl) thiobarbituric acid, oxindole, coumaranone and 1-methyl-3-phenyl-2 pyrazolinone. 5. A process as claimed in claim 4, characterized in that component B is selected from the group consisting of N-(2-hydroxyethyl)-N-ethyl-, 2 30 chloro-p-phenylenediamine, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, WO 00/15184 28 PCT/EP99/06526 4-aminophenol, p-phenylenediamine, 2-(2,5-diaminophenyl)-ethanol, 2,5 diaminotoluene, 3,4-methylenedioxy aniline, 3-amino-2,4-dichloro-, 2 methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5-(2-hydroxyethylamino)-, 2 methyl-5-amino-4-chloro-,

6-methyl-3-amino-2-chloro-, 2-aminomethyl-4 5 aminophenol, 2-hydroxymethyl-4-aminophenol, 2-amino-4-(2 hydroxyethylamino)-phenol, 3,4-methylenedioxyphenol, 3,4 diaminobenzoic acid, 2,5-diamino-, 2-dimethylamino-5-amino-, 3-amino-2 methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6 dimethoxy-, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-, 10 4-hydroxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6 triaminopyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6 dihydroxyindole, 5,6-dihydroxyindoline, 1-naphthol, 1,5-, 1,6-, 1,7-, 2,3-, 2,6-, 2,7-dihydroxynaphthalene and 2-naphthol-3,6-disulfonic acid Na salt and the physiologically compatible salts of these compounds preferably 15 formed with inorganic acids. 6. A process as claimed in any of claims 1 to 5, characterized in that substantive dyes from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols are used, preferably in a quantity of 0.01 to 20% by weight, based on the colorant as a whole. 20

7. A process as claimed in any of claims 1 to 6, characterized in that ammonium or metal salts from the group of formates, carbonates, halides, sulfates, butyrates, valerates, caproates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals, such as potassium, sodium or lithium, alkaline earth 25 metals, such as magnesium, calcium, strontium or barium, or of aluminium, manganese, iron, cobalt, copper or zinc are added.

8. A process as claimed in any of claims 1 to 7, characterized in that oxidizing agents, more particularly H 2 0 2 , are used in a quantity of 0.01 to 6% by weight, based on the solution applied. 30

9. A process as claimed in any of claims 1 to 8, characterized in that WO 00/15184 29 PCT/EP99/06526 anionic, zwitterionic or nonionic surfactants are used.

10. A process as claimed in any of claims 1 to 9, characterized in that components A and optionally B and other typical cosmetic ingredients are applied to the keratin-containing fibers, left thereon for a certain time, 5 normally about 30 minutes, and then rinsed out or washed out with a shampoo.