AU1150099A

AU1150099A - Agent for dyeing fibers containing keratin with a concentration of dehydroascorbic acid content

Info

Publication number: AU1150099A
Application number: AU11500/99A
Authority: AU
Inventors: Horst Hoffkes; Hinrich Moller
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-10-14
Filing date: 1998-10-05
Publication date: 1999-05-03
Also published as: EP1028695A1; WO1999018917A3; DE19745354A1; JP2001519372A; WO1999018917A2

Description

Agent for Dyeing Fibres Containing Keratin with a Concentration of Dehydroascrobic Acid Content This invention relates to a composition for colouring keratin-containing fibres which contains dehydroascorbic acid in combination with reactive components, to the use of this composition for 5 colouring keratin-containing fibres and to a process for colouring keratin-containing fibres. In general, keratin-containing fibres, for example hair, wool or pelts, 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. 10 The primary intermediates normally used are primary aromatic 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-toluylenediamine, 2,4,5,6 15 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-diaminopyrimidine and 2,5,6 triamino-4-hydroxypyrimidine. 20 The secondary intermediates used are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols. Particularly suitable secondary intermediates are a-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2 methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4 diaminophenoxyethanol, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4 25 diaminophenoxy)-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 specifically made to the series "Dermatology" (Editors: Ch. Culnan and H. Maibach) published by Marcel Dekker Inc., New York/Basel, 1986, Vol. 7, Ch. Zviak's work The Science of Hair Care, Chapter 7, pages 248-250 30 (substantive dyes) and Chapter 8, pages 264-267 (oxidation dyes), and to the "Europsische Inventar der Kosmetik-Rohstoffe", 1996, published by the European Commission and available in diskette form from the Bundesverband Deutscher Industrie- und Handelsuntemehmen f~r Arzneimittel, Reformwaren und K6rperpflegemittel e.V., Mannheim, Germany. Although intensive colours with good fastness properties can be obtained with oxidation dyes, 35 the colour is generally developed under the influence of oxidising agents, such as H 2 0 2 for example, which in some cases can result in damage to the fibres. In addition, some oxidation dye precursors or certain mixtures of oxidation dye precursors can occasionally have a sensitising effect in people with sensitive skin. Although substantive dyes are applied under more moderate conditions, their disadvantage is that, in many cases, the colours obtained have inadequate fastness properties.

2 The problem addressed by the present invention was to provide colorants for keratin fibres, more especially human hair, which would be at least equivalent in quality to conventional oxidation hair colorants in regard to depth of colour, grey coverage and fastness properties, but which would not necessarily have to contain oxidising agents, such as H 2 0 2 for example. Another problem addressed 5 by the invention was to provide colorants with which a wide range of colour tones could be obtained without any staining of the skin. In addition, the colorants according to the invention would have very little, if any, sensitising potential. It has now surprisingly been found that combinations of dehydroascorbic acid and at least one other component are eminently suitable for colouring keratin-containing fibres. They give colours with 10 excellent brilliance and depth of colour and lead to a wide variety of colour tones. The use of oxidising agents is not necessary but, in principle, is not ruled out either. Accordingly, the present invention relates a composition for colouring keratin-containing fibres, characterised in that it contains A) dehydroascorbic acid corresponding to formula (1): 0 0 HOO HO 0 0 15 HO (I) and B) at least one compound containing a primary or secondary amino group or hydroxy group selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, a- to w-amino acids, oligopeptides made up of 2 to 9 amino acids and aromatic hydroxy compounds 20 and/or at least one CH-active compound. In the context of the invention, keratin-containing fibres are 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 colour other natural fibres such as, for example, cotton, jute, sisal, linen or silk, modified natural fibres such as, for example, regenerated cellulose, nitro, alkyl or hydroxyalkyl or 25 acetyl cellulose and synthetic fibres such as, for example, polyamide, polyacrylonitrile, polyurethane and polyester fibres. The compositions according to the invention contain each of the compounds of components A and B in a quantity of preferably 0.03 to 65 and more preferably 1 to 40mmol, based on 1Og of the colorant as a whole. 30 The scope of the present invention also encompasses embodiments which contain reaction products of the individual components A and B. The dehydroascorbic acid present as component A is a known compound of which the production is described in the literature and which is commercially available. Suitable compounds containing a primary or secondary amino group as component B are, for 35 example, primary aromatic amines, such as N,N-dimethyl-, N,N-diethyl-, N-(2-hydroxyethyl)-N-ethyl-, N,N-bis-(2-hydroxyethyl)-, N-(2-methoxyethyl)-, 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, 2- 3 aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o toluylenediamine, 2,5-diaminotoluene, -phenol, -phenethol, 4-amino-3-methylphenol, 2-(2,5 diaminophenyl)-ethanol, 2,4-diaminophenoxyethanol, 2-(2,5-diaminophenoxy)-ethanol, 4 methylamino-, 3-amino-4-(2'-hydroxyethyloxy)-, 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 5 3-amino-2,4-dichloro-, 4-methylamino-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5-(2 hydroxyethylamino)-, 6-methyl-3-amino-2-chloro-, 2-methyl-5-amino-4-chloro-, 3,4-methylenedioxy-, 5-(2-hydroxyethylamino)-4-methoxy-2-methyl-, 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-4-hydroxy-, 4-amino-3-hydroxybenzoic acid, 10 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3 hydroxynaphthalene-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-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5 tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6 15 triaminoresorcinol, 4,5-diaminopyrocatechol, 4,6-diaminopyrogallol, 3,5-diamino-4 hydroxypyrocatechol, aromatic anilines and phenols containing another aromatic radical corresponding to formula 1l: R R in which R1 is a hydroxy group or an amino group which may be substituted by C1.4 alkyl, C14 20 hydroxyalkyl or C14 alkoxy-C1A-alkyl groups, R 2 , R 2 , R 4 , R 5 and R 5 represent hydrogen, a hydroxy group or an amino group which may be substituted by a C14 alkyl, C1A hydroxyalkyl, C14 aminoalkyl or C14 alkoxy-C14-alkyl group or a carboxylic or sulfonic acid group and Z is a direct bond, a saturated or unsaturated optionally hydroxy-substituted carbon chain containing 1 to 4 carbon atoms, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom or a group corresponding to formula Ill: 25

Z-(CH

2

-Y-CH

2 -Z')o (Ill) 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 7 group, where R 7 is hydrogen, a C14 alkyl or a hydroxy-C1A-alkyl group, the group 0-(CH2)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'-disulfonic acid monosodium or disodium salt, 30 4-amino-4'-dimethylaminostilbene, 4,4'-diaminodiphenyl methane, -sulfide, -sulfoxide, -amine, 4,4' diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenylether, 3,3',4,4' tetraaminodiphenyl, 3,3'4,4'-tetraaminobenzophenone, 1,3-bis-(2,4-diaminophenoxy)-propane, 1,8 bis-(2,5-diaminophenoxy)-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] 35 methylamine, N-phenyl-1,4-phenylenediamine. The compounds mentioned above may be used both in free form and in the form of their physiologically compatible salts, more especially as salts of inorganic acids, such as hydrochloric acid or sulfuric acid.

4 Suitable nitrogen-containing heterocyclic compounds are, for example, 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-, 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-triamino-, 4-hydroxy 5 2,5,6-triamino-, 2-hydroxy-4,5,6-triamino-, 2,4,5,6-tetraamino-, 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-amino-, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquinaldine, 2-, 6-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, 5,6 10 dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. The compounds mentioned above may be used both in free form and in the form of their physiologically compatible salts, for example as salts of inorganic acids, such as hydrochloric acid or sulfuric acid. Suitable amino acids are any naturally occurring and synthetic a-amino acids, for example the amino acids obtainable by hydrolysis from vegetable or animal proteins, for example collagen, keratin, 15 casein, elastin, soy protein, wheat gluten or almond protein. Both acidic and alkaline amino acids may be used. Preferred amino acids are arginine, histidine, tyrosine, phenyl alanine, DOPA (dihydroxyphenylalanine), omithine, lysine and tryptophane. However, other amino acids, such as 6 aminocaproic acid for example, may also be used. The oligopeptides may be naturally occurring or synthetic oligopeptides and the oligopeptides 20 present in polypeptide or protein hydrolysates providing they are sufficiently soluble in water for use in the colorants according to the invention. Examples of such polypeptides are glutathione and the oligopeptides present in the hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. These oligopeptides are preferably used together with compounds containing a primary or secondary amino group or with aromatic hydroxy compounds. 25 Suitable aromatic hydroxy compounds are, for example, 2-, 4-, 5-methyl resorcinol, 2,5 dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 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-chlororesorcinol, 1-naphthol, 1,5-, 2,3-, 2,7 30 dihydroxynaphthalene, 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-indoliummethane sulfonate, Fischer's base (1,3,3-trimethyl-2-methyleneindoline) 2,3-dimethylbenzothiazolium iodide, 2,3 35 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 3-phenyl-2-pyrazolinone. In all colorants, several different colouring substances may also be used together. Several 40 different components from the groups of compounds containing a primary or secondary amino group, 5 nitrogen-containing heterocycles, aromatic hydroxy compounds or amino acids may also be used together. It has been found to be of advantage to add alkali metal salts or ammonium salts of C1 carboxylic acids or C1. hydroxycarboxylic acids and carbonic acid to the composition according to the 5 invention. Examples of such salts are formates, acetates, propionates, butyrates, valerates, caproates, glycolates, lactates and carbonates. Hydroxyalkylammonium cations may also be used as ammonium cations. Oxidising agents, for example H20 2 , need not present where the dehydroascorbic acid is used in accordance with the invention. However, it may be desirable in some cases to add hydrogen 10 peroxide or other oxidising agents to the compositions according to the invention to obtain shades which are lighter than the keratin-containing fibres to be coloured. Oxidising agents are generally used in a quantity of 0.01 to 6wt%, based on the solution applied. A preferred oxidising agent for human hair is H 2 0 2 . The colorants according to the invention give a broad range of colour tones in the range from 15 yellow through yellow-brown, orange, brown-orange, mid-brown, dark brown, violet, dark violet to black. Their fastness properties are excellent and their sensitising potentials very low. In one preferred embodiment, the colorants according to the invention contain typical substantive dyes, for example from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, in addition to the compounds present in accordance with the invention 20 in order further to modify the colour tones. Examples of 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 and picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-amino-2 25 nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis-(2' hydroxyethylamino)-2-nitrobenzene hydrochloride and 1 -methyl-3-nitro-4-(2'-hydroxyethyl) aminobenzene. The compositions according to the invention in this embodiment contain the substantive dyes in a quantity of, preferably, 0.01 to 20wt%, based on the colorant as a whole. In addition, the compositions according to the invention may also contain naturally occurring 30 dyes such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, black alder bark, sage, logwood, madder root, catechu, sedre and alkanet. The oxidation dye precursors or the substantive dyes present, if any, do not have to be single compounds. Instead, the hair colorants according to the invention - due to the processes used for producing the individual dyes - may contain small quantities of other components providing they do 35 not adversely affect the colouring result or have to be ruled out for other reasons, for example toxicological reasons. The colorants according to the invention produce intensive colours even at physiologically compatible temperatures of <450C. Accordingly, they are particularly suitable for colouring human hair. For application to human hair, the colorants are normally incorporated in a water-containing 40 cosmetic carrier. Suitable water-containing cosmetic carriers are, for example, creams, emulsions, 6 gels or even surfactant-containing foaming solutions, for example shampoos or other formulations suitable for application to the keratin-containing fibres. If necessary, the colorants may even be incorporated in water-free carriers. The colorants according to the invention may also contain any of the known active substances, 5 additives and auxiliaries typical of such formulations. In many cases, the colorants contain at least one surfactant, 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 invention are any anionic 10 surface-active substances suitable for use on the human body. Such substances are characterised by a water-solubilising 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, amide groups and hydroxyl groups may also be present in the molecule. The following are examples of suitable anionic surfactants - in the form of the 15 sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group: * linear fatty acids containing 10 to 22 carbon atoms (soaps), e ether carboxylic acids corresponding to the formula R-O-(CH 2

-CH

2 0)x-CH2-COOH, in which R is a linear alkyl group containing 10 to 22 carbon atoms and x = 0 or 1 to 16, 20 0 acyl sarcosides containing 10 to 18 carbon atoms in the acyl group, * 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 25 group and 1 to 6 oxyethyl groups, * linear alkane sulfonates containing 12 to 18 carbon atoms, " linear a-olefin sulfonates containing 12 to 18 carbon atoms, * a-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms, * alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the formula R-O(CH 2

-CH

2 0) 30 S03H, 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, * sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354, 35 * 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 products of around 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms.

7 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 particular, salts of saturated and, more particularly, unsaturated C8.22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. 5 In the context of the invention, zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one -COOH or -S0 3 ) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl N,N-dimethyl ammonium glycinates, for example coconutalkyl dimethyl ammonium glycinate, N acylaminopropyl-N,N-dimethyl ammonium glycinates, for example coconutacylaminopropyl dimethyl 10 ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethy imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and coconutacylaminoethyl 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 addition to a C8-18 alkyl or acyl 15 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, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl 20 group. Particularly preferred ampholytic surfactants are N-coconutalkyl aminopropionate, coconutacyl aminoethyl aminopropionate and C12.1s acyl sarcosine. Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are 25 0 products of the addition of 2 to 30mol of ethylene oxide and/or 0 to 5mol of propylene oxide onto linear fatty alcohols containing 8 to 22 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 30mol of ethylene oxide onto glycerol, 30 0 C8-22 alkyl mono- and oligoglycosides and ethoxylated analogues thereof, * products of the addition of 5 to 60mol of ethylene oxide onto castor oil and hydrogenated castor oil, * products of the addition of ethylene oxide onto sorbitan fatty acid esters, e products of the addition of ethylene oxide onto fatty acid alkanolamides. 35 Examples of cationic surfactants suitable for use in the hair treatment formulations according to the invention are, in particular, quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides, such as alkyltrimethylammonium chlorides, dialkyldimethyl ammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl 40 ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.

8 Other cationic surfactants suitable for use in accordance with the invention are the quaternised protein hydrolysates. 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 stabilised 5 trimethylsilylamodimethicone), Dow Coming 929 Emulsion (containing a hydroxyamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM 55067 (manufacturer: Wacker) and Abil@-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternarypolydimethylsiloxanes, quaternium-80). Alkyl amidoamines, particularly fatty acid amidoamines, such as the stearyl amidopropyl 10 dimethyl amine obtainable as Tego Amid@S 18, are distinguished not only by their favourable conditioning effect, but also and in particular by their ready biodegradability. Quaternary ester compounds, so-called "esterquats", such as the methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the trade name of Stepantex@, are also readily biodegradable. 15 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). 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 20 that mixtures with different alkyl chain lengths dependent upon the particular raw material are obtained. 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" homologue distribution and products with a narrow homologue distribution. Products with a "normal" homologue 25 distribution are mixtures of homologues which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homologue 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 a narrow homologue distribution can be of advantage. 30 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, * cationic polymers, such as quaternised cellulose ethers, polysiloxanes containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyl diallyl ammonium 35 chloride copolymers, dimethyl aminoethyl methacrylatevinyl pyrrolidone copolymers quaternised with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride copolymers and quaternised polyvinyl alcohol, * zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl 40 methacrylate/2-hydroxypropyl methacrylate copolymers, 9 0 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.butyl acrylamide terpolymers, 5 0 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 amylose, amylopectin and dextrins, clays such as, for example, bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol, 10 0 structurants, such as glucose and maleic acid, * hair-conditioning compounds, such as phospholipids, for example soy lecithin, egg lecithin and kephalins, and also silicone oils, * protein hydrolysates, more particularly elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, condensation products thereof with fatty acids and quaternised 15 protein hydrolysates, a perfume oils, dimethyl isosorbide and cyclodextrins, * solubilisers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, * antidandruff agents, such as Piroctone Olamine and Zinc Omadine, 20 0 other substances for adjusting the pH value, * active substances, such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and salts thereof, plant extracts and vitamins, & cholesterol, * UV filters, 25 e consistency factors, such as sugar esters, polyol esters or polyol alkyl ethers, * fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, * fatty acid alkanolamides, * complexing agents, such as EDTA, NTA and phosphonic acids, 30 0 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, " pearlisers, such as ethylene glycol mono- and distearate, 35 * propellents, such as propane/butane mixtures, N 2 0, dimethyl ether, CO 2 and air and * antioxidants. To produce the colorants according to the invention, the constituents of the water-containing carrier are used in the usual quantities for this purpose. For example, emulsifiers are used in concentrations of 0.5 to 30wt% while thickeners are used in concentrations of 0.1 to 25wt%, based on 40 the colorant as a whole.

10 It can be of advantage to the colouring result to add ammonium or 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 5 magnesium, calcium, strontium or 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 65mmol and more preferably in a quantity of 1 to 40mmol, based on 100 g of the colorant as a whole. 10 The pH value of the ready-to-use colouring compositions is normally in the range from 2 to 11 and preferably in the range from 5 to 9. The present invention also relates to the use of dehydroascorbic acid corresponding to formula (1): 0 0 HO HO (I) 15 in aqueous or organic-aqueous solution in the presence of at least one compound containing a primary or secondary amino group or hydroxy group selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, a- to w-amino acids, oligopeptides made up of 2 to 9 amino acids and aromatic hydroxy compounds and/or at least one CH-active compound for colouring keratin-containing fibres. 20 The present invention also relates to a process for colouring keratin-containing fibres in which a colorant containing dehydroascorbic acid and the above-mentioned compounds of component B are used as colouring components. In order to carry out the process according to the invention, the colorants are generally applied to the hair in the form of the water-containing cosmetic carrier in a quantity of 100g, left thereon for about 30 minutes and then rinsed out or washed out with a 25 commercially available shampoo. The compounds of components A and B may either be applied to the hair simultaneously or even successively, in which case it does not matter which of the two components is applied first. The ammonium or metal salts optionally present may be added to the first component or to the second component. A time of up to 30 minutes can be allowed to pass between application of the first 30 component and application of the second component. The fibres may even be pretreated with the salt solution. Components A and B of the compositions according to the invention may be stored either separately or together either in the form of a liquid or paste-like preparation (aqueous or water-free) or as a dry powder. If the components are stored together in a liquid preparation, the preparation in 35 question should be substantially free from water to reduce any risk of the components reacting. Where the reactive components are stored separately, they are mixed thoroughly together only shortly 11 before application. Where the components are stored as a dry powder, a defined quantity of warm water (50 to 80*C) is normally added and a homogeneous mixture prepared before application. Examples Preparation of a colouring solution 5 A suspension of 10mmol of dehydroascorbic acid, 10mmol of a compound of component B, 10mmol of sodium acetate and 1 drop of a 20% fatty alkyl ether sulfate solution in 100mL of water was prepared. The suspension was briefly heated to around 800C and filtered after cooling, after which the pH was adjusted to 6. One tress of 90% grey, non-pretreated human hair was placed in this colouring solution for 30 10 minutes at 300C. The coloured tress was then rinsed for 30s with luke-warm water, dried in a stream of warm air (30-40*C) and then combed. The colours were visually evaluated in daylight. The particular shades and depths of colour are shown in the following Tables. The depth of colour was evaluated on the following scale: very faint, if any, colour 15 (+) : weak intensity + : medium intensity +(+) :medium to strong intensity ++ : strong intensity ++(+) :strong to very strong intensity 20 +++ : very strong intensity Table 1 Colouring with dehydroascorbic acid Component B Shade Depth of colour 2,5-Diaminotoluene x H 2

SO

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

SO

4 Brown-yellow + 1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane x 4 HCl Blue-black +++ 2-Methylamino-3-amino-6-methoxy-pyridine x 2 HCl Orange-brown ++ 2-(2,5-Diaminophenyl)-ethanol x H 2 S0 4 Violet-brown ++ N,N-bis-(2-hydroxyethyl)-p-phenylene-diamine x HCI Violet-brown ++ 4,4'-Diaminodiphenylamine x H 2

SO

4 Violet-black +++ 2,6-Dimethoxy-3,5-diamino-pyridine x 2 HCI Brown-black +++

Claims

1. A composition for colouring keratin-containing fibres, characterised in that it contains A) dehydroascorbic acid corresponding to formula (1): 0 0 HO HO (|) s and B) at least one compound containing a primary or secondary amino group or hydroxy group selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, a- to w-amino acids, oligopeptides made up of 2 to 9 amino acids and aromatic hydroxy compounds and/or at least one CH-active compound. 10

2. A composition as claimed in claim 1, characterised in that the compounds of component B are 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 dihydrobromide, 2-, 3-, 4-aminophenol, o-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2-(2,5 15 diaminophenyl)-ethanol, 2,5-diaminotoluene, -phenol, -phenethol, 4-methylamino-, 3-amino-4-(2' hydroxyethyloxy)-, 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4 methylamino-, 3,4-methylenedioxy-, 3-methyl-4-amino-, 2-methyl-5-(2-hydroxyethylamino)-, 6-methyl

3-amino-2-chloro-, 5-(2-hydroxyethylamino)-4-methoxy-2-methyl-, 4-amino-2-aminomethyl phenol, 4 amino-2-hydroxymethyl phenol, 3,4-methylenedioxyphenol, 1,3-diamino-2,4-dimethoxybenzene, 2-, 3 20 , 4-aminobenzoic acid, -phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5 aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxybenzoic acid, 2-, 3-, 4 aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene 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 25 aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5 tetraaminobenzene tetrahydrochloride, 2,4,5-triaminophenol trihydrochloride, pentaaminobenzene pentahydrochloride, hexaaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminopyrocatechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4 hydroxypyrocatechol sulfate, aromatic anilines and phenols containing another aromatic radical, such 30 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' tetraaminobenzophenone, 1,3-bis-(2,4-diaminophenoxy)-propane tetrahydrochloride, 1,8-bis-(2,5 diaminophenoxy)-3,6-dioxaoctane tetrahydrochloride, 1,3-bis-(4-aminophenylamino)-propane, -2 35 propanol, 1,3-bis-[N-(4-aminophenyl)-2-hydroxyethylamino]-2-propanol, N,N-bis-[2-(4-aminophenoxy) ethyl]-methylamine trihydrochloride; 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- 13 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-triamino-, 2-hydroxy-4,5,6 triamino-, 4-hydroxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 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, 5 3,5-diaminopyrazole, -1,2,4-triazole, 3-amino-, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline,

4-aminoquinaldine, 2-, 6-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, hydroxyhydroquinone, 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-chlororesorcinol, 1 15 naphthol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalene sulfonic acid, 3,6-dihydroxy-2,7-naphthalene sulfonic acid and CH-active compounds selected from the group consisting of 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetraamethyl-3-indolium-p-toluene sulfonate, 1,2,3,3-tetramethyl-3-indolium methane sulfonate, 2,3-dimethylbenzothiazolium iodide, 2,3 dimethylbenzothiazolium-p-toluene sulfonate, rhodanine, rhodanine-3-acetic acid, 1 -ethyl(methyl)-2 20 quinaldinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethyl(ethyl) thiobarbituric acid, oxindole, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone. 3. A composition as claimed in claim 1 or 2, characterised in that the compounds of components A and B are each present in a quantity of 0.03 to 65mmol and more particularly 1 to 40mmol, based on 1 0Og of the colorant as a whole. 25 4. A composition as claimed in any of claims 1 to 3, characterised in that it contains alkali metal, ammonium and/or hydroxyalkyl-substituted ammonium salts of Ci. carboxylic acids, CI-6 hydroxycarboxylic acids and/or carbonic acid.

5. A composition as claimed in any of claims 1 to 4, characterised in that oxidising agents are used in a quantity of 0.01 to 6wt%, based on the solution applied. 30

6. A composition as claimed in any of claims 1 to 5, characterised in that H 2 0 2 is used as the oxidising agent.

7. A composition as claimed in any of claims 1 to 6, characterised in that anionic, zwitterionic and/or nonionic surfactants are used.

8. The use of dehydroascorbic acid corresponding to formula (1): 0 0 HO O 35 HO (I) in aqueous or organic-aqueous solution in the presence of at least one compound containing a primary or secondary amino group or hydroxy group selected from primary or secondary aliphatic or 14 aromatic amines, nitrogen-containing heterocyclic compounds, a- to w-amino acids, oligopeptides made up of 2 to 9 amino acids and aromatic hydroxy compounds and/or at least one CH-active compound for colouring keratin-containing fibres.

9. A process for colouring keratin-containing fibres in which a colorant containing 5 A) dehydroascorbic acid corresponding to formula (1): 0 0 HO HO (I) B) at least one compound containing a primary or secondary amino group or hydroxy group selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, a- to w-amino acids, oligopeptides made up of 2 to 9 amino acids and aromatic hydroxy compounds 10 and/or at least one CH-active compound and typical cosmetic ingredients is applied to the keratin containing fibres, left thereon for a time, usually about 30 minutes, and then rinsed out again or washed out with a shampoo.