HK1026370A - Use of unsaturated aldehydes in dying fibers containing keratin - Google Patents

Description

Use of unsaturated aldehydes for dyeing keratin-containing fibers

The present invention relates to the dyeing of keratin-containing fibers, more particularly human hair, using unsaturated aldehydes.

Typically, keratin-containing fibers (e.g., hair, wool, or fur) are dyed with direct dyes or with oxidative dyes formed by oxidative coupling of one or more developer components to each other or one or more developer components to one or more coupler components. The developer and color former components are also known as oxidation dye precursors.

Commonly used developer components are primary aromatic amines containing another substituted or unsubstituted hydroxyl or amino group in the ortho, para position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolinone derivatives and 2, 4, 5, 6-tetraaminopyrimidines and derivatives thereof.

Specific representatives thereof are, for example, p-phenylenediamine, p-toluenediamine, p-aminophenol, o-aminophenol, 1- (2' -hydroxyethyl) -2, 5-diaminobenzene, N-bis (2-hydroxyethyl) p-phenylenediamine, 2- (2, 5-diaminophenoxy) ethanol, 1-phenyl-3-carboxamido-4-amino-5-pyrazolone, 4-amino-3-cresol, 2, 4, 5, 6-tetraaminopyrimidine, 2-hydroxy-4, 5, 6-triaminopyrimidine, 4-hydroxy-2, 5, 6-triaminopyrimidine, 2, 4-dihydroxy-5, 6-diaminopyrimidine, 2-dimethylamino-4, 5, 6-triaminopyrimidine, 2-hydroxyethylaminomethyl-4-aminophenol, 4' -diaminodiphenylamine, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, bis (2-hydroxy-5-aminophenyl) methane, 1, 4-bis (4-aminophenyl) diazepane, 1, 3-bis (N (2-hydroxyethyl) -N- (4-aminophenylamino)) -2-propanol, 4-amino-2- (2-hydroxyethoxy) phenol and 4, 5-diaminopyrazole derivatives as described in EP 0740741 or WO 94/08970, for example 4, 5-diamino-1- (2' -hydroxyethyl) pyrazole.

The coupling components used are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols. Particularly suitable color former components are 1-naphthol, 1, 2, 3-benzenetriol, 1, 5-, 2, 7-and 1, 7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2, 4-dichloro-3-aminophenol, 1, 3-bis (2, 4-diaminophenoxy) propane, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2, 5-dimethylresorcinol, 2, 6-dihydroxypyridine, 2-methylresorcinol, 2, 5-dimethylresorcinol, and mixtures thereof, 2, 6-diaminopyridine, 2-amino-3-hydroxypyridine, 2, 6-dihydroxy-3, 4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2, 6-bis (2-hydroxyethylamino) toluene, 2, 4-diaminophenoxyethanol, 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene, 2-methyl-4-chloro-5-aminophenol, 6-methyl-1, 2, 3, 4-tetrahydroquinoxaline, 3, 4-methylenedioxyphenol, 3, 4-methylenedioxyaniline, 2, 6-dimethyl-3-aminophenol, 2, 6-dihydroxy-3-aminophenol, 2, 6-dihydroxyl, 2-amino-2-hydroxy-2-methylbenzene, 2, 6-bis (2-hydroxyethylamino) toluene, 2, 4-diaminopyridine, 1, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol, 2-methyl-5- (2-hydroxyethylamino) phenol, and 2, 6-dihydroxy-3, 4-lutidine.

Although strong colors with good fastness properties can be obtained with oxidation dyes, the color is generally developed under the influence of oxidizing agents (e.g. hydrogen peroxide), which in some cases can lead to damage to the fibers. Furthermore, some oxidation dye precursors or mixtures of certain oxidation dye precursors may occasionally also have an allergenic effect on people with sensitive skin. Direct dyes, although used under relatively mild conditions, have the disadvantage in many cases of inadequate fastness.

DE-AS 2830497 discloses hair colorants comprising a combination of salicylaldehyde and oxidation dye precursors (e.g. 2, 5-diaminotoluene, 4-aminophenol, or 2, 4-diaminotoluene), but which have a somewhat higher allergenic potential (in combination with the additional presence of hydrogen peroxide). ED-AS 2932489 also discloses hydrogen peroxide-containing hair colorants which contain a benzaldehyde, such AS 2-hydroxy-3-methoxybenzaldehyde or 4-hydroxy-3-methoxybenzaldehyde, in combination with an oxidation dye precursor. US 5034014 and US 5199954 describe examples of hair dyeing formulations containing, for example, dimethylaminobenzaldehyde or dimethylaminocinnamaldehyde in combination with an allergenic p-phenylenediamine.

US 4391603 relates to an oxidizer-free hair colorant containing a substituted benzaldehyde. The hair colorants disclosed in this document are direct colorants, with which the color, shade and fastness values of hair colorants containing oxidic dye precursors are not achieved.

Dyeing keratin-containing fibers with aromatic aldehydes, as described in detail below, was not known in the past.

The aim of the invention is to provide a colorant for keratin fibers, more particularly human hair, which is at least qualitatively comparable to conventional hair oxidation colorants in terms of color, gray coverage and fastness properties, but which does not necessarily contain oxidizing agents, such as hydrogen peroxide. In addition, the colorants of the present invention have little (or no) allergenic potential.

The invention relates to the use of unsaturated aldehydes and corresponding mono-, bi-or omega-alkoxy acetals corresponding to the following tautomeric resonance formulae Ia and Ib for dyeing keratin-containing fibers, more particularly human hair:in the formula R¹，R²，R³And R⁴Each represents hydrogen, halogen, C_1-4Alkoxy radical, C_1-4Alkyl, aryl or C_1-4Alkoxy radical C_1-4An alkyl group; n is a number of 1 or 2; r¹And R²、R¹And R³、R²And R³、R²And R⁴Each of which may form a 5-7 membered ring with the remainder of the molecule when n ═ 1.

It has now surprisingly been found that aldehydes corresponding to formulae Ia and Ib are particularly suitable for dyeing keratin-containing fibers, even in the absence of oxidizing agents. They produce extremely bright colors and shades and can lead to a wide variety of shades. But in principle an oxidizing agent may still be present.

In the context of the present invention, keratin-containing fibers are understood to include wool, fur, feathers and, in particular, human hair. In principle, however, the colorants of the invention can also be used for dyeing other natural fibers, such as cotton, jute, sisal, flax or silk; modified natural fibers, such as regenerated cellulose, nitro-, alkyl-or hydroxyalkyl-or acetyl cellulose; and synthetic fibers such as polyamide, polyacrylonitrile, polyurethane, and polyester fibers.

Preferred unsaturated aldehydes corresponding to the formulae Ia and Ib are selected from the group consisting of glutaconedial, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3-hydroxymethylene-1-cycloheptene and 7-hydroxy-2, 4, 6-heptatrienal and their substituted derivatives and physiologically compatible salts, more particularly alkali metal and ammonium salts, particularly preferably tetrabutylammonium and sodium salts and mixtures thereof.

Mixtures corresponding to the formulae Ia and Ib are known from the literature or are commercially available.

The amount of aldehyde corresponding to formulae Ia and Ib in the colorant is preferably from 0.03 to 65mmol, more preferably from 1 to 40mmol, based in each case on 100 g of total colorant. A single compound or a mixture of several compounds of the formulae Ia and Ib can be used. They can be used as direct dyes or in the presence of compounds which enhance the color effect of the aldehydes used according to the invention, such as oxidation dye precursors.

Colorants containing aldehydes of the formulae Ia and Ib as the sole coloring component are preferred for the yellow and red range. More brilliant and more improved fastness properties of the colours, especially in the yellow, orange, brown, black range, and in the red and blue range, are obtained when the aldehydes of the formulae Ia and Ib are used together with compounds containing primary or secondary amino groups (e.g. aniline derivatives), nitrogen-containing heterocyclic compounds (e.g. primary heteroaromatic amines), aromatic hydroxy compounds or CH-active compounds. They are, on the one hand, compounds which produce only weak dyeings on keratin-containing fibers on their own and only bind to the aldehydes of the formulae Ia and Ib to give vivid colors, but, on the other hand, also include compounds which have been used as precursors for oxidation dyes.

The invention also relates to a preparation for dyeing keratin-containing fibres, more particularly human hair, comprising:

A. at least one unsaturated aldehyde corresponding to formulae Ia and Ib; and

B. at least one primary or secondary amino-or hydroxyl-containing compound selected from the group consisting of primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides consisting of 2 to 9 amino acids and aromatic hydroxyl compounds, and/or at least one CH-reactive compound. The above-mentioned compounds of component B can be used in amounts of from 0.03 to 65mmol, preferably from 1 to 40mmol, based in each case on 100 g of total colorant.

Several different aldehydes of the formulae Ia and Ib can be used together in all colorants. Similarly, several different components B can also be used together. This embodiment also includes the use of substances which represent the reaction products of unsaturated aldehydes corresponding to the formulae Ia and Ib with the compound B.

Suitable primary and secondary amino-containing compounds are, for example, primary aromatic amines such as N, N-dimethyl-, N-diethyl-, N- (2-hydroxyethyl) -N-ethyl-, N-bis (2-hydroxyethyl) -, N- (2-methoxy-amino)Ethyl) -, 2, 3-, 2, 4-, 2, 5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2, 5-dihydroxy-4-morpholinoaniline dihydrobromide salt, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, m-, p-phenylenediamine, o-, m-toluenediamine, 2, 5-diaminotoluene, -phenol, -phenethyl alcohol, 4-amino-3-methylphenol, 2- (2, 5-diaminophenyl) ethanol, 2, 4-diaminophenoxy ethanol, 2- (2, 5-diaminophenoxy) ethanol, p-phenylenediamine, p-toluenedioxy, p-tolu, 4-methylamino-, 3-amino-4- (2' -hydroxyethoxy) -, 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-hydroxyethylamino) -, 6-methyl-3-amino-2-chloro-, 2-methyl-5-amino-4-chloro-, 5- (2-hydroxyethylamino) -4-methoxy-2-methylphenol, 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, 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, and mixtures thereof, 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, pentaamino-benzene, hexaamino-benzene, 2, 4, 6-triaminoresorcinol, 4, 5-diaminocatechol, 4, 6-diamino-1, 2, 3-benzenetrisphenol, 3, 5-diamino-4-hydroxycatechol, aromatic anilines and phenols containing another aromatic group corresponding to formula II:in the formula R⁵Is hydroxy or amino, which may be substituted by C_1-4Alkyl radical, C_1-4Hydroxyalkyl radical, C_1-4Alkoxy or C_1-4alkoxy-C_1-4Alkyl substitution; r⁶、R⁷、R⁸、R⁹And R¹⁰Represents hydrogen, hydroxy or amino, which may be substituted by C_1-4Alkyl radical, C_1-4Hydroxyalkyl radical, C_1-4Alkoxy radicalBase, C_1-4Aminoalkyl radicals or G_1-4alkoxy-C_1-4Alkyl substituted, or a sulfonic acid group; x is a direct bond, a saturated or unsaturated carbon chain containing 1 to 4 carbon atoms which may optionally be substituted by hydroxyl, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom or a group corresponding to formula III:

Z-(CH₂-Q-CH₂-Z'). (III) wherein Q is a direct bond, CH₂Or a CHOH group; z and Z' independently of one another represent an oxygen atom, NR¹¹Radical (wherein R¹¹Is hydrogen, C_1-4Alkyl or hydroxy C_1-4Alkyl), O- (CH)₂)_p-NH or NH- (CH)₂)_P-O group (wherein p and p' ═ 2 or 3); o is a number from 1 to 4, such as 4, 4 '-diaminostilbene, 4, 4' -diaminostilbene-2, 2 '-disulfonic acid monosodium or disodium salt, 4, 4' -diaminodiphenylmethane, -sulfide, -sulfoxide, -amine, 4, 4 '-diaminodiphenylamine-2-sulfonic acid, 4, 4' -diaminobenzophenone, -diphenyl ether, 3 ', 4, 4' -tetraaminobiphenyl, 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, di-n-butyl ether, di-butyl ether, 1, 3-bis [ N- (4-aminophenyl) -2-hydroxyethylamino]-2-propanol, N-bis [2- (4-aminophenoxy) ethyl]Methylamine and N-phenyl-1, 4-phenylenediamine.

The compounds mentioned above can be used in their free form and in the form of their physiologically compatible salts, more particularly as salts of inorganic acids, such as the hydrochloride or sulfate salts.

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-dimethylpyridine, 2, 4-dihydroxy-5, 6-diamino-, 4, 5, 6-triamino-, 4-hydroxy-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-methylpyrimidine, 3, 5-diaminopyrazole, -1, 2, 4-triazole, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 2-aminoquinoline, 5-aminoquinoline, 2-hydroxy-4, 5-methylamino-2, 5, 6-methylamino-4, 5, 6-dimethylamino-methyl-pyrimidine, 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-dihydroxyindole, 5, 6-dihydroxyindoline, and 4-hydroxyindoline. The compounds mentioned above can be used in their free form and in the form of their physiologically compatible salts, for example as salts of inorganic acids, such as hydrochloride or sulfate.

Suitable amino acids are any natural and synthetic amino acids, for example amino acids obtained by hydrolysis of animal or vegetable proteins, such as collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Both acidic and basic amino acids can be used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan.

The oligopeptides may be natural or synthetic, and may also be oligopeptides present in polypeptides or protein hydrolysates, provided that they are sufficiently water-soluble to be used in the present colorant. Examples are glutathione or oligopeptides present in the hydrolysate of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. These oligopeptides are preferably used together with compounds containing primary or secondary amino groups or with aromatic hydroxy compounds.

Suitable aromatic hydroxy compounds are, for example, 2-, 4-, 5-methylresorcinol, 2, 5-dimethylresorcinol, resorcinol, 3-methoxyphenol, catechol, hydroquinone, 1, 2, 3-benzenetriol, 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-dihydroxynaphthalene, 2, 5-dimethylresorcinol, resorcinol, 3-methoxy-, 2- (2-hydroxyethyl) -, 3, 4-methylenedioxyphenol, 2, 4-dihydroxybenzoic acid, 2, 4-trihydroxybenzoic, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3, 6-dihydroxy-2, 7-naphthalenesulfonic acid.

Examples of CH-active compounds are 1, 2, 3, 3-tetramethyl-3H-indolium iodide, 1, 2, 3, 3-tetramethylindolium p-toluenesulfonate, 1, 2, 3, 3-tetramethyl-3H-indolium methanesulfonate, 2, 3-dimethyl-benzothiazolium iodide, 2, 3-dimethyl-benzothiazolium p-toluenesulfonate, rhodanine-3-acetic acid, 1-ethyl-2-quinaldinium iodide, 1-methyl-2-quinaldinium iodide, barbituric acid, thiobarbituric acid, 1, 3-dimethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-hydroxyindole acetate, coumaranone, and 1-methyl-3-phenyl-2-pyrazolone.

In a particularly preferred embodiment, component B is selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N-bis (2-hydroxyethyl) p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2, 5-diaminophenyl) ethanol, 2, 5-diaminotoluene, 3, 4-methylenedioxyaniline, 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, 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-, 4-hydroxy-2, 5, 6-triamino-, 2, 4, 5, 6-tetraamino-, or mixtures thereof, 2-methylamino-4, 5, 6-triaminopyrimidine, 3, 5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5, 6-dihydroxyindole and 5, 6-dihydroxyindoline and their physiologically compatible salts, preferably with mineral acids.

Oxidizing agents (e.g. H)₂O₂) Is not required. In some cases, however, it is desirable to add hydrogen peroxide or other oxidizing agents to the formulations of the present invention to obtain shades lighter than the keratin-containing fibers to be dyed. The oxidizing agent is generally used in an amount of 0.01 to 6% by weight, based on the solution used. The preferred hair coloring oxidizing agent is H₂O₂。

The coloring agent of the invention produces a wide color range from yellow-orange to brown-black. They have good firmness properties and low allergenic potential.

In a further preferred embodiment, the colorants of the invention contain, in addition to the compounds present according to the invention and optionally further oxidation dye precursors, typical direct dyes, for example dyes selected from the group consisting of nitroaniline, nitroaminophenol, azo dyes, anthraquinones or indophenols, in order to further modify the hue. Preferred direct dyes are the compounds HC yellow 2, HC yellow 4, HC yellow 5, HC yellow 6, basic yellow 57, disperse orange 3, HC red BN, basic red 76, HC blue 2, HC blue 12, disperse blue 3, basic blue 99, HC violet 1, disperse violet 4, disperse black 9, basic brown 16 and basic brown 17 which are known by their international or trade names, and 4-amino-2-nitrodiphenylamine-2' -carboxylic acid, 6-nitro-1, 2, 3, 4-tetrahydroquinoxaline, hydroxyethyl-2-nitrotoluidine, picric acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. The formulations according to this embodiment of the invention contain the direct dye in an amount of preferably from 0.01 to 20% by weight, based on the amount of total colorant.

The coloring agent of the present invention may also contain natural dyes such as lawsonia inermis, lawsonia inermis middle ash, lawsonia inermis black, chamomile flower, sandalwood, black tea, black alder bark, sage, sappan wood, madder root, catechu, sedre and alkanet.

Further dye components which can be used in the colorants of the invention are indoles and indolines and the physiologically acceptable salts thereof. Preferred examples are 5, 6-dihydroxyindole, N-methyl-5, 6-dihydroxyindole, N-ethyl-5, 6-dihydroxyindole, N-propyl-5, 6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 6-hydroxyindole, 6-aminoindole, 4-aminoindole. Preference is also given to 5, 6-dihydroxyindoline, N-methyl-5, 6-dihydroxyindoline, N-ethyl-5, 6-dihydroxyindoline, N-propyl-5, 6-dihydroxyindoline, N-butyl-5, 6-dihydroxyindoline, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

For dyes suitable for use in The Hair colourants and colouring formulations of The present invention, reference is also made to The work by Ch.Zviak, The Science of Hair Care (The Science of Hair Care), Chap.7(pp 248-250; direct dyes) and Chap.8(pp 264-267; oxidative dye precursors), published on "Dermatology" ("Dermatology'") volume 7 (Ed.: Ch.Culnan and H.Maibach), Marcel Dekker Inc., New York/base, 1986, and to The "European cosmetic materials catalog" ("European patent inventor Kohstoffee Rohstoffee"), published by Europei Schen Gemeenschafford, BunsverbandDeutscher-und Handeld Industrial disc, incorporated optical disc.

The component B compounds and optionally further oxidation dye precursors or optionally direct dyes do not have to be in each case individual compounds. In contrast, small amounts of other components may be present in the hair colorants of the present invention due to the method of producing the individual dyes, as long as these other components do not have a negative effect on the dyeing result or have to be excluded for other reasons, such as toxicity.

The colorants of the invention produce already intense dyeings at physiologically compatible temperatures < 45 ℃ and are therefore particularly suitable for dyeing human hair. For use on human hair, colorants are often incorporated into aqueous cosmetic carriers. Suitable aqueous cosmetic carriers are, for example, creams, suspensions, gels or surfactant-containing foaming solutions, such as shampoos or other formulations suitable for application to keratin-containing fibers. The coloring agent may also be incorporated into an anhydrous carrier, if desired.

The colorants of the invention may also contain any known active substances, additives and auxiliaries typical of such formulations. In many cases, the colorant contains at least one surfactant, anionic and zwitterionic, amphoteric, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has been found to be advantageous to select the surfactant from among anionic, zwitterionic or nonionic surfactants.

Anionic surfactants suitable for the formulations of the present invention are any anionic surface active materials suitable for use on the human body. Such materials are characterized by a water-soluble anionic group, such as a carboxylate, sulfonate, sulfate, or phosphate group, and a lipophilic alkyl group having from about 10 to about 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide ranges, and hydroxyl groups may also be present in the molecule. The following are suitable anionic surfactants, in the form of the sodium, potassium and ammonium salts and the ammonium salts of mono-, di-and trialkanols containing 2 or 3 carbon atoms in the alkanol group, respectively:

linear fatty acids (soaps) containing 10 to 22 carbon atoms,

-corresponds to the formula R-O- (CH)₂-CH₂O)_X-CH₂-ether carboxylic acids of COOH (where R is a straight-chain alkyl group containing 10 to 22 carbon atoms, X ═ 0 or 1 to 16),

-acyl sarcosines having 10 to 18 carbon atoms in the acyl group,

-an acyl taurine compound having 10 to 18 carbon atoms in the acyl group,

an acyl isethionic acid compound having 10 to 18 carbon atoms in the acyl group,

mono-and dialkyl esters of sulfosuccinic acid having from 8 to 18 carbon atoms in the alkyl radical and monoalkylpolyoxyethyl sulfosuccinates having from 8 to 18 carbon atoms in the alkyl radical and from 1 to 6 oxyethyl radicals,

linear alkanesulfonates having from 12 to 18 carbon atoms,

-linear alpha-olefin sulfonates containing 12 to 18 carbon atoms,

-alpha-sulfo fatty acid methyl esters of fatty acids having 12 to 18 carbon atoms,

-corresponds to the formula R-O- (CH)₂-CH₂O)_XSO₃Alkyl sulfates and alkyl polyglycol ether sulfates of H (where R is preferably a straight-chain alkyl radical having from 10 to 18 carbon atoms; X ═ 0 or from 1 to 12),

surface-active hydroxysulfonate mixtures according to DE-A-3725030,

sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ether according to DE-A-3723354,

sulfonates of unsaturated fatty acids containing 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-3926344,

the alcohols are esters of tartaric and citric acids of the addition products of around 2 to 15 ethylene oxide and/or propylene oxide molecules with fatty alcohols containing 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having from 10 to 18 carbon atoms in the alkyl radical and up to 12 glycol ether groups in the molecule, in particular saturated, more particularly unsaturated, C_8-22Salts of carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

The zwitterionic surfactant is a compound containing at least one quaternary ammonium group and at least one-COO group in the molecule^-or-SO₃ ^-A surfactant of the group. Particularly suitable zwitterionic surfactants are the so-called betaine-type surfactants, such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazoline and cocoacylaminoethyl-hydroxyethyl-carboxymethyl glycinate, each having 8 to 18 carbon atoms in the alkyl or acyl group. A preferred zwitterionic surfactant is the CTF from Cocamidopropyl BetaineA is a known fatty acid amide derivative.

The amphoteric surfactant is a compound except C in the molecule_8-18The alkyl or acyl radical containing, in addition to at least one free amino group and at least one-COOH or-SO group₃H groups and can form internal salts. Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids having in each case about 8 to 18 carbon atoms in the alkyl radical. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionates, cocoacylaminoethylaminopropionates and C_12-18Acyl sarcosines.

The nonionic surfactant contains, for example, a polyol group, a polyalkylene glycol ether group or a combination of a polyol group and a polyethylene glycol ether group as a hydrophilic group. Examples of such compounds are:

an addition product of 2 to 30 mol of ethylene oxide and/or 0 to 5 mol of propylene oxide to a branched fatty alcohol having 8 to 22 carbon atoms, a fatty acid having 12 to 22 carbon atoms and an alkylphenol having 8 to 15 carbon atoms in the alkyl radical,

c of an addition product of 1 to 30 moles of ethylene oxide on glycerol_12-22The fatty acid mono-and diesters,

-C_8-22alkyl mono-and oligoglycosides and their ethoxylated analogues,

-addition products of 5 to 60 moles of ethylene oxide on castor oil and hydrogenated castor oil,

-addition products of ethylene oxide onto sorbitan fatty acid esters,

-addition products of ethylene oxide on fatty acid alkanolamides.

Examples of cationic surfactants suitable for use in the hair treatment formulations of the present invention are in particular quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Other cationic surfactants suitable for use in the present invention are quaternized protein hydrolysates.

Also suitable for use according to the invention are cationic silicone oils, such as the commercially available products Q2-7224 (manufacturer: Dow Corning, a stable trimethylsilyl amodimethicone), Dow Corning 929 Emulsion (containing a hydroxyamino-modified polysiloxane, also known as Amnodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil^Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, Quaternium-80).

Alkylamidoamines, particularly fatty acid amidoamines, such as Tego Amid^The stearamidopropyldimethylamine obtained in S18 is remarkable not only for its good conditioning effect, but also in particular for its rapid biodegradation.

Quaternary ammonium ester compounds, so-called "Esterquats", such as those sold under the trade name Stepancex^Dialkyl ammonium methosulfates and methyl hydroxyalkyl dialkanoyloxyalkyl ammonium methosulfates are also sold as rapidly biodegradable.

An example of a quaternary ammonium sugar derivative suitable for use as a cationic surfactant is the commercially available product G1ucquat^100(CTFA name: Lauryl Methyl G1 uce-10 hydroxyxypropyl Dimonium Chloride).

The alkyl-containing compounds used as surfactants may be single compounds, but it is generally preferred that these compounds are produced from natural plant or animal sources, so that a mixture of different alkyl chain lengths is obtained depending on the particular source.

Surfactants which represent addition products of ethylene oxide and/or propylene oxide with fatty alcohols or derivatives of these addition products can be products having a "normal" homologue distribution and products having a narrow homologue distribution. Products having a "normal" homologue distribution are homologue mixtures obtained in the reaction of fatty alcohols and alkylene oxides with alkali metals, alkali metal hydroxides or alkali metal alkoxides as catalysts. In contrast, narrow homologue distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, oxides, hydroxides or alkoxides of alkaline earth metals are used as catalysts. It is advantageous to use products with a narrow homologue distribution.

Further active substances, auxiliaries and additives are, for example,

nonionic polymers such as vinylpyrrolidone/vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone/vinyl acetate copolymers, and polysiloxanes,

cationic polymers such as quaternized cellulose ethers, polysiloxanes containing quaternary ammonium groups, dimethyldiallylammonium chloride polymers, acrylamide/dimethyldiallylammonium chloride copolymers, dimethylaminoethylmethacrylate/vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone/imidazolinemethylchloride copolymers and quaternized polyvinyl alcohols,

zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride/acrylate copolymers and octylacrylamide/methyl methacrylate/aminoethyltert-butyl methacrylate/2-hydroxypropyl methacrylate copolymers,

anionic polymers such as polyacrylic acid, crosslinked polyacrylic acid, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers,

thickeners, such as agar. Guar gum, alginates, xanthan gum, gum arabic, karaya gum, carob flour, linseed gum, dextrans, cellulose derivatives, for example methylcellulose, hydroxyalkyl cellulose and carboxymethylcellulose, starches and derivatives, such as amylose, amylopectin and dextrin, clays, such as bentonite or fully synthetic hydrocolloids, such as polyvinyl alcohol,

structuring agents, such as glucose and maleic acid,

hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and cephalin, and silicone oils,

protein hydrolysates, more particularly hydrolysates of elastin, collagen, keratin, milk, soy and wheat proteins, their condensation products with fatty acids and hydrolysates of quaternized proteins,

-an aromatic oil, dimethylisosorbide and a cyclodextrin,

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, pyrrolidone carboxylic acid and its salts, plant extracts and vitamins,

-a cholesterol-containing compound selected from the group consisting of,

-a UV-absorber, which is,

consistency-providing agents, such as sugar esters, polyol esters or polyol alkyl ethers,

fats and waxes, such as spermaceti wax, beeswax, montan wax, paraffin wax, fatty alcohols and fatty acid esters,

-a fatty acid alkanolamide,

complexing agents, such as EDTA, NTA and phosphonic acid,

swelling and penetrating agents such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrroles,

-a sunscreen, such as latex,

pearlizing agents, such as ethylene glycol mono-and distearate,

propellants, such as propane/butane mixtures, N₂O, methyl ether, CO₂And air, and

-an antioxidant.

In the production of the colorants of the invention, the amounts of the components of the aqueous carrier used are the amounts customary for this purpose. For example, the emulsifier is used in a concentration of 0.5 to 30% by weight and the thickener in a concentration of 0.1 to 25% by weight, based on the total amount of the coloring agent.

The addition of ammonium or metal salts to the dyeing agent is advantageous for the dyeing result. 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 barium) or aluminum, manganese, iron, cobalt, copper or zinc; among them, sodium acetate, lithium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, ammonium chloride and ammonium acetate are preferable. The salts are preferably used in an amount of 0.03 to 65mmol, more preferably 1 to 40mmol, based on 100 g of total dye.

The pH of ready-to-use dyeing preparations is generally in the range from 2 to 11, preferably from 5 to 9.

For dyeing keratin-containing fibers, more particularly human hair, the dyeing agent is generally applied to the hair in the form of an aqueous cosmetic carrier in an amount of 100 g, left on the hair for about 30 minutes, and then rinsed or rinsed with a commercial shampoo.

The aldehydes corresponding to formulae Ia and Ib and the compounds of component B can be applied to the hair simultaneously or else successively, it not being essential which of the two components is applied first. The optional ammonium or metal salt may be added to the first component or the second component. A time interval of up to 30 minutes may be allowed between the administration of the first component and the administration of the second component. The fibers may also be pretreated with a salt solution.

The aldehydes corresponding to formulae Ia and Ib and the compounds of component B may be stored separately or together in the form of liquid or paste-like formulations (aqueous or anhydrous) or as dry powders. If the components are stored together in a liquid formulation, the formulation should be substantially anhydrous to reduce any risk of the components reacting. If the reactive components are stored separately, they are thoroughly mixed together shortly before application. If the components are stored as dry powders, a quantity of warm water (50-80 ℃) is generally added and a homogeneous mixture is prepared before application.

Examples

Preparation of the dyeing solution

A suspension of 10mmol of the aldehyde corresponding to the formulae Ia and Ib, 10mmol of the reagent, 10mmol of sodium acetate and 1 drop of a 20% solution of the fatty alkyl ether sulfate in 100 ml of water is prepared. The suspension was heated briefly to around 80 ℃, cooled and filtered, then the pH was adjusted to 6.

A strand of 90% gray hair without pretreatment was placed in this dyeing solution at 30 ℃ for 30 minutes. The dyed hair tresses were then rinsed with lukewarm water for 30 seconds, dried in a hot (30-40 ℃) air stream and combed. Visual evaluation of the color was performed in daylight.

The corresponding color and shade are shown in table I below.

The evaluation of the color was carried out according to the following criteria:

-: little or no color

(+): weak strength

+: medium strength

+(+): moderate to strong strength

++: high strength

++(+): strong to very strong strength

+++: very strong intensity Table 1 dyeing component B with 2-chloro-1-formyl-3-hydroxymethylenecyclohexene and chroma of-yellow + +2, 5-diaminotoluene XH₂SO₄Dark blue + + +2, 4, 5, 6-tetraaminopyrimidine XH₂SO₄Orange + +1, 8-bis (2, 5-diaminophenoxy) -3, 6-dioxaoctane x 4HCl gray-black + + (+) 2-methylamino-3-amino-6-methoxypyridine x 2HCl dark brown + + (+)2- (2, 5-diaminophenyl) ethanol x H₂SO₄Violet-blue + + 92-aminomethyl-4-aminophenol x 2HCl violet-red + + (+)4, 4' -diaminodiphenylamine x H₂SO₄Gray-green + + (+)2, 6-dimethoxy-3, 5-diaminopyridine x 2HCl Black + + + N, N-bis (2-hydroxyethyl) p-phenylenediamine x H₂SO₄Dark brown + + (+) Table 2 staining of fraction B with glutaconedial-tetrabutylammonium saltColor chroma-Rust Red + + (+)2, 5-diaminotoluene XH₂SO₄Dark violet + + +2, 4, 5, 6-tetraaminopyrimidine XH₂SO₄Golden +(+)1, 8-bis (2, 5-diaminophenoxy) -3, 6-dioxaoctane X4 HCl dark brown ++ (+) 2-methylamino-3-amino-6-methoxypyridine X2 HCl dark purple +++2- (2, 5-diaminophenyl) ethanol XH₂SO₄Red + + + 2-aminomethyl-4-aminophenol X2 HCl blue-violet + + +4, 4' -diaminodiphenylamine xH₂SO₄Black + + +2, 6-dimethoxy-3, 5-diaminopyridine x 2HCl Black + + + Table 3 color shade of component B dyed with glutaconedial-sodium salt-Rust Red + +2, 5-diaminotoluene x H₂SO₄Dark red-brown + + (+)2, 4, 5, 6-tetraaminopyrimidine XH₂SO₄Orange-yellow + + l, 8-bis (2, 5-diaminophenoxy) -3, 6-dioxaoctane x 4HCl dark gray + + (+) 2-methylamino-3-amino-6-methoxypyridine x 2HCl dark gray-brown + + (+)2- (2, 5-diaminophenyl) ethanol x H₂SO₄Violet-Red + + (+) 2-aminomethyl-4-aminophenol X2 HCl Red + + (+) N, N-bis (2-hydroxyethyl) p-phenylenediAmine × HCl blue-Black + + (+)4, 4' -diaminodiphenylamine × H₂SO₄Dark olive green + + +2, 6-dimethoxy-3, 5-diaminopyridine x 2HCl olive green + + L-histidine bright brown + + L-lysine copper color + + L-proline orange-brown + + (+) 3-methyl-1-phenyl-2-pyrrolidone rust red + + (+) thiobarbituric acid orange-brown + + (+) barbituric acid brown-yellow + + oxindole rust red + + 1-ethylquinaldinium iodide red + + (+) rhodanine red-brown + + (+)

Claims (13)

1. Use of unsaturated aldehydes corresponding to the formulae Ia and Ib below and corresponding mono-, di-or omega-alkoxy acetals for dyeing keratin-containing fibers, more particularly human hair:in the formula R¹，R²，R³And R⁴Each represents hydrogen, halogen, C_1-4Alkoxy radical, C_1-4Alkyl, aryl or C_1-4Alkoxy radical C_1-4An alkyl group; n is a number of 1 or 2; r¹And R²、R¹And R³、R²And R²、R²And R⁴Each of which may form a 5-7 membered ring with the remainder of the molecule when n ═ 1.

2. Use according to claim 1, characterized in that the aldehydes corresponding to the formulae Ia and Ib are present in an amount of from 0.03 to 65mmol, more particularly from 1 to 40mol, based on 100 g of the total dye dose.

3. Use according to claim 1 or 2, characterized in that the aldehydes corresponding to the formulae Ia and Ib are selected from the group consisting of glutaconedial, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3-hydroxymethylene-1-cycloheptene and 7-hydroxy-2, 4, 6-heptatrienal and substituted derivatives and salts thereof.

4. Use according to any one of claims 1 to 3, characterized in that additionally at least one compound containing a primary or secondary amino group or a hydroxyl group is used, which is selected from the group consisting of primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides consisting of 2 to 9 amino acids and aromatic hydroxyl compounds, and/or at least one CH-reactive compound.

5. Use according to any one of claims 1 to 4, characterized in that the oxidizing agent is used in an amount of 0.01 to 6% by weight, calculated on the solution used.

6. The use of claim 5, wherein hydrogen peroxide is used as the oxidant.

7. Use according to any one of claims 1 to 6, characterized in that anionic, zwitterionic and/or nonionic surfactants are used.

8. A preparation for dyeing keratin-containing fibers, more particularly human hair, comprising:

A. at least one member corresponding to formulae Ia and IbSaturated aldehydes and corresponding mono-, di-or omega-alkoxy acetals:in the formula R¹，R²，R³And R⁴Each represents hydrogen, halogen, C_1-4Alkoxy radical, C_1-4Alkyl, aryl or C_1-4Alkoxy radical C_1-4An alkyl group; n is a number of 1 or 2; r¹And R²、R¹And R³、R²And R³、R²And R⁴Each of which may form a 5-7 membered ring with the remainder of the molecule when n ═ 1, and

B. at least one primary or secondary amino-or hydroxyl-containing compound selected from the group consisting of primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides consisting of 2 to 9 amino acids and aromatic hydroxyl compounds, and/or at least one CH-reactive compound.

9. The formulation of claim 8, wherein component B is selected from the group consisting of:

a group of primary or secondary amines selected from: n- (2-hydroxyethyl) -N-ethyl-, N- (2-methoxyethyl) -, 2, 3-, 2, 4-, 2, 5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2, 5-dihydroxy-4-morpholinoaniline-dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2, 4-diaminophenoxyethanol, 2- (2, 5-diaminophenyl) -ethanol, 2, 5-diaminotoluene, -phenol, -phenethyl alcohol, 4-methylamino-, 3-amino-4- (2 '-hydroxyethoxy) -, alpha-hydroxy-methyl-, alpha-amino-, alpha-2, 5-diaminotoluene, -phenol, -phenethyl alcohol, alpha-amino-, alpha-4- (2' -hydroxyethoxy) -, 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-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro-, 6-methyl-3-amino-2-chloro-, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-aminomethyl-phenol, 4-amino-2-hydroxymethylphenol, 2-amino-4-hydroxymethyl-phenol, 2-methyl-amino-4-methyl-2-methyl-phenol, 2-methyl-amino-4-methyl-phenol, 2-methyl-amino-, 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, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalenesulfonic 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 tetrahydrochloride, 2, 4, 5-triaminophenol trihydrochloride, pentaaminophenylpentahydrochloride, hexaaminophenylhexahydrochloride, 2, 4, 6-triaminoresorcinol trihydrochloride, 4, 5-diaminophthalic acid sulfate, 4, 6-diamino-1, 2, 3-benzenetrihydrochloride, 3, 5-diamino-4-hydroxycatechol sulfate, aromatic anilines and phenols containing another aromatic group, such as 4, 4 '-diaminostilbene dihydrochloride, 4' -diaminostilbene-2, 2 '-disulfonic acid sodium salt, 4, 4' -diaminodiphenylmethane, -sulfide, -sulfoxide, -amine, 4, 4 '-diaminodiphenylamine-2-sulfonic acid, 4, 4' -diaminobenzophenone, -diphenyl ether, 3 ', 4, 4' -tetraaminobiphenyl tetrahydrate, 3 ', 4, 4' -tetraaminobenzophenone, 1, 3-bis (2, 4-diaminophenoxy) propane tetrahydrate, 1, 8-bis (2, 5-diaminophenoxy) -3, 6-dioxaoctane tetrahydrate, 1, 3-bis (4-aminophenylamino) propane, -2-propanol, 1, 3-bis [ N- (4-aminophenyl) -2-hydroxyethylamino ] -2-propanol, sodium salt of 4, 4 '-diaminodiphenyl, 3', 4, 4 '-tetraaminodiphenyl, 4' -tetraaminobenzophenone, 1, 3-bis (2, 4-diaminop, N, N-bis [2- (4-aminophenoxy) ethyl ] methylamine trihydrochloride; a group of 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-, 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-dimethylpyridine, 4, 5, 6-triamino-, 4-hydroxy-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-methylpyrimidine, 2, 3, 4-trimethylpyrrole, 2, 4-dimethyl-3-ethylpyrazole, 3, 5-diaminopyrazole, -1, 2, 4-triazole, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 2, 6-tetraaminobenz-ethyl-2, 4-amino-4, 5-diaminopyrazole, 2, 3, 4-amino-pyrazole, 2-, 3-, 8-aminoquinoline, 4-amino, 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 the physiologically compatible salts of these compounds preferably with inorganic acids; an aromatic hydroxy compound selected from the group consisting of: 2-, 4-, 5-methylresorcinol, 2, 5-dimethylresorcinol, resorcinol, 3-methoxyphenol, catechol, hydroquinone, 1, 2, 3-benzenetriol, 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-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 2-methoxy-3-dimethylamino-2- (2-hydroxyethyl) -, 3, 4-methylenedioxy-phenol, 2, 4-dihydroxybenzoic acid, 2-hydroxy, 3, 6-dihydroxy-2, 7-naphthalenesulfonic acid; and a group of CH active compounds selected from: 1, 2, 3, 3-tetramethyl-3H-indolium iodide, 1, 2, 3, 5-tetramethylindolium p-toluenesulfonate, 1, 2, 3, 5-tetramethyl-3H-indolium methanesulfonate, 2, 3-dimethyl-benzothiazolium iodide, 2, 3-dimethyl-benzothiazolium p-toluenesulfonate, rhodanine-3-acetic acid, 1-ethyl (methyl) -2-quinaldinium iodide, barbituric acid, thiobarbituric acid, 1, 3-dimethyl (ethyl) thiobarbituric acid, oxindole, coumaranone and 1-methyl-3-phenyl-2-pyrazolone.

10. The formulation of claim 9, wherein component B is selected from the group consisting of: n- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N-bis (2-hydroxyethyl) p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2, 5-diaminophenyl) ethanol, 2, 5-diaminotoluene, 3, 4-methylenedioxyaniline, 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, 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-, 4-hydroxy-2, 5, 6-triamino-, 2, 4, 5, 6-tetraamino-, or mixtures thereof, 2-methylamino-4, 5, 6-triaminopyrimidine, 3, 5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5, 6-dihydroxyindole and 5, 6-dihydroxyindoline and also the physiologically compatible salts of these compounds, preferably with mineral acids.

11. Formulation according to any one of claims 8 to 10, characterized in that a direct dye selected from the group consisting of nitroaniline, nitroaminophenol, anthraquinone or indophenol is used.

12. Formulation according to any one of claims 8 to 11, characterized in that an ammonium or metal salt is added, selected from the group consisting 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 metals such as magnesium, calcium, strontium or barium, or aluminium, manganese, iron, cobalt, copper or zinc.

13. A process for dyeing keratin-containing fibers in which a dyeing composition is applied to the keratin-containing fibers, allowed to remain on the fibers for some time, typically about 30 minutes, and then rinsed or shampooed, the dyeing composition comprising:

A. at least one unsaturated aldehyde corresponding to the formulae Ia and Ib and the corresponding mono-, di-or omega-alkoxy acetal:in the formula R¹，R²，R³And R⁴Each represents hydrogen, halogen, C_1-4Alkoxy radical, C_1-4Alkyl, aryl or C_1-4Alkoxy radical C_1-4An alkyl group; n is a number of 1 or 2; r¹And R²、R¹And R³、R²And R³、R²And R⁴Each of which may form a 5-7 membered ring with the remainder of the molecule when n ═ 1, and

B. at least one primary or secondary amino-or hydroxyl-containing compound selected from the group consisting of primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides of 2 to 9 amino acids and aromatic hydroxyl compounds, and/or at least one CH-reactive compound,

and conventional cosmetic ingredients.