WO1998047473A1

WO1998047473A1 - Use of unsaturated aldehydes in dying fibers containing keratin

Info

Publication number: WO1998047473A1
Application number: PCT/EP1998/002243
Authority: WO
Inventors: Hinrich Möller; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1997-04-24
Filing date: 1998-04-16
Publication date: 1998-10-29
Also published as: AU726113B2; BR9809417A; NO995157D0; DE19717224A1; AU7526498A; CN1252707A; JP2001524091A; HUP0002707A2; SK145599A3; CA2288055A1; NO995157L; PL336070A1; HUP0002707A3; EP0977546A1

Abstract

The invention relates to the use of unsaturated aldehydes of formulae (Ia) or (Ib), wherein R?1, R2, R3 and R4¿ independently mean hydrogen, halogen, a C¿1?-C4-alkoxy, C1-C4-alkyl, aryl radical or a C1-C4-alkoxy-C1-C4-aryl radical and n stands for 1 or 2, wherein R?1 and R2, R1 and R3, R2 and R3 and R2 and R4¿ can form together with a residual molecule a ring with 5 to 7 units when n equals 1, in addition to the corresponding mono, bis or φ-alkoxy acetals, for the dying of fibers containing keratin, specially human hair.

Description

"Use of unsaturated aldehydes for dyeing fibers containing keratin"

The invention relates to the use of unsaturated aldehydes for dyeing keratin fibers, in particular human hair.

For dyeing keratin fibers, e.g. B. hair, wool or fur, generally either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with one another or with one or more coupler components, are used. Coupler and developer components are also referred to as oxidation dye precursors.

Primary aromatic amines with a further 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 their derivatives are usually used as developer components.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenoxy) ethanol, 1 -phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 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-amino-phenol, 4,4'-diaminodiphenylamine, .4-amino-3-fluorophenol, 2-amino-4-amino-phenol, 2-hydroxymethyl-4-aminophenol, bis - (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4-aminophenyl) diazacycloheptane, 1,3-bis (N (2-hydroxyethyl) - N (4-aminophenylamino)) - 2-propanol, 4-amino-2- (2-hydroxyethoxy) phenol and 4,5-diaminopyrazole derivatives according to EP 0 740 741 or WO 94/08970 such as 4,5-diamino-1 - (2'- hydroxyethyl) pyrazole. M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used as coupler components. Particularly suitable coupler substances are 1-naphthol, pyrogallol, 1, 5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine , 1-phenyl-3-methyl-pyrazolone-5, 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, 2,6-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-meth - oxy-2-amino-4- (2-hydroxyethylamino) benzene, 2-methyl-4-chloro-5-amino-phenol, 6-methyl-1, 2,3,4-tetrahydro-quinoxaline, 3,4 -Methylene dioxyphenol, 3,4-methylenedioxyaniline, 2,6-dimethyl-3-aminophenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol, 2-methyl-5- ( 2-hydroxyethylamino) phenol and 2,6-dihydroxy y-3,4-dimethylpyridine.

Intensive dyeings with good fastness properties can be achieved with oxidation dyes, but the development of the color generally takes place under the influence of oxidizing agents such as H ₂ O ₂ , which in some cases can damage the fibers. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on people with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage is that the dyeings often have inadequate fastness properties.

German patent application DE 28 30 497 discloses hair colorants which contain salicylaldehyde in combination with oxidation dye precursors, for example 2,5-diaminotoluene, 4-aminophenol or 2,4-diaminotoluene, but which (in combination with the additionally contained hydrogen peroxide) more or less can have great potential for sensitization. The German patent application DE 29 32 489 also discloses H ₂ O ₂ -containing hair colorants which contain benzaldehydes, for example 2-hydroxy-3-methoxybenzaldehyde or 4-hydroxy-3-methoxybenzaldehyde, in combination with oxidation dye precursors. US Pat. Nos. 5,034,014 and 5,199,954 describe examples of hair dye formulation which use p-dime contain thylaminobenzaldehyde or p-dimethylamino cinnamaldehyde, for example in combination with the sensitizing p-phenylenediamine.

The US Pat. No. 4,391,603 has the object of oxidizing agent-free hair colorants which contain substituted benzaldehydes. The hair dyes disclosed there represent direct hair dyes with which the color nuances, depths of color and color fastness of hair dyes containing oxidation hair dye precursors cannot be achieved.

The use of the aromatic aldehydes described in more detail below for dyeing fibers containing keratin is not yet known.

The object of the present invention is to provide colorants for keratin fibers, in particular human hair, which are at least equivalent in quality to the usual oxidation hair colorants in terms of color depth, gray coverage and fastness properties, but without necessarily being dependent on oxidizing agents such as H ₂ O ₂ . In addition, the colorants may have no or only a very low sensitization potential.

The invention relates to the use of unsaturated aldehydes described by the tautomeric limit formulas Ia and Ib,

(la) (Ib)

in which R ² , R ³ and R ⁴ independently of one another represent hydrogen, halogen, a CC ₄ alkoxy, CrC alkyl, aryl or CC ^ alkoxy-C C ^ alkyl radical and n stand for the numbers 1 or 2 , where R ¹ and R ² , R ¹ and R ³ , R ² and R ³ and R ² and R ^{4 can} each form a 5- to 7-membered ring together with the rest of the molecule if n is 1, and the corresponding Mono-, bis- or ω-alkoxyacetals for dyeing keratin fibers, especially human hair. Surprisingly, it was found that the aldehydes shown in the formulas Ia and Ib are outstandingly suitable for dyeing keratin-containing fibers even in the absence of oxidizing agents. They result in colors with excellent brilliance and depth of color and lead to a wide range of shades. However, the use of oxidizing agents should not be excluded in principle.

Keratin-containing fibers are wool, furs, feathers and in particular human hair. In principle, however, the colorants according to the invention can also be used to dye other natural fibers, such as Cotton, jute, sisal, linen or silk, modified natural fibers, e.g. Regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as e.g. Polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used.

The unsaturated aldehydes of the formulas Ia and Ib are preferably selected from the group consisting of glutaconaldehyde, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3-hydroxymethylene-1-cycloheptene and 7-hydroxy-2,4,6 -heptatrienal and its substituted derivatives and the physiologically tolerable salts thereof, in particular the alkali and ammonium salts, the tetrabutylammonium salts and Na salts and mixtures thereof being particularly preferred.

The substances according to formulas Ia and Ib are known from the literature or are commercially available.

The aldehydes of the formulas Ia and Ib are contained in the colorants preferably in an amount of 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the total colorant. A single compound with the formula Ia or Ib or a mixture of several compounds can be used. They can be used as direct colorants or in the presence of compounds which enhance the coloring effect of the aldehydes used according to the invention, such as oxidation dye precursors. Coloring agents which contain aldehydes of the formulas Ia and Ib alone as the coloring component are preferably used for coloring in the yellow and red range. Colorings with increased brilliance and further improved fastness properties, especially in the yellow, orange, brown and black range and also in the red and blue range, are achieved if the aldehydes of the formulas la and Ib together with compounds having a primary or secondary amino group, for example Aniline derivatives, with nitrogen-containing heterocyclic compounds, for example primary heteroaromatic amines, aromatic hydroxy compounds or CH-active compounds. On the one hand, these are compounds which, on their own, only weakly dye keratin-containing fibers and only give brilliant colors together with the aldehydes of the formulas Ia and Ib. On the other hand, there are also compounds that are already used as oxidation dye precursors.

Another object of the present invention is an agent for dyeing keratin fibers, in particular human hair, which A at least one unsaturated aldehyde with the formula la or Ib and B at least one compound with primary or secondary amino group or hydroxy group selected from primary or contains secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides and aromatic hydroxy compounds composed of 2 to 9 amino acids, and / or at least one CH-active compound.

The above-mentioned compounds of component B can be used in an amount of 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the total colorant.

Several different aldehydes of the formulas Ia and Ib can also be used together in all colorants; Likewise, several different compounds of component B can also be used together. This embodiment also includes the use of substances which react Represent products of unsaturated aldehydes of the formula I with the compounds B mentioned.

Suitable compounds with primary or secondary amino groups are e.g. 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-, 4th - Aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol o-, m-, p-phenylenediamine, o-, m-toluenediamine, 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, 3-amino-2,4-dichloro-, 4-methylamino-, 2-methyl-5-amino-, 3-methyl-4-amino- , 2-methyl-5- (2-hydroxyethylamino) -, 6-methyl-3-a-mino-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 -Amino-salicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxy-benzoic 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, 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, hexaa - minobenzene, 2,4,6-triaminoresorcinol, 4,5-diamino-catechol, 4,6-diaminopyrogallol, 3,5-diamino-4-hydroxy-pyrocatechol, aromatic anilines or phenols with a further aromatic radical, as described in formula II are shown

in the R ⁵ for a hydroxyl or an amino group, which by C ^ alkyl, C _w -

Hydroxyalkyl, C 1-4 alkoxy or C _M alkoxy-C alkyl groups can be substituted,

R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 represent} hydrogen, a hydroxy or an amino group,

C ^ alkyl, C _M hydroxyalkyl, C ^ alkoxy, C ^ aminoalkyl or C ^ alkoxy-C ^ - alkyl groups may be substituted, or represent a sulfonic acid group, and

X for a direct bond, a saturated or unsaturated, possibly through

Hydroxy group-substituted carbon chain with 1 to 4 carbon atoms, a

Carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or one

Group with the formula III

Z- (CH ₂ -Q-CH ₂ -Z ') ₀ (III)

in which Q denotes a direct bond, a CH ₂ or CHOH group,

Z and Z 'independently of one another for an oxygen atom, an NR ¹¹ group in which R ^{11 is} hydrogen, a C 1-4 alkyl or a hydroxy C 1-4 alkyl group, the group O- (CH ₂ ) _p -NH or NH - (CH ₂ ) _p , -O, where p and p 'are 2 or 3, and o is a number from 1 to 4, such as 4,4'-diaminostilbene, 4,4'-diaminostilbene-2,2 'disulphonic acid mono- or di-Na salt, 4,4'-diaminodiphenylmethane, sulphide, sulphoxide, amine, 4,4'-diaminodiphenylamine-2-sulphonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, 3, 3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraamino-benzophenone, 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] methylamine, N-phenyl-1,4-phenylenediamine.

The abovementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.

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-, 2nd , 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-methyl-pyrimidine, 3,5-diaminopyrazole, -1, 2,4-thazole, 3-amino, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-amino quinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline as well as indole and indoline derivatives, such as 4 -, 5-, 6-, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. The aforementioned compounds can be used both in free form and in the form of their physiologically tolerable salts, e.g. B. as salts of inorganic acids such as hydrochloric or sulfuric acid.

All naturally occurring and synthetic amino acids are suitable as amino acids, e.g. obtained by hydrolysis from vegetable or animal proteins, e.g. Collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein, accessible amino acids. Both acidic and alkaline amino acids can be used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan.

The oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided that they have sufficient water solubility for use in the colorants according to the invention. Examples are e.g. Glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Use together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds is preferred.

Suitable aromatic hydroxy compounds are, for example, 2-, 4-, 5-methylresorcinol, 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-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy- 2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

Examples of CH-active compounds which may be mentioned are 1, 2,3,3-tetramethyl-3H-indium 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, rhodanine-3-acetic acid, 1-ethyl-2-quinal dinium iodide, 1-methyl-2-quinal dinium iodide barbituric acid, Thiobarbituric acid, 1, 3-dimethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

The compounds of component B are particularly preferably selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-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-, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5- Diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline, and those formed with preferably inorganic acids n physiologically acceptable salts.

The presence of oxidizing agents, for example H ₂ O ₂ , can be dispensed with. However, it may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention to obtain shades lighter than the keratin-containing fiber to be colored. Oxidizing agents are generally used in an amount of 0.01 to 6% by weight, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ . The colorants according to the invention result in a wide range of color shades in the range from yellow-orange to brown-black; the fastness properties are excellent, the sensitization potential is very low.

In a preferred embodiment, the colorants according to the invention contain, in addition to the compounds contained according to the invention and possibly further oxidation dye precursors, customary direct dyes, e.g. from the group of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those under the international names or trade names HC Yeliow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, 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 known compounds and 4-amino-2-nitrodiphenylamine-2 ' -carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol 4-ethylamino-3-nitrobenzoic acid and 2- Chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. The agents according to the invention in accordance with this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten bark, sage, blue wood, madder root, catechu, sedre and alkanna root.

Further dye components contained in the colorants according to the invention can also be indoles and indolines, and also their physiologically tolerable salts. 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 and 4-aminoindole. Also preferred are 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. With regard to the dyes which can be used in the hair dyeing and tinting agents according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as volume 7 of the "Dermatology" series (publisher: Ch. Culnan and H. Maibach), publisher Marcel Dekker Inc., New York, Basel, 1986, and the "European inventory of cosmetic raw materials" , published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicines, Reformed Products and Personal Care Products, Mannheim.

It is not necessary that the compounds of component B and possibly further oxidation dye precursors or the optional direct dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the production processes for the individual dyes, further components may also be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.

The colorants according to the invention produce intensive colorations even at physiologically tolerable temperatures of below 45 ° C. They are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants can usually be incorporated into a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are e.g. Creams, emulsions, gels or also surfactant-containing foaming solutions such as Shampoos or other preparations that are suitable for use on the keratin fibers. If necessary, it is also possible to incorporate the colorants into anhydrous carriers.

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

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

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16, acyl sarcosides with 10 to 18 C- Atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha olefin sulfonates with 12 to 18 carbon atoms, methyl alpha sulfofatty acid esters of fatty acids with 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

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

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C ₈ . ₁₈ -alkyl or -acyl group in the molecule contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylamino propionate and C ₁₂ . ₁₈ acyl sarcosine.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example Addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to

22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group,

C ₁₂ - ₂₂ fatty acid monoesters and diesters of adducts from 1 to 30 mol

Ethylene oxide on glycerin,

C ₈ . ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs,

Addition products of 5 to 60 mol of ethylene oxide with castor oil and hardened

Castor oil,

Addition products of ethylene oxide onto sorbitan fatty acid esters

Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the hair treatment compositions according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaterium-80).

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid®S 18, are characterized in particular by their good biodegradability. Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", kylammoniummethosulfate such as those sold under the trademark Stepantex ^® and methyl dialkyl ammonium methosulfates-hydroxyalkyldialkoyloxyalkyl.

An example of a quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat®100, according to the CTFA nomenclature a "lauryl methyl gluceth-10 hydroxypropyl dimonium chloride".

The compounds with alkyl groups used as surfactants can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. By contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides,

hydroxides or alcoholates can be used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Other active ingredients, 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 with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate-quaternized di- methylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imide-azolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-methyl-methacrylate / tert-methyl-acrylate, tert-methyl-acrylate-methyl acrylate / tert-methyl-methacrylate-2-methyl-acrylate-tert-methyl-acrylate-tert-methyl-acrylate-methyl-acrylate-tert-methyl-acrylate-2-methyl acrylate-tert-methyl acrylate Polymers such as polyacrylic acids, cross-linked 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 / tert-acrylate / N-acrylate / N-acrylate / N

Butylacrylamide terpolymers,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans,

Cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and

Dextrins, clays such as e.g. B. bentonite or fully synthetic hydrocolloids such as e.g.

Polyvinyl alcohol,

Structurants such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils,

Protein hydrolyzates, especially elastin, collagen, keratin, milk protein,

Soy protein and wheat protein hydrolyzates, their condensation products with

Fatty acids and quaternized protein hydrolyzates,

Perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol,

Glycerin and diethylene glycol,

Anti-dandruff agents such as piroctone olamine and zinc omadine, other substances for adjusting the pH value,

Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins,

Cholesterol,

Light stabilizers,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, Fats and waxes such as whale, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, opacifiers such as latex,

Pearlescent agents such as ethylene glycol mono- and distearate,

Blowing agents such as propane-butane mixtures, N ₂ 0, dimethyl ether, CO ₂ and air as well as antioxidants.

The constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; e.g. emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant.

For the coloring result it can be advantageous to add ammonium or metal salts to the coloring agents. Suitable metal salts are e.g. Formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkaline earth metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or Barium, or of aluminum, manganese, iron, cobalt, copper or zinc, with 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 an amount of 0.03 to 65, in particular 1 to 40 mmol, based on 100 g of the total colorant.

The pH of the ready-to-use coloring preparations is usually between 2 and 11, preferably between 5 and 9.

For dyeing the keratin fibers, in particular for dyeing human hair, the colorants are generally in the form of the water-containing cosmetic carrier in an amount of 100 g applied to the hair, left there for about 30 minutes and then rinsed out or washed out with a commercially available hair shampoo.

The aldehydes of the formulas Ia and Ib and the compounds of component B can either be applied to the hair at the same time or else in succession, it being irrelevant which of the two components is applied first. The optionally contained ammonium or metal salts can be added to the first or the second component. There may be an interval of up to 30 minutes between the application of the first and the second component. Pretreatment of the fibers with the saline solution is also possible.

The aldehydes of the formulas Ia and Ib and the compounds of component B can either be stored separately or together, either in a liquid to pasty preparation (aqueous or anhydrous) or as a dry powder. If the components are stored together in a liquid preparation, this should be largely anhydrous to reduce a reaction of the components. When stored separately, the reactive components are only intimately mixed with one another immediately before use. In dry storage, a defined amount of warm (50 to 80 ° C) water is usually added before use and a homogeneous mixture is produced.

Examples

Preparation of a coloring solution

A slurry of 10 mmol of an aldehyde with the formula Ia or Ib, 10 mmol of a reactant, 10 mmol of sodium acetate and a drop of a 20% fatty alkyl ether sulfate solution in 100 ml of water were prepared. The slurry was briefly heated to about 80 ° C and filtered after cooling, the pH was then adjusted to 6.

A strand of 90% gray, untreated human hair was placed in this dyeing solution at 30 ° C. for 30 minutes. The colored streak was then rinsed for 30 seconds with lukewarm water, dried in a warm (30-40 ° C.) air stream and then combed out. Then the colorations are assessed visually in daylight.

The respective color shades and color depths are shown in Table 1 below.

The color depth was rated on the following scale:

no or very pale color

(+) weak intensity

+ medium intensity

+ ( ⁺ ) medium to strong intensity ++ strong intensity

++ (+) strong to very strong intensity

+++ very strong intensity Table 1

Colorings with 2-chloro-1-formyl-3-hydroxymethylene-cyclohexene

Component B shade nuance

Color depth yellow ++

2,5-diaminotoluene x H ₂ SO ₄ dark blue +++

2,4,5,6-tetraaminopyrimidine x H ₂ SO ₄ orange ++

1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane x 4 HCl gray black

++ (+) 2-methylamino-3-amino-6-methoxypyridine x 2HCI dark brown

++ (+) 2- (2,5-diaminophenyl) ethanol x H ₂ SO ₄ violet blue

+++

2-aminomethyl-4-aminophenol x 2HCI violet red

++ (+)

4,4'-diaminodiphenylamine x H ₂ SO ₄ gray green

++ (+)

2,6-dimethoxy-3,5-diaminopyridine x 2HCI black

+++ N, N-bis- (2-hydroxyethyl) -p-phenylenediamine x H ₂ SO ₄ dark brown ++ (+)

T a b e l l e 2

Colorings with glutaconaldehyde tetrabutylammoium salt

Component B shade nuance

Depth of color rust red

++ (+) 2,5-diaminotoluene x H ₂ SO ₄ dark violet

+++ 2,4,5,6-tetraaminopyrimidine x H ₂ S0 ₄ golden yellow

++ (+) 1, 8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane x 4 HCl dark brown

++ (+) 2-methylamino-3-amino-6-methoxypyridine x 2HCI dark purple

+++ 2- (2,5-diaminophenyl) ethanol x H ₂ SO ₄ red

+++ 2-aminomethyl-4-aminophenol x 2HCI blue violet

+++

4,4'-diaminodiphenylamine x H ₂ SO ₄ black

+++

2,6-Dimethoxy-3,5-diaminopyridine x 2HCI black +++ Table 3

Colorings with Giutaconaldehyde sodium salt

Component B shade nuance

Color depth

- rust red ++

2,5-diaminotoluene x H ₂ SO ₄ dark red-brown

++ (+)

2,4,5,6-tetraaminopyrimidine x H ₂ SO ₄ orange-yellow ++

1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane X 4 HCl dark gray

++ (+)

2-methylamino-3-amino-6-methoxypyridine x 2HCI dark yellow brown

++ (+)

2- (2,5-diaminophenyl) ethanol x H ₂ SO ₄ violet red

++ (+)

2-aminomethyl-4-aminophenol x 2HCI red ++ (+)

N, N-bis- (2-hydroxyethyl) -p-phenylenediamine x HCl blue-black ++ (+)

4,4'-diaminodiphenylamine x H ₂ SO ₄ dark olive green +++

2,6-dimethoxy-3,5-diaminopyridine x 2HCI olive green ++

L-histidine light brown ++

L-Lysine copper ++

L-Proline orange brown ++ (+)

3-methyl-1-phenyl-2-pyrazolinone rust red ++ (+)

Thiobarbituric acid orange brown ++ (+)

Barbituric acid brown yellow ++ Oxindol rust red ++

1-ethylquinium dinium iodide rust red ++ (+)

Rhodanine red-brown ++ (+)

Claims

claims

1. Use of unsaturated aldehydes with the formulas Ia and Ib

(la) (Ib)

in the R ¹ , R ² , R ³ and R ⁴ independently of one another for hydrogen, halogen, a CrC ^ alkoxy, C _r C ₄ alkyl, aryl or C C alkoxy-C C ^ alkyl radical and n for the Numbers 1 or 2 stand, where R ¹ and R ² , R ¹ and R ³ , R ² and R ³ as well as R ² and R ⁴ together with the rest of the molecule can each form a 5- to 7-membered ring if n is 1 is, and the corresponding mono-, bis- or ω-alkoxyacetals for dyeing keratin-containing fibers, especially human hair.

2. Use according to claim 1, characterized in that the aldehydes of the formulas la or Ib are contained in an amount of 0.03 to 65, in particular 1 to 40 mmol, based on 100 g of the total colorant.

3. Use according to claim 1 or 2, characterized in that the aldehydes of the formulas la or Ib are selected from glutaconaldehyde, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3-hydroxymethylene-1-cycloheptene and 7-hydroxy-2,4,6-heptatrienal, its substituted derivatives and the salts thereof.

4. Use according to one of claims 1 to 3, characterized in that in addition at least one compound having a primary or secondary amino group or hydroxyl group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, from 2 to 9 amino acids Oli constructed - gopeptides and aromatic hydroxy compounds, and / or at least one CH-active compound is used.

5. Use according to one of claims 1 to 4, characterized in that oxidizing agents in an amount of 0.01 to 6 wt .-%, based on the application solution, are used.

6. Use according to claim 5, characterized in that H ₂ O _{2 is} used as the oxidizing agent.

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

8. Containing compositions for dyeing keratin fibers, in particular human hair

A at least one unsaturated aldehyde of the formula la or Ib

(la) (Ib)

in which R ¹ , R ² , R ³ and R ⁴ independently of one another are hydrogen, halogen, a C _r C ₄ alkoxy, C _r C ₄ alkyl, aryl or C ₁ -C ₄ alkoxy C ₁ - C ₄ alkyl radical and n represent the numbers 1 or 2, where R ¹ and R ² , R ¹ and R ³ , R ² and R ³ and R ² and R ⁴ each together with the rest of the molecule form a 5- to 7- can form a membered ring, if n is 1, and the corresponding mono-, bis- or ω-alkoxyacetals and B at least one compound with primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides and aromatic hydroxy compounds composed of 2 to 9 amino acids, and / or at least one CH-active compound.

9. Composition according to claim 8, characterized in that component B is selected from primary or secondary amines selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, N- (2-methoxyethyl), 2,3-, 2,4-, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, N, N-bis- (2-hydroxyethyl) -p-phenylene diamine, 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, -phenethol, 4-methylamino-3-amino-4- (2'-hydroxyethyloxy) -, 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4-methylamino, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6 -Methyl-3-amino-2-chloro, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl, 4-amino-2-aminomethylphenol, 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-hydroxy-benzoic 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-hydroxy-naphthalene-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, pentaaminobenzene pentahydrochloride, hexaami-nobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzene catechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5- Diamino-4-hydroxycatechol sulfate, aromatic anilines or phenols with a further aromatic radical such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, Na salt, 4, 4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4 , 4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diamino-benzophenone, -diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl-tetrahydrochloride, S ^' ^^ '- tetraamino-benzophenone, 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-propanol, 1,3-bis - [N- (4-Amino-phenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] - methylamine trihydrochloride, selected from nitrogen-containing heterocyclic compounds from the Group consisting of 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5 -amino-, 3-amino-2-methylamino-6-methoxy-, 2,3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2,4,5-triamino -, 2,6-Dihydroxy-3,4-dimethylpyridine, 4,5,6-triamino-, 2-hydroxy- 4,5,6-thamino-, 4-hydroxy-2,5,6-triamino-, 2nd , 4,5,6-tetraamino-, 2-methylamino- 4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methyl-pyrimidine, 2nd , 3,4-trimmethylpyrrole, 2,4-dimethyl-3-ethyl-pyrrole, 3,5-diaminopyrazole, -1, 2,4-triazole, 3-amino-, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquininaldine, 2-, 6-aminoonicotinic acid, 5-aminoisoquinoline , 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline as well as 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 in each case from the physiologically tolerable salts of these compounds, preferably formed with inorganic acids, aromatic hydroxy compounds selected from the group consisting of consisting of 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucin, 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, 3,6-dihydroxy-2,7-naphthalenesulfonic acid, and CH-active compounds out selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolinium iodide, 1, 2,3,5-tetramethylindolinium-p-toluenesulfonate, 1, 2,3,5-tetramethylindolinium methanesulfonate, 2,3 -Dimethyl-benzothiazolium-iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl (methyl) -2-quinal dinium iodide, barbituric acid, thiobar-bituric acid, 1, 3-dimethyl ( ethyl) thiobarbituric acid, oxindole, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

10. Composition according to claim 9, characterized in that the compound of component B is selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis - (2-hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-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-, 2-methylamino-4,5, 6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline as well as from each preferably physiologically tolerable salts of these compounds formed with inorganic acids.

11. Agent according to one of claims 8 to 10, characterized in that direct dyes from the group of nitrophenylenediamines, nitro-aminophenols, anthraquinones or indophenols are used.

12. Composition according to one of claims 8 to 11, characterized in that ammonium or metal salts selected from the group of formates, carbonates, halides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates, Propionates, phosphates and phosphonates of alkaline earth metals, such as potassium, sodium or lithium, alkaline earth metals, such as magnesium, calcium, strontium or barium, or of aluminum, manganese, iron, cobalt, copper or zinc, will be added.

13. A process for dyeing keratin-containing fibers, which contains a colorant

A at least one unsaturated aldehyde of the formula la or Ib

(la) (Ib)

in the R \ R ² , R ³ and R ⁴ independently of one another for hydrogen, halogen, a C _r C ₄ alkoxy, CC ₄ alkyl, aryl or C _r C ₄ alkoxy C _r C ₄ alkyl radical and n represents the numbers 1 or 2, where R ¹ and R ² , R ¹ and R ³ , R ² and R ³ and R ² and R ^{4 can} each form a 5- to 7-membered ring together with the rest of the molecule, if n is 1, and the corresponding mono-, bis- or ω-alkoxyacetals and B at least one compound with primary or secondary amino group or hydroxy group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, from 2 up to 9 amino acids built oligopeptides and aromatic hydroxy compounds, and / or at least one CH-active compound, as well as usual cosmetic ingredients applied to the keratin fibers, left on the fiber for some time, usually about 30 minutes, and then rinsed out again or washed out with a shampoo.