CZ374099A3 - Use of unsaturated aldehydes - Google Patents

Abstract

The use of unsaturated aldehydes of formulas Ia and 1b, where R is R 2, R 3 and R 4 are independently hydrogen, halogen, C 1-4 4alkoxy, C1-4alkyl or C1-4alkoxy-C1-4alkyl and n is 1 or 2, wherein R 1 and R 2, R 1 and R 3, R 2 and R 3 and R 2 and R 4 can each be taken together with the rest of the molecules to form 5 to A 7-membered ring, if n is equal to 1, and a corresponding mono-, bis- or n -alkoxyacetals for keratinic dyeing fibers, especially human hair.

Description

Technical field

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

BACKGROUND OF THE INVENTION

Generally, either direct-acting dyes or oxidative dyes which are formed by the oxidative reaction of one or more of the development components (Entwicklerkomponenten) with one another or with one or more binding components (Kupplerkomponenten) are generally used for dyeing keratin fibers, e.g. hair, wool or fur. Binding and development components are also referred to as oxidative dye intermediates.

Primary aromatic amines with other unsubstituted or substituted hydroxy or amino groups in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof are usually used as developing components.

Particular representatives of this group are, for example, p-phenylenediamine, ptoluylenediamine, 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-pyrazolone-5,4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4, 5,6 'triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2hydroxyethylaminomethyl-4-aminophenol, 4,4' -diaminodiphenylamine, 4 amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, bis- (2-hydroxy-5-aminophenyl) -methane, 1,4-bis- (4-aminophenyl) -diazacycloheptane, 1 , 3-bis (N (2-hydroxyethyl) N (4) ·

(2-aminophenylamino) -2-propanol, 4-amino-2- (2-hydroxyethoxy) phenol, and

4,5-diaminopyrazole derivatives according to EP 0 740 741, respectively. WO 94/08970, such as 4,5-diamino-1- (2'-hydroxyethyl) pyrazole.

The binding components used are generally phenylenediamine derivatives, naphthols, resorcin and resorcin derivatives, pyrazolones and maminophenols. Particularly suitable binding components are 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 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-3aminophenol, 2-methylresorcinol, 5-methylresorcin, 2,5-dimethylresorcin,

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-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, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol, 2-methyl-5- (2-hydroxyethylamino) -phenol and 2,6- dihydroxy-3,4-dimethylpyridine.

Although oxidative dyes can achieve intensive coloring with good stability, color development is due, among other things, to oxidative agents such as H2O2, which can in some cases result in fiber damage. In addition, some oxidative dye intermediates or certain mixtures of oxidative dye intermediates may sometimes have a sensitizing effect on persons with sensitive skin. Direct acting dyes are used under gentle conditions, but have the disadvantage that dyes often have insufficient fastness.

DE 28 30 497 discloses hair dyes containing salicylaldehyde in combination with oxidative dye intermediates such as 2,5-diaminotoluene, 4-aminophenol or 2,4-diaminotoluenol, which may (in combination with in addition to the hydrogen peroxide present) have less or more intense sensitizing potential. German published application DE 29 32 489 discloses hair dyes also containing H2O2 comprising benzaldehydes such as 2-hydroxy-3-methoxybenzaldehyde or 4-hydroxy-3-methoxybenzaldehyde in combination with oxidative dye intermediates. US 5,034,014 and US 5,199,954 disclose examples of hair dye formulations containing p-dimethylaminobenzaldehyde or p-dimethylaminoaldehyde cinnamic acid, for example in combination with p-phenylenediamine, which also has sensitizing effects.

U.S. Pat. No. 4,391,603 discloses oxidant-free hair dyes based on substituted benzaldehydes. The hair dyes disclosed in this patent are direct acting hair dyes with which the color shades, color depth and color fastness of hair dyes containing the oxidative hair dye intermediates cannot be achieved.

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

It is an object of the present invention to provide dyes for keratin fibers, in particular human hair, which are at least qualitatively equal to conventional oxidative hair dyes in terms of color depth, gray overlap and stability without the need for oxidizing agents such as H ₂ O ₂ . In addition, these dyes must have no sensitizing potential or can have only a very small potential.

«· · · · · · · · · · · · · · · · · · · · · · ·

-4 Summary of the Invention

It is an object of the invention to use unsaturated aldehydes of tautomeric formulas Ia and Ib, respectively

wherein R ^1, R ^2, R ³ and R ⁴ are independently hydrogen, halogen, _Ci-4 an alkoxy, _Ci-4 -alkyl, aryl or _{Ci-4-alkoxy-Ci-C4} alkyl radical n represents 1 or 2, wherein R ¹ and R ² , R ¹ and R ³ , R ² and R ³ and R ² and R ⁴ may each form, together with the rest of the molecule, a 5- to 7-membered ring when n is equal to 1, and the corresponding mono bis- or ωalkoxyacetals for coloring keratin fibers, especially human hair.

Surprisingly, it has been found that the aldehydes of formulas Ia and 1b, respectively, are very suitable even in the absence of oxidizing agents for dyeing keratin fibers. They provide color with excellent brilliance and high-quality colors and lead to a large number of color tones. In principle, however, the use of oxidizing agents should not be excluded.

Keratin fibers are wool, fur, feathers and especially human hair. However, the dyes according to the invention can in principle 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 acetyicellulose and synthetic fibers. fibers such as polyamide, polyacrylonitrile, polyurethane and polyester fibers.

The unsaturated aldehydes of the formulas Ia and Ia are preferably selected from glutaconaldehyde, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3-hydroxymethylene-1-cycloheptene and 7-hydroxy-2,4,6-heptatrienal and substituted derivatives thereof and physiologically acceptable salts, especially alkali metal and ammonium salts, with tetrabutylammonium and sodium salts and mixtures thereof being particularly preferred.

Compounds of formulas Ia and Ib, respectively, are known from the literature or are commercially available.

The aldehydes of the formulas Ia and Ib, respectively, are preferably present in the dyes in an amount of 0.03 to 65, in particular 1 to 40 mmol, in each case per 100 g of total dye. A single compound of the formula Ia or Ib, respectively, or a mixture of several compounds may be used. They can be used as direct acting dyes, or in the presence of compounds which enhance the dyeing effect of the aldehydes used according to the invention, as intermediates of oxidative dyes.

Dyes which contain, as coloring component, the aldehydes of the formulas Ia and Ib, respectively, are preferably used for coloring in the yellow and red areas. Coloring with increased brilliance and further improved stability, especially in the areas of yellow, orange, brown and black, as well as in the areas of red and blue, are obtained when aldehydes of formulas Ia and Ib, respectively, are used together with compounds having a primary or secondary amine group. for example aniline derivatives, with nitrogen-containing heterocyclic compounds, for example primary heteroaromatic amines, aromatic hydroxy compounds or CH-active compounds. These are, on the one hand, compounds which, in themselves, stain the keratin fibers only weakly and only in conjunction with the aldehydes of the formulas Ia and Ib, respectively, give a brilliant coloration. On the other hand, however, compounds are also used which are themselves intermediates of oxidative dyes.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

6 ··· * ·· · ···· _ ·· ·· ·· ··· · · ··

Another object of the present invention is a composition for dyeing keratinic fibers, particularly human hair, comprising A at least one unsaturated aldehyde of formula Ia and 1b, respectively, and

B at least one compound having a primary or secondary amino or hydroxy group selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides composed of two to nine amino acids and aromatic hydroxy compounds and / or at least one CH-active compound.

The abovementioned compounds of component B can always be used in an amount of 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of total dye.

A plurality of different aldehydes of formulas Ia and 1b, respectively, can also be used together in all dyes; likewise, a plurality of different compounds of component B may also be used together. These embodiments also include the use of compounds which are the reaction products of the unsaturated aldehydes of formula I with said compounds B.

Suitable compounds with a primary or secondary amine group are, for example, primary aromatic amines such as Ν, Ν-dimethyl-, Ν, Ν-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-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2- , 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol o-, m-, p-phenylenediamine, o-, m-toluylenediamine, 2,5-diaminotoluene, -phenol, -phenethol, 4- amino-3-methylphenol, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 4-methylamino-, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-methylenediamino-,

3,4-methylenedioxyaniline, 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

- 7 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, acid

4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-,

1,2.4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcin, 4,5-diaminopyrocatechin, 4,6-diamino-pyrogallol, 3,5- diamino-4-hydroxypyrocatechin, aromatic anilines or phenols with another aromatic residue, such as compounds of formula II

wherein R ⁵ represents a hydroxyl or amino group which may be substituted by C 1-4 -alkyl, C 1-7 -alkyl. ₄ -hydroxyalkyl, Cf. ₄ -alkoxy or C. _4- Alkoxy-C- | _4- alkyl,

R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent a hydrogen atom, a hydroxyl or an amino group which may be substituted by C 1-6 groups. _4- alkyl; ₄ -hydroxyalkyl, C1-6alkyl. _4- alkoxy, Ct. _4- aminoalkyl or C 1-6 alkyl; _4- alkoxy-C _1-4 alkyl, or is a sulfonic acid group, and

X represents a direct bond, a saturated or unsaturated carbon chain of 1 to 4 carbon atoms, optionally substituted by hydroxyl

9 9 9 9 9 9 9 9 9 9 9

9 9 9 9 9 9 9 9 9

- 8 9 9 9 9 9 9 9 9 9 9 9 9

9 9 9 9 9 9 9 9 9

99 99 999 99 99 groups, a carbonyl, sulfonyl or imine group, an oxygen or sulfur atom or a group of formula IIIa

Z- (CH ₂ -Q-CH ₂ -Z ') ₀ (III) wherein Q represents a direct bond, CH ₂ or CHOH,

Z and Z 'are independently O, NR ^11, wherein R ¹¹ is hydrogen, C |. _{A 4-} alkyl or hydroxyC 1-4 alkyl group, an O- (CH ₂ ) p -NH or NH- (CH ₂ ) _p '-O group, where p and c are 2 or 3, and o represents a number from 1 to 4, such as for example 4,4'-diaminostilbene, mono- or disodium salt of 4,4'-diaminostilbene-2,2'-disulfonic acid, 4,4'-diaminodiphenylmethane, -sulfide, -sulfoxide, -amine, 4,4'- diaminodiphenylamine-2sulfonic acid, 4,4'-diaminobenzophenone, diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraaminobenzophenone, 1,3-bis- (2,4-diaminophenoxy) propane, 1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane,

1,3-bis- (4-aminophenylamino) -propane, -2-propanol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) -ethyl] -methylamine, N-phenyl-1,4-phenylenediamine.

Said compounds may be used both in free form and in the form of their physiologically acceptable salts, in particular as salts with organic 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-, 2, 6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino-, 4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2- 9-

• · ···· ·· • · • • · ·· • • · • · ♦ • • « • • • · Φ • • · • · • • • • • • · • • • · · · • · · • · ··

hydroxy-4,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4 -methoxy-6-methyl-pyrimidine,

3,5-diaminopyrazole, -1,2,4-triazole, 3-amino-, 3-amino-5hydroxypyrazole, 2,3-, 8-aminoquinoline, 4-aminoquininaldin, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5 -, 6-aminoindazole, 5-, 7-aminobenzimidazole, -benzthiazole, 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 above compounds can be used both in free form and in the form of their physiologically acceptable salts, for example as salts of inorganic acids such as hydrochloric or sulfuric acid.

Suitable amino acids are all naturally occurring and synthetic amino acids, for example available by hydrolysis from plant or animal proteins, such as collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Both acidic and alkaline-reacting amino acids can be used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine, and tryptophan.

Oligopeptides can be naturally occurring or synthetic oligopeptides, but also oligopeptides contained in hydrolysates of polypeptides or proteins, as long as they have sufficient water solubility for use in the dyes of the invention. Examples include glutathione or oligopeptides contained in hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. It is preferred to use them together with compounds having a primary or secondary amine group or with aromatic hydroxyl compounds.

Suitable aromatic hydroxy compounds are, for example, 2-, 4-, 5-methylresorcin, 2,5-dimethylresorcin, resorcin, 3-methoxyphenol, pyrocatechin, hydroquinone, pyrogallol, floroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino- , 2- (2-hydroxyethyl) -, 3,4 • 9 · 9 ·

- 10 99 99

9 9 4

9 9 4 9 9 4

9 9 ·

9 99 methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -acetophenone, 2-, 4-chlororesorcin, 1-naphthol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

CH-active compounds include, for example, 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-dimethylbenzothiazolium iodide , 2,3-dimethylbenzothiazolium-p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl-2-quinaldinium iodide, 1-methyl-2-quinaldinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, diethylthiobarbituric acid, 3-indolyl acetate, coumarone and 1-methyl-3-phenyl-2-pyrazolinone.

Compounds of component B are particularly preferably selected from N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, - (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-triaminopyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6dihydroxyindoline and their physiologically acceptable salts with preferably with inorganic acids.

Preferably, it is preferable not to use oxidizing agents, for example H ₂ O ₂ . However, it may be necessary to add 99 to the resources of ·· · ··

9 98 9 9 0 9

9 9 9 9 9

9 9 0 9 9 9 9

9 9 9 9 9 9 Hydrogen peroxide or other oxidizing agents to achieve shades that are lighter than dyed keratin fibers. The oxidizing agents are generally used in an amount of from 0.01 to 6% by weight, based on the ready-to-use solution. The preferred oxidant for human hair is H2O2.

The dyes of the invention provide a wide variety of shades ranging from yellow-orange to black-brown; the color fastness is excellent and the sensitization potential is very low.

In a preferred embodiment, the dyes according to the invention contain, in addition to the compounds according to the invention and, if appropriate, other oxidation dye intermediates, customary direct-acting dyes, for example from the group of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct-acting dyes are compounds known under international designation or trade names, for example HC Yellow 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, and 4-amino-2-nitrodiphenylamine 2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline and hydroxyethyl-2-nitrotoluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro -6-ethylamino-1-hydroxynitrobenzene. The compositions according to the invention according to these embodiments contain direct-acting dyes, preferably in an amount of from 0.01 to 20% by weight, based on the hair coloring agent as a whole.

Furthermore, the compositions according to the invention may also contain naturally occurring dyes such as red henna, henna neutral, black henna, chamomile flowers, sandalwood, black tea, mulberry

99 99

9999

9

9 9 9 9 9 • 9 9 · ·

999 99 99

- 12 · »9 9 9 12 12 12 12 12 12 12 12 12 12 12 12

Bark, sage, blue wood, stained, catechu, saddle and alkane powder.

Other coloring ingredients included in the dyes of the invention may also be indoles and indolines and their physiologically acceptable 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. Further preferred are 5,6-dihydroxyindoline, Nmethyl-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 to be used in the hair coloring and tinting compositions of the invention, further reference is made to the monograph Ch. Animal, The Science of Hair Care, Chapter 7 (pp. 248-250; direct-acting dyes) and Chapter 8, pp. 264-267; oxidative dye intermediates), issued as part 7 of the Dermatology series (ed. Ch., Culnan and H. Maibach), Verlag Marcel Dekker Inc, New York, Basel, 1986 and the European Inventory der Kosmetik-Rohstoffe ', published by the European Community, obtainable in the form of diskettes from the Bundesverband Deutscher Industrie- und Handelsunternehmen für Arzneimittel, Reformwaren und Kórperpflegemittel at its own expense, Mannheim.

It is not necessary that the precursors of the oxidative dyes or the direct-acting dyes, if any, are always uniform compounds. The hair coloring compositions of the present invention may more often contain other ingredients in smaller amounts, as long as these ingredients do not adversely affect coloration or may not be excluded for other reasons, for example toxicological.

The dyes of the present invention provide intense coloration even at physiologically acceptable temperatures below 45 ° C. They are therefore particularly suitable for coloring human hair. For use on human hair may be

dyes are usually added to a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions such as shampoos or other preparations suitable for use on keratin fibers. If necessary, it is also possible to add colorants to the anhydrous carriers.

In addition, the coloring compositions of the present invention may contain all of the customary active, adjuvant and auxiliary substances in these formulations. In many cases, the coloring agents comprise at least a surfactant, and in principle, both anionic and zwitterionic, amphiphytic, nonionic and cationic surfactants may be suitable. In many cases, however, it has proven advantageous to select surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in the compositions of the invention are all anionic surfactants suitable for use on the human body. These are characterized by a hydrophilic anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group of about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be included in the molecule. Examples of such suitable anionic surfactants are, for example, in the form of sodium, potassium, ammonium as well as mono-, di- and trialkanolammonium salts of 2 or 3 carbon atoms in the alkanol group, as follows:

straight chain fatty acids of 10 to 22 carbon atoms (soaps), ether carboxylic acids of the formula RO- (CH 2 -CH 2 O) _X -CH 2 -COOH, wherein R represents a straight alkyl group of 10 to 22 carbon atoms and x = 0 or 1-16 , C10-C18 acyl sarcosides in the acyl group,

Acyl taurides having from 10 to 18 carbon atoms in the acyl group, acyl isethionates having from 10 to 18 carbon atoms in the acyl group, mono- and dialkyl esters of sulfosuccinic acid having 8 to 18 atoms carbon in the alkyl group and monoalkyl polyoxyethyl esters of sulfosuccinic acid of 8 to 18 carbon atoms in the alkyl group of 1 to 6 ethoxy groups, straight chain alkanesulfonates of 12 to 18 carbon atoms, alpha-olefin sulfonates of 12 to 18 carbon atoms, methyl esters alpha - fatty acids of C 12 -C 18 fatty acids, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ CH ₂ O) _x -OSO ₃ H, where R is preferably a straight C 10 -C 18 alkyl group and x is 0 or 1 to 1 12, mixtures of surfactant hydroxysulfonates according to DE-A37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylenopropylene glycol ethers according to DE-A-37 23 354, unsaturated sulfonates h fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344, esters of tartaric and citric acids with alcohols which are the condensation products of approximately 2 to 15 molecules of ethylene oxide and / or propylene oxide into fatty alcohols with 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 group and up to 12 glycol ether groups per molecule, and in particular salts of saturated and particularly unsaturated C 8 to C ₂₂ carboxylic acids such as oleic, stearic, isostearic and palmitic acid.

• ·

Zwitterionic surfactants are those surfactants which have at least one quaternary ammonium group and at least one -COO ^W or -SC4 group in the molecule. Particularly preferred zwitterionic surfactants are the so-called betaines, such as coconut alkyl N-N, N-dimethylammonium glycinate, coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, coconut acyl-carboxyethyl-3-methyl-3-methyl-3-carboxyethyl, in each case having 8 to 18 carbon atoms in the alkyl or acyl group, such as coconut acylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known as CTFA Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition -i8-C ₈ one alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO3H and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, Nalkylpropionic acids, N-alkylaminobutyric acids, Nalkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, Nalkyltaurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic atoms, in each case having approximately 8 to 18 carbon atoms alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylaminopropionate and C12-18 acyl sarcosine.

Nonionic surfactants include, for example, a polyol group, a polyalkylene glycol ether group, or a combination of a polyol ether and a polyglycol ether group as a hydrophilic group. These compounds are, for example:

condensation products 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with straight-chain fatty alcohols with 8 • φ φ φ φ φ

- 16 to 22 carbon atoms, C 12 -C 22 fatty acids and C 8 -C 15 alkylphenols in the alkyl group,

C12-22 mono- and diesters of fatty acids of the condensation products from 1 to 30 moles of ethylene oxide with glycerol,

C8-22-alkyl mono- and -oligoglycosides and their ethoxylated analogs, 5 to 60 moles of ethylene oxide condensation product with castor oil and hardened castor oil, condensation products of ethylene glycol and sorbitol fatty acid ester, condensation products of ethylene oxide and alkanolamides of fatty acids.

Examples of cationic surfactants useful in the hair care compositions of the present invention are compounds. Preferred are alkyltrimethylammonium chlorides, and trialkylmethylammonium chlorides, particularly quaternary ammonium ammonium halides such as dialkyldimethylammonium chlorides, e.g. Other cationic surfactants useful herein are quaternized protein hydrolysates.

Particularly suitable according to the invention are cationic silicone oils such as commercial products Q2-7224 (manufacturer: Dow Corning; stabilized trimethylsilylamodimethicone), Dow Corning 929 Emulsion (containing hydroxylamino modified silicone, also referred to as amodimethicone), SM-2059 (manufacturer: General Electric) , SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, Quaternium-80).

Alkylamidoamines, in particular fatty acid amidoamines such as the Tego Amid® S 18 obtainable stearylamido • · · ·········· · · · · · · · · · · · · · ·

F-f · · f f f

In addition to a good conditioning effect, propyldimethylamine has a particularly good biodegradability.

Equally well biodegradable are the quaternary ester compounds, the so-called "Esterquats" compounds, such as the dialkylammonium methosulfates and methylhydroxyalkyldialkoyloxyalkylammonium methosulfates supplied under the trade mark Stepantex®.

An example of a quaternary sugar derivative useful as a cationic surfactant is the product Glucquat®100, referred to in the CTFA nomenclature as "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds used as surfactants with alkyl groups can always be uniform substances. However, as a rule, it is preferable to start from these natural vegetable or animal raw materials in the manufacture of these substances, so that mixtures of substances with different alkyl chain lengths depending on the raw material used are obtained.

For surfactants which are the condensation products of ethylene and / or propylene oxide with fatty alcohols or derivatives of these condensation products, products with a "normal" homolog distribution and products with a narrow homolog distribution can be used. The "normal" homolog distribution is a mixture of homologues obtained by the reaction of a fatty alcohol and an alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. In contrast, a reduced homolog distribution is obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, and alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. It may be advantageous to use products with a restricted homologous distribution.

Other active, auxiliary and auxiliary substances are, for example

4 • 4 nonionic polymers, for example vinylpyrrolidone / vinyl acrylate polymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes containing quaternary groups dimethyldialylamoniumchloridové polymers akrylamiddimethyldialylamoniumchloridové copolymers dimethylaminoethylmethakrylátvinylpyrrolidonové copolymers quaternized with diethyl sulfate vinylpyrrolidonimidazoliniummethochloridové copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropylmethacrylate copolymers, anionic polymers, such as polymers, polyacrylic acids, polyacrylic acids, cross-linked polyacrylic acids butylmale acrylate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, thickening agents such as agar, guar gum, alginate, xanthan gum, gum arabic, karaya gum, saint gum seeds, dextrans, cellulose derivatives such as methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, fractions and starch derivatives such as amylose, amylopectin and dextrin, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, structurants such as glucose and maleic acid,

- 19 compounds with hair conditioning properties such as phospholipids, for example, soy lecithin, egg lecithin and cephalin and silicone oils, protein hydrolysates, in particular hydrolysates of elastin, collagen, keratin, milk protein, soy protein and wheat protein, their fatty acid condensation products, and quaternized protein hydrolysates, perfuming oils, dimethylisosorbide and cyclodextrin, solubilizers such as ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, anti-dandruff agents such as those known under the names Piroctone Olamine and Zink Omadine, other pH adjusters, active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins, cholesterol, light-protective agent, consistency adjuster such as sugar esters, polysters yols or polyolyl ethers, fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides, complexing agents such as EDTA, NTA and phosphonic acids, swelling and penetrating agents such as glycerol, propylene glycolmono , carbonates, bicarbonates, guanidine, urea and primary, secondary and tertiary phosphates, opacifiers such as latex,

4,444 · · · «

944 94 9 499 · • 4444 444 94 4 on ···· · · · ·. . «

- - ♦ · · »··· ·· ·· ·· pearlizers composition as ethylenglykolmono- and distearate, propellants such as propane-butane mixtures, N ₂ O, dimethyl ether,

CO ₂ and air and antioxidants.

The water-containing carrier components are used to produce the dyes of the invention in conventional amounts for this purpose; emulsifying agents are used, for example, in concentrations of from 0.5 to 30% by weight and thickening agents in concentrations of 0.1 to 25% by weight of the dye as a whole.

For the dyeing result, it may be advantageous to add ammonium salts or metal salts to the dyes. Suitable metal salts are, for example, formates, carbonates, halides, sulphates, butyrates, valerates, caproates, acetates, lactates, glycolates, tartrates, citrates, gluconates, propionates, phosphates and phosphonates of alkali metals such as potassium, sodium or lithium; , calcium, strontium or barium or aluminum, manganese, iron, cobalt, copper or zinc salts, sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, ammonium chloride and ammonium acetate. These salts are present in an amount of 0.03 to 65, in particular 1 to 40 mmol, based on 100 g of total dye.

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

For dyeing keratin fibers, in particular for dyeing human hair, hair dyes are generally applied in the form of an aqueous cosmetic carrier in an amount of 100 g, allowed to act for about 30 minutes and then rinsed or washed with a conventional hair shampoo.

The aldehydes of the formulas Ia and Ib, respectively, and the compounds of component B may be applied to the hair either simultaneously or also sequentially, whereby

- 21 • 9 • 9

9 4 4 4 9 It does not matter which of the two components is applied first. The ammonium or metal salts which may be present can be added to the first or second component. Up to 30 minutes may elapse between the application of the first and second components. Pretreatment of the fibers with salt solutions is also possible.

The aldehydes of formulas I and Ib, respectively, and the compounds of component B may be stored either separately or together, either in a liquid or pasty formulation (aqueous or non-aqueous) or as a dry powder. If the components are stored together in a liquid composition, it should be as anhydrous as possible to prevent the components from reacting. In separate storage, the reactive components are first thoroughly mixed with each other immediately prior to use. For dry storage, a usually defined amount of hot (50-80 ° C) water is added prior to use and a homogeneous mixture is prepared.

DETAILED DESCRIPTION OF THE INVENTION

Preparation of staining solution

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

In this dyeing solution, a 30% human hair strand grayed out at 30 ° C for 30 min without prior treatment was loaded. The stained strand was then rinsed with lukewarm water for 30 min, dried in a flow of excitation (30-40 ° C) and then combed. The stains were then assessed visually in daylight.

The respective color tones and color saturation are listed in Table 1 below.

· · 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4

ΛΛ · «· · ·

- ££ - ·· ··· ··· ·· ··

The color saturation was evaluated according to the following scale:

: no or very pale coloring (+): weak intensity +: medium intensity + (+): medium to strong intensity ++: strong intensity ++ (+): strong to very strong intensity +++: very strong intensity

Table 1

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

Component B Color tone saturation 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-diamino-phenoxy) -3,6-dioxaoctane x 4 HCl black / black ++ (+)

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

- 23 Table 1 - continued

Folder B

2- (2,5-diaminophenyl) -ethanol x H2SO4

2-Aminomethyl-4-aminophenol x 2HCl

4,4'-diaminodiphenylamine x H ₂ SO ₄

2,6-dimethoxy-3,5-diaminopyridine x 2HCl

Color tone saturation violet blue +++ violet red ++ (+) gray-green ++ (+) black +++

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

- 24 · »* * *

Table 2

Staining with -tetrabutylammonium salt of glutaconaldehyde

Folder B

2,5-diaminotoluene x H ₂ SO ₄

Color tone rust reddish ++ (+) dark purple +++

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

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

2-Aminomethyl-4-aminophenol x 2HCl blue violet +++

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

2,6-dimethoxy-3,5-diaminopyridine x 2HCI black +++ • 9,999 ·

99

- 25 Table 3

Staining with glutaconaldehyde sodium

Folder B

Color tone rust red color ++

2,5-diaminotoluol x H2SO4

2,4,5,6-tetraaminopyrimidine x H ₂ SO ₄ dark reddish ++ (+) orange yellow ++

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

2-methylamino-3-amino-6-methoxypyridine x 2HCl

2- (2,5-diaminophenyl) -ethanol x H2SO4 dark yellow brown ++ (+) violet red ₊₊ ( ₊ )

2-Aminomethyl-4-aminophenol x 2HCl

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

4,4'-diaminodiphenylamine x H2SO4 red ++ (+) blue-black ++ (+) dark olive green +++ ·· 9 99 9

9 9

9 9

9 9 9

9 9 9 • 9 9

9 9 9

9 ·

9 9

- 26 Table 3 - continued

Folder B

2,6-dimethoxy-3,5-diaminopyridine x 2HCl

L-histidine

L-lysine

L-proline

3-Methyl-1-phenyl-2-pyrazolinone

Thiobarbituric acid

Barbituric acid

Oxindol

1-ethylchinaldinium iodide

Rhodanin

Color tone saturation olive green ++ light brown + + copper ++ orange brown ++ (+) rust red ++ (+) orange brown ++ (+) green-yellow ++ rust red ++ rust red ++ (+) reddish ++ (+)

Represented by:

Claims (13)

Use of unsaturated aldehydes of the formulas Ia and Ib, respectively, wherein R ¹ , R ² , R ³ and R ⁴ are independently hydrogen, halogen, C 1 -C ₄ -alkoxy, C 1 -C ₄ -alkyl, aryl or C 1 -C ₄ -alkoxyC- i-C4 alkyl radical n represents 1 or 2, wherein R ¹ and R ^2, R ³ and R ^1, R ² and R ^3, and R ² and R ⁴ each may form together with the rest of the molecule 5- to 7-membered ring if n is equal to 1, and the corresponding mono-, bis- or ω-alkoxyacetals for dyeing keratin fibers, especially human hair. Use according to claim 1, characterized in that the aldehydes of the formulas Ia and Ib, respectively, are present in an amount of 0.03 to 65, in particular 1 to 40 mmol, in each case, based on 100 g of total dye. Use according to claim 1 or 2, characterized in that the aldehydes of formulas Ia and Ib respectively are selected from glutaconaldehyde, 1-formyl-3-hydroxymethylene-1-cyclohexene, 1-formyl-3-hydroxymethylene-1-cycloheptene and · ···· ·· 9 9 9 9 9 9 9 9 9 9 9 9 99 99 9 · 99 99 9 9 9 9 9 9 28 hydroxy-2,4,6-heptatrienal and substituted derivatives and salts thereof. Use according to any one of claims 1 to 3, characterized in that at least one compound with a primary or secondary amino or hydroxy group selected from primary or secondary aliphatic or aromatic amines, nitrogen heterocyclic compounds, amino acids, oligopeptides composed of two to two is used. nine amino acids and aromatic hydroxyl compounds and / or at least one CH-active compound. Use according to any one of claims 1 to 4, characterized in that the oxidizing agents are used in an amount of 0.01 to 6% by weight, based on the solution to be used. Use according to claim 5, characterized in that H2O2 is used as the oxidizing agent. Use according to one of Claims 1 to 6, characterized in that anionic, zwitterionic and / or nonionic surfactants are used. 8. A composition for coloring keratinic fibers, in particular human hair, comprising And at least one unsaturated aldehyde of formula Ia and 1b, respectively, wherein R ¹ , R ² , R ³ and R ⁴ are independently hydrogen, halogen, C ₁ -C ₄ -alkoxy, C 1 -C 4 -alkyl, aryl or C 1 -C ₄ -alkyl; _C4 -alkoxyCi.C ₄ -alkyl radical and n is 1 or 2, wherein R ¹ and R ^2, R ³ and R ^1, R ² and R ^3, and R ² and R ⁴ each may form together with the rest of the molecule to 5- A 7-membered ring when n is equal to 1, and the corresponding mono-, bis- or ω-alkoxyacetals, and B at least one compound having a primary or secondary amino or hydroxyl group selected from primary or secondary aliphatic or aromatic amines, nitrogen heterocyclic compounds, amino acids, oligopeptides composed of two to nine amino acids and aromatic hydroxyl compounds and / or at least one CH-active compound. A composition according to claim 8, wherein component B is selected from 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, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene, -phenol, -phenetol, 4-methylamino-, 3 · 9 · · »· - 30 9 4 9 • 9 9 • 4 9 4 9 4 4 hexaaminobenzene pentahydrochloride, 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-aminomethyl-phenol, 4-amino-2-hydroxymethyl-phenol, 1,3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, -phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 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-hydroxy-naphthalene-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, 2,4,6-triaminoresorcin trihydrochloride hexahydrochloride, 4,5-diaminopyrocatechin sulfate, 4,6-diaminostrogene dihydrochloride, 3,5-diamino-4-hydroxypyrocatechin sulfate, aromatic anilines or phenols with one other aromatic residue such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2 'sodium salt disulfonic, 4,4'-diaminodiphenylmethane, -sulfide, -sulfoxide, amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, tetrahydrochloride 3,3 ', 4,4'3, 3 ', 4,4'-tetraaminobenzophenone, 1,3-bis- (2,4-diaminophenoxy) propane, 1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane tetrahydrochloride, 1,3-bis- (4-aminophenylamino) -propane, -2-propanol, 1,3-bis- [N- (4-tetraaminodiphenyl, tetrahydrochloride) aminophenyl) -2-hydroxyethylamino] -2 -propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] -methylamine trihydrochloride, from nitrogenous heterocyclic compounds selected from the group 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-triamino-, 4-hydroxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6- triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methyl-pyrimidine, 2,3,4-trimethylpyrrole, 2,4-dimethyl-3-ethylpyrrole, 3,5-diaminopyrazole , -1,2,4-triazole, 3-amino-, 3-amino-5hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquinoline, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-aminobenzimidazole, -benzthiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives such as 4-, 5-, 6-, 7-aminoindole, 4-, 5-, 6-, 7- hydroxyindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, and physiologically acceptable salts of these compounds, preferably with inorganic acids, aromatic hydroxys compounds selected from 2-, 4-, 5-methylresorcin, 2,5-dimethyiresorcin, resorcin, 3-methoxyphenol, pyrocatechin, hydroquinone, pyrogallol, floroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 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-naphthalenesulfone and φ Φ Φ w w w φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ Φ 9 9 9 9 • Φ Φ ΦΦ ΦΦ CH-active compounds selected from 1,2,3,3-tetramethyl-3H-indolinium iodide, 1,2,3,5-tetramethylindolinium p-toluenesulfonate, 1,2,3,5-tetramethylindolinium methanesulfonate, 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, rhodanine, rhodanin-3-acetic acid, 1-ethyl (methyl) -2-quinaldinium iodide, barbituric acid, thiobarbituric acid, 1,3dimethyl (ethyl) thiobarbituric acid, oxindole, and 1-methyl-3-phenyl-2-pyrazolinone. The composition of claim 9, wherein the compound of component B is selected from the group N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, Nbis (2-hydroxyethyl) -p-phenylenediamine, 4-aminophenol, 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-triaminopyrimidine, 3 5-diaminopyrazole, 3 amino-5-hydroxypyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline and physiologically acceptable salts of these compounds, preferably with inorganic acids. Composition according to one of Claims 8 to 10, characterized in that the direct-acting dyes • 4444 • 4 33 are selected from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols. • 4 4 4 • 4 4 4 44 Composition according to one of Claims 8 to 11, characterized in that the ammonium or metal salts are selected from the group of formates, carbonates, halides, sulphates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, citrates, gluconates , propionates, phosphates and phosphonates, alkali metals such as potassium, sodium or lithium, alkaline earth metal salts such as magnesium, calcium, strontium or barium or aluminum, manganese, iron, cobalt, copper or zinc. 13. A method for dyeing keratin fibers comprising applying a dye containing keratin fibers And at least one unsaturated aldehyde of formula Ia or Ib, respectively H R2 R4 <1a) R2 R4 OH (Ib) wherein R ^1, R ^2, R ³ and R ⁴ are independently hydrogen, halogen, Ci-C4-alkoxy, _Ci-4 -alkyl, aryl or _Ci-4 -alkoxyCi.C ₄ -alkyl radical and n is 1 or 2, where R ¹ and R ² , R ¹ and φφ · «·» - 34 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · R ³ , R ² and R ³ and R ² and R ⁴ may in each case form, together with the remainder of the molecule, a 5- to 7-membered ring when n is equal to 1 and the corresponding mono-, bis- or ω-alkoxyacetals, and B at least one compound with a primary or secondary amino or hydroxyl group selected from primary or secondary aliphatic or aromatic amines, nitrogen heterocyclic compounds, amino acids, oligopeptides composed of two to nine amino acids and aromatic hydroxyl compounds and / or at least one CH-active compound and a common of the cosmetic ingredient, leave for some time, usually about 30 minutes on the fibers, and then rinse or wash with shampoo.