WO2000015183A1

WO2000015183A1 - Agents for dyeing fibres containing keratin

Info

Publication number: WO2000015183A1
Application number: PCT/EP1999/006525
Authority: WO
Inventors: Hinrich Möller; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1998-09-15
Filing date: 1999-09-04
Publication date: 2000-03-23
Also published as: AU5745499A; DE19842070A1; EP1112055A1; JP2002524483A

Abstract

The invention relates to agents for dyeing fibres containing keratin, especially human hair, containing 5-arylpenta-2,4-dienylcarbonyl compounds of formula (I) wherein R1 represents a hydrogen atom or a C¿1?-C4-alkyl group and R?2 and R3¿ can be the same or different and represent a hydrogen atom, a halogen atom, a C¿1?-C4-alkyl group, a C1-C4-alkoxy group, a hydroxy-C1-C4-alkoxy group, a hydroxy group, a nitro group or an amino group which can be substituted by C1-C4-alkyl group or can be part of a heterocycle, or a C1-C4-acyl group, and wherein two of the radicals can also form a fused benzol ring together; or physiologically compatible salts thereof.

Description

"Means for dyeing fibers containing keratin"

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains 5-arylpenta-2,4-dienylcarbonyl compounds, the use of 5-arylpenta-2,4-dienylcarbonyl compounds as a coloring component in hair dye compositions and a process for dyeing fibers containing keratin, especially 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 derivatives thereof are usually used as developer components.

Special representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2.5 Diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol dehvates, pyrazolones and m-aminophenols are generally used as coupler components. Suitable coupler substances are, in particular, α-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomino methyl ether, m-phenylenediamine, 2,4 -diaminophenoxyethanol, 1-phenyl-3- methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3- aminophenol, 2-methylresorcinol and 5-methylresorcinol.

With regard to other conventional dye components, reference is expressly made to the "Dermatology" series, edited by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, Cape. 7, pages 248 - 250 (direct dyes), and chap. 8, pages 264 - 267 (oxidation dyes), as well as the "European Inventory of Cosmetic Raw Materials", 1996, published by the European Commission, available in disk form from the Federal Association of German Industrial and Commercial Enterprises for Medicines, Health Care Products and Personal Care Products, Mannheim .

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.

The use of the 5-arylpenta-2,4-dienylcarbonyl compounds described in more detail below for dyeing fibers containing keratin has hitherto not been 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 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. Surprisingly, it has now been found that the 5-arylpenta-2,4-dienylcarbonyl compounds shown in the formula I 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.

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, containing 5-arylpenta-2,4-dienylcarbonyl compounds having the formula I or their physiologically tolerable salts,

in which R ^{1 represents} a hydrogen atom or a Crd alkyl group and

R ² and R ^{3 can be the} same or different and represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group, C _r C ₄ alkoxy group, hydroxy-C _r C ₄ alkoxy group, a hydroxy group, nitro group, λmino group, which can be substituted by C ₁ -C ₄ alkyl groups or can be part of a heterocycle, or can be a C d-acyl group, it also being possible for two of the radicals together to form a fused-on benzene ring.

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 compounds with the formula I can be used as ice and alstrans isomers. The compounds of the formula I are preferably selected from the Group of the following 5-arylpenta-2,4-dienylcarbonyl compounds: 4-

Dimethylaminophenylpenta-2,4-dienal, 4-diethylaminophenylpenta-2,4-dienal, 4-methoxyphenylpenta-2,4-dienal, 3,4-dimethoxyphenylpenta-2,4-dienal, 2,4-

Dimethoxyphenylpenta-2,4-dienal, 4-piperidinophenylpenta-2,4-dienal, 4-morpholinophenylpenta-2,4-dienal, 4-pyrrolidinophenylpenta-2,4-dienal or 4-dimethylaminophenylhexa-2,4 -dien-2-one, 4-diethylaminophenylhexa-2,4-dien-2-one, 4-methoxyphenylhexa-2,4-dien-2-one, 3,4-dimethoxyphenylhexa-2,4-dien-2 -one, 2,4-dimethoxyphenylhexa-2,4-dien-2-one, 4-pipehdinophenylhexa-2,4-dien-2-one, 4-morpholinophenylhexa- 2,4-dien-2-one and 4 -Dimethylamino-1-naphthyl) -penta-2,4-dienal.

These substances are known from the literature or are commercially available.

The abovementioned 5-arylpenta-2,4-dienylcarbonyl compounds having the formula I are preferably used in the agents according to the invention in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the entire colorant. They can be used as substantive colorants or in the presence of oxidation dye precursors.

Coloring agents which contain the 5-arylpenta-2,4-dienylcarbonyl compounds having the formula I alone as the coloring component are preferably used for dyeing in the brown area. Colorings with even greater brilliance and improved fastness properties (light fastness, wash fastness, rub fastness), especially in the yellow, orange, violet, brown and black range, are achieved if the compounds of the formula I used according to the invention together with at least one further component (hereinafter referred to as component B), selected from compounds 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, oligopeptides and aromatic hydroxy compounds composed of 2 to 9 amino acids, and / or CH-active compounds can be used. On the one hand, these are compounds which, on their own, only weakly dye keratin-containing fibers and only give brilliant dyeings together with the 5-arylpenta-2,4-dienylcarbonyl compounds of the formula I. On the other hand, there are also compounds that are already used as oxidation dye precursors. 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 5-arylpenta-2,4-dienylcarbonyl compounds of the formula I can also be used together in all colorants; Likewise, several different compounds of component B can also be used together.

The embodiment described above also includes the use of those substances which are reaction products of 5-arylpenta-2,4-dienylcarbonyl compounds of the formula I with the compounds of component B mentioned, as substantive colorants. Such reaction products can e.g. can be obtained by briefly heating the two components in stoichiometric amounts in aqueous alkali metal hydroxides, in which case they either precipitate out of the solution as a solid or are isolated therefrom by evaporation of the solution. The reaction products can also be used in combination with other dyes or dye precursors.

Suitable compounds with a primary or secondary amino group as component B are, for example, primary aromatic amines such as N, N-dimethyl-, N, N-diethyl-, N- (2-hydroxyethyl) -N-ethyl-, N, N-bis- ( 2-hydroxyethyl) -, N- (2-methoxyethyl-), 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4 -morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o-toluenediamine, 2,5-diaminotoluene, -phenol , - phenethol, 4-amino-3-methylphenol, 2- (2,5-diaminophenyl) -ethanol, 2,4-diaminophen-oxyethanol, 2- (2,5-diaminophenoxy) -ethanol, 4-methylamino-, 3rd -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-hydroxyoxyamino) -, 6-methyl-3-amino-2-chloro, 2-methyl-5-amino-4-chloro , 3,4-methylene dioxy-, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-hydroxymethylphenol, 1, 3-diam ino-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-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2- sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5- , 1,2,4-triaminobenzene, 1, 2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobenzate catechol, 4,6-diaminopyrogallol , 3,5-diamino-4-hydroxycatechol, aromatic nitriles, anilines, in particular nitro group-containing anilines, such as 4-nitroaniline, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2- hydroxyethylamino) benzene, 2-nitro-1-amino-4- [bis- (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2-amino-6- chloro-4-nitrophenol, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aroma table rest, as shown in Formula II

(left)

in the R ⁴ for a hydroxyl or an amino group which can be substituted by C _1-4 alkyl, C _M -

Hydroxyalkyl, C alkoxy or C _1-4 alkoxyC _1-4 alkyl groups may be substituted,

R ⁴ , R ⁶ , R ⁷ , R ⁸ and R ^{9 represent} hydrogen, a hydroxy or an amino group,

C _M alkyl, C _1-4 hydroxyalkyl, C _1-4 alkoxy, C _1-4 aminoalkyl or C ^ alkoxy-C ^ alkyl groups may be substituted, and

X for a direct bond, a saturated or unsaturated carbon chain with 1 to 4 carbon atoms optionally substituted by hydroxy groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula

IN THE

Z- (CH ₂ -Y-CH ₂ -Z ') ₀ (III) in which Y is a direct bond, a CH ₂ or CHOH group,

Z and Z independently of one another for an oxygen atom, an NR ¹⁰ group, in which R ^{10 is} hydrogen, a C _M alkyl or a hydroxyC _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'-disulfonic acid mono- or di-Na salt, 4-amino-4'-dimethylaminostilbene, 4,4'-diaminodiphenylmethane, -sulfide, -sulfoxide, -amine, 4,4'-diaminodiphenylamine-2-sulfonic 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 -, 2,6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino-, 4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2nd -Hydroxy-4,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, -1,2,4-triazole, 3-amino, 3-amino-5-hydroxypyrazole, 2-, 3-, 8- Aminoquinoline, 4-aminoquininaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-aminobenzimidazole, benzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 5,6-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. 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 that can be mentioned are 1,2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium-p-toluenesulfonate, 1, 2,3,3-tetramethyl - 3H-indolium methanesulfonate, Fischer's base (1,3,3-trimethyl-2-methyleneindoline), 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.

Preferred amino acids are all naturally occurring and synthetic α-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. But also other amino acids, e.g. 6-aminocaproic acid can be used.

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 include glutathione and the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Agents which contain the compounds of the formula I together with compounds having a primary or secondary amino group or with aromatic hydroxy compounds are preferred. 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 as well as those formed with preferably inorganic acids en 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 the shades that are 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 .

In a preferred embodiment, the colorants according to the invention contain, in addition to the compounds contained according to the invention, customary direct dyes, for example from the group of the nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as those under the international names or trade names HC Yellow, for further modification of the color shades 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as picramic acid 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride and 1-methyl-3-nitro-4- (2'-hydroxyethyl) aminobenzene . Contain the inventive agents according to this embodiment the substantive dyes preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant.

It is not necessary that the 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 water-free carriers.

Furthermore, the colorants according to the invention can contain all active ingredients, 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, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be in the molecule be included. 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 trialkanolammonium 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,

Mono and dialkyl sulfosuccinic acid with 8 to 18 carbon atoms in the alkyl group and mono alkyl polyoxyethyl sulfosuccinate 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, alpha-sulfofatty acid methyl ester 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, the addition products of about 2 to 15 molecules of ethylene oxide and / or propylene oxide to 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 ₃ ⁽⁾ 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 cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-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 cocoacylaminoethyl-hydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C _8-18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate 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 ethylene oxide and / or 0 to 5 mol propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group , C ₁₂ . ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ . ₂₂ alkyl mono- and oligogiycosides and their ethoxylated analogs, addition products of 5 to 60 mol ethylene oxide onto castor oil and hardened castor oil, Addition products of ethylene oxide with 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 Corning; 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, Quaternium-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", such as those sold under the trademark Stepantex ^® methylhydroxyalkyldialkoyloxyalkylammonium.

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 usually preferred at Production of these substances from natural vegetable or animal raw materials, so that mixtures of substances 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, dimethyldiallylammonium methyldiallylammonium chloride copolymers, diethyl sulfate-quaternized dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone

Imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyacrylic acids, for example, anionic polymers, such as anionic polymers , Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert.-butylacrylamide terpolymers, Thickeners such as agar agar, guar gum, algihate, 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 cephaline, as well as 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 like latex,

Pearlescent agents such as ethylene glycol mono- and distearate,

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

Antioxidants. The constituents of the water-containing carrier are used to produce the colorants according to the invention in amounts customary for this purpose; For example, 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 alkali 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.

Another object of the present invention relates to the use of 5-arylpenta-2,4-dienylcarbonyl compounds having the formula I or their physiologically tolerable salts

in which R ^{1 represents} a hydrogen atom or a CrC ^ alkyl group and

R ² and R ^{3 may be the} same or different and, for a hydrogen atom, a halogen atom, a C _r C ₄ alkyl group, C _r C ₄ alkoxy group, hydroxy-C _r C ₄ alkoxy group, a hydroxy group, nitro group, amino group, the can be substituted by C ₁ -C ₄ alkyl groups or can be part of a heterocycle, or can be a CC ^ acyl group, where two of the radicals together can form a fused-on benzene ring, as a coloring component in oxidation hair dyes.

Yet another object of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, in which a colorant containing

A) at least one 5-arylpenta-2,4-dienylcarbonyl compound having the formula I or its physiologically tolerable salts

in which R ^{1 represents} a hydrogen atom or a CrC alkyl group and

R ² and R ^{3 may be the} same or different and represent a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, CrOralkoxy group, hydroxy-C 1, -

C ₄ alkoxy group, a hydroxy group, nitro group, amino group through

C _r C ₄ alkyl groups may be substituted or may be part of a heterocycle, or may be a C C acyl group, it also being possible for two of the radicals together to form a fused-on benzene ring,

B) at least one compound with primary or secondary amino group or

Hydroxyl 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, 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 or washed out with a shampoo.

The 5-arylpenta-2,4-dienylcarbonyl compounds of the formula I and the compounds of component B can either be applied to the hair simultaneously or 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. Between application the first and second components can be up to 30 minutes apart. Pretreatment of the fibers with the saline solution is also possible.

The 5-arylpenta-2,4-dienylcarbonyl compounds of the formula I 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 millimoles of a 5-arylpenta-2,4-dienylcarbonyl compound of Formula I, 10 millimoles of an oxidation dye precursor, 10 millimoles of sodium acetate, and a drop of a 20 percent fatty alkyl ether sulfate solution in 100 milliliters 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 coloring solution at 30 ° C. for 30 minutes. The tress was then rinsed with lukewarm water for 30 seconds, dried with warm air and then combed out.

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 Colorings with 5- (4-N, N-dimethylaminophenyl) -penta-2,4-dien-1-al

T a t> e I l e 1

Component B pH value Color shade Color depth

- 6.0 orange brown +

- 2.0 brown pink +

2,5-diaminotoluene x H ₂ SO 2.0 dark gray ++

2-methylamino-3-amino-6-methoxypyridine x 6.0 dark orange-brown ++ 2HCI

2- (2,5-diaminophenyl) ethanol x H ₂ SO 6.0 dark gray ++

2- (2,5-diaminophenyl) ethanol x H ₂ SO 2.0 gray blue ++

2-aminomethyl-4-aminophenol x 2HCI 6.0 dark brown ++

2-aminomethyl-4-aminophenol x 2HCI 2.0 violet brown ++

N, N-Bis- (2-hydroxyethyl) -p-phenylenediamine x 6.0 dark violet red ++ (+) H ₂ SO ₄

Claims

claims

1. Means for dyeing keratin fibers, in particular human hair, containing at least one 5-arylpenta-2,4-dienylcarbonyl compound having the formula I or its physiologically tolerable salts as the coloring component

in which R ^{1 represents} a hydrogen atom or a C 1-4 alkyl group and

R ² and R ^{3 may be the} same or different and represent a hydrogen atom, a halogen atom, a C C alkyl group, C _r C ₄ alkoxy group, hydroxy-C C ₄ alkoxy group, a hydroxy group, nitro group, amino group, which are represented by CC ₄ Alkyl groups can be substituted or be part of a heterocycle, or a C C -acyl group, where two of the radicals together can form a fused benzene ring.

Agent according to claim 1, characterized in that as compounds with the formula I 4-dimethylaminophenylpenta-2,4-dienal, 4-diethylaminophenylpenta- 2,4-dienal, 4-methoxyphenylpenta-2,4-dienal, 3,4-dimethoxyphenyipenta -2,4- dienal,

2,4-Dimethoxyphenylpenta-2,4-dienal, 4-piperidinophenylpenta-2,4-dienal, 4-morpholinophenylpenta-2,4-dienal, 4-pyrrolidinophenylpenta-2,4-dienal and 4-dimethylaminophenylhexa-2,4 -dien-2-one, 4-diethylaminophenylhexa-2,4-dien-2-one, 4-methoxyphenylhexa-2,4-dien-2-one,

3,4-dimethoxyphenylhexa-2,4-dien-2-one, 2,4-dimethoxyphenylhexa-2,4-dien-2-one, 4-piperidinophenylhexa-2,4-dien-2-one, 4-morpholinophenylhexa- 2,4-dien-2-one and 4-dimethylamino-1-naphthyl) - penta-2,4-dienal are used.

Agent according to one of claims 1 to 2, characterized in that the 5-aryipenta-2,4-dienylcarbonyl compounds having the formula I in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant, are present.

4. Composition according to one of claims 1 to 3, characterized in that it additionally has at least one compound having a 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 to 9 amino acids Contains oligopeptides and aromatic hydroxy compounds, and / or at least one CH-active compound.

5. Composition according to claim 4, characterized in that the further compound is selected from primary or secondary amines from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, N- (2-methoxyethyl-), 2nd , 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-methylene-diamino-, 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-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5-, 1, 2,4-triaminobenzene, 1, 2,4,5-tetraaminobenzene tetrahydrochloride, 2 , 4,5-triamino-phenol-trihydrochloride, pentaaminobenzene-pentahydrochloride, hexaaminobenzene-hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzate cate- chin sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxycatechol sulfate, aromatic nitriles, anilines, in particular anilines containing nitro groups, such as 4-nitroaniline, 4-nitro-1, 3-phenylenediamine, 2- Nitro-4-amino-1- (2-hydroxyethylamino) benzene, 2-nitro-1-amino-4- [bis- (2-hydroxyethyl) amino] benzene, 4-amino-2-n-trodiphenylamine-2 ' carboxylic acid, 2-amino-6-chloro-4-nitrophenol, 1-amino-5-chloro-4- (2-hydroyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical such as 4, 4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, sodium salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenylamine 2-sulfonic acid, 4,4'-diaminobenzophenone, diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl tetrahydrochloride, 3,3', 4,4'-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-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methylamine trihydrochloride, nitrogen-containing heterocyclic compounds selected from the group consisting of 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-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-ethyl-pyrrole, 3,5-diaminopyrazole, -1, 2,4-triazole, 3-amino, 3-amino-5- hydroxypyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquininaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, - benzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives n, such as 4-, 5-, 6-, 7-aminoindole, 4-, 5-, 6-, 7-hydroxyindole, 5,6-dihydroxyindoi, 5,6-dihydroxyindoline and 4-hydroxyindoline, and in each case from those with preferably inorganic acids formed physiologically acceptable salts of these compounds, aromatic hydroxy compounds selected from the group consisting of 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, and

CH-active compounds 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-quinaldinium iodide, barbituric acid,

Thiobarbituric acid, 1, 3-dimethyl (ethyl) thiobarbituric acid, oxindole, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

6. Composition according to claim 5, characterized in that the further compound is selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-, 2-chloro-p-phenylenediamine, N, N-bis- (2nd -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-di- methylamino-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-hydroxy-pyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline, and in each case from the preferred ise physiologically compatible salts of these compounds formed with inorganic acids.

7. Composition according to one of claims 1 to 6, characterized in that there are direct dyes from the group of nitrophenyienediamines, nitroamino-phenols, anthraquinones or indophenols preferably in an amount of 0.01 to 20 wt .-%, based on the entire colorant.

8. Composition according to one of claims 1 to 7, 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 alkali 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.

9. Agent according to one of claims 1 to 8, characterized in that it contains oxidizing agents, in particular H ₂ O ₂ , in an amount of 0.01 to 6 wt .-%, based on the application solution.

10. Composition according to one of claims 1 to 9, characterized in that it contains anionic, zwitterionic or nonionic surfactants.

11. Use of 5-arylpenta-2,4-dienylcarbonyl compounds with the formula I or their physiologically tolerable salts

in which R ^{1 represents} a hydrogen atom or a CC ^ alkyl group

R ² and R ^{3 may be the} same or different and represent a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group, C ^ Or alkoxy group, hydroxy-C _r C ₄ alkoxy group, a hydroxy group, nitro group, amino group CC ₄ alkyl groups can be substituted or be part of a heterocycle, or a C ^ C-acyl group, where two of the radicals together can form a fused-on benzene ring, as a coloring component in oxidation hair dye.

12. A process for dyeing keratin-containing fibers, in particular human hair, which contains a colorant A) at least one 5-arylpenta-2,4-dienylcarbonyl compound with the formula or its physiologically tolerable salts

in which R ^{1 represents} a hydrogen atom or a C _r C ₄ alkyl group and

R ² and R ^{3 may be the} same or different and, for a hydrogen atom, a halogen atom, a C ^ C-alkyl group, C _r C ₄ - alkoxy group, hydroxy-C _T O _t -alkoxy group, a hydroxy group, nitro group, amino group C _r C ₄ alkyl groups can be substituted or be part of a heterocycle, or a C <, - C ₄ -acyl group, where two of the radicals together can form a fused-on benzene ring, B) at least one compound with a 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 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, for some time, usually about 30 minutes, leave on the fiber and then rinsed or rinsed again r is washed out with a shampoo.