WO2000076466A1

WO2000076466A1 - Xanthene derivatives for dying keratin fibers

Info

Publication number: WO2000076466A1
Application number: PCT/EP2000/005044
Authority: WO
Inventors: Hinrich Möller; Bernd Meinigke
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-06-10
Filing date: 2000-06-02
Publication date: 2000-12-21
Also published as: DE19926377A1; AU5810600A

Abstract

The invention relates to an agent for dying keratin fibers, especially human hairs, containing at least one xanthene derivative of formula (I), in which R1 represents a hydrogen atom, a C¿1?-C4 carboxyl group or a sulfo group; R?2, R3, R4, R5¿ represent a hydrogen atom, a C¿1?-C4 alkyl group, a C1-C4 alkoxy group or a hydroxy group; if X?2¿ represents an oxygen atom, then X1 represents a hydroxy group which can also be presented as an alkali salt, alkaline-earth salt, or as an ammonium salt, or; if X1 represents an amino group, which can optionally carry one or two methyl substituents or which forms a fused 5, 6, or 7 member ring together with R2 and/or R3, then X2 represents a group ?+NA1A2 U-¿, wherein A?1 and A2¿, independent of one another, represent hydrogen or a methyl group or form a fused 5, 6, or 7 member ring together with R4 and/or R5, and; U- represents an equivalent of a halogenide anion, sulfate anion, sulfonate anion or a carboxylate anion. The invention also relates to physiologically acceptable salts of the inventive agent.

Description

XANTHENE DERIVATIVES FOR COLORING KERATIN-CONTAINING FIBERS

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, which contains xanthene derivatives, the use of these xanthene derivatives as a coloring component in hair dye compositions and a process for dyeing keratin-containing fibers, in particular human hair.

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

Primary aromatic amines with a further free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof are usually used as developer components used.

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 - diaminophenyethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2 -Hydroxy-methyl-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 derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives are generally used as coupler components. Particularly suitable coupler substances are α-naphthol, 1, 5-, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol , 2-amino-4- (2-hydroxyethylamino) anisole (Lehmanns Blau), 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, 5-methylresorcinol, 3-amino-6-methoxy-2-methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

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 .

With oxidation dyes intensive dyeings can be achieved with good fastness properties, but the development of the color is usually done under the influence of oxidizing agents such. B. H ₂ O ₂ , which in some cases can damage the fiber. 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 xanthene derivatives described in more detail below for dyeing keratin-containing fibers is not yet known.

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

Surprisingly, it has now been found that the xanthene derivatives shown in the formula I are also outstandingly suitable for dyeing keratin-containing fibers in the absence of oxidizing agents. They result in colorations with outstanding brilliance and depth of color and lead to diverse color nuances. However, the use of oxidizing agents should not be excluded in principle.

The invention relates to an agent for dyeing keratin fibers, in particular human hair, containing at least one xanthene derivative of the formula I,

(I)

in which R ^{1 represents} a hydrogen atom, a C 1-4 carboxyl or a sulfo group,

R ² , R ³ , R \ R ⁵ stand for a hydrogen atom, a C ₁ -C ₄ alkyl group, CC ₄ alkoxy group or hydroxy group, and if X ^{2 stands} for an oxygen atom, then X ^{1 is} a hydroxy group which can also be present as an alkali, alkaline earth or ammonium salt, or when X ^{1 represents} an amino group which can optionally carry one or two methyl substituents or together with R ² and / or R ³ a fused 5-, 6- or 7-membered ring, then X ^{2 is} a group ⁺ NA ¹ A ² U ^" , in which A ¹ and A ² independently of one another represent hydrogen or a methyl group or together with R ⁴ and / or R ⁵ a fused 5-, 6th - or 7-membered ring form and U ^" stands for an equivalent of a halide, sulfate, sulfonate or carboxylate anion, or physiologically acceptable salts thereof.

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 for dyeing other natural fibers, such as, for. B. cotton, jute, sisal, linen or silk, modified natural fibers, such as. B. regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers such as. B. polyamide, polyacrylonitrile, polyurethane and polyester fibers can be used.

The compounds with the formula I are preferably selected from the group of the following xanthene derivatives pyrogallol red, 9-phenyl-2,6,7-trihydroxy-3-fluorene, rhodamine 116 perchlorate, rhodamine 101, rhodamine-110 chloride, fluorescein and any of these Mixtures.

Most of these substances are known from the literature or are commercially available or can be prepared by known synthetic processes.

The above-mentioned xanthene derivatives with 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 total colorant. They can be used as direct coloring agents as the only coloring component or both in a mixture with other direct drawing agents and also in the presence of conventional oxidation dye precursors or other hair coloring systems.

Coloring agents which contain the xanthene derivatives with the formula I alone as the coloring component are preferably used for coloring in the range from red-orange, red-brown and violet. Colorings with an even higher brilliance and improved fastness properties (light fastness, wash fastness, rub fastness) over a wide range of shades from orange, red, brown orange, medium brown, violet, dark violet to blue black and black are achieved if the compounds used according to the invention with formula I 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, from 2 to 9 amino acids, oligopeptides and aromatic hydroxy compounds , and / or CH-active compounds can be used. On the one hand, these are compounds which, on their own, stain only weakly keratin-containing fibers and only brilliant together with the xanthene derivatives of the formula I. Colorings result. 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 xanthene derivatives 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 such substances which are reaction products of xanthene derivatives of the formula I with the compounds of component B mentioned as direct colorants. Such reaction products can e.g. B. can be obtained by briefly heating the two components in stoichiometric amounts in an aqueous neutral to weakly alkaline medium, where 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. [Is that possible]

Suitable compounds with primary or secondary amino group as component B are e.g. B. 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-phenylene diamine, 2-chloro-p-phenylene diamine, 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, - phenethole, 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-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-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-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-diaminobenzene catechol, 4,6-diaminopyrogallol, 3,5-diamino-4-hydroxybenzate catechol, aromatic nitriles , Anilines, especially 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- (2nd -hydroyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as shown in formula II

in the R ⁶ for a hydroxyl or an amino group which can be substituted by C _1-4 -alkyl-, C _1-4 -hydroxyalkyl-, C _1-4 -alkoxy- or C _1-4 -alkoxy-C _{1- 4} -alkyl groups, R ⁷ , R ⁸ , R ⁹ , R ⁰ and R ^{11 represents} hydrogen, a hydroxy or an amino group which can be substituted by C _1-4 alkyl, C _1-4 hydroxyalkyl, C _1-4 alkoxy, C _1-4 aminoalkyl or C ^ alkoxy-C ^ alkyl groups can be substituted, and

Q 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

Z- (CH ₂ -Y-CH ₂ -Z ') ₀ (IM)

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 ¹² group in which R ^{12 is} hydrogen, a C _1-4 alkyl or a hydroxy-C ^ alkyl group, the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _p '-0, where p and p' are 2 or 3, and o is a number from 1 to 4, such as 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene - 2,2'-disulfonic acid mono- or di-Na salt, 4-amino-4'-dimethylaminostilbene and its hydrochlorind, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4 ' -Diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, 3,3 ', 4,4'-tetra-aminodiphenyl, 3,3', 4,4'-tetraamino-benzophenone, 1, 3rd -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 e.g. B. 2-, 3-, 4-amino, 2-amino-3-hydroxy, 2,6-diamino, 2,5-diamino, 2,3-diamino, 2-dimethylamino-5-amino -, 2-methylamino-3-amino-6-methoxy-, 2,3-diamino-6-methoxy-, 2,6-dimethoxy-3,5-diamino-, 2,4,5-triamino-, 2, 6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino-, 4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2-hydroxy-4 , 5,6-triamino-, 2,4,5,6-tetraamino-, 2-methyiamino-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- Aminochinaldine, 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 e.g. B. 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, Phloroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy, 3-dimethylamino, 2- (2-hydroxyethyl) -, 3,4-methylenedoxoxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, phenylacetic acid , Gallic acid, 2,4,6-trιhydroxybenzoic acid, -acetophenone, 2-, 4-chloro-resorcinol, 1-naphthol, 1, 5-, 2,3-, 2,7-dihydroxy-naphthalene, 6-dimethyl-4-hydroxy-2 - Naphthahnsulfonsaure, 3,6-Dιhydroxy-2,7-naphthalιnsulfonsaure

Examples of CH-active compounds which may be mentioned are 1, 2,3,3-tetramethyl-3H-indolumium, 1, 2,3,3-tetramethyl-3H-indolum-p-toluenesulfonate, 1, 2,3,3-tetramethyl - 3H-ιndolιum methanesulfonate, Fischer's base (1, 3,3-Tπmethyl-2-methylenιndolιn), 2,3-dimethyl-benzothiazo umiodide, 2,3-dimethyl-benzothιazolιum-p-toluenesulfonate, rhodanine, Rhodanιn-3- Essιgsaure, 1-methyl-2-chιnaldιnιum-ιodιd, 1-ethyl-2-chιnaldιnιum-ιodιd, 1, 4-dimethylquinonium iodide, barbituric acid, thiobarbituric acid, 1, 3-dimethylthioobarbthio-3-carboxylic acid, Oxindole, 3-indoxy acetate, coumaranone and 1-methyl-3-phenyl-2-pyrazolionone

Preferred amino acids are all naturally occurring and synthetic α-amino acids, for. B the amino acids accessible by hydrolysis from vegetable or animal proteins, e.g. collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Both acidic and alkaline amino acids can be used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan. However, other amino acids, such as 6-aminocaproic acid, can also be used

The oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates, provided they have sufficient water solubility for use in the colorants according to the invention. Examples include glutathione and those in the hydrolysates of Oligopeptides containing collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein are preferred. 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 3

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, 2-amino-4- (2-hydroxyethylamino) anisole, 2- (2nd , 4-diaminophenoxy) ethanol, 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-dih ydroxyindoline and their physiologically tolerable salts formed with preferably inorganic acids.

On the presence of oxidizing agents, e.g. B. H ₂ O ₂ , can be omitted. However, it can It may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention in order to obtain shades which 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 according to the invention, customary direct dyes, for example, for further modification of the color shades. B. from the group of nitro phenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as. B. under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 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. The inventive agents according to this embodiment contain the 40 direct dyes preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant.

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

In addition, the preparations according to the invention can also contain reactive carbonyl compounds, such as aldehydes and other oxo compounds in combination with suitable amines, phenols or CH-active compounds, as are described in many patents.

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 process for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. B. 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. B. creams, emulsions, gels or surfactant-containing foaming solutions such. B. 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 substances, additives and auxiliaries known in such preparations. In many cases, the colorants contain at least one surfactant, in principle both anionic and ZwA zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and 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, Λ%

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 those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^ or -Sθ ₃ ^H 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 cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C ₈ . ₁₈ -alkyl or -acyl group in the molecule contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-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. <J

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 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to

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

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

Ethylene oxide on glycerol,

C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogues,

Addition products of 5 to 60 moles of ethylene oxide with 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). Alkylamidoamines, especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amιd®S 18, are characterized not only by a good conditioning effect, but also by their good biodegradability

Also very well biodegradable quaternary Esterverbindungen, so-called "esterquats", such as the methylhydroxyalkyldialkoyloxyalkylammonium marketed under the trade Stepantex® ^®

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 in each case be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained

In the case of the surfactants which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. "Normal" homolog distribution is understood to mean mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. In 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 are 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, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone copolymers

Imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as, for example, acrylic amidopropyl-trimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers such as polyesters, anionic polyesters - Acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate

Copolymers, vinyl acetate / butyl maleate / isobomylacrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert.-butylacrylamide terpolymers,

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic cum, 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. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol, structurants such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils,

Protein hydrolyzates, in particular 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; z. 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. B. 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 xanthene derivatives having the formula I.

(l)

in which R ^{1 represents} a hydrogen atom, a CC ₄ carboxyl or a sulfo group,

R ² , R ³ , R ⁴ , R ^{5 represent} a hydrogen atom, a C ₁ -C ₄ alkyl group, C _r C ₄ alkoxy group or a hydroxyl group, if X ^{2 represents} an oxygen atom, then X ^{1 is} a hydroxyl group , which can also be in the form of an alkali, alkaline earth or ammonium salt, or if X ^{1 represents} an amino group which can optionally carry one or two methyl substituents or together with R ² and / or R ³ a fused 5-, 6th - or forms a 7-membered ring, then X ^{2 is} a group ⁺ NA ¹ A ² U ^" , in which A ¹ and A ² independently represent hydrogen or a methyl group or together with R ⁴ and / or R ^{5 is} a fused-on 5- , 6- or 7- membered ring form and U ^" stands for an equivalent of a halide, sulfate, sulfonate or carboxylate anion, or their physiologically acceptable salts as a coloring component in

Oxidation hair dye.

Yet another object of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, in which a colorant comprising A) at least one xanthene derivative with the formula I, M

in which R ^{1 represents} a hydrogen atom, a C 1 -C 4 carboxyl or a sulfo group,

R ² , R ³ , R ⁴ , R ⁵ stand for a hydrogen atom, a C ^ C ^ alkyl group, C _r C ₄ alkoxy group or hydroxy group, if X ^{2 stands} for an oxygen atom, then X ^{1 is} a hydroxy group which can also be present as an alkali, alkaline earth or ammonium salt, or if X ^{1 represents} an amino group which can optionally carry one or two methyl substituents or together with R ² and / or R ³ a fused 5-, 6- or 7-membered ring forms, then X ^{2 is} a group ⁺ NA ¹ A ² U ^' , wherein A ¹ and A ² independently of one another represent hydrogen or a methyl group or together with R ⁴ and / or R ⁵ a fused 5-, 6th - or 7-membered ring form and U ^" stands for an equivalent of a halide, sulfate, sulfonate or carboxylate anion, or their physiologically acceptable salts and B) at least one compound having a primary or secondary amino group or hydroxy group selected from primary or secondary aliphatic or aromatis Chen 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-containing fibers, some time, usually about 30 minutes, Leave on the fiber and then rinsed out or washed out with a shampoo. The xanthene derivatives of the formula I and the compounds of component B can either be applied to the hair simultaneously or else in succession, it being irrelevant which of the two components is applied first. The optionally contained ammonium or metal salts can be added to the first or the second component. There may be an interval of up to 30 minutes between the application of the first and the second component. Pretreatment of the fibers with the saline solution is also possible.

The xanthene derivatives 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 (30 to 80 ° C) water is usually added before use and a homogeneous mixture is produced.

A>

Examples

Preparation of a coloring solution

A slurry of 5 mmol of a xanthene derivative with the formula I, possibly 5 mmol of an oxidation dye precursor of component B and 5 mmol of sodium acetate and a drop of a 20% strength fatty alkyl ether sulfate solution in 50 ml of water at 60 ° C. were prepared. The slurries were mixed together after cooling to 30 ° C and adjusted to pH 6 with dilute NaOH or hydrochloric acid.

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 2Λ

Table 1

Colorings with xanthene derivatives without component B

Table 2

Colorings with fluorescein Na salt

Table 3

Coloring with pyrogallol red

Claims

11 Patent claims

1. Means for dyeing keratin-containing fibers, in particular human hair, containing at least one xanthene derivative with the formula as a coloring component

(I)

in which R ^{1 represents} a hydrogen atom, a C 1-4 carboxyl or a sulfo group,

R ² , R ³ , R ⁴ , R ⁵ stand for a hydrogen atom, a CrC-alkyl group, CC ₄ alkoxy group or hydroxy group, if X ^{2 stands} for an oxygen atom, then X ^{1 is} a hydroxy group, which is also known as an alkali , Alkaline earth or ammonium salt, or if X ^{1 represents} an amino group which may optionally carry one or two methyl substituents or together with R ² and / or R ³ forms a fused-on 5-, 6- or 7-membered ring , then X ^{2 is} a group ⁺ NA ¹ A ² U ^" , in which A ¹ and A ² independently represent hydrogen or a methyl group or together with R ⁴ and / or R ⁵ a fused-on 5-, 6- or 7-membered group Form ring and U ^" stands for an equivalent of a halide, sulfate, sulfonate or carboxylate anion, or their physiologically acceptable salts.

2. Composition according to claim 1, characterized in that as compounds with the formula I pyrogallol red, 9-phenyl-2,6,7-trihydroxy-3-fluorene, rhodamine 116 perchlorate, V \

Rhodamine 101, rhodamine-110 chloride, fluorescein and any mixtures thereof can be used.

3. Composition according to one of claims 1 to 2, characterized in that the xanthene derivatives with the formula I are contained in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant.

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) , 2,3-, 2,4-, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, N, N-bis- (2-hydroxyethyl) -p-phenylene diamine, 2,5-dihydroxy -4-morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene , - phenol, -phenethol, 4-methylamino-, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-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-, 3rd , 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-A-mino-5-hydroxynaphthalene-2, 7-disulfonic acid, 3-amino-2-naphthoic acid, 3-amino-phthalic acid, 5-amino-isophthalic acid, 1,3,5-, 1, 2,4-triaminobenzene, 1, 2,4,5-tetra- ι ^χ nobenzol tetrahydrochloride, 2,4,5-triaminophenol trihydrochloride, pentaaminobenzene pentahydrochloride, hexaaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzene catechol sulfate, 4,6-diaminopyrogalol gallol dihydrochloride, 3,5-diamino-4-hydroxycatechol sulfate, 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 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 tetrahydroc chloride, 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-methylpyrimidine, 2,3,4-trimethylpyrrole, 2,4-dimethyl-3-ethylpyrrole, 3.5 -Diaminopyrazole, -1, 2,4-triazole, 3-amino, 3-amino-5-hydroxypyrazole, 2-, 3-, 8-ami nochinolin, 4-amino-quinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-amino-benzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole- and indoline derivatives such as 4-, 5-, 6-, 7-aminoindole, 4-, 5-, 6-, 7-hydroxyindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, as well as from each of the with preferably inorganic acids formed physiologically compatible 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-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-quinaldinium iodide, 1, 4-dimethylquinolinium iodide, 1-methyl-2-quinaldinium iodide, 1, 4-

Dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxyacetate, 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 (2- Hydroxyethyl) -p-phenylenediamine, 4-aminophenol, p-phenylenediamine, 2- (2,5-diaminophenyl) -ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 2-amino-4- (2- hydroxyethylamino) anisole, 2- (2,4-diaminophenoxy) ethanol, 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-methylene dioxyphenol, 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-di-methoxy-, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triamino-, 4-hydroxy- 2 , 5,6-triamino, 2,4,5,6-tetraamino, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 5,6 - Dihydroxyindole and 5,6-dihydroxyindoline and in each case from the physiologically tolerable salts of these compounds, which are preferably 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 nitrophenylenediamines, nitroaminophenols, If

Anthraquinones or indophenols preferably in an amount of 0.01 to 20 wt .-%, based on the total 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, are to 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 xanthene derivatives with the formula I,

(I)

in which R ^{1 represents} a hydrogen atom, a CrC ^ carboxyl or a sulfo group,

R ² , R ³ , R ⁴ , R ^{5 represent} a hydrogen atom, a C ₁ -C ₄ alkyl group, C _r C ₄ alkoxy group or a hydroxyl group, w if X ^{2 stands} for an oxygen atom, then X ^{1 is} a hydroxy group, which can also be present as an alkali, alkaline earth metal or ammonium salt, or if X ^{1 stands} for an amino group, which can optionally carry one or two methyl substituents or together with R ² and / or R ³ forms a fused-on 5-, 6- or 7-membered ring, then X ^{2 is} a group ⁺ NA ¹ A ² U ^" , in which A ¹ and A ² independently of one another represent hydrogen or a methyl group or together with R ⁴ and / or R ^{5 form} a fused-on 5-, 6- or 7-membered ring and U ^" stands for an equivalent of a halide, sulfate, sulfonate or carboxylate anion, or their physiologically acceptable salts as one coloring component in

Oxidation hair dye.

12. A process for dyeing keratin-containing fibers, in particular human hair, in which a colorant comprising A) at least one xanthene derivative of the formula I,

R3 R4

(l) in which R ^{1 represents} a hydrogen atom, a C ¹ -C ₄ carboxyl or a sulfo group,

R ² , R ³ , R ⁴ , R ⁵ stand for a hydrogen atom, a CrC ^ alkyl group, CC ₄ - alkoxy group or hydroxy group, if X ^{2 stands} for an oxygen atom, then X ^{1 is} a hydroxy group, which is also known as an alkali, alkaline earth metal - Or ammonium salt, or, if X ^{1 represents} an amino group, optionally one or can carry two methyl substituents or together with R ² and / or R ³ forms a fused-on 5-, 6- or 7-membered ring, then X ^{2 is} a group ⁺ NA ¹ A ² U ^" , in which A ¹ and A ^{2 are} independent of one another represent hydrogen or a methyl group or together with R ⁴ and / or R ^{5 form} a fused-on 5-, 6- or 7-membered ring and U ^" represents an equivalent of a halide, sulfate, sulfonate or carboxylate anion, or physiologically acceptable salts thereof and B) 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, oligopeptides and aromatic hydroxy compounds, and / or at least a CH-active compound, as well as usual cosmetic ingredients, applied to the keratin fibers for some time, usually approx. 30 minutes left on the fiber and then rinsed out or washed out with a shampoo.