DE10047480A1 - Use of acridine-aldehydes and/or -ketones, some of which are novel compounds, in dyeing hair in a wide variety of intense shades, even in the absence of oxidizers - Google Patents

Abstract

An agent for dyeing keratin fibers (especially human hair) contains an acridine-aldehyde and/or -ketone, the novel compounds 9-formyl-10-methylacridinium-p-toluene sulfonate and 9-((dimethylaminophenylimino)-methyl)-10-methylacridinium-methylsulfate being claimed per se. An agent for dyeing keratin fibers (especially human hair) contains an acridine-aldehyde and/or -ketone of formula (I), the novel compounds 9-formyl-10-methylacridinium-p-toluene sulfonate and 9-((dimethylaminophenylimino)-methyl)-10-methylacridinium-methylsulfate being claimed per se. R<1> = H. 1-4C alkyl or aryl; R<2> - R<5> = H, halogen, 1-4C alkyl, hydroxyalkyl, alkoxy, hydroxyalkoxy or acyl, OH, NO2, sulfo or amino (optionally 1-4C alkyl-substituted), optionally with 2 such groups forming a condensed aromatic ring ; R<6> = H, 1-4C alkyl, hydroxyalkyl or aralkyl, 1-6C carboxy- or sulfo-alkyl, aryl, hetroaryl or negatively-charged oxygen, with R<6> and the positive charge on N optionally being omitted; and X = an anion, especially halide, sulfonate (eg benzene-, p-toluene-, methane- or trifluoro-sulfonate), Me- or Et-sulfate, perchlorate, (hydrogen)sulfate, tetrafluoroborate, tetrachlorozincate or alkanoate; with the provisos that X<-> is omitted when (i) R<6> = a negatively-charged O atom or the sulfo group for R<2> - R<5> or the 1-6C carboxy- or sulfo-alkyl group for R<6> is present as a sulfonate or carboxylate; or (ii) R<6> and the positive charge on N are not present

Description

The invention relates to an agent for dyeing keratin fibers, in particular human hair containing acridine aldehydes and / or ketones this compound as a coloring component in oxidation hair dye and a Process for dyeing keratin fibers, especially human hair.

For dyeing keratin fibers, e.g. B. hair, wool or furs come in general either direct dyes or oxidation dyes that are caused by oxidative coupling of one or more developer components with each other or with one or more coupler components are created for use. Coupler and Ent winder components are also referred to as oxidation dye precursors.

Primary aromatic amines with a. Are usually used as developer components further free or substituted hydroxy or in the para or ortho position Amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyra zolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

Special representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-Te traaminopyrimidine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-di aminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4- amino-pyrazolone-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-diaminopy rimidin and 2,5,6-triamino-4-hydroxypyrimidine.

As coupler components, m-phenylenediamine derivatives, naphthols, Resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives used. Suitable coupler substances are, in particular, α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, Resorcinol monomethyl ether, p-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-chloro sorcinol, 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, the "The matology ", edited by Ch. Culnan, H. Maibach, published by Marcel Dekker Inc., New York, Basel, 1986, vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, pages 248-250 (Direct dyes), and Chap. 8, pages 264-267 (oxidation dyes), and the "European inventory of cosmetic raw materials", 1996, published by the Euro pean commission, available in diskette form from the Federal Association of German Industrial and trading company for pharmaceuticals, health products and personal care products e. V., Mannheim, referred to.

With oxidation dyes intensive dyeings with good fastness properties can be achieved, 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 acridine aldehydes and / or ketones described below for Dyeing fibers containing keratin is not yet known.

The object of the present invention is to provide colorants for keratin fibers, in particular human hair, which are at least equivalent 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 those shown in the formula I. Acridine aldehydes and / or ketones are also present in the absence of oxidizing agents excellent for dyeing keratin fibers. They give color with excellent brilliance and depth of color and lead to diverse color nuances. The  However, the use of oxidizing agents should not be ruled out in principle become.

The invention relates to an agent for dyeing keratin fibers, in particular human hair, containing at least one acridine aldehyde and / or an acridine ketone with the formula I.

in the mean
R ^{1 represents} a hydrogen atom, a C _1-4 alkyl group or an aryl group,
R ² , R ³ , R ⁴ and R ⁵ , which may be the same or different, represent a hydrogen atom, halogen atom, a C ₁ -C ₄ alkyl group, C ₁ -C ₄ hydroxyalkyl group, C ₁ -C ₄ alkoxy group, C ₁ -C ₄ -hydroxyalkoxy group, hydroxy group, nitro group, sulfo group, amino group, which can be substituted by C ₁ -C ₄ alkyl groups, or a C ₁ -C ₄ acyl group, where two of the radicals together can form a fused aromatic ring .
where the groups COR ¹ , R ² , R ³ , R ⁴ and R ⁵ can be bound to any ring of the cyclic system,
R ^{6 is} a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₁ - C ₆ carboxyalkyl group, a C ₁ -C ₆ sulfoalkyl group, an aryl group, C ₁ -C ₄ - Aralkyl group, heteroaryl group or a negatively charged oxygen atom, where R ⁶ and the positive charge on the N atom can be omitted,
X ^- an anion, in particular halide, sulfonate, such as benzenesulfonate, p-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate, methyl sulfate, ethyl sulfate, perchlorate, sulfate, hydrogen sulfate, tetrafluoroborate or tetrachlorozincate, alkanoate,
where X ^{- is} omitted if R ^{6 represents} a negatively charged oxygen atom or the sulfo group for R ² , R ³ , R ⁴ and R ⁵ or the C ₁ -C ₆ carboxyalkyl group or C ₁ -C ₆ sulfoalkyl group for R ⁶ are present as sulfonate or carboxylate, or R ⁶ and the positive charge on the N atom are not present.

Wool, furs, feathers and especially human fibers are among the fibers containing keratin Understand hair. In principle, however, the colorants according to the invention can also for dyeing other natural fibers such as 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, poly urethane and polyester fibers are used.

The compounds with the formula I are largely known from the literature, commercially available or can be prepared by known synthetic methods. The formylacridinium ver bonds can e.g. B. easily from the acridinecarboxaldehydes by the expert known reactions with alkylating agents, such as alkyl halides, methanesulfonates, Trifluoromethanesulfonates, benzenesulfonates or p-toluenesulfonates can be produced.

The compounds of the formula I are preferably selected from acridine-1-carboxal dehyde, acridine-2-carboxaldehyde, acridine-3-carboxaldehyde, acridine-4-carboxaldehyde, acri din-9-carboxaldehyde, benz [c] acridine-7-carboxaldehyde, 1-formyl-10-methyl-acridinium, 2- Formyl-10-methyl-acridinium, 3-formyl-10-methyl-acridinium, 4-formyl-10-methyl-acri dinium, 9-formyl-10-methyl-acridinium, 9-formyl-2,10-dimethyl-acridinium, 9-formyl 10-ethyl-acridinium, 9-formyl-2-chloro-10-methyl-acridinium, 9-formyl-2-methoxy-10-me ethyl acridinium, 9-formyl-2-chloro-10-methyl-acridinium, 9-formyl-3,6-dichloro-10-methyl acridinium, 9-acetyl-10-methyl-acridinium, 9-benzoyl-10-methyl-acridinium iodide, bro mid, methyl sulfate, ethyl sulfate, p-toluenesulfonate, trifluoromethanesulfonate, methanesulfonate, -tetrafluoroborate, 9-formylacridine-N-oxide, 7-formyl-10-methylbenz [c] acridinium methyl sulfate as well as any mixtures thereof.

According to a preferred embodiment of the invention, the group COR ^{1 is arranged} in the 9 position of the acridine system.

The abovementioned acridine aldehydes and / or ketones with the formula I are preferably 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 applies. They can be used as direct colorants or in the presence of conventional ones Oxidation dye precursors are used.

Coloring agent, which as a coloring component acridine aldehydes and / or ketones with the For mel I alone, are preferably used for lighter colors. Stains with even greater brilliance and improved fastness properties (light fastness, washing fastness, fastness to rubbing) over a wide range of shades of brown are achieved, if the compounds of formula I used according to the invention together with  at least one further component (hereinafter referred to as component B), selected from compounds with primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing gene heterocyclic compounds and aromatic hydroxy compounds, amino acids, oligopeptides composed of 2 to 9 amino acids, and / or CH-active Connections. On the one hand, these are connections that stand alone Dye keratin fibers only weakly and only together with the compounds of Formula I give brilliant colors. On the other hand, there are also connections gene that are already used as oxidation dye precursors.

Several different acridine aldehydes and / or ke can also be used in all colorants tones of formula I are used together; Likewise, several ver different compounds of component B are used together.

The embodiment described above also includes the use of such substances, the reaction products of acridine aldehydes and / or ketones Represent formula I with the said compounds of component B as direct dyes. Such reaction products can e.g. B. by short Warm the two components in stoichiometric amounts in aqueous neutral to weakly alkaline medium can be obtained, either as a solid from the Precipitate solution or be isolated by evaporation of the solution. The Reaction products can also be used in combination with other dyes or Dye precursors are used.

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 dihydrobro mid, 2-, 3-, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o-toluenediamine, 2,5-diaminotoluene, -phenol, -phenol, 4-amino -3-methylphenol, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophen oxyethanol, 2- (2,5-diaminophenoxy) ethanol, 4-methylamino, 3-amino-4- (2 ' -hydroxyethyloxy) -, 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro, 4-methyl amino, 2-methyl-5-amino, 3-methyl-4 -amino-, 2-methyl-5- (2-hydroxyethylamino) -, 6-methyl-3-amino-2-chloro, 2-methyl-5-amino-4-chloro, 3,4-methylenedioxy, 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-hydroxybenzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino- 4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2, 7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4, 5-Triaminophenol, Pentaamino benzene, Hexaaminobenzene, 2,4,6-Triaminoresorcin, 4,5-Diaminobrenzcatechin, 4,6-Diami nopyrogallol, 3,5-Diamino-4-hydroxybrenzcatechin, 1,4-Bis- (4-aminophenyl ) -1,4-diazacy cloheptan, bis- (5-amino-2-hydroxyphenyl) methane, aromatic nitriles, nitro group-containing amino compounds, such as 3-amino-6-methylamino-2-nitro-pyridine, picramic acid, 1 - (2 (3) -Nitro-4-amino) -phenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloride, 1-Hy droxy-2-amino-4,6-dinitro-benzene, 1-amino-2-nit ro-4-bis (2-hydroxyethyl) amino-benzene, 1-amino-2- (2-hydroxyethyl) amino-5-nitro-benzene (HC Yellow No. 5), 1-amino-2-nitro -4- (2-hydroxyethyl) aminobenzene (HC Red No. 7), 2-chloro-5-nitro-N-hydroxyethyl-1,4-phenylene-diamine, 1- (2-hydroxyethyl) amino-2-nitro -4-amino-benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro-o-toluidine, 1-amino-3-methyl-4- (2nd -hydroxyethyl) -amino-6-nitrobenzene (HC Violet No. 1), 1-Amino-2-nitro-4- (2,3-dihydroxypropyl) -amino-5-chlorobenzene an (HC Red No. 10) , 4-amino-2-nitrodiphenylamino-2'-carboxylic acid (2- (4-amino-2-nitroanilino) benzoic acid), 6-nitro-2,5-diaminopyridine, 2-amino-6-chloro-4 nitrophenol, 2-amino-6-chloro-4-nitrophenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid, disodium salt (acid blue No. 29), 1-Amino-2- (2-hydroxy-4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid, disodium salt (Palatinchrome green), 1-amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo ) -8-naphthol-3,6-disulfonic acid, disodium salt (gallion), 4-amino-4'-nitrostilbene-2,2'-disulfonic acid, disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2-nitrobenzylideneamino) benzene, 2 - [2- (Diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino -1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, anilines, especially nitro group-containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2 - diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 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

in the R ⁷ for a hydroxyl or an amino group, which by C _1-4 alkyl, C _1-4 hydroxyalkyl, C _1-4 alkoxy or C _1-4 alkoxy-C _1-4 -alkyl groups can be substituted, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 represents} hydrogen, a hydroxy or an amino group which is substituted by C _1-4 alkyl, C _1-4 hydroxyalkyl, C _1-4 alkoxy, C _1-4 aminoalkyl or C _1-4 alkoxyC _1-4 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 hydroxyl groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula III

Z- (CH ₂ -Y-CH ₂ -Z ') _o (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 ¹³ group in which R ^{13 is} hydrogen, a C _1-4 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 and its hydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4-amino-4'-dimethylaminostilbene and its hydrochloride, 4, 4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, diphenyl ether, 3,3 ', 4,4'-tetraamino diphenyl, 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-pro panol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methylamine, N-phenyl-1,4-phenylenediamine.

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

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-dia mino-, 2,4,5-triamino-, 2,6-dihydroxy-3,4-dimethylpyridine, 2,4-dihydroxy-5,6-diamino-, 4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2-hydroxy-4,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methyl-pyrimi din, 3,5-diaminopyrazole, -1,2,4-triazole, 3-amino, 3-amino-5-hydroxypyrazole, 4,5-diamino 1- (2-hydroxyethyl) pyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquindin, 2-, 6-ami nonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-aminobenzimidazole, -benzo thiazole, 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. Farther heterocyclic compounds according to the invention are those in DE-U1-299 08 573 disclosed hydroxypyrimidines are used. The aforementioned connections can be used both in free form and in the form of their physiologically acceptable salts, e.g. B. can be used 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-di methylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, Phloroglucin, hydroxyhydroquinone, 2-, 3-, 4-methoxy, 3-dimethylamino, 2- (2-hydroxy ethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxybenzoic acid, -phenylacetic acid, Gallic acid, 2,4,6-trihydroxybenzoic acid, acetophenone, 2-, 4-chlororesorcinol, 1-naphth thol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfone acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

Preferred amino acids are all naturally occurring and synthetic α- Amino acids in question, e.g. B. by hydrolysis from plant or animal Proteins, e.g. B. collagen, keratin, casein, elastin, soy protein, wheat gluten or Almond protein accessible amino acids. It can be both acidic and alkaline reacting amino acids are used. Preferred amino acids are arginine, Histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and Tryptophan. But also other amino acids, such as. B. 6-aminocaproic acid be used.

The oligopeptides can be naturally occurring or synthetic oligopeptides, but also the oligopeptides contained in polypeptide or protein hydrolyzates far beyond a sufficient for use in the colorants of the invention  Have water solubility. As examples are e.g. B. glutathione or in the Hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or man To name delprotein contained oligopeptides. Use is preferred together with compounds with primary or secondary amino group or with aromati hydroxy compounds.

Examples of CH-active compounds which 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-di methyl benzothiazolium iodide, 2,3-dimethyl benzothiazolium p-toluenesulfonate, 1,2-dime ethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-methyl-2-quinaldinium iodide, 1-E thyl-2-quinaldinium iodide, 1,4-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, diethylthiobarbituric acid, Oxindole, 3-indoxy acetate, coumaranone, 1-methyl-3-phenyl-2-pyrazolinone, indan-1,3-dione, Indan-1-one and 1-dicyanomethylene indane.

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-diamino phenyl) ethanol, 2,5-diaminotoluene, 3,4-methylenedioxyaniline, 2-amino-4- (2-hydroxyethyl amino) 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-Me thyl-3-amino-2-chloro, 2-aminomethyl-4-aminophenol, 2-diethylaminomethyl-4-aminophe nol, 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 2-hydroxymes thyl-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-triami no-, 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, 4,5-diamino-1- (2-hydroxy ethyl) pyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline, β-alanine, L-proline, L-lysine, DL-tyrosine and their physiolo formed with preferably inorganic acids gisch compatible salts.

The above Compound B compounds can be used in an amount from 0.03 to 65, in particular 1 to 40 mmol, in each case based on 100 g of the total  Colorant can be used. Furthermore, it can be special according to the invention be preferred, the compound of formula I and the compound of component B in molar ratio of 2: 1 to 1: 4, in particular approximately equimolar. When using compounds of component B, one or more Containing amino groups, the compounds of formula I on the one hand and Compounds of component B, on the other hand, preferably in such proportions used that the sum of the number of carbonyl groups of the compounds of the formula I and the sum of the number of amino groups of the compounds of component B in Ratio 2: 1 to 1: 4 stand.

To obtain further and more intense colorations, the inventive Agents can also contain color enhancers. The color enhancers are preferred selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine 3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4- Hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrolidine, proline, pyrrolidone, pyrrole don-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazidine, their derivatives and their phy Siologically compatible salts.

The aforementioned color enhancers 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, be used.

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 to achieve the 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 further modification of the color shades in addition to the ver contained according to the invention bindings also usual direct dyes, for. B. from the group of nitro phenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as. B. the 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 Picramic acid 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphenylamine-2'-carbon acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis- (2'-hydroxyethylamino) -2-ni trobenzene hydrochloride and 1-methyl-3-nitro-4- (2'-hydroxyethyl) aminobenzene. The Agents according to the invention according to this embodiment contain the direct agents 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 occur in nature Dyes such as henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, Contain sedre and alkanna root.

It is not necessary that the oxidation dye precursors or contain them optionally direct substantive dyes each represent uniform compounds. Much more can in the colorants of the invention, due to the manufacturing process for the individual dyes, in minor quantities other components be included insofar as these do not adversely affect the coloring result or from on their reasons, e.g. B. toxicological, must be excluded.

The colorants according to the invention already result in those which are physiologically compatible Temperatures below 45 ° C intense coloring. They are therefore particularly suitable for coloring human hair. For use on human hair the colorants can usually be in a water-containing cosmetic carrier be worked. 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 are suitable. If necessary, it is also possible to put the colorants in anhydrous carriers incorporate.

Furthermore, the colorants according to the invention can all be in such preparations known active ingredients, additives and auxiliary substances. In many cases, the dye contains medium at least one surfactant, in principle both anionic and zwitterionic, Ampholytic, nonionic and cationic surfactants are suitable. In many cases but it has proven to be advantageous to use the surfactants from anionic, zwitterionic or select 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 and 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 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Monosulfonic succinate and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the Alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates with 12 to 18 carbon atoms,
• Linear alpha-olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulphated 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 bin solutions 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 on fatty alcohols with 8 to Represent 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-dimethylam monium 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 cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. 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, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and for the formation of internal salts are qualified. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-cocoalkyl aminopropionate, the cocoacylaminoethylaminopropionate and the 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

• - Adducts of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols with 8 to 22 carbon atoms, to fatty acids with 12 to 22 carbon atoms Atoms and on alkylphenols with 8 to 15 carbon 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 oligoglycosides and their ethoxylated analogs,
• - Adducts 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 cat usable in the hair treatment compositions according to the invention Ionic surfactants are especially quaternary ammonium compounds. Are preferred Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chloride and trialkylmethyl ammonium chloride, e.g. B. cetyltrimethylammonium chloride, Stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaterni are further cationic surfactants which can be used according to the invention protein hydrolyzates.

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized tri methylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino modified silicone, also called amodimethicone), SM-2059 (manufacturer ler: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines like the one under the name Tego Amid®S 18 available stearylamidopropyldimethylamine, stand out next to one good conditioning effect especially due to its good biodegradability.

Quaternary ester compounds are also very readily biodegradable "Esterquats", such as the methylhydroxy sold under the Stepantex® trademark alkyldialkoyloxyalkylammoniummethosulfate.

An example of a quaternary sugar derivative that can be used as a cationic surfactant is provided represents 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 act uniform substances. However, it is usually preferred in the manufacture  of these substances from natural plant or animal raw materials, so that mixtures of substances with different, depending on the respective raw material Maintains alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide Representing fatty alcohols or derivatives of these adducts, both Pro products with a "normal" homolog distribution as well as those with a narrowed Homolog distribution can be used. Under "normal" homolog distribution understood mixtures of homologues that are used in the implementation of Fettal alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Narrow homolog distributions who on the other hand, if, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates as catalysts be used. The use of products with a narrow homolog distribution can be preferred.

Other active ingredients, auxiliaries and additives are, for example

• Non-ionic 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-dimethyldiallyl ammonium chloride copolymers, dimethylaminoethyl quaternized with diethyl sulfate methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride Copolymers and quaternized polyvinyl alcohol,
• - zwitterionic and amphoteric polymers such as acrylamidopropyl-tri methylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacry lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid drid copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers,
• Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum ara bicum, karaya gum, locust bean gum, linseed gums, dextrans, cel lulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethylcel lulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as 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 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 as well as 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 Zink 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 walrus, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• - fatty acid,
• Complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerin, propylene glycol monoethyl ether, carbo nates, hydrogen carbonates, guanidines, ureas and primary, secondary and ter tertiary phosphates, imidazoles, tannins, pyrrole,
• Opacifiers such as latex,
• - pearlescent agents such as ethylene glycol mono- and distearate,
• - blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air and
• - antioxidants.

The constituents of the water-containing carrier are used for the production of the invention moderate colorants used in amounts customary for this purpose; z. B. become Emul yaw in concentrations of 0.5 to 30% by weight and thickeners in conc trations of 0.1 to 25 wt .-% of the total colorant used.

For the coloring result it can be advantageous to use ammonium or metal as coloring agents add salts. 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 ammonium, 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, wherein Sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, Magnesium chloride, magnesium sulfate, ammonium carbonate, chloride and acetate are preferred are. These salts are preferably in an amount of 0.03 to 65, especially 1 to 40, mmol based on 100 g of the total colorant.

The pH value of the ready-to-use coloring preparations is usually between 2 and 11, preferably between 5 and 10.

The present invention further relates to the use of acridine aldehydes and / or ketones having the formula I,

in which R ¹ , R ² , R ³ , R ⁴ , R ⁶ and X ^- as defined above, as a coloring component in oxidation hair colorants.

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

• A) at least one acridine aldehyde and / or an acridine ketone with the formula I,
  in which R ¹ , R ² , R ³ , R ⁴ , R ⁶ and X ^{- are} as defined above, and
• B) at least one compound with primary or secondary amino group or Hy droxy group selected from primary or secondary aliphatic or aroma table amines, nitrogen-containing heterocyclic compounds, aromatic Hydroxy compounds, amino acids, oli composed of 2 to 9 amino acids gopeptides and / or at least one CH-active compound,

as well as usual cosmetic ingredients, applied to the keratin fibers, ei Leave some time, usually about 30 minutes, on the fiber and then again rinsed out or washed out with a shampoo.

The acridine aldehydes and / or ketones of the formula I and the compounds of com component B can either be applied to the hair simultaneously or else one after the other, it doesn't matter which of the two components comes first is applied. The optionally contained ammonium or metal salts can be added to the first or the second component. Between applying the The first and second components can be up to 30 minutes apart. Also pretreatment of the fibers with the saline solution is possible.

The acridine aldehydes and / or ketones of the formula I and the compounds of com Component B can either be stored separately or together, either in one liquid to pasty preparation (aqueous or anhydrous) or as a dry powder. If the components are stored together in a liquid preparation, it should these are largely anhydrous to reduce a reaction of the components. at the separate storage, the reactive components are only immediately before Application intimately mixed together. In dry storage, before Usually use a defined amount of warm (30 to 80 ° C) water added and made a homogeneous mixture.

Another object of the present invention relates to 9-formyl-10-methylacri dinium p-toluene sulfonate.

Yet another subject relates to 10 - [(4-dimethylaminophenylimino) methyl] -9- acridinium methyl sulfate.  

Examples Production of the connections used I. 9-Formyl-10-methylacridinium p-toluenesulfonate

A mixture of 8.1 g (39.1 mmol) acridine-9-carboxaldehyde, 10.9 g (58.6 mmol) p- Toluene sulfonic acid methyl ester and 50 ml of toluene were boiled for 12 hours with stirring heated. After cooling to room temperature, the resinous product decanted, the residue washed hot with tert-butyl methyl ether and in Vacuum dried over sulfuric acid. 6.0 g (39% of theory) of resinous, Hygroscopic 9-formyl-10-methylacridinium p-toluenesulfonate obtained.

II. 9 - [(4-Dimethylaminophenylimino) methyl] -10-methylacridinium methyl sulfate a) 9,10-dimethylacridinium methyl sulfate

A mixture of 4.0 g (20.7 mmol) of 9-methyl acridine, 2.9 g (22.8 mmol) of dimethyl sulfate and 50 ml of toluene was heated to boiling with stirring for 16 hours. After cooling down The crystalline product was filtered off at room temperature, washed with toluene and in Vacuum dried over sulfuric acid. 5.1 g (77% of theory) of yellowish 9.10 Dimethylacridinium methyl sulfate obtained with a melting point of 233-236 ° C.

b) 9 - [(4-Dimethylaminophenylimino) methyl] -10-methylacridinium methyl sulfate

A mixture of 5.1 g (16 mmol) 9,10-dimethylacridinium methyl sulfate, 2.6 g (18 mmol N, N-dimethyl-p-nitrosoaniline, 1.4 g (16 mmol) of piperidine and 30 ml of ethanol were treated for 4 hours. stirred at room temperature, the precipitate with a little ethanol and then washed out with tert-butyl methyl ether and over in vacuo Dried sulfuric acid. 1.5 g (21% of theory) of dark brown 10 - [(4- Dimethylaminophenylimino) methyl] -9-methylacridinium methyl sulfate with a melt temperature of 165 ° C.  

Preparation of a coloring solution

There was a slurry of 5 mmol of an acridine aldehyde and / or ketone Formula I, optionally 5 mmol of an oxidation dye precursor of component B or a reaction product of a compound of formula I and one Oxidation dye intermediate (component B), 5 mmol sodium acetate and a drop a 20% fatty alkyl ether sulfate solution in 50 ml of water at 50 ° C. The Slurries were mixed together after cooling to 30 ° C and mixed with ver thinned hydrochloric acid to a pH of 6.

A tress of 90% was grayed into this dyeing mixture at 30 ° C. for 30 minutes, untreated human hair. The streak was then with 30 sec lukewarm water rinsed, dried with warm air and then combed out.

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

The color depth was rated on the following scale:
-: no or very pale color
(+): weak intensity
+: medium intensity
+ (+): medium to strong intensity
++: strong intensity
++ (+): strong to very strong intensity
+++: very strong intensity

Table 1

Colorings with 9-formyl-10-methylacridinium p-toluenesulfonate

Colorings with 9 - [(4-dimethylaminophenylimino) methyl] -10-methylacridinium methyl sulfate (reaction product of 9,10-dimethylacridinium methyl sulfate and N, N-dimethyl-p-nitrosoaniline)

Claims (16)

1. Agent for dyeing keratin-containing fibers, in particular human hair, containing at least one acridine aldehyde and / or an acridine ketone with the formula I as the coloring component,
in the mean
R ^{1 represents} a hydrogen atom, a C _1-4 alkyl group or an aryl group,
R ² , R ³ , R ⁴ and R ⁵ , which may be the same or different, are a hydrogen atom, halogen atom, a C ₁ -C ₄ alkyl group, C ₁ -C ₄ hydroxyalkyl group, C ₁ -C ₄ alkoxy group, C ₁ -C ₄ -hydroxyalkoxy group, hydroxy group, nitro group, sulfo group, amino group, which can be substituted by C ₁ -C ₄ alkyl groups, or a C ₁ -C ₄ acyl group, where two of the radicals together can form a fused aromatic ring .
where the groups COR ¹ , R ² , R ³ , R ⁴ and R ⁵ can be bound to any ring of the cyclic system,
R ^{6 is} a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₁ -C ₆ carboxyalkyl group, a C ₁ -C ₆ sulfoalkyl group, an aryl group, C ₁ -C ₄ - Aralkyl group, heteroaryl group or a negatively charged oxygen atom, wherein
R ⁶ and the positive charge on the N atom can be omitted,
X ^- an anion, in particular halide, sulfonate, such as benzenesulfonate, p-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate, methyl sulfate, ethyl sulfate, perchlorate, sulfate, hydrogen sulfate, tetrafluoroborate or tetrachlorozincate, alkanoate,
where X ^{- is} omitted if R ^{6 represents} a negatively charged oxygen atom or the sulfo group for R ² , R ³ , R ⁴ and R ⁵ or the C ₁ -C ₆ carboxyalkyl group or C ₁ -C ₆ sulfoalkyl group for R ⁶ are present as sulfonate or carboxylate, or R ⁶ and the positive charge on the N atom are not present. 2. Composition according to claim 1, characterized in that as connections to the Formula I acridine-1-carboxaldehyde, acridine-2-carboxaldehyde, acridine-3-carboxaldehyde, Acridine-4-carboxaldehyde, acridine-9-carboxaldehyde, benz [c] acridine-7-carboxaldehyde, 1-formyl-10-methyl-acridinium, 2-formyl-10-methyl-acridinium, 3-formyl-10-methyl acridinium, 4-formyl-10-methyl-acridinium, 9-formyl-10-methyl-acridinium, 9-  Formyl-2,10-dimethyl-acridinium-, 9-formyl-10-ethyl-acridinium-, 9-formyl-2-chloro-10- methyl acridinium, 9-formyl-2-methoxy-10-methyl-acridinium, 9-formyl-2-chloro-10- methyl-acridinium-, 9-formyl-3,6-dichloro-10-methyl-acridinium-, 9-acetyl-10-methyl- acridinium, 9-benzoyl-10-methyl-acridinium iodide, bromide, methyl sulfate, ethyl sulfate, p-toluenesulfonate, trifluoromethanesulfonate, methanesulfonate, tetrafluoroborate, 9-formyl acridin-N-oxide, 7-formyl-10-methylbenz [c] acridinium methyl sulfate and their any mixtures can be used. 3. Composition according to one of claims 1 or 2, characterized in that the group COR ^{1 is arranged} in the 9 position of the acridine system. 4. Composition according to one of claims 1 to 3, characterized in that the Acridine aldehydes and / or ketones of 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 included. 5. Composition according to one of claims 1 to 4, characterized in that it is additional Lich at least one compound with a primary or secondary amino group or Hydroxyl group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxyverbin doses, amino acids and oligopeptides composed of 2 to 9 amino acids, and / or contains at least one CH-active compound. 6. Composition according to claim 5, 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-phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2,5-dihydroxy- 4-Morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenyl) ethanol, 2,5-diaminotoluene , -phenol, - phenethol, 4-methylamino-, 3-amino-4- (2'-hydroxyethyloxy) -, 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4-methylamino, 2-methyl-5-amino, 3-methyl-4-amino, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-4-chloro, 6 - Methyl-3-amino-2-chloro, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl, 4-amino-2-aminomethyl-phenol, 2-hydroxymethyl-4-aminophenol, 2-diethylaminomethyl -4- aminophenol, 2-dimethylaminomethyl-4-aminophenol, 2,6-dichloro-4-aminophenol, 1,3-di amino-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-A mino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3 -Amino phthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraami nobenzene-tetrahydrochloride, 2,4,5-triaminophenol-trihydrochloride, pentaaminobenzene-pentahydrochloride, Hexaaminobenzene hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminobenzene catechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxybenzate catechol sulfate, 1,4-bis- (4- aminophenyl) -1,4-diazacyclo heptane, bis (5-amino-2-hydroxyphenyl) methane, aromatic nitriles, aminov containing nitro groups compounds such as 3-amino-6-methylamino-2-nitro-pyridine, picraminic acid, 1- (2 (3) -nitro-4-amino) -phenylazo-2-hydroxy-7-trimethylammoniumnaphthalene chloride, 1-hydroxy- 2-amino-4,6-dinitro-benzene, 1-amino-2-nitro-4-bis (2-hydroxyethyl) amino-benzene, 1-amino-2- (2-hydroxyethyl) amino-5- nitro-benzene (HC Yellow No. 5), 1-amino-2-nitro-4- (2-hydroxyethyl) aminobenzene (HC Red No. 7), 2-chloro-5-nitro-N-hydroxyethyl-1, 4-phenylenediamine, 1- (2-hydroxyethyl) amino-2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro -o-toluidine, 1-amino-3-methyl-4- (2-hydroxyethyl) amino-6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4- (2,3-dihydroxypropyl ) -amino-5-chlorobenzene an (HC Red No. 10), 4-amino-2-nitrodiphenyl-amino-2'-carboxylic acid (2- (4-amino-2-nitroanilino) -benzoic acid), 6-nitro- 2,5-diaminopyridine, 2-amino-6-chloro-4-nitrophenol, 2-amino-6-chloro-4-nitro phenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol -3,6-disulfonic acid, disodium salt (acid blue No. 29), 1-amino-2- (2-hydroxy-4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid, disodium salt (Palatinchrome green), 1-amino-2- (3-chloro-2- hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid, disodium salt (gallion), 4-amino-4'-nitrostilbene-2,2'-disulfonic acid, disodium salt, 2,4-diamino-3 ', 5 'dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1-amino -4-nitro-2- (2-nitrobenzylidenamino) benzene, 2- [2- (diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'- nitrobiphenyl, 3-amino-4-nitro acenaphthene, 2-amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, anilines, especially anilines containing nitro groups, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 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 Anilines, in particular nitro group-containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 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 resp Phenols with a further aromatic radical such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid, Na salt, 4,4'-diaminodiphenylmethane, sulfide, sulfoxide, amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl tetrahydrochloride, 3,3', 4,4'-tetraamino-benzophenone , 1,3-bis (2,4-diaminophenoxy) propa n-tetrahydrochloride, 1,8-bis (2,5-diaminophen oxy) -3,6-dioxaoctane-tetrahydrochloride, 1,3-bis (4-aminophenylamino) propane, -2-per panol, 1,3 - bis [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-a minophenoxy) 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-dia mino, 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, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 2-, 3-, 8-aminoquinoline, 4-aminoquininaldine, 2-, 6-amino nicotinic acid, 5-aminoisoquinoline, 5- , 6-aminoindazole, 5-, 7-amino-benzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline as well as indole and indoline derivatives, such as 4-, 5-, 6-, 7-aminoindole, 4-, 5 -, 6-, 7-hydroxyindole, 5,6-dihydroxyindole, 5,6-dihydroxyi ndoline, 4-hydroxyindoline and the hydroxypyrimidines disclosed in DE-U1-299 08 573, and in each case from the physiologically tolerable salts of these compounds formed with preferably inorganic acids,
aromatic hydroxy compounds selected from the group consisting of 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechin, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4- Methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl) -, 3,4-methylenedioxyphenol, 2,4-, 3,4-dihydroxy benzoic 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- naphthalene sulfonic acid,
Amino acids selected from the group arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan,
Oligopeptide selected from glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein,
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, 1,2- Dimethylnaphtho [1,2-d] thiazolium p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1,2-d] thiazolium 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-indoxy acetate, coumaranone, 1-methyl-3-phenyl-2-pyrazolinone, indan-1,3-dione, indan-1-one, 1-dicyanomethylene indane. 7. Means according to claim 6, characterized in that the further connection 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-methylenedi oxyaniline, 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-hydro xyethylamino) -, 2-methyl-5-amino-4-chloro, 6-methyl-3-amino-2-chloro, 2-amino thyl-4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-dimethylaminomethyl-4- aminophenol, 2,6-dichloro-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-Hy droxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 4,5-diamino-1- (2-hydroxyethyl) - pyrazole, 5,6-dihydroxyindole and 5,6-dihydroxyindoline, β-alanine, L-proline, L-lysine, DL-  Tyrosine and in each case from those preferably formed with inorganic acids physiologically acceptable salts of these compounds. 8. Agent according to one of claims 1 to 7, characterized in that it Color enhancer selected from the group consisting of piperidine, piperidine-2-car bonic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyri din, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrole din, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazidine or any mixtures thereof. 9. Agent according to one of claims 1 to 8, characterized in that it is direct pulling dyes from the group of nitrophenylenediamines, nitroaminophenols, Anthraquinones or indophenols preferably in an amount of 0.01 to 20% by weight %, based on the total colorant. 10. Agent according to one of claims 1 to 9, characterized in that it is ammo nium or metal salts selected from the group of formates, carbonates, halo genides, sulfates, butyrates, valerates, capronates, acetates, lactates, glycolates, tartrates, Citrates, gluconates, propionates, phosphates and phosphonates of ammonium, from 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. 11. Agent according to one of claims 1 to 10, 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. 12. Composition according to one of claims 1 to 11, characterized in that it contains anionic, zwitterionic or nonionic surfactants. 13. Use of acridine aldehydes and / or an acridine ketone with the formula I.
in the mean
R ^{1 represents} a hydrogen atom, a C _1-4 alkyl group or an aryl group,
R ² , R ³ , R ⁴ and R ⁵ , which may be the same or different, are a hydrogen atom, halogen atom, a C ₁ -C ₄ alkyl group, C ₁ -C ₄ hydroxyalkyl group, C ₁ -C ₄ alkoxy group, C ₁ -C ₄ -hydroxyalkoxy group, hydroxy group, nitro group, sulfo group, amino group, which can be substituted by C ₁ -C ₄ alkyl groups, or a C ₁ -C ₄ acyl group, where two of the radicals together can form a fused aromatic ring .
where the groups COR ¹ , R ² , R ³ , R ⁴ and R ⁵ can be bound to any ring of the cyclic system,
R ^{6 is} a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₁ -C ₆ carboxyalkyl group, a C ₁ -C ₆ sulfoalkyl group, an aryl group, C ₁ -C ₄ - Aralkyl group, heteroaryl group or a negatively charged oxygen atom, wherein
R ⁶ and the positive charge on the N atom can be omitted,
X ^- an anion, in particular halide, sulfonate, such as benzenesulfonate, p-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate, methyl sulfate, ethyl sulfate, perchlorate, sulfate, hydrogen sulfate, tetrafluoroborate or tetrachlorozincate, alkanoate,
where X ^{- is} omitted if R ^{6 represents} a negatively charged oxygen atom or the sulfo group for R ² , R ³ , R ⁴ and R ⁵ or the C ₁ -C ₆ carboxyalkyl group or C ₁ -C ₆ sulfoalkyl group for R ⁶ are present as sulfonate or carboxylate, or R ⁶ and the positive charge on the N atom are not present. 14. A method for dyeing keratin fibers, in particular human hair, in which a colorant containing

• A) at least one acridine aldehyde and / or an acridine ketone with the formula I.
  in the mean
  R ^{1 represents} a hydrogen atom, a C _1-4 alkyl group or an aryl group,
  R ² , R ³ , R ⁴ and R ⁵ , which may be the same or different, are a hydrogen atom, halogen atom, a C ₁ -C ₄ alkyl group, C ₁ -C ₄ hydroxyalkyl group, C ₁ -C ₄ alkoxy group, C ₁ -C ₄ -hydroxyalkoxy group, hydroxy group, nitro group, sulfo group, amino group, which can be substituted by C ₁ -C ₄ alkyl groups, or a C ₁ -C ₄ acyl group, where two of the radicals together can form a fused aromatic ring .
  where the groups COR ¹ , R ² , R ³ , R ⁴ and R ⁵ can be bound to any ring of the cyclic system,
  R ^{6 is} a hydrogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₁ -C ₆ carboxyalkyl group, a C ₁ -C ₆ sulfoalkyl group, an aryl group, C ₁ -C ₄ - Aralkyl group, heteroaryl group or a negatively charged oxygen atom, where R ⁶ and the positive charge on the N atom can be omitted,
  X ^- an anion, in particular halide, sulfonate such as benzenesulfonate, p-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate, methyl sulfate, ethyl sulfate, perchlorate, sulfate, hydrogen sulfate, tetrafluoroborate or tetrachlorozincate, alkanoate,
  where X ^{- is} omitted if R ^{5 stands} for a negatively charged oxygen atom or the sulfo group for R ² , R ³ , R ⁴ and R ⁵ or the C ₁ -C ₆ carboxyalkyl group or C ₁ -C ₆ sulfoalkyl group for R ⁶ are present as sulfonate or carboxylate, or R ⁵ and the positive charge on the N atom are not present,
  and
• B) at least one compound having a primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, amino acids, oligonucleotides 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, left on the fiber for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo. 15. 9-Formyl-10-methylacridinium p-toluenesulfonate. 16. 9 - [(Dimethylaminophenylimino) methyl] -10-methylacridinium methyl sulfate.