EP1434560A1 - Method for dyeing and subsequent bleaching of hair - Google Patents

Abstract

The invention concerns a kit and a corresponding method for dyeing and subsequent bleaching of keratinous fibres, in particular human hair. Said method consists in: (P1a) applying on the keratinous fibres a dyeing agent containing at least a carbonyl compound (constituent A) and at least a compound with primary or secondary amino group (constituent B), selected among primary or secondary aliphatic or aromatic amines, nitrogenous heterocyclic compounds and oligopeptides consisting of 2 to 9 amino acids, (P1b) leaving said dyeing agent on the keratinous fibres for 5 to 45 minutes for producing its effect, then (P1c) rinsing or removing with a shampoo. Said method also comprises a bleaching process (P2), carried out immediately after dyeing or after a period of time. Said process consists in (P2a) applying on the keratinous fibres a bleaching agent containing at least a compound selected among a sulphur compound, an alpha -oxocarboxylic acid, an aldehyde or a reductone, (P2b) allowing the bleaching agent to produce its effect for 5 to 60 minutes on the fibres, then (P2c) rinsing the fibres.

Description

 "Process for dyeing and later decoloring hair"

The invention relates to a method and a kit for dyeing and later decolorizing keratin fibers, in particular human hair, and the use of decolorizing agents for removing oxy-dyeings from the keratin fiber.

The dyeing of keratin fibers, e.g. B. hair, wool or furs can be carried out in the conventional sense either with direct dyes or with oxidation dyes. The color pigments result from the oxidative coupling of one or more developer components with one another or with one or more coupler components. Coupler and developer components are also referred to as oxidation dye precursors. The oxidation is mostly caused by an oxidizing agent such as H ₂ O ₂ , the frequent use of which can damage the structure of the hair fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on people with sensitive skin.

Recently, new coloring principles for keratin fibers have become known, which achieve at least a color result comparable to that of oxidation hair colors, without necessarily being dependent on oxidizing agents. The above-mentioned undesirable effects of the oxidizing agent or the oxidation dye precursors do not occur with these dyeings.

In this context, hair coloring with certain carbonyl components in combination with compounds with primary or secondary amino group or hydroxy group, aromatic hydroxy compounds and / or at least one CH-acidic compound is considered a new coloring principle. Corresponding agents for coloring hair are disclosed, for example, in publication WO 00/38633. A dyeing according to this new dyeing principle is referred to below as oxo dyeing.

With regard to other conventional dye components, reference is expressly made to the “Dermatology” series, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Gare, Chapter 7, pages 248 - 250 (direct dyes) and Chapter 8, pages 264 - 267 (oxidation dyes) and the "European Inventory of Cosmetic Raw Materials", 1996, published by the European Commission, available in diskette form from the Federal Association of German Industry and Commerce for Medicines, Reformed Products and Personal Care Products, Mannheim.

Generally, colorations can be divided into three categories, permanent, semi-permanent and temporary. Oxidation hair colors cause e.g. permanent coloring of the hair. The color result is very durable and practically cannot be removed by washing your hair.

Direct dyes give the hair a semi-permanent to temporary

Coloring. Semi-permanent dyeings can be removed from the hair fiber with approx. 2-10 hair washes, temporary dyeings can be removed by washing the hair.

The oxo dyeings are almost permanent and can be removed with 25-35 washes.

Often, the consumer demands genuine, fashionable dyeings that do not damage the fiber structure and can be completely removed from the fiber in one procedure at the request of the user. In addition, it is important to the consumer that the natural color pigments are not impaired during the decoloration so that the original hair color is restored.

Decolorants and corresponding oxidative or reductive processes for decoloring hair colorations or tints are known to the person skilled in the art.

The publication DE 197 37 987 C1 discloses sulfur-containing agents for the reductive decolorization of hair which have been dyed with substantive dyes.

Furthermore, WO 98/22078 and EP 943316 A2 describe processes and agents used therein for reductive decolorization of hair colorations. In addition to dyeing with direct dyes, the decolourable hair dyeings are also permanent dyeings with oxidation dyes. WO 01/28507 describes a multi-component kit for dyeing and decoloring dyeings. The colorations are achieved with a hair dye containing aldehydes or ketones in combination with CH-acidic compounds.

Although the known methods cause visible discoloration, there is often a slight coloration of the hair. In some cases, an undesirable shift in shades can be observed after decolorization. The conventional methods are therefore in need of improvement in terms of decolorization.

The object of the present invention is to provide a method by means of which dyeings are obtained which are qualitatively at least equivalent in terms of color depth, gray coverage and fastness properties in comparison with conventional oxidation hair dyeing agents, but without necessarily relying on oxidizing agents such as H ₂ O ₂ to be. The hair fiber is less damaged. A further object of the present invention is to remove the dyeing according to the invention obtained from the keratin fiber more effectively without degenerating the natural hair pigments and without achieving a shift in shades.

It has surprisingly been found that oxo dyeings which are obtained with aldehydes or ketones in combination with amine compounds can be removed from the keratin fiber to an excellent degree by means of reductive decolorization. The decolorization achieved is an improvement over the results of the conventional processes.

The present invention therefore relates to a process for dyeing and later decolorizing keratin fibers, in particular human hair, characterized in that in a dyeing procedure P1

• Pia) a colorant containing at least one carbonyl compound (component A) and at least one compound (component B) with a primary or secondary amino group selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids and from 2 to 9 Amino acids built oligopeptides, applied to the keratin fiber,

• P1 b) leave on the keratin fiber for 5 - 45 minutes and

• P1c) is then rinsed off or washed out with a shampoo

and immediately or after a longer period in a decolorization procedure P2

P2a) a decolorizing agent comprising at least one compound selected from a sulfur-containing compound, an α-oxocarboxylic acid, an aldehyde or a reductone applied to the fiber,

• P2b) leave on the fiber for 5-60 minutes and

• P2c) is rinsed from the fiber.

In a special embodiment of the method according to the invention, a further decolorization procedure P3 follows after procedure P2, in which

• P3a) another decolorizing agent containing at least one compound selected from a sulfur-containing compound, an α-oxocarboxylic acid, an aldehyde or a reductone applied to the fiber, β P3b) left on the fiber for 5-60 minutes and

• P3c) is rinsed from the fiber.

It is preferred to carry out the decolorization procedure P3 immediately after the decolorization procedure P2.

In a preferred embodiment, the colorant contains at least one carbonyl compound of the formula I

(L)

in which

(a) R ¹ represents a group -CHO or

(b) R ³ represents a group -CO-R ⁶ , in which R ⁶ represents hydrogen, a CC ₄ - alkyl group, an aryl group or a heteroaryl group, with the proviso that according to (a) R ² , R ³ and R ⁴ or according to (b) R, R ² and R ⁴ independently of one another represent a hydrogen atom, a halogen atom, a CC ₄ alkyl group, a CC ₄ alkoxy group, a hydroxy-C C alkoxy group, a hydroxy group, a nitro group , an amino group which can be substituted by CrC ^ alkyl groups, or a -C-C ₄ acyl group, where two of the radicals together can form a fused benzene ring,

R ⁵ is an oxygen atom, a CrC ^ alkyl group, a C ₂ -C ₄ - alkenyl group, a C | -C ₄ acyl group, an aryl group, an aryl Cι-C ₄ - alkyl group or a heteroaryl group,

A is omitted if R ^{5 is} oxygen and is a halide, benzenesulfonate, tetrafluoroborate, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogen sulfate or tetrachlorozincate.

Examples of CrC alkyl groups in the compounds according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. Preferred alkyl groups are methyl and ethyl, methyl is a particularly preferred alkyl group. Preferred CC acyl groups are, for example, acetyl, propionyl and butyryl. Methoxy, ethoxy, propoxy and butoxy are examples of preferred -CC alkoxy groups, a particularly preferred alkoxy group is the methoxy group. Preferred hydroxy-CrC ₄ - alkoxy groups are 2-hydroxyethyloxy and 3-hydroxypropyloxy. Vinyl, allyl and 3-buten-1-yl are preferred C -C alkenyl groups. Examples of preferred Aryl-CrC ₄ - alkyl groups are benzyl, 2-phenylethyl and naphthylmethyl. Benzyl is particularly preferred. Preferred heteroaryl groups are 5-, 6- and 7-membered aromatic heterocycles with 1 to 3 heteroatoms, which are selected from nitrogen, oxygen and sulfur. Preferred aryl groups are, for example, phenyl, naphthyl and biphenyl, phenyl is a particularly preferred aryl group. According to the invention, suitable halogen substituents are preferably fluorine, chlorine, bromine and iodine, and chlorine and bromine are particularly preferred. According to the invention, the other terms used are derived from the definitions given here.

In a particularly preferred embodiment of the colorant used in the process according to the invention, the carbonyl compound of the formula I is selected from 2-formyl-1-methyl-quinolinium-, 4-formyl-1-methyl-quinolinium-, 5-formyl-1-methyl- quinolinium-, 6-formyl-1-methyl-quinolinium-, 7-formyl-1-methyl-quinolinium-, 8-formyl-1-methyl-quinolinium-, 5-formyl-1-ethyl-quinolinium-, 6-formyl -1-ethyl-quinolinium, 7-formyl-1-ethyl-quinolinium, 8-formyl-1-ethyl-quinolinium, 5-formyl-1-benzyl-quinolinium, 6-formyl-1-benzyl-quinolinium -, 7-formyl-1-benzyl-quinolinium-, 8-formyl-1-benzyl-quinolinium-, 5-formyl-1-allyl-quinolinium-, 6-formyl-1-allyl-quinolinium-, 7-formyl- 1-allyl-quinolinium-, 8-formyl-1-allyl-quinolinium-, 5-acetyl-1-methyl-quinolinium-, 6-acetyl-1-methyl-quinolinium-, 7-acetyl-1-methyl-quinolinium-, 8 - Formyl-1-acetyl-quinolinium, 9-formyl-10-methylacridinium salts with the counterions selected from benzenesulfonate, tetrafluoroborate, p-toluene olsulfonate, methanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, chloride, bromide, iodide and tetrachlorozincate.

Several different carbonyl compounds can also be used together in the process according to the invention. The selection of these carbonyl compounds is in no way limited to the compounds of the formula I. Carbonyl compounds which are selected from the group that is formed from 1-methyl-5-oxo-indeno [1,2-b] pyridinium trifluoromethanesulfonate and from the carbonyl compounds used in the publications mentioned below are also preferred according to the invention which is expressly referred to here:

Isatin and isatin derivatives according to formula (I) of WO-A -94/24988, in particular the base body isatin, Isatin derivatives containing sulfo or carboxyl groups according to formula (I) of WO-A1-94 / 24989, in particular isatin-5-sulfonic acid,

Isatin derivatives according to formula (I) of WO-A1 -95/24886, in particular N-allyl isatin,

• Onium aldehydes and ketones according to WO-A2-99 / 18916, in particular 2-formyl-1-methylpyridinium-benzenesulfonate and 4-benzoyl-1-methyl-pyridinium-methanesulfonate, and

Aromatic nitro aldehydes according to WO-A1-00 / 38634, in particular 2,4-dinitrobenzaldehyde.

The carbonyl compounds are usually used in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the total colorant.

The carbonyl compounds used according to the invention are used together with at least one further component (component B), selected from compounds having primary or secondary amino groups, which in turn are selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides composed of 2 to 9 amino acids , On the one hand, these are compounds which, on their own, stain keratin-containing fibers only weakly and only produce brilliant colors together with the carbonyl compounds. On the other hand, there are also compounds that are already used as oxidation dye precursors.

Several different compounds of component B can also be used together.

The embodiment described above also includes the use of such substances as substantive colorants which are reaction products from the chemical reaction of the carbonyl compounds according to the invention with the compounds of component B. Such reaction products can e.g. B. can be obtained by briefly heating the two reactants in stoichiometric amounts in an aqueous neutral to weakly alkaline medium, they either precipitate out of solution as a solid or by evaporation of the solution therefrom be isolated. The reaction products can also be used in combination with other dyes or dye precursors.

Suitable compounds with primary or secondary amino group as component B are e.g. B. primary aromatic amines such as N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p-pheny! Endiamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4-dichloro-p-phenylenediamine, 2,5-dichloro-p- phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o- Phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, 2,5, - diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethole, 4-amino-3-methylphenol, 2- (2,5- Diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 3-amino-4- (2-hydroxyethyloxy) phenol, 3,4-methylenedioxyaniline, 3-amino-2,4- dichlorophenol, 4-amino-2,6-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 3-amino - no-2-chloro-6-methylphenol, 2-meth yI-5-amino-4-chlorophenol, 5- (2-hydroxyethylamino) -4- methoxy-2-methylphenol, 4-amino-2-hydroxymethylphenol, 2- (diethylaminomethyl) -4- aminophenol, 4-amino-1 - hydroxy-2- (2-hydroxyethylaminomethyl) benzene, 1-hydroxy-2-amino-5-methyl-benzene, 1-hydroxy-2-amino-6-methyl-benzene, 2-amino-5-acetamido-phenol, 1,3-dimethyl-2,5-diaminobenzene, 5- (3-hydroxypropylamino) 2-methylphenol, 5-amino-4-methoxy-2-methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl- 3-aminophenol, 5-amino-4-fluoro-2-methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino-5- (2-hydroxyethoxy) toluene, 2,4-diamino-5- methylphenetol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) anisole, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene, 1,3- Diamino-2,4-dimethoxybenzene, 3,5-diamino-2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenylacetic acid, 3-aminophenylacetic acid, 4-aminophenylacetic acid, 2,3- Diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenz oic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3-amino-4-hydroxy-benzoic acid, 4-amino-3-hydroxy-benzoic acid, 2-aminobenzenesulfonic acid, 3 -Aminobenzenesulfonic acid, 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-triaminobenzene, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6- Triaminoresorcinol, 4,5-diamino-catechol, 4,6-diaminopyrogallol, 1- (2-hydroxy-5-aminobenzyl) -2-imidazolidinone, 4-amino-2 - ((4 - [(5-amino-2- hydroxyphenyl) methyl] - piperazinyl) methyl) phenol, 3,5-diamino-4-hydroxycatechol, 1,4-bis (4-aminophenyl) -1,4-diazacycloheptane, aromatic nitriles such as 2-amino-4-hydroxy - benzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile, nitro group-containing amino compounds, such as 3-amino-6-methylamino-2-nitro-pyridine, picraminic acid, [8 - [(4- Amino-2-nitrophenyl) -azo] -7-hydroxy-naphth-2-yl] - trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) -azo) -7-hydroxy-naphth-2-yl] trimethylammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-amino-2-nitro-4- [bis- (2-hydroxyethyl) amino] benzene, 1-amino-2 - [(2-hydroxyethyl) amino] - 5-nitrobenzene (HC Yellow No. 5), 1-amino-2-nitro-4 - [(2-hydroxyethyl) amino] -benzoI (HC Red No. 7), 2-chloro-5-nitro-N-2-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-chlorine - benzene (HC Red No. 10), 2- (4-amino-2-nitroanilino) benzoic acid, 6-nitro-2,5-diaminopyridine, 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-nitrobenzylidenamino) benzene, 2- [2- (diethylamino) e thylamino] -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, 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-a-mino-4- [bis- (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, aromatic Anilines or phenols with a further aromatic radical, as represented in the formula II

(II)

in the

R ^{7 represents} a hydroxyl or an amino group which can be substituted by C _1-4 alkyl, C _1- hydroxyalkyl, C _1-4 alkoxy or C _1-4 alkoxy-d ^ alkyl groups,

R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² independently of one another for a hydrogen atom, a hydroxyl or an amino group, which can be substituted by CC-alkyl-, CrC ₄ -hydroxyalkyl, CC - alkoxy-, CC ₄ -aminoalkyl- or CrGralkoxy-dO _t -alkyl groups can be substituted, and.

• Z ¹ 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

-Q ^, - (CH ₂ -Q-CH ₂ -Q ") o- (MI)

in the

Q is a direct bond, a CH ₂ or CHOH group,

• Q ¹ and Q "independently of one another for an oxygen atom, an NR ¹³ group, wherein R ^{13 is} a hydrogen atom, a C _1-4 -alkyl or a hydroxy-C _1-4 -alkyl group, both groups also together with the rest of the molecule can form a 5-, 6- or 7-ring means the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) p ~ O, where p and p 'are 2 or 3 , stand 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, 4,4'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenyl sulfoxide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3 , 3 ', 4,4'-tetraamino-benzophenone, 1,3-bis (2,4-diaminophenoxy) propane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 1 , 3-bis- (4-aminophenylamino) propane,, 1,3-bis- (4-aminophenylamino) -2-propanoI, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- (4-aminophenoxy) ethyl] methylamine, N-phenyl-1, 4-phenylenediamine and bis (5-amino-2-hydroxyphenyl) methane ,

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-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamino-5-amino-pyridine, 2-methylamino-3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6- Dimethoxy-3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6-dihydroxy-3,4-dimethylpyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N - (5-amino-2-pyridyl) amine, N- [2- (4-aminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) amine, 2,4-dihydroxy-5,6- diaminopyrimidine, 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino 4,5,6-triaminopyrimidine, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy-6-methylpyrimidine, 3,5-diaminopyrazole, 3,5-diamino-1, 2,4-triazole, 3-aminopyrazole, 3-amino-5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, 1-phenyl-3-methyl- 4,5-diaminopyrazole, 4-amino-2 , 3-dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 1-phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8-aminoquinoline, 4-aminoquinoline, 2-aminonicotinic acid, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-amino nobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-morpholino- aniline and indole and indoline derivatives, such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6-dihydroxyindoi, 5,6-dihydroxyindoline and 4-hydroxyindoline. According to the invention, the hydroxypyrimidines disclosed in DE-U1-299 08 573 can also be used as heterocyclic compounds. The aforementioned compounds can be used both in free form and in the form of their physiologically salts in question, e.g. B. as salts of inorganic acids such as hydrochloric or sulfuric acid.

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

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

The compounds of component B are particularly preferably selected from the group consisting of N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) ) -p-phenylenediamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino-6-chloro-4-nitrophenol, 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-dichlorophenol, 4-amino-2, 6-dichlorophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 2-methyl-5-amino-4-chlorophenol, 6-methyl -3-amino-2-chlorophenol, 2-aminomethyl-4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2-dimethylaminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 1 - (2-hydroxyethylamino) -2,5-diamino-benzene, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene, bis- (2-hydroxy-5-aminophenyl) methane, bis- (4,5-amino-2-hydroxyphenyl) -methane, 1,3-bis (2,4-diaminophenox y) propane, 1,4-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 4,4'-diaminodiphenylamine, 3,4 -Diamino benzoic acid, 2,5-diaminopyridine, 2-dimethylamino-5-aminopyridine, 2-amino-3- hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole, 3-amino-5-hydroxypyrazole, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline, 4-amino-2, 3-dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), β-alanine, L-proline, L-lysine, DL-tyrosine and their physiologically tolerable salts preferably formed with inorganic acids.

In a special embodiment, the compound having a primary or secondary amino group is not selected from 2-methylquinolinium and 4-methylquinolinium derivatives.

The above-mentioned compounds of component B can be used in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the entire colorant. Furthermore, it can be particularly preferred according to the invention to use the carbonyl compound and component B in a molar ratio of 2: 1 to 1: 2, in particular approximately equimolar. When using compounds of component B which contain one or more amino groups, the carbonyl compounds on the one hand and the compounds of component B on the other hand are preferably used in proportions such that the sum of the number of carbonyl groups of the carbonyl compounds and the sum of the number of amino groups of the compounds of component B are in a ratio of 2: 1 to 1: 2.

In order to obtain further and more intense colorations, the agents used in the process according to the invention can additionally contain color enhancers. The color enhancers are preferably 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-methylimi- dazol, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazidine, their derivatives and their physiologically tolerable salts. The aforementioned color enhancers can be used in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the entire colorant.

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

The presence of oxidizing agents, for example H ₂ O ₂ , can be dispensed with when using the compounds of the formula I in the process according to the invention. Under certain circumstances, however, it may be desirable to add hydrogen peroxide or other oxidizing agents to the agents according to the invention to achieve shades lighter than the keratin-containing fiber to be colored. Oxidizing agents are generally used in an amount of 0.01 to 6% by weight, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ .

In a preferred embodiment of the process, in addition to the compounds contained according to the invention, customary oxidation hair colors or substantive dyes are added to the colorants according to the invention in order to further modify the color shades. The substantive dyes can e.g. B. can be selected from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as those 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, Basic Brown 17, Picramic Acid and 2- Amino-6-chIoro-4-nitrophenol known compounds and 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) aminobenzoI. The colorants used in the process according to the invention in this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

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

Furthermore, the colorants used in the process according to the invention, and also the decolorizing agents, can contain all the active ingredients, additives and auxiliaries known in such preparations. In many cases, the colorants or decolorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

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

Suifo-succinic acid mono- 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 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-3926 344,

Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

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

Ampholytic surfactants are surface-active compounds which, in addition to a C _8-18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

Addition products of 2 to 30 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 analogs,

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 colorants and decolorants according to the invention are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for. B. Cetyltrime thylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

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

In addition to a good conditioning effect, alkylamidoamines, especially fatty acid amidoamines such as the ^{stearylamidopropyldimethylamine} available under the name Tego Amid ^® S 18, are notable for their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", hydroxyaikyldialkoyloxyalkylammoniummethosulfate such as those sold under the trademark Stepantex ^® methyl.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

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

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. Under "normal" homolog division are 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. On the other hand, narrow homolog distributions are obtained if, for example, hydrotaicites, 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, vinylpyrrolidone / acrylate copolymers,

Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, di-methylpolymethylrolidolamido-polyacrylate-methylpolymer-vinyl-methacrylate-methacrylate-methylpolymer

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

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

Butylacrylamide terpolymers,

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

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

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

polyvinyl alcohol,

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

Egg lecithin and cephaline, as well as silicone oils, Protein hydrolyzates, especially elastin, collagen, keratin, milk protein,

Soy protein and wheat protein hydrolyzates, their condensation products with

Fatty acids and quaternized protein hydrolyzates,

Perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,

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

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

Cholesterol,

Light stabilizers,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,

Fats and waxes such as whale, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,

fatty acid,

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 for the production of the coloring and decolorizing agents used in the process according to the invention in amounts customary for this purpose; e.g. emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant.

The pH of the ready-to-use coloring and decolorization preparations according to the invention is usually between 2 and 11, preferably in a range from pH 5 to 10. In the method according to the invention, a decolorization procedure (P2) is carried out immediately after the dyeing procedure (P1) or after a longer period of time. The longer period, which can be between P1 and P2 of the method according to the invention, corresponds to 1 to 50 days.

The sulfur-containing compound contained in the decolorizing agents used is preferably selected from alkali metal or alkaline earth metal dithionite, alkali metal or alkaline earth metal sulfite, ammonium thioglycolate, calcium thioglycolate, cysteine, N-acetylcysteine, glutathione, cysteamine or its salts, homocysteine, penicetaldehyde and mercap. A particularly preferred sulfur-containing compound is selected from an alkali metal and alkaline earth metal dithionite and L-cysteine.

Α-Oxocarboxylic acids preferably contained in the decolorizing agents are selected from α-ketoglutaric acid, pyruvic acid and glyoxylic acid.

Glycolaldehyde and glyoxal are preferred aldehydes contained in the decolorizing agents.

Furthermore, the decolorizing agents preferably contain reductones selected from ascorbic acid, isoascorbic acid or their salts and esters, 2,3-dihydroxy-2-cyclopenten-1-one and hydroxypropanedial.

The decolorizing agent used in step P3a preferably contains at least one α-oxocarboxylic acid, in particular α-ketoglutaric acid, pyruvic acid and glyoxylic acid.

To produce the decolorizing agents used in the process according to the invention, at least one compound selected from sulfur-containing compounds, α-oxocarboxylic acids, aldehydes and reductones is incorporated into a suitable carrier. Such carriers are e.g. B. thickened aqueous solutions, creams (emulsions), gels or surfactant-containing, foaming preparations, for. B. shampoos other preparations that are suitable for use on the hair.

A second subject of the invention is the use of an agent for decolorizing keratin fibers, in particular human hair, containing at least one Compound selected from sulfur-containing compounds, α-oxocarboxylic acids, aldehydes and reductones, with the proviso that the keratin fiber is visible through a colorant containing at least one carbonyl compound and as component B at least one compound with primary or secondary amino group selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids and oligopeptides composed of 2 to 9 amino acids.

A third object of the invention is a kit for coloring and decolorizing keratin fibers, in particular human hair, which as separately assembled components in

Container (1) the colorant used in the method according to the invention and container (2) the decolorizing agent used in procedure P2 according to the invention

contains.

The carbonyl component and component B of the colorant can be packaged in two different containers 1 a and 1 b.

The kit according to the invention optionally contains, in addition to container 1, or containers 1a and 1b, two separately prepared decolorizing agents with the coloring agent. This kit is used when the further decolorization procedure P3 is to be carried out in the process carried out. The kit of this embodiment consists of three components, the coloring agent used in the method according to the invention in container (1) (or in containers 1a and 1b), the decolorizing agent used in procedure P2 in container (2) and in container (3 ) contains the additional decolorizing agent used in procedure P3. Examples

i) Preparation of the colorants

Color creams containing component B of the following composition were produced:

Hydrenol ^® D ¹ 8.50 g

Lorol ^® techn. ² 2.00 g

Eumulgin ^® B2 ³ 0.75 g

Texapon ^® NSO ⁴ 20.00 g

Dehyton ^® K ⁵ 12.50 g sodium sulfite 0.10 g

Ascorbic acid 0.10 g

Component B (see table 1)

Ammonia (25%) ad pH 10

Water ad 100 g

1 C ₁₆ -C ₁₈ fatty alcohol (INCI name: Cetearyl alcohol) (COGNIS)

² C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (COGNIS)

³ cetearylstearyl alcohol with about 20 EO units (INCI name: Ceteareth-20) (COGNIS)

⁴ Lauryl ether sulfate, sodium salt (approx. 27.5% active substance; (INCI name: Sodium Laureth Sulfate) (COGNIS)

⁵ N, N-dimethyl-N- (C ₈ -C ₁₈ cocosamidopropyl) ammonium acetobetaine (approx. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (COGNIS)

The substances Hydrenol ^® D, Lorol ^® and Eumulgin ^® B2 were used in. Melted 80 ° C, mixed with 80 ° C hot water containing Texapon ^® NSO and Dehyton ^® K, and emulsified with vigorous stirring. The emulsion was then cooled with gentle stirring. Sodium sulfite, ascorbic acid and the compound of component B (according to Table 1) were added with stirring. The emulsion was adjusted to pH 10 with aqueous ammonia solution (25%) and made up to 100 g with water. Compounds used in Table 1 as components B to prepare the color cream:

B1 2,4,5,6-tetraaminopyrimidine sulfate

B2 3-methyl-4-aminophenol

B3 bis (5-amino-2-hydroxyphenyl) methane x 2 HCl

B4 4,5-diamino-1- (2-hydroxyethyl) pyrazole

B5 1 - (2-hydroxyethylamino) -2,5-diamino-benzene

B6 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane

B7 N, N-bis (2-hydroxyethyl) p-phenylenediamine

B8 1,4-bis (4-aminophenyl) -1,4-diazacycloheptane

Table 1

In addition, color gels were prepared which contain the carbonyl component. The composition of the color gels is shown in Table 2. The following carbonyl compounds (according to the invention) were used:

C1 4-Formyl-1-methylquinolinium p-toluenesulfonate

C2 4-Benzoyl-1-methylpyridinium methanesulfonate

C3 1 -methyl-5-oxo-indeno [1, 2-b] pyridinium trifluoromethane sulfonate

C4 N-allyl isatin Table 2

Methacrylic acid (stearyl alcohol + 20-EO-ester) -acrylic acid copolymer (INCI name: Acrylates / Steareth-20 methacrylate copolymer) (ROHM & HAAS (ISP))

Stearic acid isooctyl ester (INCI name: ethylhexyl stearate) (COGNIS) oleyl cetyl alcohol + 5-EO, vegetable-based (INCI name: Oleth-5) (COGNIS)

10 C ₄ .ι ₂ fatty alcohol + 4 EO (INCI name: Laureth-4) (COGNIS)

Production of color gels G1 to G3

The carbonyl compound according to Table 2 was dissolved together with sodium sulfite and ascorbic acid in the 50 ° C hot water with the addition of ammonia (25% aqueous solution). Then Natrosol ^® 250 HR was added, the pH was adjusted to 10 with ammonia and made up to 100 g with water.

Production of color gel G4

N-allyl isatin was dissolved in the propylene carbonate and with Eumulgin ^® O 5 V, Cetiol ^® 868, Dehydol ^® LS 4N and Aculyn ^® 22 with stirring. ii) Coloring and colorimetric measurements

A color gel and a coloring cream were mixed in a weight ratio of 1: 1 and applied to natural strands of hair from Kerling. The amount by weight of the color mixture applied was three times the weight of the hair to be dyed. The used color cream / color combination are shown in Table 4. After an exposure time of the color mixture of 30 minutes at 32 ° C., the strands were washed out with water and dried.

The dyeing for the comparative tests was carried out as described in the examples in WO 01/28507 A1 using the color formulations of Examples 11, 12 and 13, but for better comparability with natural white hair from Kerling.

The colorimetric measurement of all colored strands of hair was carried out using a Texflash DC 3881 from Datacolor. The so-called CIE-Lab values were determined.

iii) decolorization and colorimetric measurements

In order to decolorize the colored strands of hair, decolorants with the respective compositions according to Table 3 were produced. The Hydrenol ^® D was melted at 60 ° C. Then PEG ^® 400, Lorol ^® techn. and Texapon ^® NSO added with stirring. To the mixture cooled to room temperature, 10.00 g of the corresponding decolorizing components (sodium dithionite, α-ketoglutaric acid, glyoxylic acid, L-cysteine hydrochloride, sodium sulfite or thioglycolic acid) were added to the hair shortly before use on the hair, dissolved in water. Table 3

Polyethylene glycol (COGNIS):

one-step decolorization process (according to the invention)

The dyed lock of hair was moistened with a decolorizing agent immediately after the above-mentioned dyeing process (see Table 4). The amount by weight of the decolorizing agent applied is three times the weight of the hair to be decolored. The decolorizing agent was rinsed off the hair after an exposure time of 15 minutes. The hair was then dried and measured colorimetrically using the Texflash DC 3881 from Datacolor to determine the CIE Lab values.

single-stage decolorization process (state of the art according to WO 01/28507 AD

The naturally white strands of hair from Kerling, dyed in accordance with Examples 11 to 13 of WO 01/28507 A1, were moistened with a decolorizing agent in accordance with WO 01/280507 A1 immediately after the dyeing process (see Table 4, middle section E5 to E7). The amount by weight of the decolorizing agent applied is three times the weight of the hair to be decolored. The exposure time is 60 minutes in the case of Examples 11 and 12 and 15 minutes in the case of Example 13. The decolorizing agent was rinsed off the hair after the exposure time. The hair was then dried and measured colorimetrically using the Texflash DC 3881 from Datacolor to determine the CIE Lab values.

The comparative experiments show that the dyeing / decolorization process according to the invention achieves an improved decolorization result compared to the prior art.

two-stage decolorization process (according to the invention)

The entries marked E5 in Table 4 under the heading "decolorizing agents" represent decolorization of the colored hair strand using a two-stage decolorization process. For this purpose, the decolorizing agent E1 (see Table 3) was applied to the dyed lock of hair immediately after the above-mentioned dyeing process and rinsed out after an exposure time of 15 minutes. The decolorizing agent E3 (see Table 3) was then applied to the hair and rinsed off from the hair after an exposure time of 10 minutes. The hair was then dried and measured colorimetrically using the Texflash DC 3881 from Datacolor to determine the CIE Lab values. The amount by weight of the respective decolorizing agent applied was three times the weight of the hair to be decolorized.

Calculation of color differences

The color differences between the colored hair strand and the discolored hair strand result from the respective CIE Lab values according to the color spacing formula given below (see also DIN 6174, German standards, Benth Verlag GmbH, Berlin, 1975). The undyed hair is used as a reference.

ΔE = [(ΔL) ² + (Δa) ² + (Δb) ² ] ¹ ' ² (color difference formula) Table 4 summarizes the measured CIE Lab values and the calculated color difference of the dye-decolorization tests according to the invention using the method according to the invention. Table 5 shows the measured CIE-Lab values of the decolorization process known from the prior art. The smaller the ΔE value, the better the initial hair color is achieved again after decolorization.

Table 4 (according to the invention)

The Lab values of the undyed natural white hair from Kerling are: L = 77.13, a = 2.13, b = 18.77.

Table 5 (according to the prior art WO 01/28507 A1)

The Lab values of the undyed natural white hair from Kerling are: L = 77.13, a = 2.13, b = 18.77.

Claims

claims

1. A method for dyeing and later decolorization of keratin fibers, in particular human hair, characterized in that P1 in a dyeing procedure

• Pia) a colorant containing at least one carbonyl compound

(Component A) and at least one compound with a primary or secondary amino group (component B), selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids and from 2 to 9 amino acids composed oligopeptides, applied to the keratin fiber,

• P1 b) leave on the keratin fiber for 5 - 45 minutes and

• P1c) is then rinsed off or washed out with a shampoo

and immediately or after a longer period in a decolorization procedure P2

P2a) a decolorizing agent comprising at least one compound selected from a sulfur-containing compound, an α-oxocarboxylic acid, an aldehyde or a reductone applied to the fiber,

• P2b) leave on the fiber for 5-60 minutes and

• P2c) is rinsed from the fiber.

2. The method according to claim 1, characterized in that after the procedure P2 in a further decolorization procedure P3

P3a) a further decolorizing agent comprising at least one compound selected from a sulfur-containing compound, an α-oxocarboxylic acid, an aldehyde or a reductone applied to the fiber,

P3b) leave on the fiber for 5-60 minutes and

P3c) is rinsed from the fiber. Method according to one of claims 1 or 2, characterized in that the carbonyl compound according to formula I contained in the colorant,

A ^" (0

in which

• (a) R ¹ stands for a group -CHO or

(b) R ³ represents a group -CO-R ⁶ , in which R ⁶ represents hydrogen, a CrC ₄ alkyl group, an aryl group or a heteroaryl group, with the proviso that according to (a) R ² , R ³ and R ⁴ or according to (b) R ¹ , R ² and R ⁴ independently of one another represent a hydrogen atom, a halogen atom, a CrC ₄ alkyl group, a C 1 -C ₄ alkoxy group, a hydroxy-CrC ^ alkoxy group, a hydroxy group , a nitro group, an amino group which can be substituted by CC ₄ -alkyl groups, or a CrC ₄ -acyl group, where two of the radicals together can form a fused-on benzene ring,

R ⁵ represents an oxygen atom, a CrC ₄ alkyl group, a C ₂ -C ₄ alkenyl group, a CrOpAcyl group, an aryl group, an aryl C ₄ alkyl group or a heteroaryl group,

• A is omitted if R ^{5 is} oxygen and is a halide, benzenesulfonate, tetrafluoroborate, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogen sulfate or tetrachlorozincate, is selected. Process according to claim 3, characterized in that the compound according to formula I is selected from 2-formyl-1-methyl-quinolinium-, 4-formyl-1-methyl-quinolinium-, 5-formyl-1-methyl-quinolinium-, 6-formyl-1-methyl-quinolinium-, 7-formyl-1-methyl-quinolinium-, 8-formyl-1-methyl-quinolinium-, 5-formyl-1-ethyl-quinolinium-, 6-formyl-1 - ethyl quinolinium, 7-formyl-1-ethyl-quinolinium, 8-formyl-1-ethyl-quinolinium, 5-formyl-1-benzyl-quinolinium, 6-formyl-1-benzyl-quinolinium, 7 Formyl-1-benzyl-quinolinium, 8-formyl-1-benzyl-quinolinium, 5-formyl-1-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7-formyl-1-allyl -quinolinium-, 8-formyl-1-allylquinolinium-, 5-acetyl-1-methyl-quinolinium-, 6-acetyl-1-methyl-quinolinium-, 7-acetyl-1-methyl-quinolinium-, 8-formyl- 1-acetyl-quinolinium, 9-formyl-10-methylacridinium salts with the counterions selected from benzenesulfonate, tetrafluoroborate, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, perchlo rat, 0.5 sulfate, chloride, bromide, iodide, tetrafluoroborate and tetrachlorozincate.

Process according to one of claims 1 to 4, characterized in that component B is selected from N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl -p-phenylene diamine, N, N-bis- (2-hydroxyethyl) -p-phenylene diamine, N- (2-methoxyethyl) -p-phenylene diamine, 2,3-dichloro-p-phenylene diamine, 2,4-dichloro-p -phenylene diamine, 2,5-dichloro-p-phenylene diamine, 2-chloro-p-phenylene diamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl I-4 -aminophenol, 2-hydroxymethyl-4-aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, 2,5, -diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethole, 4- Amino-3-methylphenol, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 3-amino-4- (2-hydroxyethyloxy) phenol, 3 , 4-methylenedioxyaniol, 3-amino-2,4-dichlorophenol, 4-amino-2,6-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-amino-4-chlorophenol, 5- (2-hydroxyethylamino) -4-methoxy-2 -methylphenol, 4-amino-2-hydroxymethylphenol, 2-

(Diethylaminomethyl) -4-aminophenol, 4-amino-1-hydroxy-2- (2-hydroxyethylaminomethyl) benzene, 1-hydroxy-2-amino-5-methyl-benzene, 1-hydroxy-2-amino-6- methyl-benzene, 2-amino-5-acetamido-phenol, 1, 3-dimethyl-2,5-diaminobenzene, 5- (3-hydroxypropylamino-) 2-methylphenol, 5-amino-4-methoxy-2- methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 5-amino-4-fluoro-2-methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino-5- (2-hydroxyethoxy) toluene, 2,4-diamino-5-methylphenetol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) anisole, 2,6- Bis- (2-, hydroxyethylamino) -1-methylbenzene, 1, 3-diamino-2,4-dimethoxybenzene, 3,5-diamino-2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amino-benzoic acid , 2-aminophenylacetic acid, 3-aminophenylacetic acid, 4-aminophenylacetic acid, 2,3-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5- Aminosalicylic acid, 3-amino-4-hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 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-hydr oxynaphthalene-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-triaminobenzene, 1,2,4- Triaminoben∑ol, 1, 2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobenzate catechol, 4,6-diaminopyrogallol, 1- (2-Hydroxy-5-aminobenzyl) -2-imidazolidinone, 4-amino-2 - ((4 - [(5-amino-2-hydroxyphenyl) methyl] piperazinyl) methyl) phenol, 3,5-diamino-4 -hydroxybrenz- catechin, 1,4-bis- (4-aminophenyl) -1,4-diazacycloheptane, aromatic nitriles such as 2-amino-4-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2.4 -DiaminobenzonitriI, nitro group-containing amino compounds such as 3-amino-6-methylamino-2-nitro-pyridine, picraminic acid, [8 - [(4-amino-2-nitrophenyl) -azo] -7-hydroxy-naphth-2- yl] -trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) -azo) - 7-hydroxy-naphth-2-yl] -trimethylammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4, 6-d initrobenzene, 1-amino-2-nitro-4- [bis- (2-hydroxyethyl) amino] benzene, 1 - amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5) , 1-Amino-2-nitro-4 - [(2-hydroxyethyl) amino] benzene (HC Red No. 7), 2-chloro-5-nitro-N-2-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-chloro-benzoI (HC Red No. 10), 2- (4-amino-2-nitroanilino) benzoic acid, 6-nitro-2,5-diaminopyridine, 2-amino-6-chloro-4-nitrophenol , 1-Amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfone- 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, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene-2; 2'-disulfonic acid mono-o the -di-Na salt, 4-amino-4'-dimethylaminostilbene and its hydrochloride, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenylamine, 4, 4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraaminobenzophenone, 1 , 3-bis (2,4-diaminophenoxy) propane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,3-bis (4-aminophenylamino) propane, 1,3-bis- (4-aminophenylamino) -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 and bis (5-amino-2-hydroxyphenyl) methane, nitrogen-containing heterocyclic compounds selected from the group consisting of 2-aminopyridine , 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino -pyridine, 2-dimethylamino-5-aminopyridine, 2-meth ylamino-3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2, 6-dihydroxy-3,4-dimethylpyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) amine, N- [2- (4-aminophenyl) aminoethyl ] -N- (5-amino-2-pyridyl) amine, 2,4-dihydroxy-5,6-diaminopyrimidine, 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2- Hydroxy-4,5,6-triaminopyrimidine, 2,4,5,6-

Tetraaminopyrimidine, 2-methylamino-4,5,6-triaminopyrimidine, 2,4- Diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, 3,5-diamino-1, 2,4-triazole, 3-aminopyrazole, 3-amino- 5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, 1-phenyl-3-methyl-4,5-diaminopyrazole, 4-amino-2,3- dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 1-phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8-aminoquinoline, 4-aminoquinidine, 2-aminonicotinic acid , 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazoI, 2,5-dihydroxy-4-morpholino-aniline as well as indole and indoline derivatives such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoiine, 4-hydroxyindoline, hydroxypyrimidine derivatives, β-alanine, arginine, histidine, phenylalanine, DOPA (Dihydroxyphenylalanine), ornithine, lysine, proline, tyrosine and tryptophan as well as oligopeptides Contains glutathione or the oligopeptides contained in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein and / or each of them from the physiologically tolerable salts of these compounds formed with preferably inorganic acids.

Process according to one of claims 1 to 5, characterized in that component B is selected from N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis- (2nd -hydroxyethyl) -p-phenylenediamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino-6-chloro-4-nitrophenol, 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-dichlorophenol, 4-amino-2,6-dichlorophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- ( 2-hydroxyethylamino) phenol, 2-methyl-5-amino-4-chlorophenol, 6-methyl-3-amino-2-chlorophenol, 2-aminomethyl-4-aminophenol, 2-diethylaminomethyl-4-aminophenol, 2- Dimethylaminomethyl-4-aminophenol, 4-amino-2,6-dichlorophenol, 2-hydroxymethyl-4-aminophenol, 1- (2-hydroxyethylamino) -2,5-diamino-benzene, 2,6-bis (2- hydroxyethylamino) -1-methylbenzene, bis (2-hydroxy-5-aminophenyl) methane, bis (4,5-amino-2-hydroxyphenyl) methane, 1,3-bis (2,4-diaminophenoxy) propane, 1,4-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 4,4'-diaminodiphenylamine, 3,4-diaminobenzoic acid, 2nd , 5-diaminopyridine, 2-dimethylamino-5-aminopyridine, 2-amino-3-hydroxypyridine, 3-amino-2- methylamino-6-methoxypyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2,6-di-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2-hydroxy-4,5, 6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5,6-triamino-pyrimidine, 3,5-diaminopyrazole,

3-amino-5-hydroxy-pyrazole,

4,5-diamino-1- (2-hydroxyethyl) pyrazole, 5,6-dihydroxyindole,

5,

6- dihydroxyindoline, 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (4-

Aminoantipyrine), ß-alanine, L-proline, L-lysine, DL-tyrosine and their physiologically tolerable salts preferably formed with inorganic acids.

7. The method according to any one of claims 1 to 6, characterized in that the sulfur-containing compound is selected from alkali or alkaline earth thionite, alkali or alkaline earth sulfite, ammonium thioglycolate, calcium thioglycolate, cysteine, N-acetylcysteine, glutathione, cysteamine or its salts, homocysteine, Penicillamine and mercaptoacetaldehyde.

8. The method according to claim 7, characterized in that the sulfur-containing compound of the decolorizing agent is selected from an alkali and alkaline earth metal dithionite and L-cysteine.

9. The method according to any one of claims 1 to 8, characterized in that the α-oxocarboxylic acid of the decolorizing agent is selected from α-ketoglutaric acid, pyruvic acid and glyoxylic acid.

10. The method according to any one of claims 1 to 9, characterized in that the aldehyde of the decolorizing agent is selected from glycol aldehyde and glyoxal.

11. The method according to any one of claims 1 to 10, characterized in that the reductone of the decolorizing agent is selected from ascorbic acid, isoascorbic acid or their salts and esters, 2,3-dihydroxy-2-cyclopenten-1-one and hydroxypropanedial.

12. The method according to claim 2, characterized in that the further decolorizing agent contains at least one α-oxocarboxylic acid.

13. The method according to any one of claims 1 to 12, characterized in that the longer period between coloring and decoloring corresponds to 1 to 50 days.

14. Use of an agent containing at least one compound selected from sulfur-containing compounds, α-oxocarboxylic acids, aldehydes and reductones for decolorizing keratin fibers, in particular human hair, with the proviso that the keratin fiber is visible through a colorant containing at least one carbonyl compound and as a component B at least one compound having a primary or secondary amino group, selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids and from 2 to 9 amino acids composed of oligopeptides.

15. Kit for coloring and decolorization of keratin fibers, especially human hair, characterized in that it is in as separately assembled components in

Container (1) a coloring agent as used in one of claims 1 to 5, and in container (2) a decolorizing agent as used in one of claims 1 or 6 to 10,

contains.

16. Kit according to claim 15, characterized in that the carbonyl component and component B of the colorant are made up in two separate containers 1a and 1b.

17. Kit according to one of claims 15 or 16, characterized in that it is in an additional container

Container (3) contains another decolorizing agent, as used in the procedure P3 according to claims 2 and 7 to 12.