DE10148845A1 - Dyeing keratin fibers, especially human hair, using diazonium salt or carbonyl compound and oxidizing agent, gives strong shades of good wash fastness - Google Patents

Abstract

Dyeing keratin-containing fibers by treating with an oxidizing agent and then with a composition containing diazonium or carbonyl compound and optionally primary or secondary aromatic amine, N-containing heterocycle or aromatic hydroxy compound, amino acid oligopeptide with 2-9 amino acids, acidic methylene compound or quaternary ammonium compound, or their salts. Method for dyeing keratin-containing fibers, especially human hair, by treating first with an oxidizing agent and then with a composition containing (A) a diazonium or carbonyl compound of formulae (I) and/or (II) and (B) optionally a primary or secondary aromatic amine, N-containing heterocycle or aromatic hydroxy compound, amino acid oligopeptide with 2-9 amino acids, acidic methylene compound or quaternary ammonium compound, or their salts. The composition remains on the hair for about 30 minutes and is then removed by rinsing or washed out with shampoo. AR = benzene, naphthalene, pyridine, (iso)quinoline, quinolizine, pyrimidine, pyrrole, furan, thiophene, indole, indane, imidazole, benzimidazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, cinnoline, acenapthene, fluorene, biphenyl, diphenylmethane, benzophenone, diphenyl ether, azobenzene, stilbene and their (partially) hydrogenated derivatives; R<1>-R<3> = hydrogen, halo, 1-4C alkyl, alkoxy, acyl or hydroxyalkoxy, hydroxy, nitro, (1-4C acyl)amino, ammonio or 1-imidazli(ni)o group, optionally substituted by 1-4C (hydroxy)alkyl, or two of them form (un)saturated, optionally substituted 5-7 membered ring fused to AR, optionally itself fused to an additional aromatic, optionally substituted ring, and the AR system may, depending on its size, carry additional substituents, as defined for R<1>-R<3>; X = N2<+> Y<->, -QR<4> or -QCOR<4>; Y<-> = halo, 0.5 sulfate, hydrogensulfate, alkenesulfonate, arenesulfonate or hydroxy; Q = direct bond, oxygen, carbonyl, optionally substituted methylene, 1,3-butadien-1,4-diyl or phenylene; R<4> = hydrogen, 1-4C alkyl, 2-4C alkenyl, optionally substituted (hetero)aryl, -(CH2CH2O)z-R<5>, or the Q(CO)R<4> group forms, with R<1>-R<3>, a (un)saturated, optionally substituted 5-7 membered ring fused to AR, optionally itself fused to an additional aliphatic or aromatic, carbocyclic or heterocyclic, optionally substituted ring; R<5> = 1-4C alkyl, 2-4C alkenyl or optionally substituted (hetero)aryl; G' = direct bond, 1-4C alkylene, 2-4C alkenylene or 4-6C dialkenylene; R<6> and R<7> = hydrogen, 1-4C alkyl or together form with -CO-G-CO- an optionally substituted ring, optionally carrying an optionally substituted fused aromatic ring, where R<6> and R<7> together form 1-4C alkenylene, 4-6C dialkenylene or 1-4C alkylene.

Description

The invention relates to a method for dyeing keratin fibers, in particular human hair, in which the fibers are first treated with an oxidizing agent and then treated with a reactive coloring component.

For dyeing keratin fibers, e.g. B. hair, wool or furs come in general either direct dyes or oxidation dyes 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 Developer components are also referred to as oxidation dye precursors.

Especially among younger people there is often a desire for something special fashionable, brilliant colors such as intense red, yellow, orange, green, blue or Violet tones. The desired dyeing result can usually only be found on a very light color Starting hair can be achieved, for which purpose a more or less strong lightening of the Natural hues is necessary. By lightening, depending on the strength of the Lightening damage to the hair or irritation if the scalp is sensitive of the scalp. The subsequent coloring should therefore be very mild and nevertheless an improved durability of the coloring compared to usual Ensure hair tints to prevent costly and time-consuming re-dyeing in short To avoid gaps.

Two methods for producing intense, fashionable color tones are known from the prior art. In the first process, the co-oxidation takes place oxidatively by means of oxidizing agents such as e.g. B. H ₂ O ₂ , and oxidation dye precursors. A true-to-color coloring is obtained in this process. A disadvantage is the strain on the hair due to the oxidative coloring. In the second process, direct dyes are applied to pre-blond hair. Fashionable shades can be obtained without additional damage to the hair. The washability of the dye is usually unsatisfactory.

The object of the present invention is to provide a process for dyeing keratin-containing To provide fibers with which it is possible to create fashionably intense colorations to apply to the fibers that show good wash resistance and in the actual dyeing step does not cause strain on the fibers.

Surprisingly, it has now been found that intense fashionable shades occur Keratin-containing fibers can be produced if the fibers are first coated with a Treated oxidizer and then with compounds according to the below Compound A mentioned and optionally with compounds of component B. be treated. There are washable dyeings obtained in the Coloring step does not strain the fiber and does not sensitize the Effect scalp.

• A) mindestens eine Verbindung A mit der Formel I,
  
  
  wobei
  AR steht für Benzol, Naphthalin, Pyridin, Furan, Chinolin, Isochinolin, Chinolizin, Pyrimidin, Pyrrol, Thiophen, Indol, Indan, Imidazol, Benzimidazol, Benzothiazol, Indazol, Benzoxazol, Chinoxalin, Chinazolin, Cinnolin, Acenaphthen, Fluoren, Biphenyl, Diphenylmethan, Benzophenon, Diphenylether, Azobenzol, Diphenylamin, Stilben sowie deren teilweise oder vollständig hydrierten Derivate,
  R¹, R² und R³ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C_1-4-Alkyl-, C_1-4-Alkoxy-, C_1-4-Acyl-, C_1-4-Hydroxyalkoxy-, eine Hydroxy- oder Nitrogruppe oder eine Amino-, C_1-4-Acylamino-, Ammonio- oder eine 1- Imidazoli(ni)ogruppe, die durch C_1-4-Alkyl- oder C_1-4-Hydroxyalkylgruppen substituiert sein können, und auch zwei der Reste R¹, R² und R³ einen an AR ankondensierten gesättigten oder ungesättigten, gegebenenfalls substituierten 5-, 6- oder 7-Ring, der wiederum einen aromatischen, gegebenenfalls substituierten Ring tragen kann, bilden können, wobei das System AR in Abhängigkeit von der Größe des Ringes weitere Substituenten tragen kann, die die gleiche Bedeutung haben können wie R¹, R² und R³ und
  X steht für
  eine Gruppe N~N⁺ Y^-, worin Y^- für ein Halogenid, Nitrat, 0.5 Sulfat, Hydrogensulfat, Alkensulfonat, Arensulfonat oder eine Hydroxygruppe steht oder
  eine Gruppe -Q-R⁴ oder eine Gruppe -Q-CO-R⁴, worin
  Q für eine direkte Bindung, ein Sauerstoffatom, eine Carbonylgruppe, eine gegebenenfalls substituierte Methylen-, Vinylen-, 1,3-Butadien-1,4-diyl oder Phenylengruppe steht und
  R⁴ ist ein Wasserstoffatom, eine C_1-4-Alkyl-, C_2-4-Alkenyl-, eine gegebenenfalls substituierte Aryl- oder Heteroarylgruppe, eine Gruppe -[CH₂CH₂O]_z-R⁵ in der R⁵ eine C_1-4-Alkyl-, C_2-4-Alkenyl-, eine gegebenenfalls substituierte Aryl- oder Heteroarylgruppe bedeutet und z für eine ganze Zahl von 1 bis 5 steht,
  oder die Gruppen -Q-R⁴ oder -Q-CO-R⁴ bilden mit einem derSubstituenten R¹, R² oder R³ einen an AR ankondensierten gesättigten oder ungesättigten, gegebenenfalls substituierten 5-, 6- oder 7-Ringes, der ebenfalls einen ankondensierten aliphatischen oder aromatischen, carbozyklischen oder heterozyklischen, gegebenenfalls substituierten Ring tragen kann,
  und/oder mit der Formel II
  
  
  G steht für eine direkte Bindung, eine C₁-C₄-Alkylengruppe, eine C₂-C₄- Alkenylengruppe oder eine C₄-C₆-Dialkenylengruppe,
  R⁶ und R⁷ stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₄- Alkylgruppe, oder bilden zusammen mit der Gruppe -C(O)-G-C(O)- einen gegebenenfalls substituierten Ring, der wiederum einen ankondensierten gegebenenfalls substituierten aromatischen Ring tragen kann, wobei die Gruppen R⁶ und R⁷ zusammen eine C₁-C₄-Alkenylengruppe, eine C₄-C₆-Dialkenylengruppe oder eine C₁-C₄-Alkylengruppe bilden,
• B) und gegebenenfalls mindestens eine Verbindung, ausgewählt aus einer Gruppe, die gebildet wird, aus
  • a) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterocyclischen Verbindungen und aromatischen Hydroxyverbindungen,
  • b) Aminosäuren,
  • c) aus 2 bis 9 Aminosäuren aufgebauten Oligopeptiden,
  • d) CH-aciden Verbindungen,
  • e) quartären Ammoniumverbindungen,

sowie der physiologisch verträglichen Salze der voranstehend genannten Verbindungen, auf die keratinhaltigen Fasern aufgebracht, einige Zeit, üblicherweise ca. 30 Minuten, auf der Faser belassen und anschließend wieder ausgespült oder mit einem Shampoo ausgewaschen wird. The invention relates to a method for dyeing keratin-containing fibers, in particular human hair, in which the fibers are first treated with an agent 1 containing an oxidizing agent and then containing an agent 2

• A) at least one compound A with the formula I,
  
  
  in which
  AR stands for benzene, naphthalene, pyridine, furan, quinoline, isoquinoline, quinolizine, pyrimidine, pyrrole, thiophene, indole, indan, imidazole, benzimidazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, cinnoline, acenaphthene, fluorene, biphenanyl, diphenyl , Benzophenone, diphenyl ether, azobenzene, diphenylamine, stilbene and their partially or fully hydrogenated derivatives,
  R ¹ , R ² and R ³ independently represent a hydrogen atom, a halogen atom, a C _1-4 alkyl, C _1-4 alkoxy, C _1-4 acyl, C _1-4 hydroxyalkoxy , a hydroxy or nitro group or an amino, C _1-4 -acylamino, ammonio or a 1-imidazoli (ni) o group, which may be substituted by C _1-4 alkyl or C _1-4 hydroxyalkyl groups , and also two of the radicals R ¹ , R ² and R ^{3 can form} a saturated or unsaturated, optionally substituted 5-, 6- or 7-ring fused to AR, which in turn can carry an aromatic, optionally substituted ring, the System AR, depending on the size of the ring, can carry further substituents which can have the same meaning as R ¹ , R ² and R ³ and
  X stands for
  a group N ~ N ⁺ Y ^- , in which Y ^{- represents} a halide, nitrate, 0.5 sulfate, hydrogen sulfate, alkene sulfonate, arene sulfonate or a hydroxy group or
  a group -QR ⁴ or a group -Q-CO-R ⁴ , wherein
  Q represents a direct bond, an oxygen atom, a carbonyl group, an optionally substituted methylene, vinylene, 1,3-butadiene-1,4-diyl or phenylene group and
  R ⁴ is a hydrogen atom, a C _1-4 alkyl, C _2-4 alkenyl, an optionally substituted aryl or heteroaryl group, a group - [CH ₂ CH ₂ O] _z -R ⁵ in which R ^{5 is} one C _1-4 alkyl, C _2-4 alkenyl, an optionally substituted aryl or heteroaryl group and z is an integer from 1 to 5,
  or the groups -QR ⁴ or -Q-CO-R ⁴ together with one of the substituents R ¹ , R ² or R ^{3 form} a saturated or unsaturated, optionally substituted 5-, 6- or 7-ring which is fused onto AR and which likewise fused on can carry aliphatic or aromatic, carbocyclic or heterocyclic, optionally substituted ring,
  and / or with the formula II
  
  
  G represents a direct bond, a C ₁ -C ₄ alkylene group, a C ₂ -C ₄ alkenylene group or a C ₄ -C ₆ dialkenylene group,
  R ⁶ and R ⁷ independently of one another represent a hydrogen atom, a C ₁ -C ₄ alkyl group, or together with the group -C (O) -GC (O) - form an optionally substituted ring, which in turn is a fused-on optionally substituted aromatic ring Can wear ring, the groups R ⁶ and R ⁷ together forming a C ₁ -C ₄ alkenylene group, a C ₄ -C ₆ dialkenylene group or a C ₁ -C ₄ alkylene group,
• B) and optionally at least one compound selected from a group that is formed from
  • a) compounds with primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds,
  • b) amino acids,
  • c) oligopeptides composed of 2 to 9 amino acids,
  • d) CH-acidic compounds,
  • e) quaternary ammonium compounds,

and the physiologically tolerable salts of the abovementioned compounds, applied to the fibers containing keratin, left on the fiber for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo.

In the first process step, the fibers are treated with an oxidizing agent in a manner known per se. H ₂ O ₂ , H ₂ O ₂ releasing compounds or combinations thereof are preferably used as oxidizing agents, in particular for human hair, these compounds also being able to be applied to an inert carrier. H ₂ O ₂ can e.g. B. in combination with Na, K, NH ₄ peroxodisulfate or the corresponding peroxodiphosphonates, especially in an alkaline environment. The pH is preferably in the range from pH 6 to 11, particularly preferably in the range from pH 8.5 to pH 10.5. The oxidizing agent preparation can also compounds such. B. magnesium peroxide can be added. H ₂ O ₂ can be in the oxidizing agents in free form or bound, e.g. B. be used as sodium carbonate peroxyhydrate, urea peroxide or melamine perhydrate. The oxidizing agents are generally used in an amount of 0.01 to 6% by weight, based on the application solution.

The compounds used in the second step with the formulas I and II and Component B are largely known from the literature or commercially available or after known synthetic methods can be produced.

Particularly brilliant, washout-resistant colorations can be obtained if the compounds with the formula I are stable diazonium salts, (X = N ~ N ⁺ Y ^- ) onium aldehydes (AR = quaternized pyridine, X = -QR ⁴ with Q = carbonyl, R ⁴ = hydrogen atom ) or isatin or isatin derivatives (AR = benzene, X = Q-CO-R ⁴ with Q = carbonyl, R ³ = NH ₂ , ^R 4 = hydrogen, where R ³ and X form a 5-ring fused to AR), or any mixtures of the above compounds.

Examples of suitable diazonium salts with the formula I are 4-diazo-phenylamine sulfate (Variaminblausalz® RT), 4-diazo-4'-methoxydiphenylamine chloride (Variaminblausalz® B), 4-diazo-3,2'-dimethylazobenzenesulfate (Real Garnet Salt® GBC), 2-methoxy-4- nitrobenzene diazonium naphthalene-1,5-disulfonate (Echtrotsalz® B), 4-diazo-2,5-dimethoxy- 4'-nitroazobenzene chloride-zinc chloride double salt (real black salt® K), 2,5-dimethoxy-4- benzolyaminophenyldiazonium chloride (real blue salt® RR), 2-methoxy-4-nitrobenzenediazonium-1,5-naphthalenedisulfonate, 4-chloro-2-nitrobenzenediazonium chloride-zinc chloride- Double salt (Echtrotsalz® 3 GL), 5-chloro-2-methoxybenzenediazonium chloride-zinc chloride- Double salt (Echtrotsalz® RC), 4-benzamido-2-methoxy-5-methylbenzene diazonium chloride-zinc chloride double salt (real violet salt® B), 2-diazo-1-naphthol-4-sulfonic acid, Na salt of 2-diazo-1-naphthol-5-sulfonic acid.

Onium aldehydes which are preferably used are, for example, the benzenesulfonates, p- Toluenesulfonates, methanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides and / or tetrachlorozincates of 4-formyl-1-methylpyridinium, 3-formyl-1 - methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1- ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2- dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2- Formyl-1-methylquinolinium, 4- (2-formylvinyl) -1-methylquinolium, 4-acetyl-1-methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium and 4- (2-formylvinyl) -1-methylpyridinium, 2,6-dichloro-4-formyl-1-methylpryridinium, 2,6-diphenyl-4-formyl- 1-methylpyridinium, 4-benzoyl-1-methylpyridinium, 4-propionyl-1-methylpyridinium, 4- Pyridine aldehyde-N-oxide and N-methylpyridoxal and any mixtures of preceding connections.

Examples of isatin derivatives are isatin, isatin-5-sulfonic acid, isatin-4-carboxylic acid and Isatin-5-carboxylic acid, N-substituted isatin derivatives, such as N-hydroxmethyl-isatin, N- Hydroxyethyl isatin N- (2'-hydroxypropyl) isatin, N- (3'-hydroxypropyl) isatin, N- (2 ', 3'- Dihydroxypropyl) isatin, N- (2'-sulfoethyl) isatin, N- (3'-sulfopropyl) isatin, N-allylisatin, N- Vinylisatin, N-benzylisatin, N- (4'-methoxybenzyl) -isatin, N- (4'-carboxybenzyl) -isatin, N- (4'- Sulfobenzyl) -isatin, N- (2'-dimethylaminoethyl) -isatin, N- (2'-pyrrolidinoethyl) -isatin, N- (2'- Piperidinoethyl) isatin, N- (2-furylmethyl) isatin, N- (2-thienylmethyl) isatin, N- (2- Pyridylmethyl) isatin, N- (3-pyridylmethyl) isatin, N- (4-pyridylmethyl) isatin, N-allylisatin-5- sulfonic acid, 5-chloro-N- (2'-hydroxyethyl) isatin, 5-methyl-N- (2'-hydroxyethyl) isatin, 5- Chloroisatin, 5-nitroisatin, 5,7-dichloroisatin, 5,7-dichloro-N-allylisatin, 5-nitro-N-allylisatin, N- Hydroxymethyl-5-methylisatin, N-hydroxymethyl-5-chloroisatin, N-hydroxymethyl-5- sulfoisatin, N-hydroxymethyl-5-carboxyisatin, N-hydroxymethyl-5-nitroisatin, N- Hydroxymethyl-5-bromisatin, N-hydroxymethyl-5-methoxyisatin, N-hydroxymethyl-5,7- dichlorisatin, N-dimethylaminomethylisatin, N-diethylaminomethylisatin, N- (bis- (2'- hydroxyethyl) aminomethyl) isatin, N- (2'-hydroxyethylaminomethyl) isatin, N- (bis- (2'- hydroxypropyl) aminomethyl) isatin, N- (2'-pyrrolidino) isatin, N- (2'-piperidino) isatin, N- Pyrrolidinomethylisatin, N-piperidinomethylisatin, N-morpholinomethylsatin, N- (2- Morpholinoethyl) isatin, N- (1 ', 2', 4'-triazolyl) methylisatin, N- (1-imidazolyl) methylisatin, N- Carboxymethylaminomethylisatin, N- (2'-carboxyethylaminomethyl) isatin, N- (3'-carboxypropylaminomethyl) isatin, N- (bis- (2'-hydroxyethyl) aminomethyl) -5-methylisatin, N- Piperidinomethyl-5-chloroisatin, N- (2'-sulfoethylamino) isatin, as well as the alkali and optionally ammonium salts of the acidic compounds, quinisatin and their derivatives, such as N-methylquinisatin and the alkali and ammonium salts of the acidic compounds.

Other preferred compounds of formula I are
5- (4'-Dimethylaminophenyl) penta-2,4-dienal, 5- (4'-diethylaminophenyl) penta-2,4-dienal, 5- (4'-methoxyphenyl) penta-2,4-dienal , 5- (3 ', 4'-Dimethoxyphenyl) penta-2,4-dienal, 5- (2', 4'-Dimethoxyphenyl) penta-2,4-dienal, 5- (4'-piperidinophenyi) - penta-2,4-dienal, 5- (4'-morpholinophenyl) -penta-2,4-dienal, 5- (4'-pyrrolidinophenyl) -penta-2,4-dienal, 6- (4'-dimethylaminophenyl) -hexa-2,4-dien-2-one, 6- (4'-diethylaminophenyl) -hexa-2,4-dien-2-one, 6- (4'-methoxyphenyl) hexa-2,4-diene -2-one, 6- (3% 4'-dimethoxyphenyl) hexa-2,4-dien-2-one, 6- (2 ', 4'-dimethoxyphenyl) hexa-2,4-dien-2- on, 6- (4'-piperidinophenyl) hexa-2,4-dien-2-one, 6- (4'-morpholinophenyl) hexa-2,4-dien-2-one, 6- (4'- Pyrrolidinophenyl) hexa-2,4-dien-2-one, 5- (4'-dimethylamino-1-naphthyl) penta-2,4-dienal,
2-nitro-piperonal, 5-nitro-piperonal, 6-nitro-piperonal, 5-hydroxy-2-nitro-piperonal, 2-hydroxy-5-nitro-piperonal, 2-chloro-6-nitro-piperonal, 5- Chloro-2-nitro-piperonal, 2,6-dinitropiperonal,
2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 6-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3- nitrobenzaldehyde, 5-hydroxy-2-nitro-benzaldehyde, 2-hydroxy-5-nitro-benzaldehyde, 2-hydroxy-3-nitro-benzaldehyde, 2-fluoro-3-nitro-benzaldehyde, 3-methoxy-2-nitro- benzaldehyde, 4-chloro-3-nitro-benzaldehyde, 2-chloro-6-nitro-benzaldehyde, 5-chloro-2-nitro-benzaldehyde, 4-chloro-2-nitro-benzaldehyde, 2,4-dinitro-benzaldehyde, 2,6-dinitro-benzaldehyde, 2-hydroxy-3-methoxy-5-nitro-benzaldehyde, 4,5-dimethoxy-2-nitro-benzaldehyde, 5-nitrovanillin, 3,5-dinitrosalicylaldehyde, 5-bromo-3- nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde,
Carbazolaldehydes or carbazole ketones, especially 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4-dimethyl-3 carbazolaldehyde, 1,4,9-trimethyl-3-carbazolaldehyde,
4-trimethylammoniobenzaldehyde, 4-trimethylammoniobenzaldehyde, 4-trimethylammoniozimtaldehyde, 4-trimethylammonionaphthaldehyde, 2-methoxy-4-trimethylammoniobenzaldehyde, N- (4'-acetylphenyl) trimethylammonium, 4- (N), N (N) -N-methylammonio) -benzaldehyde-, N- (4'-benzoylphenyl) -trimethylammonium-, N- (4'-benzoylphenyl) -N, N-diethylmethylammonium-, N- (4'-formylphenyl) -N-methylpyrrolidinium- , N- (4'-formylphenyl) -N-methylpiperidinium-, N- (4'-formylphenyl) -N-methylmorpholinium- N- (4'-acetylphenyl-N-methylmorpholinium-, N- (4'-benzoylphenyl) - N-methylmorpholinium-, 3-formyl-N-ethyl-N-methylcarbazolium-, 3-formyl-9,9-dimethylcarbazolium-, 1- (4'-acetylphenyl) -3-methylimidazolium-, 1- (4'-acetylphenyl ) -3-methyl-2-imidazolinium, 1- (4'-benzoylphenyl) -3-methylimidazolium, 5-acetyl-1,3-diethyl-2-methylbenzimidazolium, 5-trimethylammonio-1-indanone salts, in particular the benzenesulfonates, p-toluenesulfonates, methanesulfonates, ethanesulfonates, propanesulfonates, perchlorates, sulfates, chlorides, Bromides, iodides, tetrachlorozincates, methyl sulfates, trifluoromethanesulfonates, hexafluorophosphates, tetcafluocbocates,
Cinnamaldehyde, salicylaldehyde, vanillin, 4-hydroxy-3-methoxycinnamaldehyde (coniferylaldehyde), 2,4-dihydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholine , 4-dimethylaminoacetophenone, 4-hydroxynaphthaldehyde, 4-dimethylaminonaphthaldehyde, 4-dimethylaminobenzylidene acetone, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldaldehyde, trans-4-4-diethylamine - (Dibutylamino) benzaldehyde, 4-diphenylaminobenzaldehyde, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 2,3,6,7 -Tetrahydro-8-hydroxy-1 H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 4- (1-imidazolyl) benzaldehyde, 2-morpholinobenzaldehyde, indole-3-carboxaldehyde, 1-methylindole-3-carboxaldehyde, N-ethylcarbazole-3-carboxaldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Tribasen Aldehy d)
1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-tciacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) acetophenone, 2- (3'-pyridoyl) acetophenone,
1-phenyl-1,2-propanedione, 1-phenyl-1,2-butanedione, 1-chlorophenyl-1,2-propanedione, 1-phenyl-3,3-dimethyl-1,2-butanedione, benzil, anisil, Salicil, 5,5'-dibromosalicil, 2,2'-furyl, 2,2'-thienyl, 2,2'-, 4,4'-pyridil, 6,6'-dimethyl-4,4'-pyridil, 4-hydroxy-, 4-methoxy-, 4-chloro-, 4-methyl-, 4-dimethylamino-, 4,4'-dihydroxy-, -dimethyl-, -dibromo-, -dichloro-, -di-dimethylamino-, 2 , 4-dihydroxy-, 3,3'-dimethoxy, 2'-chloro-3,4-dimethoxy-, 3,4,5,3 ', 4', 5'-hexamethoxy-benzil,
Acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophyne, 2,4-hydroxyphenyphenophenone Dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2, 3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3, 4,5-trimethoxy-acetophenone-diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxy-acetophenone, 4-amino-acetophenone, 4-dimethylaminoacetophenone, 4-morpholino-acetophenone, 4- Piperidino-acetophenone, 4-imidazolino-acetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxy-benzophenone, 2- Aminobenzophenone, 4,4'-dihydroxy-benzophenone, 2,4-dihydroxy-benzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-a cetonaphthon, 1-hydroxy-2-acetonaphthon, chromon, chromon-2-carboxylic acid, flavon, 3-hydroxyflavon, 3,5,7-trihydroxyflavon, 4 ', 5,7-trihydroxyflavon, 5,6,7-trihydroxyflavon, quercetin , Indanon, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone,
heterocyclic carbonyl compounds, such as 2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindol-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ', 3', 3'-trimethyl-2'-indolinylidene) acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 1-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 1- Acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoroacetone, chromon-3-aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein, imidazole-2-aldehyde,
Indanone derivatives, such as. B. 1,2-indanedione, 2-oximo-1-indanone, indan-1,2,3-trione-2-oxime, 5-methoxy-indan-1,2,3-trione-2-oxime, 2- nitro-1,3-indandione,
quaternized azafluorenones, such as the trifluoromethanesulfonates, benzenesulfonates, p-toluenesulfonates, methanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides, tetrachlorozincates, hexafluorophosphates, tetrafluoroborates of 1-methyl-5-oxo-indenoidin [1,2-] '-methyl-4'-azonio-9'-fluorenone), 1-ethyl-5-oxo-indeno [1,2-b] pyridinium, 1-benzyl-5-oxo-indeno [1,2-b] pyridinium , 2-methyl-5-oxo-indeno [1,2-c] pyridinium, 2-methyl-9-oxo-indeno [2,1-c] pyridinium, 1-methyl-9-oxo-indeno [2,1 b] pyridinium.

Carbonyl compounds of the formula II which are preferably used according to the invention Glutacondialdehyde, fumaraldehyde, glyoxal, malondialdehyde, Bemsteindialdehyd, Mucondialdehyde, 1,2-naphthoquinone, 4-sulfonic acid-1,2-naphthoquinone, 1,2- Benzoquinone, 1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone (juglone), 1,4- Naphthoquinone, spinulosin, atromentin, aurentioglyocladin, 5-hydroxy-1,4- naphthoquinone, 2,5-dihydroxy-6-methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxy-1,4- benzoquinone, 2,5-dihydroxy-3,6-diphenyl-1,4-benzoquinone, 2,5-dihydroxy-6-isopropyl-1,4- benzoquinone, 4,5-dimethoxy-1,2-benzoquinone, 2-hydroxy-1,4-naphthoquinone, faflolin, 5,8-dihydroxy-1,4-naphthoquinone, naphthopurpurin, 2-hydroxy-3- (3'-methyl-2'-butenyl) - 1,4-naphthoquinone, plumbagin, 3,5-dihydroxy-2-methyl-1,4-naphthoquinone, 2-hydroxy-3- methyl-1,4-naphthoquinone, 3,5-dihydroxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4- naphthoquinone, 2-methoxy-5-hydroxy-1,4-naphthoquinone, 3-methoxy-5-hydroxy-1,4- naphthoquinone and 9,10-phenanthrenequinone.

The compounds of component B are, on the one hand, compounds that stand alone Dye keratin fibers only weakly and only together with the compounds of Formulas I and / or II give brilliant colorations. On the other hand, there are also Compounds that are already used as oxidation dye precursors or direct pullers become.

Suitable compounds with primary or secondary amino group as component B are e.g. B. primary and secondary aromatic amines such as N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-pphenylenediamine, 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, diaminophenethol, 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-methylenedioxyphenol, 3,4-methylenedioxyaniline, 3-amino- 2,4-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-methylbenzene, 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-diaminobes zoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3-amino-4-hydroxybenzoic 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-imidazoüdinone, 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-hydroxybenzonitrile, 4-A mino-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-hydroxynaphth-2-yl] trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) azo) -7-hydroxynaphth-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] 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-chlorobenzene (HC Red No. 10), 2- (4-amino-2-nitroanilino) benzoic acid, 6-nitro-2,5-diaminopyridine, 2-amino-6-chl or-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'-nitrostilben-2,2'-disulfonic acid disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methylazobenzene (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-nitroacenaphthene, 2-amino-1-nitronaphthalene, 5-amino -6-nitrobenzo-1,3-dioxole, anilines, in particular 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, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as shown in formula III


in the
R ⁸ represents a hydroxyl or an amino group which is substituted by C _1-4 alkyl, C _1-4 hydroxyalkyl, C _1-4 alkoxy or C _1-4 alkoxyC _1-4 alkyl groups can be substituted
R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ independently of one another represent a hydrogen atom, a hydroxyl or an amino group, which can be substituted by C _1-4 -alkyl-, C _1-4 -hydroxyalkyl-, C _1-4 Alkoxy, C _1-4 aminoalkyl or C _1-4 alkoxyC _1-4 alkyl groups can be substituted,
Z ¹ stands for a direct bond, a saturated or unsaturated carbon chain with 1 to 4 carbon atoms optionally substituted by hydroxy groups, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group with the formula IV

-Z ² - (CH ₂ -Z ⁴ -CH ₂ -Z ³ ) _o - (IV)

in the
Z ⁴ denotes a direct bond, a CH ₂ or CHOH group,
Z ² and Z ³ independently of one another for an oxygen atom, an NR ¹⁴ group, in which R ^{14 is} hydrogen, a C _1-4 -alkyl or a hydroxy-C _1-4 -alkyl group, both groups together with the remainder of the molecule 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, and
o means 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-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- (5th amino-2-hydroxyphenyl) methane.

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

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-triazoi, 3-aminopyrazof, 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-aminoquinodine, 2-aminonicotinic acid, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and indoline derivatives such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7- Aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. Furthermore as According to the invention, heterocyclic compounds can be 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. as salts of inorganic acids, such as hydrochloric or sulfuric acid.

Suitable aromatic hydroxy compounds are e.g. B. 2-methylresorcinol, 4- Methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, Pyrocatechol, hydroquinone, pyrogallol, phloroglucin, hydroxyhydroquinone, 2- Methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3-dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4- Dihydroxybenzoic acid, 2,4-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 2,3- Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid and 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, proline, lysine and Tryptophan. But also other amino acids, such as. B. 6-aminocaproic acid and β-alanine, can be used.

• a) wenn E¹ und E² für ein Sauerstoffatom stehen, E³ keine Hydroxygruppe ist, und
• b) wenn E¹ ein Schwefelatom und E² ein Sauerstoffatom ist, E³ keine Hydroxygruppe ist,

quaternierte Stickstoffverbindungen der Formel C19


worin,
M⁵¹ und M⁵² stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine Hydroxygruppe, eine C₁-C₄-Hydroxyalkylgruppe, eine C₁-C₆- Aminoalkylgruppe, eine C₁-C₄-Dialkylamino-C₁-C₄-alkylgruppe, eine lineare oder verzweigte C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Sulfonsäuregruppe, eine Carboxylgruppe, eine Formylgruppe, eine Nitrogruppe, eine Cyanogruppe oder eine Gruppe -NM⁵⁴M⁵⁵, wobei M⁵⁴ und M⁵⁵ stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁- C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Aryl-C₁-C₄-alkylgruppe oder eine C₁- C₄-Hydroxyalkylgruppe, wobei M⁵¹ und M⁵² zusammen einen ankondensierten 5- oder 6-gliedrigen, aliphatischen oder aromatischen Ring bilden können, welcher wiederum mit den Resten M⁵⁶ und M⁵⁷ substituiert ist, wobei M⁵⁶ und M⁵⁷ stehen unabhängig voneinander für die Reste, die unter M⁵¹ definiert sind,
M⁵³ steht für ein Wasserstoffatom, eine C₁-C₄-Hydroxyalkyigruppe, eine C₁-C₆- Aminoalkylgruppe, eine C₁-C₄-Dialkylamino-C₁-C₄-alkylgruppe, eine lineare oder verzweigte C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Sulfonsäuregruppe, eine Carboxylgruppe, eine Formylgruppe, eine Nitrogruppe, eine Cyanogruppe oder eine Gruppe -NM⁵⁸M⁵⁹, wobei M⁵⁸ und M⁵⁹ stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Aryl-C₁-C₄- alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
Y steht für ein Sauerstoffatom, ein Schwefelatom, eine gegebenenfalls substituierte Methylengruppe oder eine Gruppe NM⁶⁰, wobei M⁶⁰ für die gleichen Gruppen stehen kann, die unter M⁵⁵ definiert sind,
A^- steht für ein Chlorid, Bromid, Iodid, Hexafluorophosphat, Tetrachlorozinkat, Tetrafluoroborat, Trifluormethylsulfonat, Methylsulfonat oder p-Toluolsulfonat,
Qniumverbindungen der Formeln C20 und C21


wobei M⁵¹, M⁵², M⁵³ und A^- aus den Gruppen ausgewählt werden, die unter Verbindung C19 definiert sind. Component B can also be a CH-acidic compound. Those compounds which carry a hydrogen atom bonded to an aliphatic carbon atom are generally regarded as CH-acidic, activation of the corresponding carbon-hydrogen bond being effected on account of electron-withdrawing substituents. According to the invention, the CH-acidic compounds are preferably selected from compounds according to one of the formulas C1 to C21:

M ¹ -CH ₂ -M ² (C1)

wherein
M ^{1 is} a group -COM ³ or COOM ³ , in which M ^{3 represents} a hydrogen atom or a C ₁ -C ₆ alkyl group, or a group -C (M ⁴ ) = C (C ~ N) ₂ , in which M ^{4 represents} a hydrogen atom, a C ₁ -C ₄ alkyl group or an aryl group,
M ^{2 has} the same meaning as M ¹ or is a cyano group, a substituted or unsubstituted aryl group or aryl-C ₁ -C ₄ -alkyl group, a substituted or unsubstituted, saturated or unsaturated heterocycle,
Compounds with the formula C2


wherein
M ^{5 is} a group -COM ⁷ or COOM ⁷ , in which M ^{7 represents} a hydrogen atom or a C ₁ -C ₆ alkyl group, or a cyano group, a substituted or unsubstituted aryl group or an aryl-C ₁ -C ₄ alkyl group, is a substituted or unsubstituted, saturated or unsaturated heterocycle,
M ^{6 is} a substituted or unsubstituted C ₁ -C ₆ alkyl group, an acetyloxy group, a C ₃ -C ₆ cycloalkyl group, a substituted or unsubstituted aryl group or aryl-C ₁ -C ₄ alkyl group, a substituted or unsubstituted aminoaryl group, a substituted one or is unsubstituted, saturated or unsaturated heterocycle,
Compounds with the formula C3


wherein
M ⁸ is a group -COM ¹⁰ or COOM ¹⁰ , wherein M ^{10 represents} a hydrogen atom or a C ₁ -C ₆ alkyl group, or a cyano group, a substituted or unsubstituted aryl group or aryl-C ₁ -C ₄ alkyl group substituted or unsubstituted, saturated or unsaturated heterocycle,
M ^{9 is} a substituted or unsubstituted aryl group or aryl-C ₁ -C ₄ -alkyl group, a substituted or unsubstituted aminoaryl group, a substituted or unsubstituted, saturated or unsaturated heterocycle,
Pyrazole derivatives (a), which can be selected from the following formulas C4 and C5


wherein
M ¹¹ and M ¹² independently of one another represent a substituted or unsubstituted C ₁ -C ₆ alkyl group, an acetyloxy group, a C ₃ -C ₆ cycloalkyl group, a substituted or unsubstituted aryl group or aryl C ₁ -C ₄ alkyl group, a substituted one or unsubstituted aminoaryl group, a substituted or unsubstituted, saturated or unsaturated heterocycle,
M ^{13 is} a hydrogen atom or a substituted or unsubstituted C ₁ -C ₆ alkyl group,
(b) two pyrazole rings bonded via M ¹¹ or M ¹² with the formula C4 or C5 barbituric acid derivatives with the following formula C6


wherein
M ¹⁴ and M ¹⁵ independently of one another represent a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₃ -C ₆ cycloalkyl group, an aryl-C ₁ -C ₄ alkyl group, a substituted or unsubstituted aryl group, or a bicyclic bonded via the radicals M ¹⁴ or M ¹⁵ ,
X represents an oxygen or a sulfur atom,
Pyridine derivatives with the formulas C7a and C7b


wherein
M ^{16 is} a substituted or unsubstituted C ₁ -C ₆ alkyl group or substituted or unsubstituted aryl group,
M ^{17 is} a hydrogen atom, a substituted or unsubstituted C ₁ -C ₆ alkyl group or a substituted or unsubstituted aryl group,
M ^{18 is} a hydrogen atom, a cyano group, a substituted or unsubstituted C ₁ -C ₆ -alkyl group, a group COOM ¹⁹ , in which M ^{19 is} a hydrogen atom or a substituted or unsubstituted C ₁ -C ₆ -alkyl group,
Compounds with the following formula C8


wherein
A represents an oxygen atom, a sulfur atom, a sulfonyl group or a group NM ^20a , where M ^{20a represents} a hydrogen atom, a substituted or unsubstituted C ₁ -C ₆ alkylene group,
M ²⁰ and M ²¹ independently represent a hydrogen, a chlorine, a bromine atom, a hydroxy group, a nitro group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a carboxamide group, a Sulfonamide, a carboxyl, a C ₁ -C ₄ acyl, a cyano group or an amino group -NM ²² M ²³ , in which M ²² and M ²³ independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group,
Compounds with the formulas C9 and C10


wherein
A 'represents an oxygen atom, a sulfur atom or a group NM ²⁵ , in which M ^{25 represents} a hydrogen atom or a substituted or unsubstituted C ₁ -C ₆ -alkyl group,
M ²⁴ stands for a hydrogen, a chlorine, a bromine atom, a hydroxyl group, a nitro group, a C ₁ -C ₆ alkyl, a C ₁ -C ₆ alkoxy, a carboxamide, a sulfonamide, one Carboxyl, a C ₁ -C ₄ acyl, a cyano group or an amino group -NM ²⁶ M ²⁷ , in which M ²⁶ and M ²⁷ independently represent hydrogen and a C ₁ -C ₆ alkyl group
Compounds with the formula C11


wherein
M ^{28 is} a hydrogen atom, a hydroxy group, a substituted or unsubstituted C ₁ -C ₆ alkyl group or a substituted or unsubstituted aryl or C ₁ -C ₆ alkylaryl group;
M ²⁹ represents a hydrogen atom or a C ₁ -C ₄ alkyl group
Indanedione derivatives with the formula C12


wherein
M ^{30 is} a hydrogen, a chlorine, a bromine atom, a nitro, a C ₁ -C ₆ alkyl, a C ₁ - C ₆ alkoxy, a carboxamide, a sulfonamide or a cyano group,
Compounds with the formula C13


wherein
Z represents an oxygen atom or a group NM ³² , where M ^{32 represents} a hydrogen atom or a C ₁ -C ₆ -alkyl group,
Z 'represents a sulfur atom or a group NM ³³ , in which M ^{33 represents} a hydrogen atom or a C ₁ -C ₆ alkyl group,
M ³¹ represents a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₄ carboxyalkyl group,
Dioxopyrazole compounds with the formula C14


wherein
M ³⁴ and M ³⁵ independently of one another represent a hydrogen, a chlorine, a bromine atom, a hydroxyl group, a nitro group, a C ₁ -C ₆ alkyl, a C ₁ -C ₆ alkoxy, a carboxamide, a sulfonamide, a carboxyl, a C ₁ -C ₄ acyl, a cyano group or an amino group -NM ³⁶ M ³⁷ , in which M ~ and M3 'independently of one another represent hydrogen or a C ₁ -C ₆ alkyl group,
5-oximidazole derivatives with the formula C15


wherein
M ³⁸ and M ³⁹ independently of one another represent a hydrogen, a chlorine, a bromine atom, a hydroxy group, a nitro group, a C ₁ -C ₆ alkyl, a C ₁ -C ₆ alkoxy, a carboxamide, a sulfonamide, a carboxyl, a C ₁ -C ₄ acyl, a cyano group or an amino group -NM ⁴¹ M ⁴² , in which M ⁴¹ and M ⁴² independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group .
M ⁴⁰ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
Derivatives of dehydrobutyrolactone with the formula C16


wherein
M ⁴³ and M ⁴⁴ independently of one another represent a hydrogen, a chlorine, a bromine atom, a hydroxyl group, a nitro group, a C ₁ -C ₆ alkyl, a C ₁ -C ₆ alkoxy, a carboxamide, a sulfonamide, a carboxyl, a C ₁ -C ₄ acyl, a cyano group or an amino group -NM ⁴⁵ M ⁴⁶ , in which M ⁴⁵ and M ⁴⁶ independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group
Compounds with the formula C17


wherein
D ¹ is a fused aromatic or heteroaromatic ring,
D ² is a carbonyl group or a methylene group CD ^I D ^II , in which D ^I or D ^II each have a substituent with a Hammett constant between 0.4 and 2.0 or both substituents in total a Hammett constant between 0.4 and have 2.0;
D ³ represents a carbonyl group, an oxygen atom, a sulfur atom, a group NM ⁴⁷ if D ^{2 is} not oxygen, or a group C = S, a group C = NR ₄ , a sulfinyl group, a sulfonyl group, where R ⁴⁷ and R ⁴⁸ independently of one another represent a hydrogen atom or a C ₁ -C ₄ -alkyl radical,
Hydroxypyrimidine derivatives with the formula C18


wherein
M ⁴⁹ and M ^{50 are} independently of one another a hydrogen atom or a substituted or unsubstituted C ₁ -C ₆ -alkyl group,
E ^{1 represents} an oxygen, a sulfur atom or a group NH,
E ^{2 represents} a group NH or an oxygen atom,
E ^{3 represents} an amino group or a hydroxy group,
with the proviso that

• a) when E ¹ and E ^{2 represent} an oxygen atom, E ^{3 is} not a hydroxy group, and
• b) when E ^{1 is} a sulfur atom and E ^{2 is} an oxygen atom, E ^{3 is} not a hydroxy group,

quaternized nitrogen compounds of formula C19


wherein,
M ⁵¹ and M ⁵² independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₁ -C ₆ aminoalkyl group, a C ₁ -C ₄ dialkylamino-C ₁ -C ₄ -alkyl group, a linear or branched C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, a sulfonic acid group, a carboxyl group, a formyl group, a nitro group, a cyano group or a group -NM ⁵⁴ M ^55, where M ⁵⁴ and M ⁵⁵ are independently a hydrogen atom, a C ₁ - C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an aryl-C ₁ -C ₄ alkyl group or a C ₁ - C ₄ -Hydroxyalkylgruppe, where M ⁵¹ and M ⁵² together can form a fused-on 5- or 6-membered, aliphatic or aromatic ring, which in turn is substituted by the radicals M ⁵⁶ and M ⁵⁷ , where M ⁵⁶ and M ⁵⁷ independently of one another represent Residues defined under M ⁵¹ ,
M ⁵³ represents a hydrogen atom, a C ₁ -C ₄ hydroxyalkyl group, a C ₁ -C ₆ aminoalkyl group, a C ₁ -C ₄ dialkylamino-C ₁ -C ₄ alkyl group, a linear or branched C ₁ -C _{4 6-} alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, a sulfonic acid group, a carboxyl group, a formyl group, a nitro group, a cyano group or a group -NM ⁵⁸ M ⁵⁹ , where M ⁵⁸ and M ⁵⁹ are independent of one another for a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an aryl-C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group,
Y stands for an oxygen atom, a sulfur atom, an optionally substituted methylene group or a group NM ⁶⁰ , where M ⁶⁰ can stand for the same groups which are defined under M ⁵⁵ ,
A ^- stands for a chloride, bromide, iodide, hexafluorophosphate, tetrachlorozincate, tetrafluoroborate, trifluoromethyl sulfonate, methyl sulfonate or p-toluenesulfonate,
Qnium compounds of the formulas C20 and C21


wherein M ⁵¹ , M ⁵² , M ⁵³ and A ^- are selected from the groups defined under Compound C19.

According to the invention, CH-acidic compounds also include enamines which arise from quaternized N-heterocycles with an CH-acidic alkyl group conjugated to the quaternary nitrogen by alkaline treatment. Examples of suitable enamines are compounds having the general formula C22


wherein
M ⁶¹ stands for an aromatic radical, in particular for a 5-membered or 6-membered aryl residue which is optionally substituted by a C ₁ -C ₄ -alkyl, C ₁ -C ₄ -hydroxyalkyl, hydroxyl, methoxy or halogen group, preferably a phenyl radical, or a 5-membered or 6-membered, fused, aliphatic or aromatic, carbocyclic or heterocyclic ring, preferably a phenyl residue, a quinoline or pyridyl residue,
M ⁶² stands for a hydrogen atom, a linear or branched C ₁ -C ₈ alkyl, a linear or branched C ₁ -C ₈ hydroxyalkyl or a C ₁ -C ₈ alkoxyalkyl group, with between the C atoms of the alkyl chain an oxygen atom can sit, and
M ⁶³ represents a linear or branched C ₁ -C ₈ alkyl group, a C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkylamino-C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkylmercapto-C ₁ - C ₆ alkyl group, a C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkylene group, a C ₁ -C ₆ alkylamino-C ₁ -C ₆ alkylene , is a C ₁ -C ₆ alkylmercapto-C ₁ -C ₆ alkylene group, a straight-chain or branched C ₁ -C ₆ alkylene group, or an oxygen atom, a nitrogen atom or a sulfur atom, with the proviso that the radicals M ⁶¹ and M ⁶³ together with the nitrogen atom and the carbon atom of the basic enamine structure form a cyclic compound if M ⁶³ is a linear or branched C ₁ -C ₈ alkylene group, a C ₁ -C ₈ alkoxyalkylene group, a C ₁ -C ₆ alkylamino -C ₁ -C ₆ alkylene group, a C ₁ -C ₆ alkylmercapto-C ₁ -C ₆ alkylene group, an oxygen atom, a nitrogen atom or a sulfur atom, preferably M ⁶³ on the aromatic radical M ⁶¹ mi t is connected to the carbon which is ortho to the enamine-substituted carbon.

The compounds with the formulas C1, C2 and C3 are preferably selected from Malonic acid, malonic esters and their derivatives and acetoacetic acid, Acetoacetic acid esters and their derivatives.

Examples of compounds with the formula C4 are pyrazol-5-one, 3-methyl-pyrazol-5-one, 1-phenyl-3-methyl-pyrazol-5-one, 1- (β-cyanoethyl) -3-methyl-pyrazol-5-one, 1,3-dimethylpyrazol-5-one, 1- (β-acetoxyethyl) -3-methyl-pyrazol-5-one, 1- (2'-chlorophenyl) -3-methylpyrazol-5-one, 1-phenyl-3-carbomethoxy-pyrazol-5-one, 1- (3'-aminophenyl-pyrazol-5-one, 1- (4'-aminophenyl) pyrazol-5-one, 3-methyl-pyrazol-5-one-1-carboxamide, 1-phenyl-pyrazole- 5-one-3-carboxamides, amino-pyrazole, 1-phenyl-5-aminopyrazole, 1-benzyl-5-aminopyrazole, 1-cyclohexyl-5-amino-pyrazole, 1-ethyl-3-methyl-5-amino-pyrazole, 1-benzyl-3- phenyl-5-aminopyrazole, 1-isopentyl-5-aminopyrazole, 1-furfuryl-5-aminopyrazole, 2- Methyl-4H-pyrazolo (5) - [2,3-a] benzimidazole, [1- (3'-thiacyclopentyl) -3-methyl-pyrazole-5- on-S-dioxide], 2-methyl-1H-3,3a, 8-triazacyclopenta [a] indene.

The barbituric acid derivatives with the formula C6 are preferably selected from Barbituric acid, thiobarbituric acid, di-N-ethylthiobarbituric acid, di-N- Methylthiobarbituric acid, di-n-butyl barbituric acid, di-isobutyl barbituric acid, Di-N-amylbarbituric acid, di-iso-amyl-barbituric acid, di-n-hexyf-barbituric acid, Di-benzyl barbituric acid, di-β-phenylethyl barbituric acid, di-cyclohexyl barbituric acid, D1-phenylbarbituric acid, di-p-tolyl barbituric acid, di-p-methoxybenzyl barbituric acid, N-methyl-N'-n- butyl barbituric acid, N-methyl-N'-benzyl barbituric acid, N-methyl-N'-β-phenylethylbarbituric acid, N-methyl-N'-γ-phenylpropyl barbituric acid, N-methyl-N'-γ-phenylbutylbarbituric acid, N-methyl-N'-α-isobutyl-γ-phenylpropyl barbituric acid, N-methyl-N'- cyclohexyl barbituric acid, N-methyl-N'-phenyl barbituric acid, N-methyl-N'-p-toloyl barbituric acid, N-methyl-N'-norbornylmethyl barbituric acid and the corresponding N- Ethyl and N-n-butyl derivatives of the above compounds.

Preferred examples of the pyridine derivatives with the formula C7 are mentioned 2,6-dihydroxy-3-cyano-4-methyl-pyridine, cyanopyridones, aminonitropyridones and Aminocyanopyridones, especially N-methyl-3-cyano-4-methyl-6-hydroxy-pyridon-2, N-ethyl-3- cyano-4-methyl-6-hydroxy-pyridone-2, N-β-methoxyethyl-3-cyano-4-methyl-6-hydroxypyridin-2-one, N-β-hydroxyethyl-3-cyano-4-methyl-6-hydroxy-pyridin-2-one, N-butyl 3 cyano-4-methyl-6-hydroxy-pyridin-2-one and N-phenyl-3-cyano-4-methyl-6-hydroxy-pyridin-2-one.

The compounds with the formula C8 can be selected from 6-hydroxybenzofuran (2H) -one and 3-indoxy acetate.

The compounds with the formula C9 can be selected from indol-2-one, 1,3- Dihydro-indof-2-one, 3H-benzofuran-2-one, 1-methyl-1,3-dihydro-indol-2-one, 5-methoxy-3H- benzofuran-2-one, 5-nitro-1,3-dihydro-indol-2-one, 1-methyl-5-nitro-1,3-dihydro-indol-2-one, 6-methoxy-1,3-dihydro-indol-2-one, 5-chloro-1,3-dihydro-indol-2-one, 5,6-difluoro-1,3- dihydro-indol-2-one, 6-hydroxy-5-methoxy-1,3-dihydro-indol-2-one, 5,6-dimethoxy-1,3- dihydro-indol-2-one and 6-trifluoromethyl-1,3-dihydro-indol-2-one.

Examples of compounds having the formula C10 are imidazo [1.2-a] pyridin-2-one, and 6- Bromoimidazo [1,2-a] pyridin-2-one.

The compounds with the formula C11 are preferably selected from the derivatives in which in the formula C11 the radicals M ²⁸ and M ²⁹ stand for a hydrogen atom, such as 2,4-dihydroxyquinoline.

A suitable example of an indanedione derivative with the formula C12 is 1,3-indanedione.

The compounds having the formula C13 are preferably selected from rhodanine, Rhodanine-3-acetic acid and 4-imino-4,5-dihydro-thiazol-2-ylamine.

1,2-Diphenyldioxopyrazole can be mentioned as the preferred compound with the formula C14 become.

The compounds having the formula C15 are preferably selected from 2-phenyl 3,5-dihydro-imidazol-4-one and 3-methyl-2-p-toloyl-3,5-dihydro-imidazol-4-one.

A preferred example of a compound of formula C16 is Phenyldihydrobutyrolacton.

The compounds having the formula C17 are preferably selected from 1,1-dioxo- 1,2-dihydro-11,6-benzo [b] -thiophen-3-one, 1-dicyanomethylene indane, 1,3- Bis (dicyanomethylene) indane and 2- (1 ', 1'-dioxo-1', 2'-dihydro-11 ', 6'-benzo [b] -thiophene-3'- ylidene) malononitrile.

Examples of hydroxypyrimidine derivatives with the formula C18 are 2,4-diamino-6-hydroxypyrimidine, 2,6-diamino-4-hydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4-amino-6- hydroxy-2-sulfanylpyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4,6-dihydroxy-1 - mercaptopyrimidine and 2,4,6-trihydroxypyrimidine, being 2,4-diamino-6-hydroxypyrimidine is particularly preferred.

Preferred compounds with the formula C19, C20 or C21 are 1,2- Dimethylnaphtho [1,2-d] thiazolium p-toluenesulfonate, 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl-benzothiazolium-p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3-H-indofium iodide, 1,2,3,3-tetramethyl-3H-indouump-toluenesulfonate, 1-methyl-2-quinaldinium iodide, 1-ethyl-2-quinaldinium iodide and 1,4- Dimethylchinoliniumiodid.

Preferred enamines having the formula C22 are those in which the radicals M ⁶¹ and M ⁶³ form a cyclic compound together with the nitrogen atom and the carbon atom of the basic enamine structure, the 1,3,3-trimethyl-2-methylene-indoline, the 1- (2-Hydroxyethyl) -3,3-dimethyl-2-methylene-indoline and 3-ethyl-2-methylene-benzothiazoline are particularly preferred.

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

Examples of quaternary ammonium salts are tetramethyl, tetraethyl, tetrapropyl, Tetrabutyl, benzyltrimethylammonium chloride, bromide, iodide, hydrogen sulfate, 0.5 sulfate and the quaternized hydroxyethyl cellulose derivatives (INCI name: Polyquaternium 10).

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, 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, 2,6-dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 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-methylenedioxyphenol, 3,4-diaminobenzoic acid, 2,5-diaminopyridine, 2-dimethyfamino-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-triaminopyrimidine, 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), 2,3-dimethylbenzothiazolium p-toluenesulfonate, 1,2,3,3- Tetramethyl-3H-indolinium-p-toluenesulfonate, thiobarbituric acid, rhodanine, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 1,2-dimethylnaphtho [1,2-d] thiazolium p-toluenesulfonate, 1-methyl-2-quinaldinium p-toluenesulfonate, 1,4-dimethylquinolinium p-toluenesulfonate, β- Alanine, L-proline, L-lysine, DL-tyrosine and their preferably with inorganic acids formed physiologically acceptable salts.

Very particularly preferred compounds of component B are according to the invention N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2,5-diaminotoluene, 2- (2,5-diaminophenyl) - ethanol, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2- (diethylaminomethyl) -4-aminophenol, 1-hydroxy-2-amino-5-methyl-benzene, 2,4- Diaminophenoxyethanol, 3-amino-2,4-dichlorophenol, 2-methyl-5-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 6-methyl-3-amino-2-chlorophenol, 2-methyl-5-amino-4- chlorophenol, 3,4-methylenedioxyaniline, 3,4-diaminobenzoic acid, 3,5-diamino-2-methoxy 1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) anisole, 2,6-bis- (2-hydroxyethylamino) -1- methylbenzene, 1,3-bis- (2,4-diaminophenoxy) propane, 4,5-diamino-1- (2- hydroxyethyl) pyrazole, 1,4-bis (4-aminophenyl) -1,4-diazacycloheptane, bis- (2-hydroxy-5- aminophenyl) methane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 4,4'- Diaminodiphenylamine, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6- methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 5,6-dihydroxyindole, 5,6- Dihydroxyindoline, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triamino-pyrimidine, 4- Hydroxy-2,5,6-triamino-pyrimidine and their preferably inorganic acids formed physiologically acceptable salts.

Components A and B are preferably used in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the finished product used Colorant (agent 2) used.

To achieve further and more intense colorations can be in the invention Process in addition to the compounds used as component B. Color enhancers are used. The color intensifiers 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-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5- carboxylic acid, pyrazole, 1,2,4-triazole, piperazine, methoxybutanol, propylene carbonate, Ethylene carbonate, its derivatives and its 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 total Colorant (agent 2) can be used. Should one of the defined as a color enhancer Compounds both as color enhancers and as component B for use come, the amounts of these compounds the respective upper limits of 65 mmol or 40 mmol. In this embodiment, the Upper limits are preferred at 130 mmol, in particular at 80 mmol.

In all colorants (agent 2), several different compounds with the Formulas I and II and component B are used; as well can several different color amplifiers can be used together.

In a less preferred embodiment, the process according to the invention for further modification of the color shades in addition to those used according to the invention Compounds additionally conventional direct dyes, e.g. B. from the group of Nitrophenylenediamines, 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 BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as 6-nitro 1,2,3,4-tetrahydro, 4-N-ethyl-1,4-bis (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride and 1-methyl-3-nitro-4- (2'-hydroxyethylamino) benzene are used. in the According to this embodiment, the inventive methods are the direct ones Dyes preferably in an amount of 0.01 to 20 wt .-%, based on the components used, added.

Furthermore, the preparations used according to the invention can also be used in nature occurring dyes, such as those in red henna, neutral henna, henna black, chamomile flower, sandalwood, black tea, sapwood, sage, blue wood, Madder root, catechu, sedre and alkanna root are included.

With regard to other conventional dye components, it is expressly stated "Dermatology", edited by Ch. Culnan, H. Maibach, 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 European 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.

It is not necessary that the compounds contained in the invention with the Formulas I and II or the optional color enhancers and substantive dyes each represent uniform connections. Rather, according to the invention Colorants used (agent 2), due to the manufacturing process for the individual dyes, contain minor components in minor amounts to the extent that these do not adversely affect the coloring result or from others Reasons, e.g. B. toxicological, must be excluded.

The colorants (agent 2) used according to the invention already result in physiologically acceptable temperatures of less than 45 ° C intense colorings. she are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants (agent 2) can usually be in one water-containing cosmetic carriers are incorporated. Suitable water-containing cosmetic carriers are e.g. B. creams, emulsions, gels or surfactants foaming solutions such as B. shampoos or other preparations for the Application on the keratin fibers are suitable. If necessary, it is too possible to incorporate the colorants (agent 2) into anhydrous carriers.

Furthermore, the agents 1 and / or agents 2 used according to the invention can all be used in such preparations contain known active ingredients, additives and auxiliaries. In many cases The agents contain at least one surfactant, in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In In many cases, however, it has proven advantageous to use anionic, select zwitterionic or nonionic surfactants.

• - lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• - Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• - Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in derAlkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• - lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• - lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• - Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• - Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• - Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030,
• - sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,
• - Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,
• - Ester der Weinsäure und Citronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2 bis 15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

Suitable anionic surfactants in preparations used according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 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 acid and dialkyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates 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 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
• Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
• - Esters of tartaric acid and citric acid with alcohols, the addition products of about 2 to 15 molecules of ethylene oxide and / or propylene oxide 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 -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl-3 -carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are 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-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 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

• - Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C- Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• - C_12-22-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• - C_8-22-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga,
• - Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• - Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester
• - Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide.

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

• Addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,
• C _12-22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,
• C _{8-22 alkyl} mono- and 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
• - Adducts of ethylene oxide with fatty acid alkanolamides.

Examples of the hair treatment compositions used in the invention Cationic surfactants that can be used are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides are preferred. Dialkyldimethylammoniumchloride and Trialkylmethylammoniumchloride, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic that can be used according to the invention Surfactants are the quaternized 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 Trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines 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, so-called "Esterquats", such as those sold under the Stepantex® trademark Methylhydroxyalkyldialkoyloxyalkylammonium.

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 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 manufacturing these substances are based on natural vegetable or animal raw materials, so that mixtures of substances with different raw materials dependent alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide Fatty alcohols or derivatives of these addition products can represent both products with a "normal" homolog distribution as well as those with a narrowed Homolog distribution can be used. Under "normal" homolog distribution Mixtures of homologs understood, which one in the implementation of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Narrowing homolog distributions will be on the other hand, if, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts become. The use of products with a narrow homolog distribution can be preferred.

• - nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• - kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallylammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylaminoethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazoliniummethochlorid- Copolymere und quaternierter Polyvinylalkohol,
• - zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyltrimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methylmethacrylat/tert.-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• - anionische Polymere wie beispielsweise Polyacrylsäuren, vemetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.-Butylacrylamid-Terpolymere,
• - Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, CelluloseDerivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• - Strukturanten wie Glucose und Maleinsäure,
• - haarkonditionierende Verbindungen wie Phosphoüpide, beispielsweise Sojalecithin, E1-Lecitin und Kephaline, sowie Silikonöle,
• - Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• - Parfümöle, Dimethylisosorbid und Cyclodextrine,
• - Lösungsvermittler wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• - Antischuppenwirkstoffe wie Piroctone Olamine und Zink Omadine,
• - weitere Substanzen zur Einstellung des pH-Wertes,
• - Wirkstoffe wie Panthenol, Pantothensäure, Allantoin, Pyrrolidoncarbonsäuren und deren Salze, Pflanzenextrakte und Vitamine,
• - Cholesterin,
• - Lichtschutzmittel,
• - Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• - Fette und Wachse wie Walrat, Bienenwachs, Montanwachs, Paraffine, Fettalkohole und Fettsäureester,
• - Fettsäurealkanolamide,
• - Komplexbildner wie EDTA, NTA und Phosphonsäuren,
• - Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate, Imidazole, Tannine, Pyrrol,
• - Trübungsmittel wie Latex,
• - Perlglanzmittel wie Ethylenglykolmono- und -distearat,
• - Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft sowie
• - Antioxidantien.

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-dimethyldiallylammonium chloride copolymers, diethyl sulfate-quaternized dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidaternolino-copolymers,
• - zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / 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 anhydride copolymers and acrylic acid / tert-acrylamide / nyl acrylate / nyl acrylate / nyl acrylate / nyl acrylate / nyl acrylate /
• - Thickeners 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. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,
• Structurants such as glucose and maleic acid,
• hair-conditioning compounds such as phosphoupids, for example soy lecithin, E1 lecithin and cephalins, and silicone oils,
• Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol 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 whale, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• - fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA and phosphonic acids,
• Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole,
• Opacifiers 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 components of the water-containing carrier are used for the production of Suitable methods according to the invention in amounts customary for this purpose used; z. B. are emulsifiers in concentrations of 0.5 to 30 wt .-% and Thickeners in concentrations of 0.1 to 25% by weight of the total preparation used.

For the dyeing result it can be advantageous to add ammonium or add metal salts. Suitable metal salts are e.g. B. formates, carbonates, Halides, sulfates, butyrates, valemates, 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, 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 mmol, in particular from 1 to 40 mmol based on 100 g of the total colorant (agent 2).

The pH value of the ready-to-use coloring preparations is usually between 2 and 12, preferably between 4 and 10.

Components A and optionally component B and those optionally Color enhancers can either be stored separately or together, either in a liquid to pasty preparation (aqueous or anhydrous) or as dry powder. When stored separately, the components only become immediate intimately mixed before use. In dry storage, before Usually use a defined amount of warm (30 to 80 ° C) water added and made a homogeneous mixture.

Examples

Dark blonde hair strands from Kerling were bleached 1 × with Poly® Blonde ultra (Schwarzkopf handle). Then one of the dye mixtures AF listed in Table 1 was applied. After an exposure time of 30 min. at 32 ° C the dye mixture was rinsed out. After drying, the color of the strands was determined using the German Color Atlas. The strands were also measured colorimetrically using the Texflash DC 3881 (Datacolor). The so-called CIE-Lab values were determined, from which the color difference AE results according to the following color distance formula:

ΔE = [(ΔL) ² + (Δa) ² + (Δb) ² ] ^1/2

(see also DIN 6174, German standards, Benth Verlag GmbH, Berlin, 1975).

To determine the wash resistance, the strands were 6 × with the shampoo Poly® Kur Aloe & Mango Balsam Shampoo (Schwarzkopf-Henkel) washed and then measure again colorimetrically. The strand of hair before shampooing served to determine the ΔE value (see Table 2) as standard.

For comparison, the same ultrabonded starting strands were used in Table 2 mentioned commercial products Poly®Live Töner and Igora® Fleur (both based on direct dyes; Schwarzkopf-Henkel) applied and analogous to the strands A-F treated.

All the strands treated with direct drawers gave significantly higher color difference values after washing six times and thus a significantly poorer wash resistance than the strands treated with the AF dye mixtures according to the invention. Legend for Table 1 Natrosol® 250 HR: hydroxyethyl cellulose (INCI name: hydroxyethyl cellulose) (HERCULES)
Texapon®: NSO lauryl ether sulfate, sodium salt (approx. 27.5% active substance; (INCI name: Sodium Laureth Sulfate) (COGNIS)
Dehyton® K: N, N-Dimethyl-N- (C ₈ -C ₁₈ cocosamidopropyl) ammonium acetobetaine (approx. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (COGNIS)
Hydrenol® D: C ₁₆ -C ₁₈ fatty alcohol (INCI name: Cetearyl alcohol) (COGNIS)
Lorol®, techn .: C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (COGNIS)
Eumulgin® B 2: Cetearylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (COGNIS) Table 1

Table 2 Color results of the dyeings and color retention after shampooing six times

Claims (20)

1. A process for dyeing keratin fibers, in particular human hair, wherein the fibers are first treated with an agent 1 containing an oxidizing agent and then an agent 2 containing A) at least one compound A with the formula I,


in which
AR stands for benzene, naphthalene, pyridine, furan, quinoline, isoquinoline, quinolizine, pyrimidine, pyrrole, thiophene, indole, indan, imidazole, benzimidazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, cinnoline, acenaphthene, fluorene, biphenanyl, diphenyl , Benzophenone, diphenyl ether, azobenzene, diphenylamine, stilbene and their partially or fully hydrogenated derivatives,
R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a C _1-4 alkyl, C _1-4 alkoxy, C _1-4 acyl or C _1-4 hydroxyalkoxy , Hydroxy or nitro group or an amino, C _1-4 -acylamino, ammonio or a 1-imidazoli (ni) o group, which may be substituted by C _1-4 alkyl or C _1-4 hydroxyalkyl groups, and also two of the radicals R ¹ , R ² and R ^{3 can form} a saturated or unsaturated, optionally substituted 5-, 6- or 7-ring fused to AR, which in turn can carry a fused-on aromatic, optionally substituted ring, the System AR, depending on its size, can carry further substituents which can have the same meaning as R ¹ , R ² and R ³ and
X stands for
a group N ~ N ⁺ Y ^- , where Y ^{- represents} a halide, nitrate, 0.5 sulfate, hydrogen sulfate, alkene sulfonate, arene sulfonate or a hydroxy group or
a group -QR ⁴ or a group -Q-CO-R ⁴ , wherein
Q represents a direct bond, an oxygen atom, a carbonyl group, an optionally substituted methylene, vinylene, 1,3-butadiene-1,4-diyl or phenylene group and
R ⁴ is a hydrogen atom, a C _1-4 alkyl, C _2-4 alkenyl, an optionally substituted aryl or heteroaryl group, a group - [CH ₂ CH ₂ O] _z -R ⁵ in which R ^{5 is} one C _1-4 alkyl, C _2-4 alkenyl, an optionally substituted aryl or heteroaryl group and z is an integer from 1 to 5,
or the groups -QR ⁴ or -Q-CO-R ⁴ form with one of the substituents R ¹ , R ² or R ³ a saturated or unsaturated, optionally substituted 5-, 6- or 7-ring which is also fused to AR and which also has one can carry fused-on aliphatic or aromatic, carbocyclic or heterocyclic optionally substituted ring,
and / or with the formula II


in which
G represents a direct bond, a C ₁ -C ₄ alkylene group, a C ₂ -C ₄ alkenylene group or a C ₄ -C ₆ dialkenylene group,
R ⁶ and R ⁷ independently of one another represent a hydrogen atom, a C ₁ -C ₄ alkyl group, or together with the group -C (O) -GC (O) - form an optionally substituted ring, which in turn is a fused-on optionally substituted aromatic ring Can wear ring, the groups R ⁶ and R ⁷ together forming a C ₁ -C ₄ alkenylene group, a C ₄ -C ₆ dialkenylene group or a C ₁ -C ₄ alkylene group, B) and optionally as component B at least one compound selected from a group which is formed from a) compounds with primary or secondary amino group or hydroxy group, selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, b) amino acids, c) oligopeptides composed of 2 to 9 amino acids, d) CH-acidic compounds, e) quaternary ammonium compounds, and the physiologically tolerable salts of the abovementioned compounds, applied to the fibers containing keratin, left on the fiber for some time, usually about 30 minutes, and then rinsed out or washed out with a shampoo. 2. The method according to claim 1, characterized in that H ₁ O ₂ , H ₂ O ₂ releasing compounds such as sodium carbonate peroxyhydrate, urea peroxide or melamine perhydrate, or combinations of these, are used in agent 1 as oxidizing agent. 3. The method according to claim 2, characterized in that the agent 1 contains an additional oxidizing agent, selected from Na, K, NH ₄ peroxodisulfate and the corresponding peroxodiphosphonates. 4. The method according to claim 2 or 3, characterized in that the agent 1st additionally contains magnesium peroxide. 5. The method according to any one of claims 1 to 4, characterized in that the Compound A is selected from stable diazonium salts, onium aldehydes and Isatin and isatin derivatives of the formula 1. 6. The method according to claim 5, characterized in that the compound having the formula I is selected from
Diazonium salts such as 4-diazo-phenylamine sulfate, 4-diazo-4'-methoxydiphenylamine chloride, 4-diazo-3,2'-dimethylazobenzenesulfate, 2-methoxy-4-nitrobenzenediazoniumnaphthalene-1,5-disulfonate, 4-diazo-2.5 -dimethoxy-4'-nitroazobenzene chloride- zinc chloride double salt, 2,5-dimethoxy-4-benzolyaminophenyldiazonium chloride, 2-methoxy-4-nitrobenzene diazonium-1,5-naphthalenedisulfonate, 4-chloro-2-nitrobenzene diazonium chloride-zinc chloride double salt, 5- Chlorine-2-methoxybenzene diazonium chloride-zinc chloride double salt, 4-benzamido-2-methoxy-5-methylbenzene diazonium chloride-zinc chloride double salt, 2-diazo-1-naphthol-4-sulfonic acid, Na salt of 2-diazo-1- naphthol-5-sulfonic acid,
Onium aldehydes, such as the benzenesulfonates, p-toluenesulfonates, methanesulfonates, perchlorates, sulfates, chloroformes, bromides, iodides and / or tetrachlorozincates of 4-formyl-1-methylpyridinium, 3-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium -Formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium , 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 4- (2-formylvinyl) -1-methylquinolium, 4-acetyl-1-methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1 -methylquinoline and 4- (2-formylvinyl) -1-methylpyridinium, 2,6-dichloro-4-formyl-1-methylpryridinium, 2,6-diphenyl-4-formyl-1-methylpyridinium, 4-benzoyl-1-methylpyridinium , 4-propionyl-1-methylpyridinium, 4-pyridinaldehyde-N-oxide and N-methylpyridoxal,
Isatin or isatin derivatives, such as isatin, isatin-5-sulfonic acid, isatin-4-carboxylic acid and isatin-5-carboxylic acid, N-substituted isatin derivatives, such as N-hydroxymethyl-isatin, N-hydroxyethyl-isatin N- (2- Hydroxypropyl) isatin, N- (3-hydroxypropyl) isatin, N- (2, 3-dihydroxypropyl) isatin, N- (2-sulfoethyl) isatin, (3-sulfopropyl) isatin, N-allyl isatin, N - vinylisatin, N-benzylisatin, N- (4-methoxybenzyl) -isatin, N- (4-carboxybenzyl) -isatin, N- (4-sulfobenzyl) -isatin, N- (2-dimethylaminoethyl) -isatin, N- ( 2-pyrrolidinoethyl) isatin, N- (2-piperidinoethyl) isatin, (2-morpholinoethyl) isatin, N- (2-furylmethyl) isatin, N- (2-thienylmethyl) isatin, N- (2- Pyridylmethyl) isatin, N- (3-pyridylmethyl) isatin, N- (4-pyridylmethyl) isatin, N-allylisatin-5-sulfonic acid, 5-chloro-N- (hydroxyethyl) isatin, 5-methyl-N - (Hydroxyethyl) isatin, 5-chloroisatin, 5-nitroisatin, 5,7-dichloroisatin, 5,7-dichloro-N-allylisatin, 5-nitro-N-allylisatin, N-hydroxymethyl-5-methylisatin, N-hydroxymethyl -5-chloroisatin, N-hydroxymet hyl-5-sulfoisatin, N-hydroxymethyl-5-carboxyisatin, N-hydroxymethyl-5-nitroisatin, N-hydroxymethyl-5-bromisatin, N-hydroxymethyl-5-methoxyisatin, N-hydroxymethyl-5,7-dichloroisatin, N- Dimethylaminomethylisatin, N-diethylaminomethylisatin, N- (bis- (2-hydroxyethyl) -aminomethyl) -isatin, N- (2-hydroxyethylaminomethyl) -isatin, N- (bis- (2-hydroxypropyl) -aminomethyl) -isatin, N- (2-pyrrolidino) isatin, N- (2-piperidino) isatin, N-pyrrolidinomethylisatin, N-piperidinomethylisatin, N-morpholinomethylisatin, N- (2-morpholinoethyl) isatin, N- (1,2,4-triazolyl ) -methylisatin, N- (1-imidazolyl) -methylisatin, N-carboxymethylaminomethylisatin, N- (2-carboxyethylaminomethyl) -isatin, N- (3-carboxypropylaminomethyl) -isatin, N- (bis (2-hydroxyethyl) aminomethyl ) -5-methylisatin, N-piperidinomethyl-5-chloroisatin, N- (2-sulfoethylamino) isatin, and the alkali and optionally ammonium salts of the acidic compounds, quinisatin and their derivatives, such as N-methylquinisatin and the alkali and ammonium salts the acid connections. 7. The method according to any one of claims 1 to 6, characterized in that the Compounds of the formula II are selected from glutacondialdehyde, fumaraldehyde, Glyoxal, malondialdehyde, amber dialdehyde, mucondialdehyde, 1,2-naphthoquinone, 4-sulfonic acid-1,2-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, 2,3- Dimethoxy-5-methyl-1,4-benzoquinone (juglone), 1,4-naphthoquinone, spinulosin, Atromentin, aurentioglyocladin, 5-hydroxy-1,4-naphthoquinone, 2,5-dihydroxy-6- methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxy-1,4-benzoquinone, 2,5-dihydroxy- 3,6-diphenyl-1,4-benzoquinone, 2,5-dihydroxy-6-isopropyl-1,4-benzoquinone, 4,5- Dimethoxy-1,2-benzoquinone, 2-hydroxy-1,4-naphthoquinone, fafiolin, 5,8-dihydroxy 1,4-naphthoquinone, naphthopurpurin, 2-hydroxy-3- (3'-methyl-2'-butenyl) -1,4- naphthoquinone, plumbagin, 3,5-dihydroxy-2-methyl-1,4-naphthoquinone, 2-hydroxy-3- methyl-1,4-naphthoquinone, 3,5-dihydroxy-1,4-naphthoquinone, 2,5-dihydroxy-1,4- naphthoquinone, 2-methoxy-5-hydroxy-1,4-naphthoquinone, 3-methoxy-5-hydroxy-1,4- naphthoquinone and 9,10-phenanthrenequinone. 8. The method according to any one of claims 1 to 7, characterized in that the Compounds with the formulas I and II, and the compounds of component B each in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the finished coloring agent used (agent 2). 9. The method according to any one of claims 1 to 8, characterized in that the Component B is selected from N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p- phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, N, N-bis- (2- hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-phenylene diamine, 2,4-dichloro-p-phenylene diamine, 2,5-dichloro-p-phenylene diamine, 2- Chloro-p-phenylenediamine, 2,5-dihydroxy-4-morphoiinoaniline, 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-diaminophenethol, 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-methylenedioxyphenol, 3,4-methylenedioxyaniline, 3-amino-2,4-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-hydroxypropyiamino) 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-diaminobenzoic 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-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4- Diaminobenzonitrile, nitro group-containing amino compounds, such as 3-amino-6- methylamino-2-nitro-pyridine, picramic 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] 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-chlorobenzene (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-methylazobenzene (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-nitroacenaphthene, 2- Amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, anilines, in particular 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, 1- Amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, 4,4'-diaminostilbene and the like 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-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. 10. The method according to any one of claims 1 to 9, characterized in that the Component B is selected from 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-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-aminobenzimidazole, 5-aminobenzothiazole, 7- Aminobenzothiazole, 2,5-dihydroxy-4-morpholinoaniline and indole and Indoline derivatives, such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6- Dihydroxyindole, 5,6-dihydroxyindofine, 4-hydroxyindoline and hydroxypyrimidines, as well as the physiologically acceptable salts of these compounds. 11. The method according to any one of claims 1 to 10, characterized in that the Component B selected is selected from aromatic hydroxy compounds from the group consisting of 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, Pyrogallol, phloroglucin, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4- Methoxyphenol, 3-dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy- 2,7-naphthalene sulfonic acid. 12. The method according to any one of claims 1 to 11, characterized in that the Component B is selected from amino acids, selected from the group β- Alanine, arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), Ornithine, lysine, proline and tryptophan. 13. The method according to any one of claims 1 to 12, characterized in that the Component B is selected from oligopeptides selected from glutathione or in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or oligopeptides containing almond protein. 14. The method according to any one of claims 1 to 13, characterized in that the Component B is selected from CH-acidic compounds, selected from Malonic acid, malonic esters and their derivatives and acetoacetic acid, Acetoacetic acid esters and their derivatives, pyrazol-5-one, 3-methyl-pyrazol-5-one, 1- phenyl-3-methyl-pyrazol-5-one, 1- (β-cyanoethyl) -3-methyl-pyrazol-5-one, 1,3-dimethylpyrazol-5-one, 1- (β-acetoxyethyl) -3-methyl-pyrazol-5-one, 1- (2'-chlorophenyl) -3-methylpyrazol-5-one, 1-phenyl-3-carbomethoxy-pyrazol-5-one, 1- (3'-aminophenyl-pyrazol-5- on, 1- (4'-aminophenyi) pyrazol-5-one, 3-methyl-pyrazol-5-one-1-carboxamide, 1- Phenyl-pyrazol-5-one-3-carboxamide, amino-pyrazole, 1-phenyl-5-aminopyrazole, 1- Benzyl-5-aminopyrazole, 1-cyclohexyl-5-aminopyrazole, 1-ethyl-3-methyl-5-aminopyrazole, 1-benzyl-3-phenyl-5-amino-pyrazole, 1-isopentyl-5-amino-pyrazole, 1-furfuryl- 5-aminopyrazole, 2-methyl-4H-pyrazolo (5) - [2, 3-a] benzimidazole, [1- (3'-Thiacyclopentyl) -3-methyl-pyrazol-5-on-S-dioxide], 2-methyl-1H-3,3a, 8-triazacyclopenta [a] indene, barbituric acid, thiobarbituric acid, di-N-ethylthiobarbituric acid, di- N-methylthiobarbituric acid, di-n-butyl barbituric acid, di-isobutyl barbituric acid, di-N- amyl barbituric acid, di-iso-amyl barbituric acid, di-n-hexyl barbituric acid, Di-benzyl barbituric acid, di-β-phenylethyl barbituric acid, D1-cyclohexyl barbituric acid, Di-phenylbarbituric acid, di-p-tolyl barbituric acid, di-p-methoxybenzyl barbituric acid, N-methyl N'-n-butyl barbituric acid, N-methyl-N'-benzyl barbituric acid, N-methyl-N'-βphenyfethyl barbituric acid, N-methyl-N'-γ-phenylpropyl barbituric acid, N-methyl-N'-γ- phenylbutyl barbituric acid, N-methyl-N'-α-isobutyl-γ-phenylpropyl barbituric acid, N- Methyl-N'-cyclohexyl-barbituric acid, N-methyl-N'-phenyl-barbituric acid, N-methyl-N'-p- toloyl barbituric acid, N-methyl-N'-norbornylmethyl barbituric acid and the corresponding N-ethyl and N-n-butyl derivatives of the above compounds, 2,6-dihydroxy-3-cyano-4-methyl-pyridine, cyanopyridones, aminonitropyridones and Aminocyanopyridones, especially N-methyl-3-cyano-4-methyl-6-hydroxy-pyridone 2, N-ethyl-3-cyano-4-methyl-6-hydroxy-pyridone-2, N-β-methoxyethyl-3-cyano-4- methyl-6-hydroxy-pyridin-2-one, 2,6-dihydroxy-3-cyano-4-methyl-pyridine, N-β- Hydroxyethyl-3-cyano-4-methyl-6-hydroxy-pyridin-2-one, N-butyl-3-cyano-4-methyl-6- hydroxy-pyridin-2-one and N-phenyl-3-cyano-4-methyl-6-hydroxy-pyridin-2-one, from 6- Hydroxybenzofuran (2H) -one, 3-indoxy acetate, imidazo [1.2-a] pyridin-2-one, 6-bromoimidazo [1.2-a)] pyridin-2-one, 2,4-dihydroxyquinoline, 1,3-indanedione, rhodanine, Rhodanine-3-acetic acid, 4-imino-4,5-dihydro-thiazol-2-ylamine, 1,2- Diphenyldioxopyrazole, 2-phenyl-3,5-dihydro-imidazol-4-one, 3-methyl-2-p-toloyl-3,5- dihydro-imidazol-4-one, phenyldihydrobytyrolactone, 1,1-dioxo-1,2-dihydro-11,6- benzo [b] -thiophene-3-one, 1-dicyanomethylene indane, 1,3-bis (dicyanomethylene) indane, 2- (1 ', 1'-dioxo-1', 2'-dihydro-11 ', 6'-benzo [b] -thiophene-3'-ylidene) -malononitrile, 2,4-diamino- 6-hydroxypyrimidine, 2,6-diamino-4-hydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4,6- Dihydroxy-1-mercaptopyrimidine, 2,4,6-trihydroxypyrimidine, 1,2-dimethylnaphtho [1,2- d] thiazolium p-toluenesulfonate, 2,3-dimethyl-benzothiazolium iodide, 2,3-dimethyl Benzothiazolium p-toluenesulfonate, 1-ethyl-2-methyl-naphtho [1,2-d] thiazolium-p- toluoisulfonate, 1,2,3,3-tetramethyl-3-H-indolium iodide, 1,2,3,3-tetramethyl-3H- indolium p-toluenesulfonate, 1,4-dimethylquinolinium iodide, 1-methyl-2-quinaldinium iodide, 1-ethyl-2-quinaldinium iodide, 1,3,3-trimethyl-2-methylene-indoline, 1- (2-hydroxyethyl) - 3,3-dimethyl-2-methylene indoline and 3-ethyl-2-methylene benzothiazoline. 15. The method according to any one of claims 1 to 14, characterized in that the Component B selected is selected from quaternary ammonium compounds from tetramethyl, tetraethyl, tetrapropyl, tetrabutyl, Benzyltrimethylammonium chloride, bromide, iodide, hydrogen sulfate, 0.5 sulfate and the quaternized Hydroxyethyl cellulose derivatives (INCI name: Polyquaternium 10). 16. The method according to any one of claims 1 to 15, characterized in that the Component B is 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, 2-methyl-5-aminophenol, 3- Methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethyfamino) 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, 2,6- Dichloro-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 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-methylenedioxyphenol, 3,4-diaminobenzoic 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-dimethyi-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 2,3- Dimethylbenzothiazolium p-toluenesulfonate, 1,2,3,3-tetramethyl-3H-indolinium-p- toluenesulfonate, thiobarbituric acid, rhodanine, 2,3-dimethyl-benzothiazolium-p- toluenesulfonate, 1,2-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 1-methyl-2- quinaldinium p-toluenesulfonate, 1,4-dimethylquinolinium p-toluenesulfonate, β-alanine, L- Proline, L-lysine, DL-tyrosine and their preferably with inorganic acids formed physiologically acceptable salts. 17. The method according to any one of claims 1 to 16, characterized in that color enhancers 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, Arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1,2,4-triazole, piperazine, methoxybutanol, propylene carbonate, ethylene carbonate or any mixtures of which are used. 18. The method according to any one of claims 1 to 17, characterized in that direct dyes from the group of nitrophenylenediamines, Nitroaminophenols, anthraquinones or indophenols preferably in an amount of 0.01 to 20 wt .-%, based on the total colorant (agent 2), are used. 19. The method according to any one of claims 1 to 18, characterized in that on average 1 and / or agent 2 anionic, zwitterionic and / or nonionic surfactants be used. 20. The method according to any one of claims 1 to 19, characterized in that ammonium or metal salts selected from the group of formates, carbonates, Halides, sulfates, butyrates, valemates, 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, be used.