DE19821263A1 - Enzymatic bleach system containing mediator to enhance performance in bleaching textile fabric - Google Patents

Abstract

Enzymatic bleach system with enzyme-enhancing compounds for treating textile fabrics, e.g. for (partly) replacing stone-wash procedures, conventional mechanical or enzymatic (cellulase) bleaching and/or modifying the colour or state of the surface, contains (a) oxidation catalyst(s), (b) oxidant(s) and (c) mediator(s) selected from (c.1) hydroxylamines and hydroxamic acids and their derivatives, (cyclo)aliphatic, heterocyclic or aromatic compounds containing N-hydroxyl, oxime, N-oxy or N,N'-dioxy function(s), (c.2) amides (II), e.g. hydrazides or 1,2,4-triazolidin-3,5-diones (urazoles), (c.3) imides (III), e.g. hydantoins and/or (c.4) oxo-carbon compounds (IV).

Description

Enzymes are used in increasing amounts and for different Applications used in the textile industry. For example, the use of amylases plays a role in the "desizing process" great role, which means the use of strong acids, bases or Oxidizing agents can be prevented. Cellulases are also used for so-called bio-polishing as well as for so-called bio-stoning, a process that mostly along with the conventional process of stone washing Pumice stones when treating denim denim to remove the Indigo dye is used.

WO 94/29510, WO / 96/18770, DE 196 12 194 A1 and DE 44 45 088 A1 describe methods for enzymatic delignification in which Enzymes can be used together with mediators. As mediators are generally compounds with the structure NO, NOH, or HRNOH disclosed. However, these systems are on use in pulp bleaching limited. Since the mechanisms involved in lignin-removing pulp bleaching and around such a process is, here, the basis, completely different from discoloration, removal and / or "destruction" of Denim dyes in the jeans area such as especially Indigo dyes etc., it is completely surprising that a number of substances of the mentioned NO, NOH, HNROH-type is also suitable for this application. WO 97/06244 describes systems for bleaching pulp, the "dye transfer inhibition "and the bleaching of stains in the Detergent application with enzymes (peroxidases, laccases) and  enzyme-enhancing (hetero) aromatic compounds such as Nitroso compounds work, described. However, as in the patents WO 94/12619, WO 94/12620 and WO 94/12621 only the insert described above is provided. The mechanisms of discoloration of stains in the Detergent bleaching or "dye transfer inhibition" are completely different than those involved in the decolorization, removal and / or "destruction" of indigo Dyes, e.g. B. in denim treatment. It is therefore completely surprising that a number of substances from the mentioned NO, NOH, HNROH types also for this application suitable is.

From the mentioned WO 94/12619, WO 94/12620 and WO 94/12621 Process known in which the activity of the peroxidase by means of so-called enhancer substances are promoted. Such Enhancer substances are described in WO 94/12620 on the basis of their Characterized half-life. According to WO 94/12621 Enhancer substances characterized by the formula A = N-N = B, where A and B are each defined cyclic radicals. According to WO 94/12621 Enhancer substances organic chemicals that have at least two contain aromatic rings, at least one with each defined radicals is substituted.

All three applications concern (as already mentioned) "dye transfer inhibition "and the use of the respective enhancer substances together with peroxidases as detergent additive or detergent composition in the detergent area or also cellulose bleaching area. The combination of these enhancer substances are limited to peroxidases.

Another patent in the field of detergent bleaching is WO 92/18687. The use of mixtures containing peroxidases is known there. Other detergent bleaching patents:

A special system made of oxidases and suitable substrates as well Hydrogen peroxide is described in DE-OS 42 31 761. DE-OS 19 18 729 relates to another special detergent system that consists of Glucose and glucose oxidase or from starch, amyloglucosidase and  Glucose oxidase (GOD), as well as an additive from hydroxylamine or Hydroxylamine compounds exist, the hydroxylamine or its Derivatives are used to inhibit the catalase commonly found in GOD and has in no way been described as a mediator additive. Further prior art (detergent bleaching patents) is provided by EP 0 267 046 B1, US 4,863,636; WO 92/18687 and EP 0 704 523 A1, wherein these Systems mostly with hydrolases + bleach activators that activate added peroxide or per compounds act or z. B. by Complexing metal salts prevent the decomposition of the peroxides or especially have a positive effect on dye transfer inhibition. In no case are they pure mediator connections that the Enhance enzyme action directly and in a targeted manner and also belong to Chemicals not used in the group included in the present Invention is preferred.

Further detergent bleaching patents are WO 94/29425 and DE 44 45 088 A1 and WO 97/48786. These include a Multi-component bleaching system, or a multi-component bleaching system from oxidoreductases, oxidizing agents, mediators and mediator-reinforcing or recycling compounds for use with wash-active substances, or a multi-component system for Use with detergent substances consisting of Oxidation catalysts and oxidizing agents as well as aliphatic, cycloaliphatic, heterocyclic or aromatic NO, NOH or H-NR-OH-containing compounds.

Furthermore, oxidoreductases, mainly laccases, but also peroxidases for the treatment of mainly denim jeans used.

It is known from patent application WO 96/12846 that laccase or also peroxidase + certain enhancer substances, especially Phenothiazine or Phenoxazine derivatives, for two application forms in the  Treatment of cellulose-containing fabrics such as cotton, viscose, Rayon, (Artificial silk) ramie, linen, tencelm, silk or mixtures of these Fabrics or mixtures of these fabrics with synthetic fibers such. B. Blends of cotton and spandex (stretch denim), mainly but denim fabrics (mainly jeans) are used: On the one hand, the system (oxidoreductases + enhancer substances) should Bleaching denim instead of the usual hypochlorite bleach, usually after stone washing pretreatment, which are used enzymatic treatment only to a partial replacement of hypochlorite leads because the desired bleaching result cannot be achieved. On the other hand, the system can be used together with cellulase in stone washing instead of the usual mechanical treatment with pumice stones be used what the performance of "cellulase-only treatment" should improve.

The main disadvantages of the system described in WO / 96/12846 include the following:

• 1) Laccase must be used in considerable quantities (approx. 10 IU / g denim) to achieve the desired result.
• 2) The optimal duration of treatment is e.g. T. 2-3 hours.
• 3) The preferred mediator (here phenothiazine-10-propionic acid) must be in approx. 2 to about 14 mg per g of denim can be used, which is a significant cost caused.
• 4) It must be worked in buffer systems (approx. 0.1 mol / L), since otherwise no performance can be achieved, which also makes the system considerably more expensive.
  This is e.g. B. not necessary in the system according to the invention.
• 5) By coloring the enhancer component (long-lived radical) a "browning" of the tissue.

The general main advantage of a laccase and / or oxidoreductase system + compounds that enhance enzyme activity (enhancers, mediators etc.) when used in the treatment of textiles described above (e.g.  Jeans fabrics), with a more optimal system than in the state of the art exists, is that you can achieve fashion looks, one usual hypochlorite bleaching not possible. The dyes normally used in denim jeans are VAT Dyes such as indigo, or indigo derivatives such. B. Thioindigo, however also so-called Sulfur dyes. It is possible by using such special enzymatic systems (due to the high specificity of such systems) in mixed color systems such as e.g. B. Indigo and Sulfur dye only to decolorize the indigo dye while the sulfur dye is not oxidized. This leads depending on the used enzyme-enhancing compound to almost everyone desired coloring of the fabric (e.g. shades of gray etc.), often is desired. An additional advantage is that the enzymatic treatment is much gentler than bleaching with hypochlorite, which leads to leads to less fiber damage. In the stone wash process, the ecological effect matters (also in addition to the lesser fiber damage caused by the enzymes) if one e.g. B. considers that per kg of jeans denim about 1 kg of stone sludge through this purely mechanical process arises. As stated in the prior art, in the textile industry, mainly a large one for dyed fabrics (such as denim denim) Need for alternative bleaching processes (to the conventional Hypochlorite bleach) and / or treatment methods as an alternative to Stone washing to achieve the so-called "bleached look", not lastly because of the environmental problems that also exist here.

The present invention aims to overcome the disadvantages of conventional processes: stone washing / bleaching after stone washing or general bleaching of dyed and / or undyed textile fabrics: especially Environmental problems and fiber damage and also the disadvantages of known oxidoreductase / enhancer systems to minimize or remedy.  

It has now surprisingly been found that various substances (Enzyme Enhancing Compounds) from the variety of the in Patent applications WO 94/29425 DE 44 45 088 A1 and WO 97/48786 substances from the group of NO-, NOH- and HRN-OH- Compounds or substances from other classes of compounds such as amides such as e.g. B. hydrazides, urazoles or imides such as hydantoins or oxocarbons (Mediators), together with laccases or peroxidases, which are used in the Cellulose bleach already shows a very good performance in comparison for the usual stone washing and hypochlorite bleaching of fabrics such as cotton, viscose, rayon (rayon), ramie, linen, tencelm, Silk or mixtures of these fabrics or mixtures of these fabrics with Synthetic fibers such as B. Blends of cotton and spandex (stretch Denim), especially but jeans denim is at least equivalent Offer performance at comparable costs, but with the considerable improvements in the area of fiber protection and Environmental relevance.

It was also found completely surprisingly that the addition of small amounts of mediator reinforcing compounds (Media amplifier), either via a batch transfer mechanism, through Red / Ox mediation, e.g. B. by regeneration of entire system, especially by regeneration of the main mediator, by a Increasing the oxidation potential by extending the radical lifetime or through different simultaneous properties, too the respective ones already present in the bleaching system according to the invention Mediators a further significant increase in effect (bleaching) can be reached.

These mediation enhancers can be of the NO, NOH, HRN-OH type or the amide type such as B. hydrazides, urazoles or the imide type such. B. Hydantoins belong to or oxocarbon type compounds. Also with the appropriate enzymes generated cation radicals from z. B. ABTS-like substances of general formula R = N-N = R (where N → means nitrogen and R → means residues), cation radicals Phenothiazine derivatives, from phenoxazine derivatives or from  nonphenolic aryl substituted alcohols (metoxy alcohols), such as e.g. B. veratryl alcohol (nonphenols) or of special cation radical-forming phenolic compounds or radical cations for "Wurster" or radical anions or combinations of several called mediation enhancers.

The described problems of the "prior art" systems are solved by the present invention, which provides an enzymatic bleaching system with compounds which enhance enzyme activity for the treatment of textile fabrics (e.g. for the partial or total replacement of stonewashing procedures, be it conventional) mechanically or enzymatically e.g. with cellulases etc.) and / or their bleaching and changing the surface in terms of color and surface quality, containing:

• a) at least one oxidation catalyst,
• b) at least one oxidizing agent,
• c) at least one mediator selected from the group of Hydroxyl amines, hydroxylamine derivatives, hydroxamic acids, Hydroxamic acid derivatives, aliphatic, cycloaliphatic, heterocyclic or aromatic compounds that have at least an N-hydroxy, oxime, N-oxi, or N, N'-dioxi function contain and / or at least one mediator from the Group of amides such as hydrazides or 1,2,4-triazolidin-3,5-diones (Urazole) and / or at least one mediator from the group of Imides such as hydantoins and / or at least one mediator from the Group of oxocarbons.

Furthermore, at least one mediation enhancer can be selected from the group of carbonyl compounds, aliphatic ethers, phenol ethers or olefins (alkenes), and / or at least one mediation enhancer, selected from the group of the above mediators of NO-, NOH- HRN-OH type and / or the amides such as hydrazides or urazoles and / or  the imides such as hydantoins and / or the oxocarbons are used will.

Likewise, at least one mediation enhancer selected from the group of the cation radical-forming substances of the phenothiazine type and / or the phenoxazine type and / or the (R = NN = R) type (N means nitrogen, R means residues) (e.g. ABTS),
and / or of aryl-substituted alcohols (non-phenols) such as. B. veratryl alcohol, and / or phenol derivatives such as p-hydroxycinnamic acid, 2,4-dichlorophenol, p-hydroxybenzene sulfonate, vanillin (4-hydroxy-3-methoxy-benzaldehyde), p-hydroxybenzoic acid, 5-amino-2-hydroxy benzoic acid (5-aminosalycilic acid) and / or radical cation compounds according to "Wurster" (Lit .: Angewandte Chemie, 91, 1979, pp. 982-997; Chem. Unserer Zeit, 12, 1978, pp. 89-98; Römpp Chemie Lexikon, 9th edition, 1995) and / or radical anions, e.g. B. semiquinones, which can arise in the enzymatic oxidation of hydroquinones, are used.

According to the invention, both one and more of the mentioned mediators and mediation enhancers are used. The use of one mediator and one is preferred Mediation enhancer. Working with a mediator is also conceivable and two or more mediation enhancers. The reverse is also true possible to use two or more mediators with one mediation booster use, but it is for an improved performance of the Bleaching system according to the invention is an essential requirement that Mediator / mediation amplifier ratio 5000: 1 to 1: 1 especially is preferably 500: 1 to 1: 1, while the ratio at simultaneous use of multiple mediators and Mediation enhancers within these mediator or Mediation enhancer concentrations from the respective combinations depends. The individual components of the invention are described below extended multi-component system described in more detail:  

Oxidation catalysts

The multicomponent system according to the invention preferably contains at least one oxidation catalyst. As oxidation catalysts preferably used enzymes. For the purposes of the invention, the term includes Enzyme also enzymatically active proteins or peptides or prosthetic Groups of enzymes. Likewise, the enzymes from wild-type strains or come from genetically modified host strains.

The particularly preferred enzymes include laccases and peroxidases, the peroxidases because of their z. T. Optimal pH effects reaching far further into the alkaline environment have considerable advantages when used for bleaching in detergents. In the multicomponent system according to the invention, oxidoreductases of classes 1.1.1. to 1.97 according to the International Enzyme Nomenclature: Committee of the International Union of Biochemistry and Molecular Biology (Enzyme Nomenclature, Academic Press, Inc., 1992, pp. 24-154). The following enzymes are preferably used:
Class 1.1 enzymes, particularly preferably the class 1.1.5 enzymes with quinones as acceptors and the class 1.1.3 enzymes. with oxygen as the acceptor, cellobiose: quinone-1-oxidoreductase (1.1.5.1) is particularly preferred in this class.

Enzymes of class 1.2 can also be used. Are particularly preferred here the enzymes of group (1.2.3) with oxygen as the acceptor. Enzymes of class 1.3 can also be used. Here are the too Enzymes of class (1.3.3) with oxygen as acceptor and (1.3.5) with Quinones etc. are particularly preferred as acceptors.

Bilirubin oxidase (1.3.3.5) is particularly preferred. Class 1.4 enzymes can also be used. Particularly preferred are also class 1.4.3 enzymes with oxygen as acceptor.  

Enzymes of class 1.5 can also be used. Here too are special prefers enzymes with oxygen (1.5.3) and with quinones (1.5.5) as Acceptors. Enzymes of class 1.6 can also be used. Especially Enzymes of class 1.6.5 with quinones as acceptors are preferred here. Enzymes of class 1.7 can also be used. Here are special prefers class 1.7.3 with oxygen as acceptor. Enzymes of class 1.8 can also be used. Especially Class 1.8.3 with oxygen and (1.8.5) with quinones as is preferred Acceptors. Enzymes of class 1.9 can also be used. Is particularly preferred here the group 1.9.3 with oxygen as acceptor (cytochrome oxidases). Enzymes of class 1.12 and enzymes of class 1.13 and 1.14 (Oxigenases / Lipoxigenases) into consideration, here in particular Monophenol monooxygenase (1.14. 99.1). Enzymes of class 1.15 which are based on Superoxide radicals act as acceptors. It is particularly preferred here Superoxide dismutase (1.15.11).

Enzymes of class 1.16 can also be used. Especially Enzymes of class 1.16.3.1 (ferroxidase, e.g. Ceruloplasmin). Enzymes belonging to groups 1.17 and 1.1 8 should also be mentioned (Effect on reduced ferredoxin as donor) and 1.19 (Effect on reduced flavodoxin as donor) and 1.97 (other oxidoreductases) belong to.

The most preferred enzymes include those of the class 1.10. Of the enzymes in this class, the enzymes in particular are catechol Oxidase (Tyrosinase) (1.10.3.1), L-Ascorbate Oxidase (1.10.3.3), O- Aminophenol oxidase (1.10.3.4) and laccase (benzene diol: oxigen Oxidoreductase) (1.10.3.2) preferred, the laccases in particular are preferred.  

The enzymes of group 1.11 are also particularly preferred. The cytochrome-C peroxidases are very particularly preferred here (1.11.1.5), catalase (1.11.1.6), the peroxidase (1.11.1.6) the iodide Peroxidase (1.11.1.8), the glutathione peroxidase (1.11.1.9), the Chloride peroxidase (1.11.1.10), the L-ascorbate peroxidase (1.11.1.11), the phospholipid hydroperoxide glutothione peroxidase (1.11.1.12), the manganese peroxidase (1.12.1.13), the diaryl propane peroxidase (Ligninase, lignin peroxidase).

The enzymes mentioned are commercially available or can be copied Win standard procedures. As organisms for the production of the enzymes plants, animal cells, bacteria and fungi come in Consideration. Basically, both naturally occurring as well genetically modified organisms are enzyme producers. Likewise are Parts of unicellular or multicellular organisms as enzyme producers conceivable, especially cell cultures.

In particular for the production of the preferred enzymes of group 1.11.1, and Group 1.10.3 enzymes, particularly for the production of laccases and other ligninolytic enzymes (lignin peroxidases) for example white rot fungi etc. such as pleurotus, phlebia and trametes, Agaricus, Lentinus, Botrytis, Cryphonectria, Hypholoma, Heterobasidion, Phanerochaete u. a. used.

Oxidizing agent

The multicomponent system according to the invention contains at least one oxidizing agent. The oxidizing agents that can be used are, for example, air, oxygen, ozone, peroxide compounds such as H ₂ O ₂ , organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, persitric acid, metachloroperoxibenzoic acid, perchloric acid, per compounds such as perborates, percarbonates, persulfates or oxygen species and their radicals such as OH radical, OOH radical, OH⁺ radical, superoxide (O ₂ ⁻), dioxygenyl cation (O ₂ ⁺), singlet oxygen, ozonide (O ₃ ⁻), dioxirane, dioxitane or fremy radicals can be used.

Buffer systems

The use of special buffer systems is normally not necessary to achieve the optimal performance, but the following buffer systems can possibly be used in the multi-component system according to the invention:
Oxalate, borate, acetate, glycine, malic acid, succinate, phosphate, citrate / phosphate, citrate buffers etc.

The systems mentioned are depending on the optimum pH effect of the respective Systems (laccase / peroxidase + mediators etc.) are used.

Mediators

This component of the bleaching system contains at least one compound as a mediator, selected from the group of the NO, NOH, HRN-OH compounds (as also described in patent applications WO 94/29425, DE 44 45 088 A1 and in particular in WO 97/48786 (page 11 to page 25) are described in detail) such. B. hydroxylamines, hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, the aliphatic, cycloaliphatic, heterocyclic or aromatic compounds which contain at least one N-Hxdroxy-, oxime, N-oxy, or N, N'Dioxy function. Particularly preferred are, for. B. hydroxylamines. (open-chain or cyclic, aliphatic or aromatic, heterocyclic) of the general formula (A):

The following are particularly preferred: N, N-dipropylhydroylamine, N, N- Diisopropylhydroxylamine, N-hydroxylpyrrolidine, N-hydroxypiperidine, N-  Hydroxyhexahydroazepine, N, N-dibenzylhydroxylamine, Phenylhydroxylamine, 3-hydroxylamino-3-phenyl-propionic acid, 2-hydroxylamino-3-phenylpropionic acid, N-sulfomethylhydroxylamine.

Further preferred compounds are: 1-hydroxy-benzimidazoles, such as 1-hydroxy-benzimidazole-2-carboxylic acid, 1-hydroxybenzimidazole, 2-methyl-1-hydroxy-benzimidazole, 2-phenyl-1-hydroxybenzimidazole and 1-hydroxyindoles, such as B. 2-phenyl-1-hydroxyindole and in particular derivatives of 1-hydroxybenzotriazole and the tautomeric benzotriazole-1-oxide or 1H-hydroxybenzotriazole, as well:
Aziridines, diaziridines, pyrroles, dihydropyrroles, tetrahydropyrroles, pyrazoles, dihydropyrazoles, tetrahydropyrazole imidazoles, dihydroimidazoles, tetrahydroimiazoles, dihydroimidazoles, 1,2,3-triazoles, 1,2,4-triazoles, tetrazoleurs. Pyridines, pyridazines, pyrimidines, pyrazines, piperazines, 1,2,3-triazines, 1,2,4-triazines, tetrazines, azepines, oxazoles, isoxazoles, thiazoles, isothiazoles, thiadiazoles, morpholines, and their benzofused derivatives such as: indoles, Isoindoles, indolizines, indazoles, benzimidazoles, benztriazoles, quinolines, isoquinolines, phthalazines, quinazolines, quinoxalines, phenazines, benzazepines, benzothiazoles, benzoxazoles.

Likewise preferred are condensed N-heterocycles such as triazolo and Tetrazolo compounds containing at least one N-hydroxy, oxime, N-oxi, N, N-dioxi function and, in addition to N, another heteroatom such as O, S, Se, Te can contain.

Other preferred compounds according to the invention are; Quinoline N-oxide, Isoquinoline-N-oxide, N-hydroxy-1,2,3,4-tetrahydroisoquinoline, β- (N-oxy-1,2,3,4-tetrahydro-isoquinolino) propionic acid, 1,3-dihydroxy-2- N-benzylimidobenzimidazoline.

Also particularly preferred as mediators are those belonging to the group of cyclic N-hydroxy compounds with at least one optionally substituted five- or six-membered ring having the following structure (formula B):

and their salts, ethers or esters, where X and Y, are the same or different, and O, S, or NR ¹ , where R ^{1 is} hydrogen, hydroxyl, formyl, carbamoyl, sulfono radical, ester or salt the residue sulfono, sulfamoyl, nitro, amino, phenyl, aryl-C ₁ - C ₅ alkyl -, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ -carbonyl-, carbonyl-C ₁ -C ₆ -alkyl- phospho-, phosphono-, phosphonooxy radical, ester or salt of the phosphonooxy radical,
where the carbamoyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ₂ and the aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl-, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl-C ₁ -C ₆ alkyl radicals may be saturated or unsaturated, branched or unbranched and
can be substituted one or more times with a radical R ₂ , where R _{2 is} identical or different and hydroxyl, formyl, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono, ester or salt of sulfono Radicals, sulfamoyl, nitro, amino, phenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy radical.

Compounds of the general formula C, D, E or F are furthermore particularly preferred as mediators,

where X, Y, have the meanings already mentioned and the radicals R ³ -R ^{18 are} identical or different and have a halogen radical, carboxy radical, salt or ester of a carboxy radical or the meanings mentioned for R ¹ , where R ⁹ and R ¹⁰ or R ¹¹ and R ^{12 may} not simultaneously mean a hydroxyl or amino radical and, if appropriate, two of the substituents R ³ -R ⁶ , R ⁷ -R ⁸ , R ⁹ -R ¹² , R ¹³ -R ¹⁸ to one Ring -B can be linked, where -B- has one of the following meanings:
(-CH = CH) -n with n = 1 to 3, -CH = CH-CH = N- or

and where appropriate the radicals R ⁹ -R ^{12 can} also be connected to one another by one or two bridge elements -Q-, where -Q- is the same or different and has one of the following meanings: -O-, -S-, -CH ₂ .-, -CR ¹⁹ = CR ²⁰ -, where R ¹⁹ and R ^{20 are the} same or different and have the meaning of R ³ . Likewise preferred as mediators are compounds of the general formulas C, D, E or F in which X and YO are or S.

Examples of such compounds are N-hydroxy-phthalimides and substituted N-hydroxy-phthalimide derivatives, N-hydroxymaleimides and substituted N-hydroxymaleimide derivatives, N-hydroxy-naphthalic acid imides and substituted N-hydroxy-naphthalic acid imide derivatives, N-hydroxysuccinimides and substituted N-hydroxysuccinimide derivatives, particularly preferably:
N-hydroxyphthalimide, N-hydroxy-benzene-1,2,4-tricarboximide, N, N'-dihydroxy-pyromellitic acid diimide, N, N'-dihydroxy-benzophenone-3,3 ', 4,4'-tetracarbon- acid diimide, N-hydroxymaleimide, pyridine-2,3-dicarboxylic acid-N-hydroxylmid, N-1-hydroxysuccinimide, N-1-hydroxy tartarimide, N-hydroxy-5-norbornene-2,3-dicarboxylic acid amide, exo-N- Hydroxy-7-oxabicyclo [2.2.1] -hept-5-en-2,3-dicarboximide, N-hydroxy-cis-cyclohexane-1,2-dicarboximide, N-hydroxy-cis-4-cyclohexene-1,2 - Dicarboximide, N-hydroxynapthalimide sodium salt and N-hydroxyglutarimide and their salts and esters.

Compounds which are selected from the group of oximes according to the following general formulas G and H are also particularly preferred as mediators:

and their salts, ethers, or esters, where
X is the same or different and is O, S, or NR ¹ , where
R ^{1 is} hydrogen, hydroxyl, formyl, carbamoyl, sulfono radical, ester or salt of the sulfono radical, sulfamoyl, nitro, amino, phenyl, aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl C ₁ -C ₆ alkyl, phosphophosphono-, phosphonooxy radical, ester or salt of phosphonooxy residues means
where carbomyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ² and the aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl-, C ₁₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl-C ₁ -C ₆ alkyl radicals may be saturated or unsaturated, branched or unbranched and
can be substituted one or more times with a radical R ² , where
R ^{2 is the} same or different and hydroxyl, formyl, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono, ester or salt of the sulfono radical, sulfamoyl, nitro, amino, phenyl , C ₁₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy radical and
the radicals R ³ and R ^{4 are} identical or different and represent halogen, carboxy radical, ester or salt of the carboxy radical, or have the meanings given for R ¹ , or to form a ring (-CR ⁷ R ⁸ ) _n are linked with n equal to 2, 3 or 4 and
R ⁵ and R ^{6 have} the meanings given for R ¹ and
R ⁷ and R ^{8 are the} same or different and halogen, carboxy radical, ester or
Salt of the carboxy radical, or have the meanings given for R ¹ .

Likewise preferred as mediators are compounds with the general Formula G, in which X is O or S and the remaining radicals are have the meanings given above. An example of one Connection is 2-Hydroxylminomalonate, dimethyl ester.

Isonitroso derivatives of are also particularly preferred as mediators cyclic ureids of the general formula H such as 1-methylvioluric acid, 1,3-dimethylvioluric acid, thiovioluric acid, alloxan-4,5-dioxime, especially  preferably alloxan-5-oxime hydrate (violuric acid) and very particularly preferably dimethylviolanoic acid and / or its esters, ethers or salts.

Further preferred mediators are compounds from the class of the N-aryl-N-hydroxy amides of the general formulas I, J and K:

and their salts, ethers or esters, where
A monovalent homo- or heteroaromatic mono- or dinuclear radical and
D means double-bonded homo- or heteroaromatic mono- or dinuclear radical
and these aromatics by one or more, the same or different
R ¹ radicals selected from the group halogen, hydroxy, formyl, cyano, carbamoyl, carboxy radical, ester or salt of the carboxy radical, sulfono radical, ester or salt
of the sulfono radical, sulfamoyl, nitro, nitroso, amino, phenyl, aryl C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ -carbonyl-, carbonyl-C ₁ -C ₆ - alkyl, phospho-, phosphono-, phosphonooxy radical, ester or salt of the phosphonooxy radical can be substituted and
where carbamoyl, sulfamoyl, amino and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ² , aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl-, C ₁ -C ₅ -alkoxy-, C ₁ -C ₁₀ -carbonyl-, carbonyl-C ₁ -C ₆ - alkyl radicals can be saturated or unsaturated branched or unbranched and can be substituted one or more times with a radical R ² , where
R ^{2 is the} same or different and hydroxyl, formyl, cyano, carbamoyl, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono-, sulfamoyl, nitro, nitroso-, amino-, phenyl -, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ - C ₅ alkylcarbonyl radical and
two residues R ¹ or R ^{2 can be} linked in pairs via a bridge [-CR ³ R ⁴ -] _m with m equal to 0, 1, 2, 3 or 4 and
R ³ and R ^{4 are} identical or different and carboxy radical, ester or salt of the carboxy radical, phenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ alkyl carbonyl radical and one or more non-adjacent groups [-CR ³ R ⁴ -] by oxygen, sulfur or an imino radical optionally substituted by a C ₁ to C ₅ alkyl radical and two adjacent groups [-CR ³ R ⁴ -] by a group [- CR ³ = CR ⁴ -] can be replaced and
B in the amidic form present monovalent acid residue of acids selected from the group carboxylic acid with up to 20 carbon atoms, carbonic acid, half-ester of carbonic acid or carbamic acid, sulfonic acid, phosphonic acid, phosphoric acid, monoesters of phosphoric acid, diesters of phosphoric acid and
C is an amidic form of the double-bonded acid residue of acids selected from the group consisting of mono- and dicarboxylic acids with up to 20 atoms, carbonic acids, sulfonic acids, phosphonic acids, phosphoric acids, monoesters of phosphoric acid.

Likewise particularly preferred as mediators are compounds of the general formulas K ₁ , K ₂ , K ₃ , K ₄ and K ₅ :

and their salts, ethers or esters, where
Ar ¹ monovalent homo- or heteroaromatic mononuclear aryl radical and
Ar ² means double-bonded homo- or heteroaromatic mononuclear aryl radical, which is selected by one or more, identical or different radicals R ⁷ selected from the group consisting of hydroxyl, cyano, carboxy radical, ester or salt of the carboxy radical, sulfono radical, ester or salt of the sulfono radical, nitro, nitroso, amino, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl-C ₁ -C ₆ alkyl radical can be substituted
where the amino radicals can be unsubstituted or substituted one or more times with a radical R ⁸ and the C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ - C ₁₀ carbonyl, carbonyl C ₁ -C ₆ -alkyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁸ , are identical or different and are hydroxyl, carboxy radical, ester or salt of carboxy- residue, sulphono, nitro, amino, C ₁ - C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ -alkylcarbonyl radical, and two radicals R ⁷ in pairs via a bridge [ -CR ³ R ⁴ -] _{m can be} linked to m equal to 0, 1, 2, 3 or 4 and
R ³ and R ^{4 have} the meanings already mentioned and one or more non-adjacent groups [-CR ³ R ⁴ -] by oxygen, sulfur or an imino residue optionally substituted by a C ₁ -C ₅ alkyl radical and two adjacent groups [-CR ³ R ⁴ -] can be replaced by a group [-CR ³ = CR ⁴ -] and
R ⁵ same or different monovalent radicals selected from the group phenyl, aryl-C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl - rest means
where phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁹ and aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl-, C ₁ -C ₅ -alkoxy-, C ₁ -C ₁₀ carbonyl radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁹ , where R ^{9 is the} same or different and hydroxyl, formyl, cyano, carboxy radical , Ester or salt of the carboxy radical, carbamoyl, sulfono, sulfamoyl, nitro, nitroso, amino, phenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy radical and
R ^{6 is} divalent radicals selected from the group of ortho-, meta-, para-phenylene, aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkylene, C ₁ -C ₅ -alkylenedioxy radical, where phenylene radicals may be unsubstituted or substituted one or more times with a radical R ⁹ and the aryl-C ₁ -C ₅ -alkyl, C ₁ -C ₁₂ -alkyl, C ₁ -C ₅ -alkoxy radicals are saturated or can be unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁹ , where p is 0 or 1 and g is an integer from 1-3. Ar ^{1 is} preferably phenyl radical and Ar ^{2 is} ortho-phenylene radical, where Ar ¹ is selected from the group C ₁ -C ₃ -alkyl-, C ₁ - by up to five from Ar ² by up to four identical or different radicals. C ₃ - alkylcarbonyl, carboxy radical, sulfono radical, ester or salt of the sulfono radical, hydroxy, cyano, nitro, nitroso and amino radicals can be substituted, wherein amino radicals are selected with two different radicals can be substituted from the group hydroxy and C ₁ -C ₃ alkylcarbonyl.

R ^{5 is} preferably a monovalent radical selected from the group consisting of hydrogen, phenyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy radical, the C ₁ -C ₁₂ alkyl radicals and the C ₁ -C ₅ alkoxy radicals can be saturated or unsaturated, branched or unbranched.

R ⁶ preferably denotes divalent radicals selected from the group consisting of ortho- or para-phenylene, C ₁ -C ₁₂ alkylene, C ₁ -C ₅ alkylenedioxy radicals, the aryl-C ₁ -C ₅ alkyl-, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy radicals can be saturated or unsaturated, branched or unbranched and can be substituted one or more times with a radical R ⁹ . R ⁹ preferably denotes carboxy radical, ester or salt of the carboxy radical, carbamoyl, phenyl, C ₁ -C ₃ alkoxy radical.

Particularly preferred mediators in the bleaching system according to the invention are:
N-hydroxyacetanilide, N-hydroxypivaloylanilide, N-hydroxyacrylanilide, N-hydroxybenzoyl anilide, N-hydroxy-methyl-sulfonylanilide, N-hydroxy-N-phenyl-methylcarbamate, N-hydroxy-3-oxo-butyrylanilide, N-hydroxy- 4-cyanoacetanilide, N-hydroxy-4-methoxyacetanilide, N-hydroxyphenacetin, N-hydroxy-2,3-dimethyl-actetanilide, N-hydroxy-2-methylacetanilide, N-hydroxy-4-methylacetanilide, 1-hydroxy-3, 4-dihydroquinolin- (1H) -2-one, N, N'-dihydroxy-N, N'-diacetyl-1,3-phenylenediamine, N, N'-dihydroxysuccinic acid dianilide, N, N'dihydroxymaleic acid dianilide, N, N '-Dihydroxy-oxalic acid dianilide, N, N'-dihydroxyphosphoric acid dianilide, N-acetoxyacetanilide, N-hydroxymethyloxalylanilide, N-hydroxymaleic acid monoanilide, particularly preferred:
N-hydroxyacetanilide, N-hydroxyformanilide, N-hydroxy-N-phenyl methyl carbamate, N-hydroxy-2-methylacetanilide, 1-hydroxy-3,4-dihydroquinolin- (1H) -2-one, and N-acetoxyacetanilide.

Also preferred as mediators in the bleaching system according to the invention are compounds of the class of the stable nitroxyl radicals (nitroxides) of the general formulas L, M and N:

in which
Ar is a monovalent homo- or heteroaromatic mono- or dinuclear radical and
where these aromatics by one or more, identical or different radicals R ¹ , selected from the group halogen, formyl, cyano, carbamoyl, carboxy, ester or salt of the carboxy radical, sulfono radical, ester or salt of sulfono residues, sulfamoyl, nitro, nitroso, amino, phenyl, aryl C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ -carbonyl-, carbonyl-C ₁ -C ₆ -alkyl, phospho-, phosphono-, phosphonooxy radical, ester or salt of the phosphonooxy radical may be substituted and
where phenyl, carbamoyl and sulfamoyl radicals can be unsubstituted or substituted one or more times with a radical R ² , the amino radical can be substituted once or twice with R ² and the aryl-C ₁ -C ₅ -alkyl, C ₁ - C ₁₂ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl-C ₁ -C ₆ alkyl radicals can be saturated or unsaturated, branched or unbranched and with one Radical R ² can be substituted one or more times,
where R ² may be present one or more times and is identical or different and hydroxyl, formyl, cyano, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono-, sulfamoyl, nitro, nitroso -, Amino, phenyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ alkylcarbonyl radical and
where radical R ³ can be present one or more times and are identical or different and halogen, hydroxy, mercapto, formyl, cyano, carbamoyl, carboxy radical, ester or salt of the carboxy radical, sulfono radical , Ester or salt of the sulfono radical, sulfamoyl, nitro, nitroso, amino, phenyl, aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl-, C ₁ -C ₅ - alkoxy, C ₁ -C ₁₀ carbonyl, carbonyl-C ₁ -C ₆ alkyl, phospho-, phosphono-, phosphonooxy radical, ester or salt of the phosphonooxy radical
and where R ³ can also be hydrogen in the case of bicyclic stable nitroxyl radicals (structure N) and
where carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ⁴ and the aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl -, C ₁ -C ₅ -alkoxy-, C ₁ -C ₁₀ - carbonyl-, carbonyl-C ₁ -C ₆ -alkyl radicals can be saturated or unsaturated, branched or unbranched and with a radical R ⁴ one or more times can be substituted, wherein
R ^{4 is the} same or different and hydroxyl, formyl, cyano, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono, sulfamoyl, nitro, nitroso, amino, phenyl, C ₁ -C ₅ -alkyl-, C ₁ -C ₅ -alkoxy radical, C ₁ -C ₅ -alkylcarbonyl radical and two radicals R ³ or R ^{4 in} pairs over a bridge [-CR ⁵ R ⁶ -] _m with m can be linked to 0, 1, 2, 3 or 4 and
R ⁵ and R ^{6 are} identical or different and halogen, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfamoyl, phenyl, benzoyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ -alkoxy radical, C ₁ -C ₅ alkylcarbonyl radical and
one or more non-adjacent groups [-CR ⁵ R ⁶ -] by oxygen, sulfur or an imino radical optionally substituted with C ₁ -C ₅ alkyl- and two adjacent groups [-CR ⁵ R ⁶ -] by a group [- CR ⁵ = CR ⁶ -], [-CR ⁵ = N-] or [-CR ⁵ = N (O) -] can be replaced.

Particularly preferred mediators are nitroxyl radicals of the general formulas (N ₁ ) and (N ₂ ):

in which
R ^{1 is the} same or different and is phenyl-, aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl-, C ₁ -C ₅ -alkoxy-, C ₁ -C ₁₀ -carbonyl-, carbonyl- C ₁ -C ₆ alkyl means and
phenyl radicals can be unsubstituted or substituted one or more times with a radical R ³ and the aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl-, C ₁ -C ₅ -alkoxy-, C ₁ -C ₁₀ -carbonyl-, carbonyl-C ₁ -C ₆ -alkyl radicals may be saturated or unsaturated, branched or unbranched and may be substituted one or more times with a radical R ³ , where R ^{3 is present} one or more times can and is the same or different and hydroxyl, formyl, carboxy radical, ester or salt of the carboxy radical, carbamoyl, sulfono, sulfamoyl, nitro, nitroso, amino, phenyl, benzoyl, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy radical, C ₁ -C ₅ alkylcarbonyl radical
and R ² can be present one or more times and is identical or different and is hydrogen, hydroxyl, mercapto, formyl, cyano, carbamoyl, carboxy radical, ester or salt of the carboxy radical, sulfono radical, Ester or salt of the sulfono radical, sulfamoyl, nitro, nitroso, amino, phenyl, aryl C ₁ -C ₅ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₅ alkoxy -, C ₁ -C ₁₀ -carbonyl-, carbonyl-C ₁ -C ₆ - alkyl, phospho-, phosphono-, phosphonooxy radical, ester or salt of the phosphonooxy radical and
where carbamoyl, sulfamoyl, amino, mercapto and phenyl radicals can be unsubstituted or substituted one or more times with a radical R ³ and the aryl-C ₁ -C ₅ -alkyl-, C ₁ -C ₁₂ -alkyl -, C ₁ -C ₅ -alkoxy-, C ₁ -C ₁₀ - carbonyl-, carbonyl-C ₁ -C ₆ -alkyl radicals can be saturated or unsaturated, branched or unbranched and with a radical R ³ one or more times can be substituted and
a [-CR ² R ² -] group by oxygen, an imino residue optionally substituted with C ₁ -C ₅ alkyl, a (hydroxy) imino residue, a carbonyl function or one which is mono- or disubstituted with R ³ vinylidene function can be replaced and
two adjacent groups [-CR ² R ² -j can be replaced by a group [-CR ² = CR ² -] or [-CR ² = N-] or [-CR ² = N (O) -].

Particularly preferred mediators are:
2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-oxo-2,2,6,6 -tetramethyl-piperidine-1-oxyl, 4-acetamido-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4- (ethoxyfluorophosphinyloxy) -2,2,6,6-tetramethyl-piperidine-1-oxyl , 4- (isothiocyanato) -2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-maleimido-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4- (4-nitrobenzoyloxy) -2,2,6,6-tetra methyl-piperidine-1-oxyl, 4- (phosphonooxy) -2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-cyano-2,2,6, 6-tetramethyl-piperidine-1-oxyl, 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolidin-1-oxyl, 4-phenyl-2,2,5,5-tetramethyl-3-imidazoline- 3-oxide-1-oxyl, 4-carbamoyl-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-1-oxyl, 4-phenacylidene-2,2,5,5-tetramethyl-imidazolidine 1-oxyl, 3- (aminomethyl) -2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 3-carboxy-2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 3-cyano- 2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 3-maleimido-2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 3- (4-nitro phenoxycarbonyl) -2,2,5 , 5-tet ramethyl-pyrrolidine-N-oxyl.

Of these, the following are particularly preferred:
2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-oxo-2,2,6,6 -tetramethyl-piperidine-1-oxyl, 4-acetamido-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4- (isothiocyanato) - 2,2,6,6-tetramethyl-piperidine-1-oxyl , 4-Maleimido-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4- (4-nitrobenzoyloxy) -2,2,6,6-tetramethyl-piperidine-1-oxyl, 4- (phosphonooxy) -2 , 2,6,6-tetramethyl-piperidine-1-oxyl, 4-cyano-2,2,6,6-tetramethyl-piperidine-1-oxyl, 3-carbamoyl-2,2,5,5-tetramethyl-3 - pyrrolidine-1-oxyl, 4-phenyl-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-1-oxyl, 4-carbamoyl-2,2,5,5-tetramethyl-3-imidazoline -3-oxide-1-oxyl, 4-phenacylidene-2,2,5,5-tetramethyl-imidazolidine-1-oxyl.

Further particularly preferred mediators are compounds selected from the group of amides such as. B. the hydrazides or Urazole, which surprisingly does not have the disadvantages of the prior art Have known mediators.

Preferred mediators in the bleaching system according to the invention are compounds of the general formulas I (amides) and II (hydrazides):

Where X stands for C = O or O = S = O. (Carboxylic acid or Sulfonic acid amides).

The radicals R can be the same or different and independently represent hydrogen, alkyl, aryl or acyl groups (carboxylic acid or sulfonic acid residues). Cyclic hydrazides of the general formula III are particularly preferred

Where X stands for C = O or O = S = O (cyclic hydrazides of Dicarboxylic acids or disulfonic acids).

The radicals R can be the same or different and are independent of one another Represent hydrogen, alkyl, aryl or acyl groups.

G stands for the following atoms or groups of atoms: CH ₂ , CH ₂ -CH ₂ , CHR ¹ - CHR ¹ , CH = CH, CR ² = CR ² , NH, NR ³ , C = O, ortho-C ₆ H ₄ (ortho substituted phenyl radical), ortho C ₁₀ H ₆ (ortho substituted naphthyl radical), where the radicals R ¹ to R ^{3 can be} identical or different and can independently represent hydrogen, alkyl, aryl or acyl radicals. Also preferred are urazoles (formula IV) and phthalhydrazides (formula V):

Where R ⁴ can be hydrogen, alkyl, alkoxy, carboxy, nitro or amino.

The radicals R can be the same or different and are independent of one another Represent hydrogen, alkyl, aryl or.

The following compounds are particularly preferred:
Maleic hydrazide, 2-nitrobenzliydrazide, p-toluenesulphonylhydrazide, Nicotinic hydrazide, Isonicotinic acid hydrazide, 4,4'-Oxydibenzenesul fonylhydrazide, Bencoic hydrazide, Phthalhydrnzide, 3-aminophthal hydrazide, 1-Naphthoic-hydyid-hydyid-hydrazide, Hydroxybenzhydrazide, Oxamic hydrazide, Oxalyl dihydrazide, Terephthalic dihydrazide, Isophthalic-dihydrazide, L-Tyrosine hydrazide, Oxalic-bis- (benzylidenehydrazide), Salicyliden salicylhydrazide, Thiophene-2-carbonic acid hydrazide, Furan-2-carbonic.

5-Amino-5-hydroxypyrazoles, 2,3- Dihydro-1,4-phthalazinedione, phthalhydrazides, 7-nitroindazoles and 1,2- Dihydropyrazine-3,6-dione.

The following compounds are also particularly preferred:
4-phenylurazole, 1-phenylurazole, 4-methylurazole, 4-tert-butylurazole and urazole, in particular:
4-tert-butylurazole and urazole.

It was also surprisingly found that the invention Bleaching system with mediators selected from the group of imides such as B. the hydantoine does not have the disadvantage of the prior art known mediators.

Preferred mediators in the bleaching system according to the invention are compounds of the general formula VI (imides):

The radicals R can be the same or different and are independent of one another Represent hydrogen, alkyl, aryl, acyl or amino groups.

Imides of the general formula VII are particularly preferred:

The radicals R can be the same or different and are independent of one another Represent hydrogen, alkyl, aryl, acyl or amino groups.

Cyclic imides of the general formula VIII are also particularly preferred:

The radicals R can be identical or different and independently represent hydrogen, alkyl, aryl, acyl or amino groups, and where group G represents one of the following atoms or atom groups: CH ₂ , CHR ¹ , CR ¹ R ² , CH = CH, CR ³ = CR ⁴ , NH, NR ⁵ , C = O, O, and where R ¹ to R ^{5 can be the} same or different and can independently represent one of the following groups: hydrogen, alkyl, aryl, alkoxy, Carboxy.

The derivatives of hydantoin IX are further particularly preferred:

The following compounds are particularly preferred:
Diethyl 5-hydantoyl phosphonate, 5-methyl-5-phenyl-hydantoin, hydantoyl-5-acetic acid, 1,3-dibromo-5,5-dimethylhydantoin.

It was also surprisingly found that the bleaching system according to the invention with mediators selected from the group of oxocarbons does not have the disadvantages of the mediators known from the prior art. Preferred mediators in the bleaching system according to the invention are compounds of the general formula X, such as α-hydroxycarbonyl compounds of the general formula X a, α-dicarbonyl compounds of the general formula X b, β-hydroxycarbonyl compounds of the general formula X c, and β-dicarbonyl compounds of the general formula X d,

where the radicals R ¹ to R ⁸ can each independently represent one of the following atoms or atom groups: hydrogen, halogen, alkyl, alkyloxy, aryl, aryloxy, hydroxy, oxo, formyl, thioxo, mercapto, alkylthio, sulfeno, sulfino, sulfo, Sulfamoyl, amino, imino, amido, amidino, hydroxycarbamoyl, hydroximino, nitroso, nitro, hydrazono and where the radicals R ¹ and R ² ; R ³ and R ⁴ ; R ⁵ and R ⁶ ; R ⁷ and R ⁸ can form a common group and where n ≧ 1.

Compounds of the general formula XI are particularly preferred, open-chain compounds with a double bond (enols),

where the radicals R ⁹ to R ¹⁰ can each independently represent one of the following atoms or atom groups: hydrogen, halogen, alkyl, alkyloxy, aryl, aryloxy, hydroxy, oxo, formyl, thioxo, mercapto, alkylthio, sulfeno, sulfino, sulfo, Sulfamoyl, amino, imino, amido, amidino, hydroxycarbamoyl, hydroximino, nitroso, nitro, hydrazono and where the radicals R ⁹ and R ¹⁰ can form a common group.

Likewise particularly preferred are compounds of general structure XII, cyclic compounds, residues not OH, derivatives of squaric acid, OH group derivatized,

where the radicals R ¹¹ to R ¹² can each independently represent one of the following atoms or atom groups: hydrogen, halogen, alkyl, alkyloxy, aryl, aryloxy, hydroxy, oxo, formyl, thioxo, mercapto, alkylthio, sulfeno, sulfino, sulfo, Sulfanioyl, amino, imino, amido, amidino, hydroxycarbamoyl, hydroximino, nitroso, nitro, hydrazono and m ≧ 0.

Cyclic oxocarbons of the general formula XIII (general empirical formula: H ₂ C _x O _x , and also their dianions of the general formula C _x O _x ^2- where x is ≧ 3) are particularly preferred.
Structural element:

The following are particularly preferred:

Triangular acid

Square acid

Croconic acid

Rhodizonic acid

Imidazoles are further preferred mediator substances.  

Mediation enhancer

The component can include, for example, aliphatic ethers, olefins (alkenes) and phenol ethers, such as:
2,3-dimethoxybenzyl alcohol, 3,4-dimethoxybenzyl alcohol, 2,4-dimethoxybenzyl alcohol, 2,6-dimethoxybenzyl alcohol, homovanillyl alcohol, ethylene glycol monophenyl ether, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4-hydroxy-3-methoxybenzyl alcohol, 2 5-dimethoxybenzyl alcohol, 3,4-dimethoxybenzylamine, 2,4-dimethoxybenzylamine hydrochloride, coniferyl alcohol, 2-alkylphenol, 2-allyl-6-methylphenol, allylbenzene, 3,4-dimethoxy-propenylbenzene, p-methoxystyrene, 1-allylimidazole, 1-vinylimidazole, styrene, stilbene, allylphenyl ether, cinnamic acid benzyl ester, cinnamic acid methyl ester, 2,4,6-triallyloxy-1,3,5-triazine, 1,2,4-trivinylcyclohexane, 4-allyl-1,2-dimethoxy-benzene 4 Tert-butylbenzoic acid vinyl ester, squalene, benzoin allyl ether, cyclohexene, dihydropyran, N-benzyl cinnamic acid anilide, homovanillyl alcohol, veratrol, anisole.

Carbonyl compounds are also preferably used, such as: 4-aminobenzophenone, 4-acetylbiphenyl, benzophenone, benzil, Benzophenone hydrazone, 3,4-dimethoxybenzaldehyde, 3,4-dimethoxybenzoic acid, 3,4- Dimethoxybenzophenone, 4-dimethylaminobenzaldehyde, 4-acetylbiphenylhydrazone, benzophenone-4-carboxylic acid, benzoylacetone, Bis (4,4'-dimethylamino) benzophenone, benzoin, benzoin oxime, N-benzoyl-N- phenyl-hydroxylamine, 2-amino-5-chloro-benzophenone, 3-hydroxy-4- methoxybenzaldehyde, 4-methoxybenzaldehyde, anthraquinone-2-sulfonic acid, 4-methylaminobenzaldehyde, benzaldehyde, benzophenone-2-carboxylic acid, 3,3 ', 4,4, - Benzophenonetetracarboxylic acid dianhydride, (S) - (-) - 2- (N-bezylpropyl) - aminobenzophenone, benzylphenylacetic anilide, N-benzylbenzanilide, 4,4'-bis (dimethylamino) thiobenzophenone, 4,4'-bis (diacetylamino) benzophenone, 2-chlorobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,5-dimethoxy-4-hydroxybenzaldehyde hydrazine, hydroxybenzophenone, 2-hydroxy-4- methoxybenzophenone, 4-methoxybenzophenone, 3,4-dihydroxybenzophenone, p-anisic acid, p-anisaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzoic acid,  4-hydroxybenzaldehyde, salicylaldehyde, vanillin, vanillic acid.

Furthermore, this component of the bleaching system can act as a mediation enhancer at least one compound selected from the group consisting of NO-NOH-, HRN- OH compounds (as also in the patent applications WO 94/29425, DE 44 45 088 A1 or in particular in WO 97/48786 (page 11 to page 25) in detail are described and how they are summarized in the description of the present Invention are described) included such as B. hydroxylamines, hydroxylamine derivatives, hydroxamic acids, hydroxam acid derivatives, aliphatic, cycioaliphatic, heterocyclic or aromatic Compounds containing at least one N-Hxdroxy-, Oxim-, N-Oxy- or N, N'Dioxy- Function included. Furthermore, the bleaching system according to the invention can contain at least one Mediation enhancers from the group of amides such as hydrazides or 1,2,4- Triazolidin-3,5-dione (urazoles) and / or from the group of imides such as hydantoins and / or from the group of oxocarbons as described in detail above as mediators the description of the present invention.

Furthermore, the bleaching system according to the invention can contain at least one Mediation enhancer from the group of the cation radical forming substances of the Phenothiazine type and / or phenoxazine type and / or (R = N-N = R) type (e.g. ABTS) and / or a mediation enhancer from the group of cation-forming aryl-substituted alcohols (nonphenols) such as. B. Veratryl alcohol and / or from the group of cation-forming phenol derivatives such as p- Hydroxycinnamic acid, 2,4-dichlorophenol, p-hydroxybenzene sulfonate, vanillin (4-hydroxy-3-methoxy-benzaldehyde), p-Hy droxybenzoic acid, 5-amino-2-hydroxy-benzoic acid (5-aminosalycilic acid).

Furthermore, radical cation compounds according to "Wurster" (Lit .: Angewandte Chemie, 91, 1979, pp. 982-997; Chem. Unserer Zeit, 12, 1978, pp. 89-98; Römpp Chemie Lexikon, 9th edition, 1995 ) as general:
para-diephenyl diamines and particularly preferred:
N, N-dimethyl-p-phenylenediamine; N, N-diethyl-p-phenylenediamine; N, N, N ', N'-tetramethyl-p-phenylenediamine;2,3,5,6-tetramethyl-p-phenylenediamine;
Radical anions such as e.g. B. Semiquinones and others. Other preferred mediation enhancer compounds are imidazole compounds.

Other components

In addition, the bleaching system may and may not contain phenolic compounds phenolic compounds containing one or more benzene cores.

In addition to the oxidizing agents mentioned above according to the invention, particular preference is given to: air, oxygen, H ₂ O ₂ , organic peroxides, sodium perborate and / or sodium percarbonate.

Oxygen can also be generated in situ by H ₂ O ₂ + catalase or similar systems or H ₂ O from GOD + glucose or similar systems.

A bleaching system containing cation-forming metal salts is also preferred. Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ^3+, Mn ⁴⁺ , Cu +, Cu ²⁺ , Ti ³⁺ , Cer ⁴⁺ , Mg ²⁺ and Al ³⁺ are preferably used as cations.

Furthermore, the bleaching system can additionally contain polysaccharides and / or proteins. The polysaccharides are glucans, mannans, dextrans, levans, Pectins, alginates or plant gums and / or your own mushrooms or polysaccharides produced in the mixed culture with yeasts. As are proteins Gelatin, albumin and the like a. applicable.

Simple sugar, oligomer sugar, amino acids, Polyethylene glycol, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes.

The enzymatic bleaching system according to the invention with enzyme-enhancing effects Compounds find use in the treatment of textile fabrics such as Cotton, viscose, rayon (rayon), ramie, linen, tencelm, silk or Mixtures of these fabrics or mixtures of these fabrics with synthetic fibers such as e.g. B. Blends of cotton and spandex (stretch denim), especially but denim jeans, e.g. B. for partial or complete replacement of stone wash procedures, be it conventionally mechanical or enzymatic (e.g. with cellulases), their bleaching (e.g.  bleached look) and changing the surface in terms of color or Surface texture (fashion styles).

The enzymatic bleaching system is used in all conventional treatment apparatus in a pH range between 2 and 11, preferably 3-8, with and without buffer systems, at temperatures between 10 and 80 ° C, preferably 30-60 ° C and with consistencies of 1- 20%, in the case of peroxidase systems with the addition of peroxides or peroxide-generating systems and in the case of laccase systems in the presence of oxygen or air or their addition or slight O ₂ or air overpressure.

The invention is explained in more detail below with the aid of examples:

Example 0 Bleaching test with hypochlorite (zero test)

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

4 ml of NaOCl solution (4% active chlorine per 1 g of denim) are added.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 1 (comparative experiment with phenothiazine-10-propionic acid) Bleach with laccase + phenothiazine-10-propionic acid

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU laccase = conversion of 1 µmol syrigaldazine per min / ml enzyme solution) + 37 µmol phenothiazine-10-propionic acid per g denim admitted.  

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 1a (comparative experiment with N-hydroxysuccinimide-10-phenothiazine propionate) Bleach with laccase + N-hydroxysuccinimide-10-phenothiazine propionate

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU laccase = conversion of 1 µmol syrigaldazine per min / ml enzyme solution) + 37 µmol N-hydroxysuccinimide-10-phenothiazine propionate per g denim added.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 2 Bleach with laccase + violuric acid

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (I IU laccase = conversion of 1 µmol syrigaldazine per min / ml enzyme solution) + 37 µmol violuric acid per g denim added.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 3 Bleach with laccase + dimethylviolanoic acid

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU laccase = conversion of 1 µmol syrigaldazine per min / ml enzyme solution) + 37 µmol dimethylviolanoic acid per g denim.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 4 Bleach with peroxidase + violuric acid

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 5 with 0.5 n H ₂ SO ₄ .

0.1 mg peroxidase (Horseradish) + 37 µmol violuric acid per g denim admitted.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 5 Bleach with peroxidase + dimethylviolanoic acid

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 5 with 0.5 n H ₂ SO ₄ .

0.1 mg peroxidase (Horseradish) + 37 µmol dimethylviolanoic acid per g Denim admitted.  

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 6 Bleach with laccase + N-benzoyl-N-phenylhydroxylamine

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU laccase = conversion of 1 µmol syrigaldazine per min / ml enzyme solution) + 37 µmol N-benzoyl-N-phenylhydroxylamine per g denim admitted.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 7 Bleach with laccase + 1-hydroxy-2-methyl-imidazole

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU laccase = conversion of 1 µmol syrigaldazine per min / ml enzyme solution) + 37 µmol 1-hydroxy-2-methyl-imidazole per g denim admitted.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 8 Bleach with laccase + 1,3-dibromo-5-5-dimethylhydantoin

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU laccase = conversion of 1 µmol syrigaldazine per min / ml enzyme solution) + 37 µmol 1,3-dibromo-5-5-dimethylhydantoin per g Denim admitted.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C and with a reaction for 10192 00070 552 001000280000000200012000285911008100040 0002019821263 00004 10073s from 45 min.

It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 9 Bleach with laccase + dimethylviolanoic acid + mediation enhancer Violuric acid

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol violuric acid per g Denim admitted.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1

Example 10 Bleach with laccase + dimethylviolanoic acid + mediation enhancer N-benzoyl-N-phenylhydroxylamine

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol N-benzoyl-N- phenylhydroxylamine added per g of denim.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1

Example 11 Bleach with laccase + dimethylviolanoic acid + mediation enhancer Phthalhydrazide

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol phthalhydrazide per g Denim admitted.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Example 12 Bleach with laccase + dimethylviolanoic acid + mediation enhancer Urazole

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol urazole per g denim admitted.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1

Example 13 Bleach with laccase + dimethylviolanoic acid + mediation enhancer 1,3-dibromo-5-5-dimethylhydantoin

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol 1,3-dibromo-5-5- Dimethylhydantoin added per g of denim.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1

Example 14 Bleach with laccase + dimethylviolanoic acid + mediation enhancer Square acid

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol square acid per g Denim admitted.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1

Example 15 Bleach with laccase + dimethylviolanoic acid + mediation enhancer ABTS

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol ABTS per g denim admitted.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1

Example 16 Bleach with laccase + dimethylviolanoic acid + mediation enhancer N, N-dimethyl-p-phenylenediamine

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol N, N-dimethyl-p- phenylenediamine added per g of denim.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1

Example 17 Bleach with laccase + dimethylviolanoic acid + mediation enhancer Promazin

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol promazine per g Denim admitted.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1

Example 18 Bleach with laccase + dimethylviolanoic acid + mediation enhancer Hydroquinone sulfonic acid potassium salt

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol Hydroquinone sulfonic acid potassium salt added per g denim.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1

Example 19 Bleach with laccase + dimethylviolanoic acid + mediation enhancer 5-amino-2-hydroxybenzoic acid

1 g of denim fabric is placed in a 200 ml Erlenmeyer flask (consistency 2%). The pH of the solution (tap water), which after the addition of all components comprises 50 ml, is preset to pH 4.5 with 0.5 n H ₂ SO ₄ .

10 IU laccase (1 IU = conversion of 1 µmol syrigaldazine per min / ml Enzyme solution) + 37 µmol dimethylviolanoic acid and 0.37 µmol 5-amino-2- hydroxybenzoic acid added per g of denim.

The test is carried out in a shaking water bath (200 rpm), at 45 ° C. and a reaction time of 45 min. It is then washed with tap water and the piece of tissue is air-dried. Then the brightness is determined with an Elrepho device.
The corresponding values can be found in Table 1.

Table 1

Claims (44)

1. Enzymatic bleaching system with enzyme-enhancing compounds for use in the treatment of textile fabrics, e.g. B. for the partial or complete replacement of stone-wash procedures, conventional mechanical or enzymatic (with cellulases), their bleaching and / or changes in the surface in terms of color or surface texture, containing:

• a) at least one oxidation catalyst,
• b) at least one oxidizing agent,
• c) at least one mediator selected from the group of hydroxylamines, hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, aliphatic, cycloaliphatic, heterocyclic or aromatic compounds which contain at least one N-hydroxy, oxime, N-oxi, or N, N ' Contain dioxi function and / or at least one mediator from the group of amides such as hydrazides or 1,2,4-triazolidin-3,5-dione (urazoles) and / or at least one mediator from the group of imides such as hydantoins and / or at least one mediator from the group of oxocarbons.

2. Bleaching system according to claim 1, characterized in that at least one compound selected from the group of NO, NOH, HRN-OH compounds such as hydroxylamines, hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, the aliphatic, cycloaliphatic, heterocyclic or aromatic compounds as mediator that contain at least one N-Hxdroxy-, Oxim-, N-Oxy- or N, N'Dioxy-function is used like:
Hydroxylamines (open-chain or cyclic, aliphatic or aromatic, heterocyclic) of the general formula (A) (radicals "R", see description):
such as the compounds N, N-dipropylhydroylamine, N, N-diisopropylhydroxylamine, N-hydroxylpyrrolidine, N-hydroxypiperidine, N-hydroxyhexahydroazepine, N, N-dibenzylhydroxylamine, phenylhydroxylamine, 3-hydroxylamino-3-phenylpropionic acid, 2-hydroxylamino-3- phenylpropionic acid, N-sulfomethylhydroxylamine, such as 1-hydroxy-benzimidazoles such as:
1-hydroxy-benzimidazole-2-carboxylic acid, 1-hydroxybenzimidazole, 2-methyl-1-hydroxy benzimidazole, 2-phenyl-1-hydroxybenzimidazole and 1-hydroxyindoles such as: 2-phenyl-1-hydroxyindole and derivatives of 1-hydroxybenzotriazole and tautomeric benzotriazole-1-oxide or 1H-hydroxybenzotriazole and compounds such as:
Aziridines, diaziridines, pyrroles, dihydropyrroles, tetrahydropyrroles, pyrazoles, dihydropyrazoles, tetrahydropyrazoles, imidazoles, dihydroimidazoles, tetrahydroimi dazoles, dihydroimidazoles, 1,2,3-triazoles, 1,2,4-triazoles, pyridoles, pyridine, tetrazoleidene , Pyrimidines, pyrazines, piperazines, 1,2,3-triazines, 1,2,4-triazines, tetrazines, azepines, oxazoles, isoxazoles, thiazoles, isothiazoles, thiadiazoles, morpholines, and their benzofused derivatives such as: indoles, isoindoles, indolizines , Indazoles, benzimidazoles, benztriazoles, quinolines, isoquinolines, phthalazines, quinazolines, quinoxalines, phenazines, benzazepines, benzothiazoles, benzoxazoles, such as condensed N-heterocycles such as triazolo and tetrazolo compounds, which have at least one N-hydroxy, oxime, N-oxi -, N, N-dioxi function and, in addition to N, a further heteroatom such as O, S, Se, Te, and compounds such as: quinoline-N-oxide, isoquinoline-N-oxide, N-hydroxy-1,2,3 , 4-tetrahydroisoquinoline, β- (N-oxy-1,2,3,4-tetrahydro-isoch inolino) propionic acid, 1,3-dihydroxy-2-N-benzylimidobenzimidazoline. 3. bleaching system according to claim 1 or 2, characterized in that as a mediator at least one compound selected from the group of cyclic N-hydroxy compounds with at least one optionally substituted five- or six-membered ring of the following general formulas B, C, D, E and F is used (X and Y residue description "R", see description):
like connections like:
N-hydroxy-phthalimides, substituted N-hydroxy-phthalimide derivatives, N-hydroxymaleimides, substituted N-hydroxymaleimide derivatives, N-hydroxy-naphthalic acid imides, substituted N-hydroxy-naphthalic acid imide derivatives, N-hydroxysuccinimides and substituted N- Hydroxysuccinimide derivatives such as:
N-hydroxyphthalimide, N-hydroxy-benzene-1,2,4-tricarboximide, N, N'-dihydroxy-pyromellitic acid diimide, N, N'-dihydroxy-benzophenone-3,3 ', 4,4'-tetracarbonic acid diimide, N-hydroxymaleimide, pyridine-2,3-dicarboxylic acid-N-hydroxyimide, N-1-hydroxysuccinimide, N-1-hydroxy tartarimide, N-hydroxy-5-norbornene-2,3-dicarboximide, exo-N-hydroxy-7 oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-hydroxy-cis-cyclohexane-1,2-dicarboximide, N-hydroxy-cis-4-cyclohexene-1,2-dicarboximide, N-hydroxy naphthalimide sodium salt and N-hydroxy glutarimide. 4. Bleaching system according to claim 1 to 3, characterized in that at least one compound selected from the group of oximes according to the following general formulas G and H is used as mediator (residues: R, see description):
such as cyclic isonitroso derivatives of cyclic ureids such as 1-methylvioluric acid, 1,3-dimethylvioluric acid, thiovioluric acid, alloxan-4,5-dioxime and alloxan-5-oxime hydrate (violuric acid), dimethylviolanic acid and / or their esters, ethers or salts. 5. bleaching system according to claim 1 and 4, characterized in that the mediator is selected from the group of oximes dimethylviolanoic acid. 6. bleaching system according to claim 1 to 5, characterized in that as a mediator at least one compound selected from the group of N-aryl-N-hydroxy amides of the general formulas I, J, K, K ₁ , K ₂ , K ₃ , K ₄ and K ₅ (residues: A, B, C, D, R, A _r1 , A _r2 , q, see description) is used:
like connections like:
N-Hydroxyacetanilide, N-Hydroxypivaloylanilid, N-Hydroxyacrylanilide, N-Hydroxybenzoyl-anilide, N-Hydroxy-methyl-sulfonylanilide, N-Hydroxy-N-phenyl methyl carbamate, N-Hydroxy-3-oxo-butyrylanilide, N-Hydroxy-4 -cyanoacetanilide, N-hydroxy-4-methoxyacetanilide, N-hydroxyphenacetin, N-hydroxy-2,3-dimethyl actetanilide, N-hydroxy-2-methylacetanilide, N-hydroxy-4-methylacetanilide, 1-hydroxy-3,4- dihydroquinolin- (1H) -2-one, N, N-dihydroxy-N, N'-diacetyl-1,3-phenylenediamine, N, N'-dihydroxysuccinic acid dianilide, N, N 'dihydroxymaleic acid dianilide, N, N'-dihydroxy -oxalic acid dianilide, N, N'-dihydroxyphosphoric acid dianilide, N-acetoxy acetanilide, N-hydroxymethyloxalylanilide, N-hydroxymaleic acid monoanilide and N-hydroxyformanilide. 7. bleaching system according to claim 1 to 6, characterized in that at least one compound selected from the group of the stable nitroxyl radicals (nitroxides) of the general formulas L, M, N, N ₁ and N _{2 is} used as the mediator (residues: Ar, R, see description):
like connections like:
2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-oxo-2,2,6,6 -tetramethyl-piperidine-1-oxyl, 4-acetamido-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4- (ethoxyfluorophosphinyloxy) -2,2,6,6-tetramethyl-piperidine-1-oxyl , 4- (isothiocyanato) -2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-maleimido-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4- (4-nitrobenzoyloxy) -2,2,6,6-tetra-methyl-piperidine-1-oxyl, 4- (phosphonooxy) -2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-cyano-2,2,6 , 6-tetramethyl-piperidine-1-oxyl, 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolidin-1-oxyl, 4-phenyl-2,2,5,5-tetramethyl-3-imidazoline -3-oxide-1-oxyl, 4-carbamoyl-2,2,5,5-tetramethyl-3-imidazoline-3-oxide-1-oxyl, 4-phenacylidene-2,2,5,5-tetramethyl imidazolidine 1-oxyl, 3- (aminomethyl) -2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 3-carboxy-2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 3-cyano- 2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 3-maleimido-2,2,5,5-tetramethyl-pyrrolidine-N-oxyl, 3- (4-nitrophenoxycarbonyl) -2,2,5, 5th tramethyl-pyrrolidine-N-oxyl, 4- (isothiocyanato) - 2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-carbamoyl-2,2,5,5-tetramethyl-3-imidazoline-3- oxide-1-oxyl. 8. bleaching system according to claim 1 to 7, characterized in that such mediators from the group of amides such as hydrazides, cyclic hydrazides, urazoles and phthalhydrazides are used according to the following general formula I, II, III, IV and V:
Where X stands for C = O or O = S = O. (Carboxylic acid or sulfonic acid amides). The radicals R can be the same or different and independently represent hydrogen, alkyl, aryl or acyl groups (carboxylic acid or sulfonic acid residues).
Where X stands for C = O or O = S = O (cyclic hydrazides of dicarboxylic acids or disulfonic acids). The radicals R can be the same or different and independently of one another are hydrogen, Represent alkyl, aryl or acyl groups. G stands for the following atoms or groups of atoms: CH ₂ , CH ₂ -CH ₂ , CHR ¹ -CHR ¹ , CH = CH, CR ² = CR ² , NH, NR ³ , C = O, ortho-C ₆ H ₄ (ortho substituted phenyl radical), ortho C ₁₀ H ₆ (ortho substituted naphthyl radical), where the radicals R ¹ to R ^{3 can be} identical or different and can independently represent hydrogen, alkyl, aryl or acyl radicals, where R ⁴ can be hydrogen, alkyl, alkoxy, carboxy, nitro or amino. The radicals R can be the same or different and independently of one another are hydrogen, alkyl, aryl or. 9. bleaching system according to claim 1 and 8, characterized in that as mediators from the group of amides such as hydrazides, cyclic hydrazides, urazoles and phthalhydrazide compounds such as:
Maleic hydrazide, 2-nitrobenzhydrazide, p-toluenesulphonylhydrazide, Nicotinic hydrazide, Isonicotinic acid hydrazide, 4,4 ', - Oxydibenzenesulfonylhydrazide, Bencoic hydrazide, Phthalhydrazide, 3-Aminophthal hydrazide, 1-Naphthoic-hydrazide-3-hydrazide, Hydroxybenzhydrazide, Oxamic hydrazide, Oxalyl dihydrazide, Terephthalic dihydrazide, Isophthalic-dihydrazide, L-Tyrosine hydrazide, Oxalic-bis- (benzylidenehydrazide), Salicyliden salicylhydrazide, Thiophene-2-carbonic acid hydrazide, Furan-2-carbonic -5-hydroxypyrazole, 2,3-dihydro-1,4-phthalazinedione, 7-nitroindazole and 1,2-dihydropyrazine-3,6-dione, 4-phenylurazole, 1-phenylurazole, 4-methylurazole, 4-tert.- Butylurazole and urazole can be used. 10. bleaching system according to claim 1 to 9, characterized in that as mediators from the group of imides such as hydantoins, cyclic imides and hydantoin derivatives such those are used according to the following general formula VI, VII VIII and IX:
The radicals R can be the same or different and independently represent hydrogen, alkyl, aryl, acyl or amino groups.
The radicals R can be the same or different and independently represent hydrogen, alkyl, aryl, acyl or amino groups.
The radicals R can be identical or different and independently represent hydrogen, alkyl, aryl, acyl or amino groups, and where group G represents one of the following atoms or atom groups: CH ₂ , CHR ¹ , CR ¹ R ² , CH = CH, CR ³ = CR ⁴ , NH, NR ⁵ , C = O, O, and where R ¹ to R ^{5 can be the} same or different and can independently represent one of the following groups: hydrogen, alkyl, aryl, alkoxy, Carboxy
and compounds (derivatives of hydantoin) such as: diethyl-5-hydantoyl-phosphonate, 5-methyl-5-phenyl-hydantoin, hydantoyl-5-acetic acid, 1,3-dibromo-5,5-dimethylhydantoin. 11. bleaching system according to claim 1 to 10, characterized in that as mediators from the group of oxocarbons such as α-hydroxycarbonyl compounds, α-dicarbonyl compounds, β-hydroxycarbonyl compounds and β-dicarbonyl compounds, open-chain compounds with double bond (enols) those of the general formulas Xa, Xb, Xc, Xd and XI are used,
where the radicals R ¹ to R ⁸ can each independently represent one of the following atoms or atom groups: hydrogen, halogen, alkyl, alkyloxy, aryl, aryloxy, hydroxy, oxo, formyl, thioxo, mercapto, alkylthio, sulfeno, sulfino, sulfo, Sulfamoyl, amino, imino, amido, amidino, hydroxycarbamoyl, hydroximino, nitroso, nitro, hydrazono and where the radicals R ¹ and R ² ; R ³ and R ⁴ ; R ⁵ and R ⁶ ; R ⁷ and R ⁸ can form a common group and where n ≧ 1,
where the radicals R ⁹ to R ¹⁰ can each independently represent one of the following atoms or atom groups: hydrogen, halogen, alkyl, alkyloxy, aryl, aryloxy, hydroxy, oxo, formyl, thioxo, mercapto, alkylthio, sulfeno, sulfino, sulfo, Sulfamoyl, amino, imino, amido, amidino, hydroxycarbamoyl, hydroximino, nitroso, nitro, hydrazono and where the radicals R ⁹ and R ¹⁰ can form a common group and compounds of the general structure XII are used:
cyclic compounds, residues not OH, derivatives of squaric acid, OH group derivatized,
where the radicals R ¹¹ to R ¹² can each independently represent one of the following atoms or atom groups: hydrogen, halogen, alkyl, alkyloxy, aryl, aryloxy, hydroxy, oxo, formyl, thioxo, mercapto, alkylthio, sulfeno, sulfino, sulfo, Sulfamoyl, amino, imino, amido, amidino, hydroxycarbamoyl, hydroximino, nitroso, nitro, hydrazono and m ≧ 0
and compounds from the group of cyclic oxocarbons of the general formula XIII are used (general empirical formula: H ₂ C _x O _x , and their dianions of the general formula C _x O _x ^2- where x is ≧ 3 (structural element):
and compounds such as triangular acid, squaric acid, croconic acid and rhodizonic acid and their derivatives are used. 12. Bleaching system according to claim 1 to 11, characterized in that as Mediators compounds from the group of imidazoles are used such as 1-hydroxy-2-methylimidazole. 13. Bleaching system according to claims 1 to 12, characterized in that at least one compound selected from the group of aliphatic ethers, olefins (alkenes) and phenol ethers and carbonyl compounds is used as a media enhancer, such as:
2,3-dimethoxybenzyl alcohol, 3,4-dimethoxybenzyl alcohol, 2,4-dimethoxybenzyl alcohol, 2,6-dimethoxybenzyl alcohol, homovanillyl alcohol, ethylene glycol monophenyl ether, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4-hydroxy-3-methoxybenzyl alcohol, 2 5-dimethoxybenzyl alcohol, 3,4-dimethoxybenzylamine, 2,4-dimethoxybenzylamine hydrochloride, coniferyl alcohol, 2-alkylphenol, 2-allyl-6-methylphenol, allylbenzene, 3,4-dimethoxy-propenylbenzene, p-methoxystyrene, 1-allylimidazole, 1-vinylimidazole, styrene, stilbene, allylphenyl ether, cinnamic acid benzyl ester, cinnamic acid methyl ester, 2,4,6-triallyloxy-1,3,5-triazine, 1,2,4-trivinylcyclohexane, 4-allyl-1,2-dimethoxy-benzene, 4-tert-butylbenzoic acid vinyl ester, squalene, benzoin allyl ether, cyclohexene, dihydropyran, N-benzyl cinnamic acid anilide, homovanillyl alcohol, veratrol, anisole, 4-aminobenzophenone, 4-acetylbiphenyl, benzophenone, benzil, benzophenone-ethoxy-benzo-3,4-ethoxy-benzo-3-benzoxy-3,4-ethoxy-benzo-3-benzoxy 3,4-dimethoxybenzophenone, 4- Dimethylaminobenzaldehyde, 4-acetylbiphenylhydrazone, benzophenone-4-carboxylic acid, benzoylacetone, bis (4,4'-dimethylamino) benzophenone, benzoin, benzoin oxime, N-benzoyl-nphenyl-hydroxylamine, 2-amino-5-chloro-benzophenone, 3- Hydroxy-4-methoxybenzaldehyde, 4-methoxybenzaldehyde, anthraquinone-2-sulfonic acid, 4-methylaminobenzaldehyde, benzaldehyde, benzophenone-2-carboxylic acid, 3,3 ', 4,4, -benzophenonetetracarboxylic acid dianhydride, (S) - (-) - 2 - (N-Bezylpropyl) aminobenzophenone, benzylphenylacetic anilide, N-benzylbenzanilide, 4,4'- bis (dimethylamino) thiobenzophenone, 4'-bis (diacetylamino) benzophenone, 2-chlorobenzophenone, 4,4'-dihydroxybenzene 2,4-dihydroxybenzophenone 3,5-dimethoxy-4-hydroxybenzaldehyde hydrazine, hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-methoxybenzophenone, 3,4-dihydroxybenzophenone, p-anisic acid, p-anisaldehyde, 3,4-dihydroxybenzaldehyde, 3 , 4-dihydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzoic acid, 4-hydroxybenzaldehyde, salicylaldehyde d, vanillin, vanillic acid. 14. Bleaching system according to claim 1 to 13, characterized in that as Media amplifier at least one connection selected from the Group of NO, NOH, HRN-OH compounds such as hydroxylamines, Hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, the aliphatic, cycloaliphatic, heterocyclic or aromatic Compounds containing at least one N-Hxdroxy-, Oxim-, N-Oxy-, or N, N'Dioxy function included is used. 15. bleaching system according to claim 1 to 14, characterized in that it at least one mediation amplifier from the compound class of Contains hydrazides. 16. Bleaching system according to claim 1 to 15, characterized in that it at least one mediation amplifier from the compound class of Contains urazole. 17. Bleaching system according to claim 1 to 16, characterized in that it at least one mediation amplifier from the compound class of Contains hydantoins. 18. Bleaching system according to claim 1 to 17, characterized in that it at least one mediation amplifier from the compound class of Contains oxocarbons.   19. Bleaching system according to claim 1 to 18, characterized in that it at least one mediation amplifier from the compound class of cation-forming compounds of the phenothiazine type and / or Phenoxazine type and / or the (R = N-N = R) type (e.g. ABTS) and / or the aryl-substituted alcohol type such as veratryl alcohol (non-phenol) and / or Phenol derivatives such as p-hydroxycinnamic acid, 2,4-dichlorophenol, p- Hydroxy-benzene sulfonate, vanillin (4-hydroxy-3-methoxy-benzaldehyde), p-hydroxybenzoic acid, 5-amino-2-hydroxybenzoic acid (5-aminosalicylic acid) and / or the radical cations according to "Wurster" (substituted para-phenylenediamines) contains. 20. Bleaching system according to claim 1 to 19, characterized in that it at least one mediation amplifier from the compound class of Radical anions such as B. by enzymatic oxidation from hydroquinones contains generated semiquinones. 21. Bleaching system according to claim 1 to 20, characterized in that it at least one mediation amplifier from the compound class of Contains imidazoles such as 1-hydroxy-2-methyl-imidazole. 22. Bleaching system according to claim 1 to 21, characterized in that this bleaching system mediator substances selected from the group of NO, NOH, HRNOH compounds and / or the amides such as. B. Hydrazides and urazoles and / or selected from the group of imides such as e.g. B. the hydantoins and / or selected from the group of Oxocarbons are added and that this bleaching system Mediation enhancer selected from the group of NO, NOH, HRNOH compounds and / or the amides such as hydrazides and urazoles and / or the imides such as hydantoins and / or the oxocarbons and / or of the generated cation radicals from the group of ABTS-like Substances of the general formula R = N-N = R and / or the Cation radicals from the group of phenothiazine derivatives, and / or the group of phenoxazine derivatives and / or cation radicals from the Group of aryl-substituted alcohols such as veratryl alcohol (nonphenols)  and / or the group of phenols according to claim 19 and / or from the Group of the "Wurster" radical cations and / or compounds from the Group of radical anions as mediators as well as Mediation enhancers can be added in one or more. 23. Bleaching system according to claim 1 to 22, characterized in that the corresponding amounts of mediator in relation to the corresponding Mediation amplifier amounts in the range from 5000: 1 with preference 500: 1 to 1: 1 can be added. 24. Bleaching system according to claim 1 to 23, characterized in that it in addition to these substances phenolic compounds and / or non-phenolic compounds with one or more benzene cores contains. 25. Bleaching system according to claim 1 to 24, characterized in that it as an oxidation catalyst one or more oxidoreductases of the classes 1.1.1.-1.97 contains. 26. Bleaching system according to claim 1 to 25, characterized in that it one or more oxidoreductases, which are oxygen, peroxides or Use quinones as an electron acceptor. 27. Bleaching system according to claim 1 to 26, characterized in that it contains laccase (1.10.3.2.) as oxidoreductase. 28. Bleaching system according to claim 1 to 27, characterized in that it as oxidoreductase peroxidases, e.g. B. Horseradish (bacterial and others), Contains lignin peroxidases, manganese peroxidases. 29. Multi-component system according to claim 1 to 28, characterized characterized as oxidoreductases such as those of white rot fungi, other fungi, bacteria, animals or plants  obtained from natural or genetically modified organisms be contains. 30. Bleaching system according to claim 1 to 29, characterized in that it enzymes modified as catalysts, enzyme components, prosthetic Groups or mimic substances, preferably heme or heme groups containing compounds or complexes, or copper or Contains compounds or complexes containing copper groups. 31. Bleaching system according to one of claims 1 to 30, characterized in that it is used as an oxidizing agent, for. B. air, oxygen, ozone, peroxides, such as H ₂ O ₂ and organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, persitric acid, metachloroperoxibenzoic acid, perchloric acid, per compounds, such as perborates, percarbonates, persulfates, oxygen species and their radicals such as OH radical , OOH radical, superoxide (O _2- ) radical, OH⁺ radical, singlet oxygen, ozonide (O _3- ), dioxygenyl cation (O ₂ ⁺), dioxirane, dioxitane or fremy radicals. 32. bleaching system according to claim 1 to 31, characterized in that the enzymatic bleaching system in all usual treatment or Washing equipment is used. 33. bleaching system according to claim 1 to 32, characterized in that the Tissue treatment in a pH range from 2 to 11, preferably at pH 3 up to 8, with and without buffer systems and at a temperature of 10 to 80 ° C, preferably at 30 to 60 ° C and at fabric densities of 1 to 20% is carried out. 34. bleaching system according to claim 1 to 33, characterized in that at Peroxidase systems with the addition of peroxides, and with oxidases or Laccase systems in the presence of air or oxygen and / or Supply of air or oxygen or light air or oxygen Overpressure is worked.   35. bleaching process according to claim 1 to 34 for use in the treatment of textile fabrics e.g. B. for partial or complete Replacement of stone wash procedures, be it conventional or mechanical enzymatic (with cellulases), their bleaching and change in Surface in terms of color or texture. 36. Bleaching process according to claim 1 to 35 for use in the treatment of textile fabrics, the fabric being made of Cellulose fibers, a mixture of cellulose fibers and others natural vegetable fibers or cellulose fibers and synthetic Fibers. 37. bleaching process according to claim 1 to 36 for use in the Treatment of textile fabrics, the textile fabric being denim, preferably colored with indigo dye or thioindigo dye Denim fabric.