DE4445088A1 - Biological bleach system additives for detergents, esp. low temp. active type - Google Patents

Abstract

Multi-component bleach systems (M) for use in wash-active substances comprise the following components: (A) opt. at least one oxidoreductase oxidn. catalyst; (B) at least one suitable oxidising agent; (C) at least one mediator chosen from hydroxylamines or their derivs., hydroxamic acids or their derivs., or (cyclo)aliphatic, heterocyclic or aromatic cpds. contg. at least one N-hydroxy, oxime, N-oxide or N,N'-dioxide functional gp.; (D) opt. at least one co-mediator chosen from aryl substd. alcohols, carbonyl cpds., aliphatic ethers, phenol ethers and/or alkenes; and (E) a very small amt. of at least one free amine of the mediator cpd. used.

Description

The present invention relates to a new multi-component bleaching system for the use of detergent substances. The conventional ones are particularly in the low temperature range Bleaching systems in household detergents unsatisfactory.

The standard bleaching agent must be below a washing temperature of 60 ° C H₂O₂ / sodium perborate / sodium percarbonate by adding chemical bleach activators such as TAED and SNOBS activated will. Furthermore, after better biodegradable, biocompatible and low dose bleaching systems for Low temperature laundry wanted. While for protein starch and Fat solution as well as for fiber treatment in the washing process Enzymes in technical use stand for So far no detergent bleach has an enzymatic principle available.

WO 1/05239 describes the use of various oxidative agents Kender enzymes (oxidases and peroxidases) to prevent the "Dye transfers" described. Peroxidases are known in able to use different pigments (3-hydroxyflavon and betalain by horseradish peroxidase, carotene by peroxidase) "discolor".

The patent itself describes the decolorization (also "bleaching" ge named) from detached from the laundry present in the fleet Textile dyes (conversion of a colored substrate into a undyed, oxidized fabric). The enzyme is said to be opposite e.g. B. hypochlorite, which is also the dye on or in the tissue attacks, have the advantage of only dissolved dye decolorize, using hydrogen peroxide or an equivalent Precursor or in situ generated hydrogen peroxide at the Catalysis of discoloration are involved. The enzyme reaction can partly by adding additional oxidizable Enzyme substrate, e.g. B. metal ions such as MN ++, halide ions such as Cl- or Br- or organic phenols such as p-hydroxycinnamic acid 2.4 Dichlorophenol. Here the formation of short-lived radicals or other oxidized states of the added substrate postulated for bleaching or a other modification of the colored substance are responsible.  

In US 4 077 6768 the use of "iron porphin", "haemin chloride" or "iron phthalocynanine" or derivatives together with hydrogen peroxide to prevent the "dye Transfers ". However, these substances are Excess peroxide quickly destroyed, which is why Hydrogen peroxide formation must take place in a controlled manner.

Methods are known from WO / 126119, WO 94/12620 and WO 94/12621 in which the Peroxidase activity can be required using so-called enhancer substances.

The enhancer substances are described in WO 94/12620 based on their half-life characterized.

According to WO 94/12621, enhancer substances are characterized by the formula A = N-N = B, where A and B are each defined cyclic radicals.

According to WO 94/12620, enhancer substances are organic chemicals that have at least two contain aromatic rings, at least one of which is substituted with defined radicals is.

All three applications concern "dye transfer inhibition" and the use of the respective Enhancer substances together with peroxidases as a detergent additive or Detergent composition in the detergent sector.

The combination of these enhancer substances are limited to peroxidases while your own Application PCT / EP94 / 01967 (DE P43 19 696.9) mainly relates to laccases as enzymes limited.

The object of the present invention is to provide an improved multi-component bleaching system To provide use with detergent substances that v. a. the real ones Media substances in their effect enhanced or in situ, d. H. during the washing process regenerates.

This object is achieved in that the improved multi-component bleaching system

• a. optionally at least one oxidation catalyst and
• b. at least one suitable oxidizing agent and
• c. selects at least one mediator from the group of hydroxylamines, Hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, the aliphatic, cycloaliphatic, heterocyclic or aromatic compounds containing at least one Contain N-hydroxy, oxime, N-oxi, or N, N'-dioxi function and
• d. optionally at least one comediator from the group of the aryl-substituted alcohols, Carbonyl compounds, aliphatic ethers, phenol ethers and / or olefins (alkenes) and  
• e. a small amount of at least one free amine of each mediator used

includes.

It has surprisingly been found that when substances are added (Comediators) from the group of aryl-substituted alcohols, carbonyl compounds, aliphatic ethers, phenol ethers and / or olefins (alkenes) to the mediators from the group the hydroxylamines, hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, the aliphatic, cycloaliphatic, heterocyclic or aromatic compounds which together contain at least one N-hydroxy, oxime, N-oxi, or N, N'-dioxi function with the free amines of the respective mediators and oxidation catalysts on the one hand The bleaching process is significantly improved and the mediator consumption is reduced can.

The multicomponent system according to the invention preferably comprises at least one Oxidation catalyst.

The multicomponent system according to the invention preferably comprises at least a comediator.

Oxidation catalysts in the multi-component system according to the invention preferably used enzymes. For the purposes of the invention, the term enzyme also includes enzymatically active proteins or peptides or prosthetic groups of enzymes.

Oxidoreductases can be used as the enzyme in the multicomponent system according to the invention 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) can be used.

Enzymes of the classes mentioned below are preferably used:
Class 1.1 enzymes, which comprise all dehydrogenases which act on primary, secondary alcohols and semiacetals, and which are accepted as NAD + or NADP + (subclass 1.1.1), cytochrome (1.1.2), oxygen (O₂) (1.1.3) , Disulfides (1.1.4), quinones (1.1.5) or the other acceptors (1.1.99).

From this class, the enzymes of class 1.1.5 with quinones are particularly preferred Acceptors and the class 1.1.3 enzymes. with oxygen as the acceptor.  

Cellobiose: quione-1-oxidoreductase (1.1.5.1) is particularly preferred in this class.

Enzymes of class 1.2 are also preferred. This enzyme class (1.1.5.1) includes such Enzymes that oxidize aldehydes to corresponding acids or oxo groups. The Acceptors can be NAD +, NADP + (1.2.1), cytochrome (1.2.2), oxygen (1.2.3), sulfides (1.2.4), iron-sulfur proteins (1.2.5) or other acceptors (1.2.99).

The enzymes of group (1.2.3) with oxygen as the acceptor are particularly preferred here.

Enzymes of class 1.3 are also preferred.

This class includes enzymes that act on CH-CH groups of the donor.

The corresponding acceptors are NAD +, NADP + (1.3.1) cytochrome (1.3.2), oxygen (1.3.3), quinones or related compounds (1.3.5), iron-sulfur proteins (1.3.7) or other acceptors (1.3.99).

Also here are the enzymes of class (1.3.3) with oxygen as acceptor and (1.3.5) with Quinones etc. are particularly preferred as acceptors.

Also preferred are class 1.4 enzymes based on CH-NH₂ groups of the donor Act.

The corresponding acceptors are NAD +, NADP + (1.4.1), cytochrome (1.4.2), oxygen (1.4.3), disulfides (1.4.4), iron-sulfur proteins (1.4.7) or other acceptors (1.4.99).

Enzymes of class 1.4.3 with oxygen as the acceptor are also particularly preferred here.

Also preferred are class 1.5 enzymes which target CH-NH groups of the donor Act. The corresponding acceptors are NAD +, NADP + (1.5.1), oxygen (1.5.3), Disulfides (1.5.4), quinones (1.5.5) or other acceptors (1.5.99).

Enzymes with oxygen (O₂) (1.5.3) and with quinones are also particularly preferred here (1.5.5) as acceptors.  

Enzymes of class 1.6 which act on NADH or NADPH are also preferred.

The acceptors here are NADP + (1.6.1), heme proteins (1.6.2), disulfides (1.6.4), quinones (1.6.5), NO₂ groups (1.6.6) and a flavin (1.6.8) or some other acceptors (1.6.99).

Enzymes of class 1.6.5 with quinones as acceptors are particularly preferred here.

Also preferred are class 1.7 enzymes which act on NO₂ compounds other than Donors act and as acceptors cytochrome (1.7.2), oxygen (O₂) (1.7.3), Have iron-sulfur proteins (1.7.7) or others (1.7.99).

Class 1.7.3 with oxygen as the acceptor is particularly preferred here.

Also preferred are class 1.8 enzymes based on sulfur groups as donors act as acceptors NAD +, NADP + (1.8.1.), cytochrome (1.8.2), oxygen (O₂) (1.8.3), disulfides (1.8.4), quinones (1.8.5), iron-sulfur proteins (1.8.7) or others (1.8.99).

Class 1.8.3 with oxygen (O₂) and (1.8.5) with quinones is particularly preferred Acceptors.

Also preferred are class 1.9 enzymes which act as donors on heme groups and as acceptors oxygen (O₂) (1.9.3), NO₂ compounds (1.9.6) and others (1.9.99) to have.

Group 1.9.3 with oxygen (O₂) as the acceptor is particularly preferred here (Cytochrome oxidases).

Also preferred are class 1.12 enzymes which act on hydrogen as a donor. The acceptors are NAD + or NADP + (1.12.1) or others (1.12.99).

Enzymes of class 1.13 and 1.14 (oxigenases) are also preferred.  

Preferred enzymes are also those of class 1.15 which are based on superoxide radicals Acceptors work.

Superoxide dismutase (1.15.1.1) is particularly preferred here.

Enzymes of class 1.16 are also preferred.

NAD + or NADP + (1.16.1) or oxygen (O₂) (1.16.3) act as acceptors.

Enzymes of class 1.16.3.1 (ferroxidase, eg ceruloplasmin) are particularly preferred here.

Further preferred enzymes are those belonging to group 1.17 (effect on CH₂ groups that are oxidized to -CHOH-), 1.18 (effect on reduced ferredoxin as Donor), 1.19 (effect on reduced flavodoxin as donor) and 1.97 (others Oxidoreductases).

Enzymes 1.11. Which are based on a peroxide are also particularly preferred Act acceptor. This only subclass (1.11.1) contains the peroxidases.

The cytochrome C peroxidases (1.11.1.5), catalase (1.11.1.6) are particularly preferred here, peroxidase (1.11.1.6), iodide peroxidase (1.11.1.8), glutathione peroxidase (1.11.1.9), the chloride peroxidase (1.11.1.10), the L-ascorbate peroxidase (1.11.1.11), the Phospholipid hydroperoxide glutathione peroxidase (1.11.1.12), the manganese peroxidase (1.12.1.13), the diarylpropane peroxidase (ligninase, lignin peroxidase).

Enzymes of class 1.10 which are based on biphenols and relatives are very particularly preferred Connections work. They catalyze the oxidation of biphenols and ascorbates. As Acceptors act as NAD +, NADP + (1.10.1.), Cytochrome (1.10.2), oxygen (1.10.3) or others (1.10.99).  

Of these, in turn, are class 1.10.3 enzymes with oxygen (O₂) as the acceptor particularly preferred.

Of the enzymes in this class, the enzymes 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 (Benzene diol: oxigen oxidoreductase) (1.10.3.2.) Are particularly preferred.

These enzymes are commercially available or can be obtained using standard methods. As Organisms for the production of the enzymes come, for example, from plants, animal cells, Bacteria and fungi into consideration. Basically, both naturally occurring as genetically modified organisms can also be enzyme producers. Parts of unicellular or multicellular organisms conceivable as enzyme products, especially Cell cultures.

For the particularly preferred enzymes, such as those from group 1.11.1, but above all 1.10.3 and especially for the production of laccases are, for example, white rot fungi like Pleurotus, Phlebia and Trametes.

The multi-component system according to the invention comprises at least one oxidizing agent. As oxidizing agents, for example air, oxygen, ozone, H₂O₂ organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, persitric acid, metachloroperoxidbenzoic acid, perchloric acid, perborates, peracetate, persulfates, peroxides or oxygen species and their radicals such as OH, OOH, superoxide (singlet oxygen) O₂ ^- ), ozonide, dioxygenyl cation (O₂⁺), Dioxrane, Dioxitane or Fremy radicals are used.

Such oxidizing agents are preferably used, either by the corresponding oxidoreductases can be generated, for. B. Dioxiranes from laccases plus Carbonyls or which can chemically regenerate the mediator (e.g. Caro's acid + Benztriazole gives hydroxybenztriazole) or can directly implement this.  

The multicomponent system according to the invention comprises as a mediator (component C) preferably at least one compound which has at least one N-hydroxy, Contains oxime, N-oxi, or N-dioxi function and / or one of the following Compounds of formula I, II, III, IV or V mentioned, wherein the compounds of Formulas II, III, IV and V preferred, the compounds of formula III and IV and V particularly preferred and compounds of the formula IV and V particularly preferred are.

Hydroxylamines: (open chain or cyclic, aliphatic or aromatic, heterocyclic) of the general formula I

where in the general formula I the substituents R¹ and R², which may be the same or different, independently of one another represent one of the following groups: hydrogen, C₁-C₁₂-alkyl, carbonyl-C₁-C₅-alkyl, phenyl-, aryl-, whose C₁-C₁₂-alkyl-, carbonyl-C₁-C₆-alkyl-, phenyl-, aryl-unsubstituted or can be substituted one or more times with the radical R³ and the radical R³ can be one of the following groups: hydrogen, Halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₄-alkyl, phenyl, sulfono-, whose Esters and salts, sulfamoyl, carbamoyl, phospho-, phosphono-, phosphonooxy and their salts and esters, the amino, carbamoyl and sulfamoyl groups of the radical R³ still unsubstituted or mono- or disubstituted with hydroxy, C₁ -C₃-alkyl-, C₁-C₃-alkoxy- may be substituted
and wherein the radicals R¹ and R² together can form a group -B- and -B- represents one of the following groups: (-CHR⁴-) _n , (-CR⁴ = CH-) _m and where R⁴ is a substituent which is like R³ is defined and n represents an integer from 1 to 6 and m represents an integer from 1 to 3.

Examples Hydroxylamines

N, N-dipropylhydroxylamine
N, N-diisopropylhydroxylamine
N-hydroxyipyrrolidine
N-hydroxypiperidine
N-hydroxyhexahydroazepine
N, N-dibenzylhydroxylamine
Phenylhydroxylamine
3-hydroxylamino-3-phenylpropionic acid
2-hydroxylamino-3-phenylpropionic acid
N-sulfomethyldroxylamine

Compounds of the general formula II are:

where X stands for one of the following groups: (-N = N-), (-N = CR₁₀-) _p , (-CR₁₀ = N-) _p , (-CR₁₁ = CR₁₂-) _p

and p is 1 or 2,
where the radicals R⁹ to R¹², R¹⁵ and R¹⁶ may be the same or different and may independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkoxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino, carbamoyl and sulfamoyl groups of the radicals R⁹ to R¹², R¹⁵ and R¹⁶ may furthermore be unsubstituted or mono- or disubstituted by hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy,
and wherein the radicals R¹⁵ and R¹⁶ can form a common group -G- and -G- represents one of the following groups: (-CR⁵ = CR⁶-CR⁷ = CR⁸-) or (-CR⁸ = CR⁷-CR⁶ = CR⁵-).
The radicals R⁵ to R⁸ can be the same or different and independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-akyloxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sulfamoyl groups of the radicals R⁵ to R⁸ continue to be unsubstituted or can be substituted once or twice with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy
and wherein the C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl groups of the radicals R⁵ to R⁸ are unsubstituted or can be substituted one or more times with the radical¹⁸ and where the radical R¹⁸ can be one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, and their esters and salts
and wherein the carbamoyl, sulfamoyl, amino groups of the radical R¹⁸ can be unsubstituted or can furthermore be mono- or disubstituted with the radical¹⁹ and the radical R¹⁹ can be one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters , amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl.

Examples

1-hydroxy-1,2,3-triazole-4,5-dicarboxylic acid
1-phenyl-1H-1,2,3-triazole-3-oxide
5-chloro-1-phenyl-1H-1,2,3-triazole-3-oxide
5-methyl-1-phenyl-1H-1,2,3-triazole-3-oxide
4- (2,2-dimethylpropanoyl) -1-hydroxy-1H-1,2,3-triazole
4-hydroxy-2-phenyl-2H-1,2,3-triazole-1-oxide
2,4,5-triphenyl-2H-1,2,3-triazole-1-oxide
1-benzyl-1H-1,2,3-triazole-3-oxide
1-benzyl-4-chloro-1H-1,2,3-triazole-3-oxide
1-benzyl-4-bromo-1H-1,2,3-triazole-3-oxide
1-benzyl-4-methoxy-1H-1,2,3-triazole-3-oxide

Compounds of general structure III are:

where X stands for one of the following groups: (-N = N-), (-N = CR₁₀-) _p , (-CR₁₀ = N-) _p , (-CR₁₁ = CR₁₂-) _p

and p is 1 or 2.

The radicals R⁵ to R¹² can be the same or different and independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sulfamoyl groups of the radicals R⁵ to R¹² further unsubstituted or mono- or disubstituted with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy
and wherein the C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, aryl-C₁-C₆-alkyl groups of the radicals R⁵ to R¹² are unsubstituted or continue to be - Can be substituted several times with the radical R¹³ and the radical R¹³ can be one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆ -alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and their esters and salts
and wherein the carbamoyl, sulfamoyl, amino groups of the radical R¹³ can be unsubstituted or can furthermore be mono- or disubstituted by the radical R¹⁴ and the radical R¹⁴ can be one of the following groups: hydrogen, hydroxy, formyl, carboxy and also their groups Salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl.

Examples 1-hydroxy-benzimidazole

1-hydroxybenzimidazole-2-carboxylic acid
1-hydroxybenzimidazole
2-methyl-1-hydroxybenzimidazole
2-phenyl-1-hydroxybenzimidazole

1-hydroxyindoles

2-phenyl-1-hydroxyindole

Substances of the general formula IV are:

where X stands for one of the following groups: (-N = N-), (-N = CR¹⁰-) _m , (-CR¹⁰ = N-) _m , (-CR¹¹ = CR¹²-) _m ,

and m is 1 or 2.

The above applies to the radicals R⁵ to R⁸ and R¹⁰ to R¹².

R¹⁷ can be: hydrogen, C₁-C₁₀ alkyl, C₁-C₁₀ carbonyl, their C₁-C₁₀ alkyl and C₁-C₁₀-carbonyl unsubstituted or with a radical R¹⁸ which is defined as R³, or can be substituted several times.

Of the substances of formula IV are, in particular, derivatives of  1-hydroxybenzotriazole and the tautomeric benzotriazole-1-oxide and their esters and salts preferred (compounds of the formula V)

The radicals R⁵ to R⁸ can be identical or different and independently of one another represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sulfamoyl groups of the radicals R⁵ to R⁸ continue to be unsubstituted or can be substituted once or twice with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy
and wherein the C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl groups of the radicals R⁵ to R⁸ are unsubstituted or continue to be substituted one or more times with the radical R¹⁸ can and where the radical R¹⁸ can be one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆- alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and their esters and salts
and wherein the carbamoyl, sulfamoyl, amino groups of the radical R¹⁸ can be unsubstituted or can furthermore be mono- or disubstituted by the radical R¹⁹, and the radical R¹⁹ can be one of the following groups: hydrogen, hydroxy, formyl, carboxy and also their groups Salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl.

Examples 1H-hydroxybenzotriazoles

1-hydroxybenzotriazole
1-hydroxybenzotriazole, sodium salt
1-hydroxybenzotriazole, potassium salt
1-hydroxybenzotriazole, lithium salt
1-hydroxybenzotriazole, ammonium salt
1-hydroxybenzotriazole, calcium salt
1-hydroxybenzotriazole, magnesium salt
1-hydroxybenzotriazole-6-sulfonic acid
1-hydroxybenzotriazole-6-sulfonic acid, monosodium salt
1-hydroxybenzotriazole-6-carboxylic acid
1-hydroxybenzotriazole-6-N-phenylcarboxamide
5-ethoxy-6-nitro-1-hydroxybenzotriazole
4-ethyl-7-methyl-6-nitro-1-hydroxybenzotriazole
2,3-bis (4-ethoxyphenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
2,3-bis (2-bromo-4-methylphenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
2,3-bis (4-bromo-phenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazo-l
2,3-bis (4-carboxyphenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotri-azole
4,6-bis (trifluoromethyl) -1-hydroxybenzotriazole
5-bromo-1-hydroxybenzotriazole
6-bromo-1-hydroxybenzotriazole
4-bromo-7-methyl-1-hydroxybenzotriazole
5-bromo-7-methyl-6-nitro-1-hydroxybenzotriazole
4-bromo-6-nitro-1-hydroxybenzotriazole
6-bromo-4-nitro-1-hydroxybenzotriazole
4-chloro-1-hydroxybenzotriazole
6-chloro-5-isopropyl-1-hydroxybenzotriazole
5-chloro-6-methyl-1-hydroxybenzotriazole
6-chloro-5-methyl-1-hydroxybenzotriazole
4-chloro-7-methyl-6-nitro-1-hydroxybenzotriazole
5-chloro-1-hydroxybenzotriazole-1-hydroxybenzotriazole
6-chloro-1-hydroxybenzotriazole-1-hydroxybenzotriazole
4-chloro-5-methyl-1-hydroxybenzotriazole
5-chloro-4-methyl-1-hydroxybenzotriazole
4-chloro-6-nitro-1-hydroxybenzotriazole
6-chloro-4-nitro-1-hydroxybenzotriazole
7-chloro-1-hydroxybenzotriazole
6-diacetylamino-1-hydroxybenzotriazole
2,3-dibenzyl-4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
4,6-dibromo-1-hydroxybenzotriazole
4,6-dichloro-1-hydroxybenzotriazole
5,6-dichloro-1-hydroxybenzotriazole
4,5-dichloro-1-hydroxybenzotriazole
4,7-dichloro-1-hydroxybenzotriazole
5,7-dichloro-6-nitro-1-hydroxybenzotriazole
5,6-dimethoxy-1-hydroxybenzotriazole
2,3-di- [2] naphthyl-4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole
4,6-dinitro-1-hydroxybenzotriazole
4,6-dinitro-2,3-diphenyl-2,3-dihydro-1-hydroxybenzotriazole
4,6-dinitro-2,3-di-p-totolyl-2,3-dihydro-1-hydroxybenzotriazole
5-hydrazino-7-methyl-4-nitro-1-hydroxybenzotriazole
5,6-dimethyl-1-hydroxybenzotriazole
4-methyl-1-hydroxybenzotriazole
5-methyl-1-hydroxybenzotriazole
6-methyl-1-hydroxybenzotriazole
5- (1-methylethyl) -1-hydroxybenzotriazole
4-methyl-6-nitro-1-hydroxybenzotriazole
6-methyl-4-nitro-1-hydroxybenzotriazole
5-methoxy-1-hydroxybenzotriazole
6-methoxy-1-hydroxybenzotriazole
7-methyl-6-nitro-1-hydroxybenzotriazole
4-nitro-1-hydroxybenzotriazole
6-nitro-1-hydroxybenzotriazole
6-nitro-4-phenyl-1-hydroxybenzotriazole
5-phenylmethyl-1-hydroxybenzotriazole
4-trifluoromethyl-1-hydroxybenzotriazole
5-trifluoromethyl-1-hydroxybenzotriazole
6-trifluoromethyl-1-hydroxybenzotriazole
4,5,6,7-tetrachloro-1-hydroxybenzotriazole
4,5,6,7-tretrafluoro-1-hydroxybenzotriazole
6-tetrafluoroethyl-1-hydroxybenzotriazole
4,5,6-trichloro-1-hydroxybenzotriazole
4,6,7-trichloro-1-hydroxybenzotriazole
6-sulfamido-1-hydroxybenzotriazole
6-N, N-diethylsulfamido-1-hydroxybenzotriazole
6-N-methylsulfamido-1-hydroxybenzotriazole
6- (1H-1,2,4-triazol-1-ylmethyl) -1-hydroxybenzotriazole
6- (5,6,7,8-tetrahydroimidazo [1,5-a] pyridin-5-yl) -1-hydroxybenzotri-azole
6- (Phenyl-1H-1,2,4-triazol-1-ylmethyl) -1-hydroxybenzotriazole
6 - [(5-methyl-1H-imidazo-1-yl) phenylmethyl] -1-hydroxybenzotriazole
6 - [(4-methyl-1H-imidazo-1-yl) phenylmethyl] -1-hydroxybenzotriazole
6 - [(2-methyl-1H-imidazo-1-yl) phenylmethyl] -1-hydroxybenzotriazole
6- (1H-Imidazol-1-yl-phenylmethyl) -1-hydroxybenzotriazole
5- (1H-Imidazol-1-yl-phenylmethyl) -1-hydroxybenzotriazole
6- [1- (1H-Imidazol-1-yl) ethyl] -1-hydroxybenzotriazole monohydrochloride

3H-benzotriazole-1-oxides 3H-benzotriazole-1-oxide

6-acetyl-3H-benzotriazole-1-oxide
5-ethoxy-6-nitro-3H-benzotriazole-1-oxide
4-ethyl-7-methyl-6-nitro-3H-benzotriazole-1-oxide
6-amino-3,5-dimethyl-3H-benzotriazole-1-oxide
6-amino-3-methyl-3H-benzotriazole-1-oxide
5-bromo-3H-benzotriazole-1-oxide
6-bromo-3H-benzotriazole-1-oxide
4-bromo-7-methyl-3H-benzotriazole-1-oxide
5-bromo-4-chloro-6-nitro-4H-benzotriazole-1-oxide
4-bromo-6-nitro-3H-benzotriazole-1-oxide
6-bromo-4-nitro-3H-benzotriazole-1-oxide
5-chloro-3H-benzotriazole-1-oxide
6-chloro-3H-benzotriazole-1-oxide
4-chloro-6-nitro-3H-benzotriazole-1-oxide
4,6-dibromo-3H-benzotriaziol-1-oxide
4,6-dibromo-3-methyl-3H-benzotriazole-1-oxide
4,6-dichloro-3H-benzotriazole-1-oxide
4,7-dichloro-3H-benzotriazole-1-oxide
5,6-dichloro-3H-benzotriazole-1-oxide
4,6-dichloro-3-methyl-3H-benzotriazole-1-oxide
5,7-dichloro-6-nitro-3H-benzotriazole-1-oxide
3,6-dimethyl-6-nitro-3H-benzotriazole-1-oxide
3,5-dimethyl-6-nitro-3H-benzotriazole-1-oxide
3-methyl-3H-benzotriazole-1-oxide
5-methyl-3H-benzotriazole-1-oxide
6-methyl-3H-benzotriazole-1-oxide
6-methyl-4-nitro-3H-benzotriazole-1-oxide
7-methyl-6-nitro-3H-benzotriazole-1-oxide
5-chloro-6-nitro-3H-benzotriazole-1-oxide

2H-benzotriazole-1-oxide

2- (4-acetoxy-phenyl) -2H-benzotriazole-1-oxide
6-acetylamino-2-phenyl-2H-benzotriazole-1-oxide
2- (4-ethylphenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (3-aminophenyl) -2H-benzotriazole-1-oxide
2- (4-aminophenyl) -2H-benzotriazole-1-oxide
6-amino-2-phenyl-2H-benzotriazole-1-oxide
5-bromo-4-chloro-6-nitro-2-phenyl-2H-benzotriazole-1-oxide
2- (4-bromophenyl) -2H-benzotriazole-1-oxide
5-bromo-2-phenyl-2H-benzotriazole-1-oxide
6-bromo-2-phenyl-2H-benzotriazole-1-oxide
2- (4-bromophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (4-bromophenyl) -6-nitro-2H-benzotriazole-1-oxide
5-chloro-2- (2-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (3-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (2-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (3-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (2,4-dibromophenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (2,5-dimethylphenyl) -2H-benzotriazole-1-oxide
5-chloro-2- (4-nitrophenyl) -2H-benzotriazole-1-oxide
5-chloro-6-nitro-2-phenyl-2H-2H-benzotriazole-1-oxide
2- [4- (4-Chloro-3-nitro-phenylazo) -3-nitrophenyl] -4,6-dinitro-2H-benzotriazole-1-oxide
2- (3-chloro-4-nitro-phenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (4-chloro-3-nitrophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
4-chloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
5-chloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-chloro-4-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
2- (2-chlorophenyl) -2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -2H-benzotriazole-1-oxide
5-chloro-2-phenyl-2H-benzotriazole-1-oxide
2- [4- (4-chlorophenylazo) -3-nitrophenyl] -4,6-dinitro-2H-benzotriazole-1-oxide
2- (2-chlorophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- {4- [N ′ - (3-chlorophenyl) hydrazino] -3-nitrophenyl} 4,6-dinitro-2H-benzotriazole-1-oxide
2- {4- [N ′ - (4-chlorophenyl) hydrazino] -3-nitrophenyl} 4,6-dinitro-2H-benzotriazole-1-oxide
2- (2-chlorophenyl) -6-methyl-2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -6-methyl-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -6-methyl-2H-benzotriazole-1-oxide
2- (3-chlorophenyl) -6-nitro-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -6-nitro-2H-benzotriazole-1-oxide
2- (4-chlorophenyl) -6-picrylazo-2H-benzotriazole-1-oxide
5-chloro-2- (2,4,5-trimethylphenyl) -2H-benzotriazole-1-oxide
4,5-dibromo-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,5-dichloro-6-nitro-2-phenyl-2H-benzotriazole-1-oxide
4,5-dichloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,7-dichloro-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,7-dimethyl-6-nitro-2-phenyl-2H-benzotriazole-1-oxide
2- (2,4-dimethylphenyl) -4,6-dinitro-benzotriazole-1-oxide
2- (2,5-dimethylphenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (2,4-dimethylphenyl) -6-nitro-2H-benzotriazole-1-oxide
2- (2,5-dimethylphenyl) -6-nitro-2H-benzotriazole-1-oxide
4,6-Dinitro-2- [3-nitro-4- (N'-phenylhydrazino) phenyl -] - 2H-benzotriazole-1-oxide
4,6-Dinitro-2- [4-nitro-4- (N'-phenylhydrazino) phenyl -] - 2H-benzotriazole-1-oxide
4,6-dinitro-2-phenyl-2H-benzotriazole-1-oxide
2- (2,4-dinitrophenyl) -4,6-dinitro-2H-benzotriazole-1-oxide
2- (2,4-dinitrophenyl) -6-nitro-2H-benzotriazole-1-oxide
4,6-dinitro-2-o-tolyl-2H-benzotriazole-1-oxide
4,6-dinitro-2-p-tolyl-2H-benzotriazole-1-oxide
4,6-Dinitro-2- (2,4,5-trimethylphenyl) -2H-benzotriazole-1-oxide
2- (4-methoxyphenyl) -2H-benzotriazole-1-oxide
2- (4-methoxyphenyl) -6-methyl-2H-benzotriazole-1-oxide
5-methyl-6-nitro-2-m-tolyl-2H-benzotriazole-1-oxide
5-methyl-6-nitro-2-o-tolyl-2H-benzotriazole-1-oxide
5-methyl-6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-methyl-4-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-methyl-2-phenyl-2H-benzotriazole-1-oxide
4-methyl-2-m-tolyl-2H-benzotriazole-1-oxide
4-methyl-2-o-tolyl-2H-benzotriazole-1-oxide
4-methyl-2-p-tolyl-2H-benzotriazole-1-oxide
6-methyl-2-m-tolyl-2H-benzotriazole-1-oxide
6-methyl-2-o-tolyl-2H-benzotriazole-1-oxide
6-methyl-2-p-tolyl-2H-benzotriazole-1-oxide
2- [1] naphthyl-4-6-dinitro-2H-benzotriazole-1-oxide
2- [2] naphthyl-4-6-dinitro-2H-benzotriazole-1-oxide
2- [1] naphthyl-6-nitro-2H-benzotriazole-1-oxide
2- [2] naphthyl-6-nitro-2H-benzotriazole-1-oxide
2- (3-nitrophenyl) -2H-benzotriazole-1-oxide
6-nitro-2-phenyl-2H-benzotriazole-1-oxide
4-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-nitro-2-o-tolyl-2H-benzotriazole-1-oxide
6-nitro-2-p-tolyl-2H-benzotriazole-1-oxide
6-nitro-2- (2,4,5-trimethylphenyl) -2H-benzotriazole-1-oxide
2-phenyl-2H-benzotriazole-1-oxide
2-o-tolyl-2H-benzotriazole-1-oxide
2-p-tolyl-2H-benzotriazole-1-oxide

Also preferred are heterocycles which contain at least one N-hydroxy, oxime, N-oxy, N, N-dioxy function or a further heteroatom, such as O, S, Se, Te, such as:
Aziridines, diaziridines, pyrroles, dihydropyrroles, tetrahydropyrroles, pyrazoles, dihydropyrazoles, tetrahydropyrazoles, imidazoles, dihydroimidazoles, tetrahydroimidazoles, dihydroimidazoles, 1,2,3-triazoles, 1,2,4-triazoles, pyridoles, pyridoles, pyridine Pyrimidines, pyrazines, piperazines, 1,2,3-triazines, 1,2,4-triazines, 1,2,3-triazines, tetrazines, azepines, oxazoles, isoxazoles, thiazoles, isothiazoles, thiadiazoles, morpholines, and their benzocondensed 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, a further heteroatom such as O, S, Se, Te can contain.

[1,2,4] triazolo [4,3-a] pyridines
[1,2,4] triazolo [1,5-a] pyridines
[1,2,4] triazolo [4,3-a] quinolines
[1,2,4] triazolo [4,3-b] isoquinolines
[1,2,4] triazolo [3,4-a] isoquinolines
[1,2,4] triazolo [1,5-b] isoquinolines
[1,2,4] triazolo [5,1-a] isoquinolines
[1,2,3] triazolo [1,5-a] pyridines
[1,2,3] triazolo [4,5-b] pyridines
[1,2,3] triazolo [4,5-c] pyridines
[1,2,3] triazolo [1,5-a] quinolines
[1,2,3] triazolo [5,1-a] isoquinolines
[1,2,4] triazolo [4,3-b] pyridazines
[1,2,4] triazolo [1,5-b] pyridazines
[1,2,4] triazolo [4,5-d] pyridazines
[1,2,4] triazolo [4,3-b] cinnoline
[1,2,4] triazolo [3,4-a] phthalazines
[1,2,4] triazolo [4,3-a] pyrimidines
[1,2,4] triazolo [4,3-c] pyrimidines
[1,2,4] triazolo [1,5-a] pyrimidines
[1,2,4] triazolo [1,5-c] pyrimidines
[1,2,4] triazolo [4,3-c] quinazoline
[1,2,4] triazolo [1,5-a] quinazoline
[1,2,4] triazolo [1,5-c] quinazoline
[1,2,4] triazolo [5,1-b] quinazoline
[1,2,3] triazolo [1,5-a] pyrimidines
[1,2,3] triazolo [1,5-c] pyrimidines
[1,2,3] triazolo [4,5-d] pyrimidines
[1,2,3] triazolo [1,5-a] quinazoline
[1,2,3] triazolo [1,5-c] quinazoline
[1,2,4] triazolo [4,3-a] pyrazine
[1,2,4] triazolo [1,5-a] pyrazine
[1,2,4] triazolo [1,5-a] pyrazine
[1,2,3] triazolo [4,5-b] pyrazine
[1,2,4] triazolo [4,3-a] quinoxaline
[1,2,3] triazolo [1,5-a] quinoxaline
[1,2,4] triazolo [4,3-b] [1,2,4] triazine
[1,2,4] triazolo [3,4-c] [1,2,4] triazine
[1,2,4] triazolo [4,3-d] [1,2,4] triazine
[1,2,4] triazolo [3,4-f] [1,2,4] triazine
[1,2,4] triazolo [1,5-b] [1,2,4] triazine
[1,2,4] triazolo [5,1-c] [1,2,4] triazine
[1,2,4] triazolo [1,5-d] [1,2,4] triazine
[1,2,4] triazolo [4,3-a] [1,3,5] triazine
[1,2,4] triazolo [1,5-a] [1,3,5] triazine
Tetrazolo [1,5-a] pyridine
Tetrazolo [1,5-b] isoquinolines
Tetrazolo [1,5-a] quinoline
Tetrazolo [5,1-a] isoquinolines
Tetrazolo [1,5-b] pyridazines
Tetrazolo [1,5-b] cinnoline
Tetrazolo [5,1-a] phthalazines
Tetrazolo [1,5-a] pyrimidines
Tetrazolo [1,5-c] pyrimidines
Tetrazolo [1,5-a] quinazoline
Tetrazolo [1,5-c] quinazoline
Tetrazolo [1,5-a] pyrazine
Tetrazolo [1,5-a] quinoxaline
Tetrazolo [1,5-b] [1,2,4] triazines
Tetrazolo [5,1-c] [1,2,4] triazines
Tetrazolo [1,5-d] [1,2,4] triazines
Tetrazolo [5,1-f] [1,2,4] triazines

Other

Quinoline N-oxide
Isoquinoline N-oxide
N-hydroxy-1,2,3,4-tetrahydro-isoquinoline
β- (N-oxy-1,2,3,4-tetrahydro-isoquinolino) propionic acid
1,3-dihydroxy-2N-benzylimido-benzimidazoline

The multicomponent system (d) according to the invention comprises, for example, aliphatic ethers, aryl-substituted ones Alcohols such as B.

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-methoxybenzyl alcohol
2,5-dimethoxybenzyl alcohol
3,4-dimethoxybenzylamine
2,4-dimethoxybenzylamine hydrochloride
Veratryl alcohol
Coniferyl alcohol

Olefins (alkenes) e.g. B.

2-allylphenol
2-allyl-6-methylphenol
Allylbenzene
3,4-dimethoxypropenylbenzene
p-methoxystyrene
1-allylimidazole
1-vinylimidazole
Styrene
Stilbene
Allylphenyl ether
Benzyl cinnamate
Cinnamic acid methyl ester
2,4,6-triallyloxy-1,3,5-triazine
1,2,4-trivinylcyclohexane
4-allyl-1,2-dimethoxybenzene
4-tert-Butylbenzoic acid vinyl ester
Squalene
Benzoin allyl ether
Cyclohexene
Dihydropyran
N-benzylcinnamic acid anilide

With preference phenol ethers such. B.

2,3-dimethoxybenzyl alcohol
3,4-dimethoxybenzyl alcohol
2,4-dimethoxybenzyl alcohol
2,6-dimethoxybenzyl alcohol
Homovanillyl alcohol
4-hydroxybenzyl alcohol
4-hydroxy-3-methoxybenzyl alcohol
2-methoxybenzyl alcohol
2,5-dimethoxybenzyl alcohol
3,4-dimethoxybenzylamine
2,4-dimethoxybenzylamine hydrochloride
Veratryl alcohol
Coniferyl alcohol
Veratrol
Anisole

With preference carbonyl compounds such. B.

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-Benzylpropyl) 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
4-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

By adding the compounds of the multicomponent system mentioned under d) and e) there is a cascade reaction mediation or recycling of the actual ones Mediator connections in situ d. H. during the reaction and surprisingly leads to a significant improvement in the bleaching response.

The substances of the multi-component bleaching system listed under a), b), c), d), e) are preferably used in a ratio of 2: 0.2: 10: 0.2: 0.2: 0.2, with each component of the system can be multiplied by 2 to 10.

In addition, the bleaching system can contain phenolic compounds and / or non-phenolic compounds Contain compounds with one or more benzene cores.

In addition to the oxidizing agents mentioned above according to the invention, particular preference is given to Air, oxygen, H₂O₂, organic peroxides, sodium perborate and / or sodium percarbonate.

Oxygen can also by H₂O₂ + CATALASE or similar systems or H₂O₂ from GOD + glucose or similar systems "in situ" to be generated.

A cation-forming metal salt is also preferred Multi-component bleaching system. Fe2 +, Fe3 +, Mn2 +, Mn3 +, Mn4 +, Cu +, Cu2 +, Ti3 +, Cer4 +, Mg2 + and Al3 + be used.

Furthermore, the bleaching system can additionally contain polysaccharides and / or Contain proteins. The polysaccharides are glucans, mannans, Dextrans, levans, pectins, alginates or plant gums and / or own mushrooms or mixed cultures with yeasts polysaccharides produced. As proteins are gelatin, Albumin u. a. applicable.

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

The multi-component bleaching system according to the invention can be used in combination with known active washing Detergent additives.

The bleaching system works in a pH range of 2 to 12, preferably 4 to 10 and at temperatures between 10 ° C. and 60 ° C, preferably 20 ° to 40 ° C.  

Example 1

Influence of the laccase / mediator system on (BC2) coffee soiled Standard cotton rag.

Example: In 100 ml washing solution (in 300 ml Erlenmeyer flasks) one cloth each (5 × 5 cm) at 40 ° C for 40 min under reciprocal Shake (120 cpm) incubated.

Before starting incubation, the wash solution is a ten minute Subjected to temperature adjustment. The washing solution is made with STW (Standard Tap Water) at 14 ° dH. scheduled. As an enzyme dosage 200,000 IU Laccase from Coriolus versicolor / 100 ml, as Mediatordosage is used 200 mg hydroxybenzotriazole / 100 ml.

After pouring off the "wash liquor", use a cold, powerful water jet 3 × filled and poured.

Table 1 shows the results compared to a commercial one Liquid detergent (without bleaching system) and a full detergent (with bleach).

Example 2

Influence of the Laccase Mediator System on (BC3) tea soiled Standard wool cloth.

In 100 ml washing solution (in 300 ml Erlenmeyer flasks) one each Cloth rags (5 × 5 cm) at 40 ° C for 40 min under Reciprocate 120 rpm incubated.

Before starting incubation, the wash solution is a ten minute Subjected to temperature adjustment. The washing solution is made with STW (Standard Tap Water) at 14 ° dH. scheduled. As an enzyme dosage 200,000 IU Laccase from Coriolus versicolor / 100 ml and as Mediatordosage 200 mg hydrobenzotriazole / 100 ml added.  

After pouring off the "wash liquor", use a cold, powerful water jet 3 × filled and poured.

The results are shown in Table 2.

Example 3

A test was carried out in accordance with Example 1. As Mediator served acetoxybenzotriazole.

The result is shown in Table 3.

Table 3

Table 1

Table 2

Claims (30)

1. multi-component bleaching system consisting of oxidoreductases, oxidizing agents, mediators and mediator-reinforcing or recycling compounds for use with washing-active substances,
characterized in that

• a. optionally at least one oxidation catalyst and
• b. at least one suitable oxidizing agent and
• c. at least one mediator selects 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'-dioxi Function included and
• d. optionally at least one comediator from the group of aryl-substituted alcohols, carbonyl compounds, aliphatic ethers, phenol ethers and / or olefins (alkenes) and
• e. comprises a small amount of at least one free amine of a mediator used in each case.

2. Multi-component system according to claim 1, characterized in that in addition to these substances there are phenolic compounds and / or contains non-phenolic compounds with one or more benzene nuclei. 3. Multi-component system according to claim 1 or 2, characterized in that an oxidation catalyst is used. Preferably Class 1.1.1-1.97 oxidoreductases. 4. Multi-component system according to claim 3, characterized in that oxidoreductases which oxygen, peroxides or quinones as Use electron acceptor.   5. Multi-component system according to claim 3, characterized in that laccase (1.10.3.2.) is used as the oxidoreductase. 6. Multi-component system according to claim 1 or 2, characterized in that as NO, NOH or H-NR-OH-containing aliphatic, cycloaliphatic, heterocyclic or aromatic compounds N-hydroxy, oxime, N-oxi and N, N'-dioxi compounds, hydroxamic acid derivatives in one or Multi-component systems are used. 7. Multi-component system according to claim 6, characterized in that hydroxylamines of the general formula I are used as NO-, NOH- or H-NR-OH-containing compounds; in the general formula I the substituents R 1 and R 2, which may be the same or different, independently of one another represent one of the following groups:
Hydrogen, C₁-C₁₂-alkyl, carbonyl-C₁-C₆-alkyl, phenyl, aryl-, their C₁-C₁₂-alkyl, carbonyl-C₁-C₆-alkyl, phenyl, aryl-unsubstituted or continue to be or can be substituted several times with the radical R³ and the radical R³ can represent one of the following groups: hydrogen, halogen, hydroxy-, formyl-, carboxy- and salts and esters thereof, amino-, nitro-, C₁-C₁₂-alkyl , C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl-, phenyl-, sulfono-, their esters and salts, sulamoyl-, carbamoyl-, phospho-, phosphono-, phosphonooxy- and their salts and esters where the amino- , carbamoyl and sulfamoyl groups of the radical R³ may furthermore be unsubstituted or mono- or disubstituted by hydroxy-, C₁-C₃-alkyl-, C₁-C₃-alkoxy-substituted and the radicals R¹ and R² together form a group -B- can form and -B- represents one of the following groups: (-CHR⁴-) _n , (-CR⁴ = CH-) _m and where R⁴ is a substituent as defined as R³ un d n represents an integer from 1 to 6 and m represents an integer from 1 to 3. 8. Multi-component system according to claim 6, characterized in that substances of the general formula II are used as NO, NOH or H-NR-OH-containing compounds where X stands for one of the following groups: (-N = N-), (-N = CR₁₀-) _p , (-CR₁₀ = N-) _p , (-CR₁₁ = CR₁₂-) _p and p is 1 or 2,
where the radicals R⁹ to R¹², R¹⁵ and R¹⁶ can be the same or different and can independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sulfamoyl groups of the radicals R⁹ to R¹², R¹⁵ and R¹⁶ can furthermore be unsubstituted or mono- or disubstituted by hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy, and the radicals R¹⁵ and R¹⁶ can form a common group -G- and -G - represents one of the following groups: (-CR⁵ = CR⁶-CR⁷ = CR⁸-) or (-CR⁸ = CR⁷-CR⁶ = CR⁵-).
The radicals R⁵ to R⁸ can be identical or different and independently of one another represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C1-C6-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and where the amino, carbamoyl and sulfamoyl groups of the radicals R⁵ to R⁸ continue to be unsubstituted or can be substituted once or twice with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy
and wherein the C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl groups of the radicals R⁵ to R⁸ are unsubstituted or continue to be substituted one or more times with the radical R¹⁸ can and wherein the radical R¹⁸ can be one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆- alkyl, phenyl, aryl, and their esters and salts
and wherein the carbamoyl, sulfamoyl, amino groups of the radical R¹⁸ are unsubstituted or can furthermore be mono- or disubstituted by the radical R¹⁹
and wherein the radical R¹ darstellen can represent one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl , aryl. 9. Multi-component system according to claim 6, characterized in that compounds of the general formula III are used as NO, NOH or H-NR-OH-containing compounds; where X represents one of the following groups:
(-N = N-), (-N = CR₁₀-), (-CR₁₀ = N-) _p , (-CR₁₁ = CR₁₂-) _p and p is 1 or 2.
The radicals R⁵ to R¹² can be the same or different and independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sulfono, esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and their amino, carbamoyl and sulfamoyl groups continue to be unsubstituted or mono- or can be substituted twice with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy
and wherein the C₁-C₁₂-alkyl, C₁-C₆-alkoxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, aryl-C₁-C₆-alkyl groups of the radicals R⁵ to R¹² are unsubstituted or continue to be or can be substituted several times with the radical R¹³
and wherein the radical R¹³ can represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl , phenyl, aryl, sulfono, sulfeno, sulfino and esters
and wherein the carbamoyl, sulfamoyl, amino groups of the radical R¹³ are unsubstituted or can furthermore be mono- or disubstituted by the radical R¹⁴
and wherein the radical R¹ darstellen can represent one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl , aryl. 10. Multi-component system according to claim 6, characterized in that compounds of the general formula IV are used as NO, NOH or H-NR-OH-containing compounds, where X is one of the following groups: (-N = N-), (-N = CR¹⁰-) _p , (-CR¹⁰ = N-) _p , (-CR¹¹ = CR¹²-) _p and p is 1 or 2.
The above applies to the radicals R⁵ to R⁸ and R¹⁰ to R¹².
R¹⁷ can be: hydrogen, C₁-C₁₀-alkyl, C₁-C₁₀-carbonyl, whose C₁-C₁₀-alkyl and C₁-C₁₀-carbonyl may be unsubstituted or substituted one or more times by a radical R¹⁸ which is defined as R³ . 11. Multi-component system according to claim 6, characterized in that 1-hydroxybenzotriazole and the tautomeric benzotriazole-1-oxide, and their esters and salts according to the following formula V are used as NO, NOH or H-NR-OH-containing compounds. The radicals R⁵ to R⁸ can be identical or different and independently of one another represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C₁-C₁₂-alkyl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, sulfono esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphono, phosphonooxy and their salts and esters and wherein the amino, carbamoyl and sulfamoyl groups of the radicals R⁵ to R⁸ continue to be unsubstituted or can be substituted once or twice with hydroxy, C₁-C₃-alkyl, C₁-C₃-alkoxy and where the C₁-C₁₂-alkyl-, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl-, aryl- Groups of the radicals R⁵ to R⁸ can be unsubstituted or further substituted one or more times with the radical R¹⁸ and the radical R¹⁸ can be one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro , C₁-C₁₂-alk yl, C₁-C₆-alkyloxy, carbonyl-C₁-C₆-alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and esters and wherein the carbamoyl, sulfamoyl, amino groups of the radical R¹⁸ are unsubstituted or continue to be used once or twice the radical R¹⁹ can be substituted and the radical R¹⁹ can represent one of the following groups: hydrogen, hydroxyl, formyl, carboxy and their salts and esters, amino, nitro, C₁-C₁₂-alky, C₁-C₆-alkyloxy, carbonyl-C₁ -C₆ alkyl, phenyl, aryl. 12. Multi-component system according to claim 6, characterized in that as NO, NOH or H-NR-OH-containing compounds those of azoles are used. 13. Multi-component system according to claim 6, characterized in that as NO-, NOH- or H-NR-OH-containing compounds those of condensed heterocycles which contain a triazolo or tetrazolo unit, such as. B. [1,2,4] Triazolo [4,3-a] pyridines
[1,2,4] triazolo [1,5-a] pyridines
[1,2,4] triazolo [4,3-a] quinolines
[1,2,4] triazolo [4,3-b] isoquinolines
[1,2,4] triazolo [3,4-a] isoquinolines
[1,2,4] triazolo [1,5-b] isoquinolines
[1,2,4] triazolo [5,1-a] isoquinolines
[1,2,3] triazolo [1,5-a] pyridines
[1,2,3] triazolo [4,5-b] pyridines
[1,2,3] triazolo [4,5-c] pyridines
[1,2,3] triazolo [1,5-a] quinolines
[1,2,3] triazolo [5,1-a] isoquinolines
[1,2,4] triazolo [4,3-b] pyridazines
[1,2,4] triazolo [1,5-b] pyridazines
[1,2,4] triazolo [4,5-d] pyridazines
[1,2,4] triazolo [4,3-b] cinnoline
[1,2,4] triazolo [3,4-a] phthalazines
[1,2,4] triazolo [4,3-a] pyrimidines
[1,2,4] triazolo [4,3-c] pyrimidines
[1,2,4] triazolo [1,5-a] pyrimidines
[1,2,4] triazolo [1,5-c] pyrimidines
[1,2,4] triazolo [4,3-c] quinazoline
[1,2,4] triazolo [1,5-a] quinazoline
[1,2,4] triazolo [1,5-c] quinazoline
[1,2,4] triazolo [5,1-b] quinazoline
[1,2,3] triazolo [1,5-a] pyrimidines
[1,2,3] triazolo [1,5-c] pyrimidines
[1,2,3] triazolo [4,5-d] pyrimidines
[1,2,3] triazolo [1,5-a] quinazoline
[1,2,3] triazolo [1,5-c] quinazoline
[1,2,4] triazolo [4,3-a] pyrazine
[1,2,4] triazolo [1,5-a] pyrazine
[1,2,4] triazolo [1,5-a] pyrazine
[1,2,3] triazolo [4,5-b] pyrazine
[1,2,4] triazolo [4,3-a] quinoxaline
[1,2,3] triazolo [1,5-a] quinoxaline
[1,2,4] triazolo [4,3-b] [1,2,4] triazine
[1,2,4] triazolo [3,4-c] [1,2,4] triazine
[1,2,4] triazolo [4,3-d] [1,2,4] triazine
[1,2,4] triazolo [3,4-f] [1,2,4] triazine
[1,2,4] triazolo [1,5-b] [1,2,4] triazine
[1,2,4] triazolo [5,1-c] [1,2,4] triazine
[1,2,4] triazolo [1,5-d] [1,2,4] triazine
[1,2,4] triazolo [4,3-a] [1,3,5] triazine
[1,2,4] triazolo [1,5-a] [1,3,5] triazine
Tetrazolo [1,5-a] pyridine
Tetrazolo [1,5-b] isoquinolines
Tetrazolo [1,5-a] quinoline
Tetrazolo [5,1-a] isoquinolines
Tetrazolo [1,5-b] pyridazines
Tetrazolo [1,5-b] cinnoline
Tetrazolo [5,1-a] phthalazines
Tetrazolo [1,5-a] pyrimidines
Tetrazolo [1,5-c] pyrimidines
Tetrazolo [1,5-a] quinazoline
Tetrazolo [1,5-c] quinazoline
Tetrazolo [1,5-a] pyrazine
Tetrazolo [1,5-a] quinoxaline
Tetrazolo [1,5-b] [1,2,4] triazines
Tetrazolo [5,1-c] [1,2,4] triazines
Tetrazolo [1,5-d] [1,2,4] triazines
Tetrazolo [5,1-f] [1,2,4] triazines 14. Multi-component system according to claim 1 or 2, characterized in that as an oxidizing agent such. B. air, oxygen, ozone, H₂O₂, organic peroxides, peracids such as peracetic acid, performic acid, Persulfuric acid, persitric acid, metachlorperoxibenzoic acid, perchloric acid, Perchlorates, peracetates, persulfates, peroxides, oxygen species and radicals such as OH, OOH singlet oxygen, ozone, superoxide (O₂), ozonide, dioxygenyl cation (O₂⁺), Dioxirane, Dioxitane, Fremy radical can be used. 15. Multi-component system according to claim 1 or 2, characterized in that compounds of component d) are aliphatic ethers, aryl-substituted alcohols, for. B. 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-methoxybenzyl alcohol
2,5-dimethoxybenzyl alcohol
3,4-dimethoxybenzylamine
2,4-dimethoxybenzylamine hydrochloride
Veratryl alcohol
Coniferyl alcohol
are. 16. Multi-component system according to claim 1 or 2, characterized in that compounds of component d) olifins (alkenes) z. B. 2-Allylphenol
2-allyl-6-methylphenol
Allylbenzene
3,4-dimethoxypropenylbenzene
p-methoxystyrene
1-allylimidazole
1-vinylimidazole
Styrene
Stilbene
Allylphenyl ether
Benzyl cinnamate
Cinnamic acid methyl ester
2,4,6-triallyloxy-1,3,5-triazine
1,2,4-trivinylcyclohexane
4-allyl-1,2-dimethoxybenzene
4-tert-Butylbenzoic acid vinyl ester
Squalene
Benzoin allyl ether
Cyclohexene
Dihydropyran
N-benzylcinnamic acid anilides. 17. Multi-component system according to claim 1 or 2, characterized in that compounds of component d) phenol ether z. B. 2,3-Dimethoxybenzyl alcohol
3,4-dimethoxybenzyl alcohol
2,4-dimethoxybenzyl alcohol
2,6-dimethoxybenzyl alcohol
Homovanillyl alcohol
4-hydroxybenzyl alcohol
4-hydroxy-3-methoxybenzyl alcohol
2-methoxybenzyl alcohol
2,5-dimethoxybenzyl alcohol
3,4-dimethoxybenzylamine
2,4-dimethoxybenzylamine hydrochloride
Veratryl alcohol
Coniferyl alcohol
Veratrol
Are anisole. 18. Multi-component system according to claim 1 or 2, characterized in that compounds of component d) carbonyl compounds z. B. 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-Benzylpropyl) 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
4-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
Are vanillic acid. 19. Multi-component bleaching system according to claim 1 or 2, characterized in that as component e) as a free amine in the case of in situ Generation or reaction mediation in cascade form with hydroxybenztriazole, benzotriazole is used. 20. Multi-component system according to claim 1 and 2, characterized in that the oxidoreductases of white rot fungi, other fungi, Bacteria, animals or plants are derived from natural or natural enzymes genetically modified organisms.   21. Multi-component bleaching system according to claim 1 and 2, characterized in that the catalysts are modified enzymes, enzyme components, prosthetic groups or mimic substances such as heme groups or heme groups containing Connections are. 22. Multi-component bleaching system according to claim 14, characterized in that O₂ by H₂O₂ + catalase or other systems or H₂O₂ GOD + glucose or other systems is generated in situ. 23. Multi-component bleaching system according to claim 1 to 22, characterized in that it contains cation-forming metal salts. 24. Multi-component bleaching system according to claim 23, characterized in that the cations Fe2 +, Fe3 +, Mn2 +, Mn3 +, Mn4 +, Cu +, Cu2 +, Ti3 +, Cer4 +, Mg2 + and Al3 + are. 25. Multi-component bleaching system according to claim 1 and 24, characterized in that it additionally contains polysaccharides and / or proteins. 26. Multi-component bleaching system according to claim 25, characterized in that the polysaccharides glucans, mannans, dextrans, levans, pectins, Alginates or plant gums and / or own mushrooms or mixed cultures Yeast produced polysaccharides or the proteins gelantine, albumin and the like. a. are. 27. Multi-component bleaching system according to claims 1-26, characterized in that it contains simple sugar, oligomer sugar, amino acids, Contains polyethylene glycols, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes. 28. Use of the multi-component bleaching system according to one of claims 1-27, characterized as an additive to wash formulations with known active wash Substances or detergent additives. 29. Multi-component bleaching system according to claim 28, characterized in that the pH range is between 2 and 12, preferably between 4 and 10 lies.   30. Multi-component bleaching system according to claim 29, characterized in that the temperature is between 10 ° C and 60 ° C, preferably between 20 ° C-40 ° C lies.