SK104096A3 - Multicomponent system for modifying, decomposing or bleaching lignin, lignin-containing materials or similar substances and method of using this system - Google Patents

Abstract

System for transforming, degrading or bleaching lignin, lignin-contg. materials or similar materials, comprises a poly-component system comprising: (a) opt. ≥ 1 oxidation catalyst; (b) ≥ 1 oxidising agent; (c) ≥ 1 mediator selected from hydroxylamines, hydroxylamine derivs., hydroxamic acids, hydroxamic acid derivs. and aliphatic, cycloaliphatic, heterocyclic and aromatic cpds. which contain ≥ 1 N-hydroxy, oxime, N-oxy or N,N-dioxy function; (d) opt. ≥ 1 co-mediator selected from aryl-substd. alcohols, carbonyl cpds., aliphatic ethers, phenol ethers and alkenes; and (e) a small amt. of a free amine of one of the mediators used.

Description

MULTI-COMPONENT SYSTEM FOR CHANGING, RELEASING OR BLACING LIGHINES, LIGHINS CONTAINING MATERIALS OR SIMILAR SUBSTANCES AND METHODS OF USING THEM

Technical field

The present invention relates to a multi-component system for altering, degrading or bleaching lignin, lignin-containing materials or the like and a method for its use.

BACKGROUND OF THE INVENTION

The methods used to make pulp to date are the sulphate process and the sulphite process. In both of these processes, the pulp is produced at boiling and pressure. The sulfate process works by adding sodium hydroxide and sodium sulfide, while the sulfite process uses calcium bisulfite and sulfur dioxide.

All methods aim to remove lignin from the plant material used, i.e., wood or annual plants.

Lignin, which forms a major component of plant material (stems and strains) with cellulose and hemicelluloses, must be removed, otherwise it is not possible to produce non-yellowing and mechanically highly loaded papers.

Wood-based production methods work with wood (wood chips) or refiner (TMP), the wood being defibrilized by grinding after appropriate pre-treatment (chemically, thermally or chemically-thermally).

These wood raw materials still have a large proportion of lignin. They are used, inter alia, for the production of newspapers, illustrated magazines and the like.

In recent years, the possibility of using enzymes to degrade lignin has been discovered. The mechanism of action of such lignolytic systems was elucidated only a few years ago, when sufficient amounts of enzyme were found to be sufficient in the white rot fungus Phanerochaete chrysosporium using suitable culture conditions and inducer additives. Hitherto unknown lignin peroxidases and manganese peroxidases have been discovered. Since Phanerochaete chrysosporium is very effective in lignin degradation, it has been attempted to isolate its enzymes and to use these enzymes in purified form for lignin degradation. However, this failed because these enzymes have been shown to lead primarily to repolymerization of the lignin and not to its degradation.

This also applies similarly to other lignolytic enzyme preparations, such as laccases, which degrade lignin by means of oxygen instead of hydrogen peroxide. It could be found that in all cases similar processes occur. In fact, radicals are formed which, in turn, react with each other and thus lead to polymerization.

Thus, only methods that work with in-vivo systems (fungal systems) are now available. The main focus of optimization attempts is biopulping and biobleaching.

Biopulping refers to the processing of wood chips using live mushroom systems.

There are two types of application forms:

1. Pretreatment of wood chips prior to refining or milling to save energy in the production of wood chips (for example, TMP or wood pulp).

Another advantage is the mostly occurring improvement of the mechanical properties of the substance, the disadvantage is the poorer final whiteness.

2. Pretreatment of wood chips (Softwood / Hardwood) prior to pulp cooking (kraft process, sulfite process).

The aim here is to reduce the amount of cooking chemicals, improve cooking capacity and extended cooking.

An advantage here is also the achievement of improved kappa. - reduction after cooking compared to cooking without this treatment.

The disadvantage of this method is the clearly long processing times (several weeks) and, above all, the impossibility of eliminating the risk of contamination during processing, if the uneconomical sterilization of wood chips should be avoided.

The biobleaching procedure works equally with in - vivo systems. The boiled pulp (Softwood / Hardwood) is inoculated with a sponge prior to bleaching and processed for days to weeks. Only after this long processing time will there be a significant reduction in capacity and whiteness, which makes the process uneconomical to implement in current bleaching sequences.

Another application, mostly performed with immobilized mushroom systems, is the treatment of wastewater from pulp processing plants, in particular bleaching wastewater, to discolour them and reduce AOX (reduction of chlorinated compounds in wastewater causing a chlorine or chlorine dioxide bleaching stage).

In addition, the use of hemicelluloses, including but not limited to, xylanases and mannanases, is known as bleichbooster.

These enzymes are intended mainly to act on the residual lignin after the brewing process, partially overlapping the reprecipitated xylan and by degrading it to increase the lignin accessibility for the bleaching chemicals used in the following bleaching sequences (especially chlorine dioxide). The savings of bleaching chemicals in the laboratory have been confirmed to a greater extent only conditionally, so that this type of enzyme can only be used as a bleaching additive.

Another recently investigated possible use of lignolytic enzymes or fungi has been apparent in the liquefaction of coal. Preliminary tests show the principal possibility of attacking and liquefying lignite and hard coal by in - vivo treatment with, for example, white rot fungi such as Phanerochaete chrysosporium (incubation period of several weeks) (Bioengineering 4.92, 8 µg.).

A possible hard coal structure exhibits a three-dimensional lattice of polycyclic, aromatic ring systems with some similarity to lignin structures.

Chelated substances (siderophores such as ammonium oxalate) and biotensides are believed to be cofactors in addition to lignolytic enzymes.

PCT / EP87 / 00635 discloses a system for removing lignin from lignin cellulosic material whilst bleaching using lignolytic enzymes from white rot fungi with the addition of reducing and oxidizing agents and phenolic compounds as mediators.

In DE 40 08 893 C2, in addition to the redox system, so-called " mimic substances that stimulate the active center (prosthetic group) of lignolytic enzymes. Thus, a significant improvement in performance can be achieved.

PCT / EP92 / 01086 discloses, as an additional improvement, the use of a redox cascade with the aid of phenolic or non-phenolic aromas tuned to the oxidation potential.

In all three processes, the limitation for mass production is the possibility of using only at low material densities (up to a maximum of 4%) and in the procedures of the latter two applications there is a risk of leaching metals using chelate compounds. decomposition of peroxides.

WO 94/12619, WO 94/12620 and WP 94/12621 disclose methods in which peroxidase activity is promoted by so-called " Enhancer - Substance.

Enhancer substances are characterized in WO 94/12619 based on their half-life.

According to WO 94/12620, Enhancer substances are characterized by the formula A = N - N = B, wherein A and B are correspondingly defined cyclic residues.

According to WO 94/12621, the Enhancer substances are organic chemicals that contain at least two aromatic rings, at least one of which is substituted by defined defined residues.

All three applications relate to dye transfer inhibition and the use of the corresponding Enhancer substances together with peroxidases as detergent additives or detergent compositions in the detergent field. Although applicability for lignin processing is contemplated in the specification, the actual experiments with the substances specifically mentioned in these applications show that they do not show any effect as mediators for enhancing the whitening effect of peroxidases in the treatment of lignin-containing materials.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a system for altering, degrading or bleaching lignin, lignin-containing materials or the like more efficiently than known systems.

The above task has been solved using a multi-component system that includes:

(a) optionally at least one oxidation catalyst,

b) at least one suitable oxidizing agent,

c) at least one mediator selected from the group consisting of hydroxylamines, hydroxylamine derivatives, hydroxamic acid, hydroxamic acid derivatives or aliphatic, cycloaliphatic, heterocyclic and aromatic compounds containing at least one N-hydroxyl, oxime, N-oxy- or Ν, Ν '; -dioxa-function,

d) optionally at least one comediator selected from the group consisting of aryl-substituted alcohols, carbonyl compounds, aliphatic ethers, phenol ethers and / or olefins (alkenes); and

e) a small amount of at least one free amine corresponding to the mediator used.

Preferably, the multi-component system of the present invention comprises at least one oxidation catalyst.

Preferably, the multi-component system of the present invention comprises at least one comediator.

Enzymes are preferably used as oxidation catalysts in the multi-component system of the present invention. For the purposes of the present invention, the term enzyme also includes enzymatically active proteins or peptides or prosthetic enzyme groups.

Class 1.1.1 oxidoreductases can be used as enzymes in the multi-component system of the present invention. 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, p. 24,154).

Preferably, enzymes from the following classifications are used:

Enzymes of Class 1.1, which include all dehydrogenases which act on primary alcohols, secondary alcohols and semiacetals and which have NAD ⁺ or NADP ⁺ (subclass 1.1.1), cytochromes (1.1.2), oxygen (O2) (113) as acceptors ), disulfides (1.1.4), quinones (1.1.5) or other acceptors (1.1.99).

Of this class, class 1.1.5 enzymes with quinones as acceptors and class 1.1.3 enzymes are particularly preferred. with oxygen as acceptor.

Cellobiose: quinone-1-oxidoreductase (1.1.5.1) is particularly preferred in this group.

Further preferred are class 1.2 enzymes. This class of enzymes (1.1.5.1) includes those which oxidize aldehydes to the corresponding acids or oxo groups.

The acceptors may be NAD ⁺ , NADP ⁺ (1.2.1), cytochromes (1.2.2), oxygen (1.2.3), sulphides (1.2.4), iron - sulfur proteins (1.2.5) or other acceptors (1.2. 99).

Particularly preferred are the enzymes of group (1.2.3) with oxygen as acceptor.

Further preferred are class 1.3 enzymes.

Enzymes that act on the CH-CH-groups of the donor are included in this group.

Corresponding acceptors are NAD ⁺ , NADP ⁺ (1.3.1), cytochromes (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 particularly preferred here are enzymes of class (1.3.3) with oxygen as acceptor and class (1.3.5) with quinones and the like of acceptors.

Further preferred are enzymes of class 1.4 which act on the CH-NH2- groups of the donor.

Corresponding acceptors are NAD ⁺ , NADP ⁺ (1.4.1), cytochromes (1.4.2), oxygen (1.4.3), disulfides (1.4.4), iron - sulfur proteins (1.4.7) or other acceptors (1.4. 99).

Also particularly preferred herein are enzymes of class 1.4.3 with oxygen as acceptor.

Also preferred are enzymes of class 1.5 which act on the CH-NH- groups of the donor.

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).

Also particularly preferred are enzymes of class 1.5.3 with oxygen as acceptor and classes

1.5.5 with quinones as acceptors.

Also preferred are enzymes of class 1.6 which act on NADH or NADPH.

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

Particularly preferred are enzymes of class 1.6.5 with quinones as acceptors.

Also preferred are enzymes of class 1.7 which act as donors on other NO2 compounds.

Corresponding acceptors are cytochromes (1.7.2), oxygen (O2) (1.7.3), ferrous sulfur proteins (1.7.7) or other acceptors (1.7.99).

Particularly preferred are enzymes of class 1.7.3 with oxygen as acceptor.

Also preferred are enzymes of class 1.8 which act as a donor to the sulfur moieties.

The corresponding acceptors are NAD ⁺ , NADP ⁺ (1.8.1), cytochromes (1.8.2), oxygen (O2) (1.8.3), disulfides (1.8.4), quinones (1.8.5), iron-sulfur proteins (1.8). 1.8.7) or other acceptors (1.8.99).

Enzymes of class 1.8.3 with oxygen as acceptor and class 1.8.5 with quinones as acceptor are particularly preferred.

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

Particularly preferred herein is group 1.9.3 with oxygen (O2) as acceptor with (cytochrome oxidase).

Further preferred are enzymes of class 1.12 which act as a donor to hydrogen.

Acceptors here are NAD ⁺ and NADP ⁺ (1.12.1) or other compounds (1.12.99).

Further preferred are enzymes of classes 1.13 and 1.14 (oxigenases).

Also preferred are enzymes of class 1.15 which act on superoxide radicals as acceptors.

Superoxide dismutase (1.15.1.1) is particularly preferred.

Further preferred are enzymes of class 1.16.

!

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

Particularly preferred are enzymes of class 1.16.3.1 (feroxidase, e.g., ceruloplasmin).

Further preferred enzymes are those belonging to class 1.17 (treatment of CH2 groups that are oxidized to -CHOH-), 1.18 (treatment of reduced feredoxin as a donor), 1.19 (treatment of reduced flavodoxin as a donor) and 1.97 (other oxidoreductases ).

Also particularly preferred are the enzymes of group 1.11 which act on the peroxide as an acceptor. This single subclass (1.11.1) contains peroxidases.

Particularly preferred are cytochrome C peroxidases (1.11.1.5), catalase (1.11.1.6), peroxidase ((1.11.1.6), iodide peroxidase (1.11.1.8), glutathione peroxidase (1.11.1.9), chloride peroxidase (1.11.1.10), L-ascorbate peroxidase (1.11.1.11), phospholipid hydroperoxide - glutathione peroxidase (1.11.1.12), manganese peroxidase (1.11.1.13) and diarylpropane peroxidase (ligninase, lignin - peroxidase) ( 1.11.1.14).

Enzymes of class 1.10 which act on biphenols and related compounds are particularly preferred. They catalyze the oxidation of biphenols and ascorbates. NAD ⁺ , NADP ⁺ (1.10.1), cytochromes (1.10.2), oxygen (1.10.3), or others (1.10.99) work as acceptors.

Of the above, enzymes of class 1.10.3 are again particularly preferred. with oxygen (O2) as the acceptor.

Among the enzymes of this class, the enzymes catechol oxidase (tyrosinase) (1.10.3.1), L-ascorbate oxidase (1.10.3.3), o-aminophenol oxidase (1.10.3.4) and laccase (benzenediol: oxygen oxidoreductase (1.10) are preferred. 3.2.2), with lasease (benzenediol: oxygen oxidoreductase) being particularly preferred (1.10.3.2).

These enzymes are commercially available or can be obtained by standard methods. Suitable organisms for the production of enzymes are, for example, plants, animal cells, bacteria and fungi. In principle, organisms both naturally occurring and genetically engineered can be modified by enzyme producers. Parts of unicellular or multicellular organisms, especially cell cultures, are also possible as enzyme producers.

For example, white rot fungi such as Pleurotus, Phlebia and Trametes are used for the production of particularly preferred enzymes, such as those of class 1.11.1, in particular 1.10.3, and especially for the production of laccases.

The multi-component system of the present invention comprises at least one oxidizing agent. As oxidizing agents, for example, air, oxygen, ozone, hydrogen peroxide, organic peroxides, peracids such as peracetic acid, peroxyacetic acid, persulphuric acid, perdusic acid, metachloroperoxybenzoic acid and perchloric acid, perborates, peracetates, persulphates, peroxides or oxygenates can be used. species and their radicals, such as OH, OOH, Singulett oxygen, superoxide (O2 '), ozonide, dioxygenyl cation (O2 ⁺ ), dioxiran, dioxethane or Fremy radical.

Preference is given to using oxidizing agents which can either be generated by corresponding oxidoreductases, for example dioxanes from laccases plus carbonyl, or which can chemically regenerate the mediator (for example, Carosch acid + benztriazole provides hydroxybenztriazole), or can be reacted directly.

The multi-component system of the present invention includes as a mediator (component (c)) preferably at least one compound which comprises at least one N-hydroxyl, oxime, N-oxy- or N-dioxy function and / or one of the following compounds of formulas I, II, III , IV or V, with compounds of formulas II, III, IV and V being preferred, compounds of formulas III, IV and V being particularly preferred and compounds of formulas IV and V being particularly preferred.

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

R ¹ - N - R ² (I)

OH where

R 1 and R 4 may be the same or different and are each independently hydrogen, C 1 -C 12 alkyl, C 1 -C 6 carbonylalkyl, phenyl or aryl, or substituted one or more times with the radical R®, whereby

R @ 5 represents a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, and salts and esters thereof, amino, nitro, C1-C12-alkyl, C1-C6-alkoxy, C1-C6-carbonylalkyl alkyl, phenyl, sulfone, and esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphone, phosphonooxy, and salts and esters thereof, wherein the amino, carbamoyl, and sulfamoyl groups of R @ 8 may be further unsubstituted or once or double substituted by hydroxy, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms, or

R 1 and R ² may together form -B-, wherein

B is (-CHR ⁴ -) n or (-CR ⁴ = CH-) m, m

R ⁴ has the meanings given for R ®, n represents an integer from 1 to 6 and m represents an integer from 1 to 3.

Examples:

Hydroxyl

N, N-dipropylhydroxylamín

N, N-diizopropylhydroxylamín

N-hydroxy

N-hydroxy

N-hydroxyhexahydroazepín

Ν, Ν-dibenzylhydroxylamine phenylhydroxylamine 3-hydroxylamino-3-phenylpropionic acid 2-hydroxylamino-3-phenylpropionic acid N-sulfomethylhydroxylamine.

The compounds of formula II are

1I

R ⁹

II

X is (-N = N-), (-N = CR ¹⁰ -) p, (-CR ¹⁰ = N-) p, (-CR ¹¹ = CR ¹² -) _p

Γ o · 0 ' | | -N = N - or - N = N - 4 * *

where p is 1 or 2 and

R ⁹ to R ¹² , R ¹⁵ and R ¹⁶ are the same or different and independently of one another are hydrogen, halogen, hydroxy, formyl, carboxy, as well as salts and esters thereof, amino, nitro, alkyl of 1 to 12 C 1 -C 6 alkoxy, C 1 -C 6 carbonylalkyl, phenyl, sulfone and esters and salts thereof, suifamoyl, carbamoyl, phosphono, phosphone, phosphonooxy and their salts and esters, wherein the amino, carbamoyl and sulfamoyl radicals R to R 12 R 15 _and R 16 may further be unsubstituted or mono- or disubstituted by hydroxy, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms, or R 15 ₃ R 16 may together to form a group -G-, where G represents a group (-CR ⁵ = CR ⁶ -CR ⁷ = CR ⁸ -) or (-CR ⁸ = CR ⁷ -CR ⁸ = CR ⁵ -), where

R ⁸ to R ⁸ may be the same or different and are independently hydrogen, halogen, hydroxy, formyl, carboxy, as well as salts and esters thereof, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy of C 1 -C 6 carbonylalkyl, C 1 -C 6 alkyl, phenyl, sulfone and its esters and salts, sulfamoyl, carbamoyl, phosphono, phosphone, phosphonooxy and salts and esters thereof, wherein the amino, carbamoyl and the sulfamoyl group of the radicals R ⁵ to R ⁸ may further be unsubstituted or mono- or di-substituted by hydroxy, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms, and wherein the alkyl group of 1 to 12 carbon atoms, alkoxy of 1 C 1 -C 6 -carbonylalkyl like the atoms in the alkyl, phenyl and aryl radicals R ⁸ to R ⁸ may be unsubstituted or furthermore mono- or polysubstituted by radicals R ^8, wherein R 18 represents hydrogen, halogen, hydroxy, formyl, carboxyl, and its salts and esters, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, carbonylalkyl of 1 to 6 carbon atoms in alkyl, phenyl, aryl and their salts and esters, wherein the amino, carbamoyl the radical and the sulfamoyl group of the radical may be unsubstituted or substituted once or twice by the radical r19, where r19 represents a hydrogen atom, a hydroxyl group, a formyl group, a carboxy group and salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, alkoxy groups C 1 -C 6 -carbonyl, C 1 -C 6 -carbonylalkyl C 6 -C 6 alkyl, phenyl and aryl.

Examples:

1-hydroxy-1,2,3-triazole-4,5-dicarboxylic acid

1-phenyl-1 H -1,2,3-triazol-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-triazol-l-oxide

-benzyl-1H-1,2,3-triazole-3-oxide

-benzyl-4-chloro-1H-1H-triazole-S-oxide

1-Benzyl-4-bromo-1H-1,2,3-triazole-3-oxide

1-benzyl-4-methoxy-1 H -1,2,3-triazol-3-oxide.

Compounds of formula III are:

III

X is a group (N = N-), (-N = CR ¹ 0-) P, (-crl = N-) p, (-CR ¹¹ = CR ¹² -) p

Ο- ι —N = N - or 0 ' I - NzzN - IN

where p is 1 or 2 and

R 5 to R 12 are the same or different and independently of one another are hydrogen, halogen, hydroxy, formyl, carboxy, as well as salts and esters thereof, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 C 1 -C 6 carbonylalkyl, phenyl, aryl, sulfono and esters and salts thereof, sulfamoyl, carbamoyl, phosphono, phosphono, phosphonooxy and salts and esters thereof, wherein the amino, carbamoyl and the sulfamoyl group of the radicals R @ 1 to R @ 12 may further be unsubstituted or mono- or double-substituted by hydroxy, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms, and wherein alkyl of 1 to 12 carbon atoms, alkoxy of 1 C 1 -C 6 -carbonylalkyl; the carbon atom, the phenyl group, the aryl group and the arylalkyl group having 1 to 6 carbon atoms in the alkyl radicals R ^{@ 8} to R ^@ 12 may be unsubstituted or further substituted one or more times with R @ ¹⁸ , R @ 13 being hydrogen, halogen, hydroxy, a formyl group, a carboxy group, and salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 carbonylalkyl, phenyl, aryl, sulfone, sulfo and sulfino and esters and salts thereof, wherein the amino, carbamoyl and sulfamoyl groups of the radical R 13 may be unsubstituted or further substituted once or twice with the radical R ¹⁴ , wherein:

R ¹⁴ represents a hydrogen atom, a hydroxy group, a formyl group, a carboxy group, and salts and esters thereof, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, carbonylalkyl of 1 to 6 carbon atoms in alkyl, phenyl, and aryl.

Examples:

1-hydroxybenzimidazole-2-carboxylic acid hydroxybenzimidazoles

-hydroxybenzimidazol

2-methyl-1-hydroxybenzimidazole

2-phenyl-1-hydroxybenzimidazole

1-hydroxyindoles

2-phenyl-1-hydroxyindole.

Compounds of formula IV are:

iy taking

X is (-N = N-), (-N = CR ¹⁰ -) m, (-CR ¹⁰ = N-) m, (-CR ¹ - = CR ¹² ) _m ,

about- 0 ' | -N = N - * or I +

where m is 1 or 2 and

R ⁵ -R ⁶ and R ¹⁰ -R 6 are as defined above and

R 17 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkylcarbonyl group having 1 to 10 carbon atoms, the alkyl and alkylcarbonyl group being unsubstituted or substituted one or more times with R ¹⁶ , where R ¹⁸ has the meanings given for R ⁶ .

Of the compounds of formula IV, 1-hydroxybenzotriazole derivatives and tautomeric benzotriazole-1-oxide as well as their esters and salts (compounds of formula V) are particularly preferred.

wherein r5 to r8 may be the same or different and are independently hydrogen, halogen, hydroxy, formyl, carboxy, as well as salts and esters thereof, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy with C 1 -C 6 carbonylalkyl, C 1 -C 6 alkyl, phenyl, sulfone and its esters and salts, sulfamoyl, carbamoyl, phosphono, phosphone, phosphonooxy and salts and esters thereof, wherein the amino, carbamoyl and the sulfamoyl group R @ 8 to R @ 6 may further be unsubstituted or mono- or di-substituted by hydroxy, C1 -C3 alkyl or C1 -C3 alkoxy, and wherein the C1 -C12 alkyl group is C1 -C3 alkyl. 1 to 6 carbon atoms, carbonylalkyl having 1 to 6 carbon atoms the alkyl radicals, the phenyl group and the aryl group of the radicals r5 to R1 may be unsubstituted or further substituted one or more times with the radical R1, wherein _R18 represents a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group and salts thereof; esters, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, carbonylalkyl of 1 to 6 carbon atoms in alkyl, phenyl, aryl, sulfone, sulfo and sulfino and their salts and esters wherein the amino, carbamoyl and sulfamoyl groups of the radical r18 may be unsubstituted or further substituted once or twice with the radical R @ 1, wherein r19 represents a hydrogen atom, a hydroxy group, a formyl group, a carboxy group and salts and esters thereof; C1 -C12 alkoxy; C 1 -C 6 -carbonyl, C 1 -C 6 -carbonylalkyl, phenyl and aryl.

Examples:

H-hydroxybenzotriazoles 1 H-hydroxybenzotriazole 1 H-hydroxybenzotriazole, sodium salt 1 H-hydroxybenzotriazole, potassium salt 1 H-hydroxybenzotriazole, lithium salt 1 H-hydroxybenzotriazole, ammonium salt 1 H-hydroxybenzotriazole, calcium salt 1 H-hydroxybenzotriazole, calcium salt 1 H-hydroxybenzotriazole 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- (2-bromo-phenyl) -4,6-dinitro-2,3-dihydro-1-hydroxybenzotriazole

2,3-bis- (4-carboxy-phenyl) -4,6-indino-2,3-dihydro-1-hydroxybenzotriazole

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

5-chloro-1-hydroxybenzotriazole

6-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

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 _l 3-diphenyl-2,3-dihydro-1-hydroxybenzotriazole

4,6-di-itro-2,3-di-p-tolyl-2,3-dihydro-1-hydroxy-benzotriazole

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-yl-roxybenzotriazole

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-Tetrafluoro-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-diethyl-sulfamido-1-hydroxybenzotriazole

6-N-methylsulfamide-1-hydroxybenzotriazole

6- (1H-1,2,3-triazol-1-ylmethyl) -1-hydroxybenzotriazole

6- (5,6,7,8-tetrahydroimidazo- [1,5-a] pyridin-5-yl) -1-hydroxybenzotriazole

6- (phenyl-1H-1,2,3-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

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-3H-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-benzotriazole-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-ethyl-phenyl) -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-dimethyl-phenyl) -2H-benzotriazole-1-oxide

5-chloro-2- (4-nitrophenyl) -2H-benzotriazole-1-oxide

5-chloro-6-nitro-2-phenyl-2H-benzotriazole-1-oxide

2- [4- (4-chloro-3-nitro-phenylazo) -3-nitrophenyl] -4,6-dinitro-2H-benzotriazole-1-oxide

2- (4-chloro-4-nitrophenyl) -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-chloro-phenyl) -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-nitro-phenyl] -2H-benzotriazole

1-oxide

2- [4- [N '- (4-chlorophenyl) hydrazino] -3-nitro-phenyl] -2H-benzotriazole

1-oxide

2- (2-chloro-phenyl) -6-methyl-2H-benzotriazole-1-oxide

2- (3-chloro-phenyl) -6-methyl-2H-benzotriazole-1-oxide

2- (4-chloro-phenyl) -6-methyl-2H-benzotriazole-1-oxide

2- (3-chlorophenyl) -6-nitro-2H-benzotriazole-1-oxide

2- (4-chloro-phenyl) -6-nitro-2H-benzotriazole-1-oxide

2- (4-chloro-phenyl) -6-picrylazo-2H-benzotriazole-1-oxide

5-chloro-2- (2,4,5-trimethyl-phenyl) -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- benzotriazol-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-nitľO-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-trimethyl-phenyl) -2H-benzotriazole-1-oxide

2-phenyl-2H-benzotriazole-1-oxide

2-o-tolyl-2H-benzotriazole-1-oxide

2-p-tolyl-2H-benzotriazole-1-oxide.

Further preferred are heterocycles containing at least one N-hydroxyl, oxime,

N-oxy and Ν, Ν-dioxy-function or another heteroatom such as oxygen, sulfur, selenium and tellurium, such as:

Aziridines, diaziridines, pyrroles, dihydropyrols, tetrahydropyrols, pyrazoles, dihydropyrazoles, tetrahydropyrazoles, imidazoles, dihydroimidazoles, tetrahydroimidazoles, 1,2,3-triazoles, 1,2,4-triazoles, tetrazoles, pentazoles, piperidines, pyridines, pyridazines, pyrimidines, pyrazines, piperazines, 1,2,3-triazines, 1,2,4-triazines, tetrazines, azepines, oxazoles, isoxazoles, thiazoles, isothiazoles, thiadiazoles, morpholines, and their benzo fused derivatives such as indoles, isoindoles, indolizines, indazoles, benzimidazoles, benztriazoles, quinolines, isoquinolines, phthalazines, quinazolines, quinoxalines, phenazines, benzazepines, benzothiazoles and benzoxazoles.

Also preferred are fused N-heterocycles, such as triazolo compounds and tetrazolo compounds, which may contain at least one N-hydroxyl, oxime, Noxy- and Ν, d-dioxy function and in addition to nitrogen another heteroatom such as oxygen, sulfur, selenium and tellurium .

[1.2.4] triazolo [4,3-a] pyridines [1.2.4] triazolo [1,5-a] pyridines [1.2.4] triazolo [4,3-aquinolines [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 [1,5-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-aisoquinolines [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] quinolinyl [1.2.4] triazolo [3,4-a] phthalazine [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] quinazolines [1.2.4] triazolo [1,5-a] quinazolines [1.2.4] triazolo [5,1-b] quinazolines [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] quinazolines [1.2 .3] triazolo [1,5-c] quinazolines [1.2.4] triazolo [4,3-a] pyrazines [1.2.4] triazolo [1,5-a] pyrazines [1.2.3] triazolo [4,5-b] pyrazines [1.2.4] triazolo [4,3-a] quinoxalines [1.2.3] triazolo [1,5-a] quinoxalines [1.2.4] triazolo [4,3-b] [1,2,4] triazine [ 1.2.4] βπ3ζοΐο [3,4-ο] [1,2,4] triazine [1.2.4] triazolo [4,3-d] [1,2,4] triazine [1.2.4] tnazolo [3, 4-f] [1,2,4] triazolo [1,2.4] triazolo [1,5-b] [1,2,4] triazolo [1,2.4] triazolo [5,1-c] [1 , 2,4] triazolo n [1,2.4] triazolo [1,5-d] [1,2,4] triazine [1,2.4] triazolo [4,3-a] [1,3,5] triazione n [1.2.4] triazolo [1,5-a] [1,3,5] triazine tetrazolo [1,5-a] pyridines tetrazolo [1,5-b] isoquinolines tetrazolo [1,5-a] quinolines tetrazolo [5,1-aisoquinolines tetrazolo [1,5-b] pyridazines tetrazolo [1,5-b] quinolines tetrazolo [5,1-aphthalazines tetrazolo [1,5-a] pyrimidines tetrazolo [1,5-c] pyrimidines tetrazolo [1,5-a] quinazolines tetrazolo [1,5-c] quinazolines tetrazolo [1,5-a] pyrazines tetrazolo [1,5-a] quinoxal tetrazolo [1,5-b] [1,2,4] ] triazines ny 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-tetra hyd ro-isoquinolin and no I pyrimidin acid B (N-oxy-1,2,3, 4-tetrahydroisoquinoline _t) propionic acid

1,3-dihydroxy-2N-benzylimido-benzimidazoline.

The multi-component system (d) of the present invention includes aliphatic ethers and aryl-substituted alcohols 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-methoxybenzyl alcohol

2,5-dimethoxybenzyl alcohol

3,4-dimethoxybenzylamine

2,4-dimethoxybenzylamine hydrochloride veratrylalcohol coniferyl alcohol.

Olefins (alkenes) for example

2-allylphenol

2-allyl-6-methylphenol allylbenzene

3.4-Dimethoxy-propenylbenzene p-methoxystyrol 1-allylimidazole 1-vinylimidazole styrene stilbene allylphenyl ether cinnamic acid methyl ester cinnamic acid methyl ester

2,4,6-triallyloxy-1,3,5-triazine

1,2,4-triivinylcyklohexán

4-allyl-1,2-dimethoxybenzene vinyl ester of 4-tert-butylbenzoic acid squalene benzoin allyl cyclohexene dihydropyran N-benzyl cinnamic anilide, preferably phenol ethers such as e.g.

2,3-dimethoxybenzyl alcohol

3,4-dimethoxybenzyl alcohol

2,4-dimethoxybenzyl alcohol

2,6-dimethoxybenzyl alcohol homavanillyl 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, preferably carbonyl compounds, e.g.

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 ₁ 4'-dimethylamino) -benzophenone benzoin benzoin oxime

N-benzoyl-N-phenyl-hydroxylamine

2-amino-5-chlorobenzophenone

3-hydroxy-4-methoxybenzaldehyde

4-methoxybenzaldehyde anthraquinone-2-sulfonic acid

4-methylaminobenzaldehyde benzaldehyde benzophenone-2-carboxylic acid 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride (S) - (-) - 2- (N-benzylpropyl) -aminobenzophenone benzylphenylacetic acid anilide

N-benzylbenzanilid

4,4'-bis (dimethylamino) -tiobenzofenón

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 to 3,5-dimethoxy-4-hydroxybenzoic acid

4-hydroxybenzaldehyde salicylaldehyde vanillin vanillinic acid.

The addition of the compounds mentioned under d) and e) of the multi-component system results in mediating the reaction in cascade form or recycling its own mediator compounds in situ, i.e. during the reaction, and this leads surprisingly to a significant improvement in the capaci- tation or reduction of the mediator dose.

The additives mentioned in (d) are preferably used in an amount of 0.01 to 0.5 mg per gram of lignin-containing material. It is particularly preferred to use 0.01 to 0.1 mg per gram of lignin-containing material.

The free amine of the corresponding mediator is used in a mediator / amine ratio of 100:

to 1: 1, preferably 20: 1 to 1: 1, particularly preferably 10: 1 to 2: 1.

The efficacy of a multi-component system in altering, degrading or bleaching lignin, lignin-containing materials or the like is often further enhanced when magnesium ions are present in addition to said components. The magnesium ions may be added, for example, as a salt, preferably as magnesium sulfate. The concentration is in the range of 0.1 to 2 mg / g of lignin-containing material, preferably in the range of 0.2 to 0.6 mg / g.

In many cases, the efficiency of the multi-component system of the present invention can be further improved by providing the multi-component system in addition to magnesium ions with a complexing agent such as ethyleneaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid, diethylenetriaminepentamethylenephosphonic acid (DTMPA), nitrilotriacetic acid (NTA), polyphosphoric acid (PPA) and the like. The concentration is in the range of 0.2 to 5 mg / g of lignin-containing material, preferably in the range of 1 to 3 mg / g.

The multi-component system of the present invention in the lignin treatment process is used, for example, by mixing the corresponding selected components a) to e) simultaneously or in any order with an aqueous suspension of lignin-containing material.

Preferably, the process is carried out using the multi-component system of the present invention in the presence of oxygen or air at normal pressure to 1.0 MPa and at a pH in the range of 2-11, at a temperature in the range of 20-95 ° C, preferably 40-95 ° C. and at a fabric density of 0.5 to 40%.

For the use of enzymes in pulp bleaching, it is extraordinary and surprising to find that the use of the multi-component system of the present invention allows an increase in substance density and a substantial improvement in the kappa value.

Surprisingly, the increased density of the substance therefore leads to a better activity of the multi-component system.

From an economic point of view, the process according to the invention is preferably carried out at a density of 12 to 15%, particularly preferably 14 to 15%

Surprisingly, it has further been found that acidic washing (pH 2 to 6, preferably 4 to 5) or

The Q-stage (pH 2 to 6, preferably 4 to 5) before the enzyme-mediator stage results in a substantial reduction in the kappa value of many pulps compared to the treatment without this pretreatment. In the Q step, conventional substances (such as EDTA and DTPA) are used as chelating agents for this purpose. They are preferably used in concentrations of 0.1% to 1%, particularly preferably 0.1% to 0.5%.

In the method of the present invention, preferably 0.1 to 100 IU of enzyme per gram of lignin-containing material is used, particularly preferably 1 to 40 IU of enzyme per gram of lignin-containing material.

In the process according to the invention preferably 0.01 to 100 mg of oxidizing agent per gram of lignin-containing material is used, particularly preferably 0.01 to 50 mg of oxidizing agent per gram of lignin-containing material.

In the process of the present invention, preferably 0.5 to 80 mg of mediator per gram of lignin-containing material is used, particularly preferably 0.5 to 40 mg of mediator per gram of lignin-containing material.

With the multi-component system of the present invention, for example, whitening kraft cellulose (Softwood) can achieve a completely surprising result of a reduction in the kappa value from about 30 to 10 in 1 to 4 hours at a high concentration in the region of about 15%. ), the concentration of component c) (mediator) is substantially reduced.

It is also possible to add a reducing agent which, together with the oxidizing agent present, serves to adjust the redox potential.

As the reducing agents, sodium bisulfite, sodium ditionite, ascorbic acid, thiocompounds, mercapto compounds, glutathione and the like can be used.

The reaction takes place, for example, with a laccase under oxygen supply or oxygen overpressure, with peroxidases (e.g. lignin peroxidase, manganese peroxidase) with hydrogen peroxide.

Oxygen can also be generated in situ using hydrogen peroxide and catalase and hydrogen peroxide using glucose and GOD or other systems.

In addition, it is possible to add a radical-forming substance or a radical-receiving substance (capture, for example, OH- or COH-radicals) to the system. These can improve interplay within the red / ox- and radical mediators.

Other metal salts may also be added to the reaction solution.

These are important in the interaction with chelating agents as radical forming agents or red / ox-centers. The salts form cations in the reaction solution. Such ions include, but are not limited to, ferrous, ferric, manganese, manganese, manganese, copper, calcium, titanium, cerium, and aluminum ions.

In addition, the chelates present in the solution may serve as mimicsubstancies for enzymes, for example, for laccase (copper complexes) or for lignin peroxidases or manganese peroxidases (hemcomplexes). The term mimicsubstance refers to those substances which stimulate the prosthetic groups of the oxidoreductases and can, for example, catalyze oxidation reactions.

Further, sodium oxychloride (NaOCl) may be added to the reaction mixture. This compound can form singulett oxygen together with hydrogen peroxide.

Finally, it is also possible to work with detergents. Nonionic, anionic, cationic and amphoteric surfactants are suitable as such. Detergents can improve the penetration of enzymes and mediators into the fibers.

Likewise, polysaccharides and / or proteins may be beneficial to the reaction. Polysaccharides which may be mentioned are, in particular, glucans, mannans, dextranes, levans, pectins, alginates and vegetable gums and / or self-produced polysaccharides produced by yeast or mixed with yeast, and proteins include gelatin and albumin.

Said substances serve mainly as protective colloids for enzymes.

Other proteins that may be added are proteases such as pepsin, bromelain, papain and the like. These can serve, inter alia, to provide better access to lignin by degrading extensin C, a hydroxyproline-rich protein present in the wood.

Other protective colloids include amino acids, simple sugars, oligomeric sugars, PEG types of various molecular weights, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes.

The process of the present invention can be used not only in the delignification (bleaching) of kraft, sulphite, organosol and other celluloses and wood masses, but also in pulp production in general, both from woody plants and annual plants, provided defibrillation is ensured by conventional cooking procedures ( associated with possibly mechanical or pressure processes), i.e. very gentle boiling up to the kappa - a value which may be in the range of about 50 to 120 kappa.

In pulp bleaching as well as in cellulose production, the treatment may be repeated several times, either after washing or extraction of the treated substance with or without sodium hydroxide. This leads to even more reduced capacities and a significant increase in whiteness. It is also possible to use an O 2 -stage before the enzyme / mediator treatment or, as already mentioned, an acidic wash or a Q-stage (chelate stage).

Coal liquefaction (lignite, lignite) uses a similar procedure as for delignification (bleaching) of wood or pulp of annual plants.

DETAILED DESCRIPTION OF THE INVENTION

In the following, the present invention is illustrated in more detail by way of examples.

Example 1/2

Enzymatic bleaching of kraft cellulose

Example 1 g of pulp (Softwood, O2 delignified), density of 30% (about 100 g of moisture) is added to the following solution:

1. Mix 120 ml of tap water with 150 mg of hydroxybenzotriazole (HBT), 15 mg of benzotriazole (BT) and 3 mg of benzophenone (B) with stirring and adjust the pH with 0,5 m sulfuric acid so that after addition of the pulp and the enzyme had a final pH of 4.5. To this is added 4 IU (1 IU = conversion of 1 μΜ syringaldazine / min / ml enzyme) of laccase from Coriolus versicolor per gram of substance. The solution is made up to 200 ml and the substance is added. The mixture is mixed for 2 minutes in a kneading dough.

Subsequently, the substance is placed in an autoclave preheated to 45 ° C and incubated for 1 to 4 hours under a pressure of 1 to 10 bar.

The fabric was then washed through a nylon screen (30 µm) and extracted for one hour at 60 ° C, 8% fabric density and 2% NaOH for g fabric.

After washing the substance again, the kappa value is determined.

The results are shown in Table 1 below.

Table 1

System kapa pred extraction kapa po extraction degradation lignin (%) 1. O-value 11 10 9.1 2. L + 5 mg HBT / g 7.5 5.8 47.3 3. L + 5 mg HBT / g BT / B 6.9 4.9 54.5 4. L + 5 mg HBT / g 8.5 22.8 5. L + 5 mg HBT / g BT / B 6.1 44.6

2., 3. at a pressure of 1.0 MPa

4th, 5th air

B = benzophenone

L = lactase

Example 2

The procedure is as in Example 1, but with 75 mg of hydroxybenzotriazole, 7.5 mg of benztriazole and 0.02 mg of veratryl alcohol.

The results are shown in Table 2 below.

Table 2

System kapa pred extraction kapa po extraction degradation lignin (%) O-Value 11 10 9.1 L + 2.5 mg HBT / g 8.5 7.6 31 L + 2.5 mg HBT / g BT / VA 8.1 6.4 42

VA = veratryl alcohol

L = lactase

Example 3

Enzymatic bleaching of kraft cellulose (Softwood) g atro pulp (Softwood, O2 delignified), density 30% (about 100 g moisture) is added to the following solution:

1. Mix 120 ml of tap water with 60 mg of DTPA and 15 mg of magnesium sulfate with stirring. The pH is adjusted with 0.5 m sulfuric acid to give a pH of 4.5 after the addition of pulp and enzyme. To this is added 4 IU (1 IU = conversion of 1 μΜ syringaldazine / min / ml enzyme) of laccase from Coriolus versicolor per gram of substance. The solution is made up to 200 ml and the substance is added. The mixture is mixed for 2 minutes in a kneading dough.

The substance is then placed in an autoclave preheated to 45 ° C and under positive pressure

0.1 to 1.0 MPa is incubated for 1 to 4 hours.

The fabric was then washed through a nylon screen (30 µm) and extracted for one hour at 60 ° C, 8% fabric density and 2% NaOH for g fabric.

After washing the substance again, the kappa value is determined.

The results are shown in Table 3 below

System kapa pred extraction kapa po extraction degradation lignin (%) O-Value 28.7 26.8 6.7 L + 10 mg HBT / g 21 17.8 38.2 L + 10 mg HBT / g + 19.1 14.09 48.1

(A) = 2 mg / g DTPA

0.5 mg / g MgSO4

L = lactase

Example 4

Enzymatic bleaching of kraft pulp with upstream

Q-grade g atro pulp (Softwood 1 and Softwood 2), a batt density of 30% (about 100 g moisture) is added to the following solution:

1st Q-level:

120 ml of tap water is added to. The mixture is mixed with 90 mg of DTPA by stirring and the pH is adjusted with 0.5 m sulfuric acid to give a pH of 4.5 after the addition of pulp and enzyme. The solution is made up to 200 ml, the substance is added and the mixture is mixed for 2 minutes in a dough mixer.

The substance is then placed in a sealed container and left at 90 ° C.

The batch is then washed well (tap water), adjusted to a density of 30% and added to the following solution:

2. Lacase / extraction step:

120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole with stirring. The pH is adjusted with 0.5 m sulfuric acid to give a pH of 4.5 after the addition of pulp and enzyme. To this is added 4 IU (1 IU = conversion of 1 μΜ syringaldazine / min / ml enzyme) of laccase from Coriolus versicolor per gram of substance. The solution is made up to 200 ml and the substance is added. The mixture is mixed for 2 minutes in a kneading dough.

Subsequently, the substance is placed in an autoclave preheated to 45 ° C and incubated for 1 to 4 hours under a pressure of 1 to 10 bar.

The fabric was then washed through a nylon screen (30 µm) and extracted for one hour at 60 ° C, 8% fabric density and 2% NaOH for g fabric.

After washing the substance again, the kappa value is determined. In a parallel experiment, the kappa value is determined after the Q-stage.

The results are shown in Table 4 below:

Table 4

System kapa before Q kapa po Q kapa pred extraction kapei po extraction kapa n.Q-E O-value (SW 1) 28 23.5 28 24.4 22.4 L + 10 mg HBT / g (SW 1) 28 24.5 17.6 L + 10 mg HBT / g (SW 1) 28 23.5 18.6 14.8 O-value (SW 2) 22.7 21.6 22.7 2.1.5 21.6 L + 10 mg HBT / g (SW 2) 22.7 21.9 16.4 L + 10 mg HBT / g (SW 2) 22.7 21.6 16.1 14.4

L = kappa laccase - reduction:

SW 1: 37.2% without Q and 47.2% with Q. SW 2: 27.8% without Q and 36.6% with Q.

Example 5

Enzymatic bleaching of kraft pulp g and pulp (Softwood 1 / Softwood 2), density of 30% (about 100 g of moisture) is added to the following solution:

120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole (Softwood 1) and 150 and 300 mg of hydroxybenzotriazole (Softwood 2), respectively, with stirring. The pH is adjusted with 0.5 m sulfuric acid to give a pH of 4.5 after the addition of pulp and enzyme. To this is added 4 IU (1 IU = conversion of 1 μΜ syringaldazine / min / ml enzyme) of laccase from Coriolus versicolor per gram of substance. The solution is made up to 200 ml and the substance is added. The mixture is mixed for 2 minutes in a kneading dough.

At 15% density of the substance, 30 g of pulp = 100 g of wet pulp are made up to a total quantity of 200 g, ie 80 ml of tap water is introduced and made up to 100 ml. Otherwise, it is operated at 10% density.

Subsequently, the substance is placed in an autoclave preheated to 45 ° C and incubated for 1 to 4 hours under a pressure of 1 to 10 bar.

The fabric was then washed through a nylon screen (30 µm) and extracted for one hour at 60 ° C, 8% fabric density and 2% NaOH for g fabric.

After washing the substance again, the kappa value is determined.

The results are shown in Table 5 below.

Table 5

System kapa pred extraction kapa po extraction density substances removal lignin (%) O-value SW 1 28.7 26.7 6.6 10 mg HBT / g SW 1 21 17.8 10 38 10 mg HBT / g SW1 18.9 14.8 15 47.7 O-value SW 2 15 14.1 6 5 mg HBT / g SW2 10.1 7.2 10 52 5 mg HBT / g SW2 7.8 5.4 15 64 10 mg HBT / g SW2 7 5.1 10 66

Example 6

Enzymatic bleaching of kraft pulp (atwood pulp (Softwood O2 delignified), 30% density (about 100 g moisture)) is added to the following solution:

1. 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole under stirring, and the pH is adjusted with 0.5 m sulfuric acid to give a pH of 4.5 after the addition of the pulp and the enzyme. To this is added 1 IU or 10 IU (1 IU = conversion of 1 μΜ syringaldazine / min / ml enzyme) of laccase from Coriolus versicolor per gram of substance. 1000 IU of lignin peroxidase / g of substance, 1000 IU of peroxidase (horseradish) / g of substance and 1000 IU of tyrosinase / g of substance are added in separate doses. The solution is made up to 200 ml and the substance is added. The mixture is mixed for 2 minutes in a kneading dough.

Subsequently, the substance is placed in an autoclave preheated to 45 ° C and incubated for 1 to 4 hours under a pressure of 1 to 10 bar.

The fabric was then washed through a nylon screen (30 µm) and extracted for one hour at 60 ° C, 8% fabric density and 2% NaOH for g fabric.

After washing the substance again, the kappa value is determined.

The results are shown in Table 6 below.

Table 6

enzyme kapa (pulp) before processing kapa (pulp) after processing lignin 15.2 11.3 Peroxidase (horseradish) 19036 Servos 15.2 11.75 tyrosinase T-7753 Sigma 15.2 11:35 laccase 10 IU 15.2 5.5 laccase 1 IU 15.2 10.0

Example 7

Enzymatic bleaching of kraft pulp g and pulp (Softwood / Hardwood), density of 30% (about 100 g of moisture) is added to the following solution:

1. 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole with stirring, the pH is adjusted with 0.5 m sulfuric acid to give a pH of 4.5 after the addition of pulp and enzyme. To this is added 20 IU (1 IU = conversion of 1 μΜ syringaldazine / min / ml enzyme) of laccase from Coriolus versicolor per gram of substance. The solution is made up to 200 ml and the substance is added. The mixture is mixed for 2 minutes in a kneading dough.

Subsequently, the substance is placed in an autoclave preheated to 45 ° C and incubated for 1 to 4 hours under a pressure of 1 to 10 bar.

The fabric was then washed through a nylon screen (30 µm) and extracted for one hour at 60 ° C, 8% fabric density and 2% NaOH for g fabric.

After washing the substance again, the kappa value is determined.

The kappa value was reduced from 15 to 6 (Hardwood) and from 30 to 15 (Softwood).

Example 8

Enzymatic bleaching of straw pulp g atro straw pulp, density of 30% (about 100 g of moisture) is added to the following solution:

1. 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole under stirring, and the pH is adjusted with 0.3 m sulfuric acid to give a pH of 4.5 after the addition of pulp and enzyme. To this is added 20 IU (1 IU = conversion of 1 pM syringaldazine / min / ml enzyme) of laccase from Coriolus versicolor per gram of substance. The solution is made up to 200 ml and the substance is added. The mixture is mixed for 2 minutes in a kneading dough.

Subsequently, the substance is placed in an autoclave preheated to 45 ° C and incubated for 1 to 4 hours under a pressure of 1 to 10 bar.

The fabric was then washed through a nylon screen (30 µm) and extracted for one hour at 60 ° C, 8% fabric density and 2% NaOH for g fabric.

After washing the substance again, the kappa value is determined.

Kappa - value was reduced from 65 to 14.

Example 9

Enzymatic bleaching of sulphite pulp g atro pulp (sulphite pulp), density 30% (about 100 g moisture) is added to the following solution:

1. 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole under stirring, and the pH is adjusted with 0.5 m sulfuric acid to give a pH of 4.5 after the addition of the pulp and the enzyme. To this is added 20 IU (1 IU = conversion of 1 μΜ syringaldazine / min / ml enzyme) of laccase from Coriolus versicolor per gram of substance. The solution is made up to 200 ml and the substance is added. The mixture is mixed for 2 minutes in a kneading dough.

Subsequently, the substance is placed in an autoclave preheated to 45 ° C and incubated for 1 to 4 hours under a pressure of 1 to 10 bar.

The fabric was then washed through a nylon screen (30 µm) and extracted for one hour at 60 ° C, 8% fabric density and 2% NaOH for g fabric.

After washing the substance again, the kappa value is determined.

The kappa value was reduced from 15.5 to 5.2.

Example 10

Enzymatic bleaching of kraft pulp (Softwood / 02 delignified / Hardwood / double processing) g atro pulp (Hardwood or Softwood), density 30% (about 100 g moisture) is added to the following solution:

1. 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole under stirring, and the pH is adjusted with 0.5 m sulfuric acid to give a pH of 4.5 after the addition of the pulp and the enzyme. To this is added 20 IU (1 IU = conversion of 1 pM syringaldazine / min / ml enzyme) of laccase from Coriolus versicolor per gram of substance. The solution is made up to 200 ml and the substance is added. The mixture is mixed for 2 minutes in a kneading dough.

Subsequently, the substance is placed in an autoclave preheated to 45 ° C and incubated for 1 to 4 hours under a pressure of 1 to 10 bar.

The fabric was then washed through a nylon screen (30 µm) and extracted for one hour at 60 ° C, 8% fabric density and 2% NaOH for g fabric.

a) Enzyme + mediator is added immediately after incubation, blended (2 min.) and the reaction is re-run (same dosing as in the first treatment).

b) Directly after incubation, after a washing step and pressing the fabric to 30% of the fabric density, the reaction is carried out once again by feeding all components.

c) After washing the substance again, extracting and pressing the substance to 30% of the substance density, the reaction is carried out once again by feeding all the components.

Decrease in capacity - values

Hardwood Softwood

(a) from 15 to 5

(b) from 15 to 3,5

(c) from 15 to 2,5

Example 11

(a) from 15,5 to 4,2

(b) from 15,5 to 3

(c) from 15,2 to 2,2.

Enzymatic bleaching of wood pulp g and wood pulp (spruce), substance density 30% (about 100 g moisture) is added to the following solution:

1. 120 ml of tap water are mixed with 300 mg of Nhydroxyhexahydroazepine with stirring, the pH is adjusted with 0.5 m sulfuric acid to a pH of 4.5 after the addition of pulp and enzyme. To this is added 1 IU (1 IU = conversion of 1 μΜ syringaldazine / min / ml enzyme) of laccase from Coriolus versicolor per gram of substance. The solution is made up to 200 ml and the substance is added. The mixture is mixed for 2 minutes in a kneading dough.

Subsequently, the substance is placed in an autoclave preheated to 45 ° C and incubated for 1 to 4 hours under a pressure of 1 to 10 bar.

The fabric was then washed through a nylon screen (30 µm).

In this experiment, an increase in the whiteness level of 7% whiteness units is achieved

ISO.

Claims (49)

PATENT CLAIMS 1. A system for the alteration, degradation or bleaching of lignin, lignin-containing materials or the like, comprising: (a) optionally at least one oxidation catalyst, b) at least one suitable oxidizing agent, c) at least one mediator selected from the group consisting of hydroxylamines, hydroxylamine derivatives, hydroxamic acid, hydroxamic acid derivatives or aliphatic, cycloaliphatic, heterocyclic and aromatic compounds containing at least one N-hydroxyl, oxime, Noxy- or Ν, Ν'-dioxy -Features, d) optionally at least one comediator selected from the group consisting of aryl-substituted alcohols, carbonyl compounds, aliphatic ethers, phenol ethers and / or olefins (alkenes); and e) a small amount of at least one free amine corresponding to the mediator used. A multi-component system according to claim 1, characterized in that in addition to said components a) to e) it also comprises magnesium ions. Multi-component system according to claim 1 or 2, characterized in that it comprises an oxidation catalyst, preferably oxidoreductases of classes 1.1.1 to 1.97. A multi-component system according to claim 3, characterized in that it comprises oxidoreductases which use oxygen, peroxides or quinones as electron acceptor. Multicomponent system according to claim 3, characterized in that it contains laccase (1.10.3.2) as an oxidoreductase. A multi-component system according to claim 1 or 2, characterized in that as NO-, NOH- or H-NR-OH-containing aliphatic, cycioaliphatic, heterocyclic or aromatic compounds, it comprises Ν-hydroxy-, oxime-N-oxy and Ν-. , Ν'-dioxy compounds and hydroxamic acid derivatives in a single-component or multi-component system. Multi-component system according to claim 6, characterized in that it contains hydroxylamines of the formula I as NO-, NOH- or H-NR-OH-containing compounds. R1 - N - ^R2 (H OH where R ¹ and R ² may be the same or different and are each independently hydrogen, C 1 -C 12 alkyl, C 1 -C 6 carbonylalkyl, phenyl or aryl, or substituted one or more times R ³ , wherein R ³ represents hydrogen, halogen, hydroxy, formyl, carboxyl, and its salts and esters thereof, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, a carboxyalkyl group having from 1 to 6 alkyl, phenyl, sulfone, and esters and salts thereof, sulfamoyl, carbamoyl, phospho, phosphone, phosphonooxy and salts and esters thereof, wherein the amino, carbamoyl and sulfamoyl groups of the radical R ³ may be further unsubstituted or once or double substituted by hydroxy, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms, or R ¹ and R ² may together form -B-, wherein B is (-CHR ⁴ -) n or (-CR ⁴ = CH-) m, wherein R ⁴ is as defined for R 3, n is an integer from 1 to 6 and m is an integer from 1 to 3. Multi-component system according to claim 6, characterized in that it contains compounds of the formula II as NO-, NOH- or H-NR-OH-containing compounds. R ⁹ II X is a group (N = N), (N = CRlO-) _at (0 -CR ¹ = N-) p, (-CR ¹¹ = CR ¹² -) _p Ο- r 1 ABOUT | Ι N = N or - fst = N - F where p is 1 or 2 and R 9 to R ¹² , R 15 _and r 16 are the same or different and independently of one another are hydrogen, halogen, hydroxy, formyl, carboxy, as well as salts and esters thereof, amino, nitro, alkyl of 1 to 12 carbon atoms, (C 1 -C 6) alkoxy, (C 1 -C 6) carbonylalkyl, phenyl, sulfono and esters and salts thereof, sulfamoyl, carbamoyl, phosphono, phosphone, phosphonooxy and their salts and esters, wherein the amino group, the carbamoyl group and the sulfamoyl group of radicals r 9 to R ¹² , R ¹⁵ and R ¹⁶ may further be unsubstituted or mono- or di-substituted by hydroxy, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms, or R 15 _and r 16 may together form -G-, wherein G is (-CR ⁶ = CR ⁶ -CR 7 = CR ⁶ -) or (-CR 8 = CR 7 -CR ⁶ = CR ⁵ -), wherein R ⁶ to R ⁶ may be the same or different and are each independently hydrogen, halogen, hydroxy, formyl, carboxy, as well as salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, C 1 -C 12 alkyl C 1 -C 6 carbonylalkyl, C 1 -C 6 alkyl, phenyl, sulfone and its esters and salts, sulfamoyl, carbamoyl, phosphono, phosphone, phosphonooxy and salts and esters thereof, wherein the amino, carbamoyl and the sulfamoyl group of the radicals R 5 to R ⁸ may further be unsubstituted or mono- or di-substituted with hydroxy, C 1 -C 3 alkyl or C 1 -C 3 alkoxy and wherein the C 1 -C 12 alkyl group is C 1 -C 12 alkoxy. C 1 -C 6 carbonylalkyl The radicals R @ ⁸ to R @ ⁸ may be unsubstituted or further substituted one or more times with R @ ¹⁸ , wherein R @ ¹⁸ represents a hydrogen atom, a halogen atom, a hydroxyl group, a formyl group, a carboxy group, and its atoms. salts and esters, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, carbonylalkyl of 1 to 6 carbon atoms in alkyl, phenyl, aryl and their salts and esters, wherein the amino, a carbamoyl group and a sulfamoyl radical R ^- * ⁸ can be unsubstituted or mono- or disubstituted by the radical R ¹⁹ wherein R ¹⁹ represents a hydrogen atom, a hydroxy group, a formyl group, a carboxy group, and salts and esters thereof, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, carbonylalkyl of 1 to 6 carbon atoms in alkyl, phenyl, and aryl. A multi-component system according to claim 6, characterized in that it contains compounds of formula III as NO-, NOH- or H-NR-OH-containing compounds. III X is (-N = N-), (-N = CR 4 -) p, (-CR 4 = N-) p, (-CR ¹¹ = CR ¹² -) _p Ο- Ι 0 ' 1 -N = N - or 1 - (st = N) where p is 1 or 2 and R 5 to R 12 are the same or different and independently of one another are hydrogen, halogen, hydroxy, formyl, carboxy, as well as salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, C 1 -C 12 alkoxy C 1 -C 6 carbonylalkyl, phenyl, aryl, sulfono and esters and salts thereof, sulfamoyl, carbamoyl, phosphono, phosphono, phosphonooxy and their salts and esters, wherein the amino, carboyl and the sulfamoyl group of the radicals R @ 5 to R @ 5 may further be unsubstituted or mono- or disubstituted by hydroxy, C1 -C3 alkyl or C1 -C3 alkoxy, and wherein the C1 -C12 alkyl group is C1 -C3 alkoxy. C 6 -C 6 carbonylalkyl, C 1 -C 6 carbonylalkyl, phenyl, aryl and C 1 -C 6 arylalkyl in the alkyl radicals of R ⁶ to R 12 may be unsubstituted or further substituted one or more times with R 13, wherein: R 13 represents a hydrogen atom, a halogen atom, a hydroxy group, a formyl group, a carboxy group, and salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 carbonylalkyl alkyl, phenyl, aryl, sulphono, sulfenoskupinu and sulfino salt thereof, wherein the amino, carbamoyl, sulphamoyl radical R 3 may be a carbon carbon radical, and their esters and the group, and unsubstituted or furthermore mono- or disubstituted by the radical R ^ _t wherein R 14 is a hydrogen atom, hydroxy, formyl, carboxy, and salts and esters thereof, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, carbonylalkyl of 1 to 6 carbon atoms in alkyl, phenyl and aryl. A multi-component system according to claim 6, characterized in that it comprises compounds of formula IV as NO, NOH- or H-NR-OH-containing compounds wherein: X is (-N = N-), (-N = CR 1 -) _m , (-CR 1 = N-) _m (-CR ¹ - = CR ¹² -) _m , 0 * 1 0 N = N or 1 • ť - (\ h = N - + wherein m is 1 or 2 and R ⁵ to R ¹⁰ to R ** ² are as defined above and a R 17 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkylcarbonyl group having 1 to 10 carbon atoms, which alkyl and alkylcarbonyl group may be unsubstituted or substituted one or more times with the radical R @ 1, wherein R @ 18 has the meanings given for R @ ³ . A multi-component system according to claim 6, characterized in that it contains 1-hydroxybenzotriazole and tautomeric benzotriazole-1-oxide as well as their esters and salts of the general formula V in the form of NO, NOH- or H-NR-OH-containing compounds. in which R ³ to R ³ may be the same or different and are each independently hydrogen, halogen, hydroxy, formyl, carboxy, as well as salts and esters thereof, amino, nitro, C 1 -C 12 alkyl, C 1 -C 12 alkyl C 1 -C 6 carbonylalkyl, C 1 -C 6 alkyl, phenyl, sulfone and its esters and salts, sulfamoyl, carbamoyl, phosphono, phosphone, phosphonooxy and salts and esters thereof, wherein the amino, carbamoyl and the sulfamoyl group of the radicals R ³ to R ³ may further be unsubstituted or mono- or double-substituted by hydroxy, alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms, and wherein the alkyl group of 1 to 12 carbon atoms, C 1 -C 6 carbonyl, C 1 -C 6 carbonylalkyl alkyl, phenyl, and aryl groups of radicals R @ ³ to R @ ³ R8 may be unsubstituted or further substituted one or more times with the radical _R18 wherein _R18 represents a hydrogen atom, a halogen atom, a hydroxy group, a formyl group, a carboxy group, and salts and esters thereof, amino, nitro, C1-C12alkyl, alkoxy groups (C 1 -C 6) -carbonyl, (C 1 -C 6) -carbonyl, phenyl, aryl, sulfone, sulfo, and sulfino, and salts and esters thereof, wherein the amino, carbamoyl and sulfamoyl groups of R ¹ may be unsubstituted or further substituted once or twice with R ^, wherein R19 represents a hydrogen atom, a hydroxy group, a formyl group, a carboxy group, and salts and esters thereof, amino, nitro, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 6 carbon atoms, carbonylalkyl of 1 and 6 carbon atoms in alkyl, phenyl, and aryl. A multi-component system according to claim 6, characterized in that it contains compounds derived from azoles as NO, NOH- or H-NR-OH-containing compounds. A multi-component system according to claim 6, characterized in that it contains, as NO, NOH- or H-NR-OH-containing compounds, fused heterocycles containing a fused triazole or tetrazole unit, such as [1.2.4] triazolo [4]. , 3-a] pyridinyl [1.2.4] triazolo [1,5-a] pyridinyl [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 [1,5-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 1,2,3] triazolo [5,1-a] isoquinoline [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] quinolines [1, 4] triazolo [eta] < 4 > -azaphthalazines [1 < 4 > 4,3-c] pyrimidines [1.2.4] triazolo [1,5-a] pyrimidines [1.2.4] triazolo [1,5-c] pyrimidines [1.2.4] tria zolo [4,3-c] quinazolines [1.2.4] triazolo [1,5-a] quinazolines [1.2.4] triazolo [5,1-b] quinazolines [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] quinazolines [1.2.3] triazolo [ 1,5-c] quinazolines [1,2,4] triazolo [4,3-a] pyrazines [1.2.4] triazolo [1,5-a] pyrazines [1,1'-triazolo [4,3-a] pyrazines [1.2. 4] triazolo [4,3-a] quinoxalines [1.2.3] triazolo [1,5-a] quinoxalines [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] ] triaza n [1.2.4] triazolo [1,5-d] [1,2,4] triaza n [1.2.4] triazolo [4,3-a] [1,3,5] triaza n [1.2. 4] triazolo [1,5-a] [1,3,5] triazine tetrazolo [1,5-a] pyridines tetrazolo [1,5-b] isoquinolines tetrazolo [1,5-aquinolines tetrazolo [5,1- a] isoquinolines tetrazolo [1,5-b] pyridazines tetrazolo [1,5-b] quinolines tetrazolo [5,1-a] phthalazines tetra zolo [1,5-a] pyrimidines tetrazolo [1,5-c] pyrimidines tetrazolo [1,5-a] quinazolines tetrazolo [1,5-c] quinazolines tetrazolo [1,5-a] pyrazines tetrazolo [1,5] -a] quinoxalines 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. A multi-component system according to claim 1 or 2, characterized in that it contains, for example, air, oxygen, ozone, hydrogen peroxide, organic peroxides, peracids such as peracetic acid, peroxyacetic acid, persulfic acid, perdusic acid, metachloroperoxybenzoic acid as oxidizing agent. and perchloric acid, perborates, peracetates, persulphates, peroxides or oxygen species and radicals such as OH, OOH, Singullet-oxygen, superoxide (O2). ozonide, a dioxygenyl cation (O2 ⁺ ), dioxirane, dioxethane or a Fremy radical. Multicomponent system according to claim 1 or 2, characterized in that it contains as compounds of component d) aliphatic ethers and aryl-substituted alcohols, e.g. 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 veratrylalcohol coniferyl alcohol. Multi-component system according to claim 1 or 2, characterized in that it contains olefins (alkenes), for example 2-allylphenol, as compounds of component d). 2-allyl-6-methylphenol allylbenzene 3,4-dimethoxy-propenylbenzene p-methoxystyrol 1 -allylimidazole 1-vinylimidazole styrene stilbene allylphenyl ether benzyl cinnamate methyl cinnamate 2,4,6-triallyloxy-1,3,5-triazine 1.2.4- trivinylcyclohexane 4-Allyl-1,2-dimethoxybenzene vinyl ester of 4-tert-butylbenzoic acid Squalene benzoin allyl cyclohexene dihydropyran N-benzylcinnamic acid anilide. A multi-component system according to claim 1 or 2, characterized in that it comprises phenol ethers, e.g. 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. Multi-component system according to claim 1 or 2, characterized in that it contains carbonyl compounds 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 benzoinoxime N-benzoyl-N-phenyl-hydroxylamine 2-amino-5-chlorobenzophenone 3-hydroxy-4-methoxybenzaldehyde 4-methoxybenzaldehyde anthraquinone-2-sulfonic acid 4-methylaminobenzaldehyde benzaldehyde benzophenone-2-carboxylic acid 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride (S) - (-) - 2- (N-benzylpropyl) -aminobenzophenone benzylphenylacetic acid anilide N-benzylbenzanilid 4,4'-bis (dimethylamino) -tiobenzofenón 4,4-bis (diacetylamino) benzophenone 2-chlorobenzophenone 4,4'-dihydroxybenzophenone 2,4- dihydroxybenzophenone 3,5-Dimethoxy-4-hydroxybenzaldehyde hydrazine n 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 vanillinic acid. 19. A multi-component system according to claim 1 or 2, characterized in that it comprises as component e) the free amine in the case of in situ generation or mediating the reaction in cascade form of hydroxybenztriazole and benztriazole. 20. A method of altering, degrading or bleaching lignin and lignin-containing materials and the like, comprising mixing selected components a) to e) according to claim 1 simultaneously or in any order with an aqueous suspension of lignin-containing material. The process according to claim 20, characterized in that the reaction is carried out at a pH in the range of 2 to 11, at a temperature in the range of 20 to 95 ° C, preferably 40 to 95 ° C, at a substance density in the range 0.5 to 40 % and at an air or oxygen supply at a pressure ranging from 0.1 to 1.0 MPa. Method according to claims 20 and 21, characterized in that the density of the substance is preferably in the range of 13 to 15%. Method according to claims 20 and 21, characterized in that an acidic wash or a Q-stage is carried out before the reaction. A method according to claim 23, characterized in that the acidic wash is carried out at a temperature in the range of 60 to 100 ° C and at a pH in the range of 4 to 6.5 for 30 to 90 minutes at a fabric density of 4 to 20%. The method according to claim 23, characterized in that the Q-stage is carried out with 0.05 to 1.0%, preferably 0.2 to 0.5%, of a chelating agent at a temperature in the range of 60 to 100 ° C, at pH 4 to 5.5 for 30 to 90 minutes and a density of 4 to 20%. Method according to claim 23, characterized in that the conditions of 1 hour, 90 ° C, pH 4.5 - 5 and 10% density of the substance are maintained for acidic washing and Qstage. A method according to claims 20 and 21, characterized in that hemicellulases, cellulases, amylase, pectinase or lipase or a mixture consisting of two or more of these enzymes are added to the reaction mixture. Method according to claims 20 and 21, characterized in that modified enzymes, enzyme components, prosthetic groups or mimics, such as heme groups and heme groups containing compounds, are used. Method according to claims 20 and 21, characterized in that phenolic compounds and / or non-phenolic compounds with one or more benzene rings are used in addition to these substances. A process according to claims 20 and 21, characterized in that a reducing agent is added to the reaction mixture. The process according to claim 30, wherein the reducing agent is sodium bisulfite, sodium ditionite, ascorbic acid, thiol compounds, mercapto compounds or glutathione. Process according to claims 20 and 21, characterized in that the oxygen is generated in situ using a hydrogen peroxide + catalase system or a hydrogen peroxide using a GOD + glucose system. Process according to claims 20 and 21, characterized in that metal salt-forming cations are added to the reaction mixture. Process according to Claim 33, characterized in that cations are ferrous, ferric, manganese, manganese, manganese, calcium, copper, titanium, cerium and aluminum. Process according to claims 20 and 21, characterized in that a complexing agent is additionally added to the reaction mixture. Process according to claim 35, characterized in that ethyleneaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (DTPA) is used as complexing agent. (HEDTA), diethylenetriaminepentamethylenephosphoric acid (DTMPA), c nitrilotriacetic acid (NTA), polyphosphoric acid (PPA) or other iron-, manganese- or copper-complexers, such as diethylamine or hydiroxylamine. Method according to claims 20 and 21, characterized in that NaOCI is used. Process according to claims 20 and 21, characterized in that detergents are additionally used. Method according to claim 38, characterized in that nonionic, ionic, anionic, cationic and amphoteric surfactants are used as detergents. Process according to claims 20 and 21, characterized in that polysaccharides and / or proteins are additionally added to the reaction mixture. Method according to claim 40, characterized in that glucans, mannans, dextrans, levans, pectins, alginates, vegetable gums and / or fungi produced or mixed in yeast-produced polysaccharides are used as polysaccharides. Method according to claim 40, characterized in that gelatin and / or albumin are used as proteins. • Process according to claims 20 and 21, characterized in that simple sugars, oligomeric sugars, amino acids, polyethylene glycols, polyethylene oxides, polyethyleneimines and polyethylene siloxanes are used as additives. Method according to claims 20 and 21, characterized in that a radical generation or radical uptake system is added. A method according to claim 1 and 2 and 20 and 21, characterized in that it is used for delignification or bleaching of pulps according to all known brewing procedures. Process according to claim 45, characterized in that the cooking process is a sulphate process, a sulphite process, an organosol process, an ASAM method, an enabatch process and the like. A method according to claim 46, characterized in that it is carried out after, between or before all conventional bleaching stages and other sequences such as the Q-stage, acidic washing and the like. A method according to claims 45 to 47, characterized in that it is carried out in a plurality of stages, wherein washing or washing and extraction with lye are carried out between each stage or neither washing nor extraction is carried out. 49. The multi-component system of claim 1 for liquefying coal.