WO1996018770A2 - Multicomponent system for modifying, decomposing or bleaching lignin, lignin-containing materials or similar substances and method of using this system - Google Patents

Abstract

The present invention concerns a multicomponent system for modifying, decomposing or bleaching lignin, lignin-containing materials or similar substances, and a method of using this system. The multicomponent system is characterized in that it comprises: a) optionally at least one oxidation catalyst; and b) at least one suitable oxidizing agent; and c) at least one mediator selected from the group comprising hydroxylamines, hydroxylamine derivatives, hydroxamic acids, hydroxamic acid derivatives, aliphatic, cycloaliphatic, heterocyclic or aromatic compounds containing at least one N-hydroxy, oxime, N-oxi- or N,N'-dioxi function; and d) optionally at least one comediator from the group comprising aromatic alcohols, carbonyl compounds, aliphatic ethers, phenolethers and/or olefins (alkenes); and e) a small amount of at least one free amine of the respective mediator used.

Description

Multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances as well as processes for its use

The present invention relates to a multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances, and methods for its use.

The sulfate and sulfite processes are the main processes used today for pulp production. With both methods, cooking and under pressure Produces pulp. The sulfate process works with the addition of NaOH and Na ₂ S, while in the sulfite process

Ca (HSO ₃ ) ₂ + SO ₂ is used.

The main aim of all processes is to remove the lignin from the plant material, wood or annual plants used.

The lignin, which is the main constituent of the plant material (stem or stem) with cellulose and hemicellulose, must be removed, otherwise it will not be possible to produce non-yellowing and mechanically heavy-duty papers.

The wood-based production processes work with stone grinders (wood sanding) or with refiners (TMP), which defibrillate the wood by grinding after appropriate pretreatment (chemical, thermal or chemical-thermal).

These wood materials still contain a large part of the lignin. You will v. a. used for the production of newspapers, magazines, etc.

For some years now, the possibilities of using enzymes for lignin degradation have been researched. The mechanism of action of such lignolytic systems was only elucidated a few years ago, when it was possible to use adequate cultivation conditions and inductor additives to produce sufficient amounts of enzyme in the white rot fungus Phanerochaete chrysosporium come. The previously unknown lignin peroxidases and manganese peroxidases were discovered. Since Phanerochaete chrysosporium is a very effective lignin degrader, attempts were made to isolate its enzymes and to use them in purified form for lignin degradation. However, this did not succeed because it turned out that the enzymes primarily lead to a repolymerization of the lignin and not to its degradation.

The same applies to other lignolytic enzyme species such as laccases, which oxidatively break down the lignin using oxygen instead of hydrogen peroxide. It was found that similar processes occur in all cases. This is because radicals are formed which react with one another again and thus lead to polymerization.

Today there are only processes that work with in vivo systems (mushroom systems). The main focus of optimization attempts is so-called biopulping and biobleaching.

Biopulping is the treatment of wood chips with living fungal systems.

There are 2 types of application forms:

1. Pretreatment of wood chips before refining or grinding to save energy in the production of wood materials (eg TMP or wood pulp). Another advantage is the mostly existing improvement in the mechanical properties of the fabric, a disadvantage the poorer final whiteness.

2. Pretreatment of wood chips (Softwood / Hardwood) before cellulose cooking (power process, sulfite process).

The goal here is to reduce cooking chemicals, improve cooking capacity and "extended cooking".

As an advantage, improved kappa reduction after cooking compared to cooking without pretreatment is also achieved.

Disadvantages of these procedures are clearly the long treatment times (several weeks) and especially the unresolved risk of contamination during treatment if you want to do without the uneconomical sterilization of the wood chips.

Biobleaching also works with in-vivo systems. The boiled pulp (Softwood / Hardwood) is inoculated with fungus before bleaching and treated for days to weeks. Only after this long treatment time does a significant decrease in kappa number and increase in whiteness become apparent, which makes the process uneconomical for implementation in the usual bleaching sequences.

Another application, usually carried out with immobilized fungal systems, is the treatment of pulp wastewater, in particular bleaching wastewater, to decolorize it and reduce the AOX (reduction of chlo compounds in wastewater that cause chlorine or chlorine dioxide bleaching stages).

In addition, it is known that hemicellulases etc. Use xylanases, mannanases as "bleach boosters".

These enzymes are said to act primarily against the reclaimed xylan, which partially covers the residual lignin after the cooking process, and by breaking it down, they increase the accessibility of the lignin for the bleaching chemicals used in the subsequent bleaching sequences (especially chlorine dioxide). The savings in bleaching chemicals demonstrated in the laboratory have only been partially confirmed on a large scale, so that this type of enzyme can only be classified as a bleaching additive.

Another, recently investigated possible use of lignolytic enzymes or fungi was identified in the "coal liquefaction". Preliminary investigations show the basic possibility of brown or hard coal using in vivo treatment with e.g. Attack and liquefy white rot fungi such as Phanerochaete chrysosporium (incubation period several weeks). (Bioengineering 4.92.8 year.)

The possible structure of hard coal shows a three-dimensional network of polycyclic, aromatic ring systems with a "certain" similarity to lignin structures. In addition to the lignolytic enzymes, chelate substances (siderophores such as ammonium oxalate) and biosurfactants are believed to be cofactors.

The application PCT / EP87 / 00635 describes a system for removing lignin from lignin-cellulose-containing material with simultaneous bleaching, which works with lignolytic enzymes from white rot fungi with the addition of reducing and oxidizing agents and phenolic compounds as mediators.

In DE 4008893C2 in addition to the Red / Ox system

"Mimic substances" that simulate the active center (prosthetic group) of lignolytic enzymes added. In this way, a significant improvement in performance could be achieved.

In the application PCT / EP92 / 01086, a redox cascade is used as an additional improvement with the aid of phenolic or non-phenolic aromatics "matched" in the oxidation potential.

In all three processes, the limitation for large-scale use is the applicability with low consistencies (up to a maximum of 4%) and with the last two applications the risk of "leaching out" of metals when using the chelate compounds, especially in the case of downstream peroxide bleaching stages to destroy the peroxide being able to lead. Methods are known from WO / 12619, WO 94/12620 and WO 94/12621 in which the activity of peroxidase is promoted by means of so-called enhancer substances.

The enhancer substances are characterized in WO 94/12619 on the basis of their half-life.

According to WO 94/12620, 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 which contain at least two aromatic rings, at least one of which is substituted with defined radicals.

All three applications relate to "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. In the description of the application, reference is made to the usability for treating lignin, but our own experiments with the substances specifically disclosed in the applications showed that they had no effect as mediators for increasing the bleaching effect of the peroxidases when treating materials containing lignin!

The object of the present invention is to provide a system for changing, breaking down or bleaching lignin containing lignin To provide materials or similar substances that are more effective than known systems.

The object is achieved by a multi-component system, which is characterized in that it 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, which contain at least one N-hydroxy, oxime, N-oxi or N, N'-dioxi function 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.

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 one comediator. Enzymes are preferably used as oxidation catalysts in the multicomponent system according to the invention. For the purposes of the invention, the term enzyme also encompasses enzymatically active proteins or peptides or prosthetic groups of enzymes.

Oxidoreductases of classes 1.1.1 to 1.97 according to the International Enzyme Nomenclature, Committee of the International Union of Biochemistry and Molecular Biology (Enzyme Nomenclature, Academic Press, Inc., 1992, pp. 24-154) can be used as the enzyme in the multicomponent system according to the invention .

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 acceptors NAD ⁺ or NADP ⁺ (subclass 1.1.1), cytochromes (1.1.2), oxygen (O ₂ ) (1.1 .3), disulfides (1.1.4), quinones (1.1.5) or other acceptors (1.1.99).

From this class, the enzymes of class 1.1.5 with quinones as acceptors and the enzymes of class 1.1.3 with oxygen as acceptors are particularly preferred. Cellobiose is particularly preferred in this class:

quione-1-oxidoreductase (1.1.5.1).

Enzymes of class 1.2 are also preferred. This class of enzymes (1.1.5.1) includes those enzymes that oxidize aldehydes to the 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 target

CH-CH groups of the donor act.

The 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).

The enzymes of class (1.3.3) with oxygen as acceptor and (1.3.5) with quinones etc. as acceptor are also particularly preferred here. Also preferred are class 1.4 enzymes which act on CH-NH ₂ groups of the donor.

The corresponding acceptors are NAD ⁺ , NADP ⁺ (1.4.1), cytochrome (1.4.2), oxygen (1.4.3), disulfide (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 act on 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).

Here too, enzymes with oxygen (O ₂ ) (1.5.3) and with quinones (1.5.5) are particularly preferred 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), NO ₂ 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 as donors on other NO ₂ compounds and as acceptors cytochromes (1.7.2), oxygen (O ₂ ) (1.7.3), 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 which act as donors on sulfur groups and NAD ⁺ , NADP ⁺ (1.8.1), cytochromes (1.8.2), oxygen (O ₂ ) (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 (O ₂ ) and (1.8.5) with quinones as acceptors is particularly preferred.

Also preferred are class 1.9 enzymes which act as donors on heme groups and have oxygen (O ₂ ) (1.9.3), NO ₂ compounds (1.9.6) and others (1.9.99) as acceptors.

Group 1.9.3 with oxygen (O ₂ ) as acceptor (cytochrome oxidases) is particularly preferred here.

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 act as acceptors on superoxide radicals.

Superoxide dismutase is particularly preferred here

(1.15.1.1).

Enzymes of class 1.16 are also preferred

NAD ⁺ or NADP ⁺ (1.16.1) or oxygen (O ₂ ) (1.16.3) act as acceptors.

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

Further preferred enzymes are those of group 1.17 (action on CH ₂ groups which are oxidized to -CHOH-), 1.18 (action on reduced ferredoxin as donor), 1.19 (action on reduced flavodoxin as donor) and 1.97 (others Oxidoreductases).

The enzymes of group 1.11 are also particularly preferred. which act on a peroxide as an acceptor. This only subclass (1.11.1) contains the peroxidases. The cytochrome C peroxidases (1.11.1.5), catalase (1.11.1.6), the peroxidase (1.11.1.6), the iodide peroxidase (1.11.1.8) and the glutathione peroxidase (1.11.1.9) are particularly preferred here. , 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) (1.11.1.14).

Enzymes of class 1.10 which act on biphenols and related compounds are very particularly preferred. They catalyze the oxidation of biphenols and ascorbates. NAD ⁺ , NADP ⁺ (1.10.1), cytochrome act as acceptors

(1.10.2), oxygen (1.10.3) or others (1.10.99).

Of these in turn, class 1.10.3 enzymes with oxygen (O ₂ ) as the acceptor are 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 (benzenediol: oxigen oxidoreductase) (1.10.3.2) are preferred, the laccases (benzenediol: oxigen oxidoreductase)

(1.10.3.2) are particularly preferred.

These enzymes are commercially available or can be obtained using standard methods. Plants, animal cells, bacteria and fungi, for example, come into consideration as organisms for the production of the enzymes. Basically, both naturally occurring as well as genetically modified organisms are enzyme producers. Parts of unicellular or multicellular organisms are also conceivable as enzyme producers, especially cell cultures.

White rot fungi such as pleurotus, phlebia and trametes are used, for example, for the particularly preferred enzymes, such as those from group 1.11.1, but especially 1.10.3, and in particular for the production of laccases.

The multi-component system according to the invention comprises at least one oxidizing agent. The oxidizing agents that can be used are, for example, air, oxygen, ozone, H ₂ O ₂ , organic peroxides, peracids such as peracetic acid, performic acid, persulfuric acid, persitric acid, metachloroperoxibenzoic acid, perchloric acid, perborates, peracetates, persulfates, peroxides or oxygen species and their radicals such as OH, OOH, Singlet oxygen, superoxide (O ₂ -), ozonide, dioxygenyl cation

(O ₂ ⁺ ), dioxiranes, dioxetanes or Fremy radicals can be used.

Preferably oxidizing agents are used which can either be generated by the corresponding oxidoreductases e.g. Dioxiranes from laccases plus carbonyls or which can chemically regenerate the mediator (e.g. Caro's acid + benzotriazole gives hydroxybenztriazole) or can directly convert it.

The multicomponent system according to the invention preferably comprises at least one compound as mediator (component c), which contains at least one N-hydroxyl, oxime, N-oxi or N-dioxi function and / or one of the compounds of the formula I, II, III, IV or V mentioned below, where the compounds of the formulas II, III, IV and V are preferred, the compounds of the formula III, IV and V are particularly preferred and compounds of the formula IV and V are particularly preferred.

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

where 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, C ₁ -C ₁₂ -alkyl-, carbonyl-C ₁ -C ₆ -alkyl- , phenyl, aryl, the C ₁ -C ₁₂ alkyl, carbonyl-C ₁ -C ₆ alkyl, phenyl, aryl unsubstituted or further substituted one or more times with the radical R ³ and wherein the radical R ^{3 can represent} one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy , carbonyl-C ₁ -C ₆ -alkyl-, phenyl-, sulfono-, their esters and salts, sulfamoyl-, carbamoyl-, phospho-, phosphono-, phosphonooxy- and their salts and esters, the amino-, carbamoyl- and sulfamoyl groups of the radical R ³ continue to be unsubstituted or can be mono- or disubstituted by hydroxy-, C ₁ -C ₃ -alkyl-, C ₁ -C ₃ -alkoxy- and the radicals R ¹ and R ² together can form a group -B-and -B- represents one of the following groups: (-CHR ⁴ -) _n , (-CR ⁴ = CH-) _m and where R ^{4 is} a substituent as defined as R ³ and n represents an integer from 1 to 6 and m represents one represents an integer from 1 to 3.

Examples:

Hydroxylamines

N, N-dipropylhydroxylamine

 N, N-diisopropylhydroxylamine

 N-hydroxypyrrolidine

 N-hydroxypiperidine

 N-hydroxyhexahydroazepine

 N, N-dibenzylhydroxylamine

 Phenylhydroxylamine

 3-hydroxylamino-3-phenylpropionic acid

 2-hydroxylamino-3-phenylpropionic acid

 N-sulfomethylhydroxylamine

Compounds of the general formula II are:

where X stands for one of the following groups: (-N = N-), (-N = CR ¹⁰ -) _p , (-CR ¹⁰ = N-) _p , (-CR ¹¹ = CR ¹² -) _p

or and p is 1 or 2,

where the radicals R ⁹ to R ¹² , R ¹⁵ and R ^{16 can be} identical or different and can independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₅ 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 R ⁹ to R ¹² , R ¹⁵ and R ^{16 can} furthermore be unsubstituted or mono- or disubstituted by hydroxy, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy , and wherein the radicals R ¹⁵ and R ¹⁶ can form a common group -G- and -G- represents one of the following groups: (-CR ⁵ = CR ⁶ -CR ⁷ = CR ^8- ) or (-CR ⁸ = CR ⁷ -CR ⁶ = CR ⁵ -).

The radicals R ⁵ to R ⁸ 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, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -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 R ⁵ to R ⁸ further may be unsubstituted or mono- or disubstituted with hydroxy, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy and where the C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl -C ₁ -C ₆ alkyl, phenyl, aryl groups of the radicals R ⁵ to R ^{8 may be} unsubstituted or may furthermore be substituted one or more times with the radical R ¹⁸ and the radical R ^{18 can be} one of the following groups : Hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ alkyl, phenyl, aryl, and their esters and salts and where the carbamoyl, sulfamoyl, amino groups of the radical R ^{18 can be} unsubstituted or can furthermore be mono- or disubstituted with the radical R ¹⁹ and the radical R ^{19 can be} one of the following

Groups can be: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ 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 Are compounds of general structure III;

The radicals R ⁵ to R ¹² 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, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -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 R ⁵ to R ^{12 may} furthermore be unsubstituted or mono- or disubstituted by hydroxy, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy and where the C ₁ -C ₁₂ -alkyl-, C ₁ -C ₆ -alkyloxy-, carbonyl-C ₁ -C ₆ -alkyl, phenyl, aryl, aryl-C ₁ -C ₆ -alkyl groups of the radicals R ⁵ to R ¹² unsubstituted or furthermore one or more times can be substituted with the radical R ¹³ and the radical R ^{13 can represent} one of the following groups:

Hydrogen, halogen, hydroxy, formyl, carboxy and their Salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and their esters and salts and where the carbamoyl, sulfamoyl, amino groups of the radical R ^{13 can be} unsubstituted or can furthermore be mono- or disubstituted by the radical R ¹⁴ and the radical R ^{14 can be} one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ 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 = CR ¹⁰ -) _m , (-CR ¹⁰ = N-) _m , (-CR ¹¹ = CR ¹² -) _m

and m is 1 or 2.

What has been said above applies to the radicals R ⁵ to R ⁸ and R ¹⁰ to R ¹² .

R ¹⁷ can be: hydrogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkylcarbonyl, their C ₁ -C ₁₀ alkyl and C ₁ -C ₁₀ alkylcarbonyl unsubstituted or with a radical R ^{18 which} , like R ^{3 is} defined, can be substituted one or more times.

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

The radicals R ⁵ to R ⁸ 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, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -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 R ⁵ to R ^{8 can} furthermore be unsubstituted or mono- or disubstituted by hydroxy, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy and where the C ₁ -C ₁₂ -alkyl-, C ₁ -C ₆ -alkyloxy-, carbonyl-C ₁ -C ₆ -alkyl-, phenyl-, aryl groups of the radicals R ⁵ to R ^{8 are} unsubstituted or can furthermore be substituted one or more times with the radical R ¹⁸ and the radical R ^{18 can represent} one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ -a lkyloxy, carbonyl-C ₁ -C ₆ alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and their esters and salts, and the carbamoyl, sulfamoyl, amino groups of the radical R ^{18 are} unsubstituted or continue to be used once or twice the radical R ¹⁹ can be substituted and the radical R ^{19 can represent} one of the following groups: hydrogen, hydroxyl, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -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-hydroxybenzotriazole

 2,3-bis (4-carboxyphenyl) -4,6-dinitro-2,3-dihydro-1-hydroxy-benzotriazole

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

4,6-dinitro-2,3-di-p-tolyl-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-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-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-hydroxy-benzotriazole

 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 mono hydrochloride

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-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-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-l-oxide

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

 2- (4-chlorophenyl) -6-nitro-2H-benzotriazole-l-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-l-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, pyridine, 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 benzofused derivatives such as: indoles, isoindoles, indolizines, indazoles,

Benzimidazoles, benztriazoles, quinolines, isoquinolines,

Phthalazines, quinazolines, quinoxalines, phenazines, benzazepines, benzothiazoles, benzoxazoles. Likewise preferred are condensed N-heterocycles such as triazolo and tetrazolo compounds which have at least one N-hydroxy, oxime, N-oxi, N, N-dioxi function and in addition to N a further heteroatom such as O, S, Se, Te 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] pyridines

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 [l, 5-a] pyrazines

Tetrazolo [1,5-a] quinoxaline

Tetrazolo [1,5-b] [1,2,4] triazine tetrazolo [5,1-c] [1,2,4] triazine tetrazolo [1,5-d] [1,2,4] triazine 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-tetrahydroisoquinolino) propionic acid

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

The multi-component system (d) according to the invention comprises, for example, aliphatic ethers, aryl-substituted alcohols such as 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

 Veratryl alcohol

 Coniferyl alcohol

Olefins (alkenes)

e.g.

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

preferably phenol ether

such as.

 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

preferably carbonyl compounds such as

 4-aminobenzophenone

 4-acetylbiphenyl

 Benzophenone

 Benzil

 Benzophenone hydrazone

 3,4-dimethoxybenzaldehyde

 3,4-dimethoxybenzoic acid

 3,4-dimethoxybenzophenone

 4-dimethylaminobenzaldhyd

 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), the reaction is mediated in cascade form or the actual mediator compounds are recycled in situ, i.e. during the reaction and surprisingly leads to a substantial improvement in kappa reduction or a reduction in mediator dosage.

The additives mentioned under d) in claim 1 are preferably used in amounts of 0.01 to 0.5 mg per g of lignin-containing material. 0.01 to 0.1 mg per g of lignin-containing material are particularly preferably used. The free amine of the respective mediator is preferably used in a mediator / amine ratio of 100: 1 to 1: 1, particularly preferably 20: 1 to 1: 1, particularly preferably 10: 1 to 2: 1.

The effectiveness of the multi-component system when changing, breaking down or bleaching lignin, lignin-containing materials or similar substances is often further increased if Mg ²⁺ ions are present in addition to the components mentioned. The Mg ²⁺ ions can be used, for example, as a salt, such as MgSO ₄ . The concentration is in the range of 0.1-2 mg / g of lignin-containing material, preferably 0.2-0.6 mg / g.

In some cases, a further increase in the effectiveness of the multicomponent system according to the invention can be achieved in that the multicomponent system, in addition to the Mg ²⁺ ions, also complexing agents such as, for example, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediamine triacetic acid (HEDTA), diethylenetriaminepentamethylene (phosphinetriaminepentamethylene DTMPA), nitrilotriacetic acid (NTA), polyphosphoric acid (PPA) etc. The concentration is in the range of 0.2-5 mg / g of lignin-containing material, preferably 1-3 mg.

The merh component system according to the invention is used in a process for treating lignin, for example, by mixing the respectively selected components a) to e) according to claim 1 simultaneously or in any order with an aqueous suspension of the lignin-containing material.

A method using the multicomponent system according to the invention in the presence of acid is preferred fabric or air at normal pressure up to 10 bar and in a pH range of 2 to 11, at a temperature of 20 to 95 ° C, preferably 40 - 95 ° C, and a consistency of 0.5 to 40%.

A finding that is unusual and surprising for the use of enzymes in pulp bleaching is that when the multicomponent system according to the invention is used, a

Increasing the consistency allows a significant increase in kappa reduction.

Surprisingly, an increased consistency led to better activity of the multi-component system.

For economic reasons, a process according to the invention is preferably carried out at consistencies of 12 to 15%, particularly preferably 14 to 15%.

Surprisingly, it was also found that an acidic wash (pH 2 to 6, preferably 4 to 5) or Q stage (pH 2 to 6, preferably 4 to 5) before the enzyme mediator stage led to a considerable reduction in the kappa number in some pulps Comparison to treatment without this special pretreatment leads. The substances used for this purpose (such as EDTA, DTPA) are used as chelating agents in the Q stage. They are preferably used in concentrations of 0.1% / to 1% / to, particularly preferably 0.1% / to to 0.5% / to.

In the process according to the invention, preferably 100 to 100,000 IU enzyme per g lignin-containing material are used. 1,000 to 40,000 IU enzyme per g lignin-containing material are particularly preferably used. In the process according to the invention, preferably 0.01 mg to 100 mg of oxidizing agent are used per g of lignin-containing material. 0.01 to 50 mg of oxidizing agent per g of lignin-containing material are particularly preferably used.

In the method according to the invention, 0.5 to 80 mg of mediator per g of lignin-containing material is preferably used. 0.5 to 40 mg of mediator per g of lignin-containing material is particularly preferably used.

Using the multi-component system according to the invention, for example in the bleaching of sulfate pulps (soft wood), it was possible to achieve the completely surprising result of reducing the kappa number from approximately 30 to 10 within 1 to 4 hours, even with a high consistency in the range of approximately 15%. wherein by adding components d) and e) according to claim 1, a considerable reduction in the concentration of component c) (mediator) is possible.

At the same time, reducing agents can be added which, together with the oxidizing agents present, serve to set a certain redox potential.

Sodium bisulfite, sodium dithionite, ascorbic acid, thio compounds, mercapto compounds or glutathione etc. can be used as reducing agents. The reaction takes place, for example, in the case of laccase with the addition of oxygen or oxygen pressure, in the case of the peroxidases (for example lignin peroxidases, manganese peroxidases) with hydrogen peroxide. For example, the oxygen can also be generated in situ by hydrogen peroxide + catalase and hydrogen peroxide by glucose + GOD or other systems.

In addition, radical formers or radical scavengers (trapping, for example, OH or OOH radicals) can be added to the system. These can improve the interaction within the Red / Ox and radical mediators.

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

These are important in conjunction with chelating agents as radical formers or red / ox centers. The salts form cations in the reaction solution. Such ions include Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ³⁺ , Mn ⁴⁺ , Cu ²⁺ , Ca ²⁺ , Ti ³⁺ , Cer ⁴⁺ , Al ³⁺ .

The chelates present in the solution can also serve as mimic substances for the enzymes, for example for the laccases (copper complexes) or for the lignin or manganese peroxidases (heme complexes). Mimic substances are substances that simulate the prosthetic groups of (here) oxidoreductases and can catalyze oxidation reactions, for example. NaOCl can also be added to the reaction mixture. In combination with hydrogen peroxide, this compound can form singlet oxygen.

Finally, it is also possible to work using detergents. Non-ionic, anionic, cationic and amphoteric surfactants are suitable as such. The detergents can improve the penetration of the enzymes and mediators into the fiber.

It may also be beneficial for the reaction to add polysaccharides and / or proteins. Here in particular as polysaccharides are glucans, mannans, dextrans, levans,

Pectins, alginates or plant gums and / or own polysaccharides formed by the fungi or produced in the mixed culture with yeasts and to name gelatin and albumin as proteins.

These substances mainly serve as protective colloids for the enzymes.

Other proteins that can be added are proteases such as pepsin, bromelin, papain, etc. These can include serve to achieve better access to lignin by breaking down the extensin C present in the wood, a protein rich in hydroxyproline.

Other protective colloids are amino acids, simple sugar, oligomer sugar, PEG types of various moles molecular weights, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes in question.

The process according to the invention can be used not only in the delignification (bleaching) of sulfate, sulfite, organosol, etc. Pulp and wood pulp are used, but also in the production of pulp in general, whether from wood or annual plants, if defibrillation by the usual cooking methods (possibly connected with mechanical processes or pressure) i.e. a very gentle cooking up to kappa numbers, which can be in the range of approx. 50 - 120 kappa, is guaranteed.

In the bleaching of cellulose as well as in the production of cellulose, the treatment can be repeated several times, either after washing and extraction of the treated material with NaOH or without these intermediate steps. This leads to kappa values which can be reduced still further and to substantial increases in whiteness. Likewise, an O ₂ stage can be used before the enzyme / mediator treatment or, as already mentioned, an acid wash or a Q stage (chelate stage) can be carried out.

A similar procedure is used for the "liquefaction" of coal (hard coal, lignite) as for the delignification (bleaching) of wood or annual plant pulp.

The invention is explained in more detail below with the aid of examples: Example 1/2 Example: Enzymatic bleach and sulfate pulp.

Example 1:

30 g dry cellulose (Softwood O ₂ delignified), consistency 30% (approx. 100 g moist) are added to the following solutions:

1) 120 ml of tap water are mixed with stirring with 150 mg of hydroxybenzotriazole (HBT), 15 mg of benzotriazole (BT) and 3 mg of benzophenone (B), the pH is adjusted with 0.5 m H ₂ SO ₄ so that after addition of the pulp and the enzyme pH 4.5 results. For this, 4,000 IU (1 IU = conversion of 1 μM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ° C and incubated under 1-10 bar pressure for 1-4 hours.

The fabric is then washed over a nylon sieve (30 µm) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.

After washing the fabric again, the kappa number is determined.

(see table 1)

(see table 2) Changes to Example / Table 2: with 75 mg hydroxybenzotriazole, 7.5 mg benzotriazole and 0.02 mg veratryl alcohol.

Example 3

Example: Enzymatic bleaching of sulfate pulp.

30 g dry cellulose (Softwood), consistency 30% (approx. 100 g moist) are added to the following solution:

1. 120 ml of tap water are mixed with 60 mg of DTPA and 15 mg of MgSO ₄ with stirring. The pH is adjusted with 0.5 M H2SO ₄ so that pH 4.5 results after adding the pulp and the enzyme. For this, 4,000 IU (1 IU = conversion of 1 μM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar overpressure for 1-4 hours.

The fabric is then washed over a nylon sieve (30 μm) and extracted for 1 hour at 60 ° C., 8% fabric density and 2% NaOH per g fabric.

After washing the fabric again, the kappa number is determined. The results are shown in Table 3.

Example 4

Example: Enzymatic bleaching of sulfate pulps with

 upstream Q stage.

30 g dry cellulose (Softwood 1 and Softwood 2), consistency 30% (approx. 100 g wet) become the following solutions

given:

1) Q stage: 120 ml of tap water are mixed with 90 mg of DTPA and the pH is adjusted with 0.5 m of H2SO ₄ so that pH 4.5 results after the addition of the cellulose. The solution is made up to 200 ml and mixed for 2 min with a dough kneader.

The fabric is then left in a sealed beaker at 90 ° C.

Then it is washed well (tap water), the fabric is brought to 30% consistency and added to the following solution:

2) Laccase / extraction stage: 120 ml of tap water are included

300 mg of hydroxybenzotriazole were added with stirring. The pH is adjusted with 0.5 m H2S04 so that pH 4.5 results after adding the pulp and the enzyme. For this, 4,000 IU (1 IU = conversion of 1 μM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours.

The fabric is then washed over a nylon sieve (30 µm) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.

After washing the fabric again, the kappa number is determined. In parallel approaches, the kappa number is determined according to the Q level. The results are shown in Table 4.

Example 5

Example: Enzymatic bleach and sulfate pulp.

30 g dry cellulose (Softwood 1 / Softwood 2), consistency 30% (approx. 100 g wet) are added to the following solutions:

120 ml of tap water are mixed with 300 mg of hydroxybenztriazole (Softwood 1) and 150 or 300 mg of hydroxybenztriazole (Softwood 2) with stirring, the pH is adjusted with 0.5 m H ₂ SO ₄ so that after adding the pulp and Enzyme pH 4.5 results. For this, 4,000 IU (1 IU = conversion of 1 μM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. It is made up to 200 ml and the substance is added. It is for 2 min. mixed with a dough kneader. At 15% consistency, 30 g dry = 100 g moist cellulose are added to a total amount of 200 g, ie 80 ml tap water are specified and made up to 100 ml. Otherwise the procedure is as for 10% consistency.

The substance is then placed in a reaction bomb preheated to 45 ° C and incubated under 1-10 bar pressure for 1-4 hours.

The fabric is then washed over a nylon sieve (30 µm) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.

After washing the fabric again, the kappa number is determined.

The results are shown in Table 5.

Examples / tables:

example 1

Enzymatic bleaching of sulfate pulp (Softwood) (O ₂ delignified)

2.) 3.) under pressure 10 bar

4.) 5.) Air

B = benzophenone

Laccase

Example 2

Enzymatic bleaching of sulfate pulp (Softwood) (O ₂ delignified)

 VA = veratryl alcohol

 L = laccase

Example 3

Enzymatic bleaching of sulfate pulp (Softwood)

 (A) = 2 mg / g substance DTPA

0.5 mg / g substance MgSO ₄

L = laccase

Example 4

L = Laccase kappa reduction: SW1: 37.2% without Q and 47.2% with Q SW2: 27.8% without Q and 36.6% with Q

Example 5:

Example 6

Example: Enzymatic bleach and sulfate pulp

30 g dry cellulose (Softwood O ₂ delignified), consistency 30% (approx. 100 g moist) are added to the following solutions:

1) 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole with stirring, the pH is adjusted with 0.5 m H ₂ SO ₄ so that pH 4.5 results after addition of the pulp and the enzyme. 1000 or 10,000 IU (IU = conversion of 1 μM syringaldazine / min / ml enzyme) Laccase from Coriolus versicolor per g substance are added. 1000 IU lignin peroxidase / g substance, 1000 IU peroxidase (horseradish) / g substance and 1000 IU tyrosinase / g substance are added in separate batches. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

Then the substance is placed in a reaction bomb preheated to 45 ° C and under 1-10 bar pressure for 1-4

Incubated for hours.

The fabric is then washed over a nylon sieve (30 μm) and extracted for 1 hour at 60 ° C., 8% fabric density and 2% NaOH per g fabric.

After washing the fabric again, the kappa number is determined (see Table 6). Table 6)

Example 7

Example: Enzymatic bleach and sulfate pulp

30 g dry cellulose (Softwood / Hardwood), consistency 30% (approx. 100 g wet) are added to the following solutions:

1) 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole with stirring, the pH is adjusted with 0.5 m H2SO ₄ so that pH 4.5 results after addition of the pulp and the enzyme. For this purpose, 20,000 IU (IU = conversion of 1 μM syringaldazine / min / ml enzyme) laccase from Coriolus versico given per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours.

The fabric is then washed over a nylon sieve (30 µm) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.

After washing the fabric again, the kappa number is determined.

A Kappa reduction of 15 to 6 Hardwood and from 30 to 15 at Softwood was reduced.

Example 8

Example: Enzymatic bleaching of straw pulp

30 g dry straw pulp, consistency 30% (approx. 100 g moist) are added to the following solutions:

1) 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole with stirring, the pH is adjusted with 0.3 m H ₂ SO ₄ so that pH 4, 5 results after addition of the cellulose and the enzyme. For this, 20,000 IU (IU = conversion of 1 μM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes. The substance is then placed in a reaction bomb preheated to 45 ° C and incubated under 1-10 bar pressure for 1-4 hours.

The fabric is then washed over a nylon sieve (30 μm) and extracted for 1 hour at 60 ° C., 8% fabric density and 2% NaOH per g fabric.

After washing the fabric again, the kappa number is determined.

A kappa number reduction of 65 to 14 was achieved.

Example 9

Example: Enzymatic bleaching of sulfite pulp

30 g dry cellulose (sulfite pulp), consistency 30% (approx. 100 g moist) are added to the following solutions:

1) 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole with stirring, the pH is adjusted with 0.5 m H ₂ SO ₄ so that pH 4.5 results after addition of the pulp and the enzyme. For this, 20,000 IU (IU = conversion of 1 μM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours. The fabric is then washed over a nylon sieve (30 µm) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric.

After washing the fabric again, the kappa number is determined.

A kappa number reduction of 15.5 to 5.2 was achieved.

Example 10

Enzymatic bleaching of sulfate pulp (Softwood / O ₂ delignified / Hardwood (double treatment))

30 g dry cellulose (Hardwood or Softwood), consistency 30% (approx. 100 g wet) are added to the following solutions:

1) 120 ml of tap water are mixed with 300 mg of hydroxybenzotriazole with stirring, the pH is adjusted with 0.5 m H ₂ SO ₄ so that pH 4.5 results after addition of the pulp and the enzyme. For this, 20,000 IU (IU = conversion of 1 μM syringaldazine / min / ml enzyme) Coriolus versicolor laccase are added per g of substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours. The fabric is then washed over a nylon sieve (30 µm) and extracted for 1 hour at 60 ° C, 8% fabric density and 2% NaOH per g fabric. a) Immediately after the incubation, enzyme + mediator is added without washing, mixed (2 min) and the reaction is carried out again (same metering as in the first treatment). b) Immediately after the incubation, after the washing step and the pressing of the substance to 30% density, the reaction is carried out again by adding all components. c) After washing the fabric again, after extracting and pressing the fabric to 30% fabric density, the reaction is carried out again by adding all components.

Hardwood: Kappa number reduction Softwood: Kappa number reduction a) 15 to 5 a) 15.5 to 4.2

b) 15 to 3.5 b) 15.5 to 3

c) 15 to 2.5 c) 15.2 to 2.2

Example 11

Example: Enzymatic bleaching of wood pulp

30 g dry wood pulp (spruce), consistency 30% (approx. 100 g wet) are added to the following solutions:

1) 120 ml of tap water are mixed with 300 mg of N-hydroxyhexahydroacepine with stirring, the pH is adjusted with 0.5 m H ₂ SO ₄ so that pH 4.5 results after addition of the cellulose and the enzyme. For this, 1000 IU (IU = Um set of 1 μM syringaldazine / min / ml enzyme) Laccase from Coriolus versicolor per g substance. The solution is made up to 200 ml and the substance is added. It is mixed with a dough kneader for 2 minutes.

The substance is then placed in a reaction bomb preheated to 45 ° C. and incubated under 1-10 bar pressure for 1-4 hours.

The fabric is then washed over a nylon sieve (30 μm).

A whiteness increase of 7% ISO whiteness was achieved.

Claims

Claims

1. System for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances which is characterized in that it is a multi-component system, 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 or olefins (alkenes) and e. 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 it also comprises Mg ²⁺ ions in addition to said components a) to e).

3. Multi-component system according to claim 1 or 2, characterized in that an oxidation catalyst is used, preferably oxidoreductases of classes 1.1.1 - 1.97.

4. Multi-component system according to claim 3, characterized in that oxidoreductases which use oxygen, peroxides or quinones as electron acceptors are used.

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 are used in one- or multi-component systems.

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,

where 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, C ₁ -C ₁₂ -alkyl-, carbonyl-C ₁ -C ₆ -alkyl- , phenyl, aryl, the C ₁ -C ₁₂ alkyl, carbonyl-C ₁ -C ₆ alkyl, phenyl, aryl unsubstituted or further substituted one or more times with the radical R ³ and wherein the radical R ^{3 can represent} one of the following groups: hydrogen, halogen, hydroxyl, formyl, carboxy and salts and esters thereof, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy , carbonyl-C ₁ -C ₆ -alkyl-, phenyl-, sulfono-, their esters and salts, sulfamoyl-, carbamoyl-, phospho-, phosphono-, phosphonooxy- and their salts and esters where the amino-, carbamoyl- and sulfamoyl groups of the radical R ^{3 can} furthermore be unsubstituted or mono- or disubstituted by hydroxy-, C ₁ -C ₃ -alkyl-, C ₁ -C ₃ -alkoxy- and the radicals R ¹ and R ² together form a group -B- and -B- represents one of the following groups: (-CHR ⁴ -) _n ,

(-CR ⁴ = CH-) _m and where R ^{4 is} a substituent defined as R ³ and n represents an integer from 1 to 6 and m represents an integer from 1 to 3.

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

 Formula II

where X stands for one of the following groups: (-N = N-), (-N = CR ¹⁰ -) _p , (-CR ¹⁰ = N-) _p , (-CR ¹¹ = CR ¹² -) _p

and p is 1 or 2, where the radicals R ⁹ to R ¹² , R ¹⁵ and R ^{16 can be} identical or different and can independently represent one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and salts and esters thereof, amino, nitro, C ₁ -C ₁₂ alkyl !, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ 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 R ⁹ to R ¹² , R ¹⁵ and R ¹⁶ continue to be unsubstituted or mono- or disubstituted with hydroxy, C ₁ -C ₃ alkyl, C ₁ -C ₃ -alkoxy may be substituted, and wherein the radicals R ¹⁵ and R ¹⁶ can form a common group -G- and -G- represents one of the following groups: (-CR ⁵ = CR ⁶ -CR ⁷ = CR ⁸ -) or (-CR ⁸ = CR ⁷ -CR ⁶ = CR ⁵ -); the radicals R ⁵ to R ⁸ 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, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -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 R ⁵ to R ^{8 can} furthermore be unsubstituted or mono- or disubstituted by hydroxy, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy and where the C ₁ -C ₁₂ -alkyl-, C ₁ -C ₆ -alkyloxy-, carbonyl-C ₁ -C ₆ -alkyl-, phenyl-, aryl groups of the radicals R ⁵ to R ^{8 are} unsubstituted or can furthermore be substituted one or more times with the radical R ¹⁸ and where the radical R ^{18 can represent} one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and also their salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, aryl, and their esters and salts, and the carbamoyl, sulfamoyl, amino groups of the radical R ^{18 are} unsubstituted or furthermore mono- or disubstituted by the radical R ¹⁹ can and wherein the radical R ^{19 can be} one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ alkyl, phenyl, aryl. Multi-component system according to Claim 6, characterized in that compounds of the general formula III are used as compounds containing NO, NOH or H-NR-OH,

where X stands for one of the following groups: (-N = N-), (-N = CR ¹⁰ -) _p , (-CR ¹⁰ = N-) _p , (-CR ¹¹ = CR ¹² -) _p

and p is 1 or 2, the radicals R ⁵ to R ¹² 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, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ 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 can furthermore be unsubstituted or mono- or disubstituted with hydroxy, C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy and where the C ₁ -C ₁₂ alkyl -, C ₁ -C ₆ alkyloxy, carbonyl, C ₁ -C ₆ alkyl, phenyl, aryl, aryl, C ₁ -C ₆ alkyl groups of the radicals R ⁵ to R ^{12 are} unsubstituted or continue to be - Can be substituted several times with the radical R ¹³ and the radical R ^{13 can represent} one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl , C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and esters and wherein the carbamoyl, sulfamoyl, amino groups of the radical R ^{13 are} unsubstituted or continue to be - Or can be substituted twice with the radical R ¹⁴ and the radical R ^{14 can represent} one of the following groups: hydrogen, hydroxy, formyl, carboxy and their salts and esters, amino , Nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ 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.

Formula IV where X represents one of the following groups: (-N = N-), (-N = CR ¹⁰ -) _p , (-CR ¹⁰ = N-) _p , (-CR ¹¹ = CR ¹² -) _p

and p is 1 or 2; for the radicals R ⁵ to R ⁸ and R ¹⁰ to R ¹² , what has been said above applies;

R ¹⁷ can be: hydrogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkylcarbonyl, their C ₁ -C ₁₀ alkyl and C ₁ -C ₁₀ alkylcarbonyl unsubstituted or with a radical R ^{18 which} , like R ^{3 is} defined, can be substituted one or more times.

11. Multi-component system according to claim 6, characterized in that as NO, NOH or H-NR-OH-containing compounds 1-hydroxybenzotriazole and the tautomeric benzo triazol-1-oxides, and their esters and salts are used according to the following formula V.

(Formula V) the radicals R ⁵ to R ⁸ 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, C ₁ -C ₁₂ - alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ 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 R ⁵ to R ^{8 can} furthermore be unsubstituted or mono- or disubstituted by hydroxy, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy and the Ci-C ^ -alkyl- , C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ alkyl, phenyl, aryl groups of the radicals R ⁵ to R ^{8 are} unsubstituted or can furthermore be substituted one or more times with the radical R ¹⁸ and where the radical R ^{18 can represent} one of the following groups: hydrogen, halogen, hydroxy, formyl, carboxy and their salts and esters, amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ -alkyloxy, carbonyl-C ₁ -C ₆ -alkyl, phenyl, aryl, sulfono, sulfeno, sulfino and esters and where the carbamoyl, sulfamoyl, amino groups of the radical R ^{18 are} unsubstituted or continue to be one or two times can be substituted with the radical R ¹⁹ and the radical R ^{19 can represent} one of the following groups: hydrogen, hydroxyl, formyl, carboxy and their salts and esters, Amino, nitro, C ₁ -C ₁₂ alkyl, C ₁ -C ₆ alkyloxy, carbonyl-C ₁ -C ₆ alkyl, phenyl, aryl.

12. Multi-component system according to claim 6, characterized in that those containing azoles are used as NO, NOH or H-NR-OH-containing compounds.

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

[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] quinolines

 [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] pyridines

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

Tetrazolofl, 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 can be used.

14. Multi-component system according to claim 1 or 2, characterized in that the oxidizing agent is, for example, air, oxygen, ozone, H2O ₂ , organic peroxides, peracids such as peracetic acid, formic acid, persulfuric acid, persitric acid, metachloroperoxibenzoic acid, perchloric acid, perchlorates, peracetates, persulfates, peroxides , Oxygen species and radicals such as OH, OOH singlet oxygen, ozone, superoxide (O ₂ -), ozonide, dioxygenyl cation (O ₂ ⁺ ), dioxirane, dioxetane, 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 example

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

 Are coniferyl alcohol.

16. Multi-component system according to claim 1 or 2, characterized in that compounds of component d) olefins (alkenes) e.g.

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-Benzyl cinnamic anilide.

17. Multi-component system according to claim 1 or 2, characterized in that compounds of component d) 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

 Are anisole.

18. Multi-component system according to claim 1 or 2, characterized in that compounds of component d) carbonyl compounds e.g. 4-aminobenzophenone

4-acetylbiphenyl

 Benzophenone

Benzil Benzophenone hydrazone

 3,4-dimethoxybenzaldehyde

 3,4-dimethoxybenzoic acid

 3,4-dimethoxybenzophenone

 4-dimethylaminobenzaldhyd

 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-hydroxybenoic acid

 4-hydroxybenzaldehyde

 Salicylaldehyde

 Vanillin

 Are vanillic acid.

19. Multi-component system according to claim 1 or 2, characterized in that component e) is used as free amine in the case of in situ generation or reaction mediation in cascade form with hydroxybenzotriazole, benzotriazole.

20. A process for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances, characterized in that the components a) to e) according to claim 1 selected in each case are mixed simultaneously or in any order with an aqueous suspension of the lignin-containing material.

21. The method according to claim 20, characterized in that the reaction in a pH range of 2 to 11, at a temperature of 20 to 95 ° C, preferably 40 to 95 ° C, and a consistency of 0.5 to 40% and is carried out under air or oxygen at normal pressure or 1-10 bar.

22. The method according to claim 20 and 21, characterized in that the consistency is preferably 13-15%.

23. The method according to claim 20 or 21, characterized in that an acid wash or Q stage is used before the reaction.

24. The method according to claim 23, characterized in that the acidic washing is carried out at 60-100ºC at pH 4-5.5 for 30-90 min and 4-20% consistency.

25. The method according to claim 23, characterized in that the Q stage (with 0.05-1.0%, preferably 0.2-0.5% chelating agent) at 60-100 ° C at pH 4-5.5 for 30 -90 min and 4-20% consistency is carried out.

26. The method according to claim 23, characterized in that for the acidic wash and the Q stage 1 hour, 90 ° C, pH 4.5-5 and 10% consistency are observed.

27. The method according to claim 20 and 21, characterized in that the reaction solution hemicellulases, cellulases, amylases, pectinases or lipases or a mixture consisting of two or more of these enzymes are added.

28. The method according to claim 20 and 21, characterized in that modified enzymes, enzyme components,

prosthetic groups or mimic substances such as heme groups and compounds containing heme groups can be used.

29. The method according to claim 20 and 21, characterized in that in addition to these substances, phenolic compounds and / or non-phenolic compounds with one or more benzene nuclei are used.

30. The method according to claim 20 and 21, characterized in that reducing agents are added to the reaction solution.

31. The method according to claim 30, characterized in that sodium bisulfite, sodium dithionite, ascorbic acid, thiol compounds, mercapto compounds or glutathione are used as reducing agents.

32. The method according to claim 20 and 21, characterized in that oxygen is generated by H2O ₂ + catalase or H ₂ O ₂ by GOD + glucose in situ.

33. The method according to claim 20 and 21, characterized in that the reducing solution cation-forming metal salts are added.

34. The method according to claim 33, characterized in that as cations Fe ² +, Fe ³⁺ , Mn ²⁺ , Mn ³⁺ , Mn ⁴⁺ , Ca ²⁺ , Cu ²⁺ , Ti ³⁺ , Ce ⁴⁺ , Al ³⁺ can be used.

35. The method according to claim 20 and 21, characterized in that additional complexing agents are added to the reaction solution.

36. The method according to claim 35, characterized in that as a complexing agent ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentamethylenephosphonic acid (DTMPA), nitrilotriacetic acid (NTA), polyphosphoric acid (PP) or polyphosphoric acid - or copper complexors, e.g. Diethylamine,

 Hydroxylamine can be used.

37. The method according to claim 20 and 21, characterized in that NaOCl is used.

38. The method according to claim 20 and 21, characterized in that additional detergents are used.

39. The method according to claim 38, characterized in that non-ionic, ionic, anionic, cationic and amphoteric surfactants are added as detergents.

40. The method according to claim 20 and 21, characterized in that in addition polysaccharides and / or proteins are added to the reaction solution.

41. The method according to claim 40, characterized in that as polysaccharides glucans, mannans, dextrans, levans, Pectins, alginates or plant gums and / or own polysaccharides formed by the fungi or produced in the mixed culture with yeasts can be used.

42. The method according to claim 40, characterized in that gelatin and / or albumin are used as proteins.

43. The method according to claim 20 and 21, characterized in that the additives used are simple sugar, oligomer sugar, amino acids, polyethylene glycols, polyethylene oxides, polyethyleneimines and polydimethylsiloxanes

 become.

44. The method according to claim 20 and 21, characterized in that the system radical formers or radical scavengers are added.

45. The method according to claim 1 and 2 and 20 and 21, characterized in that it is used for the delignification or bleaching of pulps in time according to all known cooking methods.

46. The method according to claim 45, characterized in that the cooking process sulfate, sulfite, organosol, ASAM process, enabatch process and others. be performed.

47. The method according to claim 46, characterized in that it is after, between or before all the usual bleaching stages and other sequences such as Q level, acid wash, etc. is performed.

48. The method according to claim 45-47, characterized in that the method is carried out in several stages, with washing or washing and extraction with alkali or neither washing nor extraction taking place between each stage.

49. Multi-component system according to claim 1 for coal liquefaction.