DE102008005875A1 - Use of polymers with amino or ammonium groups to increase the durability of wood over woody fungi - Google Patents

Abstract

The present invention relates to wood preservatives which contain a content of amino-containing polymeric hydrocarbon compounds and are preferably polycationic. The use according to the invention of polymers containing amino groups, which are preferably cationic by virtue of a content of quaternary amino groups, is based on the surprising finding that this combination of properties of the polymers imparts fungicidal properties to the wood, on the one hand, and the polymers on the other treated wood so that their fungicidal properties are long available for the wood. In a further embodiment of the invention, the polymers containing amino groups, which preferably contain quaternary amino groups, are applied to wood as adhesion promoters for organic coatings, for example paints or plastic films.

Description

The The present invention relates to wood preservatives containing a content at amino-containing polymeric hydrocarbon compounds contain and are preferably polycationic.

The inventive use of amino-containing polymers containing primary, secondary and / or tertiary amino groups, preferably cationic by containing quaternary amino groups as effective constituents of wood preservatives based on the surprising finding that this combination of properties of the polymers on the one hand fungicidal properties on the other hand, that the polymers are permanently associated with the treated wood so that their fungicidal properties are long available to the wood. If the polymers contain primary, secondary and / or tertiary amino groups, the fungicidal and / or hydrophobicizing effect can be increased by alkylation, for example by derivatization with C ₁ to C ₁₂ straight-chain or branched alkyl or alkenyl radicals.

In In one embodiment, the polymers are formaldehyde fixed in the wood.

In Another embodiment of the invention will be amino-containing polymers, preferably quaternary Contain amino groups, as adhesion promoters for organic Coatings, such as paints or plastic films, on Wood applied.

State of the art

The DE 199 21 898 A1 discloses a coating process for plastic surfaces to provide them with antimicrobial action. The antimicrobial effect is achieved by grafting amino-containing, aliphatically unsaturated monomers onto the plastic surface; for this grafting reaction, the aliphatically unsaturated monomers are activated by UV irradiation.

The EP 0 862 858 A1 discloses a copolymer for antimicrobial coating of plastic surfaces. The antimicrobial copolymer is obtained by graft copolymerization of tert-butylaminoethyl methacrylate with one or more aliphatically unsaturated monomers. The copolymerization preferably takes place directly on the substrate surface to be coated antimicrobially.

Known Wood preservatives which have a fungicidal action, for example 3-iodo-2-propynyl butylcarbamate (IPBC) and triazoles (propiconazole, tebuconazole) are disadvantageous in that as they are washed out of the treated wood. Subsequently is their biocidal effect no longer available in the wood, On the other hand, they can cause harmful effects to develop the environment.

Object of the invention

It It is an object of the present invention to provide active ingredients for To provide wood preservatives which have fungicidal properties to the wood so that its durability is increased. In particular, it is the object of the present invention, active ingredients to provide for wood preservatives, which make the wood more resistant to fungal attack, especially at high ambient humidity or weathering.

in view of it is one of the former toxic components of wood preservatives Another object of the present invention, wood preservatives for To provide the wood permanently fungus-resistant Lend properties and, in a preferred embodiment, moreover remain permanently in the wood, so for example during weathering not be washed out. Advantageously, the wood preservatives of the invention nevertheless, they are not or only slightly toxic, even if they are not associated with wood, for example during the treatment of the wood or after removal from the wood.

A Another object of the present invention is to components to provide for adhesion agents, the Can be applied to wood and a connection to subsequently applied polymeric layers, for example Provide polymer films, adhesives and / or paints. In a preferred embodiment It is an object of the invention, primer for wood to provide the penetration of wood ingredients, for example the diffusion of tannin into applied layers, for example Coat layers, reduce, preferably completely prevent.

A The preferred object of the invention is to provide Wood preservatives combined with fungicidal properties act as a bonding agent.

General description of invention

The The invention solves the aforementioned objects by the provision amino group-containing polymers, which in a first embodiment act as fungicidal components of wood preservatives, as well as preferably in combination therewith, in the second embodiment as a bonding agent between wood and organic polymer layers Act. In the second embodiment, it is a special one advantageous property of the invention amino group-containing polymers that they have a blocking effect against the penetration of extractives such as tannin or others discoloring substances made of wood in polymer or lacquer layers exhibit. This barrier effect is especially rich in ingredients Wooden matter, as the penetration darker Ingredients reduced in applied polymer layers such as paints or can be prevented. For this purpose is preferably inventive Polymer applied to the wood before applying a paint.

The polymers containing amino groups suitable for the invention, preferably due to their content of quaternary amino groups are polycationic, due to their action after treatment Wood is a functionally unified group. Because the invention as Wood preservatives to be used polymers impart wood fungicides Properties, so that the fungal attack is greatly reduced.

Next the use of the polymers of the invention for the treatment of wood, for example in aqueous composition, They can also be used as part of paints, paints or paints used for wood to these coatings impart fungus-resistant properties and infestation of the varnish to prevent by mold.

In Comparable manner, the inventive Protective agents used to help in the treatment of woods or wood-based materials containing oils, waxes or resins Prevent discoloration by fungi. So are many mushrooms capable of ester bonding in natural oils to cleave enzymatically and the oils even as a source of food to use. As a result, the infestation - usually by discoloring Mushrooms (mold) - compared to untreated samples to be reinforced. This can be prevented by the oils, waxes or resins before the treatment of the wood the protective agents according to the invention are admixed and then impregnated with the mixture.

For the purposes of the invention includes the term wood in addition to solid wood other lignocellulosic materials, such as chipboard, Medium Density Fiberboard, Oriented Strand Boards (OSB), Insulation Boards lignocellulosic, plywood, veneer and packaging materials containing biodegradable compounds, cardboard and Paper.

• 1. Aminogruppenhaltige Polymere, vorzugsweise mit quartären Aminogruppen, die durch Umsetzung eines Präpolymers mit Epichlorhydrin erhältlich sind, wobei das Präpolymer sekundäre und/oder tertiäre Aminogruppen enthält und erhältlich ist durch Umsetzung von Dicarbonsäure mit Dialkylentriamin und/oder Bis(aminoalkyl)amin. Dieses Präpolymer kann auch als Polyamidoamin bezeichnet werden.

The following describes amino-containing polymers which are suitable for carrying out the invention:

• 1. Amino-containing polymers, preferably with quaternary amino groups, which are obtainable by reacting a prepolymer with epichlorohydrin, wherein the prepolymer contains secondary and / or tertiary amino groups and is obtainable by reaction of dicarboxylic acid with dialkylenetriamine and / or bis (aminoalkyl) amine. This prepolymer may also be referred to as polyamidoamine.

For the case that reacted the dicarboxylic acid with dialkylenetriamine was, the prepolymer contains secondary Amino groups derived from the dialkylenetriamine. The implementation with epichlorohydrin then leads to the formation of azetidinium groups, which have a quaternary amino group.

has the prepolymer tertiary amino groups, the come from a bis (aminoalkyl) amine, so are from the tertiary Amino groups by reaction with epichlorohydrin quaternary Amino groups bearing a Methyloxirangruppe as a substituent.

Suitable dicarboxylic acid are C ₂ - to C ₁₈ -, preferably C ₆ - to C ₈ -dicarboxylic acids, it being preferred that the carbon chain is linear and the carboxyl groups are each terminal. Particularly preferred as dicarboxylic acid is adipic acid. Furthermore, it is also possible to use unsaturated C ₂ -C ₁₈ -carboxylic acids and esters, such as monounsaturated ethylenically unsaturated. Examples are methyl acrylate, monomethyl esters of maleic acid or itaconic acid. The prepolymer can also be formed by free radical polymerization of unsaturated nitrogen-functionalized vinyl and / or allyl monomers. suitable Monomers for this include diallylamine, which has secondary amine functions in the prepolymer or methyldiallylamine to give tertiary amine functions in the prepolymer.

Suitable dialkylenetriamine or bis (aminoalkyl) amine components are compounds whose carbon chains each have 1 to 18, preferably 2 to 12, more preferably 2 to 6, carbon atoms, preferably with saturated or at least partially unsaturated branched or unbranched hydrocarbon chains. Particular preference is given to bis (aminoalkyl) amines. As bis (aminoalkyl) amine, for example with a C ₁ - to C ₁₈ -, preferably C ₂ - to C ₈ -alkyl, for example bis (3-aminopropyl) amine can be used.

to Reaction of the dicarboxylic acid to produce the prepolymer the alkylene triamines and bis (aminoalkyl) amines can be used individually, each as a mixture with different hydrocarbon chains and / or as a mixture of the same or different dialkylene triamines and bis (aminoalkyl) amines.

The subsequent implementation of this prepolymer with Epichlorohydrin is preferably carried out in a molar ratio from 0.5 to 1.5 epichlorohydrin per secondary and / or tertiary Amino group.

A general formula is shown below as I when a dialkylene triamine was used to produce the prepolymer, but is not intended to be limiting to certain reaction products of the prepolymer with epichlorohydrin to give an amino group-containing quaternary amino-containing polymer formed by the azetidinium group.

wobei R1 und R2 unabhängig voneinander C2 bis C6 gesättigte oder ungesättigte, gradkettige, verzweigte oder zyklische Kohlenwasserstoffe sind.

• 2. Als aminogruppenhaltiges Polymer können ebenfalls Polymere mit den nachfolgend aufgeführten Struktureinheiten eingesetzt werden, die sowohl Homopolymere als auch Copolymere aus zwei oder mehreren der nachfolgend dargestellten Struktureinheiten sein können:
  
  

The following formula II, which is likewise intended to represent no restriction of the reaction products of a prepolymer with epichlorohydrin, gives a schematic overview of products from the reaction of a prepolymer with epichlorohydrin, if the prepolymer contains tertiary amino groups. Tertiary amino groups of the prepolymer can be derived, for example, from the trialkylenetriamine used for its preparation.

where R 1 and R 2, independently of one another, are C 2 to C 6 saturated or unsaturated, straight-chain, branched or cyclic hydrocarbons.

• 2. Polymers having the structural units listed below which can be both homopolymers and copolymers of two or more of the structural units shown below can likewise be used as the amino group-containing polymer:
  
  

The Polyvinylamine e) can be prepared by derivatization of a nitrogen atom, for example, alkylation, to a quaternary ammonium compound be reacted, so that the polyamine group-containing polymer, a preferred contains several quaternary ammonium groups.

at this embodiment of the invention, which applies to all invention Applicable polymers, it is advantageous that the resulting polycationic ammonium group-containing polymer in situ in the wood forms and a chemical and / or physical connection with Ingredients of the wood is received. This is especially true for radical Polymerizations of the case.

• 3. Weiterhin können erfindungsgemäß einzusetzende polyaminogruppenhaltige Polymere Polyalkylenimine sein, die vorzugsweise durch Derivatisierung, beispielsweise eine Alkylierung, zumindest einige quartäre Aminogruppen aufweisen.

Free-radical polymerization in wood is particularly applicable to the compounds of groups 2, 6 and 8 listed here.

• 3. Furthermore, according to the invention to be used polyaminogruppenhaltige polymers may be polyalkyleneimines, which preferably have by derivatization, for example an alkylation, at least some quaternary amino groups.

Polyalkyleneimines are branched, secondary and tertiary amino-containing polymers whose hydrocarbon chains which link together the nitrogen atoms have from 1 to 18, preferably from 2 to 8, saturated C atoms and / or unsaturated, straight-chain and / or branched hydrocarbon chains are. As a representative of polyalkyleneamines, polyethyleneimines are referred to below, but this does not represent a restriction to a C ₂ H ₄ chain.

polyalkyleneimines For example Polyethyenimine, further derivatizations have, for example, esterification with fatty acids, with saturated or unsaturated carboxylic acids, for example, acrylic acid, methacrylic acid, maleic acid and / or fumaric acid, or derivatizations by reaction with alkylene oxides, eg. For example, ethylene oxide or propylene oxide.

• 4. In einer weiteren Ausführungsform der Erfindung ist das aminogruppenhaltige Polymer, das aufgrund quartärer Ammoniumgruppen polykationisch ist, mit einem mit Trialkylammonium substituierten Epoxid derivatisierte Hydroxyalkylcellulose. Vorzugsweise ist das Epoxid mit Dimethylalkylammonium substituiert, wobei die Alkylgruppe C₁- bis C₁₈-Alkyl sein kann, die Hydroxyalkylcellulose ist vorzugsweise Hydroxyethylcellulose oder Hydroxymethylcellulose. Eine schematische Formel III ist nachfolgend dargestellt:
  

Polyalkyleneimines, preferably polyethylenimine, particularly preferably at least partially alkylated polyethylenimine containing quaternary amino groups, are suitable as adhesion promoters between wood and polymer layers, for example polymer films or lacquer layers. These compounds also show a good barrier effect against the penetration of wood constituents in polymer layers, for example against the diffusion of extractives in paint layers.

• 4. In another embodiment of the invention, the amino group-containing polymer which is polycationic due to quaternary ammonium groups is hydroxyalkyl cellulose derivatized with a trialkyl ammonium-substituted epoxide. Preferably, the epoxide is substituted with dimethylalkylammonium wherein the alkyl group may be C ₁ to C ₁₈ alkyl, the hydroxyalkylcellulose is preferably hydroxyethylcellulose or hydroxymethylcellulose. A schematic formula III is shown below:
  

at In situ reaction can be used epoxides directly with hydroxyl groups of the wood, e.g. B. the cell wall react, so that the reaction with both hydroxyethyl cellulose, cellulose, as also the cell wall polymers can run off in the wood to the inventive To produce polymer in the wood.

As an alternative to the use of hydroxyalkyl cellulose derivatized with trialkyl ammonium substituted derivatized cellulose can be used, which is obtainable by reaction with an epoxide at the highest possible material densities. A schematic reaction formula is shown below:

When Alternative or in addition to the specified sodium hydroxide can also be a sterically hindered amine, z. B. diazabicyclo [2.2.2] octane (DABCO).

• 5. In einer weiteren Ausführungsform der Erfindung wird das aminogruppenhaltige Polymer von Stärke gebildet, die quartäre Ammoniumgruppen enthält und daher polykationisch ist. Als polykationische Stärke werden vorliegend Stärkederivate, vorwiegend Stärkeether, bezeichnet, die aus der in Gegenwart von Alkali durchgeführten Umsetzung von Stärke mit Reagenzien erhältlich sind und die tertiäre Amino- oder quartäre Ammonium-Gruppen enthalten.

As a result, therefore, a very durable finish of the wood having fungicidal properties, preferably additionally having adhesion-promoting properties, is achieved, which also particularly advantageously provides a blocking action against the diffusion of wood constituents into superficially applied polymer layers, for example paints.

• 5. In another embodiment of the invention, the amino group-containing polymer is formed from starch containing quaternary ammonium groups and therefore polycationic. As polycationic starch herein are meant starch derivatives, predominantly starch ethers, which are obtainable from the reaction of starch with reagents carried out in the presence of alkali and which contain tertiary amino or quaternary ammonium groups.

For the implementation of the starch common etherifying agents are (2-chloroethyl) diethylamine (the following compound 1), (2,3-epoxypropyl) diethylamine (hereinafter compound 2), (3-chloropropyl) trimethylammonium chloride (hereinafter compound 3a), (3-chloro 2-hydroxypropyl) trimethylammonium chloride (hereinafter Compound 3b), (2,3-epoxypropyl) trimethylammonium chloride (hereinafter compound 3c) and (4-chloro-2-butenyl) trimethyl-ammonium chloride (hereinafter compound 3d).

Polycationic starches are in the technical. Scale can also be produced by the action of cyanamides on starch, which proceeds according to the following reaction equation:

The cationic groups influence the gelatinization behavior of the Strength very strong; already at substitution degrees of approx. 0.1-0.2, polycationic starches are cold water soluble. Due to their positive charges, these starch derivatives have a high affinity towards anionic and anionically modified substrates, e.g. B. lignocellulosic materials. Polycationic starches have so far only been used as flocculants for pigments, as an aid in papermaking, used in textile production and textile printing.

• 6. In einer weiteren Ausführungsform der Erfindung sind die aminogruppenhaltigen Polymere Copolymere verschiedener Struktureinheiten, beispielsweise ausgewählt aus Umsetzungsprodukten von Vinylpyrrolidon (VP), quarternisiertem Vinylimidazol (QVI) und/oder Dimethylaminoethylmethacrylat (DMAEMA), wobei vorzugsweise Vinylpyrrolidon mit QVI und/oder DMAEMA zu einem (Block-)Copolymer umgesetzt werden.

Such a polycationic quaternary amine-containing starch is obtainable by reacting starch with epoxide substituted with trialkylammonium, for example with epoxide substituted with trimethylammonium and / or triethylammonium. The following is a schematic formula of such polycationic starch:

• 6. In a further embodiment of the invention, the amino group-containing polymers are copolymers various structural units, for example selected from reaction products of vinylpyrrolidone (VP), quaternized vinylimidazole (QVI) and / or dimethylaminoethyl methacrylate (DMAEMA), preferably vinylpyrrolidone with QVI and / or DMAEMA be converted to a (block) copolymer.

The following is a schematic representation of the structural units as a block copolymer:

At Position of the methyl groups on the quaternary nitrogen atom of the QVI may be other alkyl groups, for example Ethyl, propyl and / or tert-butyl.

• 7. In einer weiteren Ausführungsform werden die aminogruppenhaltigen Polymere aus methylenverknüpften Cyanamidderivaten und Ammoniumsalz gebildet. Deren Herstellung kann gemäß DE 35 25 104 erfolgen. Das Polykondensat ist durch Umsetzen eines monofunktionellen oder polyfunktionellen Amins mit zumindest einer primären, sekundären und/oder tertiären Aminogruppe mit einem Cyanamid, Dicyanamid, Guanidin und/oder Biguanidin, von denen bis zu 50 Mol-% durch eine Dicarbonsäure oder deren Mono- oder Diester ersetzt sein können, unter Abspaltung von Ammoniak in Gegenwart eines Katalysators erhältlich und kann auch eine quartäre Aminogruppe aufweisen. Dieses Polykondensat kann weiter umgesetzt werden mit einer N-Methylolverbindung von Harnstoff, Melaminen, Guaninen, Triazinonen, Uronen, Urethanen und/oder Säureamiden, alternativ mit einem Epihalogenhydrin oder dessen Vorstufe, weiter alternativ mit Formaldehyd, oder einer Mischung der vorgenannten Verbindungen zur weiteren Umsetzung. Weiterhin kann das Polykondensat, optional nach weiterer Umsetzung, vernetzt werden, beispielsweise mittels einer N-Methylolverbindung in Gegenwart eines Katalysators.
• 8. In einer weiteren Ausführungsform können die erfindungsgemäß einzusetzenden polykationischen aminogruppenhaltigen Polymere aus kationischen Polyacrylamiden oder Polyacrylsäuren und/oder Copolymeren aus Acrylamiden und Acrylsäuren bestehen. Copolymere können z. B. Dimethylaminpropylacrylamid (DIMAPA) sein, oder können Polymerisationsprodukte aus Alkyldimethylaminoethylmethacrylat gemäß der nachfolgenden Formel VI sein:
  
  wobei Alkyl ein ungesättigter oder ungesättigte, gradkettiger oder verzweigter Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatomen, bevorzugt 2 bis 8 Kohlenstoffatomen ist.

Commercially available are, for example, the following copolymers of vinylpyrrolidone, QVI or DMAEMA under the brand name Luviquat from BASF: Luviquat.RTM VP QVI DMAEMA counterion PQ 11PN Polyquaternium-11 6.7 0 3.3 ethyl FC 550 Polyquaternium-16 5 5 0 Cl Excellence Polyquaternium-16 0.5 9.5 0 Cl

• 7. In another embodiment, the amino group-containing polymers are formed from methylene-linked cyanamide derivatives and ammonium salt. Their production can according to DE 35 25 104 respectively. The polycondensate is by reacting a monofunctional or polyfunctional amine having at least one primary, secondary and / or tertiary amino group with a cyanamide, dicyanamide, guanidine and / or biguanidine, of which up to 50 mol% is a dicarboxylic acid or its mono- or diester may be replaced with elimination of ammonia in the presence of a catalyst and may also have a quaternary amino group. This polycondensate can be further reacted with an N-methylol compound of urea, melamines, guanines, triazinones, urones, urethanes and / or acid amides, alternatively with an epihalohydrin or its precursor, further alternatively with formaldehyde, or a mixture of the aforementioned compounds for further reaction , Furthermore, the polycondensate, optionally after further reaction, can be crosslinked, for example by means of an N-methylol compound in the presence of a catalyst.
• 8. In a further embodiment, the polycationic amino group-containing polymers to be used according to the invention can consist of cationic polyacrylamides or polyacrylic acids and / or copolymers of acrylamides and acrylic acids. Copolymers may, for. Dimethylaminopropylacrylamide (DIMAPA), or may be polymerization products of alkyldimethylaminoethyl methacrylate according to the following formula VI:
  
  wherein alkyl is an unsaturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 18 carbon atoms, preferably 2 to 8 carbon atoms.

Cationic amino group-containing polymers which have a content of structural units of acrylamide and / or acrylic acids are particularly suitable as adhesion promoters between wood and paints based on acrylic acid.

In of the preferred embodiment, the invention Wood preservative additionally the adhesion to synthetic Polymers that can be applied to wood act for example, to lacquer layers or other synthetic polymers. As a particular advantage, the inventive Wood preservative in the preferred embodiment a Barrier action against wood the penetration of wood components into applied synthetic polymer coatings of wood, z. B. against the discoloration of paint layers by the Indiffusion of wood extractives.

at Some wood species may take some time after coating Reason of moisture fluctuations to a discoloration of paints come through extractives of the wood. It is not known exactly which of the extract substances cause the discoloration, you can but assume that it is mainly simple phenolic ingredients and tannins (especially soluble tannins) is. In addition, there are terpenes, lignans and various Resin components (especially resin acids) in question.

The Protective agents according to the invention are because of their polycationic structure able to extract such extractives bind and when applied to the wood surface diffusion Extracts from the interior of the wood to the surfaces and into the paint to prevent it. Particularly critical of the Discoloration of paints are due to their economic Meaning the Nadelhozarten pine and Douglas fir as well as the tropical ones See hardwood species Merbau and Meranti.

For the application of the wood preservative is according to the invention Impregnation preferred in a pressure-resistant impregnation reactor is carried out. The wood is for approx. 5 minutes to 2 hours, preferably about 15 to 60 minutes, especially about 30 min, first a pressure of 10 to 500 mbar absolute, preferably about 50 to 200 mbar absolute, in particular about 100 mbar absolute, exposed. This pressure is maintained, with the Wood in the aqueous solution or emulsion of Protective agent immersed or covered with it. The pressure is then for about 0.5 to 4 h to about 1.5 to 20 bar absolute, preferably about 5 to 15 bar absolute, in particular about 10 to 12 bar absolute raised. Subsequently, the pressure on Ambient pressure to be drained. The substrate is made of the impregnating solution or emulsion removed, drained and then dried. This impregnation is for the purpose the invention also as a vacuum or pressure impregnation designated.

alternative the wood preservative can be applied by spraying, painting, dipping, Floods or other conventional processes superficially be applied, which in particular at the desired Effect is preferred as a primer.

to Drying can be done on the substrate before and / or after impregnation or superficial order technically or by outdoor drying be dried, preferably up to a moisture content of about 10 to 20%, more preferably about 13 to 17%. A conventional one Technical drying is by heating to about 50 to 120 ° C over a period of about 4 hours to 4 weeks, preferably about 6 hours to 3 weeks. The drying can also as vacuum drying at reduced pressure become. The technical drying is used for the coordination of Humidity and temperature on each other to crack to diminish. As a variant of this technical drying can the so-called hot steam drying can be used at Temperatures above the boiling point, d. H. at ambient pressure above 100 ° C to about 140 ° C, preferably to about 130 ° C, more preferably above 121 ° C a period of about 2 hours to two weeks, preferably about 6 to 180 h. The suitable drying temperature and drying time is depends on the dimensions of the wood to be dried and can be easily determined by a person skilled in the art. The initial relative humidity is approx. 100% and is reduced in the course of drying.

Detailed description of the invention

The Invention will now be described in more detail by way of example with reference to FIGS Figures described in which

1 FIG. 4 is a graph showing the evaluation of mold infestation of pine wood samples after treatment with various wood preservatives of the present invention; FIG.

2 the fungicidal action of wood preservatives according to the invention in agar plates using the example of A) Coniophora puteana, B) Trametes versicolor and C) Chaetomium globosum,

3 the fungicidal action of wood preservatives according to the invention using the example of the impregnation of pine wood samples with reaction products of polyamidoamine with epichlorohydrin,

4 the fungicidal action of wood preservatives according to the invention on the example of the impregnation of beech wood samples with reaction products of polyamidoamine with epichlorohydrin,

5 the fungicidal action of wood preservatives according to the invention using the example of the impregnation of pine wood samples with reaction products of dimethylamine with epichlorohydrin,

6 and 7 show the fungicidal action of wood preservatives according to the invention on the example of the impregnation of wood samples with copolymers of vinylamine and N-vinylformamide,

8A and 8B show the fungicidal action of wood preservatives according to the invention on the example of the impregnation of pine or beech wood samples with polyvinylamine,

9A and 9B show the fungicidal action of wood preservatives according to the invention on the example of the impregnation of pine or beech wood samples with polyamines,

10A and 10B show the fungicidal action of wood preservatives according to the invention on the example of the impregnation of pine or beech wood samples with polyethyleneimines,

11A and 11B show the fungicidal action of wood preservatives according to the invention on the example of the impregnation of pine or beech wood samples with poly-DADMAC,

12 shows the fungicidal action of wood preservatives according to the invention on the example of the impregnation of pine wood samples with Polyquaternium-11,

13 the fungicidal action of wood preservatives according to the invention using the example of the impregnation of pine wood samples with Polyquaternium-16,

14 the fungicidal action of wood preservatives according to the invention using the example of the impregnation of pine wood samples with Polyquaternium 16A,

15A and B show the fungicidal action of wood preservatives according to the invention using the example of the impregnation of pine wood samples with polyethyleneimine,

16A and B show the fungicidal action of wood preservatives according to the invention using the example of the impregnation of beechwood samples with polyethyleneimine,

17A and B show the fungicidal action of wood preservatives according to the invention on the example of the impregnation of pine or beech wood samples with methylene-linked condensation products of cyanamide derivatives and ammonium salt, and

18A and B show the fungicidal action of wood preservatives according to the invention using the example of the impregnation of pine or beech wood samples with cationic polyacrylamide.

Example 1: Fungicidal wood preservative

The fungicidal action of amine group-containing compounds by a Content of quaternary amine groups preferably polycationic was, for example, impregnated pine wood samples size 5 × 10 × 30 mm (radial, tangential, longitudinal) tested. The pine wood samples were in aqueous solutions with 1 wt .-% or 3 wt .-% of the respective wood preservative impregnated. The impregnation was done by immersing the specimens in aqueous solution of the protective agent on a pH adjusted from 6, made for 15 s, then drain gently. As control samples were untreated or with water (without wood preservative) treated specimens used. After the treatment, all samples were in the climatic chamber dried at 20 ° C and 65% relative humidity before they were exposed to mold spores.

• – Umsetzungsprodukt von Polyamidoamin (beispielsweise erhältlich aus Adipinsäure und Diethylentriamin) mit Epichlorhydrin (erhältlich von der Firma BASF unter der Bezeichnung Luresin^® KTU),
• – Polyvinyamin (erhältlich von der Firma BASF unter der Bezeichnung Catiofast^® VFH),
• – Poly(diallyldimethylammoniumchlorid) (Poly-DADMAC) (erhältlich von der Firma BASF unter der Bezeichnung Catiofast^® CS),
• – Copolymer aus Vinylpyrrolidon (67%) und DMAEMA (33%), als Gegenion Ethylsulfat (Polyquaternium-11, erhältlich von der Firma BASF unter der Bezeichnung Luviquat^® PQ 11PN, M = ca. 1.000.000),
• – Copolymer aus Vinylpyrrolidon (50%) und QVI (50%) (Polyquaternium-16A, erhältlich unter der Bezeichnung Luviquat^® FC 550 von der Firma BASF, M = ca. 80.000), als Gegenion Chlorid,
• – Copolymer aus Vinylpyrrolidon (5%) und QVI (95%) (Polyquaternium-16, erhältlich unter der Bezeichnung Luviquat^® Excellence von der Firma BASF, M = ca. 40.000), als Gegenion Chlorid,
• – Polyethylenimin (5000 g/Mol) (erhältlich von der Firma BASF unter der Bezeichnung Lupasol^® G 100),
• – Polyethylenimin (25.000 g/Mol) (erhältlich von der Firma BASF unter der Bezeichnung Lupasol^® G 500).

After drying, the wood samples are stored for six weeks in closed containers on a wire grid about 1 cm above a water surface to a wood moisture near the fiber saturation point of the wood (about 30%). In addition, forest soil was added to the water to achieve a high density of mold spores in the container. For each experiment, 5 parallel samples were used. With the help of a fan, the air was circulated inside the container. At the beginning of the experiment the temperature in the container was 28.5 ° C, the relative humidity was 94.3%. At the end of the experiment, the temperature was about 25.5 ° C, the relative humidity 96.0%. The assessment of mold infestation on the surface was evaluated optically on an arbitrary scale of 0 to 3, where 0 means no infestation, 1 minor infestation, 2 mean infestation and 3 infestation. 1 shows graphically the result of the fungicidal action of the wood preservatives used, namely in detail for

• - reaction product of polyamidoamine (for example obtainable from adipic acid and diethylenetriamine) with epichlorohydrin (available from BASF under the name ^® Luresin KTU)
• - Polyvinyamin (available from BASF under the name Catiofast® ^® VFH)
• - Poly (diallyl dimethyl ammonium chloride) (poly-DADMAC) (available from BASF under the name Catiofast® ^® CS)
• - copolymer of vinyl pyrrolidone (67%) and DMAEMA (33%), as a counter ion ethyl sulfate (Polyquaternium-11, available from BASF under the name Luviquat ^® PQ 11PN, M = approximately 1,000,000),
• - copolymer of vinyl pyrrolidone (50%) and QVI (50%) (Polyquaternium-16A, available under the name Luviquat ^® FC 550 by BASF, M = 80.000) as the counter ion chloride,
• - copolymer of vinyl pyrrolidone (5%) and QVI (95%) (Polyquaternium-16, sold under the name Luviquat Excellence from BASF ^®, M = 40,000), as a counter ion chloride
• - polyethyleneimine (5000 g / mol) (available from BASF under the name Lupasol ^® G 100),
• - polyethyleneimine (25,000 g / mol) (available from BASF under the name Lupasol ^® G 500).

Especially in the case of wood preservatives containing poly-DADMAC, polyquaternium-16A, polyquaternium-16B, Polyethyleneimine A and Polyethyleneimine B will have the fungicidal action clearly, with higher concentrations being stronger Show effects.

Example 2: Fungicidal action of wood preservatives in vitro

• – Polyvinylamin (erhältlich von der Firma BASF unter der Bezeichnung Catiofast^® VFH, nichtflüchtiger Anteil ca. 21%, scheinbare Viskosität 1500 MPas),
• – Polyamin (erhältlich von der Firma Bayer unter der Bezeichnung Retaminol^® K, Feststoffgehalt ca. 26%, scheinbare Viskosität 110 mPas),
• – Umsetzungsprodukt von Dimethylamin mit Epichlorhydrin (erhältlich von der Firma Bayer unter der Bezeichnung Levogen^® E-1063),
• – Poly-DADMAC (erhälich von der Firma BASF unter der Bezeichnung Catiofast^® CS, nichtflüchtiger Anteil ca. 30%, scheinbare Viskosität ca. 500 mPas),
• – Copolymer aus Vinylpyrrolidon (67%) und DMAEMA (33%), als Gegenion Ethylsulfat (Polyquaternium-11, erhältlich von der Firma BASF unter der Bezeichnung Luviquat^® PQ 11PN),
• – Copolymer aus Vinylpyrrolidon und QVI (Polyquaternium-16A, erhältlich unter der Bezeichnung Luviquat^® Excellence von der Firma BASF), als Gegenion Chlorid,
• – Polyethylenimin A (5000 g/Mol) (erhältlich von der Firma BASF unter der Bezeichnung Lupasol G 100),
• – Polyethylenimin B (25.000 g/Mol) (erhältlich von der Firma BASF unter der Bezeichnung Lupasol^® G 500),
• – Methylenverknüpftes Kondensationsprodukt aus Cyanamidderivaten und Ammoniumsalz (erhältlich unter der Bezeichnung Levogen^® PTF liquid 01, Feststoffgehalt ca. 40%, scheinbare Viskosität < 50 mPas),
• – kationisches Polyacrylamid (erhältlich von der Firma Bayer unter der Bezeichnung Baystrength^® K, Feststoffgehalt ca. 15%, scheinbare Viskosität 3500–6000 mPas) und
• – als Vergleich N-Alkyl-N,N-dimethyl-N-benzylammoniumchlorid.

The fungicidal action of wood preservatives according to the invention was determined independently of the substrate wood in agar dishes. For this detection, 90 mm petri dishes were each filled with 25 ml of 3% malt agar and wood preservatives were added to 0% (control), 0.01% by weight, 0.05% by weight, 0.1% by weight, 0, 2 wt .-%, 0.4 wt .-% and 0.8 wt .-% added. The reference substance used was the wood preservative known as N-alkyl-N, N-dimethyl-N-benzylammonium chloride, as wood preservative according to the invention

• - polyvinyl (available from BASF under the name Catiofast® ^® VFH, nonvolatile about 21%, apparent viscosity 1,500 mPas)
• - polyamine (sold by the company Bayer under the name Retaminol ^® K, solids content: about 26%, apparent viscosity 110 mPas)
• - reaction product of dimethylamine with epichlorohydrin (available ^® by Bayer under the name Levogen E-1063)
• - Poly-DADMAC (erhälich by the company BASF under the name ^® Catiofast CS, nonvolatile about 30%, apparent viscosity ca. 500 mPas)
• - copolymer of vinyl pyrrolidone (67%) and DMAEMA (33%), as a counter ion ethyl sulfate (Polyquaternium-11, available from BASF under the name Luviquat ^® PQ 11PN)
• - copolymer of vinylpyrrolidone and QVI (Polyquaternium-16A, available under the name Luviquat Excellence from BASF ^®), as a counter ion chloride,
• Polyethyleneimine A (5000 g / mol) (available from BASF under the name Lupasol G 100),
• - polyethylenimine B (25,000 g / mol) (available from BASF under the name Lupasol ^® G 500),
• - methyl Linked condensation product of Cyanamidderivaten and ammonium salt (available under the name ^® Levogen PTF liquid 01, solids content: about 40%, apparent viscosity <50 mPas)
• - cationic polyacrylamide (available from Bayer under the designation BAYSTRENGTH ^® K, solids content: about 15%, apparent viscosity 3500-6000 mPas) and
• For comparison, N-alkyl-N, N-dimethyl-N-benzylammonium chloride.

In four parallel experiments were the brown rot fungus Coniophora puteana, the white rot fungus Trametes versicolor and the mold fungus Chaetomium globosum by application of a mushroom-grown Agarstücks inoculated. At 24 ° C over 12 days or when the peel is completely overgrown was, the reached colony diameters were determined.

The measurement results for growth, measured as colony diameter, are graphically in 2 namely, under A) for Coniophora puteana, B) Trametes versicolor and C) Chaetomium globosum.

In detail shows 2A ) using the example of Polyquaternium-11, that the effect of copolymers of vinylpyrrolidone and DMEAMA against Coniophora puteana of the wood preservatives tested is the lowest, while the reference substance used as a conventional biocide even in low concentrations has the strongest fungicidal activity.

In Higher concentrations, however, reach the used Wood preservative according to the invention a clear Slowing growth, d. H. fungicidal action against Coniophora puteana.

In 2 B ) it becomes clear that the biocide used as reference substance also has a very strong fungicidal action against Trametes versicolor, even though the copolymer of vinylpyrrolidone and DMEAMA (the example of Polyquaternium-11) has the lowest effect. However, the other wood preservatives of the invention tested show, at least at higher concentrations, a significant reduction in growth, ie a fungicidal action.

Out 2C ) it is clear that the biocide used as reference substance has the strongest fungicidal action at low concentrations, while again the copolymer of vinylpyrrolidone and DMEAMA (Polyquaternium-11) shows the least fungicidal action. The other wood preservatives according to the invention also show a fungicidal action, especially at higher concentrations.

To evaluate the growth inhibition by various wood preservatives were still the parameters ED ₅₀ , ie the drug concentration at which the growth compared to the negative control (water) is reduced by 50%, and the ED ₁₀₀ , ie the drug concentration at which the water over the control (Water) is changed by 100% (growth over 12 days less than 1 cm), determined.

The values for the ED ₅₀ and ED ₁₀₀ are summarized in Table 1 below: TABLE 1 Fungicidal effect of wood preservatives as 50% (ED ₅₀ ) or 100% (ED ₁₀₀ ) inhibition of growth compared to negative control water C. puteana T. versicolor C. globosum ED ₁₀₀ ED ₅₀ ED ₁₀₀ ED ₅₀ ED ₁₀₀ ED ₅₀ polyvinylamine 0.8 0.4-0.8 > 0.8 0.2-0.4 0.8 0.2-0.4 PolyDADMAC > 0.8 0.1-0.2 > 0.8 0.1-0.2 > 0.8 0.1-0.2 Polyquaternium-11 > 0.8 > 0.8 > 0.8 0.4-0.8 > 0.8 > 0.8 Polyquaternium-16A > 0.8 0.2-0.4 > 0.8 0.1-0.2 0.8 0.05-0.1 Polyquaternium-16B 0.4 0.2-0.4 12:05 0:01 to 12:05 a.m. 0.2 12:01 Polyethyleneimine A 0.8 0.2-0.4 0.2 0.05-0.1 0.2 0:01 to 12:05 a.m. Polyethyleneimine B 0.8 0.2-0.4 0.8 0.05-0.1 0.4 0:01 to 12:05 a.m. Comparison: N-alkyl-N, N-dimethylbenzylammonium chloride 0.2 0:01 to 12:05 a.m. 12:05 <00:01 12:05 <0.01

Example 3: Fungicidal wood preservative with the reaction product of polyamidoamine with epichlorohydrin

The antiperspirant effect of polyamine compounds having quaternary amino groups available by reacting a polyamidoamine, by way of example, a copolymer of adipic acid and diethylenetriamine with epichlorohydrin, with an apparent viscosity of about 130 mPas for a nonvolatile content of about 15% (sold under the name ^® Luresin KTA or Luresin ^® KNU) was used in aqueous suspension in the concentrations indicated. Wood samples measuring 5 × 10 × 30 mm were impregnated in aqueous mixtures of the wood preservative for one hour at 50 mbar, then the vacuum was removed and the samples were left overnight in the impregnation solution. After removal from the impregnation solution, the samples were predried for 3 days at 40 ° C, then dried for 20 hours at 103 ° C and weighed. 9 or 12 parallel samples were used for the experiments.

to Determination of resistance, wood samples were made Pine wood exposed to brown rot fungus Coniophora puteana, Beech wood samples of white rot mushroom Trametes versicolor. The loss of mass was determined after 12 weeks.

As a reaction product of the polyamidoamine with epichlorohydrin was Luresin ^® KTU to 1.5 wt .-%, 4.5 wt .-% and 7.5 wt .-% used in aqueous composition or Luresin ^® KNU to 4.5 wt .-% ,

The increase in weight of pine wood samples by impregnation with Luresin ^® KTU or Luresin ^® KNU from treated water in parallel with control samples is in 3 shown. Here it can be seen that a higher concentration of Luresin ^® KTU leads to a higher weight gain (WPG), and that Luresin ^® KNU leads to a slightly higher weight gain than Luresin ^® KTU.

The result of the incubation of treated pine wood samples against Coniophora puteana is in 4 shown. Here it is clear that the treated for comparison with water instead wood preservative comparative samples suffered the highest weight loss, whereas treatment with the inventive wood preservatives, shown in the example of Luresin ^® KTU or Luresin ^® KNU suffered a significantly reduced weight loss.

Example 4: Fungicidal wood preservative with the copolymer of epichlorohydrin and dimethylamine

As an example of an inventive wood preservative one Copoymerisat of dimethylamine and epichlorohydrin (under the name Levogen ^® E-1063 liquid from Bayer available) was used. The impregnation of pine wood samples with Levogen in an aqueous mixture of 1.0% by weight, 2.9% by weight and 5.0% by weight and subsequent drying was carried out in accordance with Example 3.

The results of weight gain after drying against water treated control samples (WPG), as well as the weight loss by fungal infestation for the Levogen ^® treated pine wood samples versus the water treated control samples (weight loss) are in 5 shown. Here it is clear that the weight loss of the pinewood samples in case of fungal attack by Coniophora puteana by the treatment with copolymer of epichlorohydrin and dimethylamine was reduced, the weight loss for higher concentrations due to the increased leaching at higher concentrations during impregnation.

Example 5: Fungicidal wood preservative with polyvinylamines

As examples of the present invention to be used as wood preservatives from polyvinylamines Copoymerisate polyvinylamine and N-vinylformamide (available under the designation Luresin ^® PR 8092 of BASF) to 2 wt .-%, 6 wt .-% and 10 wt .-% and Luresin ^® PR 8086 (available from BASF) to 6 wt .-% for impregnation of pine wood samples used according to Example 3. The increase in weight due to impregnation against parallel water-treated control samples is in 6 and shows that increasing concentrations of wood preservative lead to higher weight gain, wherein the weight gain for different polyvinylamines was different despite equally concentrated aqueous mixtures.

The treated pine wood samples were exposed according to Example 3 the brown rot fungus Coniophora puteana. The weight loss determined after 12 weeks is in 7 shown. It is clear that the treatment with wood preservatives according to the invention led to a significant reduction in weight loss compared to water-treated reference wood samples.

Example 6: Fungicidal wood preservative with polyvinylamine

As an example of wood preservative according to the invention containing polyvinylamine, Catiofast ^® VFH (name BASF) was used in concentrations of 1.5% by weight, 3% by weight and 5% by weight in an aqueous mixture for impregnating pine wood samples or Beech wood samples used according to Example 3.

The results for pine wood are in 8A with weight gain (WPG) showing that increasing levels of wood preservative in an aqueous mixture result in increasing weight gains, while weight loss from Coniophora puteana infestation is significantly reduced over water-treated controls, with a slight increase in weight loss observed with increasing concentrations which is probably due to the increased leaching.

In the treatment of beechwood samples using the wood degrading fungus Trametes versicolor, the in 8B obtained with increasing concentrations of the wood preservative in an aqueous mixture, a greater weight gain (WPG), while the weight loss is reduced by fungal attack by increasing concentrations of wood preservative compared to the water-treated control samples.

Example 7: Fungicidal wood preservative with amine-containing polymer

As an example of a wood preservative containing amines group-containing polymer was Retaminol ^® K (apparent viscosity about 110 mPas at a solids content of about 26%) was used, which was highly cationic due to its content of quaternary ammonium groups. Wood samples were impregnated in accordance with Example 3 in aqueous mixtures with a content of 1 wt .-%, 2 wt .-% and 5.2 wt .-% Retaminol ^® K and then dried. The results of impregnation and weight loss after fungal attack compared to water treated control samples according to Example 3 are for pinewood in 9A (Coniophora puteana) and 9B Beech wood samples (Trametes versicolor) shown.

For Both types of wood increase with the concentration of the wood preservative the weight gain (WPG) while for pinewood the weight loss from fungal infestation due to leaching effects with increasing concentration slightly increases while the Weight loss in beech with increasing concentrations strong decreases.

In However, in both cases it is clear that the treatment with wood preservative according to the invention the resistance against the infestation with the respective wood-degrading Mushrooms greatly increased.

Example 8: Fungicidal wood preservative with polyalkylenepolyamine

As an example of a wood preservative containing Polyehtylenimin a polyethylene polyamine which (about 400 mPas apparent viscosity at a solids content of about 26%) sold under the name Retaminol ^® E is commercially available.

Wood samples were impregnated according to Example 3 in an aqueous mixture (pH = 4) with a content of Retaminol ^® E of 1 wt .-%, 2 wt .-% and 5.2 wt .-% and then dried. The results of impregnation and weight loss after fungal attack compared to water treated wood samples are in 10A for pine wood samples, infested with Coniophora puteana and 10B , Beech wood samples, infestation with Trametes versicolor, shown.

For Both types of wood can be seen to increase in weight Concentrations of the wood preservative in the aqueous Mixture increases and weight loss due to fungal attack is drastically reduced by the wood preservative. It shows Turn that beech wood through a higher content protectives reduce weight loss due to fungal attack subject.

Example 9: Fungicidal wood preservative with poly-DADMAC

As an example of a wood preservative containing poly-DADMAC Catiofast CS ^® was used (available from BASF). Wood samples were impregnated in accordance with Example 3 in aqueous mixtures with a 1.5 wt .-%, 5 wt .-% and 10 wt .-% Catiofast ^® CS. The measured weight gain (WPG) for pine wood samples as well as the weight loss from the attack with Coniophora puteana gegenü About water-treated comparative samples is in 11A the increase in weight by impregnation of beech wood samples and their weight loss by fungal attack with Trametes versicolor compared with water-treated comparative samples in 11B ,

The show measured weight increases for both types of wood, that increasing concentrations of the wood preservative in the aqueous Mixture lead to higher weight gains while the weight loss due to fungal attack each drastically the water-treated comparative samples is reduced.

Example 10: Fungicidal wood preservative containing a polyquaternium-11

As an example of a block copolymer of vinylpyrrolidone and DMAEMA was Polyquarteum-11 (Luviquat ^® PQ 11PN, available from BASF) employed to 0.2 wt .-% and 1 wt .-% in an aqueous mixture to impregnate pine wood samples.

The weight gain of pine wood specimens (WPG), as well as the weight loss of the treated pine wood specimens and water treated control specimens after fungal attack by Coniophora puteana, are in 12 shown.

Here it is clear that impregnation in an aqueous mixture with 1% Luviquat ^® PQ 11PN does not lead to the expected increase in weight by absorption of the wood preservative, nor to a fungicidal treatment of the wood, so that the weight loss is due to fungal attack similarly high as in the comparative sample. The low levels of weight gain from impregnation and weight loss are probably due to the low concentration used.

Example 11: Fungicidal wood preservative containing polyquaternium-16

As an example of a wood preservative containing block copolymer of vinylpyrrolidone and QVI (Polyquaternium-16) was Luviquat ^® FC 550 (available from BASF) in concentration of 0.4 wt .-%, 2 wt .-% and 4 % By weight in an aqueous mixture for impregnating pine wood samples and for determining the weight loss with subsequent fungal attack in accordance with Example 3.

The results, in 13 shown, show that an impregnation with 0.4 wt .-% Luviquat ^® FC 550 in aqueous mixture does not lead to weight gain (WPG), but rather to a reduction of the total weight. This shows that during impregnation not only wood preservatives are absorbed but also weight losses due to leaching during impregnation. Thus, the weight loss measurements show due to fungal infection by Coniophora puteana compared to the water-treated control samples, that a certain fungicidal action is achieved even at the lowest concentration used to Luviquat ^® FC 550, while the higher concentrations in a drastic reduction of the weight loss by Fungus effect until fully resistant to fungal attack.

Example 12: Fungicidal wood preservative containing polyquaternium-16A

As an example of a wood preservative with a copolymer of vinylpyrrolidone and QVI (Polyquaternium-16A) was Luviquat ^® Excellent (available from BASF) to 0.4 wt .-%, 2 wt .-% and 4 wt .-% in aqueous mixture for impregnation of pine wood samples and for subsequent measurement of weight loss due to fungal attack with Coniophora puteana used according to Example 3.

The results are in 14 illustrated and show that uses a weight gain (WPG) by impregnating only at a concentration of 2 wt .-% Luviquat ^® Excellent or higher, while the concentration of 0.4 wt .-% leads to an overall weight loss by impregnation.

Yet time the measurement of weight loss due to fungal attack one fungicidal action for Polyquaternium 16A also for the lowest concentration used compared to those with Water-treated comparative samples. Higher used Concentrations of wood preservative lead to a reduction of the Weight loss due to fungal attack on 0, so to a quasi-complete fungicidal equipment of pine wood.

Example 13: Fungicidal wood preservative containing polyalkyleneimine

As an example of a wood preservative containing polyalkyleneimine wood samples with various polyethyleneimines, which are commercially available under the names Lupasol ^® FC, Lupasol ^® G 35, Lupasol ^® G 100 and Lupasol ^® G 500 by the company BASF, have been in aqueous mixtures with a content of 0.4 wt .-%, 2 wt .-% or 4 wt .-% according to Example 3 impregnated.

The weight gains of wood preservative impregnation with various levels of polyethylenimines are in 15A for pine wood samples and in 15B shown for beech wood samples. In each case it becomes clear that higher concentrations of the fungicidal wood preservative lead to higher weight increases by impregnation, whereby very low concentrations used due to leaching during the impregnation can lead to an overall weight loss.

The Lower weight gain in beechwood is compared to that attributed to pinewood higher density, but no direct conclusion to the recording of the protective agent allowed by beech wood.

In a subsequent test of the fungicidal composition of wood samples against fungal attack by Coniophora puteana for pine wood samples and Trametes versicolor for beech wood samples, it is clear that polyalkyleneimines lead to a drastic reduction in weight loss in fungal infestations, as out 16A for pinewood or 16B for beech wood emerges. Furthermore, the general tendency is to recognize that higher concentrations of wood preservative used leads to an increased fungicidal finish of the wood.

Example 14: Fungicidal wood preservative containing methylene-linked condensation products Cyanamide derivatives and ammonium salt

As an example of a wood preservative based on methyl female knüpfter condensation products of Cyanamidderivaten and ammonium salts of the commercial product Levogen ^® PTF liquid was 01 to 1 wt .-%, 2 wt .-% and 5 wt .-% in an aqueous mixture to impregnate pine and beech wood used. The results of impregnation and weight loss after fungal attack are in 17A for pinewood with subsequent infestation by Coniophora puteana and 17B for beech wood samples with subsequent infestation by Trametes versicolor shown.

Both Wood species show with increasing concentration of wood preservative in the aqueous mixture, an increase in weight gain (WPG). Furthermore, both types of wood opposite to the respective Fungi after treatment with the invention Wood preservative reduced mass loss, in particular for beech wood samples higher concentrations Wood preservative to a reinforced fungicidal equipment of the wood, expressed as falling weight loss after Fungal infection, lead.

Example 15: Fungicidal wood preservative containing cationic polyacrylamides

As an example of a wood preservative with a content of cationic polyacrylamide was used BAYSTRENGTH ^® K (available from Bayer) in an aqueous mixture to 1 wt .-%, 2 wt .-% and 5 wt .-%. Wood samples were impregnated according to Example 3 and then exposed to the fungus.

The results are for pine wood samples in 18 represented after impregnation of Coniophora puteana, in 18B for beech wood samples exposed to infestation by Trametes versicolor following impregnation.

For Both types of wood increase weight gain with increasing concentrations on wood preservatives in the aqueous mixture. Likewise will clearly that the fungicidal equipment is rising Concentrations of pesticide increases, expressed as a reduction in weight loss after fungal attack.

Example 16: Prevention of paint discoloration in coated wood

To prevent discoloration, specimens of pine, douglas, mint (Intsia bijuga) and meranti (Shorea leprosula) of dimensions 2 × 6 × 15 cm ³ (tangential × radial × longitudinal) were immersed in a 3% aqueous solution for 20 seconds the polycationic amino compounds according to the invention indicated in Table 2 below. Subsequently, the paint rubbol WF350 twice applied by spraying (dry film thickness about 60 μm). After each coat application, the coating was allowed to dry for 2 hours at room temperature.

to Wood samples were checked instead of in polyamine solution in Dipped in water, otherwise identical to those treated according to the invention Treated wood samples.

After drying and conditioning the samples at 25 ° C and 60% humidity, the samples were placed in a condensate tank. This was a 40 (1) x 80 (t) x 50 (h) cm ³ stainless steel pan fitted with a lid and a heating element and temperature control at the bottom and filled with water over the heating rod , The samples were stored on a grid about 15 cm above the water surface.

to Carrying out the experiment, the tank was closed Cover heated to 60 ° C for 24 h. Subsequently the heating element was issued and the cover for more 24 hours left open. This corresponded to one cycle (cycle duration from 48 h). After each cycle was the discoloration of the paint visually appraised. In Table 2, the cycles are to occur indicated a paint discoloration.

• 1) Polyethylenimin Lupasol^® G 500 (BASF) Molekülmasse (25.000 g/mol)
• 2) Polyethylenimin Lupasol^® P (BASF) Molekülmasse (750.000 g/mol)
• 3) Polyquaternium-11 Luviquat^® PQ 11PN (BASF) Molekülmasse (1.000.000 g/mol)
• 4) Polyquaternium-16 Luviquat^® F 550 (BASF) Molekülmasse (80.000 g/mol)
• 5) Poly-DADMAC (BASF), scheinbare Viskosität: ca. 500 mPas

Tabelle 2: Lackverfärbungen in Abhängigkeit von Zykluszahl und verwendetem Holzschutzmittel Schutzmittel Kiefer Douglasie Merbau Meranti Kontrolle (Wasser) 8 5 3 8 1 > 30 20 13 > 30 2 > 30 22 16 > 30 3 22 14 9 18 4 18 11 7 14 5 14 9 5 11 The following protective agents according to the invention were investigated:

• 1) polyethyleneimine Lupasol ^® G 500 (BASF) molecular weight (25,000 g / mol)
• 2) polyethyleneimine Lupasol ^® P (BASF) molecular weight (750,000 g / mol)
• 3) Polyquaternium-11, Luviquat ^® PQ 11PN (BASF) molecular weight (1,000,000 g / mol)
• 4) Polyquaternium-16, Luviquat ^® F 550 (BASF) molecular weight (80,000 g / mol)
• 5) Poly-DADMAC (BASF), apparent viscosity: about 500 mPas

Table 2: Lackverfärbungen depending on cycle number and used wood preservative preservative jaw Douglas Merbau meranti Control (water) 8th 5 3 8th 1 > 30 20 13 > 30 2 > 30 22 16 > 30 3 22 14 9 18 4 18 11 7 14 5 14 9 5 11

Next the inventive use of wood preservatives in combination with paints these are also for use in Combination with glazes suitable.

Example 17: Fixation according to the invention polycationic amino compounds in the wood

The Leaching of the protective agent used according to the invention can be added to the impregnating solution by adding formaldehyde and application of elevated temperatures during the drying can be reduced. This way it comes to a Crosslinking between the a) polycationic polyamino compounds b) polycationic polyamino compounds and cell wall polymers and c) cell wall polymers with each other.

• 1) 4 Gew.-% Polyethylenimin, 0.5 Gew.-% Formaldehyd
• 2) 4 Gew.-% Polyethylenimin
• 3) 4 Gew.-% Polyvinylamin, 0.5 Gew.-% Formaldehyd
• 4) 4 Gew.-% Polyvinylamin
• 5) nur Wasser (Kontrolle)

Pine wood samples measuring 5 mm radially, 10 mm tangentially, 30 mm longitudinally were impregnated with the following aqueous solutions under vacuum (50 mbar) (5 parallel runs in each case):

• 1) 4% by weight of polyethyleneimine, 0.5% by weight of formaldehyde
• 2) 4% by weight of polyethyleneimine
• 3) 4% by weight of polyvinylamine, 0.5% by weight of formaldehyde
• 4) 4% by weight of polyvinylamine
• 5) only water (control)

The polyethyleneimine used had a molecular weight of 2000 g / mol (Lupasol G35, BASF), the polyvinylamine an apparent viscosity of 1500 mPas at a concentration of about 21% (Catiofast VFH; BASF).

Subsequently The samples were first of all impregnated Dried at 40 ° C for 8 h and then at 120 ° C for 18 h.

After drying, the samples were conditioned for one week under standard conditions (20 ° C, 65% relative humidity) and based on the standard EN 84 exposed to a washing out. The samples were immersed in water for 14 days and the water was changed 9 times during this period. The dry weights of the samples before impregnation and after treatment resulted in the weight gains caused by the treatment (WPG, see above).

Of the Proportion of leachable components resulted from dry weights after the chemical treatment and the dry weights after the Wash-out.

While with polyethylenimine (82%) and polyvinylamine (86% leaching) treated samples most of the incorporated Chemicals could be washed out again, were the weight loss Significantly lower in combination with formaldehyde. in this connection leaching was only 9% (polyethylenimine) and 22% (polyvinylamine), in each case the proportion of the extract substances washed out during the controls has been deducted.

Example 18: Reduction of the delivery of Formaldehyde and reduction of shrinkage of wood by inventively used polycationic amino compounds

In addition to reducing leaching, the combination of formaldehyde and polycationic polyamino compounds used according to the invention has a further advantage:
While formaldehyde alone is used to modify the wood, there is an improvement in the material properties of the wood in terms of dimensional stability and durability, but with the disadvantage of giving formaldehyde from the treated samples over an extended period of time, which is considered carcinogenic ,

Out The scientific literature is known to be the modification of solid wood with formaldehyde catalysis with strong acids such as hydrochloric acid, nitric acid or zinc chloride requires. All of these catalysts can be at higher Temperatures degradation of the cell wall polymers of the wood and thus cause a loss of strength.

tertiary Amines, as they are part of polyethyleneimines, can act as catalysts without a significant loss of strength cause.

• 1) 4 Gew.-% Formaldehyd, 2 Gew.-% Polyethylenimin, 0.1 Gew.-% Magnesiumchlorid
• 2) 4 Gew.-% Formaldehyd, 0.1 Gew.-% Magnesiumchlorid
• 3) 4 Gew.-% Formaldehyd, 2 Gew.-% Polyethylenimin
• 4) 4 Gew.-% Formaldehyd
• 5) nur mit Wasser

Pine wood samples measuring 25 mm radially, 25 mm tangentially, 15 mm longitudinally were impregnated with the following aqueous solutions under vacuum (50 mbar) (in each case 5 parallel batches):

• 1) 4% by weight of formaldehyde, 2% by weight of polyethyleneimine, 0.1% by weight of magnesium chloride
• 2) 4% by weight of formaldehyde, 0.1% by weight of magnesium chloride
• 3) 4% by weight of formaldehyde, 2% by weight of polyethyleneimine
• 4) 4% by weight of formaldehyde
• 5) only with water

The polyethyleneimine used had a molecular weight of 2000 g / mol (Lupasol ^® G35, BASF).

Subsequently The samples were first 8 h at 40 ° C and then Dried at 120 ° C for 18 h.

To drying were both with the invention Protective treated as well as water-treated samples (Controls) in the radial, tangential and longitudinal directions measured. Subsequently, the samples were first in a climatic cabinet at 20 ° C and 65% ambient humidity until conditioned to constant weight and then again the length measures determined. Then the samples submerged in water and a vacuum of about 50 mbar applied, so that a water-saturated state of the samples arose. Subsequently, as described above, the length measures certainly.

mit

S

= relative Quellung/Schwindung

L_c

= Länge der klimatisierten Proben (radial, tangential, longitudinal)

L_d

= Länge der trockenen Proben (radial, tangential, longitudinal)

From the determined lengths, the relative swelling / shrinkage was calculated:

With

S

= relative swelling / shrinkage

L _c

= Length of conditioned samples (radial, tangential, longitudinal)

L _d

= Length of dry samples (radial, tangential, longitudinal)

S_v

= Volumenquellung/-schwindung

S_r

= radiale Quellung/Schwindung

S_t

= tangentiale Quellung/Schwindung

From this, the volume swelling / shrinkage can be calculated: S v = (P r + 1) ∙ (p t + 1) - 1 [%] With

S _v

= Volume swelling / shrinkage

S _r

= radial swelling / shrinkage

S _t

= tangential swelling / shrinkage

ASE_(r,t,v)

= Anti-Quellung-Schwellungs-Wirksamkeit (radial, tangential, volumetrisch)

S_u

= Quellung/Schwindung der unbehandelten Probe

S_t

= Quellung/Schwindung der behandelten Probe

This can be used to calculate the anti-swelling efficacy (ASE, "Anti-Shrik (Swell) efficiency"), which is a measure of the increase in dimensional stability compared to an untreated control sample:

ASE _{(r, t, v)}

= Anti-swelling-swelling efficacy (radial, tangential, volumetric)

S _u

= Swelling / shrinkage of the untreated sample

S _t

= Swelling / shrinkage of the treated sample

The Anti-swelling efficacy (ASE) has been reported for the wood moisture range between absolutely dry wood (0% wood moisture) and water-saturated wood (100% wood moisture).

• 1) 58% (+/– 8%)
• 2) 44% (+/– 6%)
• 3) 38% (+/– 6%)
• 4) 12% (+/– 3%)

The following ASE values were obtained for the treatments described above:

• 1) 58% (+/- 8%)
• 2) 44% (+/- 6%)
• 3) 38% (+/- 6%)
• 4) 12% (+/- 3%)

The Results show that treatment with polyethylenimine improvement in ASE scores, both in combination according to the invention polycationic Polyamine compounds with formaldehyde alone, as well as in combination inventive polycationic polyamine compounds with formaldehyde and magnesium chloride.

Subsequently was the formaldehyde release after the bottle test according to EN 717-3 for wood-based materials measured from the treated samples, without sealing the faces. For this purpose were respectively 4 equally treated samples with defined wood moisture in a 500 mL of PET bottle with 50 mL demineralized water and put over Stored for 24 h at 40 ° C in a drying oven. Subsequently was the wood moisture of the samples and the content of formaldehyde in the water using the known acetylacetone method (see DIN standard).

• 1) 10 (+/– 1) mg
• 2) 33 (+/– 2) mg
• 3) 18 (+/– 1) mg
• 4) 49 (+/– 3) mg

Per 100 g wood mass (absolutely dry, atro), the losses of wood samples on formaldehyde were determined to be:

• 1) 10 (+/- 1) mg
• 2) 33 (+/- 2) mg
• 3) 18 (+/- 1) mg
• 4) 49 (+/- 3) mg

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 19921898 A1 [0005]
• EP 0862858 A1 [0006]
• - DE 3525104 [0042]

Cited non-patent literature

• - EN 84 [0127]

Claims (12)

Use of an amino group-containing polymer for the hydrophobing and / or fungicidal finish of lignocellulosic materials. Use according to claim 1, characterized the amino group-containing polymer is selected from the group that a. by reaction of a prepolymer with secondary and / or tertiary amino groups, obtainable by reaction of dicarboxylic acids with Dialkylenetriamines and / or bis (aminoalkyl) amines with epichlorohydrin are available, b. a homo- or copolymer with at least one of the structural units consisting of polyvinylimidazole, polyvinylalkylimidazolium, Polyvinyl pyridine, polyvinyl alkyl pyridinium, polyvinyl amine, optional N-alkylated, N, N-dialkylated or N, N, N-trialkylated, N-vinylformamide and / or poly (diallyldimethylammonium chloride) obtainable by polymerization are, c. polyalkyleneimines d. substituted with trialkylammonium Epoxide derivatized hydroxyalkyl cellulose, cellulose and or in situ cell wall polymers to be converted, e. polycationic starch, available by reacting starch with epoxy, which has been substituted with trialkylammonium, f. Polymers or Copolymers with structural units consisting of vinylpyrrolidone, vinylimidazole, quaternized vinylimidazole (QVI) and dialkylaminoethyl methacrylate are available, and G. methylene-linked Condensation products of cyanamide derivatives and an ammonium salt, H. Homopolymers and / or copolymers of acrylamides and acrylic acids and i. Mixtures of these includes. Use according to one of the preceding claims, characterized in that the polymer is quaternary amino groups contains. Use according to one of the preceding claims, characterized in that the polymer is converted by reacting its starting materials, optionally in the presence of a catalyst, in the lignocellulosic material is generated. Use according to one of the preceding claims, characterized in that the polymer additionally or in place of the hydrophobing and / or fungicidal equipment a barrier effect between lignocellulosic material and synthetic Polymer against the discoloration of synthetic polymer by Wood ingredients has. Use according to one of the preceding claims, characterized in that the polymer additionally or in place of the hydrophobing and / or fungicidal equipment causes the reduction of the formaldehyde release of wood. Use according to one of the preceding claims, characterized in that the polymer additionally or in place of the hydrophobing and / or fungicidal equipment as a bonding agent between lignocellulosic material and synthetic Polymer acts. Use according to one of the preceding claims, characterized in that the polymer is in aqueous solution or dispersion or in organic solvent. Use according to one of the preceding claims, characterized in that the polymer as a constituent of a varnish or a wood preservative paint is used. Use according to claim 7, characterized that the paint or the wood preservative paint an acrylic-based binder or alkyd base. Use according to one of the preceding claims, characterized in that the polymer is fixed in the wood with aldehyde becomes. Use according to one of the preceding claims, characterized by drying at a temperature in the range from 50 to 140 ° C before and / or after treatment with the Composition.