BIOCIDAL MIXTURES

Abstract

The invention relates to biocidal mixtures comprising penflufen-containing polymer particles, copper compounds and specific alkanolamines and to the use thereof for protecting wood and wood products, and also to wood preservatives comprising biocidal mixtures and optionally further active ingredients.

Claims

1. A biocidal mixture comprising: penflufen-containing polymer particles, at least one alkanolamine selected from the group consisting of monoalkylmonoamines, monoalkyldiamines, dialkylamines and trialkylamines, substituted by one, two or three hydroxyl groups, and at least one copper compound or copper complexes of the alkanolamine.

2. The biocidal mixture as claimed in claim 1, wherein the penflufen-containing polymer particles comprise at least one styrene polymer, styrene copolymer, acrylic polymer or acrylic copolymer.

3. The biocidal mixture as claimed in claim 1, wherein the penflufen-containing polymer particles comprise at least one polyalkyl acrylate, polyalkyl methacrylates, or copolymers of alkyl acrylates and alkyl methacrylates.

4. The biocidal mixture as claimed in claim 1, wherein the penflufen-containing polymer particles are produced by radical oil-in-water emulsion polymerization wherein at least one ethylenically unsaturated monomer is polymerized in the presence of penflufen or its salts and acid addition compounds and in the presence of a radical initiator.

5. The biocidal mixture as claimed in claim 4, wherein the ethylenically unsaturated monomers are styrene, divinylbenzene, C.sub.1-C.sub.20 alkyl acrylates, C.sub.1-C.sub.18 alkyl methacrylates, or mixtures of these monomers.

6. The biocidal mixture as claimed in claim 1, wherein the copper compounds comprise water-soluble inorganic copper compounds.

7. The biocidal mixture as claimed in claim 1, wherein the copper compounds comprise copper sulfate, copper acetate, copper carbonate, copper hydroxide, copper borate, copper fluoride, copper oxide, copper chloride, copper hydroxide carbonate, or mixtures of these compounds.

8. The biocidal mixture as claimed in claim 1, wherein the alkanolamines comprise C.sub.1-C.sub.8 monoalkylmonoamines, C.sub.1-C.sub.8 monoalkyldiamines, or secondary C.sub.1-C.sub.8 dialkylamines substituted by one or two hydroxyl groups.

9. The biocidal mixture as claimed in claim 1, wherein the alkanolamines comprise isopropanolamine, 1,1- and 1,2-diaminoethanol, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine, monoethanolamine, or mixtures of these compounds.

10. The biocidal mixture as claimed in claim 1, wherein the molar amount of copper compounds used, based on the molar amount of penflufen in the penflufen-containing polymer particles, is 90:1 to 10:1.

11. The biocidal mixture as claimed in claim 1, wherein the amount of penflufen, based on the total amount of the penflufen-containing polymer particles, is 0.5% by weight to 15% by weight.

12. A wood preservative comprising biocidal mixtures as claimed in claim 1 and at least one solvent or diluent, and also optionally thickeners, optionally defoamers, optionally in-container preservatives, and optionally further biocides.

13. A method of protecting wood, wood products or wood-plastic composites against infestation and/or destruction by microorganisms, the method comprising contacting the wood, wood products or wood-plastic composites with the mixture as claimed in claim 1.

14. The method as claimed in claim 13, wherein the contacting comprises brushing, dipping, drenching, vacuum impregnating, pressure treatment, and combinations thereof.

15. A wood, woodbase material or wood-plastic composite comprising the biocidal mixture as claimed in claim 1.

16. The biocidal mixture as claimed in claim 1, wherein: the penflufen-containing polymer particles comprise at least one styrene polymer, styrene copolymer, acrylic polymer or acrylic copolymer; the copper compounds comprise water-soluble inorganic copper compounds; the alkanolamines comprise C.sub.1-C.sub.8 monoalkylmonoamines, C.sub.1-C.sub.8 monoalkyldiamines, or secondary C.sub.1-C.sub.8 dialkylamines substituted by one or two hydroxyl groups.

17. The biocidal mixture as claimed in claim 16, wherein: the amount of penflufen, based on the total amount of the penflufen-containing polymer particles, is 0.1% by weight to 30% by weight; the molar ratio of alkanolamines to penflufen is 600:1 to 8:1; and the molar amount of copper compounds, based on the molar amount of penflufen in the penflufen-containing polymer particles, is 150:1 to 2:1.

18. The biocidal mixture as claimed in claim 17, wherein: the amount of penflufen, based on the total amount of the penflufen-containing polymer particles, is 0.5% by weight to 15% by weight; the molar ratio of alkanolamines to penflufen is 360:1 to 40:1; and the molar amount of copper compounds, based on the molar amount of penflufen in the penflufen-containing polymer particles, is 90:1 to 10:1.

19. The biocidal mixture as claimed in claim 18, wherein: the penflufen-containing polymer particles comprise at least one polyalkyl acrylate, polyalkyl methacrylates, or copolymers of alkyl acrylates and alkyl methacrylates; the copper compounds comprise copper sulfate, copper acetate, copper carbonate, copper hydroxide, copper borate, copper fluoride, copper oxide, copper chloride, copper hydroxide carbonate, or mixtures of these compounds; and the alkanolamines comprise isopropanolamine, 1,1- and 1,2-diaminoethanol, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine, monoethanolamine, or mixtures of these compounds.

Description

EXAMPLES

Example 1

[0212] 1.1 Production of the Penflufen-Containing Polymer Particle

[0213] A solution of 2.88 g of SDS (Na dodecyl sulfate), 0.163 g of sodium hydrogencarbonate in 200 g of water is admixed with an organic solution consisting of 91.7 g of methyl methacrylate, 4.3 g of penflufen, 3.84 g of hexadecane and 1.63 g of 2,2-azobis(2-methylbutyronitrile) and is treated by means of a continuous Ultraturrax (IKA T 25 digital/fitted with DK 25.11; 14 000 rpm) for 30 minutes in order to produce an emulsion. This emulsion is subsequently transferred to a 1000 ml three-neck flask, where it is washed with N.sub.2 and heated slowly with stirring to 70 C. It is thereafter stirred at this temperature for 15 hours. After cooling, a low-viscosity, whitish suspension is obtained which has a penflufen content of 1.56% (HPLC).

[0214] Average particle size (measured by laser diffraction) 0.153 m; 90% of the particles (vol %) are smaller than 0.382 m.

[0215] 1.2 Production of the Penflufen Solution for the Comparative Experiment

[0216] 7.5 g of penflufen are dissolved with stirring in a mixture of 232.5 g of Genagen 4296 (N,N-dimethyl-fatty acid amide/CAS No. 14433-76-2) and 260 g of Emulan EL (ethoxylated castor oil). The solution contains 1.5% by weight of penflufen.

[0217] 1.3 Preparation of the Copper-Ethanolamine Complex

[0218] An aqueous solution of copper-ethanolamine was prepared by dissolving 455.25 g of copper carbonate/hydroxide (also known as basic copper carbonate) in 959.00 g of ethanolamine and 1085.75 g of water and stirring. The copper content is 10% by weight.

[0219] 1.4 Production of the Mixtures of Penflufen Plus Copper-Ethanolamine Complex Investigated in Example 2

[0220] The copper-ethanolamine complex from example 1.3 is introduced into a conical flask in an amount leading to the copper/penflufen amount-by-weight ratios employed in table 1. With continual stirring, on a magnetic stirrer, the required amount of penflufen solution from example 1.2 or, respectively, the required amount of penflufen-containing polymer from example 1.1 is slowly added, and stirring is continued for 3 hours.

TABLE-US-00001 TABLE 1 (composition of the active ingredient solutions used in example 2) Penflufen Copper- Penflufen- solution ethanolamine containing (from complex polymer example (from (from 1.2 example example (comparative Active ingredient Number 1.3) 1.1) experiment)) Cu + penflufen JJT 85.6% 14.4% (40:1) 6646 by weight by weight Cu + penflufen in JJT 86.5% 13.5% polymer (40:1) 6648 by weight by weight Cu + penflufen JJT 93.7% 6.3% (100:1) 6647 by weight by weight Cu + penflufen in JJT 94.1% 5.9% polymer (100:1) 6649 by weight by weight

Example 2

[0221] The activity of the penflufen-containing polymer particles in the mixture with copper was determined in accordance with DIN EN 113. The test reference used was a mixture of penflufen and copper.

[0222] For this, test specimens measuring 25154 mm of wood species Pinus sylvestris and Fagus sylvatica were vacuum-impregnated with 0.04 to 0.4% strength aqueous solutions of active ingredient (copper and penflufen) and conditioned for 14 days. The amount of the active ingredients per kg/m.sup.3 in the treated test specimens was measured and is set out in tables A to D. After 14 days, the test specimens on an agar medium were inoculated with a fungal spore suspension in accordance with DIN EN 113. After a further 10 or 11 weeks of incubation, a determination was made of the average weight loss of the wooden test specimens.

TABLE-US-00002 TABLE A (Test fungus: Coniophora puteana; wood: Pinus sylvestris) Amount Average of active weight ingredient loss of in wood wood Active ingredients Number [kg/m.sup.3] [%] Cu + penflufen JJT 0.32 3.7 (40:1) 6646 Cu + penflufen JJT 0.46 1.6 (40:1) 6646 Cu + penflufen in JJT 0.32 0.6 polymer (40:1) 6648 Cu + penflufen in JJT 0.46 0.3 polymer (40:1) 6648 Cu + penflufen JJT 0.51 17.5 (100:1) 6647 Cu + penflufen JJT 0.71 3.4 (100:1) 6647 Cu + penflufen in JJT 0.51 2.7 polymer (100:1) 6649 Cu + penflufen in JJT 0.71 0.5 polymer (100:1) 6649

TABLE-US-00003 TABLE B (Test fungus: Poria placenta; wood: Pinus sylvestris) Amount of Average active weight ingredient loss in wood of wood Active ingredients Number [kg/m.sup.3] [%] Cu + penflufen JJT 0.32 27 (40:1) 6646 Cu + penflufen JJT 0.46 9.5 (40:1) 6646 Cu + penflufen in JJT 0.32 5.6 polymer (40:1) 6648 Cu + penflufen in JJT 0.46 1.9 polymer (40:1) 6648 Cu + penflufen JJT 0.51 50 (100:1) 6647 Cu + penflufen JJT 0.71 41 (100:1) 6647 Cu + penflufen in JJT 0.51 3.8 polymer (100:1) 6649 Cu + penflufen in JJT 0.71 0.2 polymer (100:1) 6649

TABLE-US-00004 TABLE C (Test fungus: Gloeophyllum trabeum; wood: Pinus sylvestris) Amount Average of active weight ingredient loss of in wood wood Active ingredients Number [kg/m.sup.3] [%] Cu + penflufen JJT 0.32 4.0 (40:1) 6646 Cu + penflufen JJT 0.46 1.2 (40:1) 6646 Cu + penflufen in JJT 0.32 0.2 polymer (40:1) 6648 Cu + penflufen in JJT 0.46 0.1 polymer (40:1) 6648 Cu + penflufen JJT 0.51 4.4 (100:1) 6647 Cu + penflufen JJT 0.71 0.6 (100:1) 6647 Cu + penflufen in JJT 0.51 1.3 polymer (100:1) 6649 Cu + penflufen in JJT 0.71 0.6 polymer (100:1) 6649

TABLE-US-00005 TABLE D (Test fungus: Coriolus versicolor; wood: Fagus sylvatica (beech)) Amount Average of active weight ingredient loss of in wood wood Active ingredients Number [kg/m.sup.3] [%] Cu + penflufen (40:1) JJT 6646 0.32 3.4 Cu + penflufen (40:1) JJT 6646 0.46 1.0 Cu + penflufen in polymer (40:1) JJT 6648 0.32 0.2 Cu + penflufen in polymer (40:1) JJT 6648 0.46 0.1 Cu + penflufen (100:1) JJT 6647 0.51 6.5 Cu + penflufen (100:1) JJT 6647 0.71 2.2 Cu + penflufen in polymer (100:1) JJT 6649 0.51 0.3 Cu + penflufen in polymer (100:1) JJT 6649 0.71 0.3

[0223] Surprisingly, the average weight loss of wood for mixtures which comprise penflufen and polymer and copper as active ingredients is much smaller in comparison to mixtures where penflufen and copper have been used, in other words those in which at least part of the penflufen has not been protected by the polymer.