AT398402B - WATER-THINNABLE WOOD PRESERVATIVE CONCENTRATE AND PRODUCT MADE THEREOF FOR THE PRESERVATION OF WOOD AND WOOD MATERIALS AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Description

AT 398 402 B

The present invention relates to a water-dilutable wood preservative concentrate and to compositions for preserving wood and wood-based materials made therefrom, composed of 1.5 to 43 parts by weight, preferably 8 to 40 parts by weight, at least one organochemical, water-insoluble insecticide and / or at least one organic chemical, water-insoluble fungicide, 2.5 to 35 parts by weight, preferably 15 to 25 parts by weight, at least one water-dilutable synthetic resin (calculated as a solid), 3. 40 to 5 parts by weight, preferably 30 to 15 Parts by weight, of a solvent mixture containing a water-insoluble solvent, 4. at least one nonionic emulsifier or an emulsifier mixture, and 5. optionally water.

The wood preservative concentrate which can be diluted according to the invention is characterized in that the solvent mixture additionally contains at least 3.1 an organic chemical solvent which contains water and contains hydroxyl groups and / or ether groups, and the concentrate or agent 6. 0 to 6 parts by weight, preferably 1 to 2 Parts by weight of a chemical compound which acts as a buffer material or pH regulator and contains the concentrate or agent 50 to 37 parts by weight, preferably 48 to 38 parts by weight, of the nonionic emulsifier or emulsifier mixture.

A wood preservative concentrate and wood preservative according to the generic term is described in the German, not prepublished patent application P 30 04 319.7 (DE-A1-30 04 319). However, when using nonionic insecticides and fungicides, such wood preservatives have the disadvantage that, for example, cloudy emulsions or deposition of active ingredients, and thus the risk of partial loss of the active ingredients or a reduction in the active ingredient is not always avoidable.

From DE-B1-26 44 077 and DE-A1-27 11 639 wood preservatives based on non-volatile, oily or oily solvents (eg white spirit) are also known, which contain more than 50% by weight or more than 64% % By weight preferably contain more than 72% by weight of these low-volatility mineral oils as solvents, without there being water-dilutability.

The disadvantage of these wood preservatives based on mineral oil-like solvents is that they are dependent on the oil-producing countries, so that the prices vary greatly from the respective situation on the oil market. Finally, there is a risk of a certain environmental damage, especially if wood preservatives with these mineral oils get into the soil, as well as the risk that skin allergies, in particular in connection with the mineral oils, develop in combination with the biocides. If water is added to the wood preservatives according to DE-B1-26 44 077 or DE-A1-27 11 639, two phases are formed which differ strictly from one another. Even with the addition of small amounts of water, flocculation or precipitation occurs, so that the preservative can no longer be used properly in the brushing, spraying or rolling process.

In contrast to DE-B1-26 44 077 and DE-A1-27 11 639, the wood preservative or wood preservative concentrate according to the invention is a water-dilutable wood preservative which does not contain any additional swelling / thickening agents and the like and in which the synthetic resin used is a water-dilutable synthetic resin.

From GB-A-1 253 542, spraying agents containing emulsifiers - that is to say no wood preservative concentrates - are also known; in contrast to the water-dilutable wood preservative concentrate according to the invention, these spraying agents do not have any water-soluble, organic-chemical solvents containing hydroxyl groups and / or ether groups; they contain no synthetic resin, especially no alkyd resin; there is also no chemical compound that acts as a buffer material or pH regulator; and moreover, different weight concentrations are maintained than in the wood preservative concentrate according to the invention. 2nd

AT 398 402 B

The present invention is intended to avoid the disadvantages of the prior art in the production of ready-to-use wood preservatives with the addition of water and to obtain ready-to-use clear solutions, preferably as pseudo solutions, optically clear emulsions or microemulsions, the agents thus produced having a high level of effectiveness should.

According to the invention, it was found that these goals and tasks are fulfilled by a concentrate and a means of preserving wood and wood-based materials of the type mentioned at the outset with the characteristics already mentioned.

According to a preferred embodiment of the invention, the water-insoluble solvent or solvent mixture consists of 3.2.1 at least one aliphatic and / or 3.2.2 aromatic hydrocarbon and / or 3.2.3 a liquid plasticizer or a liquid plasticizer mixture, the weight ratio of water-insoluble to water-soluble organic -chemical solvent 6: 1 to 1:20, preferably 4: 1 to 1:10.

According to a preferred embodiment, the concentrate contains, as emulsifier or emulsifier mixture, at least 4.1 an ethoxylated phenol containing a side group, preferably an ethoxylated nonylphenol and / or 4.2 an ethoxylated fatty acid and 0 to 15 parts by weight, preferably 0.001 to 7 parts by weight, of water .

Through the use of the high emulsifier concentration, a fine distribution of the active ingredients is achieved and segregation, sediment or creaming are largely prevented.

According to one embodiment, the concentrate and the preservative for wood and wood-based materials produced therefrom contains a mixture of emulsifiers with different chain lengths, of which at least one emulsifier has an ethoxylated side chain of less than 10 ethoxy groups and at least one other emulsifier has an ethoxylated side chain of more than 10 has ethoxy groups.

According to a particularly advantageous embodiment, the concentrate contains, as a water-dilutable synthetic resin, an alkyd resin which has an average oil length. By using this synthetic resin, despite the small proportion of the organic chemical solvent, e.g. based on petroleum, achieved that on the one hand a better fixation of the active ingredients is achieved and on the other hand film formation is possible depending on the synthetic resin content.

According to a particularly expedient embodiment, the concentrate contains one or more alkaline compounds as a buffer material or pH value regulator for producing a pH value of 7 to 10.

To adjust the pH value, you can an alkali (e.g. sodium or potassium hydroxide solution), a basic substance (e.g. soda), an amine, an ammonium compound or a quaternary ammonium compound or a mixture thereof.

The nonionic water-insoluble organic chemical insecticide or insecticide mixture preferably consists of 1.1 from a carbamate, a phosphoric acid ester, a phosphonic acid ester, a thiophosphoric acid ester, a dithiophosphoric acid ester or a thionophosphoric acid ester, a chlorinated hydrocarbon, a pyrethroid and / or endosulfane or two or more of these Links.

Dieldrin, aldrin and lindane are preferably used as chlorinated hydrocarbons. Of the pyrethroids, allethrin, cyclethrin, furethrin, tetramethrin resmethrin, permethrin, decamethrin and bioresmethrin as well as other synthetic or natural insecticidal agents based on pyrethroid are preferably used.

Of the insecticidal carbamates, o-isopropoxyphenyl-N-methyl-carbamate and / or o-sec-butylphenyl-N-methyl-carbamate are preferably used.

Preferred insecticidal thionophosphoric esters are insecticidal halogenated or halogen-free thionophosphoric esters of the formula 3 15 20 25 30

AT 398 402 B

p _

CN

0 - N = C

preferably (diethoxy-thiophosphoryloxyimino) phenylacetonitrile or 0.0-diethyl-0- (a-cyanobenzylidene-amino) thionophosphate and / or (diethoxythiophosphoryloxyimino) -2-chlorophenylacetonitrii and / or other phosphoric acid esters, preferably dimethoxy-0- (6-nitro -m-tolyl) phosphorothioate used. The carbamates soluble in the oily or oily solvent are preferably alkoxy-phenyl-N-alkyl carbamates of the general formula 0 V 0 - C - NH - R1 'tD - R ~ and / or an alkylphenyl-N-alkyl carbamate of the general formula Q; 0 - C - NH - R. wherein each represents an alkyl radical with 1-4 carbon atoms, preferably a methyl radical, and for Ffe an alkyl radical 35 with 1-5 carbon atoms, preferably an alkyl radical with 3 or 4 carbon atoms , is used.

The nonionic organic-chemical water-insoluble fungicide or water-insoluble fungicide mixture preferably consists of 1.2 a tetravalent organotin compound, a 1-trityl-1,2,4-triazole of the general formula 40 Ν '

N 45

50

R n in which R represents a fluorine, chlorine or bromine atom, a trifluoromethyl, nitro or cyano group or a 55 alkyl group having up to 4 carbon atoms and n represents the numbers 1 or 2, and their salts of organic or inorganic acids, or a (N-cyclohexyl-diazeniumdioxy) metal compound (or salt of N-nitroso-N-cyclohexylhydroxylamine), preferably its aluminum compound, 2,5-dimethyl-N-cyclohexyl-N-methoxy-3-furan carboxamide and / or NN-dimethyl-N'-phenyl-N'-4

AT 398 402 B (fluorodichloromethylthio) sulfamide and / or N, N-dimethyl-N'-p-tolyl-N '- (dichlorofluoromethylthio) sulfamide, or from two or more of these compounds.

Examples of oil-soluble tetravalent, fungicidal organotin compounds that can be used are: tributyltin benzoate, tris (tributyltin) phosphate, bis (tri-butyltin) oxide, tributin tin naphthenate, tributyltin octoate.

Water-soluble polyols or ethers or esters of polyols, preferably glycol ethers, are used as water-soluble organic chemical solvents containing hydroxyl groups and / or ether groups.

Organic chemical solvents containing hydroxyl groups and / or ether groups are preferably ethylene glycol (2-hydroxyethanol), diethylene glycol (2,2-dihydroxy-diethyl ether), ethyl glycol (2-hydroxy-diethyl ether), butyl glycol (1-hydroxy- 2-n-butoxy-ethane) and / or ethyl diglycol (2-hydroxy-2-et-hoxy-diethyl ether).

Low-volatile solvents or solvent mixtures are advantageously used as organic water-insoluble solvents. Oily or mineral oil-containing or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 55 ° C., are preferably used.

Appropriate mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum, gas oil and / or alkylbenzenes etc., are used as such solvents.

Mineral oils with a boiling range of 150 to 220 ° C, white spirit with a boiling range of | 70 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 260 ° C, turpentine oil and the like used.

A plasticizer that is liquid at room temperature or a liquid plasticizer mixture is used as the softening agent.

At least one alkyl, aryl or aryl alkyl phthalate, preferably dibutyl, dioctyl and benzyl butyl phthalate, alkyl phosphate or phosphoric acid ester, preferably tributyl phosphate or an adipate, preferably di- (2-ethylhexyl) adipate, an alkyl stearate or alkyl oleate is preferred as the plasticizer , preferably butyl oleate, butyl stearate or amyl stearate or a liquid glycerol ester. For certain formulations, it may be expedient to add anti-foaming agents such as silicone defoamers or alkyl phosphates, preferably tri-n-butyl phosphate. Dyes or other additives can also be added, depending on the desired properties of the agent.

The ready-to-use agent for preserving wood and wood-based materials made from the wood preservative concentrate consists of 10 to 35% by weight, preferably 15 to 30% by weight, of the concentrate (calculated as an anhydrous concentrate) with 90 to 65% by weight, preferably 85 to 70% by weight, water.

The wood preservative can be applied to the wood by the methods known per se, preferably by brushing, spraying, spraying or using impregnation methods, for example immersion, pressure and / or vacuum methods.

The invention further relates to a method for producing the wood preservative concentrate and the means for preserving wood and wood-based materials produced therefrom. According to this process, the insecticide and / or fungicide which is soluble in the organic chemical solvent or solvent mixture and the nonionic emulsifier or the nonionic emulsifier mixture are at temperatures of 10 to 80 ° C., preferably 30 to 60 ° C., and at pressures of 0.5332 to 1.1332 bar, preferably 0.7999 to 1.0532 bar, treated in the presence or in the absence of the other substances or components of these substances until a solution is formed, the remaining substances including the buffer material and optionally water being subsequently added to the solution . 5

AT 398 402 B

Examples:

Example 1 1,2,3,4,10,10-hexachloro-1,4,4a, 5,8,8a-hexahydro-1,4-endo-5,8-exo-dimethanonaphthalene (Aidrin) 3.-% 2.5 dimethyl-N-cyclohexyl-N-methoxy-3-furancarboxamide 7.5% ethoxyated nonylphenol 42% water-thinnable alkyd resin 20% butyl glycol 8% ethylene glycol 10% hydrocarbon solvent mixture 7.5% amine 2 -% 100, -% 20 percent by weight of the concentrate was diluted with 80 percent by weight of water, the ready-to-use wood preservative being obtained in the form of an optically clear liquid.

The insecticidal and fungicidal wood preservative is also suitable for protecting wood and wood-based materials against termites.

Example 2 1,2,3,4,10,10-Hexachlor-1,4,4a, 5,8,8a-hexahydro-1,4-endo-5,8-exo-dimethanonaphthalene (Aidrin) 2.4% N-Cyclohexyl-diazenium-dioxy-aluminum 10% ethoxylated nonylphenol 42% water-thinnable alkyd resin 14.6% butyl glycol 6.2% hydrocarbon solvent mixture 23.3% amine 1.5% 100% 25% by weight of the concentrate was 75% by weight Diluted water, whereby the ready-to-use wood preservative is obtained in the form of an optically clear liquid.

The insecticidal and fungicidal wood preservative is also suitable for protecting wood and wood-based materials against termites.

Example 3 0.0-Diethyl-0- (a-cyanobenzylidene-amino) thionophosphate (phoxime) 10.00% 2.5 dimethyl-N-cyclohexyl-N-methoxy-3-furancarboxamide 7.5% ethoxyated nonylphenol 44 , -% water-dilutable alkyd resin 16.3% butylglycol 7.-% hydrocarbon solvent mixture 7.5% dibutyl phthalate 6.-% amine 1.7% 100.-% 20 percent by weight of the concentrate was diluted with 80 percent by weight water, the ready-to-use wood preservative in the form an optically clear liquid is obtained.

The insecticidal and fungicidal wood preservative is also suitable for indoor use. 6

Claims (9)

AT 398 402 B Claims 1. Water-dilutable wood preservative concentrate and agent made therefrom for preserving wood and wood-based materials, composed of 1.5 to 43 parts by weight, preferably 8 to 40 parts by weight, at least one organic chemical, water-insoluble insecticide and / or at least one organic chemical, water-insoluble fungicide, 2. 5 to 35 parts by weight, preferably 15 to 25 parts by weight, at least one water-dilutable synthetic resin (calculated as a solid), 3. 40 to 5 parts by weight, preferably 30 to 15 parts by weight of a solvent mixture which contains a water-insoluble solvent, 4. at least one nonionic emulsifier or an emulsifier mixture, 5. and optionally water, characterized in that the solvent mixture additionally contains at least 3.1 a water-soluble, hydroxyl groups and / or Contains organic chemical solvent containing ether groups, and the Ko Concentrate or agent 6. 0 to 6 parts by weight, preferably 1 to 2 parts by weight, of a chemical compound which acts as a buffer material or pH regulator, and the concentrate or agent contains 50 to 37 parts by weight , preferably 48 to 38 parts by weight of the nonionic emulsifier or emulsifier mixture. 2. Water-dilutable wood preservative concentrate and agent prepared therefrom for preserving wood and wood-based materials according to claim 1, characterized in that the water-insoluble solvent mixture from 3.2.1 at least one aliphatic and / or 3.2.2 aromatic hydrocarbon and / or 3.2.3 a liquid plasticizer or . consists of a liquid plasticizer mixture and is in a weight ratio to 3.1 water-soluble organic chemical solvent of 6: 1 to 1:20, preferably 4: 1 to 1:10., 3. Water-dilutable wood preservative concentrate and agent prepared therefrom for preserving wood and wood-based materials according to claim 1 or 2, characterized in that the concentrate as an emulsifier or emulsifier mixture contains at least 4.1 an ethoxylated phenol containing a rare group, preferably an ethoxylated nonylphenol and / or 4.2 an ethoxylated fatty acid and 0 to 15 parts by weight, preferably 0.001 to 7 parts by weight, of water. 4. Water-dilutable wood preservative concentrate and agent made therefrom for preserving wood and yard materials according to one of claims 1 to 3, characterized in that the concentrate contains a alkyd resin with a medium oil length as water-dilutable synthetic resin 2.1. 5. Water-dilutable wood preservative concentrate and agent prepared therefrom for preserving wood and wood-based materials according to one of claims 1 to 4, characterized in that the concentrate as a buffer material or pH value regulator for setting a pH value of 7-10 7 AT 398 402 B 5.1 contains one or more alkaline compounds. 6. Water-dilutable wood preservative concentrate and agent made therefrom preserving wood and wood-based materials according to one of claims 1 to 5, characterized in that the nonionic insecticide or insecticide mixture 1.1 from a carbamate, a phosphoric acid ester, a phosphonic acid ester, a thio-phosphoric acid ester, one Dithiophosphoric acid ester or a thionophosphoric acid ester, a chlorinated hydrocarbon, a pyrethroid and / or endosulfan or two or more of these compounds. 7. Water-dilutable wood preservative concentrate and agent prepared therefrom for preserving wood and wood-based materials according to one of claims 1 to 5, characterized in that the nonionic water-insoluble fungicide or water-insoluble fungicide or water-insoluble fungicide mixture 1.2 from a tetravalent organotin compound, a 1-trityl 1,2,4-triazole of the general formula in which R stands for a fluorine, chlorine or bromine atom, a trifluoromethyl, nitro or cyano group or an alkyl group with up to 4 congener atoms and n for the numbers 1 or 2, and their salts of organic or inorganic acids, or one (N-Cyclohexyl-diazenium-dioxy) metal compound (or salt of N-nitroso-N-cyclohexylhydroxylamine), preferably its aluminum compound, 2,5-dimethyl-N-cyclohexyl-N-methoxy-3-furan-carboxamide and / or N, N-dimethyl-N'-phenyl-N '(fluorodichloromethylthio) sulfamide and / or N, N-dimethyl-N'-p-tolylN' - (di-chlorofluoromethylthio) sulfamide, or from two or more of these Connections exist. 8. Water-dilutable wood preservative concentrate and agent prepared therefrom for preserving wood and wood-based materials according to one of claims 1 to 7, characterized in that the ready-to-use agent prepared from the wood preservative concentrate for preserving wood and wood-based materials from 10 to 35% by weight, preferably 15 to 30% by weight of the concentrate (calculated as anhydrous concentrate) and 90 to 65% by weight, preferably 85 to 70% by weight, of water and in the form of a solution, pseudo-solution or optically clear emulsion or Micro-emulsion is present. 9. The method for producing the water-dilutable wood preservative concentrate according to one of claims 1 to 7, characterized in that the insecticide and / or fungicide soluble in the organic chemical solvent or solvent mixture and the nonionic emulsifier or the 8 AT 398 402 B nonionic emulsifier mixture at temperatures of 10 to 80 * C, preferably 30 to 60 * C, and at pressures of 0.5332 to 1.1332 bar, preferably 0.7999 to 1.0532 bar, treated in the presence or in the absence of the other substances or components of these substances until a solution is formed, with the remaining substances including the buffer material and, if appropriate, water being subsequently added to the solution. 9