Agents for preserving wood or composite-wood materials against insects

Abstract: The use of the compounds of the formula (I) as agents for preserving technical materials against insects.

Description: The present invention relates to the use of known 1(6-chloro-3-pyridylmethyl)-2-nitroimino-imidazolidine (in the following Imidacloprid) in agents for combating insects destroying wood or composite wood-materials in order to preserve these materials. Imidacloprid and its insecticidal use in the field of plant protection has already been known. Compare for example with EP-A 163855 and EP-A 192060. The use of Imidacloprid to preserve wood and composite wood-materials has not been known up to now. Different insects are known as pests infesting technical materials so that due to serious damages caused thereby undesirable effects on living environment and cultural assets principally made of these materials have posed a social problem, urgently requiring effective controlling of the pests. Termites are known as important examples of these pests. At present, use for combating technical materials destroying insects has been made of organophosphorus insecticides such as phoxim [0-(α-cyanobenzylideneamino)0,0-diethylphosphorothioate], chloropyriphos [0,0-diethyl-3,5,6-trichloro-2-pyridylphosphorothioate], etc., as well as pyrethroides series insecticides such as permethrin [5-benzyl-3-furylmethyl-3-(2-methoxy-carbonyl-1-propenyl)-2,2-dimethylcyclopropane carboxylate], decamethrin [α-cyano-3-phenoxybenzyl d,ℓ-cis-3-(2,2-dibromovinyl)-2,2-dimethyl cyclopropane carboxylate], cypermethrin [α-cyano-3-phenoxybenzyl (±) cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], fenvalerate [(RS)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate], cyflutrine [cyano-(4-fluoro-3-phenoxyphenyl) methyl-3-(2,2-dichloroethenyl)-2,2-dimethyl-cyclopropane carboxylate]. However, the above-mentioned insecticides are unsatisfactory as far as effective concentration and the long lasting effect are concerned. It has been found that Imidacloprid of the formula (I) exhibits powerful insecticidal properties on wood or composite wood-destroying insects and preferably on termites. Imidacloprid surprisingly exhibits an extremely strong insecticidal action on wood and composite wood-destroying insects and the function is substantially superior to that of known insecticidal agents. Imidacloprid can be used to preserve wood and composite wood-materials against insects Imidacloprid can therefore be used in insectidal agents for combating material destroying insects and preserving wood and wood composite-materials. It can also be used for soil treatment against termite manifestation. As individual examples of technical materials preserved by means of the insecticidal agents according to the present invention the following ones can be mentioned: wood or composite wood-materials (such as pressed wood, particle board, chip board, wafer board, plywood, wood laminated material, freshly cut timber/lumber etc.). As individual examples of insects to be combated or controled by the active substances of formula (I) according to the present invention the following ones can be mentioned: Order Isoptera Mastotermitidae Kalotermitidae such as Kalotermes spp. Cryptotermes spp. etc. Termopsidae such as Zootermopsis spp. etc. Rhinotermitidae such as Reticulitermes spp. Heterotermes spp. Coptotermes spp. etc. Termitidae such as Amitermes spp. Nasutitermes spp. Acanthotermes spp. Mikrotermes spp. etc. Order Coleoptera Lyctidae such as Lyctus brunneus etc. Bostrychidae such as Bostrychus capucinus Dinoderus minutus etc. Anobiidae such as Anobium punctatum Xyletinus peltatus Xestobium rufovillosum Ptilinus pectinicomis etc. Cerambycidae such as Hylotrupes bajulus Hesperophanus cinereus Stromatium fulvum Chlorophorus pilosus etc. Oedemeridae Serropulpidae Curculionidae Seolytida Platypodidae Order Hymenoptera Siricidae such as Sirex spp. Urocerus spp. Formicidae such as Camponotus spp. In the above Isopterous insects, especially, there may be mentioned as examples of termites in Japan: Deucotermes speratus, Coptotermes formosanus, Glyptotermes fucus, Glyptotermes satsumensis, Glyptotermes nakajimai, Glyptotermes Kodamai, Incisitermes minor, Neotermes koshunensis, Cryptotermes domesticus, Hodotermopsis japonica, Reticulitermes miyatakei, Odontotermes formosanus, Nasutitermes takasagoensis, Capritermes nitobei and so on. Imidacloprid can be prepared into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compounds, and micro-capsules. These formulations may be produced in a known manner, for example, by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents, dispersing agents, and/or foam-forming agents. In the case of using water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid diluents or carriers can be mentioned, for example, aromatic hydrocarbons, such as xylene, toluene and alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes and methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example, mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethylsulfoxide, as well as water. By liquefied gaseous diluents or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example, aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. As solid diluents there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceus earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. As emulsifying and/or foam-forming agents there may be used nonionic and ionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulfite waste liquors and methyl cellulose. Adhesives such as carboxymethyl cellulose and natural and synthetic polymers, (such as gum arabic, polyvinyl alcohol and polyvinyl acetate) can be used in the formulations in the form of powders, granules or emulsifiable concentrations. It is possible to use colorants such as inorganic pigments, for example, iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace elements, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. The formulations, in general, contain from 0.001 to 95 percent by weight of active compound, preferably from 0.5 to 90 percent by weight. Furthermore, Imidacloprid can be present as a mixture with a synergist in a formulation or a use form, of the type that is commercially useful. The term "synergist" denotes a compound which is not active in itself, but promotes the action of an active compound. The content of Imidacloprid in commercially useful formulations can vary within a wide range. The active compound concentration of the formulation for use is, for example, from 0.0000001 to 100 percent by weight, preferably from 0.0001 to 1 percent by weight. In order to protect the above-mentioned materials completely, i.e. not only against material destroying insects but also against fungi, bacteria and algae, they can be treated with compositions containing at least Imidacloprid and at least one biological active fungicide, bactericide or algicide has to be present. Wood or composite wood-materials can preferably be treated with a composition containing a) an insecticidally effective amount of Imidacloprid or mixtures thereof and b) a fungicidally effective amount of at least one compound selected from the group of Trihalosulfenyl-Compounds such as N-Dichlorofluoromethylthio-N',N ' -dimethyl-N-phenylsulfuric acid diamide (Dichlofluanide) N-Dichlorofluoromethylthio-N',N ' -dimethyl-N-p-toluylsulphamide (Tolylfluanide) N-Trichloromethylthiophthalimide (Folpet) N-Dichlorofluoromethylthiophthalimide (Fluorfolpet) etc. Iodine-Compounds such as 3-Iodo-2-propynyl-butylcarbamate (IPBC) 3-Iodo-2-propynyl-hexylcarbamate 3-Iodo-2-propynyl-cyclohexylcarbamate 3-Iodo-2-propynyl-phenylcarbamate Diiodmethyl-p-tolylsulphone (Amical 48) etc. Phenols such as ortho-Phenylphenol Tribromophenol Tetrachlorophenol Pentachlorophenol etc. Azole-Compounds such as 1-(4-Chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4 triazol-1-yl)-2-butanone (Triadimefon) β-(4-Chlorophenoxy)-α-(1,1 dimethyl-ethyl)-1H-1,2,4 triazole-1-ethanol (Triadimenol) ±α[2-(4-chlorophenyl) ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (Tebuconazole) 1-[2(2,4-dichlorophenyl) 4-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole (Propiconazol) 1-[2(2,4-dichlorophenyl)-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole (Azaconazol) (RS)-2(2,4-dichlorophenyl)-1-(1H-1,2,4 triazol-2-yl)-2-ol (Hexaconazol) 1-N-propyl-N-[2-(2,4,6-trichlorophenoxy) ethyl] carbamoylimidazol (Prochloraz) etc. Tin Compounds such as Tributyl tin octoate Tributyl tin oleate Bistributyl tin oxide Tributyl tin naphthenate Tributyl tin phosphate Tributyl tin benzoate etc. Thiocyanate Compounds such as Methylenebisthiocyanate (MBT) 2-Thiocyanomethylthiobenzothiazole (TCMTB) etc. Quarternary Ammonium Compounds such as Benzyl-dimethyl-tetradecylammoniumchloride Benzyl-dimethyl-dodecylammoniumchloride etc. Benzimidazole Compounds such as 2-(2 ' -Furyl)-1H-benzimidazole (Fuberidazole) Methylbenzimidazol-2-ylcarbamate (BCM) 2-(4 1 -thiazolyl) benzimidazole (Thiabendazole) Methyl (1-butylcarbamoyl)-2-benzimidazole carbamate (Benomyl) Isothiazolinone Compounds such as N-Methylisothiazolin-3-one 5-Chloro-N-methylisothiazolin-3-one 4,5-Dichloro-N-octylisothiazolin-3-one N-Octylisothiazolin-3-one Morpholine Compounds such as C 14 -C 11 -4-Alkyl-2,6-dimethylmorpholine (Tridemorph) Pyridine Compounds such as 1-Hydroxy-2-pyridine-thione and Sodium Iron, Manganese or Zinc-Salt thereof Tetrachloro-4-methyl sulphonyl pyridine N-Cyclohexyldiaziniumdioxy Compounds such as Tris-(N-cyclohexyldiaziniumdioxy) aluminium Bis-(N-cyclohexyldiaziniumdioxy) copper Naphthenate Compounds such as Zincnaphthenate Quinoline Compounds such as the copper salt of 8-hydroxy-quinoline Nitriles such as 1,2,3,5-Tetrachloro-4,6-cyanobenzene. Boric compounds such as boric acid, borax, borates Ureas such as N'(3,4-dichlorophenyl)-N,N-dimethylurea Furane derivatives such as Furmecyclox These fungicidally effective compounds are added to the composition in order to prevent wood or wood materials not only against wood destroying insects but also against Wood-discoloring fungi such as Ascomycetes (Caratocystis minor) Deuteromycetes (Aspergillus niger, Aureobasidium pullulans, Dactyleum fusarioides, Penicillium Variabile, Sclerophoma pithyophila, Scopularia phycomyces, Trichoderma viride, Trichoderma liguorum) Zygomycetes (Mucor spinosus) and/or Wood-destroying fungi such as Ascomycets (Chetomium alba-arenulum, Chaetonium globosum, Humicola grisea, Petriella setifera, Trichurus spiralis) Basidiomycetes (Coniophera puteana Coriolus versicolor Donbiopora expansa Glenospora graphii Gloeophyllum abietinum Gloeophyllum adoratum Gloeophyllum protactum Gloeophyllum trabeum Gloeophyllum sepiarium Lentinus cyathioformes Lentinus edodes Lentinus lepideus Lentinus squavrolosus Paxillus panuoides Pleurofus ostreatus Poria placenta Poria monticola Poria vaillantii Poria vaporia Serpula himantoides Serpula lacrymans Tyromyces palustris) Deuteromycetes (Cladosporium herbarum). Generally the compositions also will include at least one additional diluent, emulsifier, melting agent, organic binding agent, auxiliary solvents, processing additives, fixatives, plasticizers, UV-stabilizers or stability enhancers, dyes (water soluble, water insoluble), color pigments, siccatives, corrosion inhibitors, antisettlement agents, additional insecticides (such as insecticidal carbamates, organophosphorus compounds, halogenated hydrocarbons, pyrethroides etc.), anti skinning agents and the like. The above-mentioned additional ingredients and their use are described in prior art. (EP-A 0370665, DE-A 3531257, DE-A 3414244). The compositions according to the present invention generally comprise from about 10 -6 to 30 parts by weight, preferably from about 0.0005 to 15 parts by weight and more preferably from 0.005 to 2 parts by weight of the insecticide Imidacloprid and from 0.01 to 90 parts by weight, preferably from about 0.05 to 50 parts by weight and more preferably from 0.1 to 30 parts by weight of at least one of the above-mentioned fungicides. The compositions can be provided as ready for use products or as concentrates, which have to be diluted prior to use. The compositions can be applied by means of brushing, spraying, dipping, double vacuum and the like as known in the art. The compositions can be prepared by any technique known in the art. The content of the present invention will be concretely explained by way of the following examples but the present invention should not be limited only thereto. Examples for compositions: *Remark: the percentages are given in percent by weight Example 1 0.005% 1-(6-chloro-3-pyridylmethyl)-2-nitroiminoimidazolidine (imidacloprid) 5 % Butylglycol 94.995% Mineral spirits Example 2 Impregnating agent/Primer 0.01 % Imidacloprid 0.5 % Dichlofluanide 1. % Tebuconazole 9.7 % Alkyd resin (solid) 88.79 % Mineral spirits Example 3 Wood stain/low build 0.01 % imidacloprid 0.5 % Dichlofluanide 1.2 % Tebuconazole 21 % Alkyd resin (solid) 2 % Pigment 4 % Antisettlement additive, dryes etc. 71.29% Mineral spirits Example 4 Wood stain/high build 0.015% imidacloprid 0.6 % Dichlofluanide 1.5 % Tebuconazole 40 % Alkyd resin 2 % Pigment 4 % Antisettlement additive, dryer etc. 48.115% Mineral spirits Example 5 Soil treatment 20 % imidacloprid 8 % ethylene glycol 3 % emulsifiers 0.25 % thickeners 68.75 % distilled water Example 6 Wood brushing 0.1 % imidacloprid 1 % 3-bromo-2,3-diiodo-2-propenyl ethylcarbonate 98.9 % organic solvents Example 7 wood brushing 0.1 % imidacloprid 1.5 % 4-chlorophenyl-3-iodopropargylformal 98.4 % organic solvents Example 8 Formicidal test Compounds under test The active compound according to the present invention I.3: Imidacloprid Comparative Compounds I.1: 1-(6-chloro-3-pyridylmethyl)-2-nitromethylene-imidazolidine I.2: 3-(6-chloro-3-pyridylmethyl)-2-nitromethylenethiazolidine A : phoxim B : chlorpyriphos Preparation of test formulation: Solvent: 3 parts by weight of xylene Emulsifier: 1 part by weight of polyoxyethylene-alkylphenyl-ether To prepare a suitable formulation of the active compound, 1 part by weight of each of the active compounds was mixed with the above-mentioned amount of the solvent containing the above-mentioned amount of the emulsifier, and the mixture was diluted with water to a predetermined concentration. Test method: 1 ml of the aqueous solution prepared in the above-mentioned procedure was uniformly applied using a pipette onto a filter paper that was placed in petri dish of 9 cm diameter. Ten head of worker termites (Coptotermes formosanus) were replaced into the petri dish and it was kept in a constant temperature chamber at 25°C. After four days, the mortality of the termites was investigated. This test procedure was carried out in duplicate per each concentration of the active compounds under test. The test results are shown in Table 1. Compound Concentration of active compound (ppm) Mortality of termites after four days (%) I.1 40 100 8 100 1.6 100 0.32 100 I.2 40 100 8 100 1.6 100 0.32 100 I.3 40 100 8 100 1.6 100 0.32 100 A 40 100 8 100 1.6 100 0.32 90 B 40 100 8 100 1.6 100 0.32 100 Untreated 0 Example 9 Test on Residual Effect Small blocks of Japanese redpine tree ( 2 cm x 2 cm x 2 cm) were soaked for one minute into the aqueous solution prepared by the similar procedure to Example 8. After air-dried, they were kept in a constant temperature chamber at 40°C for four weeks. Then each of the thus treated blocks was placed in a polymeric cup (10 cm diameter) containing 150 ml of sandy loam of 20 % moisture content. Into each of the polymeric cups, 100 head of working termites and 10 head of soldier termites (Coptotermes formosanus) were released. After three weeks, the degree of xylophagous damage in the block and the mortality of the termites were investigated. Three tests were carried out in duplicate 25°C, and the results are shown in Table 2. The index of xylophagous damage observed on the test blocks: 0 : No damage 0.5 : One to two traces of damage each having a depth of about 1 mm from the block surface 1 : One to two evident damages each having a depth from 1 to 2 mm from the block surface 2 : More than three evident damages or more than one deep trace of damage having a depth of more than 2 mm from the block surface 3 : More than three deep damages 4 : Evidently damaged zone covering up to about one third of the whole surface area of the block 5 : Evidently damaged zone covering more than one third of the whole surface area of the block Compound Concentration of active compound (ppm) Mortality termites after three weeks (%) Degree of xylophagous damage in the pine tree block (0 -5) I.1 40 100 0 8 100 0 1.6 100 0 0.32 98 0.5 I.2 40 100 0 8 100 0 1.6 100 0 0.32 100 0 I.3 40 100 0 8 100 0 1.6 100 0 0.32 100 0 A 40 25 3 8 0 5 1.6 0 5 0.32 0 5 B 40 100 0 8 78 1 1.6 0 3 0.32 0 5 Untreated 0 5 Example 10 Toxic value against larvae of Hylotrupes bajulus The toxicity against larvae of Hylotorupes bajulus, using wood samples treated with the active compound I.3 provided in Example 8 in chloroform having concentrations of 1.44 x 10 -5 %, 1.44 x 10 -4 %, 7.2 x 10 -3 %, and 1.44 x 10 -2 % was determined according to the detailed description of DIN EN 47 (edition 1990, Beuth Verlag GMBH) which is concerned with the European standard method prescribed by the European Committee for standardization concerning wood preservatives, determination of the toxic value against larvae of Hylotrupes bajulus. An outline of the method is as follows: (see DIN EN 47 for detail) Five wood-samples (50 mm x 25 mm x 15 mm) which are treated by the active compound beforehand (impregnation treatment in vacuum) are provided and in each specimen, a regular pattern of six holes are bored, and then one head of the larvae is inserted per a hole. After four weeks, the specimens are cut up in turn and the number of live/dead of larvae is determined. In determination, where a live larvae is identified in a specimen, then the remaining specimens without cutting up are stored for a further eight weeks, and afterword, the number of live/dead larvae is determined. From this test, the Toxic threshold value was between 1.08 g/m 3 and 10.8 g/m 3 of the active compound I.3. The results are shown in Table 3. Comparative values of W. Metzner et al in "Holz als Roh- und Werkstoff, 35 (1977) 233-237", table 6 on page 236. Insecticide toxic value (g/m 3 ) Insecticide toxic value (g/m 3 ) DDT 5 - 10 Bassa (Baycarb) 17 - 30 - 44 Diazinon 12 - 18 - 32 Propoxur 18 - 30 Phoxim 7 - 12 Carbaryl 12 - 18 Chlorophoxim 12 - 20 - 32 Example 11 Effectiveness against the termite species Reticulitermes santonensis The toxicity against Reticulitermes santonensis of solutions containing the active compound I.3 in chloroform having the concentrations mentioned in Example 10 was determined according to the detailed description of DIN EN 117 Edition 1981 which is concerned with the European standard method prescribed by the European Committee for standardization concerning wood preservatives, determination of the toxic value against Reticulitermes santonesis. An outline of the method is as follows: (see DIN EN 117 for detail) The same three wood-samples with impregnation treatment in vacuum as in Example 10 are provided. They are exposed to 250 workers, 1 soldier and 1 nymph per batch for eight weeks, and afterward, the number of live/dead larvae is determined. From this test, the toxic threshold value was between 0.135 g/m 3 and 1.344 g/m 3 of the active compound I.3. The evaluation was made by the following standard: *rating values: O = no attack 1 = attempted attack 2 = slight attack 3 = average attack 4 = strong attack The results are shown in Table 5. Concentration of protect agent tested in % (m/m) No. of wood sample Quantity of solution absorbed per wood sample in g/m 3 Quantity of protective agent absorbed Results of evaluation per wood sample in g/m 3 average quantity absorbed surviving workers % Soldiers(S) or nymphs (N) * rating 1.44x10 -5 % 1 17.75 0.136 0.135 55 S/N 4 2 17.47 0.134 51 S/N 4 3 17.69 0.136 58 S/N 4 1.44x10 -4 % 4 17.75 1.363 1.344 0 - 1 5 17.39 1.336 0 - 1 6 17.37 1.334 0 - 1 1.44x10 -3 % 7 17.54 13.471 13.463 0 - 1 8 17.56 13.486 0 - 1 9 17.49 13.432 0 - 1 7.20x10 -3 % 10 17.29 66.3936 68.211 0 - 0 11 18.03 69.2352 0 - 0 12 17.97 69.0048 0 - 0 1.44x10 -2 % 13 17.79 136.627 136.627 0 - 0 14 17.72 136.090 0 - 0 15 17.86 137.165 0 - 0 control samples diluent (chloroform) 16 17.72 0 0 50 -/N 4 17 18.15 0 57 S/N 4 18 17.77 0 48 S/N 4 control samples untreated 19 0 0 0 55 S/N 4 20 0 0 62 S/N 4 21 0 0 64 -/N 4 Comparative values of W. Metzner et al in "Holz als Roh- und Werkstoff," 35 (1977) 233-237, table 10 on page 236. Insecticide toxic value g/m 3 Insecticide toxic value g/m 3 DDT > 1 500 Chlorophoxim 500 Dieldrin 50 Bassa 500 Lindan 75 Propoxur 140 Ethylparathion 200 Carbaryl 1 100 Phoxim 400

Claims: Process for preserving wood or composite wood-materials against insects, characterized in that agents containing at least 1-(6-chloro-3-pyridylmethyl)-2-nitroiminoimidazolidine (Imidacloprid) are used to treat wood or composite wood-materials. Process according to claim 1 characterized in that additional insecticides or fungicides are added. Process according to claim 1 characterized in that wood or composite wood-materials are treated by means of brushing, spraying, dipping or double vacuum technique.

Inventors: EXNER OTTO DR, OBINATA TORU, SCHWAMBORN MICHAEL DR, SONE SHINZABURO, TSUBOI SHINICHI, EXNER, OTTO, DR., OBINATA, TORU, SCHWAMBORN, MICHAEL, DR., SONE, SHINZABURO, TSUBOI, SHINICHI
Applicants: BAYER AGROCHEM KK, NIHON BAYER AGROCHEM K.K.
Application year: 1992
Main classification: A01N51
IPC codes: A01N43, A01N51, B27K3