Title of Invention

A PESTICIDAL GEL COMPOSITION

Abstract

The present invention relates to a pesticidal gel composition, comprising: 0.1 to 50% by weight of a pyrethroid compound selected from the group consisting of 2,3,5,6- tetrafluoro-4-methoxymethy lbenzy I chrysanthemate, 2,3,5, 6-tetrafluoro-4- methylbenzy I 3 -(2-chloro- 2- fluoroviny 1)- 2 ,2-dimethy lcyclopropanecarboxy late, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 3-( I-propenyl)- 2,2- dimethy lcyclopropanecarboxylate, 2,3,5 ,6-tetrafluorobenzy I (1 R)-trans- 3-(2,2- dichloroviny 1)-2 ,2-dimethy lcyclopropanecarboxy late, 2,3,5, 6-tetrafluoro-4- methylbenzyl 3-( 1-propenyl)-2,2-dimethylcylcopropanecarboxylate and 2,3,5,6- tetrafluoro-4- methoxybenzy I 3 -(2,2-dichloroviny 1)- 2,2- dimethylcyclopropanecarboxylate as an active ingredient; 2 to 20% by weight of a thermoplastic resin and 30 to 96% by weight of a plasticizer.

Full Text

PESTICIDAL GEL COMPOSITIONS Technical field of the Invention The present invention relates to pesticidal gel compositions. Background Arts USP 5,645,845 describes an insecticide-comprising gel formulation for a vapor-producing system. Such an insecticide-comprising gel formulation thereof utilizes an inorganic solid suitable-as a gel former. The insecticide-comprising gel formulation thereof is employed in a container and is heated with a heat source to kill insects. However, the insecticide-comprising gel formulation has drawbacks as inefficiently vaporizing the insecticide therein and as providing an erratic pesticidal effect. When heated for an extended amount of time, the insecticide-comprising gel formulation thereof often coagulates such that the insecticide-comprising gel formulation produces cracks on the surface thereof and looses adhesion with the heated surface in contact with the heat source. The loss of adhesion in the insecticide-comprising gel formulation thereof can result in loosing uniform surface contact with the heated surface so that the heat transfer from the heat source to the insecticide-comprising gel formulation is uneven. Further, the flowability of the insecticide-comprising gel composition failed to allow the insecticide-comprising gel formulation thereof to uniformly flow and spread out in the container when inserted into the container. The present invention provides pesticidal gel compositions, methods of controlling pests and methods of producing the pesticidal gel compositions. The pesticidal gel compositions involve a thermoplastic resin, a plasticizer and a pyrethroid compound. The methods of controlling pests involve heating the pesticidal gel compositions. The methods of producing the pesticidal gel compositions involve gelling the thermoplastic resin with the plasticizer and mixing therewith a pyrethroid compound. Detailed Description of the Invention As described above, the present invention provides pesticidal gel compositions, methods of controlling pests and methods of producing the pesticidal gel compositions. The pesticidal gel compositions involve a thermoplastic resin, a plasticizer and a pyrethroid compound. In the pesticidal gel compositions, the thermoplastic resin therein has a 3 dimensional cross-linked network, in which the thermoplastic resin is swelled therein with the plasticizer. The pyrethroid compound is supported on the thermoplastic resin. To produce the pesticidal gel compositions, the thermoplastic resin may be gelled with the plasticizer and the pyrethroid compound may be mixed therewith. For example, such pesticidal gel compositions may be produced by mixing the thermoplastic resin, the plasticizer and the pyrethroid compound under heated conditions. In such cases, the mixture is usually heated to a temperature of from lOCTC to 160*0. When mixed under the heated conditions after a sufficient amount of time, the cloudiness of the mixture disappears to provide a substantially transparent pesticidal gel composition. The pesticidal gel compositions usually have an appropriate flowability under such heated temperature conditions. Typically, 2 to 20% by weight of the thermoplastic resin, and preferably 3 to 15 % by weight of the thermoplastic resin, is gelled with the plasticizer. Examples of preferred thermoplastic resins include polyvinyl chloride), polyvinyl acetate), poly(methyl methacrylate), poly(methyl acrylate), polyester, a copolymer consisting essentially of vinyl chloride units and the like. More preferably, poly(vinyl chloride) is utilized as the thermoplstic resin. In cases of utilizing the poly(vinyl chloride), the poly(vinyl chloride) has a degree of polymerization of from 300 to 3000. Examples of the polyvinyl chloride) include ZEST 700L, ZEST 800Z, ZEST 1000Z, ZEST 1300Z, ZEST 2000Z, ZEST2500Z, the ZEST U-series and the like (available from Shin Dai-Ichi Vinyl Corporation). In the copolymer consisting essentially of the vinyl chloride units, 80% of the units to all but one of the units therein may be the vinyl chloride units, so that said copolymer consisting essentially of the vinyl chloride units can be gelled with the plasticizer. For example, a vinyl chloride-olefin copolymer may be utilized as the copolymer consisting essentially of the vinyl chloride units. Such a vinyl chloride-olefin copolymer is composed of vinyl chloride units and olefin units in random or in block units, such as a block copolymer thereof or as a random copolymer thereof. When gelling said preferred thermoplastic resins, the plasticizer may be in an amount of from 30 to 96% by weight. The plasticizer in such cases may be a citrate such as acetyltributyl citrate; a glutarate such as a di(Ci_i6)alkyl glutarate (e.g. dimethyl glutarate); an adipate such as a di(Ci-i6)alkyl adipate (e.g. dimethyl adipate, diisodecyl adipate, diisononyl adipate and diethylhexyl adipate); a succinate such as a di(Ci-i6)alkyl succinate (e.g. dimethyl succinate); a phthalate such as a di(Ci_i6)alkyl phthalate (dibutyl phthalate and dioctyl phthalate), a phosphate such as tricresyl phosphate or the like. It is preferable that with the poly(vinyl chloride), there is utilized as the plasticizer, the citrate, dialkyl glutarate, dialkyl adipate, dialkyl phthalate, phosphate esters or the like. It is preferable that the dialkyl phthalate ester, such as dibutyl phthalate, is utilized as the plasticizer with the poly(methyl acylate). The pyrethroid is present in the pesticidal gel compositions to provide a sufficient pesticidal effect when vaporized. Such an amount of the pyrethroid compound may be from about 0.1 to 50% by weight and preferably from 1 to 45% by weight. Examples of such pyrethroid compounds include 2,3,5,6-tetrafluoro-4-methoxymethylbenzylchrysanthemate5 2,3,5,6-tetrafluoro-4-methylbenzyl 3-(2-chloro-2-fluorovinyl)-2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 3-(l-propenyl)-2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluorobenzyl (lR)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methylbenzyl 3-(l-propenyl)-2,2-dimethylcylcopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and the like. An adjuvant may also be mixed into the pesticidal gel compositions. Examples of the adjuvant include pesticidally synergistic agents such as piperonyl butoxide (PBO), N-(2-ethylhexyl)-bicyclo[2.2.1.]-hept-5-ene-2,3»carboximide (MGK264) and octachlorodipropyl ether (S421), phenols such as dibutylhydroxytoluene, anti-oxidants such as tocopherol (vitamin E), stabilizers of a thermoplastic polymer such as a fatty acid salt (zinc stearate), ester solvents, natural and synthetic aroma chemicals, dyes and the like. The pesticidal gel compositions are usually heated in order to vaporize the pyrethroid compound therein. A heating source may be utilized to heat the pesticidal gel compositions. In heating the pesticidal gel compositions, the pesticidal gel compositions may be inserted into containers and then heated to a temperature of 100"C to 160^. Such a container is typically gas permeable and typically has at least one opening to allow the pesticidal gel compositions to be more easily inserted into the container. After inserting the pesticidal gel compositions into the containers-through the opening, the opening of the containers is sealed, such as with a resin film. Further, the containers are heat conductive to allow heat transfer from the heating source to the pesticidal gel compositions. When inserting the pesticidal gel compositions into the containers, it is preferable that the pesticidal gel compositions are inserted into the containers after being heated to a temperature of lOO'C to 160^3, as utilized to produce the pesticidal gel compositions. It is worth noting that when inserting into the container, the pesticidal gel compositions may be reheated, after producing the pesticidal gel compositions and cooling the produced pesticidal gel compositions to room temperature. The flowability of the pesticidal gel compositions at such a heated temperature allows the pesticidal gel compositions to be more easily inserted into the containers than when the pesticidal gel compositions are at room temperature. The container can be produced from a metal foil, a heat-resistant resin, an inorganic material or the like. Typically, such metal foils, heat-resistant resin or inorganic materials are laminated with an adhesive resin to more easily seal the opening of the container. When utilizing the metal foil, for example, there can be utilized a aluminum foil laminated with a polyolefin adhesive resin and CPP (casting polypropylene). Such an aluminum foil can be produced by laminating on one surface of the aluminum foil, the polyolefin adhesive resin so that the resulting aluminum foil has a total thickness of 50 to 300/^m. The surface of the aluminum foil is then further laminated with CPP so that the CPP is 10 to lOQum thick. The container can then be produced by using a compression forming processor with the laminated aluminum foil so that the CPP laminated surface thereof is produced as the inner surface of the container. When polyhedral, the container may have an inner height of 3 to 10mm and may have the bottom inner surface thereof have a length and width of 10 to 100mm, depending on the desired insertion amount of the pesticidal gel composition. As the resin film sealing the opening of the container, there can be utilized a transparent film such as polyethylene, polypropylene, a polyvinylchloride or the like, or a multilayered film thereof. Preferably, there is utilized a triple layered resin film of a random polypropylene polymer, polypropylene polymer and a random polypropylene polymer. Such resin films can adhere to the aluminum container by heat or ultrasound. The heat source may be a conventional heat source utilized to heat a conventional mosquito mat, such as a positive temperature coefficient thermistor which heating surface can be heated to 100 to 160°C. It is preferable that the heat source has a heating surface almost identical in area to the heat source contact surface of the container to which the pesticidal gel composition is inserted. It is more preferable to utilize a heat source having a means for securing the container to the heating surface of the heat source. As the pests which can be controlled with the pesticidal gel compositions of the present invention, there may be mentioned arthropods such as various types of unsanitary insects and acarina. Typically, such unsanitary insects and acarina are aviator pests. Examples of such aviator pests include Culex spp. such as common mosquito (Culexpipienspattens) and Culex tritaeniorhynchus\ Aedes spp. such as yellow fever mosquito (Aedes aegypti) and Aedes albopictus; Anopheles spp. such as Anopheles sinesis; Mansonia spp.; midges (Chironomidae); muscid flies (Muscidae) such as housefly (Musca domestica), false housefly (Musca stabulans) and little housefly (Fannia canicularis); blow flies (Calliphoridae); flesh flies (Sarcophagidae); moth flies (Psychodidae); breeze flies (Tabanidae); black flies (Simuliidae); stable flies (Stomoxyidae); Phoridae; biting midges (Ceratopogonidae) and the like. Examples The following examples are set forth to describe the present invention in more detail, but the present invention in not limited to such examples. Production Example 1 A mixture containing 0.2g of the polyvinylchloride ZEST 2500Z, 0.2g of the polyvinylchloride ZEST 1700Z, 4.6g of diisobutyl adipate and lg of 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 3-(l-propenyl)-2,2-dimethylcyclopropanecarboxylate was stirred in a vial while being heated at 110 to 13(TC with a silicone oil. The mixture became a substantially transparent gel after stirring the mixture under such conditions for 30 minutes. A l.lg sample of the substantially transparent gel was inserted into an aluminum tray (having a width of 35mm, length of 75mm and a height of 5mm). The substantially transparent gel was uniformly spread onto the bottom surface of the aluminum tray. The opening of the container was then sealed by heat with a polypropylene polymer film (thickness of 50 microns) to produce a container containing the pesticidal gel composition. Production Example 2 A mixture containing 0.2g of the polyvinyl chloride ZEST 2500Z, 0.2g of the polyvinyl chloride ZEST 1700Z, 4.6g of the dinormalalkyl (C63C8 and Qo alkyls) adipate and lgof 2,3,556-tetrafluoro-4-methoxymethylbenzyl 3-(l-propenyl)-2,2-dimethylcyclopropanecarboxylate was stirred in a vial while being heated at 110 to 130°C with a silicone oil. The mixture became a substantially transparent gel after stirring the mixture under such conditions for 30 minutes. A l.lg sample of the substantially transparent gel was inserted into an aluminum tray (having a width of 35mm, length of 75mm and a height of 5mm). The substantially transparent gel was uniformly spread on the bottom surface of the aluminum tray. The opening of the container was then sealed by heat with a polypropylene polymer film (thickness of 50 microns) to produce a container containing the pesticidal gel composition. Production Example 3 A mixture containing 0.4g of the polyvinyl chloride ZEST 2500Z, 4.6g of diisopropyl adipate and lg of 2,3,5,6-tetrafluoro-4-methylbenzyl 3-(2-chloro-2*fluorovinyl)-2,2-dimethylcyclopropanecarboxylate was stiged in a vial while being heated at 110 to 130^ with a silicone oil. The mixture became a substantially transparent gel after stirring the mixture under such conditions for 30 minutes. A l.lg sample of the substantially transparent gel was inserted into an aluminum tray (having a width of 35mm, length of 75mm and a height of 5mm). The substantially transparent gel was uniformly spread onto the bottom surface of the aluminum tray. The opening of the container was then sealed by heat with a polypropylene polymer film (thickness of 50 microns) to produce a container containing the pesticidal gel composition. Production Example 4 A mixture containing 0.5g of polyvinyl chloride ZEST 700Z, 4.5g of acetyltributyl citrate and 2g of 2,3,5,6-tetrafluoro-4-methylbenzyl 3-(2-chloro-2-fluorovinyl)-2,2-dimethylcyclopropanecarboxylate was stirred in a vial while being heated at 110 to 130*0 with a silicone oil. The mixture became a substantially transparent gel after stirring the mixture under such conditions for 30 ' minutes. A l.lg sample of the substantially transparent gel was inserted into an aluminum tray (having a width of 35mm, length of 75mm and a height of 5mm). The substantially transparent gel was uniformly spread on the bottom surface of the aluminum tray. The opening of the container was then sealed by heat with a polypropylene polymer film (thickness of 50 microns) to produce a container containing the pesticidal gel composition. Production Example 5 A mixture containing 0.2g of the polyvinyl chloride ZEST 2500Z, 0.2g of the polyvinyl chloride 1700Z, 4.6g of diisopropyl adipate and lg of 2,3,5,6-tetrafluorobenzyl (lR)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate was stirred in a vial while being heated at 110 to 1300 with a silicone oil. The mixture became a substantially transparent gel after stirring the mixture under such conditions for 30 minutes. A l.lg sample of the substantially transparent gel was inserted into an aluminum tray (having a width of 35mm, length of 75mm and a height of 5mm). The substantially transparent gel was uniformly spread on the bottom surface of the aluminum tray. The opening of the container was then sealed by heat with a polypropylene polymer film (thickness of 50 microns) to produce a container containing the pesticidal gel composition. Production Example 6 A mixture containing 0.2g of the polyvinyl chloride ZEST 2500Z, 0.2g of the polyvinyl chloride 1700Z, 4.6g of diisopropyl adipate and lg of 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl (lR)-trans-chrysanthemate was stirred in a vial while being heated at 110 to 130^3 with a silicone oil. The mixture became a substantially transparent gel after stirring the mixture under such conditions for 30 minutes. A l.lg sample of the substantially transparent gel was inserted into an aluminum tray (having a width of 35mm, length of 75mm and a height of 5mm). The substantially transparent gel was uniformly spread on the bottom surface of the aluminum tray. The opening of the container was then sealed by heat with a polypropylene polymer film (thickness of 50 microns) to produce a container containing the pesticidal gel conjposition. Test Example Two (2) glass tubes (height of 12 cm, inner diameter of 4cm and both ends thereof covered with a 16 mesh net) were each infested with 10 female adult common mosquitoes {Culespipiens pallens). On top of a testing cyclinder (having a height of 80cm and a diameter of 20cm), a metal platform (having a width of 7.8cm) for said glass tubes was placed across the diametrical direction and over the central portion of testing cylinder. In the metal platform, there were 2 holes symmetrically opened at locations from 4 cm from the center of the testing cyclinder. The 2 holes in the metal platform had a diameter substantially identical to the 4cm inner diameter of the glass tubes. The 2 glass tubes were placed, respectively, on the platform such that one of the ends thereof aligned with one of the holes in the metal platform and such that an air flow from the bottom of the testing cylinder can flow into the glass tubes. A second cylinder for observations (having a diameter of 20cm and a height of 30cm), which was made of transparent plastic, was then placed onto the top of the testing cylinder so that the outer diameters thereof were aligned. The container prepared in Production Example 1 was set on a heat source (having a heating surface temperature of 135 to 145*0). A small draft chamber was prepared near the testing cylinder. The prepared heat source was then placed in the draft chamber. After 16 hours of heating the container with the heat source, the heat source was transferred into the testing cylinder and placed on the bottom surface thereof. The container was then heated for 20 minutes. The number of knocked down female adult common mosquitoes were periodically counted, and the time which knocks down 50% of the tested female adult common mosquitoes (KT50) was calculate^. After heating the container for the 20 minutes, the heat source was transferred to the small draft chamber near the testing cylinder and the container was further heated. The glass tubes were recovered from the testing cylinder device, and the glass tube was placed on a gauze comprising 5% sugar water as food. The female adult common mosquitoes were then maintained in breeding conditions for 1 day. The mortality rate was then determined. After heating the container in the heat source for 316 hours, the heat source was transferred into the testing cylinder and placed the bottom surface of the testing cylinder. The container was then heated in the testing device similarly to the above. As a result, the KT50 after 16 hours of heating was 2.9 minutes, and the mortality rate of the tested female common mosquito after the day under friendly conditions was 100%. The KT50 after the 316 hours of heating was 2.4 minutes, and the mortality rate of the tested female adult common mosquitoes after the day under friendly conditions was 100%. After the 316 hours of heating, no cracks were observed in the pesticidal gel composition. Also, the pesticidal gel composition was uniformly contacted with the bottom surface of the container. What is claimed is: 1. A pesticidal gel composition, comprising: a pyrethroid compound as an active ingredient; a thermoplastic resin and a sufficient gelling amount of a plasticizer. 2. The pesticidal gel composition according to claim 1, wherein the thermoplastic resin has a 300 to 3000 degree of polymerization and wherein the thermoplastic resin is a poly(vinyl chloride), polyvinyl acetate), poly(methyl methacrylate), poly(methyl acrylate), polyester or a copolymer consisting essentially of vinyl chloride units. 3. The pesticidal gel composition according to claim 1, comprising: 0.1 to 50% by weight of the pyrethroid compound; 2 to 20% by weight of a polyvinyl chloride) or vinyl chloride-olefin copolymer and the sufficient gelling amount of the plasticizer; wherein said percentages by weight are based on the total weight of the provided pesticidal gel composition. 4. The pesticidal gel composition according to claim 3, wherein the plasticizer is a citrate, a glutarate, an adipate, a succinate, a phthalate or a phosphate. 5. A method of producing a pesticidal gel composition, said method comprising: gelling a thermoplastic resin with a plasticizer and mixing a pyrethroid compound therewith. 6. The method according to claim 5, comprising: mixing at 100 to 140°C, 0.1 to 50% by weight of the pyrethroid compound, 2 to 20% by weight of the thermoplastic resin and the sufficient gelling amount of the plasticizer; wherein said percentages by weight are based on the total weight of the provided pesticidal gel composition, wherein the theremoplastic resin has a 300 to 3000 degree of polymerization and wherein the thermoplastic resin is a poly(vinyl chloride) or a copolymer consisting essentially of vinyl chloride units. 7. A pesticide comprising: a gas permeable and heat conductive container and the pesticidal gel composition of claim 1. 8. A method of controlling pests, said method comprising: heatine the oesticide of claim 7. 9. A method of controlling pests, said method comprising: heating the pesticidal gel composition of claim 1. 10. A pesticidai gel composition, substantially as hereinabove described and exemplified. 11. A method of producing a pesticidai gel composition, substantially as hereinabove described and exemplified.

Documents:

mas-2001-81-abstract.pdf

mas-2001-81-claims duplicate.pdf

mas-2001-81-claims original.pdf

mas-2001-81-correspondance others.pdf

mas-2001-81-correspondance po.pdf

mas-2001-81-description complete duplicate.pdf

mas-2001-81-description complete original.pdf

mas-2001-81-form 1.pdf

mas-2001-81-form 26.pdf

mas-2001-81-form 3.pdf

mas-2001-81-form 5.pdf

mas-2001-81-other document.pdf