JP5793741B2 - Polyethylene sheet for ant protection - Google Patents
Polyethylene sheet for ant protection Download PDFInfo
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- JP5793741B2 JP5793741B2 JP2012112892A JP2012112892A JP5793741B2 JP 5793741 B2 JP5793741 B2 JP 5793741B2 JP 2012112892 A JP2012112892 A JP 2012112892A JP 2012112892 A JP2012112892 A JP 2012112892A JP 5793741 B2 JP5793741 B2 JP 5793741B2
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- Prior art keywords
- ant
- sheet
- density polyethylene
- linear low
- polyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 Polyethylene Polymers 0.000 title claims description 22
- 239000004698 Polyethylene Substances 0.000 title claims description 15
- 229920000573 polyethylene Polymers 0.000 title claims description 15
- 239000000463 material Substances 0.000 claims description 35
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 34
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 34
- 230000000694 effects Effects 0.000 claims description 23
- 241000256602 Isoptera Species 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000002265 prevention Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 description 20
- 238000000465 moulding Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 11
- 229920001684 low density polyethylene Polymers 0.000 description 10
- 239000004702 low-density polyethylene Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000003171 wood protecting agent Substances 0.000 description 9
- 229920013716 polyethylene resin Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000013043 chemical agent Substances 0.000 description 7
- 239000005906 Imidacloprid Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229940056881 imidacloprid Drugs 0.000 description 5
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 241000736892 Thujopsis dolabrata Species 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000005896 Etofenprox Substances 0.000 description 2
- 241000257303 Hymenoptera Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- XLLZUKPXODPNPP-UHFFFAOYSA-N [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] XLLZUKPXODPNPP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
- YREQHYQNNWYQCJ-UHFFFAOYSA-N etofenprox Chemical compound C1=CC(OCC)=CC=C1C(C)(C)COCC1=CC=CC(OC=2C=CC=CC=2)=C1 YREQHYQNNWYQCJ-UHFFFAOYSA-N 0.000 description 2
- 229950005085 etofenprox Drugs 0.000 description 2
- NYPJDWWKZLNGGM-UHFFFAOYSA-N fenvalerate Chemical compound C=1C=C(Cl)C=CC=1C(C(C)C)C(=O)OC(C#N)C(C=1)=CC=CC=1OC1=CC=CC=C1 NYPJDWWKZLNGGM-UHFFFAOYSA-N 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 231100000206 health hazard Toxicity 0.000 description 2
- 239000000077 insect repellent Substances 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 150000008048 phenylpyrazoles Chemical class 0.000 description 2
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- WCXDHFDTOYPNIE-RIYZIHGNSA-N (E)-acetamiprid Chemical compound N#C/N=C(\C)N(C)CC1=CC=C(Cl)N=C1 WCXDHFDTOYPNIE-RIYZIHGNSA-N 0.000 description 1
- PGOOBECODWQEAB-UHFFFAOYSA-N (E)-clothianidin Chemical compound [O-][N+](=O)\N=C(/NC)NCC1=CN=C(Cl)S1 PGOOBECODWQEAB-UHFFFAOYSA-N 0.000 description 1
- FMTFEIJHMMQUJI-NJAFHUGGSA-N 102130-98-3 Natural products CC=CCC1=C(C)[C@H](CC1=O)OC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C FMTFEIJHMMQUJI-NJAFHUGGSA-N 0.000 description 1
- IRTLROCMFSDSNF-UHFFFAOYSA-N 2-phenyl-1h-pyrrole Chemical compound C1=CNC(C=2C=CC=CC=2)=C1 IRTLROCMFSDSNF-UHFFFAOYSA-N 0.000 description 1
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 1
- OEDUIFSDODUDRK-UHFFFAOYSA-N 5-phenyl-1h-pyrazole Chemical compound N1N=CC=C1C1=CC=CC=C1 OEDUIFSDODUDRK-UHFFFAOYSA-N 0.000 description 1
- 239000005875 Acetamiprid Substances 0.000 description 1
- 239000005874 Bifenthrin Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 239000005888 Clothianidin Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001509964 Coptotermes Species 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 240000006055 Dacrydium cupressinum Species 0.000 description 1
- 235000018782 Dacrydium cupressinum Nutrition 0.000 description 1
- WGOWCPGHOCIHBW-UHFFFAOYSA-N Dichlofenthion Chemical compound CCOP(=S)(OCC)OC1=CC=C(Cl)C=C1Cl WGOWCPGHOCIHBW-UHFFFAOYSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 description 1
- 239000005899 Fipronil Substances 0.000 description 1
- 239000005949 Malathion Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000013697 Pinus resinosa Nutrition 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 1
- 239000005926 Pyridalyl Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005941 Thiamethoxam Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920000690 Tyvek Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229940024113 allethrin Drugs 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- FYZBOYWSHKHDMT-UHFFFAOYSA-N benfuracarb Chemical compound CCOC(=O)CCN(C(C)C)SN(C)C(=O)OC1=CC=CC2=C1OC(C)(C)C2 FYZBOYWSHKHDMT-UHFFFAOYSA-N 0.000 description 1
- OMFRMAHOUUJSGP-IRHGGOMRSA-N bifenthrin Chemical compound C1=CC=C(C=2C=CC=CC=2)C(C)=C1COC(=O)[C@@H]1[C@H](\C=C(/Cl)C(F)(F)F)C1(C)C OMFRMAHOUUJSGP-IRHGGOMRSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- JLQUFIHWVLZVTJ-UHFFFAOYSA-N carbosulfan Chemical compound CCCCN(CCCC)SN(C)C(=O)OC1=CC=CC2=C1OC(C)(C)C2 JLQUFIHWVLZVTJ-UHFFFAOYSA-N 0.000 description 1
- CWFOCCVIPCEQCK-UHFFFAOYSA-N chlorfenapyr Chemical compound BrC1=C(C(F)(F)F)N(COCC)C(C=2C=CC(Cl)=CC=2)=C1C#N CWFOCCVIPCEQCK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- SCKHCCSZFPSHGR-UHFFFAOYSA-N cyanophos Chemical compound COP(=S)(OC)OC1=CC=C(C#N)C=C1 SCKHCCSZFPSHGR-UHFFFAOYSA-N 0.000 description 1
- 229960001591 cyfluthrin Drugs 0.000 description 1
- QQODLKZGRKWIFG-QSFXBCCZSA-N cyfluthrin Chemical compound CC1(C)[C@@H](C=C(Cl)Cl)[C@H]1C(=O)O[C@@H](C#N)C1=CC=C(F)C(OC=2C=CC=CC=2)=C1 QQODLKZGRKWIFG-QSFXBCCZSA-N 0.000 description 1
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- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 1
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- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 1
- YKBZOVFACRVRJN-UHFFFAOYSA-N dinotefuran Chemical compound [O-][N+](=O)\N=C(/NC)NCC1CCOC1 YKBZOVFACRVRJN-UHFFFAOYSA-N 0.000 description 1
- DOFZAZXDOSGAJZ-UHFFFAOYSA-N disulfoton Chemical compound CCOP(=S)(OCC)SCCSCC DOFZAZXDOSGAJZ-UHFFFAOYSA-N 0.000 description 1
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- ZNOLGFHPUIJIMJ-UHFFFAOYSA-N fenitrothion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(C)=C1 ZNOLGFHPUIJIMJ-UHFFFAOYSA-N 0.000 description 1
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- AEHJMNVBLRLZKK-UHFFFAOYSA-N pyridalyl Chemical group N1=CC(C(F)(F)F)=CC=C1OCCCOC1=C(Cl)C=C(OCC=C(Cl)Cl)C=C1Cl AEHJMNVBLRLZKK-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Building Environments (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、建築物の床下に施工する防蟻シートや電線やケーブルの被覆材等の材料として使用される防蟻性素材の改良、詳しくは、長期間にわたって優れた防蟻効果を持続できる安全性の高い防蟻性ポリエチレンシートに関するものである。 The present invention is an improvement of an ant-proofing material used as a material such as an ant-proofing sheet to be constructed under the floor of a building and a covering material for electric wires and cables, and more specifically, a safety capable of maintaining an excellent ant-proofing effect for a long period The present invention relates to a highly ant-proof polyethylene sheet .
近年、多くの建築物でシロアリ被害の防止策がとられており、既知の具体策としては、防蟻剤(シロアリへの殺虫、防虫又は忌避作用を有する薬剤)を床下に散布する方法や、防蟻シート(不織布や紙、合成樹脂シート等に防蟻剤を塗布または添加したもの)を床板下面に貼り付ける方法、防蟻シートを基礎周辺に敷き詰める方法などが知られている。 In recent years, measures have been taken to prevent termite damage in many buildings, and known specific measures include a method of spraying an anti-anticide (an insecticidal, insect-repellent or repellent agent on termites) under the floor, There are known a method of sticking an ant-proof sheet (nonwoven fabric, paper, synthetic resin sheet or the like coated with or adding an ant-proofing agent) to the lower surface of the floor plate, a method of spreading the ant-proof sheet around the foundation, and the like.
また、電線やケーブルに関しても、シロアリによる食害によって断線や通信障害を起こす危険性があるため、建築物と同様のシロアリ対策が求められるが、こちらも電線類の被覆材に防蟻剤(例えば、ドリン系あるいは有機リン系の薬剤)を添加して防蟻機能を付与する技術が既に公知となっている。 Also, with regard to electric wires and cables, there is a risk of disconnection and communication failure due to termite damage, so termite countermeasures similar to those for buildings are required, but this is also an anti-anticide (for example, A technique for adding an anti-ant function by adding a drin-type or organophosphorus-type agent is already known.
しかし、上記従来のシロアリ対策では、多量の防蟻剤を使用する必要があるため、化学薬剤による環境汚染(例えば、土壌汚染等)や、建物内で揮発した化学薬剤による居住者の健康被害(例えば、シックハウス症候群)、散布薬剤の飛散・吸引による作業者の健康被害など、多くの社会問題を引き起こす懸念がある。 However, since the above-mentioned conventional termite countermeasures require the use of a large amount of anti-anticide, environmental pollution caused by chemical agents (e.g., soil contamination) and health hazards of residents caused by chemical agents volatilized in buildings ( For example, there are concerns that it causes many social problems such as sick house syndrome and health damage to workers due to scattering and suction of sprayed drugs.
しかも、樹脂成形によって形成されるシート材や電線類の被覆材に、多量の防蟻剤を添加すると樹脂材料の成形性が悪化したり、また添加された防蟻剤によって被覆材の耐久性や電気特性が低下したりするため、多量の防蟻剤を成形時に添加することは、製造面や機能面から見ても好ましくない。 In addition, when a large amount of an anti-bacterial agent is added to the sheet material or the covering material of electric wires formed by resin molding, the moldability of the resin material is deteriorated, and the durability of the coating material is increased by the added anti-anticide. Addition of a large amount of an anti-bacterial agent at the time of molding is not preferable from the viewpoint of production and function, because the electrical characteristics deteriorate.
そこで、従来においては、化学薬剤を使用しない防蟻素材として、比較的強度の低い樹脂材料(低密度ポリエチレン樹脂等)中に強度の高い材料(超高分子量のシリコーンポリマー等)を分散させたものが提案されたが(特許文献１参照)、この素材は防蟻効果を得るためにある程度の厚みが必要となるため、用途が限定されてしまう。 Therefore, in the past, a material with a high strength (such as an ultra-high molecular weight silicone polymer) dispersed in a relatively low-strength resin material (such as a low-density polyethylene resin) as an anti-rust material that does not use chemical agents. Has been proposed (see Patent Document 1), but this material requires a certain amount of thickness in order to obtain an ant-proof effect, so that its use is limited.
一方、透湿防水シートの分野では、高密度ポリエチレン繊維を部分的に溶着して繊維同士を密に絡め合わせることで、基材である不織布シートの透湿性と防蟻性を両立させる技術も提案されているが(特許文献２参照)、こちらの素材は逆に厚みを出すことが難しいため電線類の被覆材等での使用が困難となる。 On the other hand, in the field of moisture-permeable waterproof sheets, we also propose a technology that achieves both moisture permeability and ant-repellency of the nonwoven fabric sheet, which is a base material, by partially welding high-density polyethylene fibers and intertwining the fibers closely together. However, since it is difficult to increase the thickness of this material, it is difficult to use it with a covering material for electric wires.
他方、本件発明者も、以前に化学薬剤を使用しない防蟻シートとして、合成樹脂層(ポリエステルやエチレンー酢酸ビニル共重合体、ポリオレフィン等)の間に、金属層(アルミニウムや銀、銅、鉄、亜鉛等)を挟み込んで積層一体化したものを開発したが(特許文献３参照)、この素材も構造が複雑化する分、製造コストが高く付き易い。 On the other hand, the present inventor also used a metal layer (aluminum, silver, copper, iron, etc.) between synthetic resin layers (polyester, ethylene-vinyl acetate copolymer, polyolefin, etc.) as a termite-proof sheet that did not use chemical agents before. (Zinc etc.) have been developed (see Patent Document 3), but this material is also expensive to manufacture because the structure is complicated.
また、従来においては、防蟻剤の抜け易さを考慮して樹脂材料を選択することで、防虫作用の持続性をコントロールする技術が公知となっているものの(例えば、特許文献４参照)、樹脂材料そのものに防蟻効果を見い出して、その特性を材料の選択基準とする技術は見受けられない。 In addition, conventionally, a technique for controlling the sustainability of the insect-repellent action by selecting a resin material in consideration of ease of removal of the termite-proofing agent is known (for example, see Patent Document 4). There is no technology that finds an ant-repellent effect on the resin material itself, and uses that property as a material selection criterion.
本発明は、上記の如き問題に鑑みて為されたものであり、その目的とするところは、長期間にわたって優れた防蟻効果を持続させることができ、また、安全性を損なう化学薬剤の使用も著しく抑制でき、しかも、用途幅も広く製造コストの面でも有利な防蟻性ポリエチレンシートを提供することにある。 The present invention has been made in view of the problems as described above, and the object of the present invention is to maintain an excellent ant-repellent effect over a long period of time and to use a chemical agent that impairs safety. It is to provide an ant-proof polyethylene sheet that can be remarkably suppressed and that has a wide application range and is advantageous in terms of production cost.
本発明者らは、上記課題を解決するために試行錯誤的に試作と実験を重ねた結果、直鎖状低密度ポリエチレン(LLDPE)からなるシートがその分子構造に起因する優れた防蟻特性を有することを見出し、本発明を完成させた。 As a result of repeated trial and error trials and experiments to solve the above problems, the present inventors have found that the sheet made of linear low-density polyethylene (LLDPE) has excellent anti-rust properties due to its molecular structure. The present invention was completed.
即ち、本発明は、防蟻素材に防蟻剤や防蟻効果を有する他の材料を成形時から含有しない直鎖状低密度ポリエチレンから成るシートであって、前記防蟻剤や防蟻効果を有する他の材料を含有するシートを積層しない状態で使用される厚み80〜250μｍの防蟻性ポリエチレンシートを、この直鎖状低密度ポリエチレンの有する側鎖をシート全面に一様に分布させて構成した点に特徴がある。なお、直鎖状低密度ポリエチレンは、密度が0.910〜0.930g/cm3で、シングルサイト触媒を用いて重合されたものであることが好ましい。また上記防蟻性ポリエチレンシートは、押出成形によって製造した厚み80〜250μｍのシートにおいて顕著な防蟻効果を発揮する。 That is, the present invention is a sheet made of linear low-density polyethylene that does not contain an ant-proofing agent or other material having an ant-proofing effect from the time of molding. 80 to 250 μm thick ant-proof polyethylene sheet used in a state where sheets containing other materials are not laminated, and the side chains of this linear low density polyethylene are uniformly distributed throughout the sheet There is a feature in the point. The linear low density polyethylene is preferably one having a density of 0.910 to 0.930 g / cm 3 and polymerized using a single site catalyst. Moreover, the said ant-proof polyethylene sheet exhibits the remarkable ant-proof effect in the 80-250-micrometer-thick sheet | seat manufactured by extrusion molding.
そしてまた、上記防蟻性ポリエチレンシートを製造する際には、Ｔダイから溶融した直鎖状ポリエチレン樹脂を層流状態で面状に押し出すことで、低密度ポリエチレンの側鎖が全面に一様に分布したポリエチレンシートを成形できる。 And when manufacturing the said ant-proof polyethylene sheet, the side chain of the low-density polyethylene is uniformly distributed over the entire surface by extruding the linear polyethylene resin melted from the T-die in a laminar state. A distributed polyethylene sheet can be formed.
また、直鎖状ポリエチレン樹脂を溶媒中に溶解させて、この溶解されたポリエチレン樹脂を面状の支持体上に層流状態で流延して平面状に広げた後、溶媒を揮散させる方法によっても、上記低密度ポリエチレンの側鎖が全面に一様に分布したポリエチレンシートを成形できる。 In addition, by dissolving a linear polyethylene resin in a solvent, casting the dissolved polyethylene resin on a planar support in a laminar flow state and spreading it in a flat shape, the method then volatilizes the solvent. In addition, a polyethylene sheet in which the side chains of the low density polyethylene are uniformly distributed over the entire surface can be formed.
また他にも、環状ダイから溶融した直鎖状ポリエチレン樹脂をチューブ状に押し出した後、軟化状態の樹脂を内側から吹き込んだ圧縮空気によって膨張させるインフレーション法でも、上記低密度ポリエチレンの側鎖が全面に一様に分布したポリエチレンシートを成形できる。 In addition, the side chain of the low-density polyethylene is entirely exposed by an inflation method in which a linear polyethylene resin melted from a circular die is extruded into a tube shape, and then the softened resin is expanded by compressed air blown from the inside. A polyethylene sheet that is uniformly distributed can be formed.
また、上記直鎖状低密度ポリエチレンに極めて少量の防蟻剤を配合することによって、直鎖状低密度ポリエチレンの経時劣化に伴う防蟻性能の減退を補うこともでき、これにより20年以上の極めて長期間にわたる防蟻効果の維持が可能となる。 Also, by blending an extremely small amount of an anti-bacterial agent with the above-mentioned linear low density polyethylene, it is possible to compensate for the deterioration of the anti-ant performance due to the deterioration of the linear low density polyethylene over time. It is possible to maintain the ant protection effect for an extremely long period of time.
なお、防蟻剤を添加する際には、ピレスロイド系、非エステルピレスロイド系、ネオニコチノイド系、フェニルピラゾール系、フェニルピロール系、第４級アンモニウム塩系、2,2-ジクロロアリルオキシ系から選ばれた有機系木材保存剤、又はホウ酸もしくはヒバ油から選ばれた一種以上の木材保存剤を、樹脂成形品の単位面積当たり0.0091〜0.093g/m2配合すると、防蟻効果を20年以上持続させることができる。 In addition, when adding an anti-anticide, select from pyrethroid, non-ester pyrethroid, neonicotinoid, phenylpyrazole, phenylpyrrole, quaternary ammonium salt, 2,2-dichloroallyloxy Organic anti-wood preservatives or one or more kinds of wood preservatives selected from boric acid or hiba oil are added in an amount of 0.0091 to 0.093 g / m 2 per unit area of the resin molded product, resulting in an anti-ant effect over 20 years Can last.
また更に、上記直鎖状低密度ポリエチレンから成る樹脂成形品を、厚み80〜150μｍの防蟻シートとすれば、防蟻剤の体積当たりの配合量が大きくなるため、防蟻効果をより高めることができる。 Furthermore, if the resin molded product made of the above-mentioned linear low density polyethylene is made into an ant-proof sheet having a thickness of 80 to 150 μm, the compounding amount per volume of the ant-proofing agent is increased, so that the ant-proof effect is further enhanced. Can do.
本発明では、直鎖状低密度ポリエチレン自体が持つ防蟻特性を利用して防蟻素材を構成したことにより、樹脂が経年劣化して機能を失うまでの長期間、防蟻効果を持続させることができる。しかも、化学薬剤の使用が殆ど不要となるため、環境汚染や居住者、作業者の健康被害を引き起こす危険も解消できる。 In the present invention, the ant-proof material is constructed using the ant-proofing properties of the linear low-density polyethylene itself, so that the ant-proofing effect can be maintained for a long period of time until the resin loses its function over time. Can do. In addition, since the use of chemical agents is almost unnecessary, it is possible to eliminate the risk of causing environmental pollution and health hazards for residents and workers.
また、上記直鎖状低密度ポリエチレンに対し、劣化後も防蟻効果が持続するように防蟻剤を補助的に添加する場合でも、環境や健康に影響のない極めて少量の防蟻剤を添加するだけでよいため、化学薬剤を多量に添加する従来の防蟻素材と比較して人体に対する安全性を格段に向上できる In addition, to the above linear low density polyethylene, an extremely small amount of an ant preventive agent that does not affect the environment and health is added even if an ant preventive agent is supplementarily added so that the ant preventive effect continues even after deterioration. As a result, the safety to the human body can be significantly improved compared to conventional ant protection materials that add a large amount of chemical agents.
また更に、上記直鎖状低密度ポリエチレンは、他の熱可塑性樹脂と同様、自由な形状に成形することが可能であるため、多用途で使用することができ、また構造が複雑化することも成形性が損なわれることもないため、製造コストも低廉に抑えることができる。 Furthermore, since the linear low density polyethylene can be molded into a free shape like other thermoplastic resins, it can be used for many purposes and the structure may be complicated. Since the moldability is not impaired, the manufacturing cost can be kept low.
したがって、本発明により、防蟻素材が持つ基本的な防蟻性能に優れるだけでなく、自然環境や建築物の居住者、施工者にも優しく、また建築物や電線類等のシロアリ対策が必要な様々な場面で幅広く使用することができる新規の防蟻素材を提供できることから、本発明の実用的利用価値は頗る高い。 Therefore, according to the present invention, not only the basic ant-proofing performance of the ant-proof material is excellent, but it is also friendly to the natural environment, residents of the building, and construction workers, and it is necessary to take measures against termites such as buildings and electric wires. Therefore, the practical use value of the present invention is very high because a new ant-proof material that can be widely used in various scenes can be provided.
次に、本発明を実施するための具体的態様及び好ましい条件について説明する。 Next, specific embodiments and preferable conditions for carrying out the present invention will be described.
［直鎖状低密度ポリエチレン］
直鎖状低密度ポリエチレンは、チグラー・ナッタ触媒等のマルチサイト触媒や、メタロセン触媒等のシングルサイト触媒により共重合して得られるエチレン−α−オレフィン共重合体であるが、本発明では、特に共重合されるα−オレフィンが5mol%程度までのものを直鎖状低密度ポリエチレンとして用いる。
[Linear low density polyethylene]
The linear low density polyethylene is an ethylene-α-olefin copolymer obtained by copolymerization using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst. A linear low-density polyethylene having a copolymerized α-olefin up to about 5 mol% is used.
また、本発明で使用する直鎖状低密度ポリエチレンの密度は、O.910〜0.930g/cm3とする。なお、上記触媒に関しては、重合活性が高く重合効率が優れている点、より有効な防蟻効果が発揮される点でシングルサイト触媒を用いることが好ましい。また、上記重合法としては、塊状重合や溶液重合、懸濁重合、気相重合等を採用できる。 The density of the linear low density polyethylene used in the present invention is O.910 to 0.930 g / cm 3 . As for the above catalyst, it is preferable to use a single-site catalyst from the viewpoints of high polymerization activity and excellent polymerization efficiency, and more effective ant protection effect. Moreover, as said polymerization method, block polymerization, solution polymerization, suspension polymerization, gas phase polymerization, etc. are employable.
そしてまた、上記直鎖状低密度ポリエチレンを成形する際には、２種類以上の直鎖状低密度ポリエチレンをブレンドして成形することもできる。また、防蟻効果が失われない程度に、高圧法低密度ポリエチレン(HPLDPE)をブレンドして成形することもでき、これによって成形温度を下げる効果が得られる。 In addition, when the linear low density polyethylene is molded, two or more types of linear low density polyethylene can be blended and molded. Further, high pressure low density polyethylene (HPLDPE) can be blended and molded to such an extent that the ant-proofing effect is not lost, thereby obtaining the effect of lowering the molding temperature.
一方、上記成形品の形態に関しても、シート状(防蟻シート)や筒状(電線類の被覆材)など、自由に選択することができ、また、成形方法に関しても、押出成形やプレス成形、射出成形、カレンダー成形、キャスティング成形、トランスファー成形など、種々の方法を採用できる。また、必要に応じて括剤や酸化チタン、顔料等を添加することもできる。 On the other hand, regarding the form of the molded product, it can be freely selected, such as a sheet shape (anti-rust sheet) or a tubular shape (covering material for electric wires). Also, regarding the molding method, extrusion molding or press molding, Various methods such as injection molding, calendar molding, casting molding, and transfer molding can be employed. Moreover, a binder, titanium oxide, a pigment, etc. can also be added as needed.
また、防蟻シート用にシート状に成形する場合には、シートの厚みを50〜300μm、好ましくは80〜250μmとするのが良い。また、防蟻シートは、建築物の基礎のコンクリートスラブや割栗、目つぶし砂利等の上に敷いたり、支柱・ブロック塀の立上り部や床板下面に貼り付けて使用することができる。 In the case of forming a sheet for an ant-proof sheet, the thickness of the sheet is 50 to 300 μm, preferably 80 to 250 μm. In addition, the ant-proof sheet can be used by laying on a concrete slab, split chestnut, crushed gravel, or the like of the foundation of the building, or affixing it to the rising part of the column / block fence or the bottom surface of the floor board.
また更に、直鎖状低密度ポリエチレンをシート形状に成形する場合には、この直鎖状低密度ポリエチレンの有する側鎖がシート全面に一様に分布させることが望ましく、具体的には、Ｔダイから溶融した直鎖状ポリエチレン樹脂を層流状態で面状に押し出して成形するのが好ましい。 Furthermore, when the linear low density polyethylene is molded into a sheet shape, it is desirable that the side chains of the linear low density polyethylene are uniformly distributed over the entire surface of the sheet. It is preferable that the linear polyethylene resin melted from is extruded into a planar shape in a laminar flow state and molded.
また、上記側鎖がシート全面に一様に分布したポリエチレンシートは、上記方法以外にも、直鎖状ポリエチレン樹脂を溶媒中に溶解させて、この溶解されたポリエチレン樹脂を面状の支持体上に層流状態で流延して平面状に広げた後、溶媒を揮散させる方法によって成形できる。 In addition to the above method, the polyethylene sheet in which the side chains are uniformly distributed over the entire surface of the sheet is obtained by dissolving a linear polyethylene resin in a solvent, and then dissolving the dissolved polyethylene resin on a planar support. After being cast in a laminar flow state and spread in a flat shape, it can be molded by a method of volatilizing the solvent.
また他にも、環状ダイから溶融した直鎖状ポリエチレン樹脂をチューブ状に押し出した後、軟化状態の樹脂を内側から吹き込んだ圧縮空気によって膨張させるインフレーション法を採用して、上記ポリエチレンシートを成形することもできる。 In addition, after the linear polyethylene resin melted from the annular die is extruded in a tube shape, the polyethylene sheet is molded by adopting an inflation method in which a softened resin is expanded by compressed air blown from the inside. You can also.
［直鎖状低密度ポリエチレンに添加する木材保存剤(防蟻剤)］
本発明において使用される木材保存剤としては、まず、ペルメトリン、シフルトリン、シフェノトリン、ビフェントリン、プラレトリン、アレスリン、シハロトリン、フェンバレレート、フルシトリネート、フルバリネート、シクロプロトリン、ピレトリン(除虫菊)などのピレスロイド系；エトフェンプロックス、シラフルオフェンなどの非エステルピレスロイド系；イミダクロプリド、アセタミプリド、クロチアニジン、ジノテフラン、チアメトキサムなどのネオニコチノイド系が挙げられる。
[Wood preservative (anticide) added to linear low density polyethylene]
As the wood preservative used in the present invention, first, pyrethroids such as permethrin, cyfluthrin, ciphenothrin, bifenthrin, praretrin, allethrin, cyhalothrin, fenvalerate, flucitrinate, fulvalinate, cycloprotorin, pyrethrin (insecticidal chrysanthemum) and the like. Non-ester pyrethroids such as etofenprox and silafluophene; neonicotinoids such as imidacloprid, acetamiprid, clothianidin, dinotefuran, and thiamethoxam.
加えて、フィプロニルなどのフェニルピラゾール系；クロルフェナピルなどのフェニルピロール系；ジデシルジメチルアンモニウムクロライド、ジデシルジメチルポリオキシエチルアンモニウムプロピオネートなどの第４級アンモニウム塩系；ピリダリルなどの2,2-ジクロロアリルオキシ系なども挙げられる。 In addition, phenylpyrazoles such as fipronil; phenylpyrroles such as chlorfenapyr; quaternary ammonium salts such as didecyldimethylammonium chloride and didecyldimethylpolyoxyethylammonium propionate; 2,2-dichloros such as pyridalyl Examples include allyloxy.
また他にも、フェニトロチオン、プロペンタホス、シアノホス、フェンチオン、ジクロロフェンチオン、ピリミホスメチル、ダイアジノン、インキサチオン、マラチオン、チオメトン、ジスルホトン、プロチオホス、スルプロホス、プロフェノホス、ピラクロホス、ジクロルボス、ナレド、クロルフェンビンホス、プロパホス、イソフェンホス、エチオンなどの有機リン系；カルボスルファン、ベンフラカルブなどのカーバメート系;ホウ酸、八ホウ酸ナトリウム、ヒバ油なども使用できる。 In addition, fenitrothion, propentaphos, cyanophos, phenthion, dichlorofenthion, pyrimifosmethyl, diazinon, inxathion, malathion, thiometone, disulfoton, prothiophos, sulfpropos, propenophos, pyracrophos, dichlorvos, nared, chlorfenbinphos, propofos, isophenephos, etion Organic phosphorus systems such as: Carbamate systems such as carbosulfan and benfuracarb; boric acid, sodium octaborate, and hiba oil can also be used.
そして、上記の木材保存剤の中でも、特に人体に対する安全性の観点から、ピレスロイド系、非エステルピレスロイド系、ネオニコチノイド系、フェニルピラゾール系、フェニルピロール系、第４級アンモニウム塩系、2,2-ジクロロアリルオキシ系、ホウ酸、八ホウ酸ナトリウムまたはヒバ油を用いるのが好ましい。 Among the above-mentioned wood preservatives, particularly from the viewpoint of safety to the human body, pyrethroids, non-ester pyrethroids, neonicotinoids, phenylpyrazoles, phenylpyrroles, quaternary ammonium salts, 2,2 It is preferred to use dichloroallyloxy, boric acid, sodium octaborate or hiba oil.
また、上記木材保存剤の配合量に関しては、直鎖状低密度ポリエチレンから成る樹脂成形品に、単位面積当たり0.0091〜0.093g/m2配合することで、防蟻効果を少なくとも20年以上持続させることができる。なお、この数値範囲は、厚み100μmのフィルムで計算すると、0.01〜0.1重量％の配合量に相当する。 In addition, with regard to the amount of the wood preservative, by adding 0.0091 to 0.093 g / m 2 per unit area in a resin molded product made of linear low-density polyethylene, the ant-proof effect is maintained for at least 20 years or more. be able to. This numerical range corresponds to a blending amount of 0.01 to 0.1% by weight when calculated with a film having a thickness of 100 μm.
また、防蟻シートに木材保存剤を添加する場合には、防蟻シートの厚みを80〜150μｍとして、単位体積当たりの木材保存剤の配合量を多くすることにより、防蟻効果を高めるのが好ましい。そしてまた、樹脂成形品が劣化し難い環境下で使用される場合には、上記木材保存剤の配合量を減らすこともできる。 In addition, when adding a wood preservative to the ant-proof sheet, the thickness of the ant-proof sheet is set to 80 to 150 μm, and the amount of the wood preservative per unit volume is increased to enhance the ant-proof effect. preferable. In addition, when the resin molded product is used in an environment where it is difficult to deteriorate, the amount of the wood preservative can be reduced.
なお、上記木材保存剤の配合方法については、樹脂の混錬時に必要量の木材保存剤を直接添加する方法でも、木材保存剤を高濃度で配合したマスターバッチを予め調製して、このマスターバッチを直鎖状低密度ポリエチレンと混錬する方法でもよく、結果的に上記配合量となるように調整されていればよい。 As for the method for blending the above-mentioned wood preservative, a masterbatch containing a high concentration of wood preservative is prepared in advance, even by directly adding a necessary amount of wood preservative during resin kneading. May be kneaded with linear low-density polyethylene as long as the blending amount is adjusted as a result.
『防蟻シートの調整例(Ｉ)』
まず、この調製例(Ｉ)では、直鎖状低密度ポリエチレン(LLDPE)と高圧法により重合させた低密度ポリエチレン(HPLDPE)とを、以下の表１の配合割合(重量比)で混合し、これを押出成形して実施例Ａ、実施例Ｂ及び比較例Ｃのフィルム(厚み100μｍ)を調製した。
First, in this Preparation Example (I), a linear low density polyethylene (LLDPE) and a low density polyethylene (HPLDPE) polymerized by a high pressure method are mixed at a blending ratio (weight ratio) shown in Table 1 below. This was extruded to prepare films (thickness: 100 μm) of Example A, Example B, and Comparative Example C.
なお、本調製例(Ｉ)では、上記直鎖状低密度ポリエチレンに、メタロセン触媒を用いて重合させたプライムポリマー社のエボリュー(登録商標)ＳＰを使用すると共に、高圧法により重合させた低密度ポリエチレンには、旭化成工業社のサンテック(登録商標)ＬＤを使用した。 In this preparation example (I), Evolue (registered trademark) SP produced by Prime Polymer Co., Ltd. polymerized using a metallocene catalyst was used for the linear low density polyethylene, and the low density polymerized by the high pressure method. As polyethylene, Suntec (registered trademark) LD manufactured by Asahi Kasei Kogyo Co., Ltd. was used.
また、上記実施例Ａのシート材と、比較例Ｃのシート材の硬さ(デュロメータ硬さ)及び引張弾性率を以下の方法で測定した。まず硬さについては、JIS-K-7215(プラスチックのデュロメータ硬さ試験方法)を参考にして、デュロメータＤ硬さを求めた。また、試験は厚さ100μｍのフィルムを重ねて厚さ約8mmにした状態で行った。試験機は、ゴム・プラスチック硬度計アスカーD型およびゴム硬度計用定圧加重器CL-150(高分子機器(株)製)を使用した。一方、引張弾性率については、引張圧縮試験機(ミネベアTECHNO GRAPH AL-50kNB)を用いて試験を行った。 Further, the hardness (durometer hardness) and tensile modulus of the sheet material of Example A and the sheet material of Comparative Example C were measured by the following methods. First, regarding the hardness, the durometer D hardness was determined with reference to JIS-K-7215 (Plastic Durometer Hardness Test Method). The test was performed in a state where a film having a thickness of 100 μm was stacked to a thickness of about 8 mm. The tester used was a rubber / plastic hardness meter Asker D type and a constant pressure loader CL-150 (manufactured by Polymer Instruments Co., Ltd.) for rubber hardness meter. On the other hand, the tensile elastic modulus was tested using a tensile compression tester (Minebea TECHNO GRAPH AL-50kNB).
その結果、硬さ(デュロメータ硬さ)は、実施例Ａ(LLDPE)のシート材がHDD40、実施例Ｃ(HDLDPE)のシート材がHDD35であった。また、引張弾性率は、実施例Ａ(LLDPE)のシート材が平均値156MPa(５回測定の各値,159,166,154,150,150(MPa))、実施例Ｃ(HDLDPE)のシート材が平均値227MPa(５回測定の各値,266,213,185,192,277(MPa))であった。 As a result, the hardness (durometer hardness) of the sheet material of Example A (LLDPE) was HDD40, and the sheet material of Example C (HDLDPE) was HDD35. The tensile modulus of the sheet material of Example A (LLDPE) is an average value of 156 MPa (each value of five measurements, 159,166,154,150,150 (MPa)), and the sheet material of Example C (HDLDPE) is an average value of 227 MPa (5 times). The measured values were 266, 213, 185, 192, 277 (MPa)).
「シロアリに対する防蟻効果の確認試験[１]」
この確認試験[１]では、上記調製例(Ｉ)で製造した各シートを、縦15cm、横20cmに切り取って木の枠に挟み込み、これをシロアリの巣の中に3ヶ月間放置して、食害の結果を観察した。その結果、以下の表２に示すように、実施例Ａ及びＢの防蟻シートは、比較例Ｃと比較して優れた防蟻効果を有していることが確認できた。
In this confirmation test [1], each sheet produced in the above preparation example (I) was cut into 15 cm in length and 20 cm in width and sandwiched between wooden frames and left in a termite nest for 3 months. The results of eating damage were observed. As a result, as shown in Table 2 below, it was confirmed that the ant-proof sheets of Examples A and B had an excellent ant-proof effect as compared with Comparative Example C.
『防蟻シートの調製例(II)』
次に、この調製例(II)では、以下の態様で実施例１〜５及び比較例１〜４の防蟻シートを調製した。なお、本調製例においても、直鎖状低密度ポリエチレンには、プライムポリマー社のエボリュー(登録商標)ＳＰ(密度0.925g/cm3)を使用し、また高圧法により重合させた低密度ポリエチレンには、旭化成工業社のサンテック(登録商標)ＬＤ(密度0.921g/cm3)を使用した。また、念のため付言しておくと、本発明の防蟻性シートは以下の調製例に限定されない。
"Preparation example of ant-proof sheet (II)"
Next, in this preparation example (II), the ant-proof sheets of Examples 1 to 5 and Comparative Examples 1 to 4 were prepared in the following manner. Also in this preparation example, the linear low-density polyethylene was Evolue (registered trademark) SP (density 0.925 g / cm 3 ) manufactured by Prime Polymer Co., Ltd., and the low-density polyethylene polymerized by the high-pressure method was used. Used was Suntec (registered trademark) LD (density 0.921 g / cm 3 ) of Asahi Kasei Corporation. In addition, as a precaution, the ant-proofing sheet of the present invention is not limited to the following preparation examples.
「実施例１」
メタロセン触媒を用いて重合させた直鎖状低密度ポリエチレンを押出し成形(成形温度180℃)して得られた厚み100μmの防蟻性フィルム。
「実施例２」
上記実施例１で使用した直鎖状低密度ポリエチレンと高圧法により重合させた低密度ポリエチレンを同量配合し、押出し成形(成形温度175℃)して得られた厚み100μmの防蟻性フィルム。
「実施例３」
上記実施例１で使用した直鎖状低密度ポリエチレン100重量部にイミダクロプリドを0.05重童部配合し、押出し成形(成形温度180℃)して得られた厚み100μmの防蟻性フィルム。
「実施例４」
上記実施例1で使用した直鎖状低密度ポリエチレン100重量部にイミダクロプリドを0.03重量部配合し、押出し成形(成形温度180℃)して得られた厚み100μmの防蟻性フィルム。
「実施例５」
上記実施例１で使用した直鎖状低密度ポリエチレン100重量部にエトフェンプロックスを0.08重量部配合し、押出し成形(成形温度180℃)して得られた厚み100μmの防蟻性フィルム。
"Example 1"
An ant-proof film having a thickness of 100 μm obtained by extrusion molding (molding temperature 180 ° C.) of linear low-density polyethylene polymerized using a metallocene catalyst.
"Example 2"
An ant-proofing film having a thickness of 100 μm obtained by blending the same amount of the linear low-density polyethylene used in Example 1 and the low-density polyethylene polymerized by the high-pressure method and extrusion molding (molding temperature 175 ° C.).
"Example 3"
An ant-proofing film having a thickness of 100 μm obtained by mixing 0.05 parts by weight of imidacloprid with 100 parts by weight of the linear low-density polyethylene used in Example 1 and extrusion molding (molding temperature 180 ° C.).
Example 4
An ant-proofing film having a thickness of 100 μm obtained by blending 0.03 part by weight of imidacloprid with 100 parts by weight of the linear low-density polyethylene used in Example 1 and extrusion molding (molding temperature 180 ° C.).
"Example 5"
An ant-proofing film having a thickness of 100 μm obtained by blending 0.08 parts by weight of etofenprox with 100 parts by weight of the linear low density polyethylene used in Example 1 and extrusion molding (molding temperature 180 ° C.).
「比較例１」
高圧法により重合させた低密度ポリエチレンを押出し成形(成形温度160℃)して得られた厚み100μmのフィルム。
「比較例２」
上記比較例１で使用した低密度ポリエチレン100重量部にイミダクロプリドを0.05重量部配合し、押出し成形(成形温度160℃)して得られた厚み100μmの防蟻性フィルム。
「比較例３」
エチレンビニルアセテート(酢酸ビニル10重量%含有)を押出し成形して得られた厚み200μmのフィルム(密度1.00g/cm3)。
「比較例４」
上記比較例３で使用したエチレンビニルアセテート100重量部にイミダクロプリド0.05重量部とシラフルオフェン0.05重量部とを配合し、押出し成形して得られた厚み200μmの防蟻性フィルム。
"Comparative Example 1"
A film having a thickness of 100 μm obtained by extrusion molding (molding temperature 160 ° C.) of low density polyethylene polymerized by a high pressure method.
"Comparative Example 2"
An ant-proof film having a thickness of 100 μm obtained by blending 0.05 part by weight of imidacloprid with 100 parts by weight of the low-density polyethylene used in Comparative Example 1 and extrusion molding (molding temperature 160 ° C.).
“Comparative Example 3”
A 200 μm-thick film (density 1.00 g / cm 3 ) obtained by extrusion molding ethylene vinyl acetate (containing 10 wt% vinyl acetate).
“Comparative Example 4”
An ant-proof film having a thickness of 200 μm obtained by blending 0.05 parts by weight of imidacloprid and 0.05 parts by weight of silafluophene with 100 parts by weight of ethylene vinyl acetate used in Comparative Example 3 above, and extrusion molding.
「シロアリに対する防蟻効果の確認試験[２]」
この確認試験[２]では、上記調製例(II)で調製した各シートの防蟻効果を、以下の試験方法により確認した。
"Confirmation test of termite prevention effect on termites [2]"
In this confirmation test [2], the ant-proof effect of each sheet prepared in Preparation Example (II) was confirmed by the following test method.
＜試験方法＞
まず、各シートを円形状に切り取ってシート片を各種５枚ずつ用意する。そして、全てのシート片を60℃の恒温槽に一旦保存し、保存期間が１ヶ月、3ヶ月、6ヶ月、9ヶ月、12ヶ月を経過するごとにシート片を１枚ずつ取り出して、これらを下記試験に用いる。なお、60℃での保存期間6ヶ月は、常温(25℃)で保存した場合の10年間、60℃での保存期間12ヶ月は、常温(25℃)で保存した場合の20 年間に相当する。
<Test method>
First, each sheet is cut into a circular shape, and five sheet pieces are prepared. Then, once all the sheet pieces are stored in a constant temperature bath at 60 ° C., the sheet pieces are taken out one by one every time the storage period is 1 month, 3 months, 6 months, 9 months, 12 months. Used for the following tests. The storage period of 6 months at 60 ° C corresponds to 10 years when stored at room temperature (25 ° C), and the storage period of 12 months at 60 ° C corresponds to 20 years when stored at room temperature (25 ° C). .
次に、試験に用いる器具について説明する。縦向きの２本のガラス管(内径約50mm、長さ約120mmの円筒管)を、横向きのガラス管(内径約20mm、長さ約30mmの円筒管)で連通状態に連結して成るＵ字状の容器に対して、予め乾燥殺菌した砂壌土を一方の縦管に底辺から40mmの高さまで詰め、更に水を散布し含水率25%の土壌とする。 Next, the instrument used for a test is demonstrated. A U-shape consisting of two vertically oriented glass tubes (cylindrical tube with an inner diameter of about 50 mm and a length of about 120 mm) connected in a connected state by a horizontal glass tube (cylindrical tube with an inner diameter of about 20 mm and a length of about 30 mm). To the container, dry and sterilized sand loam soil is packed in one vertical pipe to a height of 40 mm from the bottom, and water is sprayed to make a soil with a moisture content of 25%.
また、もう一方の縦向きのガラス管にも、砂壌土を底辺から20mmの高さまで詰め、同様に含水率25%となるように水を散布する。そしてまた、横向きガラス管にも同様の含水率に調整した砂壌土を詰め、Ｕ字状ガラス容器の下側部分が全て砂壌土で充填された状態となるようにする。 The other vertical glass tube is filled with sand loam to a height of 20 mm from the bottom, and water is sprayed in the same way so that the water content is 25%. Further, the horizontally oriented glass tube is filled with sandy loam adjusted to the same water content so that the lower part of the U-shaped glass container is filled with sandy loam.
そして、上記40mmの高さまで詰めた一方の縦管の砂壌土の上に、シート片をピッタリと円筒内壁との間に隙間が生じないように設置する。その後、設置したシート片の上に砂壌土を更に20mmの高さまで詰め、詰め終わった砂壌土の上にアカマツ木片(一辺が約30mmの立方体状のもの)を載置する。 Then, the sheet piece is installed on the sandy loam of one of the vertical tubes packed to the height of 40 mm so that no gap is generated between the perfect piece and the cylindrical inner wall. After that, the sand loam is further packed up to a height of 20 mm on the installed sheet piece, and a red pine wood piece (a cube having a side of about 30 mm) is placed on the finished sand loam.
また更に、上記砂壌土を20mmの高さまで詰めたもう一方の縦管には、イエシロアリ(Coptotermes fo mosanous SHIRAKI)の職蟻300頭と兵蟻30頭を投入する。またここには餌用としてろ紙を細かく裁断したものも投入する。最後に、両縦管の開口部をアルミ箔で軽く閉じて(密封しない)、試験容器を28℃±2℃、相対湿度60%以上の恒温槽(暗所)に21日間静置し、白蟻の貫通状態を観察する。 Furthermore, in the other vertical pipe filled with the above sand loam to a height of 20 mm, 300 ant ants (Coptotermes fo mosanous SHIRAKI) and 30 soldier ants are introduced. In addition, the filter paper that has been finely cut is used here for bait. Finally, the openings of both vertical tubes are lightly closed with aluminum foil (not sealed), and the test container is left in a constant temperature bath (dark place) at 28 ° C ± 2 ° C and relative humidity of 60% or more for 21 days. Observe the penetration state.
そして上記試験の結果、以下の表３に示すように、実施例１〜５の方が比較例１〜４よりも防蟻剤の量が少ないにもかかわらず、優れた防蟻効果を有していることが分かった。特に、防蟻剤の有無または配合量の条件が同じ実施例１と比較例１、実施例３と比較例２を比べれば、防蟻効果の持続性が大きく向上しているのが分かる。
本発明に係る「防蟻性素材」は、防蟻シートを製造する建材メーカーや、電線や通信ケーブルを製造する電線等メーカーにおいて大きな需要が見込まれ、特に従来の防蟻素材と比較して防蟻性能を損なわずにより低コストで製造できるメリットがあることから、産業上の利用可能性は非常に大きい。 The “ant-proof material” according to the present invention is expected to have a great demand in building material manufacturers that manufacture ant-proof sheets and electric wire and communication cable manufacturers, and in particular, compared to conventional ant-proof materials. Since there is a merit that can be manufactured at a lower cost without impairing the ant performance, the industrial applicability is very large.
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| JP2869568B2 (en) * | 1990-02-15 | 1999-03-10 | 三菱電線工業株式会社 | Termite cable |
| JP3336714B2 (en) * | 1993-03-11 | 2002-10-21 | 住友化学工業株式会社 | Insect repellent resin composition |
| JP3535258B2 (en) * | 1995-04-28 | 2004-06-07 | フクビ化学工業株式会社 | Olefin-based insect repellent resin composition having durability and molded product thereof |
| EP1347683A2 (en) * | 2000-12-03 | 2003-10-01 | Battelle Memorial Institute | Barrier preventing wood pest access to wooden structures |
| JP2004067960A (en) * | 2002-08-09 | 2004-03-04 | Mitsui Chemicals Inc | 4-methyl-1-pentene polymer type insect-controlling resin composition and insect control molding |
| JP2007041113A (en) * | 2005-08-01 | 2007-02-15 | Kanaoka:Kk | Stretch film for stretch label, and the stretch label using the film |
| JP4999344B2 (en) * | 2006-03-28 | 2012-08-15 | 住友化学株式会社 | Ant-proof sheet |
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