JPH0255402B2 - - Google Patents
Info
- Publication number
- JPH0255402B2 JPH0255402B2 JP61054899A JP5489986A JPH0255402B2 JP H0255402 B2 JPH0255402 B2 JP H0255402B2 JP 61054899 A JP61054899 A JP 61054899A JP 5489986 A JP5489986 A JP 5489986A JP H0255402 B2 JPH0255402 B2 JP H0255402B2
- Authority
- JP
- Japan
- Prior art keywords
- repellent
- insecticide
- chlorine
- containing polymer
- weight
- 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.)
- Expired - Lifetime
Links
- 239000002917 insecticide Substances 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 239000000077 insect repellent Substances 0.000 claims description 14
- 238000013508 migration Methods 0.000 claims description 14
- 230000005012 migration Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000002728 pyrethroid Substances 0.000 claims description 8
- 150000005690 diesters Chemical class 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 230000005923 long-lasting effect Effects 0.000 claims description 2
- 239000005871 repellent Substances 0.000 description 27
- 230000002940 repellent Effects 0.000 description 27
- 230000000694 effects Effects 0.000 description 13
- 241000607479 Yersinia pestis Species 0.000 description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 7
- 241001674044 Blattodea Species 0.000 description 6
- 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 6
- 239000012760 heat stabilizer Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 240000004460 Tanacetum coccineum Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ROVGZAWFACYCSP-MQBLHHJJSA-N [2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(C\C=C/C=C)C(=O)C1 ROVGZAWFACYCSP-MQBLHHJJSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- FYOYCZHNDCCGCE-UHFFFAOYSA-N diphenyl hydrogen phosphite Chemical compound C=1C=CC=CC=1OP(O)OC1=CC=CC=C1 FYOYCZHNDCCGCE-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229940033518 insecticides and repellents Drugs 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 2
- 229940015367 pyrethrum Drugs 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000238660 Blattidae Species 0.000 description 1
- SUNPWPSLRLHVJP-UHFFFAOYSA-L C(C)(C)OP(=O)([O-])[O-].[Ca+2] Chemical compound C(C)(C)OP(=O)([O-])[O-].[Ca+2] SUNPWPSLRLHVJP-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 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
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 231100000517 death Toxicity 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 210000001672 ovary Anatomy 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- 229940070846 pyrethrins Drugs 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Description
（産業上の利用分野）
本発明は持続性に優れた害虫忌避樹脂成形体に
関する。
（従来の技術）
従来、生活空間に害虫が侵入するのを防止する
ため、各種防虫剤や害虫忌避剤が広く使用されて
いる。このような用途の一つに、樹脂中に防虫剤
や忌避剤を混入し、シート等に成形したものが知
られており（特開昭60−146805号公報）、この害
虫忌避剤では混入された忌避剤が樹脂成形体表面
に移行することにより、害虫忌避効果が得られる
ものである。
（発明が解決しようとする問題点）
しかしながら、樹脂中に殺中剤や忌避剤を配合
し、成形したシート等の成形体においては、害虫
に対する防虫性能や忌避性能が未だ不満足である
ことがわかつた。その理由は、一つには用いる薬
品の耐熱性があり、樹脂の溶融成形条件下で分
解、揮散等が生じ易いこと、及び二つには薬品の
耐熱性をクリアーできたとしても、成形体表面へ
の薬効成分の移行が未だ不十分であり、十分な効
力と持続性とが得られないことが考えられる。
従つて本発明は害虫に対する防虫及至忌避効果
と該効果の持続性とに優れた害虫忌避樹脂成形体
を提供することを課題とする。
（問題点を解決するための手段）
本発明においては、塩素含有重合体、ピレスロ
イド系殺虫剤及びリンのオキシ酸のモノ又はジエ
ステルを移行促進剤として含有する組成物から成
形体を製造することにより、害虫に対する防虫乃
至忌避効果とその効果の持続性とが得られる。
（作用）
本発明は、塩素含有重合体と上述の移行促進剤
との組合せが、塩素含有量合体に配合されたピレ
スロイド系殺虫剤の成形品表面への移行（ブリー
ドアウト）を徐々にしかしながら確実にしかも長
期にわたつて行ない、その結果として防虫乃至忌
避効果が確実に且つ長期にわたつて奏されるとい
う知見に基づくものである。
一般に移行（migration）とは、ゴムや可塑化
プラスチツクに配合された配合剤が、配合物内で
高濃度の側から低濃度の方（表面）へ移動する現
象として知られており、この移行現象の生成する
程度はプラスチツクと配合剤との相溶性等の性質
にも関連している。本発明の塩素含有重合体にお
いて、安定した害虫に対する防虫乃至忌避効果が
生ずるのは、塩素含有重合体中に配合された殺虫
剤乃至忌避剤が成形体表面に有効に移行すること
によるものであるが、これは移行促進剤が自ら殺
虫剤乃至忌避剤を伴なつて表面に移行するか及
び／又は移行促進剤が殺虫剤乃至忌避剤の塩素含
有重合体への相溶の程度を減じる作用を行い、そ
の結果として殺虫剤乃至忌避剤の移行を促進する
ためと思われる。何れにせよ、本発明では、害虫
に対する殺虫剤乃至忌避剤の配合量に比して著し
く少ない移行促進剤の配合で、未配合のものに比
して確実な防虫乃至忌避効果とこの効果の長期持
続性とが得られることは真に意外の知見であつ
た。また、本発明において、移行促進剤を配合し
たものでは、成形直後からの初期防虫乃至忌避効
果に優れていることは、上記移行促進剤が、殺虫
剤乃至忌避剤をも混練成形時に加わる熱に対して
安定化する作用を行つているものとも推察され
る。
（発明の作用効果）
本発明によれば、塩素含有重合体にピレスロイ
ド系殺虫剤と前述リンのオキシ酸のモノ又はジエ
ステル系移行促進剤とを配合するという簡便な手
段で、成形体表面に優れた防虫乃至忌避効果と長
期にわたる効果の持続性とを付与することがで
き、例えば台所用家具、建築用構造材、壁材或い
は窓枠部材、電子機器用容器或いは下敷等とし
て、ゴキブリその他の害虫の侵入を防止する用途
に有効に利用される。
（発明の実施態様の説明）
本発明において、移行促進剤としてはリンのオ
キシ酸のモノ又はジエステルが使用される。
リンのオキシ酸のモノ又はジエステルとしては
ホスフアイト（亜リン酸エステル）系又はホスフ
エート（リン酸エステル）系のものを挙げること
ができる。ホスフアイト系移行促進剤としては、
下記式
式中、Ｒは水素原子、カチオン性基、又は炭素
数20以下の１価炭化水素、例えばアルキル基、ア
リール基、アラールキル基又はアルカリール基で
あり、R1は炭素数20以下の１価炭化水素である、
又は下記式
式中、Ｒは上述した意味を有し、R2は２価炭
化水素基である、
で表される化合物。
また、ホスフエート系移行促進剤として下記式
式中、Ｒは水素原子、カチオン性基又は炭素数
20以下の１価炭化水素基であり、
R1は炭素数20以下の１価炭化水素基である、
で表わされる化合物であり、具体的には、ジフエ
ニルホスフアイト、ジフエニルホスフエート、モ
ノイソプロピルホスフエートカルシウム等が挙げ
られる。
本発明において、殺虫剤乃至忌避剤としては、
ピレスロイド系殺虫剤やピレトリン系殺虫剤が使
用される。ピレトリン類は除虫菊花の子房に含ま
れる殺虫成分であり、一方ピレスロイド系殺虫剤
は除虫菊成分をもとに合成された殺虫剤であり、
これらは人間や動物に対する毒性が極めて少な
く、皮膚への刺激も少なく、しかも効果に優れて
いるという特徴を有している。ピレスロイド系殺
虫剤としては、エトフエンプロツクス（化学名：
２−（４−エトキシフエニル）−２−メチルプロピ
ル３−フエノキシベンジルエーテル；三井東圧化
学(株)製）を好適に用いることができる。
塩素含有重合体としては、ポリ塩化ビニル、塩
化ビニル−酢酸ビニル共重合体、塩化ビニル−ア
クリル共重合体、塩化ビニル−ブタジエン共重合
体、或いはこれらのポリマーブレンドのような塩
化ビニル樹脂；塩化ビニリレン樹脂；後塩素化ポ
リエチレン；塩素化ポリプロピレン；塩素化ポリ
塩化ビニル；ポリクロロプレン或いはこれらの２
種以上のブレンドを挙げることができる。本発明
はこれらの内でも、塩化ビニル樹脂、特に軟質塩
化ビニル樹脂に適用したときに著効が得られる。
勿論、本発明に用いる塩素含有重合体には、そ
れ自体公知の配合剤を公知の処方に従つて配合す
ることができる。このような配合剤の適当な例
は、フタル酸ジオクチル、アジピン酸ジオクチ
ル、セバチン酸ジオクチル、ポリプロピレングリ
コールアジペート等の可塑剤；ステアリン酸カル
シウム、ステアリン酸マグネシウム、ステアリン
酸亜鉛、ジオクチル錫マレエートポリマー、ジオ
クチル錫ラウレート等の熱安定剤；高級脂肪酸ア
マイド、ポリエチレンワツクス、マイクロクリス
タリンワツクス等の滑剤；炭酸カルシウム、水酸
化アルミニウム、水酸化マグネシウム、焼成クレ
イ等の充填剤；二酸化チタン、カーボンブラツ
ク、ベンガラ、オーカー等の顔料；アニオン系、
カチオン系、ノニオン系或いは両性系の帯電防止
剤等である。
本発明において、塩素含有重合体を基準にし
て、前記防虫剤乃至忌避剤は0.05乃至５重量％、
特に0.5乃至４重量％で用いるのが好ましく、一
方リンのオキシ酸のモノ又はジエステル系移行促
進剤は0.1乃至１重量％の量で用いるのがよい。
塩素含有重合体への配合の順序には特に制限が
なく、殺虫剤乃至忌避剤とリンのオキシ酸エステ
ル系移行促進剤とを、他の配合成分と共に同時に
配合してもよく、また塩素含有重合体に他の配合
成分を最後にブレンドし、最初に殺虫剤乃至忌避
剤とリンのオキシ酸エステル系移行剤とを、この
順序、逆の順序を或いは同時にブレンドしてもよ
い。
樹脂のブレンドは、所謂乾式ブレンドした後、
成形機に供給することによつて行つてもよいし、
バンバリーミキサー、一軸或いは二軸の押出機、
ロール等に供給して予め混練によるブレンドを行
つてもよい。樹脂の成形は、押出成形、カレンダ
ーロールによるシート成形、射出成形等により容
易に行われ、シート、パネル、窓枠、その他の構
造材等が容易に得られる。
（実施例）
以下に示す実施例において効力の試験は次の通
り行つた。
(1) 強制接触試験方法
試験片（巾40mm×厚み１mm）を大きさ100mm×
100mmの台紙上に貼り合せ、チヤバネゴキブリ10
頭（雄５匹、雌５匹）を入れた円筒状の容器（内
径80mm×高さ100mm）をかぶせ、ゴキブリを強制
的に試験片に接触せしめて、致死頭数を調べた。
尚、試験片は40℃に放置し、６ヶ月間致死頭数に
ついて調べた。
(2) 忌避試験方法
試験槽（縦1000mm×横1000mm×高ま500mm）の
中央部に隔壁を設けて、Ａ室及びＢ室に二分する
と共に、該隔壁の中央部に巾100mmのＡ室及びＢ
室間の通路を設けた。一方の室Ａの下端側部に巾
40mmの試験片を貼り、Ａ室及びＢ室のほぼ中央に
エサを置くと共に、この中にワモンゴキブリ10頭
を供試した。Ａ室の中にいるゴキブリの数を調べ
た。
実施例 １
下記処方の組成物を調製した。
試料 １
塩化ビニル樹脂（重合度1350） 100重量部
Mg／Zn系熱安定剤 ６ 〃
ジオクチルアジペート（可塑剤） 45 〃
殺虫忌避剤 MTI−500*1 ３ 〃
ジフエニルフオスフアイト 0.3 〃
試料 ２
塩化ビニル樹脂（重合度1350） 100重量部
Mg／Zn系熱安定剤 ６ 〃
ジオクチルアジペート（可塑剤） 45 〃
殺虫忌避剤 MTI−500 ３ 〃
試料 ３
塩化ビニル樹脂（重合度620） 100重量部
熱安定剤 ５重量部
殺虫忌避剤 MTI−500 ３重量部
ジフエニルフオスフアイイト 0.3 〃
試料 ４
塩化ビニル樹脂（重合度620） 100重量部
熱安定剤 ５ 〃
殺虫忌避剤 MTI−500 ３ 〃
殺虫忌避剤 MTI−500は、２−（４−エトキ
シフエニル）−２−メチルプロピル−３−フエノ
キシベンジルエーテルで下記構造式
を有する。
上記各試料を、試料１及び２の場合は150℃、
試料３及び４の場合は160℃で押出成形し、巾40
mm、厚み１mmのシートに成形した。
この各シートを用いて前述した効力試験を行つ
た。
強制接触試験の結果を下記表１に示す。表１の
試験は40℃の温度下での促進試験により行われて
おり、値は試験開始24時間後の致死頭数を示して
いる。
(Industrial Application Field) The present invention relates to a pest repellent resin molded article with excellent sustainability. (Prior Art) Conventionally, various insect repellents and pest repellents have been widely used to prevent pests from entering living spaces. One of these uses is known to mix insect repellents and repellents into resin and mold them into sheets, etc. (Japanese Unexamined Patent Publication No. 146805/1983). By transferring the repellent to the surface of the resin molded article, an insect repellent effect can be obtained. (Problems to be Solved by the Invention) However, it has been found that molded products such as sheets made by blending insecticides and repellents into resin are still unsatisfactory in their insect repellent and repellent performance against pests. Ta. One of the reasons for this is that the chemicals used have heat resistance, which tends to cause decomposition and volatilization under the resin melt molding conditions, and second, even if the heat resistance of the chemicals can be met, the molded product It is thought that the transfer of the medicinal ingredients to the surface is still insufficient, and sufficient efficacy and sustainability cannot be obtained. Accordingly, an object of the present invention is to provide an insect repellent resin molded article that is excellent in insect repellent and repellent effects on insect pests and in the sustainability of the effects. (Means for Solving the Problems) In the present invention, a molded article is produced from a composition containing a chlorine-containing polymer, a pyrethroid insecticide, and a mono- or diester of a phosphorus oxyacid as a migration accelerator. , an insect repellent or repellent effect against pests and a sustainability of the effect can be obtained. (Function) The present invention provides that the combination of the chlorine-containing polymer and the above-mentioned migration accelerator gradually but reliably causes the pyrethroid insecticide blended in the chlorine-containing polymer to migrate (bleed out) to the surface of the molded product. Moreover, it is based on the knowledge that it is carried out over a long period of time, and as a result, the insect repellent or repellent effect is reliably exerted over a long period of time. Migration is generally known as a phenomenon in which compounding agents in rubber or plasticized plastic move from the higher concentration side to the lower concentration side (surface) within the compound. The degree of formation is also related to properties such as compatibility between the plastic and the compounding agent. The reason why the chlorine-containing polymer of the present invention has a stable insect repellent or repellent effect against pests is that the insecticide or repellent blended into the chlorine-containing polymer effectively transfers to the surface of the molded product. However, this is because the migration accelerator itself migrates to the surface along with the insecticide or repellent, and/or the migration accelerator acts to reduce the degree of compatibility of the insecticide or repellent with the chlorine-containing polymer. This is thought to be to promote the transfer of insecticides and repellents as a result. In any case, in the present invention, the migration accelerator is blended in a significantly smaller amount than the amount of insecticide or repellent against pests, and the insect repellent or repellent effect is more reliable and the effect lasts for a long time than when it is not blended. It was a truly surprising finding that sustainability could be achieved. Furthermore, in the present invention, the product containing a migration accelerator has an excellent initial insect repellent or repellent effect immediately after molding. It is also inferred that it has a stabilizing effect on the (Operations and Effects of the Invention) According to the present invention, a pyrethroid insecticide and the above-mentioned phosphorus oxyacid mono- or diester migration accelerator are blended into a chlorine-containing polymer, which improves the surface of the molded product. It can provide an insect repellent or repellent effect and a long-term sustainability of the effect. For example, it can be used as kitchen furniture, architectural structural materials, wall materials or window frame members, containers or underlays for electronic devices, etc. to prevent cockroaches and other pests. It is effectively used to prevent the intrusion of DESCRIPTION OF EMBODIMENTS OF THE INVENTION In the present invention, mono- or diesters of phosphorus oxyacids are used as migration promoters. Examples of mono- or diesters of phosphorus oxyacids include those based on phosphites and phosphates. As a phosphite-based migration accelerator,
The following formula In the formula, R is a hydrogen atom, a cationic group, or a monovalent hydrocarbon having 20 or less carbon atoms, such as an alkyl group, an aryl group, an aralkyl group, or an alkaryl group, and R 1 is a monovalent hydrocarbon having 20 or less carbon atoms. Hydrogen or the following formula A compound represented by the following formula, wherein R has the above-mentioned meaning, and R 2 is a divalent hydrocarbon group. In addition, as a phosphate transfer accelerator, the following formula In the formula, R is a hydrogen atom, a cationic group, or a carbon number
It is a monovalent hydrocarbon group having 20 or less carbon atoms, and R 1 is a monovalent hydrocarbon group having 20 or less carbon atoms. Examples include calcium isopropyl phosphate. In the present invention, the insecticide or repellent is
Pyrethroid and pyrethrin insecticides are used. Pyrethrins are insecticidal components contained in the ovary of pyrethrum flowers, while pyrethroid insecticides are insecticides synthesized based on pyrethrum components.
These are characterized by extremely low toxicity to humans and animals, little irritation to the skin, and excellent efficacy. As a pyrethroid insecticide, etofenprotux (chemical name:
2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether (manufactured by Mitsui Toatsu Chemical Co., Ltd.) can be suitably used. Examples of chlorine-containing polymers include vinyl chloride resins such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, vinyl chloride-acrylic copolymers, vinyl chloride-butadiene copolymers, or blends of these polymers; vinylylene chloride; Resin; Post-chlorinated polyethylene; Chlorinated polypropylene; Chlorinated polyvinyl chloride; Polychloroprene or two of these
Blends of more than one species can be mentioned. Among these, the present invention is particularly effective when applied to vinyl chloride resins, particularly soft vinyl chloride resins. Of course, the chlorine-containing polymer used in the present invention can be blended with known compounding agents according to known formulations. Suitable examples of such additives include plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sebatate, polypropylene glycol adipate; calcium stearate, magnesium stearate, zinc stearate, dioctyltin maleate polymer, dioctyltin Heat stabilizers such as laurate; lubricants such as higher fatty acid amide, polyethylene wax, and microcrystalline wax; fillers such as calcium carbonate, aluminum hydroxide, magnesium hydroxide, and calcined clay; titanium dioxide, carbon black, red iron, and ocher. Pigments such as; anionic,
These include cationic, nonionic, or amphoteric antistatic agents. In the present invention, the insect repellent or repellent is 0.05 to 5% by weight based on the chlorine-containing polymer;
In particular, it is preferably used in an amount of 0.5 to 4% by weight, while the phosphorus oxyacid mono- or diester transfer promoter is preferably used in an amount of 0.1 to 1% by weight. There is no particular restriction on the order in which they are added to the chlorine-containing polymer; the insecticide or repellent and the phosphorus oxyacid ester transfer accelerator may be added together with other ingredients, or the chlorine-containing polymer may be added to the chlorine-containing polymer at the same time. The other components may be blended last, and the insecticide or repellent and the phosphorus oxyacid ester transfer agent may be blended first in this order, in the reverse order, or simultaneously. After the resin blend is so-called dry blending,
This may be done by feeding it into a molding machine, or
Banbury mixer, single or twin screw extruder,
Blending by kneading may be performed in advance by supplying the mixture to a roll or the like. Molding of the resin is easily performed by extrusion molding, sheet molding using calender rolls, injection molding, etc., and sheets, panels, window frames, other structural materials, etc. can be easily obtained. (Example) In the examples shown below, efficacy tests were conducted as follows. (1) Forced contact test method A test piece (width 40mm x thickness 1mm) is sized 100mm x
Laminated on a 100mm mount, Cockroach 10
A cylindrical container (inner diameter 80 mm x height 100 mm) containing cockroach heads (5 males, 5 females) was placed over the test piece, and the number of dead cockroaches was determined by forcing the cockroaches to come into contact with the test piece.
The test piece was left at 40°C and the number of deaths was examined for 6 months. (2) Repellent test method A partition wall is installed in the center of the test chamber (length 1000 mm x width 1000 mm x height 500 mm) to divide it into chamber A and chamber B, and a chamber A and chamber 100 mm wide are installed in the center of the partition wall. B
A passageway was created between the rooms. There is a width on the lower end side of one chamber A.
A 40 mm test piece was pasted, food was placed approximately in the center of chambers A and B, and 10 American cockroaches were placed inside. I checked the number of cockroaches in room A. Example 1 A composition having the following formulation was prepared. Sample 1 Vinyl chloride resin (degree of polymerization 1350) 100 parts by weight Mg/Zn heat stabilizer 6 Dioctyl adipate (plasticizer) 45 Insecticide repellent MTI-500 *1 3 Diphenyl phosphorite 0.3 Sample 2 Vinyl chloride Resin (degree of polymerization 1350) 100 parts by weight Mg/Zn heat stabilizer 6 Dioctyl adipate (plasticizer) 45 Insecticide repellent MTI-500 3 Sample 3 Vinyl chloride resin (degree of polymerization 620) 100 parts by weight Heat stabilizer 5 parts by weight Insecticide repellent MTI-500 3 parts by weight Diphenyl phosphorite 0.3 〃 Sample 4 Vinyl chloride resin (degree of polymerization 620) 100 parts by weight Heat stabilizer 5 〃 Insecticide repellent MTI-500 3 〃 Insecticide repellent MTI- 500 is 2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether with the following structural formula: has. Each sample above was heated at 150℃ for samples 1 and 2.
Samples 3 and 4 were extruded at 160℃ and had a width of 40 mm.
It was molded into a sheet with a thickness of 1 mm and a thickness of 1 mm. The efficacy test described above was conducted using each of these sheets. The results of the forced contact test are shown in Table 1 below. The test in Table 1 was conducted as an accelerated test at a temperature of 40°C, and the values indicate the number of dead animals 24 hours after the start of the test.
【表】
上記第１表の結果は、フオスフアイト系移行促
進剤を併用することにより、著しい致死性と効果
の持続性とが得られることがわかる。
次に忌避試験の結果を下記表２に示す。[Table] The results shown in Table 1 above show that the combined use of a phosphite-based migration accelerator provides significant lethality and long-lasting effects. Next, the results of the repellent test are shown in Table 2 below.
Claims (1)
移行促進剤を含有する組成物において、 該移行促進剤がリンのオキシ酸のモノ又はジエ
ステルであり、塩素含有重合体当り、殺虫剤が
0.05乃至５重量％及び移行促進剤が0.1乃至１重
量％の量で存在することを特徴とする持続性を有
する害虫忌避樹脂成形体。[Scope of Claims] 1. A composition containing a chlorine-containing polymer, a pyrethroid insecticide, and a migration accelerator, wherein the migration accelerator is a mono- or diester of a phosphorus oxyacid; but
A long-lasting insect repellent resin molding, characterized in that it is present in an amount of 0.05 to 5% by weight and a migration accelerator in an amount of 0.1 to 1% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5489986A JPS62212302A (en) | 1986-03-14 | 1986-03-14 | Resin molded article for repelling insect pest, having durability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5489986A JPS62212302A (en) | 1986-03-14 | 1986-03-14 | Resin molded article for repelling insect pest, having durability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62212302A JPS62212302A (en) | 1987-09-18 |
| JPH0255402B2 true JPH0255402B2 (en) | 1990-11-27 |
Family
ID=12983447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5489986A Granted JPS62212302A (en) | 1986-03-14 | 1986-03-14 | Resin molded article for repelling insect pest, having durability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62212302A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818525A (en) * | 1986-08-08 | 1989-04-04 | Mitsui Toatsu Chemicals, Inc. | Insecticidal resin coating film |
| DE19722196C1 (en) * | 1997-05-27 | 1998-10-22 | Karl Engelhard Fabrik Pharm Pr | Di:ethyl-meta-toluamide based insect repellent composition |
| JP4649104B2 (en) * | 2003-11-07 | 2011-03-09 | 住化カラー株式会社 | Two-layer olefin resin pellets for insect repellent resin composition |
| JP4890798B2 (en) * | 2004-06-24 | 2012-03-07 | エステー株式会社 | Insect repellent, insect repellent using the same, and method |
| JP2010013761A (en) * | 2008-07-03 | 2010-01-21 | Sumitomo Chemical Co Ltd | Insecticidal filament |
| JP5604861B2 (en) * | 2009-12-18 | 2014-10-15 | 住友化学株式会社 | Molded body comprising polymer composition |
| JP7282369B2 (en) * | 2018-12-28 | 2023-05-29 | 広島化成株式会社 | Insect repellent partition sheet |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58172302A (en) * | 1982-03-25 | 1983-10-11 | シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ | Slow-release agricultural drug composition, manufacture and use |
-
1986
- 1986-03-14 JP JP5489986A patent/JPS62212302A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58172302A (en) * | 1982-03-25 | 1983-10-11 | シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ | Slow-release agricultural drug composition, manufacture and use |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62212302A (en) | 1987-09-18 |
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