TW201032712A

TW201032712A - Insecticidal polymer composition

Info

Publication number: TW201032712A
Application number: TW98143446A
Authority: TW
Inventors: Boris Breitscheidel; Michael Ishaque; Sven Harmsen; Jochen Wagner
Original assignee: Basf Se
Priority date: 2008-12-18
Filing date: 2009-12-17
Publication date: 2010-09-16
Also published as: WO2010069796A3; AR075317A1; WO2010069796A2

Abstract

The present invention relates to a polymer composition comprising a polymer, a plasticizer, and an insecticide and/or an insect repellent. Further, it relates to a process for the preparation of a molding comprising heat-molding the polymer composition. The invention also relates to a plasticizer composition comprising an insecticide and/or an insect repellent, and a plasticizer. Additionally, it relates to a molding comprising the polymer composition, and to a use of the molding for the control of insects.

Description

201032712 六、發明說明：【發明所屬之技術領域】本發明係關於一種聚合物組合物，其包含聚合物、增塑劑、殺蟲劑及/或驅蟲劑。其進一步係關於一種製備模製 •品之方法，其包含加熱模製該聚合物組合物。本發明亦係 .關於一種包含殺蟲劑及/或驅蟲劑、及增塑劑之增塑劑組合物。此外，其係關於一種包含該聚合物組合物之模製品’及一種以該模製品控制昆蟲之用途。 • 【先前技術】已知一種包含聚合物尤其是聚氣乙烯（Pvc)、增塑劑及殺蟲劑之聚合物組合物： EP 0 763 325 A1揭示一種樹脂組合物，其包含一樹脂、一活性化合物及一可蒸發的增塑劑。該活性化合物可係擬除蟲菊酯殺蟲劑。 GB 2 170 211 A揭示一種用於殺蟲之熱模製品，其包含高分子量物質、殺蟲劑、及一熱穩定性組份，其可係鄰苯 • 三甲酸二月桂基醋。 US 4，193,984揭示一種用於控制蒼蠅之分散劑，其包含 . 一含苄呋菊酯（resmethrin)殺蟲劑之第一片體、及一含香蘭 . 素（vanilin)之第二片體。用於獲得該分散劑之塑料溶膠包含PVC及鄰苯二曱酸二（2-乙基己基）酯。 US 2003/0069135 A1揭示一種農用化學調配物，其包含環己烷聚羧酸酯、水、佐劑及活性成份。 WO 02/21913揭示一種活性成份受控釋出之調配物’ i 144736.doc 201032712 ^ 3 分散於基質聚合物之活性成份及一增塑劑。本技術中已知存在多種與包含聚合物、增塑劑及殺蟲劑之聚合物組合物相關的問題：當使用可蒸發的增塑劑時，此等增塑劑係以較具有較低蒸氣壓之增塑劑更高程度蒸發至環境中。有些增塑劑被認為對環境有害或有毒性，如鄰苯一曱酸二（2-乙基己基）酯。多種增塑劑不適用於曝露於低之聚合物模製品，係因塑化作用僅於較高溫度下發生。另一問題係殺蟲劑併入聚合物組合物中會導致所得模製品之透明度下降或散射增加或表面光澤損失。【發明内容】本發明之目的係克服本技藝現階段之上述問題。該目的係藉由包含一聚合物、一增塑劑、及一殺蟲劑及/或一驅蟲劑之聚合物組合物來實現，其中該增塑劑係鄰苯二甲酸二（c9-c13烷基）酯或環己烷二羧酸二（c9_ci3烷基）酯。術語「聚合物」係指一或多種聚合物。一般而言，該聚合物係選自基於氣乙稀、乙稀、丙烯、丁二烯、乙酸乙稀醋、（甲基）丙稀酸縮水甘油基酯、直鏈或支鏈醇之 (甲基）丙稀酸酯、苯乙稀或丙稀腈之均-及共聚物。更明確而言，聚氯乙稀、C4至C8醇之聚丙稀酸酯、聚曱基丙烯酸曱酯、丙浠酸甲酯-丙稀酸丁酯共聚物、甲基丙稀酸曱酯-甲基丙稀酸丁酯共聚物、乙烯-乙酸乙稀酯共聚物、氯化聚乙烯、腈橡膠、丙烯腈-丁二烯_苯乙烯共聚物、乙烯-丙烯共聚物、乙烯-丙烯-二烯共聚物、苯乙烯-丙烯腈共聚物、丙稀腈-丁一稀橡膠、苯乙稀-丁二稀彈性體及曱基丙 144736.doc 201032712 稀酸甲醋-苯乙晞-丁二烯共聚物。最佳聚合物係聚氣乙稀 (PVC)及PVC與較佳如上所述聚合物之至少另一聚合物之混合物。最佳聚合物係pvc。聚氣乙烯可經由氯乙烯之均聚作用製得。PVC可在工業上以多種方式製備，例如懸浮聚合、微懸浮聚合、乳液聚合、及本體聚合。表徵PVC莫耳質量及根據DIN 53726測定之K值可介於57至90範圍内，較佳於61至85範圍内，及特佳於 64 至 75 範圍内。Kirk_〇thmer，Encyci〇pedia 〇f • Chemical Technol〇gy，第 4 版，24 卷，1017_1047 頁概述 PVC之特性、製備、及用途，及亦描述1>¥(：;之尺值、數量平均分子量、重量平均分子量、與根L1234測定之固有及相對粘度之間的關係。 β亥聚合物組合物之PVC含量一般係20至99重量❶/〇，較佳 30至90重量％，特佳35至8〇重量％，且尤其如至乃重量 /〇，各情況下係以該聚合物組合物之總重計，即包括該聚合物組合物之所有成份。 Φ 根據本發明之聚合物組合物包含一增塑劑，該增塑劑係鄰笨一甲酸一（(：9至C"烧基）酯或環己燒二缓酸二（c9至烷基）酯。術語「（：9至cu烷基」係指直鏈、支鏈或環狀烷基或直鏈、支鏈及/或環狀烷基之混合物，其主鏈確切地具有9至13個碳原子或其具有9至13個碳原子的主鏈混合物。術語「C9烷基」係指其主鏈具有9個碳原子之直鏈或支鏈烷基或直鏈與支鏈烷基之混合物。術語「環己炫二叛酸酯」係指1，2-、1,3-或1，4-經取代之環己烷二羧酸酯，較 144736.doc 201032712 佳係1，2-取代。鄰苯二曱酸二（C9-C13烷基）酯增塑劑之適宜實例為本技藝所熟知且可購得：鄰苯二甲酸二異壬基酯DINP(獲自 BASF SE之Palatinol® N)、鄰苯二甲酸二異癸基酯DIDP、鄰苯二甲酸二-2-丙基庚酯DPHP(獲自BASF SE之Palatinol 10-P)、鄰苯二甲酸二壬基十一烷基酯NUP(獲自BASF SE 之Palatinol 911-P)、鄰苯二甲酸二-十一烷基酯DUP(獲自 BASF SE之Palatinol 111P-1)、鄰苯二曱酸二異十一烷基酯 DIUP、鄰苯二甲酸二十三烷基酯DTDP(獲自Exxon Mobile之Jayflex® DTDP)、鄰苯二曱酸二異十三烷基酯 DTDP(獲自 Exxon Mobile之 Jayflex DTDP-Z)。環己烷二羧酸二（C9-C13烷基）酯之適用實例係1,2-環己烷二羧酸二異壬基酯（獲自BASF SE之Hexamoll® DINCH)。於一實施例中，增塑劑較佳係鄰苯二甲酸二（匸9-(：13烷基）酯，更佳係鄰苯二曱酸二（C9烷基）酯，及最佳係鄰苯二曱酸二異壬基酯。於另一實施例中，增塑劑係鄰苯二甲酸二（c9至c13烷基）酯或環己烷二羧酸二（C9至C13烷基）酯，其於50°c下具有高達5.0><1〇-611?&，較佳高達2.〇\10-611?&之蒸氣壓。適用實例係（括弧中係於50°C下之蒸氣壓）1，2-環己烷二羧酸二異壬基酯（1_3χ10·6 hPa)、鄰苯二曱酸二異壬基酯DINP (4.〇xlO·7 hPa)、鄰苯二甲酸二-2-丙基庚基酯（5.7xl0·7 hPa)、鄰苯二曱酸二壬基十一烷基酯NUP(1.6xl0_8 hPa)、鄰苯二曱酸二-十一烷基酯DUP(1.8xlO_8 hPa)、鄰苯二甲 144736.doc 201032712 酸一異十三燒基醋DTDP(1 8χ1〇·8 hPa)。—般而言，增塑劑具有小於2000 g/m〇i，較佳小於1〇〇〇 g/m〇i之分子量。。亥聚σ物組合物包含1至1〇〇 phr量之增塑劑。聚合物組合物之習知調配物單位「phr」係「每百份樹脂之份數」的縮寫且意指稱出、測得及表示之添加劑量並非於全部組合物中之百分比含量，而係每一百重量份聚合物之重量份。舉例而言’若聚合物對增塑劑之重量比係8〇:2〇，則添加劑含量係25 phr，係因20份表示80份之25重量％。增籲塑劑於本發明聚合物組合物中之含量一般係1至1 〇〇 phr，較佳係10至90phr，且最佳係3〇至8〇phr。根據本發明之聚合物組合物包含一殺蟲劑及/或一驅蟲劑’此意指包含一或多種殺蟲劑及/或一或多種驅蟲劑。於一實施例中，該聚合物組合物包含一殺蟲劑。在另一實施例中’該聚合物組合物包含一驅蟲劑。於另一實施例中’該聚合物組合物不含殺蟲劑，其不含 • 諸如除草劑、殺真菌劑或植物生長調節劑之殺蟲劑。於一較佳實施例中，該聚合物組合物不含諸如咯菌腈 (fludioxonil)或代克利（difenoconazole)之殺真菌劑。熟知本技術者熟知此等殺蟲劑，如見於Pesticide Manual,第 14版（2006)，The British Crop Protection Council， London中的彼等殺蟲劑。適用殺蟲劑係 _有機（硫代）填酸鹽：.歐殺松（acephate)、曱基β比咬磷 (azamethiphos)、谷素速（azinph〇s-methyl)、陶斯松 (chlorpyrifos)、甲基陶斯松（Chl〇rpyrifos-methyl)、氣本 144736.doc 201032712 松（chlorfenvinphos)、大利松（diazinon)、二氯松 (dichlorvos)、雙特松（dicrotophos)、大滅松 (dimethoate)、二硫松（disulfoton)、愛殺松（ethion)、撲滅松（fenitrothion)、芬殺松（fenthion)、加福松 (isoxathion)、馬拉松（malathion)、達馬松 (methamidophos)、滅大松（methidathion)、甲基巴拉松 (methyl-parathion)、美文松（mevinphos)、亞素靈 (monocrotophos) ' 滅多松（oxydemeton-methyl)、帕拉松 (paraoxon)、巴拉松（parathion)、赛達松（phenthoate)、裕必松（phosalone)、益滅松（phosmet)、福賜米松 (phosphamidon)、福瑞松（phorate)、巴赛松（phoxim)、亞特松（pirimiphos-methyl)、佈飛松（profenofos)、普硫松（prothiofos)、硫滅克鱗（sulprophos)、樂本松 (tetrachlorvinphos)、托福松（terbufos)、三落松 (triazophos)、三氣松（trichlorfon); -胺甲酸S旨：棉鈴威（alanycarb)、得滅克（aldicarb)、免敵克（bendiocarb)、免扶克（benfuracarb)、加保利 (carbaryl)、加保扶（carbofuran)、丁基加保扶 (carbosulfan)、芬諾克（fenoxycarb) 、 β夫線威 (furathiocarb)、滅賜克（methiocarb)、納奈得 (methomyl)、殿殺滅（oxamyl)、比加普（pirimicarb)、安丹（propoxur)、硫敵克（th iodic arb) 、 β坐財威 (triazamate)； -擬除蟲菊酯（pyrethroids):亞烈寧（allethrin)、畢芬寧 144736.doc 201032712 (bifenthrin)、賽扶寧（cyfluthrin)、赛洛寧 (cyhalothrin)、赛芬寧（cyphenothrin)、赛滅寧 (cypermethrin)、亞滅寧（alphacypermethrin)、β-賽滅寧 (beta-cypermethrin)、ζ·赛滅寧（zeta-cypermethrin)、第滅寧（deltamethrin)、益化利（esfenvalerate)、依芬寧 (etofenprox)、芬普寧（fenpropathrin)、芬化利 (fenvalerate)、依普寧（imiprothrin)、λ-赛洛寧（lambda-201032712 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polymer composition comprising a polymer, a plasticizer, an insecticide and/or an insect repellent. It further relates to a method of making a molded article comprising heating molding the polymer composition. The present invention is also directed to a plasticizer composition comprising an insecticide and/or an insect repellent, and a plasticizer. Further, it relates to a molded article comprising the polymer composition and a use of the molded article to control insects. • [Prior Art] A polymer composition comprising a polymer, in particular polyethylene oxide (Pvc), a plasticizer and an insecticide is known: EP 0 763 325 A1 discloses a resin composition comprising a resin, a The active compound and a volatilizable plasticizer. The active compound can be a pyrethroid insecticide. GB 2 170 211 A discloses a hot molded article for insecticidal use comprising a high molecular weight substance, an insecticide, and a heat stable component which is phthalic acid dilauryl vinegar. No. 4,193,984 discloses a dispersing agent for controlling flies comprising a first sheet containing a resmethrin insecticide and a second sheet containing vanilin. The plastisol used to obtain the dispersant comprises PVC and bis(2-ethylhexyl) phthalate. US 2003/0069135 A1 discloses an agrochemical formulation comprising a cyclohexane polycarboxylate, water, an adjuvant and an active ingredient. WO 02/21913 discloses a controlled release formulation of active ingredients 'i 144736.doc 201032712 ^ 3 Dispersing active ingredients of a matrix polymer and a plasticizer. A variety of problems associated with polymer compositions comprising polymers, plasticizers, and insecticides are known in the art: when an evaporable plasticizer is used, the plasticizers are relatively lower in vapority. The plasticizer that is pressed is evaporated to the environment to a higher degree. Some plasticizers are considered to be harmful or toxic to the environment, such as bis(2-ethylhexyl) phthalate. A variety of plasticizers are not suitable for exposure to low polymer moldings due to plasticization only at higher temperatures. Another problem is that the incorporation of the pesticide into the polymer composition results in a decrease in transparency or an increase in scattering or loss of surface gloss of the resulting molded article. SUMMARY OF THE INVENTION The object of the present invention is to overcome the above problems at this stage of the art. The object is achieved by a polymer composition comprising a polymer, a plasticizer, and an insecticide and/or an insect repellent, wherein the plasticizer is phthalic acid (c9-c13) Alkyl) ester or di(c9_ci3 alkyl) cyclohexanedicarboxylate. The term "polymer" refers to one or more polymers. In general, the polymer is selected from the group consisting of ethylene glycol, ethylene, propylene, butadiene, ethyl acetate, glycidyl (meth) acrylate, linear or branched alcohol (A) Bases - homo- and copolymers of acrylate, styrene or acrylonitrile. More specifically, polyvinyl chloride, polycondensate of C4 to C8 alcohol, decyl methacrylate, methyl propyl acrylate-butyl acrylate copolymer, methacrylate Butyl acrylate copolymer, ethylene-vinyl acetate copolymer, chlorinated polyethylene, nitrile rubber, acrylonitrile-butadiene-styrene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene Copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene rubber, styrene-butadiene dilute elastomer and mercaptopropyl 144736.doc 201032712 dilute acid methyl vinegar-phenethyl hydrazine-butadiene copolymer Things. The most preferred polymer is a mixture of polyethylene oxide (PVC) and at least one other polymer of PVC and preferably a polymer as described above. The best polymer is pvc. Polyethylene can be produced by homopolymerization of vinyl chloride. PVC can be prepared industrially in a variety of ways, such as suspension polymerization, microsuspension polymerization, emulsion polymerization, and bulk polymerization. The K-characterized mass and the K value measured according to DIN 53726 may range from 57 to 90, preferably from 61 to 85, and particularly preferably from 64 to 75. Kirk_〇thmer, Encyci〇pedia 〇f • Chemical Technol〇gy, 4th edition, Volume 24, 1017_1047. Pages outline the characteristics, preparation, and use of PVC, and also describe the size and quantity of 1>¥(:; The relationship between the molecular weight, the weight average molecular weight, and the intrinsic and relative viscosity measured by the root L1234. The PVC content of the β-polymer composition is generally 20 to 99% by weight, preferably 30 to 90% by weight, particularly preferably 35. Up to 8% by weight, and especially as far as weight/twist, in each case based on the total weight of the polymer composition, ie including all components of the polymer composition. Φ Polymer composition according to the invention Containing a plasticizer, the plasticizer is o-formic acid ((: 9 to C " alkyl) ester or cyclohexane calcined acid di (c9 to alkyl) ester. The term "(: 9 to cu "Alkyl" means a mixture of straight chain, branched or cyclic alkyl groups or straight chain, branched chain and/or cyclic alkyl groups, the main chain of which has exactly 9 to 13 carbon atoms or has 9 to 13 a mixture of main chains of carbon atoms. The term "C9 alkyl" means a straight chain or branch having 9 carbon atoms in its main chain. Alkyl or a mixture of a straight chain and a branched alkyl group. The term "cyclohexyl dibenzoate" means a 1,2-, 1,3- or 1,4-substituted cyclohexanedicarboxylate, A preferred example of a phthalic acid di(C9-C13 alkyl) ester plasticizer is well known in the art and is commercially available: diisophthalic acid phthalate. Base ester DINP (Palatinol® N from BASF SE), diisodecyl phthalate DIDP, di-2-propylheptyl phthalate DPHP (Palatinol 10-P from BASF SE), Didecyl undecyl phthalate NUP (Palatinol 911-P from BASF SE), di-undecyl phthalate DUP (Palatinol 111P-1 from BASF SE), adjacent Diisodecyl phthalate DIUP, tridecyl phthalate DTDP (Jayflex® DTDP from Exxon Mobile), diisotridecyl phthalate DTDP Jayflex DTDP-Z from Exxon Mobile. A suitable example of a di(C9-C13 alkyl) cyclohexanedicarboxylate is diisodecyl 1,2,cyclohexanedicarboxylate (available from BASF SE) Hexamoll® DINCH). In one embodiment, a plasticizer Preferably, bis(匸9-(:13 alkyl) phthalate, more preferably bis(C9 alkyl) phthalate, and the best diisodecyl phthalate. In another embodiment, the plasticizer is a di(c9 to c13 alkyl) phthalate or a di(C9 to C13 alkyl) cyclohexane dicarboxylate having up to 5.0 at 50 ° C. ><1〇-611?&, preferably up to 2. 〇\10-611?& Applicable examples (vapor pressure at 50 ° C in brackets) diisodecyl 1,2-cyclohexanedicarboxylate (1_3χ10·6 hPa), diisononyl phthalate DINP ( 4. 〇xlO·7 hPa), di-2-propylheptyl phthalate (5.7×l0·7 hPa), didecyl undecyl phthalate NUP (1.6×10 −8 hPa), Di-undecyl phthalate DUP (1.8xlO_8 hPa), phthalate 144736.doc 201032712 Acid-iso-tridecyl vinegar DTDP (1 8χ1〇·8 hPa). Generally, the plasticizer has a molecular weight of less than 2000 g/m〇i, preferably less than 1〇〇〇g/m〇i. . The polystyrene composition contains a plasticizer in an amount of from 1 to 1 Torr. The conventional formulation unit "phr" of the polymer composition is an abbreviation of "parts per hundred resin" and means that the amount of the additive, measured and expressed is not a percentage of the total composition, but each One part by weight of the polymer. For example, if the weight ratio of the polymer to the plasticizer is 8 〇: 2 〇, the additive content is 25 phr, and 20 parts means 20 parts by weight of 20 parts by weight. The content of the plasticizer in the polymer composition of the present invention is generally from 1 to 1 phr, preferably from 10 to 90 phr, and most preferably from 3 to 8 phr. The polymer composition according to the invention comprises an insecticide and/or an insect repellent' which is meant to comprise one or more insecticides and/or one or more insect repellents. In one embodiment, the polymer composition comprises an insecticide. In another embodiment, the polymer composition comprises an insect repellent. In another embodiment, the polymer composition is free of insecticides that are free of pesticides such as herbicides, fungicides or plant growth regulators. In a preferred embodiment, the polymer composition is free of fungicides such as fludioxonil or difenoconazole. Such insecticides are well known to those skilled in the art, such as those found in the Pesticide Manual, 14th Edition (2006), The British Crop Protection Council, London. Applicable insecticide system _ organic (thio) sulphate: acephate, azamethiphos, azinph〇s-methyl, chlorpyrifos, nail Chlu〇rpyrifos-methyl, 146736.doc 201032712 chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfide Disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, armor Methyl-parathion, mevinphos, monocrotophos 'oxydemeton-methyl, paraoxon, parathion, phenthoate ), phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos , prothiofos, sulphur scales (sul Prophos), tetrachlorvinphos, terbufos, triazophos, trichlorfon; - carbamic acid S: alanycarb, aldicarb, exempt Benzocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, Methicarb, methomyl, oxamyl, pirimicarb, propoxur, th iodic arb, β triazamate - pyrethroids: allethrin, bifenin 144736.doc 201032712 (bifenthrin), cyfluthrin, cyhalothrin, cyphenothrin, race Cypermethrin, alphacypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, effluent Etofenprox, fenpropathin, fenvalera Te), imiprothrin, λ-cylonin (lambda-

cyhalothrin)、百滅寧（permethrin)、帕列寧 (prallethrin)、除蟲菊精（pyrethrin)I 及 II、雷減寧 (resmethrin)、石夕護芬（silafluofen)、τ-福化利（tau-fluvalinate)、特扶寧（tefluthrin)、治滅寧 (tetramethrin)、泰滅寧（tralomethrin)、崔扶寧 (transfluthrin)、普扶寧（profluthrin)、待滅扶寧 (dimefluthrin); -昆蟲生長調節劑：a)幾丁質合成抑制劑：苯甲醯脲：克福隆（chlorfluazuron)、賽滅淨（cyramazin)、二福隆 (diflubenzuron)、福環脲（flucycloxuron)、氟芬隆 (flufenoxuron)、六伏隆（hexaflumuron)、祿芬隆 (lufenuron)、諾伐隆（novaluron)、得福隆 (teflubenzuron)、殺蟲隆（triflumuron);布芬淨 (buprofezin)、迪芬諾蘭（diofenolan)、合赛多 (hexythiazox)、依殺蜗（etoxazole)、克嘻芬達嗪 (clofentazine) ; b)蛻皮激素拮抗劑：氣蟲醯肼 (halofenozide)、曱氧蟲醯肼（methoxyfenozide)、得芬諾 144736.doc 201032712 (tebufenozide)、印棟素（azadirachtin) ; c)擬保幼激素：百利普芬（pyriproxyfen)、甲氧保幼激素（methoprene)、芬諾克（fenoxycarb) ; d)脂質生物合成抑制劑：螺瞒醋 (spirodiclofen)、螺甲瞒醋（spiromesifen)、螺蟲乙醋 (spirotetramat); -菸鹼酸受體激動劑/拮抗劑化合物：可尼丁 (clothianidin)、吱蟲胺（dinotefuran) 、 α比蟲淋 (imidacloprid) ' °塞蟲 °秦（thiamethoxam) ' 烯咬蟲胺 (nitenpyram)、咬蟲胨（acetamiprid) 、 °塞蟲嚇· 〇1^3(：1〇?]^(1)、1-(2-氯-噻唑-5-基甲基）-2-硝基亞胺基-3,5-二曱基-[1,3,5]-三嗪烷； -GABA抬抗劑化合物：安殺番（endosulfan)、乙蟲腈 (etiprole)、芬普尼（fipronil)、凡尼力普魯（vaniliprole)、比氟普魯（pyrafluprole)、比普魯（pyriprole)、5-胺基-1-(2,6-二氯-4-曱基-苯基）-4-胺亞磺醯基-1H-吡唑-3-硫代碳酸醯胺； -巨環内酯殺蟲劑：阿巴丁（abamectin)、因滅汀 (emamectin)、密滅汀（milbemectin)、萊培菌素 (lepimectin)、多殺菌素（spinosad)、斯 °比特安 (spinetoram)； -線粒體電子傳輸抑制劑（METI)I殺蟎劑：芬殺蟎 (fenazaquin)、畢達本（pyridaben) 、 °比蜗胺 (tebufenpyrad)、a坐蟲醯胺（tolfenpyrad)、氟盼瑞姆 (flufenerim)； 144736.doc -10- 201032712 -ΜΕΤΙ II及III化合物：亞酿瞒（acequinocyl)、0夫吸铃 (fluacyprim)、伏蟻騌（hydramethylnon); -解偶聯劑：溴蟲腈（chlorfenapyr); -氧化填酸化抑制劑：錫瞒丹（cyhexatin)、汰芬隆 (diafenthiuron)、芬佈賜（fenbutatin oxide)、殿蜗多 (propargite); -蜆皮干擾劑化合物：克立馬嗪（cry〇mazine); -混合功能氧化酶抑制劑：胡椒基丁醚；Cyhalothrin), permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fu (tau- Fluvalinate), tefluthrin, tetramethrin, trolomethrin, transfluthrin, profluthrin, dimefluthrin; insect growth regulator: a) Chitin synthesis inhibitor: Benzamidine urea: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, six Hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, Hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, fenfenol 144736 .doc 201032712 (tebufenozide), azadirachtin c) Probiotic juvenile hormone: pyriproxyfen, mesoprofen, fenoxycarb; d) lipid biosynthesis inhibitor: spirodiclofen, spirothyroid Spirulina (spiromesifen), spirotetramat; nicotinic acid receptor agonist/antagonist compound: clothianidin, dinotefuran, αidacloprid '° plug ° 秦 thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia thia -5-ylmethyl)-2-nitroimino-3,5-dimercapto-[1,3,5]-triazinane; -GABA antagonist compound: endosulfan, Ethiprole (etiprole), fipronil, vaniliprole, pyrafluprole, pyripolle, 5-amino-1-(2,6- Dichloro-4-indolyl-phenyl)-4-amine sulfinyl-1H-pyrazole-3-thiocarbazinamide; - macrolide lactone: abamectin, cause Emamectin, milbemectin, lepimectin, multi-kill Spinosad, spinetoram; - mitochondrial electron transport inhibitor (METI) I acaricide: fenazaquin, pyridaben, ° than tebufenpyrad, a tolfenpyrad, flufenerim; 144736.doc -10- 201032712 - ΜΕΤΙ II and III compounds: acequinocyl, fluacyprim, anthill Hydramethylnon); - uncoupling agent: chlorfenapyr; - oxidative acidification inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite ); - molting agent compound: climazine (cry〇mazine); - mixed function oxidase inhibitor: piperonyl butoxide;

-鈉通道阻斷劑：因得克（indoxacarb)、美氟综 (metaflumizone); -其他：本克洛嘆（benclothiaz)、聯苯肼醋（bifenazate)、培丹（cartap)、氟咬蟲醯胺（flonicamid)、咬蟲丙醚 (pyridalyl)、派滅淨（pymetrozine)、硫項、殺蟲環 (thiocyclam)、氟蟲醯胺（flubendiamide)、氣蟲醯胺 (chlorantraniliprole)、赛希 °比（cyazypyr)(HGW86)、赛諾芬（cyenopyrafen)、氟 °比松（flupyrazofos)、賽氟美芬 (cyflumetofen)、胺福美特（amidoflumet)、伊米塞弗斯 (imicyafos)、雙三氟蟲脲（bistrifluron)、及比氟喹綜 (pyrifluquinazon) ° 於一實施例中，該殺蟲劑包含擬除蟲菊酯，較佳為亞滅寧（alpha-cypermethrin)。於另一實施例中，該殺蟲劑包含擬除蟲菊酯、較佳為亞滅寧與°比唑殺蟲劑、較佳為溴蟲腈 (chlorfenapyr)之混合物。術語「°比唾殺蟲劑」係指氣蟲醯胺（chlorantraniliprole)、氰蟲醯胺（cyantraniliprole)、敵绳 144736.doc 201032712 威（dimetilan)、β比蟎胺（tebufenpyrad)、唑蟲酿胺 (tolfenpyrad)、乙醯蟲腈（acet〇pr〇le)、乙蟲腈（ethiprole)、芬普尼（fipronil)、白克松（pyraclofos)、比氟普魯 (pyrafluprole)、比普魯（pyriprole)或凡尼力普魯 (vaniliprole) ° 於另一實施例中，殺蟲劑及驅蟲劑可溶於增塑劑。當至少0.05重量％，較佳至少〇.1重量％，更佳至少0.5重量％殺蟲劑及驅蟲劑可於25°C下溶於所用的增塑劑時，較佳溶於鄰苯二甲酸二異壬基酯DINP時，則認為殺蟲劑及驅蟲劑可溶。於另一實施例中，當殺蟲劑及驅蟲劑溶於所用的增塑劑並以高達10重量％之濃度與聚合物基質混合時，其等在高達100°C，較佳高達130°C ’更佳高達160°c之溫度下於30 分鐘内係穩定的。術語「穩定的」意指少於10重量％之殺蟲劑發生降解。於另一實施例中，殺蟲劑及驅蟲劑於20°C下具有高達 lxlO·6 hPa，較佳高達5xl0·7 hPa之蒸氣壓（v.p.)。其實例係亞滅寧（alphacypermethrin)(v.p. 2.3 X 1 0·2 mPa(20°C ))或溴蟲腈（chlorphemapyr)(v.p. 1 ·2χ 10-2 mPa(20°C ))。其他適用殺蟲劑及其等蒸氣壓可見於Pesticide Manual，第14版（2006), The British Crop Protection Council，London 〇驅蟲劑一般係一種化合物，其阻止昆蟲接近或接觸包含該驅蟲劑之組合物。該驅蟲劑可係選自N，N-二乙基-間-甲苯曱醯胺（DEET)、N，N-二乙基-苯基乙醯胺（DEPA)、1-(3- 144736.doc 12 201032712- Sodium channel blockers: indoxacarb, metaflumizone; - others: benclothiaz, bifenazate, cartap, fluoropterin Flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, 赛希° ratio (cyazypyr) (HGW86), cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicifos, diflurid Bistrifluron, and pyrifluquinazon In one embodiment, the insecticide comprises a pyrethroid, preferably alpha-cypermethrin. In another embodiment, the insecticide comprises a mixture of pyrethroids, preferably imipenem and a carbazole insecticide, preferably chlorfenapyr. The term "° ratio of salivary insecticide" refers to chlorantraniliprole, cyantraniliprole, enemy rope 144736.doc 201032712 dimetilan, tebufenpyrad, oxazolidine (tolfenpyrad), acet〇pr〇le, ethiprole, fipronil, pyraclofos, pyrafluprole, pyriprole or Vaniliprole ° In another embodiment, the insecticide and insect repellent are soluble in the plasticizer. When at least 0.05% by weight, preferably at least 1.1% by weight, more preferably at least 0.5% by weight, of the insecticide and insect repellent can be dissolved in the plasticizer used at 25 ° C, preferably soluble in o-phthalic acid When diisodecyl formate is used, it is considered that the insecticide and insect repellent are soluble. In another embodiment, when the insecticide and insect repellent are dissolved in the plasticizer used and mixed with the polymer matrix at a concentration of up to 10% by weight, they are up to 100 ° C, preferably up to 130 °. C 'more stable up to 160 ° C in 30 minutes is stable. The term "stable" means that less than 10% by weight of the pesticide is degraded. In another embodiment, the insecticide and insect repellent have a vapor pressure (v.p.) of up to 1 x 10 6 hPa, preferably up to 5 x 10 7 hPa at 20 °C. Examples thereof are alphacypermethrin (v.p. 2.3 X 1 0·2 mPa (20 ° C)) or chlorophemapyr (v.p. 1 ·2χ 10-2 mPa (20 ° C)). Other suitable insecticides and their vapor pressures can be found in the Pesticide Manual, 14th edition (2006), The British Crop Protection Council, the London cockroach repellent is generally a compound that prevents insects from approaching or contacting the insect repellent. combination. The insect repellent may be selected from the group consisting of N,N-diethyl-m-toluidine (DEET), N,N-diethyl-phenylacetamide (DEPA), 1-(3- 144736. Doc 12 201032712

環己烷-1-基-羰基）-2-甲基胡椒鹼、（2-羥基甲基環己基）乙酸内酯、2-乙基-1,3-己二醇、丁基-乙醯基-胺基丙酸乙基酯（EBAAD)、對-薄荷烷-3,8-二醇（PMD)、IR3535(丁基乙醯基胺基丙酸乙基酯）、埃卡瑞丁（icaridin)(l-哌啶甲酸2-(2-羥基乙基）-1-曱基-丙基酯）、避蟲酮（indalone)、曱基新癸醯胺（MNDA)、不用於控制昆蟲之擬除蟲菊酯如{(+/-)-3-稀丙基-2-曱基-4-氧代環戍-2-(+) -稀基- (+) -反式-菊酸g旨 (賜白寧（Esbiothrin))、衍生自植物提取物或與植物提取物等同的驅蟲劑如擰檬烯（limonen)、丁香盼（eugenol)、（+)-阿卡莫醇（Eucamalol)、（-)-1-表-阿卡莫醇（eucamalol)或來自諸如斑皮桉（Eucalyptus maculata)、海埔薑（Vitex rotundifolia)、玫瑰草（Cymbopogan martinii)、檸檬草 (Cymbopogan citratus(lemon grass))、香茅（Cymopogan nartdus(citronella))植物之植物粗提取物。較佳驅蟲劑係 DEET、埃卡瑞丁（icaridin)、EBAAD、PMD。於一實施例中，該聚合物組合物包含一殺蟲劑及一驅蟲劑。該等混合物有利於防止昆蟲之抗性進化或控制已對一殺蟲劑產生抗性之昆蟲。適用的殺蟲劑及驅蟲劑係如上述。較佳的殺蟲劑係諸如亞滅寧（alphacypermethrin)、赛扶寧（cyfluthrin)、第滅寧（deltamethrin)、依芬寧 (etofenprox)及百滅寧（permethrin)、必芬寧（bifenthrine)之擬除蟲菊醋；或諸如丁硫克百威（carbosulphane)之非擬除蟲菊醋。最佳者係亞滅寧及漠蟲腈（chlorfenapyr)。較佳混合物包含擬除蟲菊酯及PBO。 144736.doc 13 201032712 -般而言’本發明聚合物組合物中可存在—或多種添加劑。欲利用的功能係改良其等機械、化學及處理特性。舉例而言’於本文所提及者係穩㈣、㈣劑、填充劑、顏料、阻燃劑、光穩定劑、發泡劑、聚合加工助劑、耐衝擊改質劑、勞光增白劑、抗靜電劑'及生物穩定劑。僅就說明本發明聚合物組合物之目的而言，有些此等添加劑及其等功能係藉由如下實例舉例描述’而此等描述並非限制本發明之聚合物組合物。 ❹ 舉例而言，穩定劑可中和於處理期間及/或之後自聚合物排出之氳氣酸。可使用之穩定劑係呈固體或液體形式之任何習知穩定劑，其實例係習知的Ca/Zn、Ba/Zn、Pb或Sn 穩定劑’亦及結合酸的頁矽酸鹽，如水滑石。較佳者係 a/Zn穩疋劑、二元硫酸鉛（3pb〇 . pbs〇4 · H2〇)、及亞磷酸金。最佳者係Ba/Zn穩定劑。穩定劑於本發明聚合物組合物中之含量可係〇.〇5至7 phr，較佳〇」至5 phr，最佳〇2 至4phr ’及尤其係〇3至2phr。 ❹ 潤滑劑欲作用於聚合物顆粒之間及抵消在混合、塑化、及成型期間之摩擦力。可存在於本發明聚合物組合物之潤月劑為聚β物力σ卫中之任何習知潤滑劑。可使用的該等實例係諸如油類、石蠟、及聚乙烯蠟之烴、具有6至20個碳原子之知肪醇、酿1類、諸如脂肪酸及褐煤酸之羧酸、經氧化=聚乙烯壤、金屬缓酸鹽、㈣胺、亦及與如下酵之緩酸S曰：乙#、脂肪醇、甘油、乙二醇、及季戊四醇，及以長鏈緩酸為酸組分之羧㈣。較佳使用硬脂㈣。於本發 144736.doc •14· 201032712 明聚合物組合物中之潤滑劑的含量可係0 01至10 phr，較佳係0.05至5 phr，最佳係〇.1至3 phr，及尤其係〇 2至2 phr 〇填充劑主要用於抗壓力、張力、及彎曲，亦使經塑化的聚氣乙烯具有硬度及耐熱性，該作用係有利的。本發明聚 • 合物組合物可包含諸如碳黑及其他無機填充劑之填充劑摻合物，例如，諸如白堊、石灰石及大理石之天然碳酸鈣、合成碳酸鈣、白雲石、矽酸鹽、矽石、砂、石夕藻土、及諸 ❹ 如高嶺土、雲母、及長石之矽酸鋁。使用之填充劑較佳包含碳酸鈣、白堊、白雲石、高嶺土、矽酸鹽、滑石、或碳黑，其中以白堊為最佳。於本發明混合物中之填充劑含量可係0.01至80 phr，較佳係1至60 phr，最佳係5至5〇 phr，及尤其係15至40 phr。本發明聚合物組合物亦可包含顏料以使最終產物適應各種可能用途。可將無機顏料或有機顏料用於此目的◦可使用之無機顏料實例係諸如CdS之鎘顏料、諸如C〇〇/Al2〇3之鈷顏料、及諸如〇2〇3之鉻顏料。可使用之有機顏料實例係單偶氮顏料、經縮合的偶氮顏料、偶氮甲基化物顏料、蒽醌顏料、喹吖啶酮、酞菁顏料、二噁嗪顏料，如c丄顏料紫23及苯胺黑（C.;[•顏料黑丨）。於本發明聚合物組合物中之顏料含量係〇.〇1至1〇 phr，較佳係〇〇5至5 phr，最佳係 0.1至3 phr，及尤其係〇·5至2 phr。為降低可燃性及燃燒期間產生煙霧’亦可將阻燃劑加入本發明聚合物組合物中。可使用之阻燃劑實例係三氧化二 144736.doc 201032712 録、碌酸醋、氣化石4、氫氧化銘、蝴化合物、三氧化翻、二茂鐵、碳酸妈或碳酸鎂。較佳使用三氧化二録或鱗酸酯，最佳者係磷酸酯，尤其係磷酸雙苯酯甲苯酯、磷酸二苯醋辛醋或鱗酸三甲苯醋。於本發明聚合物組合物中之阻燃劑含量係0.0H0phr，較佳係〇⑴咖，最佳係〇 2 至5 phr ’及尤其係〇.5至3 phr。為保護自本發明聚合物組合物產生之物品免受光線之表面破壞，亦可將光穩定劑加入此等聚合物組合物中。可用於此目的之光穩定劑實例係羥基二苯甲酮、羥苯基苯并三咬、或丙烯酸氰基苯基醋。較佳者係丙烯酸氰基苯基醋、最佳者係丙烯酸2-乙基己基2_氰基_3,3_二苯基醋。於本發明聚合物組合物中之光穩定劑量係〇〇1至7 phr，較佳係 0.1^5 phr» t^#〇.2^4phr^^^#,〇.5A3phr〇本發明進一步係關於一種製備模製品之方法，其包含加熱模製如本發明之聚合物組合物。較佳地，該聚合物組合物係藉由使聚合物與增塑劑組合物混合而製得，該增塑劑組合物含有溶於該增塑劑之殺蟲劑及/或驅蟲劑。加熱模製本發明聚合物組合物之一般方法係於高溫下，藉由例如授拌將獨立組份混合。L. Meier in R Gachter， H. MulleKEd.) ; Plastics Addmves Handb〇〇k，第三版章節 5·4·3、5.4·4 ’ Hanser 出版社，Munich 199〇舉例提供製備由l氣乙稀Sg及其他添加劑組成之混合物之一般論述。加熱模製之其他實例係熱成型、壓延、擠壓、塗覆、鑄造、浸塗、轉子模製、或射出模製。D.H.河州⑽七· 144736.doc * 16. 201032712Cyclohexane-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl)acetic acid lactone, 2-ethyl-1,3-hexanediol, butyl-ethenyl -ethylaminopropionate (EBAAD), p-menthane-3,8-diol (PMD), IR3535 (ethyl butyl ethionyl propionate), icaridin (1-P-Piperidinecarboxylic acid 2-(2-hydroxyethyl)-1-indolyl-propyl ester), indone (indalone), decyl neodecylamine (MNDA), not used to control insects Pyrethroids such as {(+/-)-3-dextyl-2-indolyl-4-oxocycloindole-2-(+)-thyl-(+)-trans-chrysanthemic acid g Esbiothrin, an insect repellent derived from plant extracts or equivalent to plant extracts such as limonen, eugenal, (+)-accamalol (Eucamalol), -)-1-Table-eucamalol or from eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, lemon grass (Cymbopogan citratus (lemon grass)) , crude extract of plant of the citronella (Cymopogan nartdus (citronella)) plant. Preferred insect repellents are DEET, icaridin, EBAAD, PMD. In one embodiment, the polymer composition comprises an insecticide and an insect repellent. These mixtures are useful for preventing the evolution of insect resistance or controlling insects that have developed resistance to an insecticide. Suitable insecticides and insect repellents are as described above. Preferred insecticides are, for example, alphacypermethrin, cyfluthrin, deltamethrin, etofenprox, permethrin, bifenthrine. Pyrethrum vinegar; or non-pyrogenic vinegar, such as carbosulfulphane. The best is arsenicin and chlorfenapyr. Preferred mixtures comprise pyrethroids and PBO. 144736.doc 13 201032712 In general, the presence or absence of one or more additives may be present in the polymer compositions of the present invention. The function to be utilized is to improve its mechanical, chemical and processing properties. For example, 'the ones mentioned in this article are stable (four), (four) agents, fillers, pigments, flame retardants, light stabilizers, foaming agents, polymerization processing aids, impact modifiers, Luguang brighteners , antistatic agent' and biostabilizer. For the purposes of illustrating the polymer compositions of the present invention, some of these additives and their functions are exemplified by the following examples which are not intended to limit the polymer compositions of the present invention. ❹ For example, the stabilizer neutralizes the helium acid excreted from the polymer during and/or after the treatment. Stabilizers which may be used are any conventional stabilizers in solid or liquid form, examples of which are conventional Ca/Zn, Ba/Zn, Pb or Sn stabilizers, as well as acid-binding sulphates, such as hydrotalcites. . Preferred are a/Zn stabilizers, dibasic lead sulfate (3pb〇. pbs〇4 · H2〇), and gold phosphite. The best is Ba/Zn stabilizer. The stabilizer may be present in the polymer composition of the invention in an amount of from 5 to 7 phr, preferably from 5 to phr, most preferably from 2 to 4 phr' and especially from 3 to 2 phr.润滑剂 Lubricants are intended to act between the polymer particles and counteract the friction during mixing, plasticizing, and forming. The lubricious agent which may be present in the polymer composition of the present invention is any conventional lubricant in the poly(beta). Such examples which may be used are hydrocarbons such as oils, paraffins, and polyethylene waxes, aliphatic alcohols having 6 to 20 carbon atoms, brewed sugars, carboxylic acids such as fatty acids and montanic acid, and oxidation = polyethylene. Soil, metal buffer acid salt, (iv) amine, and the following acid retardant S: B, fatty alcohol, glycerin, ethylene glycol, and pentaerythritol, and long chain slow acid as the acid component of the carboxylic acid (four). It is preferred to use hard fat (4). The amount of the lubricant in the polymer composition of the present invention may be from 0 to 10 phr, preferably from 0.05 to 5 phr, preferably from 1 to 3 phr, and especially from 144, 736. 〇 2 to 2 phr 〇 filler is mainly used for resistance to pressure, tension, and bending, and also makes the plasticized polyethylene having hardness and heat resistance, which is advantageous. The polymer composition of the present invention may comprise a filler blend such as carbon black and other inorganic fillers, for example, natural calcium carbonate such as chalk, limestone and marble, synthetic calcium carbonate, dolomite, silicate, strontium Stone, sand, Shixiazao, and Zhuji such as kaolin, mica, and feldspar. The filler to be used preferably contains calcium carbonate, chalk, dolomite, kaolin, silicate, talc, or carbon black, with chalk being the best. The filler content in the mixture of the invention may range from 0.01 to 80 phr, preferably from 1 to 60 phr, most preferably from 5 to 5 phr, and especially from 15 to 40 phr. The polymer compositions of the present invention may also comprise pigments to tailor the final product to a variety of possible uses. Inorganic pigments or organic pigments can be used for this purpose. Examples of inorganic pigments which can be used are cadmium pigments such as CdS, cobalt pigments such as C〇〇/Al2〇3, and chromium pigments such as 〇2〇3. Examples of organic pigments that can be used are monoazo pigments, condensed azo pigments, azomethane pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments, dioxazine pigments, such as c丄 pigment violet 23 And aniline black (C.; [• pigment black 丨). The pigment content in the polymer composition of the present invention is from 〇1 to 1 〇 phr, preferably from 5 to 5 phr, preferably from 0.1 to 3 phr, and especially from 5 to 2 phr. In order to reduce flammability and generate fumes during combustion, a flame retardant may also be added to the polymer composition of the present invention. Examples of flame retardants that can be used are trioxide 144736.doc 201032712 recorded, vinegar, gas fossil 4, hydroxide, butterfly compound, trioxide, ferrocene, carbonate or magnesium carbonate. Preferably, the third oxide or the phosate is used, and the most preferred one is a phosphate, especially a phenyl diphenyl phosphate, a diphenyl vinegar or a trimethyl vinegar. The flame retardant content in the polymer composition of the present invention is 0.0H0phr, preferably 〇(1) coffee, optimal 〇2 to 5 phr' and especially 〇5 to 3 phr. To protect the articles produced from the polymer compositions of the present invention from surface damage, light stabilizers can also be incorporated into such polymer compositions. Examples of light stabilizers which can be used for this purpose are hydroxybenzophenone, hydroxyphenylbenzotrile, or cyanophenyl acrylate. Preferred is cyanophenyl acrylate, and the most preferred is 2-ethylhexyl 2-cyano-3,3-diphenyl vinegar. The light stabilizing dose in the polymer composition of the present invention is from 1 to 7 phr, preferably from 0.1^5 phr»t^#〇.2^4phr^^^#, 〇.5A3phr 〇 the present invention further relates to A method of preparing a molded article comprising heating molding a polymer composition such as the present invention. Preferably, the polymer composition is prepared by mixing a polymer with a plasticizer composition comprising an insecticide and/or an insect repellent dissolved in the plasticizer. The general method of heating molding the polymer composition of the present invention is at a high temperature by mixing the separate components by, for example, mixing. L. Meier in R Gachter, H. MulleKEd.) ; Plastics Addmves Handb〇〇k, 3rd edition chapter 5·4·3, 5.4·4 ' Hanser Press, Munich 199〇 provides an example of preparation of ethylene glycol Sg A general discussion of mixtures of other additives. Other examples of heat molding are thermoforming, calendering, extrusion, coating, casting, dip coating, rotor molding, or injection molding. D.H. Hezhou (10) VII 144736.doc * 16. 201032712

Polymer Processing，Chapman及Hall，London 1989以舉例方式描述此等處理方法之細節。本發明聚合物組合物特別適於藉由浸塗、延展、鑄造、旋轉模製、離心鑄造、或射出模製，或另藉由旋轉式絲網印刷加熱模製糊狀物（塑料溶膠、有機溶膠、或塑料凝膠）以形成最終產物。根據本發明之增塑劑組合物包含一殺蟲劑及/或驅蟲劑、及一增塑劑，其中該增塑劑係鄰苯二甲酸二（(：9至（：" 烷基）酯或環己烷二羧酸二（(：9至（：13烷基）酯。適用殺蟲劑 ® 係如上所示。較佳地，殺蟲劑及/或驅蟲劑係溶於增塑劑中。適用增塑劑係如上所示。該增塑劑組合物尤其適於製備如本發明模製品之方法。本發明進一步係關於一種包含如本發明聚合物組合物之模製品。該等模製品係藉由如本發明之方法獲得。該模製品較佳係透明的。當模製品透光度係至少5〇%，較佳至少 65/〇更佳至少80%，尤其至少90%時，通常則認為其係鲁透明的。透光度可根據ASTM D 1003於厚度為2 mm之平板上確定。於另一實施例中，透光度係根據ASTM D 1〇〇3於厚度為0.5 mm之箔片上測定。於另一實施例中，當根據ASTM D 1〇〇3於厚度為2 mm之、’板上測疋之模製品濁度係高達，較佳高達μ%，更门達3 0 /。，尤其咼達丨5〇/。，更尤其高達丨〇%時可認為其係透明的。於另一實施例中，該模製品保持與不含殺蟲劑及/或驅蟲劑之相同模製品相同的透明纟。該模製品之透光度或濁 144736.doc •17· 201032712 度較佳在± 1 〇%内變化。更佳地，透光度係降低小於透光度絕對值之15%，較佳小於1〇%及更佳小於5〇/(^此降低可於200至750 nm ’較佳於350及650 nm下測定。模製品或包含模製品之最終產物之較佳實例係： -箔片’如自黏箔片、汽車箔片、傢具箔片、文具箔片、農用箱片、食物箔片（保鮮膜）、屋頂板、油罐襯墊箔片、貯器襯墊箔片、游泳池襯墊箔片、結構箔片、雨衣、旋轉門、浴簾、充氣艇、浮帶； -用於帶式及旋轉門之條帶及薄板； _電纜，例如導線電纜、電力電纜、通訊電纜、盤繞簾線、電腦電纜、及汽車電纜； -塗層’例如用於合成皮革（應用於汽車及帶囊製造）、貨車防水布、帳篷、桌布、防護服、乙烯基壁布、及傳送帶之彼等物； -地板覆蓋物，例如海綿狀的地板覆蓋物（緩衝乙烯基）、非均質緊密覆蓋物、均質緊密覆蓋物、及用於地毯塗層及層板之彼等物； _異型材，例如工業軟管、園林軟管、密封墊（例如用於冰箱）、樓梯扶手、及窗異型材； •鞋類（長靴、涼鞋）、鞋底、玩具、手套（工業用、醫療用）、封閉蓋、及擦除器； -球類、玩偶、交通錐、貨車防水布材料、平臺防水布、帳，、帶囊製造產品、通風管路、合成皮革、地板-及覆蓋物、壁紙（包括由機械或化學方法發泡的彼等 144736.doc 201032712 物）、敷層、保護手套、防護服、及金屬基材上之保護覆蓋物，其他實例為折疊式風肖、用於機動車輛之底部保護、及用於擰開瓶蓋、冠形瓶蓋、及螺旋瓶蓋之密封物。於較仏實施例中，該模製品係用於帶式及/或旋轉門，之條帶或薄板。該條帶或薄板較佳係透明的。本發明進-步係關於—種以根據本發明之模製品用於控帝】昆蟲之用途。該等昆蟲較佳係飛行昆蟲。術語「控制昆 •纟」係指殺死與該模製品接觸之昆蟲或使見蟲遠離該模製 ::。例如’若模製品係旋轉門中之條帶或薄板，則控制係才曰防止昆蟲進入門内成者早主 -w昆蟲於试圖飛過該門接觸模製品時將其殺死。蟲」係指昆蟲綱乃至蜘蛛綱之動物類。專家將待控制之昆蟲選擇殺蟲劑及/或驅蟲劑。術語「飛行 Γ路Γ能於空中停留至少60秒之昆蟲。適宜實例係绳 • 滑翔蟻、跳傘料，較佳係蜗類及蜂類。得進有數種優勢可使用具有低蒸氣壓之增塑劑以獲 =入環境之極低蒸發度。可使用對環境有害性較小之增 T提供良好的塑化特性適聚=用，係因增塑劑於低溫 ^, 祆合物模製品可係透明的。該箄聚合物模製品仍具有光澤表面。的該等昆蟲的長時間内(例如數個月)係穩β莫製品於控制已知擬除蟲菊醋易受曰光降解:、：二=有活性。儘管 *時間储存且應_'二二可 144736.doc -19· 201032712 【實施方式】以下本發明實例將進一步解釋本發明，然而，本發明並非受此等實例界限。實例 PVC粉末：經塑化的聚氣乙烯係藉由懸浮聚合反應製得，其Tg為75至85°c，比重為1.38 kg/m3，體積密度為0.47 kg/Ι，揮發物含量<3 g/kg，經還原之viskoxita為128 mg/g，對應K值為71，篩析：>96%停留於0.063 mm篩上，<2%停留於0.25 mm篩上（購自Solvin之Solvin® 271SP) ° 增塑劑：鄰苯二曱酸二異壬基酯，CAS編號為28553-12-0，澄清液體，於20°C下動態黏度為68至82 mPas，酸值 <0.06 mg KOH/g，含水量<0.05重量％，平均質量為 418.6 g/mol，於7 hPa下之沸點範圍為253至267°C，於 100°C下之蒸氣壓：2.6xl0·4 hPa(購自BASF SE之 Palatino®I N)。亞滅寧（Alphacypermethrin):來自擬除蟲菊酯類之殺蟲劑。Polymer Processing, Chapman and Hall, London 1989 describe the details of such processing methods by way of example. The polymer composition of the present invention is particularly suitable for molding a paste by dip coating, stretching, casting, rotational molding, centrifugal casting, or injection molding, or by rotary screen printing (plastisol, organic Sol, or plastic gel) to form the final product. The plasticizer composition according to the present invention comprises an insecticide and/or an insect repellent, and a plasticizer, wherein the plasticizer is phthalic acid di((:9 to (:" alkyl) Ester or cyclohexanedicarboxylic acid di((:9 to (:13 alkyl) ester. Suitable insecticides® are as indicated above. Preferably, the insecticide and/or insect repellent is soluble in plasticization. Suitable plasticizers are as indicated above. The plasticizer composition is particularly suitable for the preparation of a moulding according to the invention. The invention further relates to a moulding comprising a polymer composition according to the invention. The molded article is obtained by the method of the present invention. The molded article is preferably transparent. When the molded article has a transmittance of at least 5%, preferably at least 65/〇, more preferably at least 80%, especially at least 90% It is generally considered to be completely transparent. Transmittance can be determined on a plate having a thickness of 2 mm according to ASTM D 1003. In another embodiment, the transmittance is 0.5 in thickness according to ASTM D 1〇〇3. Mm on the foil is measured. In another embodiment, when the thickness is 2 mm according to ASTM D 1〇〇3, the 'on-board test is molded. The turbidity system is as high as, preferably up to μ%, more than 30%, especially in the range of 〇5〇/, more particularly up to 丨〇%, which is considered to be transparent. In another embodiment, The molded article maintains the same transparent enamel as the same molded article without the insecticide and/or insect repellent. The transmittance or turbidity of the molded article is 144736.doc • 17· 201032712 degrees preferably within ± 1 〇% More preferably, the transmittance is reduced by less than 15% of the absolute value of the transmittance, preferably less than 1% and more preferably less than 5 〇 / (^ this reduction can be from 200 to 750 nm 'better than 350 and 650 Measured at nm. Preferred examples of molded articles or final products comprising molded articles are: - foils such as self-adhesive foil, automotive foil, furniture foil, stationery foil, agricultural box, food foil (preservation) Membrane), roofing sheet, tank liner foil, reservoir liner foil, swimming pool liner foil, structural foil, raincoat, revolving door, shower curtain, inflatable boat, floating belt; Strips and sheets of revolving doors; _ cables, such as wire cables, power cables, communication cables, coiled cords, computer cables, and automotive cables - Coatings such as synthetic leather (for automotive and bag manufacturing), tarpaulin tarps, tents, tablecloths, protective clothing, vinyl wall coverings, and conveyor belts; - floor coverings such as sponges Floor coverings (buffered vinyl), non-homogeneous tight coverings, homogeneous compact coverings, and their use in carpet coatings and laminates; _ profiled materials such as industrial hoses, garden hoses, seals Pads (eg for refrigerators), stair railings, and window profiles; • Footwear (boots, sandals), soles, toys, gloves (industrial, medical), closures, and erasers; - Balls, Dolls, traffic cones, tarpaulin tarps, platform tarpaulins, accounts, bags manufacturing products, ventilation ducts, synthetic leather, flooring - and coverings, wallpapers (including those that are foamed by mechanical or chemical methods). Doc 201032712), coatings, protective gloves, protective clothing, and protective coverings on metal substrates, other examples are folding wind, for bottom protection of motor vehicles, and for unscrewing caps and crowns Caps, screw caps and the seal. In a more preferred embodiment, the molded article is for a belt and/or revolving door, strip or sheet. The strip or sheet is preferably transparent. The invention further relates to the use of a molded article according to the invention for controlling insects. These insects are preferably flying insects. The term "controlling 纟纟" means killing or contacting the insects in contact with the molded article. For example, if a molded article is a strip or sheet in a revolving door, the control system prevents the insect from entering the door and kills the insect when it attempts to fly over the door to contact the molded article. "Bug" refers to the insect class and even the arachnid. Experts will select insecticides and/or insect repellents for the insects to be controlled. The term "flying rafts can stay in the air for at least 60 seconds. Suitable examples of tethers ● gliding ants, skydiving materials, preferably worms and bees. There are several advantages to use plasticizing with low vapor pressure. The agent can obtain the extremely low evaporation degree into the environment. It can be used to provide good plasticizing properties for the increase of T which is less harmful to the environment. The use of plasticizers at low temperatures can be used. The bismuth polymer molding still has a glossy surface. The insects are stable for a long time (for example, several months) to control the known pyrethroid vinegar to be susceptible to photodegradation: 2 = active. Although *time storage and should be _'22 144736.doc -19· 201032712 [Embodiment] The following examples of the invention will further explain the invention, however, the invention is not limited by such examples. Powder: The plasticized polystyrene is obtained by suspension polymerization with a Tg of 75 to 85 ° C, a specific gravity of 1.38 kg/m 3 , a bulk density of 0.47 kg / Ι, and a volatile content of < 3 g / Kg, reduced viscoxita is 128 mg/g, corresponding K value is 71, sieve analysis: >9 6% stays on 0.063 mm sieve, < 2% stays on 0.25 mm sieve (Solvin® 271SP from Solvin) ° Plasticizer: diisononyl phthalate, CAS number 28553-12 -0, clear liquid, dynamic viscosity at 20 ° C of 68 to 82 mPas, acid value < 0.06 mg KOH / g, water content < 0.05% by weight, average mass of 418.6 g / mol, at 7 hPa The boiling point range is 253 to 267 ° C, and the vapor pressure at 100 ° C: 2.6 x 10 · 4 hPa (Palatino® IN from BASF SE). Alphacypermethrin: from pyrethroids Insecticide.

Ba/Zn-穩定劑：鋇/辞穩定劑（購自Akr.os Chemicals之 Lankromark LZB 753)。實例1-PVC箔片之製備藉由行星混合器使100 g PVC粉末、67 g(45 phr)增塑劑、30 g(20 phr)亞滅寧之5重量％增塑劑溶液、3 g(2 phr)Ba/Zn穩定劑於80°C下混合。然後，於蒸氣加熱的實驗 144736.doc -20- 201032712 室混合碾機中於170°C溫度下使該混合物塑化並於較薇中藉由輥子將其加工成薄層。使該薄層冷卻至室溫並隨後於溫度180°C及壓力220 bar下將其壓成箔片。所得的pvc箔片具有0·5 mm之厚度及係由60.0重量％pVC、38·2重量％增塑劑、〇·6重量％亞滅寧及1.2重量％83/211穩定劑組成。實例2-對控制昆蟲之測試測試方法測試方法Α及Β之目的係確定經亞滅寧處理之pvc膜對兩籲種飛行有害昆蟲··家蠅（Musca domestica)及黃熱病蚊子 (Aedes aegypti)及一爬行類動物：阿根廷工犧（Unepithema humile)之接觸效能。測試方法之每一平均值係基於約仂至 60個昆蟲（即4組10至15個成蟲）。如實例乂所述製備的經處理膜含有0.6%亞滅寧。該膜於2(rc下存放9個月。對2個月後之一樣品及9個月後之另一樣品進行如述測試。結果分別地概述於表1A及1B中。Ba/Zn-stabilizer: 钡/辞 Stabilizer (available from Akr.os Chemicals, Lankromark LZB 753). Example 1 - Preparation of PVC foil 100 g of PVC powder, 67 g (45 phr) of plasticizer, 30 g (20 phr) of arsenic 5% by weight of plasticizer solution, 3 g (by a planetary mixer) 2 phr) Ba/Zn stabilizer was mixed at 80 °C. Then, the mixture was plasticized in a steam-heated experiment 144736.doc -20-201032712 in a mixing mill at a temperature of 170 ° C and processed into a thin layer by a roller in a velvet. The thin layer was allowed to cool to room temperature and then pressed into a foil at a temperature of 180 ° C and a pressure of 220 bar. The resulting pvc foil had a thickness of 0.5 mm and consisted of 60.0% by weight of pVC, 38.2% by weight of plasticizer, 〇6% by weight of arsenic and 1.2% by weight of 83/211 stabilizer. Example 2 - Tests for Controlling Insects Test Methods Test Methods The purpose of Α and Β is to determine the pvc membrane treated by yin-nanning against two kinds of flying harmful insects · Musca domestica and yellow fever mosquito (Aedes aegypti) And a reptile: the contact effectiveness of Unepithema humile. Each of the average values of the test methods is based on about 60 insects (i.e., 4 groups of 10 to 15 adults). The treated film prepared as described in Example 含有 contained 0.6% arsenic. The film was stored at 2 (rc for 9 months. One sample after 2 months and another sample after 9 months were tested as described above. The results are summarized in Tables 1A and 1B, respectively.

家蠅及黃熱病蚊子之測試方法A ® 於6盎司拋棄式透明塑膠杯（直徑為95 ^及高度為55 cm)中進行直接接觸測試。將每一杯子倒置地放置於經 0.6%亞滅寧處理或未經處⑨之膜上。％一浸有1〇%蔬糖的牙芯作為食物源插穿容器底部（為引入昆蟲由尺寸為7之穿孔器刺穿）。將約10至15個家绳或黃熱病蚊子引入每—杯子中，每種4份。處理後（HAT)2、6及24小時對擊倒率進行評價。Test Method for Housefly and Yellow Fever Mosquito A ® was tested for direct contact in a 6 ounce disposable clear plastic cup (95 cm diameter and 55 cm height). Each cup was placed upside down on a film treated with 0.6% arsenic or not. A dental core impregnated with 1% sugar is inserted as a food source through the bottom of the container (for the introduction of insects, a perforator of size 7 is pierced). About 10 to 15 house ropes or yellow fever mosquitoes are introduced into each cup, 4 each. The knockdown rate was evaluated after 2, 6 and 24 hours after the treatment (HAT).

關於阿根廷蟻（Argentine ants)之測試方法B 144736.doc -21 · 201032712 於倒置於經0.6%亞滅寧處理或未經處理之膜上之60χ 15 mm塑膠皮氏（Petri)培養孤中進行直接接觸測試。首先使皮氏培養皿爬滿10隻阿根廷工蟻（Argentine ants)。將浸有 1 0%蔗糖之牙粒作為食物源置於一塑膠圓盤上並隨後置於 PVC膜上。重複4次。於HAT 2、4、6及24時對死亡率進行評價’包含致死率。表1A，以存放2個月之樣品處理不同小時後（HAT)之致死率或擊倒率1 [%]。家蠅黃熱病蚊子阿根廷工蟻 HAT [小時] 2 6 24 2 6 24 2 6 24 實例1之PVC 93 98 100 88 100 100 55 90 93 未經處理之膜 0 0 0 0 0 0 0 3 5 1)對家蠅及蚊子採用擊倒率讀數，對阿根廷工蟻採用致死率讀數。表1B，以存放9個月之樣品處理不同小時後（HAT)之致死率或擊倒率1 [%]。家蠅黃熱病蚊子 HAT [小時] 2 6 24 2 6 24 實例1之PVC 100 100 100 90 96 100 未經處理之膜 0 0 9 2 2 6 1)對家蠅及蚊子採用擊倒率讀數，對阿根廷工蟻採用致死率讀數。實例3-PVC箔片之光澤及透光度分析將實例1中製備之PVC箔片樣品（含亞滅寧之箔片）與不含殺蟲劑之相同箔片比較。根據實例1製備該對照箔片（不含殺蟲劑之箔片），且僅不添加亞滅寧。根據DIN 67530 144736.doc -22- 201032712 (German industry norm，德國工業標準）藉由光澤計（BYK Gardner Micro-Tri-Gloss)以指定角度（參見表2)測定光澤。光澤計值（以光澤單位GU表示）係與具有1.567折射率之黑色磨光玻璃標準相關。如表2所示，含有或不含有殺蟲劑的PVC之光澤無明顯差異。Test Method for Argentine Ants B 144736.doc -21 · 201032712 Directly placed in 60χ 15 mm plastic Petri cultures placed on a 0.6% arsenic-treated or untreated membrane Contact test. First, the Petri dish was filled with 10 Argentine ants. The dental granules soaked with 10% sucrose were placed on a plastic disc as a food source and then placed on a PVC membrane. Repeat 4 times. Mortality was assessed at HAT 2, 4, 6 and 24, including mortality. Table 1A shows the lethality or knockdown rate 1 [%] after different hours of treatment (HAT) for samples stored for 2 months. Housefly yellow fever mosquito Argentine worker ant HAT [hour] 2 6 24 2 6 24 2 6 24 Example 1 PVC 93 98 100 88 100 100 55 90 93 Untreated film 0 0 0 0 0 0 0 3 5 1) Houseflies and mosquitoes use a knockdown rate reading to take a fatality reading for Argentine workers. Table 1B shows the lethality or knockdown rate 1 [%] after different hours of treatment (HAT) for samples stored for 9 months. Housefly yellow fever mosquito HAT [hours] 2 6 24 2 6 24 Example 100 PVC 100 100 100 90 96 100 Untreated film 0 0 9 2 2 6 1) Knockdown rate readings for house flies and mosquitoes, Argentine worker ants use a fatality reading. Example 3 - Gloss and Transmittance Analysis of PVC Foil A PVC foil sample prepared in Example 1 (a foil containing arsenic) was compared with the same foil without the insecticide. The control foil (foil containing no insecticide) was prepared according to Example 1 and only sub-nectin was not added. Gloss is determined according to DIN 67530 144736.doc -22- 201032712 (German industry norm, German Industrial Standard) by means of a gloss meter (BYK Gardner Micro-Tri-Gloss) at a specified angle (see Table 2). Gloss measurements (expressed in gloss units GU) are associated with a black polished glass standard having a refractive index of 1.567. As shown in Table 2, there was no significant difference in the gloss of PVC with or without insecticide.

樣品 60°角度下之光澤 85°角度下之光澤不含殺蟲劑之箔片 143.5 GU 108,9 GU 含亞滅寧之箔片 145,0 GU 110,9 GU 此外，於200與750 nm之間分析不含殺蟲劑的箔片及含有亞滅寧的箔片之透光度。所得圖顯示於圖1中，其中線A 指不含殺蟲劑之箔片及線B指含亞滅寧之箔片。兩樣品之透光度不存在明顯差異。因此，殺蟲劑之添加對透光度不具有不利影響。此意指，即使添加殺蟲劑箔片仍係透明。【圖式簡單說明】圖1顯示不含殺蟲劑之箔片及含亞滅寧之箔片於200至 750 nm下之透光度。 144736.doc -23-Gloss at a 60° angle of the sample at a gloss angle of 85° without the insecticide foil 143.5 GU 108,9 GU Foil containing arsenic 145,0 GU 110,9 GU In addition, at 200 and 750 nm The transparency of the foil containing no insecticide and the foil containing arsenic was analyzed. The resulting graph is shown in Figure 1, wherein line A refers to a foil that does not contain an insecticide and line B refers to a foil containing a sub-nanning. There was no significant difference in the transmittance of the two samples. Therefore, the addition of the insecticide does not adversely affect the light transmittance. This means that even the addition of the pesticide foil is transparent. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the transparency of a foil containing no insecticide and a foil containing arsenic at 200 to 750 nm. 144736.doc -23-

Claims

201032712 VII. Patent application scope:

a polymer composition comprising a polymer, a plasticizer, and an insecticide and/or an insect repellent, wherein the plasticizer is di- or di-decyl phthalate or cyclohexane dicarboxylate Acid di(C9 to C丨3 alkyl) ester. 9 13 A polymer composition as claimed, wherein the insecticide and the insect repellent are soluble in the plasticizer. 3. The polymer composition of claim (8), wherein the pesticide comprises pyrethroid vinegar. The polymer composition of claim 1 or 2, wherein the plasticizer is a di(c9 to c13 alkyl) phthalate. A polymer composition according to claim 1 or 2, wherein the plasticizer is di(C9 alkyl) phthalate. 6. The polymer composition of claim 2 or 2 wherein the polymer is polyvinyl chloride (PVC). '

A method for producing a molded article, which comprises heating molding the polymer composition according to any one of claims 1 to 6. The method of claim 7, wherein the composition is prepared by mixing a polymer with a plasticizer composition, the plasticizer composition comprising an insecticide dissolved in the plasticizer. θ 9. A plasticizer composition comprising an insecticide and/or an insect repellent, and a plasticizer, wherein the plasticizer is phthalic acid bis(CM" mercapto) vinegar cyclohexane Dicarboxylic acid di(C9 to c13 alkyl) ester. 10. The plasticizer composition of claim 9, wherein the insecticide and/or insect repellent is dissolved in the plasticizer. I44736.doc 201032712 11. A inclusion as requested

Molding of the polymer composition of any of 1 to 6 12. The molded article of claim 1 is transparent. 13. — kind of as requested! *^ The molded article is used to control the use of insects. 14. The use of claim π where the insects are flying insects. 144736.doc 2-