201234961 六、發明說明: 【發明所屬之技術領域】 本發明關於具有聚合物樹脂之產物,該聚合物樹脂包 含經由倂入而分佈在整個樹脂中之芬普尼(Fipronil )。 本發明亦關於使用這類產物來保護作物、動物或人類對抗 昆蟲的方法。 【先前技術】 關於殺蟲劑控制’眾所周知可將殺蟲劑倂入聚合物材 料中以防止昆蟲通過該材料。然而,當涉及到控制殺蟲劑 釋入聚合物樹脂中之速率時,這被認爲是個棘手的問題, 因爲釋出過快將快速耗盡樹脂之殺蟲效果,釋出過於緩慢 則不具有所期望之效率或在殺蟲劑脫落或被移除(例如透 過洗滌)之情況中不具有合適之再生性質。若殺蟲劑易於 在產物之表面結晶(稱爲粉化)則狀況更複雜,此導致殺 蟲劑因結晶造成梯度改變而從聚合物之主體被萃取出來。 爲了取得殺蟲劑適當之移動率而調整聚合物組成的方 法是習知的。例如:Van Voris等人所著,讓渡給先正達 (Syngenta)公司之國際專利申請案WO02/43 487中揭露 殺蟲劑與HDPE (高密度聚乙烯)及LDPE (低密度聚乙烯 )之混合物並陳述取決於所需之釋出率來選擇聚合物。然 而,殺蟲劑之釋出速率通常亦取決於殺蟲劑及聚合物樹脂 之形式。例如:薄片具有與纖維不同之釋出速率,而該聚 合物之摻合物必須據此調整。此外,殺蟲劑之類型以及物 201234961 理狀態(例如結晶型或流體)會影響移動速率。 芬普尼爲苯基吡唑殺蟲劑-在各種殺蟲劑之間-其已被 擬議倂入聚乙烯基質中。芬普尼在建築物方面(諸如地板 下、房子內部及周圍)的用途已揭露於讓渡給Super Sack 之美國專利案編號6370834中。芬普尼可能被認爲有利於 對抗對擬除蟲菊酯類(pyrethroids)(此爲常用於蚊帳之 殺蟲劑),特別是溴氰菊醋(deltamethrin)和氯菊醋( permethrin)具有抗性之飛蚊。然而,這需要找到一種適 當之聚合物樹脂,使芬普尼可在其中以足夠之速率從聚合 物內移至聚合物表面,以補充該表面之殺蟲劑含量。 由住友公司提出之日本專利申請案JP 06-3 1 5 3 3 2 (核 發爲JP 33367 1 4 )中揭露具有殺蟲劑(較佳爲氯菊酯或吡 丙醚(pyriproxyfen))之線性低密度聚乙烯(LLDPE) 樹脂。LLDPE通常爲乙烯與至少一種選自具有4至12個 碳原子之α -烯烴的α -烯烴之共聚物。所給定之LLDPE的 密度爲0.870至0.93 5克/立方厘米,宜爲0.870至0.915 克/立方厘米。其中提及之殺蟲劑很多,包括胺基甲酸酯 、擬除蟲菊酯及芬普尼。 由住友公司提出之國際專利申請案 W02008/0001926 中揭露一種用於擠出絲之樹脂組成物。該組成物包含密度 爲935至965公斤/米3之乙烯均聚物及0.1至10份重農 藥/100份重乙烯均聚物。該組成物之熔體流動速率爲0.3 至7克/10分鐘,熔體流率比爲10至50且密度爲935至 980公斤/立方厘米。該專利申請案中亦揭露氯菊酯 201234961 + LLDPE之母料,其係在細絲擠出前與HDPE混合。芬普 尼爲許多可能之殺蟲劑之一。 國際專利申請案W020 1 0/0046348中揭露具有HDPE 與LLDPE之摻合物的樹脂,其中亦提出具有二種類型之 紗的紡織產物。第一種類型之紗包括擬除蟲菊酯而第二種 紗包含芬普尼;用於擬除蟲菊酯之較佳紗爲等量之HDPE 和LLDPE的摻合物,而芬普尼紗中之HDPE至少較LDPE 高出6倍。 日本專利刊物號08-3 02080中揭露一種樹脂組成物, 其包含(A ) 1 00份之相當低移動性烯烴聚合物,諸如 HDPE、MDPE或以聚丙烯爲底之聚合物,(B) 10-400份 之相當高移動性以乙烯爲底之聚合物,諸如 LDPE、 LLDPE或乙烯共聚物,及(C ) 0.3-15份之以擬除蟲菊酯 爲底之昆蟲防治劑。201234961 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a product having a polymer resin comprising Fipronil distributed throughout the resin via intrusion. The invention also relates to methods of using such products to protect crops, animals or humans against insects. [Prior Art] Regarding insecticide control, it is known that insecticides can be incorporated into a polymer material to prevent insects from passing through the material. However, when it comes to controlling the rate at which the pesticide is released into the polymer resin, this is considered to be a thorny problem because the release of the compound will quickly deplete the insecticidal effect of the resin, and if it is released too slowly, it will not have The desired efficiency does not have suitable regenerative properties in the event that the pesticide is shed or removed (e.g., by washing). If the insecticide is susceptible to crystallization on the surface of the product (referred to as pulverization), the condition is more complicated, which results in the pesticide being extracted from the bulk of the polymer due to a gradient change in crystallization. A method of adjusting the polymer composition in order to obtain an appropriate mobility of the insecticide is conventional. For example, the use of insecticides and HDPE (High Density Polyethylene) and LDPE (Low Density Polyethylene) is disclosed in the international patent application WO 02/43 487 to Syngenta, Inc., to Van Voris et al. The mixture is stated and the polymer is selected depending on the desired release rate. However, the release rate of the pesticide is usually also dependent on the form of the pesticide and the polymer resin. For example, the flakes have a different rate of release from the fibers, and the blend of the polymers must be adjusted accordingly. In addition, the type of pesticide and the state of the object 201234961 (such as crystalline or fluid) can affect the rate of movement. Fenpini is a phenylpyrazole insecticide - between various insecticides - which has been proposed to break into polyethylene matrices. The use of Finkney in terms of buildings, such as under the floor, inside and around the house, has been disclosed in U.S. Patent No. 6,370,834 issued to Super Sack. Finkney may be considered to be beneficial against pyrethroids, which are commonly used as insecticides in mosquito nets, especially deltamethrin and permethrin. Flying mosquitoes. However, this requires finding a suitable polymer resin in which the fentanyl can be moved from the polymer to the polymer surface at a sufficient rate to supplement the insecticidal content of the surface. The linear application of insecticide (preferably permethrin or pyriproxyfen) is disclosed in Japanese Patent Application No. JP 06-3 1 5 3 3 2 (issued as JP 33367 1 4) by Sumitomo Corporation. Density polyethylene (LLDPE) resin. The LLDPE is usually a copolymer of ethylene and at least one α-olefin selected from α-olefins having 4 to 12 carbon atoms. The density of a given LLDPE is from 0.870 to 0.93 5 g/cc, preferably from 0.870 to 0.915 g/cc. Many of the pesticides mentioned include urethane, pyrethroid and fenapini. A resin composition for extruding a wire is disclosed in International Patent Application No. WO 2008/0001926. The composition comprises an ethylene homopolymer having a density of from 935 to 965 kg/m3 and from 0.1 to 10 parts by weight of agrochemical/100 parts by weight of ethylene homopolymer. The composition has a melt flow rate of 0.3 to 7 g/10 minutes, a melt flow ratio of 10 to 50, and a density of 935 to 980 kg/cm 3 . The patent application also discloses a masterbatch of permethrin 201234961 + LLDPE which is mixed with HDPE prior to filament extrusion. Fenpney is one of many possible insecticides. A resin having a blend of HDPE and LLDPE is disclosed in International Patent Application No. WO 120/01/00463, which also discloses a textile product having two types of yarns. The first type of yarn comprises pyrethroids and the second type comprises fipronil; the preferred yarn for pyrethroids is a blend of equal amounts of HDPE and LLDPE, and Fenney yarn HDPE is at least 6 times higher than LDPE. Japanese Patent Publication No. 08-3 02080 discloses a resin composition comprising (A) 100 parts of a relatively low mobility olefin polymer such as HDPE, MDPE or a polypropylene based polymer, (B) 10 - 400 parts of a highly mobile ethylene-based polymer such as LDPE, LLDPE or ethylene copolymer, and (C) 0.3-15 parts of a pyrethroid-based insect control agent.
Skovmand之 W020 1 0/1 1 5709中揭露一種聚合物組成 物及從包含溶解在合適之油及/或蠟中之活性成分(如驅 蟲劑)的聚合物組成物製成之紡織品(如驅蟲網),其中 該油和/或蠟亦可溶混在基質中。A polymer composition and a textile made from a polymer composition comprising an active ingredient (such as an insect repellent) dissolved in a suitable oil and/or wax (for example) is disclosed in S. K. 1 0/1 1 5709. Insect nets, wherein the oil and/or wax are also miscible in the matrix.
Kyucheol Chi,等人之文章 “ Rheological and Mechanical Properties in Polyethylene Blends"(發表於 polymer Engineering and Science, December 1 996, V o 1. 38, no.12 p 1 969- 1 9 75 中)中硏究 LLDPE/HDPE, LLDPE/LDPE及HDPE/LDPE摻合物之熔體流變學和力學 性質。 201234961 從以上可以看出,先前技藝中對含有芬普尼之樹脂有 各種建議。其中似乎沒有明確提出密度是否應如JP 06-3 1 63 3 2 中所報告般低,或如 W02008/0001 926 及 W02010/0046348中所報告般高之建議。 此外,沒有發現可在市場上銷售之令人滿意的產物( 如蚊帳)。因此,具有移動性芬普尼之持久聚合物樹脂仍 有需要改良。 【發明內容】 本發明之目的 本發明之目的係提供一種包含聚合物樹脂之產物(尤 其是扁平紗),其乎該聚合物樹脂具有良好之芬普尼移動 性質。主要地,本發明之目的係提供對昆蟲(尤其是蚊子 )具有持久殺蟲效果之芬普尼的合適載體。本發明之目的 亦爲找到一種控制昆蟲之方法,尤其是控制蚊子,以降低 人類、農場動物及農作物的風險。 本發明之詳細說明 本發明之目的可藉由密度爲0.890至0.930克/立方厘 米之樹脂(例如:0.8 90至0.920克/立方厘米)達到。“ ccm ” 一詞代表立方厘米。所規定之密度爲不含殺蟲劑之 樹脂密度。芬普尼係經由倂入而分佈在樹脂中且將從樹脂 之主體移至樹脂表面。 本發明中“樹脂”一詞係指用於產物生產中之成形過 -8- 201234961 程(例如:擠出或造型)的樹脂。例如:該樹脂爲單一聚 合物,或者該樹脂爲聚合物之摻合物。在產物或一部分產 物(例如纖維或薄膜)被塑型前或擠出前與其他聚合物混 合或共聚化之聚合物不在“樹脂”一詞之含義內。 由實驗得到之結果證實,使芬普尼適當移動(其對持 久之殺蟲產物,尤其是蚊帳及牆面遮蓋物有助益)需要該 樹脂具有非常特殊之性質及設限之參數。 【實施方式】 下文中,以表格形式呈現接觸蚊帳(已併入芬普尼之 紗)後測量死蚊子的實驗結果。其中顯示出具不同密度之 四種不同材料的數據。將蚊帳洗滌及乾燥後立即進行之測 量稱爲“初始”,而“1個月後”係相對於蚊帳洗滌的時 間。在蚊子接觸蚊帳後24小時對兩種類型之蚊子進行測 基質 密度 (克/立方厘米) 真正死亡(%) 河內致倦庫蚊 芽莊埃及斑蚊 初始 1個月後 初始 1個月後 HDPE/LDPE 90/10 0.947 0 15 n/a n/a PP 0.940 0 25 n/a n/a HDPE/LLDPE 65/35 0.931 65 100 40 90 HDPE/LLDPE 50/50 0.901 100 100 100 100 201234961 從數據來看,密度爲0.901之HDPE/LLDPE 50:50組 合物在洗滌後可非常快速地再取得高殺蟲效力(該效力係 以蚊子TD (真正的死亡)百分比形式表示)。在洗滌後 不久,必要表面濃度爲足以使所有接觸蚊帳之蚊子死亡。 具有0.93 1之較高密度的混合物在洗滌後不久效力較低, 但洗滌後確實很快地再次達到高效力。 相比之下,較高密度之HDPE/LLDPE,甚至是PP,無 法使芬普尼良好移行至表面,如此,該接觸之蚊子的死亡 率低。因此,現已察覺其密度高達0.93克/立方厘米之 LLDPE/HDPE摻合物可取得使芬普尼良好移行之性質,而 密度高於0.93時將保留過高之芬普尼。 雖然,此樹脂已被發現對含有芬普尼之扁平紗特別有 用,本發明具有較普遍之特點且可用於其他種類之基質, 例如纖維、薄膜或圓柱形細絲。 “倂入”一詞意指該殺蟲劑係分佈於整個樹脂中,例 如以分散液之形式倂入。殺蟲劑可全部或部分溶解於聚合 物中,例如:部分以晶體形式存在而部分溶解。該晶體可 作爲貯存庫,逐漸溶解在樹脂中以補充殺蟲劑之含量。使 用合倂技術(尤其是在薄形產物,例如纖維)具有超越薄 塗層技術(諸如注入),防止芬普尼因水解作用而降解的 優勢。 “持久”一詞係指3個月以上,較佳爲1年或2年以 上,甚至3年或4年以上,諸如5年。 在所有以從第一個數値到第二個數値或介於第一個數 -10- 201234961 値和第二個數値之間的方式給定之所有區間方面,該區間 爲開放區間或封閉區間。所有%値均以重量百分比形式表 示。除非另有說明,芬普尼相對於樹脂之濃度百分比意指 相對於無芬普尼之樹脂的重量;因此,0.5%芬普尼係指 除1公斤樹脂以外之5克芬普尼。“主要地”一詞係指在 不具有殺蟲劑的樹脂中濃度超過50%。 較佳之樹脂爲熱塑性樹脂,尤其是烯烴。聚乙烯PE 或聚丙烯PP爲合適之選擇,例如:可選擇包含低密度PP 或由低密度PP組成之基質。可選擇PE與PP之混合物, 例如 LDPE或 LLDPE與 HDPE之混合物,或 LDPE或 LLDPE與PP之混合物。例如:HDPE或PP可爲均聚物或 共聚物。 於一些體系中,該聚合物中至少90%爲聚乙烯,例如 :至少95%或甚至100%。該聚乙烯可爲均聚物、共聚物 或不同類型之聚乙烯的混合物。 LLDPE與HDPE之摻合物爲一種選項;另一種選項爲 LLDPE與PP之摻合物。LLDPE與HDPE,或LLDPE與 pP之間的有用比率爲80:20至30:70、或70:30至30:70、 或 70:30 至 40:60、或 70:30 至 50:5 0、或 65:3 5 至 40:60 、或 65:3 5 至 5 5:4 5、或 5 5:45 至 45:5 5。 經由使用高密度聚合物(例如HDPE )與低密度聚合 物(例如LLDPE)之摻合物可適當調整樹脂之密度,由此 可適當調整移動率。由於移動速度快,LLDPE之含量愈高 ’再生的時間愈快,但產物(例如紗)的加工更困難。 -11 - 201234961 另一方面’當HDPE之含量過高時,芬普尼以過慢之 速度移動。例如:實驗顯示出具有90% HDPE及10% LLDPE -且其密度超出上述範圍之基質意味著其芬普尼移 動率對實際用途(尤其是蚊帳)而言過慢,因爲蚊帳纖維 表面上之芬普尼的再生速度並不夠快至足以提供穩定充足 之芬普尼劑量以擊倒並殺死昆蟲,尤其是蚊子。之所以如 此係因爲芬普尼一旦移動到基質表面上將因各種因素而損 失,爲了取得滿意之擊倒及滅殺昆蟲,移動率應足夠高以 便再生而成功與芬普尼的損失競爭。 在損失因素之中,較特別的爲水解作用及由紫外線輻 射造成之崩解。在聚合物基質之內部,該倂入之芬普尼可 受到防止水解之保護,且基質中亦在倂入紫外線保護劑以 保護芬普尼對抗紫外線輻射。然而,一旦在表面上,保護 作用不再明顯且芬普尼發生大量損失。 特別是,在HDPE和LLDPE之樹脂混合物中,約等 量之HDPE及LLDPE含量已被證明是可行的。 在紗產物(尤其是對抗蚊子之殺蟲劑蚊帳)方面, HDPE和LLDPE間之比例的非排他性有用範圍爲70:3 0至 50:50 或 55:45 至 45:55 。 現已使用密度在0.88至0.91克/立方厘米區間內之 LLDPE (例如在190°C及2.16公斤之試驗負載下,其熔體 流動速率係介於1.5與1.7克/10分鐘之間)來創造有用之 材料。亦使用密度在0.94至0.96克/立方厘米之區間內的 HDPE (例如在19(TC及2.16公斤之試驗負載下’其熔體 -12- 201234961 流動速率係介於0.7至〇·9克/ i〇分鐘)來創造另一種有用 之材料。這兩種材料之摻合物被認爲具有優勢。 在本發明之測試材料方面,需提出一些注意事項。如 上文槪述者’目前已發現密度爲FPN移動之關鍵參數。一 方面需要低密度,但另一方面高濃度之LLDPE對擠出之 紗的可操作性並不是那麼好。現已實驗發現一種解決此兩 難的方案’此解決方案係立基於密度與LLDPE濃度之相 關性並非線性行爲。令人驚訝地,當增加HDPE之濃度時 ’ HDPE與LLDPE之混合物的密度降低,而非增加,直到 達到40%HDPE之濃度後才隨著HDPE之濃度增加而增加 。一組HDPE及LLDPE之實驗中發現下列用於所列密度 之數値。 HDPE LLDPE 密度[克/立方厘米] 100% 0% 0,954 50% 50% 0,901 40% 60% 0,893 30% 70% 0,892 0% 100% 0,896 此意味 HDPE/LLDPE混合物之低密度可在很大之 LLDPE濃度範圍中取得。例如:密度小於0.93 0意味這些 材料中之LLDPE的範圍係在25%至100%,而密度小於 0.920意味LLPDE之範圍係在30%至100%。 有利的是,芬普尼係以每公斤樹脂0.1-20克,或2-10克、或3-8克、或4-6克之整體濃度提供於樹脂中。 -13- 201234961 實驗發現在具有LLDPE及HD PE之基質中,對0.5% 芬普尼(FPN)之濃度而言,50:50 LLDPE: HDPE摻合物 之密度低於單獨之LLDPE的密度。此點極其令人吃驚。 例如,對密度0.954克/立方厘米之HDPE與密度0.896克/ 立方厘米之LLDPE的50:50混合物而言,添加0.5%芬普 尼可產生密度爲0.893克/立方厘米之殺蟲樹脂,此殺蟲樹 脂中雖然含有較重之HDPE並含有較重之芬普尼,其密度 甚至比純LLDPE還要低。咸信,此種效果適用於濃度爲 0.2%-1%之芬普尼,尤其是0.3%至0.8%。在實驗中, LLDPE: HDPE比例爲60:40及70:30時,包含芬普尼之樹 脂的密度亦小於0.920克/立方厘米。 因此,與根據以上參數之不含殺蟲劑之樹脂的發明無 關,包含 LLDPE和 HDPE比例爲 70:30至 30:70、或 60:40 至 40:60 以及 0.2% 至 1% (例如 0.3% 至 0.8%)芬 普尼的樹脂(其中該包含芬普尼之樹脂的密度爲〇. 8 9 0-0.93 0克/立方厘米)亦可達到使芬普尼具良好之移動性的 目的,並可提供芬普尼合適載體,對昆蟲具有持久之殺蟲 效果。或者,該包含(例如0.3%至0.8%)芬 普尼之樹脂的密度爲0.890-0.920克/立方厘米。或者, LLDPE/HDPE摻合物中芬普尼之含量爲0.4-0.6%。然而, 可選擇地,這些參數可與上述不具有芬普尼之樹脂的參數 組合。 根據本發明之有用產物的實例有薄膜、防水油布、纖 維、編織物或非織物。該織品可爲具有熔融擠出之紗的編 -14- 201234961 織物或非織物。一種應用爲用於蚊帳之纖維。 與上述樹脂相關之利益爲從扁平紗製造之織物,該織 物中之扁平紗已從薄聚合物片切成薄片。該織物可爲編織 物或非織物。例如’這類扁平紗之厚度爲〇.〇15至0.065 毫米、或0.02 5至0.50毫米、或〇·〇3〇至〇 040毫米。寬 度之實例爲1-6毫米、2-5毫米或3-4毫米。 在這類薄紗方面,先前技藝中普遍預期該聚合物必須 主要包含HDPE (具高重量密度之樹脂)以使移動減緩至 能令紗之殺蟲效力持久的程度》然而,令人驚訝地,此類 型之殺蟲紗中須經由使用相當大量之LLDPE以使密度低 ,在某些情況下甚至主要使用LLDPE。其重量密度爲 0.890至0.930克/立方厘米或0.890至0.920克/立方厘米 的樹脂在具有上述尺寸之殺蟲力持久的扁紗、薄紗中的用 途令人驚異。 較佳之整體濃度爲每公斤樹脂包含0.1-20克、或1-10克、或3-8克或4_6克芬普尼。 除了芬普尼,現已發現在樹脂中包含,例如濃度爲1 -10克/公斤' 2-5克/公斤或3-4克/公斤之增效劑(尤其是 增效醚(piperonyl butoxide) (PBO))及殺蟲劑是有利 的。有用之組合爲每公斤樹脂包含0.1-20克芬普尼及1-10克或2-5克PBO,1-1〇克或4-6克芬普尼及2·5克 ΡΒ0/公斤樹脂,或1-10克或4-6克芬普尼及3-4克ΡΒ0/ 公斤樹脂。 在織物中之紗型樹脂方面,該表面積濃度係取決於織 -15- 201234961 物之厚度,但最佳範圍係在180至1500毫克/米2’例如 400至1 000毫克/米2。該表面濃度可因控制芬普尼移動至 表面而長久保持。 於一些體系中,該產物爲厚度介於0.015至0.065毫 米之間,寬度介於1至6毫米之間’且樹脂中包含0.1-20 克芬普尼/公斤聚合物(例如:2至10或3至8克/公斤’ 相當於0.2%至1%或0.3%至0.8% ’所有百分比均爲重 量百分比)之扁絲。例如:該聚合物中至少90%爲HDPE 與LLDPE之摻合物。 於一些體系中係提供具有如上述之扁平紗的殺蟲織物 (例如:藉由針織或編織製成),且樹脂中之芬普尼的移 動率係經調整以使表面濃度爲180- 1 500毫克芬普尼/米2 織物。 例如:該樹脂包含比例爲80:20至3 0:70或70:3 0至 3 0:70之LLDPE和HDPE,其中該樹脂未具有殺蟲劑時的 密度爲0.890至0.930克/立方厘米,其中該LLDPE之密 度在0.88至0.91克/立方厘米的區間內且在190 °C及2.16 公斤之測試負載下,熔體流動速率係介於1 .5與1.7克/1 〇 分鐘之間,其中芬普尼之整體濃度你介於0.1-20克/公斤 樹脂或3-8克/公斤樹脂。可選擇地,該樹脂包含濃度介於 1-10或3-4克/公斤樹脂之PBO。 如上文中已提及者,若樹脂中之LLDPE含量高,則 延長度變高,這使得以這類紗進行紡織或針織變得困難。 當需要使樹脂中之LLDPE含量高(例如60%,或甚至80 -16- 201234961 %)才能使產物移動速率最佳且效力持久,且需要進一步 之製造步驟時’下列解決方案是可行的。在此情況中係將 具有芬普尼之第一細絲與主要包含LLDPE之樹脂結合成 單一紗,例如與由較強的材料製造之第二細絲合股,以取 得足夠的強度。例如,該較強的材料爲HDPE、或PP、或 主要爲HDPE或PP之聚合物的摻合物。或者,該較強的 材料可能包含聚酯’其中該聚酯一詞包括聚乙烯對苯二甲 酯類型。 例如’此較強之細絲並不含殺蟲劑,僅對合倂之紗具 有穩定效果。另外’該第二細絲包含其他殺蟲劑或增效劑 ,或此兩者。相對於上述國際專利申請案W02010/046348 中揭露含有擬除蟲菊酯及芬普尼之紗或細絲的組合物,根 據本發明之芬普尼細絲具有低密度(例如主要包含L L D P E )’而在W020 1 0/〇463 48中之芬普尼細絲具有高密度, 因爲其主要包含HDPE’尤其是,HDPE至少超過LLDPE 6倍以上。 雖然原則上芬普尼可用於蚊帳,但這並不理想,因爲 皮膚面臨受芬普尼刺激的風險,除非僅將芬普尼用於通常 不會觸及之蚊帳上端。然而,有鑑於此,尋找其他方式配 發芬普尼較有利。如國際專利申請案WO 2009/059607中 較詳細之解釋,蚊子吸血後將找一個地方休息,通常係在 房子的牆壁上。因此’若將至少一部分之牆面以具有如上 文解釋之殺蟲樹脂的產物覆蓋(例如爲牆襯之形式,通常 爲圓形或扁平紗之編織物或非織物類織物)較有利。如同 -17- 201234961 一篇國際專利申請案中亦有解釋,在許多非洲國家中,住 宅包含具有牆壁、屋頂及介於牆壁上緣與屋頂之間的空間 (通常爲高0.2米至0.4米之空間)之棚屋。本發明亦對 覆蓋這些開口以防止昆蟲進入棚屋之編織物或非織物類織 物、或薄膜、或防水油布有助益。特別是,具有扁平紗之 織物(如上所述)對這類牆壁遮蓋物或開口之遮蓋物有助 益。 於一些體系中,乙烯之含量至少爲樹脂重量之80%或 90%。其餘部分可由殺蟲劑及各種添加劑構成,該各種添 加劑係,例如其他聚合物、增效劑、紫外線防護劑、防腐 劑、抗水解劑、清潔劑、塡料、碰擊修改劑、防霧劑、發 泡劑、澄清劑、成核劑、偶聯劑、防止靜電之電導率加強 劑、安定劑(諸如抗氧化劑)、碳及氧自由基清除劑和過 氧化吻分解劑類、阻燃劑、脫模劑、光學增白劑、擴散劑 、抗阻斷劑、抗移動劑、移動促進劑、泡沫形成劑、防污 劑、防垢劑、增稠劑、潤濕劑、增塑劑黏接劑或抗黏接劑 、香水、顏料及染料。 該產物在作爲對抗昆蟲,保護作物、動物或人類的屏 障上是有用的。 —般而言,非排他性應用包括蚊帳、窗簾、地毯及紗 窗、門屏、帳篷、馬毯、織物或包裝網布、包裝袋、建築 材料、家具、皮革、電線及電纜。 該產物在農業領域中,例如:保護作物及保護動物上 亦有用。該產物包括地膜及用於溫室及動物棚和廐之網狀 -18- 201234961 物或膜。其他用途包括豬圈及牛、家禽和馬匹之圍欄。 例如:該產物可作爲沿著或圍繞農場之圍欄以防止昆 蟲進入該領域或作爲沿著或圍繞動物領域的圍欄以防止昆 蟲接觸到該領域之動物。國際專利申請案 W00300382中 提出一種實例。該圍欄可爲沿著或圍繞露天區之直立網狀 物的形式。或者,該產物可用於遮蓋作物,例如以薄膜或 網狀之形式。該產物亦可以用於溫室,例如以薄膜或網狀 形式使用。 與發明相關之其他特殊應用爲, -殺蟲毯,例如W003055307中所揭露者, -空氣淨化雨棚,例如W02006024304中所揭露者, -防水油布,例如WOO3/063 5 87中所揭露者。 雖然,本發明之主要目的是防止蚊子,但亦包括控制 及/或打擊各種害蟲,諸如蜱、蟑螂、臭蟲、蟎、蚤、蝨 '水蛭、蒼蠅、白蟻 '螞蟮、飛蛾、蜘蛛、蚱蜢、蟋蟀、 蠹蟲、蚜蟲、薊馬、粉蝨、蠓、甲蟲及其他飛行和爬行昆 蟲。 對於陳述之參數値的區間,該區間終點可選擇性地包 含在該區間內。 雖然上述樹脂主要對芬普尼有用,其亦可用於其他殺 蟲劑’尤其是吡唑類、其他苯基吡唑及新菸鹼類,例如呋 蟲胺(Dinotefuran )。此外,其可能有助於擬除蟲菊酯、 有機磷酸酯、胺基甲酸酯、吡咯及菸鹼類,該包括溴氰菊 酯(Deltamethrin) '氯菊醋(Permethrin)及溴蟲清( -19- 201234961Kyucheol Chi, et al., "Reological and Mechanical Properties in Polyethylene Blends" (published in Polymer Engineering and Science, December 1 996, V o 1. 38, no. 12 p 1 969- 1 9 75) Melt rheology and mechanical properties of /HDPE, LLDPE/LDPE and HDPE/LDPE blends 201234961 It can be seen from the above that there have been various proposals for resins containing Fenpney in the prior art. Whether it should be as low as reported in JP 06-3 1 63 3 2, or as high as reported in W02008/0001 926 and W02010/0046348. In addition, no satisfactory products are found that can be marketed. (For example, a mosquito net.) Therefore, there is still a need for improvement in a durable polymer resin having a mobile Fenpney. SUMMARY OF THE INVENTION An object of the present invention is to provide a product comprising a polymer resin (especially a flat yarn) The polymer resin has good Fenpney mobile properties. Mainly, the object of the present invention is to provide a long-lasting insecticidal effect on insects, especially mosquitoes. A suitable carrier for Fenpney. The object of the present invention is also to find a method for controlling insects, in particular for controlling mosquitoes, to reduce the risk of humans, farm animals and crops. DETAILED DESCRIPTION OF THE INVENTION The object of the invention is by density A resin of 0.890 to 0.930 g/cc (for example: 0.890 to 0.920 g/cc) is reached. The term "ccm" stands for cubic centimeters. The density specified is the density of the resin free of insecticide. It is distributed in the resin by intrusion and is moved from the main body of the resin to the surface of the resin. The term "resin" in the present invention means the molding used in the production of the product - for example, extrusion or molding. Resin. For example, the resin is a single polymer, or the resin is a blend of polymers. The product or a part of the product (such as fiber or film) is mixed or copolymerized with other polymers before being molded or before extrusion. The polymer is not within the meaning of the term “resin.” The results obtained from the experiments confirm that Fampney is properly moved (for persistent insecticidal products, especially mosquito nets and Face masks are helpful.) The resin needs to have very specific properties and set parameters. [Embodiment] In the following, the experiment of measuring dead mosquitoes after touching mosquito nets (which have been incorporated into Fennipney yarn) is presented in tabular form. The results show data for four different materials with different densities. Measurements taken immediately after washing and drying of the mosquito net are referred to as "initial" and "after 1 month" are relative to the time of net cleaning. Two types of mosquitoes were tested for substrate density (g/cm3) 24 hours after mosquitoes were exposed to mosquito nets. True death (%) Intravenously caused by Culex pipiens pallens, 1 year after the initial 1 month, HDPE/ LDPE 90/10 0.947 0 15 n/an/a PP 0.940 0 25 n/an/a HDPE/LLDPE 65/35 0.931 65 100 40 90 HDPE/LLDPE 50/50 0.901 100 100 100 100 201234961 From the data point of view, density The HDPE/LLDPE 50:50 composition, which is 0.901, can regain high insecticidal efficacy very quickly after washing (this effect is expressed as a percentage of mosquito TD (true death)). Shortly after washing, the necessary surface concentration is sufficient to cause all mosquitoes that come into contact with the mosquito net to die. A mixture having a higher density of 0.93 1 is less effective shortly after washing, but does quickly reach high efficiency again after washing. In contrast, higher density HDPE/LLDPE, or even PP, does not allow fampney to migrate well to the surface, so that the mosquitoes in contact have a low mortality rate. Thus, it has now been observed that LLDPE/HDPE blends having densities as high as 0.93 g/cc can achieve a property of good transfer of Fenpney, while those with a density above 0.93 will retain too high a Fenpney. Although this resin has been found to be particularly useful for flat yarns containing Fenpney, the present invention has more general characteristics and can be used in other types of substrates such as fibers, films or cylindrical filaments. The term "intrusion" means that the insecticide is distributed throughout the resin, for example in the form of a dispersion. The insecticide may be dissolved in the polymer in whole or in part, for example, partially in the form of crystals and partially dissolved. The crystal can be used as a reservoir and gradually dissolved in the resin to supplement the insecticide content. The use of hydrazine technology (especially in thin products such as fibers) has advantages over thin coating techniques (such as injection) to prevent degradation of fenpni by hydrolysis. The term "long lasting" means more than 3 months, preferably 1 year or more, or even 3 years or more, such as 5 years. In all intervals given from the first number to the second number or between the first number -10- 201234961 値 and the second number, the interval is open or closed Interval. All %値 are expressed as weight percent. Unless otherwise stated, the percentage of concentration of Fenpney relative to the resin means the weight relative to the resin without Fenfenib; therefore, 0.5% Fenpney means 5 grams of Fenpney except 1 kilogram of resin. The term "primarily" refers to a concentration of more than 50% in a resin that does not have an insecticide. Preferred resins are thermoplastic resins, especially olefins. Polyethylene PE or polypropylene PP is a suitable choice, for example, a matrix comprising low density PP or consisting of low density PP may be selected. A mixture of PE and PP, such as LDPE or a mixture of LLDPE and HDPE, or a mixture of LDPE or LLDPE and PP, may be selected. For example, HDPE or PP can be a homopolymer or a copolymer. In some systems, at least 90% of the polymer is polyethylene, for example: at least 95% or even 100%. The polyethylene can be a homopolymer, a copolymer or a mixture of different types of polyethylene. A blend of LLDPE and HDPE is an option; another option is a blend of LLDPE and PP. The useful ratio between LLDPE and HDPE, or LLDPE and pP is 80:20 to 30:70, or 70:30 to 30:70, or 70:30 to 40:60, or 70:30 to 50:50. Or 65:3 5 to 40:60, or 65:3 5 to 5 5:4 5, or 5 5:45 to 45:5 5 . The density of the resin can be appropriately adjusted by using a blend of a high-density polymer (e.g., HDPE) and a low-density polymer (e.g., LLDPE), whereby the mobility can be appropriately adjusted. Due to the fast moving speed, the higher the content of LLDPE, the faster the regeneration time, but the processing of products such as yarn is more difficult. -11 - 201234961 On the other hand, when the content of HDPE is too high, Fenpney moves at a slower speed. For example, experiments have shown that a matrix with 90% HDPE and 10% LLDPE - and its density outside the above range means that its Fenpney mobility is too slow for practical use (especially mosquito nets) because of the surface of the mosquito net fiber. Pune's regeneration rate is not fast enough to provide a stable enough Fenbney dose to knock down and kill insects, especially mosquitoes. The reason for this is that since Fampney will be lost due to various factors once it has moved to the surface of the substrate, in order to achieve satisfactory knockdown and killing of insects, the mobility should be high enough to regenerate and successfully compete with the loss of Fenpney. Among the loss factors, more particular are hydrolysis and disintegration caused by ultraviolet radiation. Inside the polymer matrix, the intrusion of Fenpini is protected against hydrolysis and the matrix is also impregnated with a UV protectant to protect Fenpney against UV radiation. However, once on the surface, the protection is no longer apparent and fampini suffers a large loss. In particular, in the resin blend of HDPE and LLDPE, about the same amount of HDPE and LLDPE has proven to be feasible. In the case of yarn products (especially insecticide nets against mosquitoes), the non-exclusive useful range of ratios between HDPE and LLDPE is 70:30 to 50:50 or 55:45 to 45:55. LLDPE has been used with a density in the range of 0.88 to 0.91 g/cc (for example, at 190 ° C and a test load of 2.16 kg, the melt flow rate is between 1.5 and 1.7 g/10 min) to create Useful materials. HDPE with a density in the range of 0.94 to 0.96 g/cm3 is also used (for example, at 19 (TC and 2.16 kg test load), its melt -12-201234961 flow rate is between 0.7 and 〇·9 g/i 〇 min) to create another useful material. The blend of these two materials is considered to have advantages. In the test materials of the present invention, some precautions need to be made. As the above description, the density has been found to be The key parameters of FPN movement. On the one hand, low density is required, but on the other hand, the high concentration of LLDPE is not so good for the squeezing of the extruded yarn. Now a solution to solve this dilemma has been found. Based on the correlation between density and LLDPE concentration and non-linear behavior. Surprisingly, when increasing the concentration of HDPE, the density of the mixture of HDPE and LLDPE is reduced, not increased, until the concentration of 40% HDPE is reached. The concentration increased and the following results were found for a set of HDPE and LLDPE. HDPE LLDPE Density [g/cm3] 100% 0% 0,954 50% 50% 0,901 40% 60% 0,893 30 % 70% 0,892 0% 100% 0,896 This means that the low density of HDPE/LLDPE blends can be achieved over a wide range of LLDPE concentrations. For example, a density of less than 0.93 0 means that the range of LLDPE in these materials is between 25% and 100%. And a density of less than 0.920 means that the range of LLPDE is between 30% and 100%. Advantageously, Fenpney is 0.1-20 grams per kilogram of resin, or 2-10 grams, or 3-8 grams, or 4-6 The overall concentration of gram is provided in the resin. -13- 201234961 It was found that in the matrix with LLDPE and HD PE, the density of the 50:50 LLDPE: HDPE blend is low for the concentration of 0.5% Fenpney (FPN). The density of LLDPE alone is extremely surprising. For example, for a 50:50 mixture of HDPE with a density of 0.954 g/cm3 and LLDPE with a density of 0.896 g/cm3, 0.5% Fenpney can be added. Insecticide resin with a density of 0.893 g/cm3, although the insecticidal resin contains heavier HDPE and contains heavier Fenpney, its density is even lower than that of pure LLDPE. Fenpini at a concentration of 0.2% to 1%, especially 0.3% to 0.8%. In the experiment, LLDPE: HD When the PE ratio is 60:40 and 70:30, the density of the resin containing Fenpney is also less than 0.920 g/cm3. Therefore, it is not related to the invention of the resin containing no insecticide according to the above parameters, including LLDPE and HDPE. a ratio of 70:30 to 30:70, or 60:40 to 40:60, and 0.2% to 1% (for example, 0.3% to 0.8%) of Fenpney resin (wherein the density of the resin containing Fenpney is 〇 8 9 0-0.93 0 g / cm 3 ) can also achieve the purpose of making Fenpney with good mobility, and can provide a suitable carrier for Fennip, which has a long-lasting insecticidal effect on insects. Alternatively, the resin comprising (e.g., 0.3% to 0.8%) fentanyl has a density of from 0.890 to 0.920 g/cc. Alternatively, the FFPni content of the LLDPE/HDPE blend is from 0.4 to 0.6%. Alternatively, however, these parameters may be combined with the above parameters of the resin which does not have a finfenni. Examples of useful products according to the invention are films, tarpaulins, fibers, woven or non-woven fabrics. The fabric may be a woven or non-woven fabric having a melt extruded yarn -14-201234961. One application is for fibers used in mosquito nets. An advantage associated with the above resins is a fabric made from a flat yarn in which the flat yarn has been cut into thin slices from a thin polymer sheet. The fabric can be woven or non-woven. For example, the thickness of such flat yarns is 〇15〇0.065 mm, or 0.025至0.50 mm, or 〇·〇3〇 to 040040 mm. Examples of widths are 1-6 mm, 2-5 mm or 3-4 mm. In the case of such gauze, it is generally expected in the prior art that the polymer must primarily comprise HDPE (a resin having a high weight density) to slow the movement to such an extent that the insecticidal efficacy of the yarn is sustained. However, surprisingly, In this type of insecticidal yarns, a relatively large amount of LLDPE has to be used to make the density low, and in some cases even LLDPE is mainly used. The use of a resin having a weight density of 0.890 to 0.930 g/cm 3 or 0.890 to 0.920 g/cm 3 in a flat yarn or tissue having a long-lasting insecticidal power of the above-mentioned size is surprising. Preferably, the overall concentration is from 0.1 to 20 grams, or from 1 to 10 grams, or from 3 to 8 grams, or from 4 to 6 grams of fentanyl per kilogram of resin. In addition to Fenpney, it has been found to include, for example, synergists (especially piperonyl butoxide) at a concentration of 1 - 10 g/kg '2-5 g/kg or 3-4 g/kg in the resin. (PBO)) and insecticides are advantageous. A useful combination is 0.1-20 g of Fenpney and 1-10 g or 2-5 g of PBO, 1-1 g or 4-6 g of Fenpney and 2.5 g of /0/kg resin per kg of resin. Or 1-10 grams or 4-6 grams of Fenpney and 3-4 grams of ΡΒ 0 / kg resin. In terms of the yarn type resin in the fabric, the surface area concentration depends on the thickness of the woven fabric -15 - 201234961, but the optimum range is 180 to 1500 mg / m 2 ', for example, 400 to 1 000 mg / m 2 . This surface concentration can be maintained for a long time by controlling the movement of Fenpney to the surface. In some systems, the product has a thickness between 0.015 and 0.065 mm and a width between 1 and 6 mm 'and contains 0.1-20 g of Fenpney per kg of polymer in the resin (eg 2 to 10 or 3 to 8 g/kg 'corresponds to 0.2% to 1% or 0.3% to 0.8% 'all percentages are by weight) of flat yarn. For example, at least 90% of the polymer is a blend of HDPE and LLDPE. In some systems, a pesticidal fabric having a flat yarn as described above (for example, made by knitting or weaving) is provided, and the mobility of the fenpni in the resin is adjusted so that the surface concentration is 180 - 1 500. Milligram of Fenpney/m 2 fabric. For example, the resin comprises LLDPE and HDPE in a ratio of 80:20 to 30:70 or 70:30 to 30:70, wherein the resin has a density of 0.890 to 0.930 g/cm 3 when it has no insecticide. Wherein the density of the LLDPE is in the range of 0.88 to 0.91 g/cm 3 and the melt flow rate is between 1.5 and 1.7 g / 1 〇 minutes at a test load of 190 ° C and 2.16 kg, wherein The overall concentration of Fenpney is between 0.1-20 g/kg resin or 3-8 g/kg resin. Alternatively, the resin comprises a PBO having a concentration of from 1 to 10 or 3-4 grams per kilogram of resin. As already mentioned above, if the LLDPE content in the resin is high, the elongation becomes high, which makes it difficult to sew or knit such yarns. The following solutions are feasible when it is desired to have a high LLDPE content in the resin (e.g., 60%, or even 80-16 to 201234961%) in order to optimize product movement rate and durability, and when further manufacturing steps are required. In this case, the first filament having Fenpney is combined with a resin mainly comprising LLDPE into a single yarn, for example, a second filament made of a stronger material to obtain sufficient strength. For example, the stronger material is a blend of HDPE, or PP, or a polymer that is primarily HDPE or PP. Alternatively, the stronger material may comprise a polyester' wherein the term polyester includes the polyethylene terephthalate type. For example, 'this stronger filament does not contain insecticides, and it only has a stabilizing effect on the yarns. Further, the second filament comprises other insecticides or synergists, or both. A composition comprising a pyrethroid and a fenapril yarn or filament is disclosed in the above-mentioned International Patent Application No. WO2010/046348, which has a low density (for example mainly comprising LLDPE). The Fennip filaments in W020 1 0/〇463 48 have a high density because they mainly contain HDPE', in particular, HDPE is at least 6 times more than LLDPE. Although in principle, Fenpney can be used for mosquito nets, this is not ideal because the skin is at risk of being stimulated by Fenpney, except that Finkney is only used on the top of mosquito nets that are not normally touched. However, in view of this, it is more advantageous to find other ways to distribute Fenpney. As explained in more detail in International Patent Application WO 2009/059607, mosquitoes will find a place to rest after bloodsucking, usually on the wall of the house. Thus, it is advantageous if at least a portion of the wall is covered with a product having a pesticidal resin as explained above (e.g., in the form of a wall lining, typically a woven or non-woven fabric of circular or flat yarn). As explained in an international patent application -17- 201234961, in many African countries, a house contains walls, roofs and spaces between the upper edge of the wall and the roof (usually 0.2 to 0.4 meters high). Space) shack. The present invention also facilitates the weaving or non-woven fabrics, or films, or tarpaulins that cover the openings to prevent insects from entering the shed. In particular, fabrics having flat yarns (as described above) are useful for covering such wall coverings or openings. In some systems, the ethylene content is at least 80% or 90% by weight of the resin. The remainder may be composed of insecticides and various additives, such as other polymers, synergists, UV protectants, preservatives, anti-hydrolysis agents, detergents, tanning agents, impact modifiers, anti-fogging agents. , foaming agent, clarifying agent, nucleating agent, coupling agent, conductivity-preventing agent for preventing static electricity, stabilizer (such as antioxidant), carbon and oxygen radical scavenger and peroxide decomposing agent, flame retardant , release agent, optical brightener, diffusing agent, anti-blocking agent, anti-moving agent, mobile accelerator, foam forming agent, antifouling agent, antiscaling agent, thickener, wetting agent, plasticizer Adhesives or anti-adhesives, perfumes, pigments and dyes. This product is useful as a barrier against insects, protecting crops, animals or humans. In general, non-exclusive applications include mosquito nets, curtains, carpets and screens, door screens, tents, horse blankets, fabric or packaging mesh, bags, construction materials, furniture, leather, wires and cables. This product is also useful in the agricultural sector, for example, to protect crops and to protect animals. The product includes a mulch film and a mesh or membrane for use in greenhouses and animal sheds and cockroaches -18-201234961. Other uses include pig pens and fences for cattle, poultry and horses. For example, the product can act as a fence along or around the farm to prevent insects from entering the field or as a fence along or around the animal field to prevent insects from contacting the animal in the field. An example is presented in International Patent Application No. W00300382. The fence may be in the form of an upright mesh along or around the open area. Alternatively, the product can be used to cover crops, for example in the form of a film or a mesh. The product can also be used in greenhouses, for example in the form of a film or a mesh. Other special applications associated with the invention are - insecticidal blankets, such as those disclosed in WO 003055307, - air purifying canopies, such as those disclosed in WO2006024304, - tarpaulins, such as those disclosed in WO 3/063 5 87. Although the main object of the present invention is to prevent mosquitoes, it also includes controlling and/or combating various pests such as cockroaches, cockroaches, bed bugs, cockroaches, cockroaches, cockroaches, cockroaches, flies, termites, grasshoppers, moths, spiders, pelicans. , cockroaches, mites, mites, thrips, whiteflies, crickets, beetles and other flying and crawling insects. For the interval of the stated parameter 値, the end of the interval can optionally be included in the interval. Although the above resins are mainly useful for Fenpney, they can also be used for other insecticides', especially pyrazoles, other phenylpyrazoles and neonicotinoids, such as Dinotefuran. In addition, it may contribute to pyrethroids, organophosphates, urethanes, pyrroles and nicotinics, including deltamethrin, Permethrin and chlorfenapyr ( -19- 201234961
Chlorphenapyr)之類別。此殺蟲劑清單並不詳盡。這類樹 脂對於具有合倂之殺蟲劑從樹脂主體移動至樹脂表面的持 久產物有助益。 在殺蟲上更廣義之情況下,樹脂可被定義爲包含線性 低密度聚乙烯LLDPE和高密度聚乙烯HDPE,以及經由倂 入而分佈在整個樹脂中之殺蟲劑(例如呋蟲胺),其中 LLDPE與HDPE之間的比例係介於70:3 0與3 0:70之間, 且其中該樹脂未具有殺蟲劑時的密度爲0.8 90至0.930克/ 立方厘米。或者,該樹脂包含LLDPE與PP之摻合物,密 度爲0.890至0.930克/立方厘米。 上述之其他參數同樣適用於此廣義之情況中,尤其是 以下可選擇之面向 -密度爲0.890至0.93 0克/立方厘米; -LLDPE與 HDPE或 LLDPE與 PP之間的比例爲 80:20 至 30:70、或 70:30 至 30:70、或 70:30 至 40:60、或 70:30 至 50:50、或 6 5:3 5 至 40 : 60、或 65:3 5 至 5 5:45、 或 55:45 至 45:55; -LLDPE之密度係在0.88至0.91克/立方厘米之區間 內,例如在190t及2.16公斤的測試負載下,其熔體流動 速率介於1.5與1.7克/10分鐘之間; -HDPE之密度係在0.94至0.96克/立方厘米之區間 內,例如在1 90 °C及2.1 6公斤的測試負載下,其熔體流動 速率介於0.7與0.9克/10分鐘之間; -該樹脂包含濃度介於1-1〇克/公斤樹脂或1-1〇克/ -20- 201234961 公斤或4-6克/公斤樹脂之PBO; -該聚合物中90%爲聚乙烯; 除了廣義的情況外,各面向都可單獨使用或該面向可 以各種不同的組合使用,例如:如目前所主張之芬普尼的 專利範圍所界定者。 例如,廣義之產物可能包含下列面向:該樹脂包含比 例爲80:20和30:70之LLDPE和HDPE或PP,其中該樹 脂未具有殺蟲劑時的密度爲0.890至0.930克/立方厘米, 其中該LLDPE之密度係在0.88至0.91克/立方厘米之區 間內,且可選擇地,在1 9 0 °C及2 . 1 6公斤的測試負載下, 其熔體流動速率係介於1.5與1.7克/10分鐘之間。 上述之 LLDPE/HDPE的比率亦可應用於 LDPE/HDPE 及LDPE/PP摻合物。 具有各種殺蟲劑選項(例如呋蟲胺)之廣義產物亦適 用於上述之扁平紗、蚊帳和牆壁遮蓋物,以及上列之不同 的其他用途。 下文中,本發明就各種相互依存之面向描述。 面向1. 一種具有熱塑性聚合物樹脂之產物,其包含經 由倂入而分佈在整個樹脂中之芬普尼(Fipronil ),其中 該樹脂不具有殺蟲劑時的密度爲0.890至0.930克/立方厘 米。 面向2.如面向1之產物,其中該密度爲0.890至 0.920克/立方厘米。 面向3.如面向1或2之產物,其中該樹脂包含聚烯烴 -21 - 201234961 面向4.如面向3之產物,其中該樹脂中至少90 %爲 聚乙烯^ 面向5.如面向4之產物,其中該聚乙烯爲線性低密度 聚乙烯LLDPE與高密度聚乙烯HDPE之摻合物,其中 LLDPE與HDPE間之比例係介於80:20與30:70之間。 面向6.如面向5之產物,其中該LLDPE與HDPE間 之比例爲65:35至40:60 。 面向7.如面向5或6之產物,其中該LLDPE之密度 係在0.88至0.91克/立方厘米之區間內,且在190 °C及 2.16公斤之測試負載下其熔體流動速率介於1.5與1.7克 /1 〇分鐘之間。 面向8 .如面向3之產物,其中該樹脂包含線性低密度 聚乙烯LLDPE與聚丙烯PP之摻合物。 面向9.如前述任一面向之產物,其中芬普尼係以每公 斤樹脂包含2-10克之整體濃度提供於樹脂中。 面向10.如面向5之產物,其中該樹脂包含至少90% 之聚乙烯(其係爲比例爲80 : 20與40 : 60之LLDPE與 HDPE的摻合物),其中該樹脂未具有殺蟲劑時的密度爲 0.890至0.930克/立方厘米,其中該LLDPE之密度係在 0.88至0.91克/立方厘米之區間內,且在19(TC及2.16公 斤之測試負載下其熔體流動速率介於1.5與1.7克/10分鐘 之間,其中芬普尼係以每公斤樹脂2-10克之整體濃度提 供0 -22- 201234961 面向11.如面向5之產物,其中該摻合物之lldpe: HDPE比例爲70:30至40:60,且該包含芬普尼之樹脂的密 度小於0.920克/立方厘米。 面向12.如前述任一面向之產物,其爲其中之第一細 絲與第二細絲合股之合股紗形式,該第一細絲包含具有芬 普尼且主要爲LLDPE之樹脂,且其中該第二細絲爲穩定 之烯烴細絲且主要爲H D P E或P P。 面向1 3 ·如面向1 2之產物,其中該第二細絲不含殺蟲 劑。 面向1 4 ·如面向1 2或13之產物,其中該第二細絲包 含增效劑。 面向15.如前述任一面向之產物,其中該樹脂亦包含 與芬普尼組合之具有增效殺蟲作用的增效劑。 面向16.如面向15之產物,其中該樹脂包含濃度介於 1-10克/公斤之ΡΒΟ。 面向17.如前述任一面向之產物,其中該產物爲下列 群組中之至少一者:編織物、非織物,紡織品及網狀物。 面向18.如前述任一面向之產物,其中該產物爲蚊帳 〇 面向19.如面向1-16中任一項之產物’其中該產物係 厚度爲0.015至0.065毫米之扁平紗。 面向20.如面向19之產物,其中該厚度爲0.025至 0.05 0毫米。 面向21.如面向19或20之產物’其中該產物係寬度 -23- 201234961 爲1至6毫米之扁平紗。 面向22.如面向21之產物,其中該寬度爲2至5毫米 〇 面向23.如面向19-22中任一項之產物,其中該紗爲 編織物之一部分。 面向24.如面向19-22中任一項之產物,其中該紗爲 非織物之一部分。 面向25.如面向23或24之產物,其係與房子組合, 其中該織物爲該房子中至少一部分牆壁表面之遮蓋物。 面向26.如面向23或24之產物,其係與房子組合, 其中該織物爲該房子中牆壁上緣與牆壁上方屋頂間之開口 的遮蓋物之一部分。 面向27.如面向1-15中任一項之產物,其中該產物係 厚度爲0.015至0.065毫米且寬度爲1至6毫米之扁平紗 ,且其中該樹脂包含0.1-20克芬普尼/公斤聚合物且該樹 脂之90%爲包含超過50% LLDPE之聚乙烯。 面向28.—種保護作物、動物或人類對抗昆蟲的方法 ,其係經由提供如面向1 -27中任一項之產物來作爲對抗 昆蟲之屏障》 面向29.如面向28之方法’其中該方法包含提供沿著 或圍繞農場或動物領域之直立網狀物形式的該產物以防止 昆蟲進入該領域。 面向30.如面向29之方法’其中該方法包含在溫室中 提供爲網狀或薄膜形式之該產物以保護溫室中之植物對抗 -24- 201234961 昆蟲。 -25Chlorphenapyr) category. This list of pesticides is not exhaustive. Such resins are useful for the long-lasting products of the combined insecticide moving from the resin body to the surface of the resin. In the broader case of insecticidal, a resin can be defined as comprising a linear low density polyethylene LLDPE and a high density polyethylene HDPE, and an insecticide (eg, dinotefuran) distributed throughout the resin via intrusion, Wherein the ratio between LLDPE and HDPE is between 70:30 and 30:70, and wherein the resin has a density of 0.890 to 0.930 g/cc when it has no insecticide. Alternatively, the resin comprises a blend of LLDPE and PP having a density of from 0.890 to 0.930 grams per cubic centimeter. The other parameters mentioned above are equally applicable to the general case, in particular the following optional face-to-density is 0.890 to 0.93 0 g/cc; - the ratio between LLDPE and HDPE or LLDPE to PP is 80:20 to 30 : 70, or 70:30 to 30:70, or 70:30 to 40:60, or 70:30 to 50:50, or 6 5:3 5 to 40:60, or 65:3 5 to 5 5: 45, or 55:45 to 45:55; -LLDPE density is in the range of 0.88 to 0.91 g / cm3, for example, at 190t and 2.16 kg of test load, the melt flow rate is between 1.5 and 1.7 grams Between 10 and 10 minutes; - HDPE density is in the range of 0.94 to 0.96 g / cm3, for example, at 1 90 ° C and 2.1 6 kg of test load, the melt flow rate is between 0.7 and 0.9 g / Between 10 minutes; - the resin contains PBO at a concentration of 1-1 g / kg resin or 1-1 g / -20 - 201234961 kg or 4-6 g / kg resin; - 90% of the polymer Polyethylene; in addition to the broad case, each aspect can be used alone or the combination can be used in various combinations, for example, as currently claimed by Finkney's patent scope Makers. For example, a broad product may comprise the following: the resin comprises LLDPE and HDPE or PP in a ratio of 80:20 and 30:70, wherein the resin has a density of 0.890 to 0.930 g/cc when not having an insecticide, wherein The density of the LLDPE is in the range of 0.88 to 0.91 g/cm 3 and, optionally, the melt flow rate is between 1.5 and 1.7 at a test load of 19 ° C and 2.16 kg.克/10 minutes between. The above ratio of LLDPE/HDPE can also be applied to LDPE/HDPE and LDPE/PP blends. The broad product with various insecticide options (e.g., dinotefuran) is also suitable for the flat yarns, mosquito nets and wall coverings described above, as well as the other uses listed above. In the following, the invention is described in terms of various interdependent aspects. Aspect 1. A product having a thermoplastic polymer resin comprising Fipronil distributed throughout the resin via intrusion, wherein the resin has a density of 0.890 to 0.930 g/cc when not having an insecticide . Aspect 2. For a product oriented to 1, wherein the density is from 0.890 to 0.920 g/cc. Or 3. The product according to 1 or 2, wherein the resin comprises polyolefin-21 - 201234961 facing 4. The product facing 3, wherein at least 90% of the resin is polyethylene ^ facing 5. For example, the product facing 4 The polyethylene is a blend of linear low density polyethylene LLDPE and high density polyethylene HDPE, wherein the ratio between LLDPE and HDPE is between 80:20 and 30:70. For 6. For products oriented to 5, the ratio between the LLDPE and HDPE is 65:35 to 40:60. Aspect 7. For products oriented to 5 or 6, wherein the LLDPE has a density in the range of 0.88 to 0.91 g/cm 3 and a melt flow rate of 1.5 at 190 ° C and a test load of 2.16 kg. 1.7 g / 1 〇 minutes. Aspect 8. A product oriented to 3, wherein the resin comprises a blend of linear low density polyethylene LLDPE and polypropylene PP. Aspect 9. The product of any of the foregoing, wherein the Fenpney is provided in the resin in an overall concentration of from 2 to 10 grams per kilogram of resin. Aspect 10. The product of 5, wherein the resin comprises at least 90% polyethylene (which is a blend of LLDPE and HDPE in a ratio of 80:20 and 40:60), wherein the resin does not have an insecticide The density is 0.890 to 0.930 g/cm 3 , wherein the density of the LLDPE is in the range of 0.88 to 0.91 g/cm 3 , and the melt flow rate is 1.5 at a test load of 19 (TC and 2.16 kg). Between 1.7 g/10 min, wherein Fenpney is supplied at a total concentration of 2-10 g per kg of resin. 0 -22- 201234961 is oriented to 11. For a product oriented to 5, wherein the ratio of lldpe: HDPE of the blend is 70:30 to 40:60, and the density of the resin containing Fenpney is less than 0.920 g/cm 3 . Faced with the product of any of the foregoing, which is the first filament and the second filament In the form of a plied yarn, the first filament comprises a resin having a fentanyl and predominantly LLDPE, and wherein the second filament is a stable olefin filament and is predominantly HDPE or PP. Facing 1 3 · as facing 1 2 a product in which the second filament does not contain an insecticide. Facing 1 4 · as facing 1 2 The product of 13, wherein the second filament comprises a synergist. Aspect 15. The product of any of the foregoing, wherein the resin further comprises a synergist having synergistic insecticidal action in combination with Fenpney. A product oriented toward 15, wherein the resin comprises a concentration of between 1 and 10 grams per kilogram. Aspect 17. The product of any of the preceding aspects, wherein the product is at least one of the group consisting of: a braid, Non-woven fabric, woven fabric and mesh. Aspect 18. The product of any of the foregoing, wherein the product is a mosquito net 〇 face 19. The product of any one of 1 to 16 wherein the product has a thickness of 0.015 to 0.065 A millimeter flat yarn. Oriented to a product such as 19, wherein the thickness is 0.025 to 0.05 mm. Facing 21. such as the product facing 19 or 20 'where the product width -23 - 201234961 is 1 to 6 mm Flat yarn. Oriented to a product such as 21, wherein the width is 2 to 5 mm, and the surface is a product of any one of 19 to 22, wherein the yarn is a part of the braid. a product according to any one of 19-22, wherein the yarn is One part of the fabric. Face 25. A product such as facing 23 or 24, which is combined with a house, wherein the fabric is a covering of at least a portion of the wall surface of the house. Aspects 26. For products facing 23 or 24, a combination of a house, wherein the fabric is part of a cover of an opening between the upper edge of the wall and the roof above the wall. Aspect 27. The product of any of 1 to 15, wherein the product has a thickness of 0.015 to 0.065 Flat yarns of millimeters and widths of 1 to 6 mm, and wherein the resin comprises 0.1-20 grams of Fenpney/kg polymer and 90% of the resin is polyethylene comprising more than 50% LLDPE. A method for protecting crops, animals or humans against insects by providing a product as claimed in any one of 1 to 27 as a barrier against insects. 29. Facing a method of 28, wherein the method This product is provided in the form of an upright web that is provided along or around the farm or animal field to prevent insects from entering the field. Aspect 30. The method of 29, wherein the method comprises providing the product in the form of a mesh or a film in a greenhouse to protect plants in the greenhouse against -24-201234961 insects. -25