200845894 九、發明說明 【發明所屬之技術領域】 本發明係關於一種用於提供無生命殺蟲材料，例如織 物或網片之方法，該材料具有聚合物基質，於其內可遷移 地ί爹入至少一種協乘劑（synergist)。本發明也關於此種 ' 無生命材料。 【先前技術】 許多不同昆蟲都會作爲影響人類的傳染性疾病之媒體 及傳播者而造成實質的問題，而有極度的努力投入於控制 此等昆蟲。許多努力業經專注在控制屬於雙翅目 (Diptera)(涵蓋蚊、蚋、黑蠅、采采蠅及其他叮蠅）、 . 半翅目 （Hemiptera)(涵蓋臭蟲）及蚤目 (Siphonaptera )(涵蓋跳蚤）之昆蟲。控制此等蟲之方 法包含牆壁內面及表面處理，空氣噴霧，以及窗簾及蚊帳 • 之浸漬。窗簾及蚊帳之浸漬相較於房子之表面噴霧具有要 處理的部位遠較爲減少之優點。蚊帳之浸漬會減少睡覺期 間之騷擾且即使該網由於使用而稍微撕裂也證明係有效 者。 用除蟲菊酯（pyrethroid )浸漬的網片或織物之效用 部分建基於此等殺蟲劑之快速殺蟲性質，但也建基於大部 分此等殺蟲劑固有的驅除作用。試驗證明浸漬蚊帳可使進 入房間的蚊子數目減少到高達75%。由此，該網亦提供對 在同一房間睡覺的其他人提供某些保護，即使彼等沒有被 -4 - 200845894 蚊帳蓋住亦然。 用網進行的大規模野外實驗證明彼等可降低瘧疾感 比例，如以總兒童死亡率直接或間接測量者。據此 WHO，世界衛生組織，業已選擇網片作爲對抗瘧疾及其 蚊子產生疾病之活動所用之優先領域。 在某些區域中，蚊子對除蟲菊酯具有抗性。此等抗 類型之一，所謂的擊倒抗性（knock down resistance) KDR，也提供對驅除作用之抗性。此讓蚊子在網上休息 長時間且因此累積致命劑量的殺蟲劑，但也給蚊子在死 叮人之可能性。另一種抗性形式係代謝抗性，此類昆蟲 有抵消殺蟲作用之酵素。於此情況中，可十分有利地添 協乘劑，例如糊椒基丁氧化物（piperonyl butoxide (PBO )於網中。 使用協乘劑於和蚊帳或織物相關的塗料中之舉已揭 於Ye Qian之中國專利申請CN1099825，Mooney 等人 國際專利申請WO 90/1 4006、Karl等人之W006 1 28870 及Koradin等人之WO06 1 28867、Fujita等人之日本專 申請 JP 02-062804、 JP 04-185766、 JP 06-346373、及 07-3 1 6003、Samson 之 US 5,503,9 1 8、及 Hataipitisuk 美國專利申請第US20070009563A1號中。將協乘劑與 蟲劑一起摻加到聚合物基質內之舉係揭示在Albright等 之美國專利申請第 US2006028 895 5 號及 K.ellerby Fletchei·之國際專利申請w〇 00/40084之中。 一般及全世界的蚊帳用較佳材料係棉及聚酯。由於 染 他 藥 或 更 刖 具 加 ) 示 之 、 利 JP 之 殺 人 和 彼 -5- 200845894200845894 IX. INSTRUCTIONS OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for providing an inanimate insecticidal material, such as a fabric or a mesh, having a polymer matrix in which it can be migrated At least one synergist (synergist). The invention also relates to such 'inanimate materials'. [Prior Art] Many different insects cause substantial problems as media and communicators of infectious diseases affecting humans, and there is an extreme effort to control these insects. Many efforts have focused on controlling Diptera (covering mosquitoes, crickets, black flies, tsetse flies and other ticks), Hemiptera (covering bed bugs), and Siphonaptera (covering) Flea) insects. The methods of controlling such insects include the inner surface and surface treatment of the walls, air spray, and the impregnation of curtains and mosquito nets. The impregnation of curtains and mosquito nets has the advantage of being reduced from the surface of the house to be treated. The impregnation of the mosquito nets reduces harassment during sleep and proves to be effective even if the net is slightly torn due to use. The effectiveness of the mesh or fabric impregnated with pyrethroid is based on the fast insecticidal properties of such insecticides, but is also based on the repellent effect inherent in most of these insecticides. Tests have shown that impregnated mosquito nets can reduce the number of mosquitoes entering the room by up to 75%. As a result, the network also provides some protection for others sleeping in the same room, even if they are not covered by a mosquito net of -4 - 200845894. Large-scale field trials using nets have shown that they can reduce the proportion of malaria, such as those measured directly or indirectly by total child mortality. According to this WHO, the World Health Organization has chosen mesh as a priority area for activities against malaria and its mosquito-borne diseases. In some areas, mosquitoes are resistant to pyrethrins. One of these resistance types, the so-called knockdown resistance KDR, also provides resistance to repellent effects. This allows the mosquito to rest online for a long time and thus accumulates a lethal dose of pesticide, but also gives the mosquito the possibility of dying. Another form of resistance is metabolic resistance, and such insects have enzymes that counteract insecticidal effects. In this case, it is very advantageous to add a synergistic agent, such as piperonyl butoxide (PBO) in the web. The use of synergistic agents in coatings related to mosquito nets or fabrics has been disclosed in Ye. Qian's Chinese patent application CN1099825, Mooney et al., international patent application WO 90/1 4006, Karl et al., W006 1 28870, and Koradin et al., WO06 1 28867, Fujita et al., Japan, JP 02-062804, JP 04- 185766, JP 06-346373, and 07-3 1 6003, Samson's US 5, 503, 9 1 8 and Hataipitisuk US Patent Application No. US20070009563A1. The synergistic agent is incorporated into the polymer matrix together with the insecticide. It is disclosed in U.S. Patent Application No. US2006028 895 5 to Albright et al. and K.ellerby Fletchei International Patent Application No. 00/40084. The preferred materials for mosquito nets in general and worldwide are cotton and polyester. He medicine or more sputum plus) shows that, the murder of JP JP and his-5 - 200845894
等的較佳強度，彼等的似棉觸感及低可燃性，WHO業已 選擇聚酯網爲蚊帳之有利材料。與此相反者，尼龍網係可 燃者’且聚乙烯網，如具有商品名稱 〇lySet®之 Sumitomo®網係硬挺者。該〇iyset®網係基於一種單絲聚乙 烯（polyethene )纖維，其中在纖維形成中有摻入殺蟲 劑。由於聚酯之250 t高熔化溫度對於除蟲菊酯具破壞 性’因此此種將殺蟲劑摻加到纖維內之方法係已知不能用 於聚酯（聚對苯二甲酸乙二酯（PET ))纖維者。For better strength, such as cotton feel and low flammability, WHO has chosen polyester mesh as a favorable material for mosquito nets. In contrast, nylon mesh is a flammable person's polyethylene mesh, such as the Sumitomo® mesh fastener with the trade name 〇lySet®. The 〇iyset® mesh is based on a monofilament polyethene fiber in which an insecticide is incorporated into the fiber formation. Since the 250 t high melting temperature of polyester is destructive to pyrethrins, the method of incorporating insecticides into fibers is known to be unsuitable for polyester (polyethylene terephthalate ( PET )) Fiber.
Skovmand的WO 0 1 /3 7662揭示浸漬網片或織物，其 係用於殺死昆蟲或壁蟲及/或驅除昆蟲或壁蟲，其包含殺 蟲劑，較佳者除蟲菊酯，和膜形成性組份，其藉由形成防 水膜而減低殺蟲劑組份自網片或織物的洗除和降解。膜形 成性組份除了聚合物骨架固定劑之外還包括石蠟油或蠟衍 生物、矽衍生物、矽油或躐衍生物，及聚氟碳衍生物。網 片或織物係經由添加殺蟲劑及/或驅蟲劑的溶液或水乳液 及膜形成性組份而浸漬。殺蟲劑係在織物或網片的浸漬程 序中溶解於有機溶劑內。 在WO 0 1 /3 7 662中揭示的組成物及浸漬方法業經用爲 Vestergaard Frandsen®的商品名稱Permanet®蚊帳之基本處 方。此網顯示現今全世界最高標準之耐洗性蚊帳且爲與蚊 帳有關的WHO贊助活動中之較佳蚊帳。 因此，想要提供一種高標準之織物或網片，其可有效 地對抗殺蟲劑耐性且其具有與PermaNet®—樣成功的耐洗 性之潛力。 -6- 200845894 【發明內容】 因此，本發明之目的爲提供一種改良的無生命殺蟲材 料，特別是織物或網片，其具有殺蟲浸漬及協乘劑。 '此目的係用無生命殺蟲材料達到，例如用織物或網 ~ 片’其具有可遷移地摻入至少一種協乘劑之聚合物基質。 該基質之表面經用含有至少一種殺蟲劑的塗料塗覆。此目 的也經由一種製造無生命殺蟲材料的方法達成，該材料爲 例如織物或網片，其在用含有至少一種殺蟲劑的塗料予以 塗覆之前，具有可遷移地摻入至少一種協乘劑之聚合物基 質。 藉由於聚合物基質中摻加具有遷移至基質表面的能力 . 之協乘劑’提供一種產品，其對用於塗覆基質的最後殺蟲 組成物開啓多種選擇。例如，其可用耐洗性聚合物膜塗 覆，如PermaNet®所用者。 φ 原則上，可以將一或更多種殺蟲劑與其他協乘劑摻加 在聚合物基質中。於此情況中，重要的是要考慮基質中的 協乘劑或多種協乘劑之遷移速度及其他殺蟲劑或多種殺蟲 劑之遷移速度。例如，可經由選擇性操作的遷移促進劑及 ' 遷移抑制劑之適當選擇予以調節。 爲了使協乘劑有效，必須確保該協乘劑也能從基質表 面遷移至塗層之表面。於此情況中也可使用恰當的遷移促 進劑及/或遷移抑制劑。 一種較佳的組合係下述聚合物基質，其具有摻加在基 200845894WO 0 1 /3 7662 to Skovmand discloses impregnated mesh sheets or fabrics for killing insects or wallworms and/or repelling insects or wallworms, which comprise insecticides, preferably pyrethrins, and membranes. A forming component that reduces the washing and degradation of the pesticide component from the web or fabric by forming a water repellent film. The film-forming component includes, in addition to the polymer skeleton fixing agent, a paraffin oil or a wax derivative, an anthracene derivative, an eucalyptus oil or an anthracene derivative, and a polyfluorocarbon derivative. The mesh or fabric is impregnated by the addition of a solution or aqueous emulsion of an insecticide and/or insect repellent and a film-forming component. The insecticide is dissolved in an organic solvent in the impregnation process of the fabric or mesh. The composition and impregnation method disclosed in WO 0 1 /3 7 662 is used as the basic part of the trade name Permanet® mosquito net of Vestergaard Frandsen®. This network shows the world's highest standards of washable mosquito nets and is the preferred mosquito net for WHO-sponsored activities related to mosquito nets. Therefore, it is desirable to provide a high standard of fabric or mesh that is effective against insecticide resistance and that has the potential for successful washability with PermaNet®. -6- 200845894 SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an improved inanimate insecticidal material, particularly a fabric or mesh, which has insecticidal impregnation and co-agents. 'This object is achieved with an inanimate insecticidal material, for example with a fabric or mesh' which has a polymer matrix which mimetically incorporates at least one synergistic agent. The surface of the substrate is coated with a coating containing at least one insecticide. This object is also achieved by a method of making an inanimate pesticidal material, such as a woven or mesh sheet, having a migratory incorporation of at least one synergistic effect prior to coating with a coating comprising at least one insecticide. The polymer matrix of the agent. By the addition of a polymer matrix having the ability to migrate to the surface of the substrate. The synergist' provides a product that opens up a variety of options for the final pesticidal composition used to coat the substrate. For example, it can be coated with a washable polymer film, such as those used by PermaNet®. φ In principle, one or more insecticides and other co-agents can be added to the polymer matrix. In this case, it is important to consider the rate of migration of the multi-agent or multi-agents in the matrix and the migration rate of other insecticides or insecticides. For example, it can be adjusted via a selectively selected migration promoter and a suitable selection of a migration inhibitor. In order for the synergist to be effective, it must be ensured that the synergistic agent can also migrate from the surface of the substrate to the surface of the coating. Suitable migration promoters and/or migration inhibitors can also be used in this case. A preferred combination is a polymer matrix having a blending base 200845894
質材料中的協乘劑例如PBO，但在基質中沒有殺蟲劑，且 具有殺蟲塗料，其係在聚合物基質表面之至少一部分上’ 例如含有第滅寧（del tame t hr in )者。於此方面，必要者 爲該基質係以無殺蟲劑形式提供但在初始狀態中有協乘 劑。因此，在另一具體實例中，到至少塗覆程序爲止，該 無生命材料之基質係無殺蟲劑者。雖然，該基質於初始狀 態中沒有摻加殺蟲劑，於後面的塗覆步驟後，殺蟲劑可從 塗層遷移至聚合物基質內，此仍在本發明範圍之內。因 此，在另一具體實例中，該基質具有初始無殺蟲劑之固體 狀態，其含有至少一種協乘劑，且其中其具有最後之固體 狀態，其含有殺蟲塗層。 在一具體實例中，基質可含有一或更多種協乘劑，例 如PBO，但無殺蟲劑，而該塗層不包含協乘劑但包括一或 多種殺蟲劑，例如第滅寧。 在一實用具體實例中，藉由將熔融熱塑性聚合物擠壓 通過擠壓噴嘴形成聚合物基質。協乘劑係透過擠壓噴嘴之 內或上游處的一通道添加至熔融聚合物中。此可能在某些 組合中具有關鍵性，特別是，若該基質係由聚酯（一種用 於纖維及網片之較佳材料）製成時。所以如此係因爲聚酯 之熔化溫度係約25 0°C，遠超過協乘劑如PB 0保持完整的 溫度。不過，協乘劑，例如PB0，的分解程度不僅取決於 溫度，而且也取決於P B 0暴露於該溫度之時間，因該分 解程序係逐漸進行之故。瞭解此點之下，也業經識別，且 實驗地證實協乘劑，如PB0，可耐高溫，例如1 8 0 °C或更 200845894 高，高於通常所認爲的分解溫度，若暴露 保持較短。 因此，爲了減少暴露於高溫之時間， 特別的擠壓噴嘴之原理。此原理係一具有 過該通到將協乘劑在擠壓程序中添加到熔 中該通道係裝設在噴嘴出口之上游短距離 術語“短距離”指一距離其導致協乘劑溫度 度下逝去之時間內在擠壓基質內留下仍爲 劑。例如，該距離可經選擇以在協乘劑中 加及協乘劑對此溫度增加的最長暴露時間 度及最長時間係受預定的上値所限制。 此“足量”是多少係取決於協乘劑及 度。在某些情況中，可接受9 9 %之分解， 劑仍在長期抵消殺蟲劑抗性的有效量範圍 情況中，可能接受低於90%之分解率。因 一種將協乘劑摻加於熱塑性聚合物內之方 聚合物之熔化溫度係遠超過協乘劑的分解 實驗中，令人驚訝地發現對於聚酯，不管 壓溫度，仍有超過5 0%之協乘劑保留完整 .在一較佳具體實例中，該通道係裝設 例如在距噴嘴出口數毫米或公分之內。此 進入噴嘴時其首先接受到聚合物之溫度。 被環狀協乘劑供給導管所圍繞，該導管將 著聚合物流之整個邊緣透過噴嘴注射到熔 於該溫度之時間 業經發明出一種 通道之噴嘴，透 融聚合物內，其 處。在此文中， 之增加且在此溫 足量的完整協乘 產生最大溫度增 ，其中該最大溫 可接受的分解程 若1 %剩餘協乘 內之時。在其他 此，本發明提供 法，其中不管該 溫度之事實。在 高於250°C的擠 在擠壓的側邊， 暗示著當協乘劑 例如，噴嘴可能 協乘劑實質地沿 融聚合物內。 -9- 200845894 此亦導致在注入前冷卻協乘劑之可能性，使得自聚合 物的熱攝取所導致之協乘劑溫度增加可加速聚合物硬化及 冷卻。此外，經擠壓的聚合物可在擠壓噴嘴下游短距離處 積極地冷卻，例如藉由冷空氣注射。 該製程，其中基質係經塗覆者，可由在WO 0 1 /3 7662 中揭不的關於織物或網片之浸漬以給予殺蟲及/或驅除性 質之方法達到，其包括： a)製備含殺蟲劑及/或驅蟲劑和膜形成性組份的溶液 或水乳液，該膜形成性組份可經由在無生命材料之表面 上，例如圍繞著纖維，形成耐水和隨意地抗油性膜而減少 殺蟲劑組份從該無生命材料洗掉和降解；及將該溶液或乳 液施加到該無生命材料，或 b )製備含殺蟲劑及/或驅蟲劑的第一溶液或水乳液及 製備膜形成性組份的第二溶液或水乳液，該膜形成性組份 可經由在無生命材料之表面上，例如圍繞著纖維，形成耐 水和隨意地抗油性膜而減少殺蟲劑組份從該無生命材料洗 掉和降解；及將該殺蟲劑及/或驅蟲劑的溶液或水乳液施 加到該無生命材料，然後將該膜形成性組份的溶液或乳液 施加到該無生命材料， 其中該膜形成性組份包含聚合物骨架固定劑及一或多 種選自石蠟油或躐、矽、矽油或鱲，及聚氟碳，或其衍生 物組成之群組中之組份。 在另一具體實例中，該膜形成性組份包括選自石躐油 或鱲、砂、砂油或蠟、及聚氟碳、或其衍生物組成的群組 -10- 200845894 中之組份的混合物’較佳者爲聚氣碳和石續油之混合物或 聚氟院基和聚矽氧院之混合物。例如，該砂油或躐係聚砂 氧烷。 在另一具體實例中，係將聚氟碳、石躐油或躐、较、 矽油或蠘、或其衍生物附加於聚合物骨架。例如，該聚合 物骨架固定劑係一種樹脂、聚胺基甲酸酯或聚丙烯酸系。 在一較佳具體實例中，該膜形成性組份包括一種聚合 物骨架固定劑，其可在該無生命材料之乾燥程序或固化程 序或乾燥和固化程序中聚合成在聚合物骨架上具有聚氟碳 側鏈之膜。 組合的溶液或乳液，其中在施加在無生命材料之前將 該殺蟲劑組成物摻加到該耐洗劑之內，可用爲浸漬用組成 物或爲浸漬用組成物的一部分，以儘量地與其他組份混 合。此類組份可爲其他殺蟲劑、協乘劑、防u V劑、防腐 劑、清潔劑、塡充劑、衝擊改質劑、防霧劑、發泡劑、澄 清劑、晶核劑、偶合劑、傳導性提高劑以防靜電、安定劑 諸如抗氧化劑、碳及氧自由基清除劑和過氧化物分解劑及 類似者、耐燃劑、脫模劑、光學增亮劑、展佈劑、防堵 劑、抗遷移劑、遷移促進劑、泡沬形成劑、防污劑、防垢 劑、增稠劑、其他殺生物劑、潤濕劑、增塑劑、黏著劑或 防黏著劑、芳香劑、顏料及染料及其他液體包括水或有機 溶劑。 該浸漬組成物亦可經部分地吸收在吸收性織物中，其 可延長殺蟲活性及改良耐洗性。於該纖維爲多絲紗的情況 -11 - 200845894 中，殺蟲劑可能截留在絲間，導致此經截留的殺蟲劑之更 高耐洗性。本發明方法可用於手浸泡，不過，其經證明特 別適用於工業生產。 本發明保護性組成物係關於可給出耐水性或耐水和油 性之單組份或多組份混合物。可添加一或數種清潔劑以增 加藥劑對織物之可濕性，以穩定化所用乳液，或增加固定 作用。可使用交聯劑或催化劑以增加固定作用。該殺害蟲 組成物及保護性組成物可依次地（方法a )或在一程序中 (方法b)添加。藉由最後通過熱表面諸如熨斗或熱滾筒 或用熱空氣加熱，可獲得改良的整飾及固化。 聚合物骨架在WO 0 1 /37662中有更詳細的討論。 可與本發明相關地使用之其他殺蟲塗料係經揭示在 Liu等人之 WO 2006/092094中者，其關於網片/織物塗 料，含有殺害蟲劑、水性黏著劑、如水性聚胺基甲酸酯乳 膠或聚丙烯酸酯乳膠、及交聯劑、如環氧聚合物交聯劑。 許多不同調合物-亦可與本發明相關地應用者-經揭示在 WO 2006/092094，其，更特別地，揭示一種用於驅除及殺 死蚊子/昆蟲的整飾（finishing)液體，其配方（基於質量 百分比）包括： 殺蟲劑及/或驅蟲劑 0.05%-40.00% 黏著劑 5.00%-40.00% 交聯劑 0 · 0 2 5 % -1 . 5 0 % ;及 餘者爲水，所有組份的總量爲100%。 該WO 2006/092094中之殺蟲劑係一種具有有效含量 -12- 200845894 1 - 5 0 %之水性殺害蟲劑，該水性殺害蟲劑係從一或二種下 列物質製備成者：第滅寧、賽扶寧（cyfluthrin )、賽洛寧 (cyhalothrin)、順-賽滅寧（cis-cypermethrin)、百滅 寧（permethrin)及依芬寧（etofenpox); 在該W0 2006/092094中的驅蟲劑係一種具有有效含 量1 - 5 0 %之水性驅蟲劑，且該水性驅蟲劑係從一或二種下 列物質製備者：二乙基甲苯甲醯胺（diethyltoluamide， DEET)、苯二甲酸二甲酯（Dimethyl Phthalate )及百滅 寧； 在W0 2006/092094中的該殺害蟲劑和驅蟲劑之水性 劑型包括一或二種下列劑型：可濕粉、水可分散粉、水可 分散的懸浮液、水可分散的片劑、水中乳液、微膠囊懸浮 液、及水可分散性顆粒； 該WO 2006/092094中之黏著劑係一種具有40-50%固 體含量之水性黏著劑，其含有一或二種下列物質：聚丁二 烯乳膠、水性聚胺基甲酸酯乳膠、聚丙烯酸乳膠、聚丙烯 酸酯乳膠或醋酸乙烯酯乳膠； 該WO 2006/092094中之交聯劑含有一或二種下列物 質：環氧聚合物交聯劑、甲基-醚化六羥甲基蜜胺樹脂初 級縮合交聯劑、多官能性氮丙啶交聯劑、各種羥甲基交聯 劑、由羥乙基及環氧基組成之交聯劑、及環氧氯丙烷和己 二胺的聚縮合物之醋酸酯交聯劑。 較佳地，與本發明相關的殺蟲劑係一種除蟲菊酯，較 佳者第滅寧或百滅寧，但也可用其他除蟲菊酯，如在w〇 •13- 200845894 01/37662中揭示的表單。不過，本發明也可與胺基甲酸酯 或有機磷酸酯相關地用於浸漬組成物中。可能的殺蟲劑之 更廣泛表單出現在WO 01/37662或WO 06/128870中且含 有驅蟲劑之例子。 此外，術語殺蟲劑也應用於本發明浸漬組成物之殺蟲 劑組合物。例如，爲了也可對抗耐藥性昆蟲，可將除蟲菊 酯與胺基甲酸酯或有機磷酸酯組合。而且，可將二或更多 種殺蟲劑施用在網片或織物的不同部分上，例如藉由印刷 或噴布技術，不混合且均勻地使用，其針對毒物學及登記 理由可爲有益者。在使用網片於大量活動中之時，替代性 或補充性殺蟲劑也可爲具有絕育作用之殺蟲劑因此使蚊子 不孕及避免有蚊子後代。此類殺蟲劑可爲苯甲醯脲群或三 哄類。 其他可能組合包含如揭示於 WO 06/1 27407中之美氟 綜（metaflumizone )、如揭示於 WO 0 6 1 2 8 8 7 0 中之 N-芳 基肼或如揭示於WO 06128867中之1-苯基三唑，例如與 除蟲菊酯組合。 此外，或替代地，可將殺蟲劑與協乘劑在塗料中組 合，例如丁氧化糊椒基、亞颯、增效醛（Tropital )、增 效特 （Bucarpolate )、愛殺松 （ethion )、佈飛松 (profenofos )、或大滅松（dimethoate )、糊椒基環壬 烯、TPP、順丁烯二酸二甲酯、NIA-16388 (NIA) 、s_ 421 、 MGK-264 ( 雙環庚烯二羰醯亞胺 (bicycloheptenedicarboximide ) ) 、S，S，S .三丁基三硫代 200845894 磷酸酯（DEF ) 、-N-辛基三庚烯二羰醯亞胺、芝麻素 (sesamin )、芝麻素酚 （sesamolin )、或增效菊 (sesamex ) 〇 與本發明有關的塗料所用其他替代物經揭示在 US20070095 63中，其中根據本發明不同具體實例的溶液 之配方包含如下4部分：i•來自除蟲菊酯群組之殺蟲劑諸 如弟滅宇、益化利（esfenvalerate)、依芬寧、必分亭 (biphenthrin )、百滅寧及賽洛寧，彼等皆爲快速活化性 且具有高沸點。2 ·線穩定化增進劑，例如，全氟丙烯酸 酯、樹脂、黏著劑、及聚丙烯酸酯。3.增稠劑諸如澱粉、 樹膠、和二氧化鈦。4 ·溶劑，例如，水。 無生命材料 在下文中，給出本發明範疇中的無生命材料之多個例 子：選自紗、纖維、織物、針織-商品、不織物、網片材 料、箔、帆布（tarpaulin )組成之群組中之紡織品材料或 塑膠材料及塗料組成物。該網片材料，例如，可能藉由圓 形針織或經織製備，或藉由縫合數部分的網片以獲得所欲 網片。該紡織品材料或塑膠材料可從多種天然及合成纖維 製成’且也呈編織或不織形式的紡織品混合物，針織品、 紗或纖維等形式。用於合成纖維之材料爲，例如，聚醯 胺、聚酯、聚丙烯腈、聚烯烴例如聚丙烯或聚乙烯、聚四 氟乙烯（Tefl〇n )。聚胺、聚烯烴及聚酯、例如聚對苯二 甲酸乙二酯、皆爲最佳者。 -15- 200845894 紡織品材料或塑膠材料之應用包含床單、床墊、枕 頭、墊子、椅墊、窗簾'壁覆蓋物、地毯及窗、碗櫃及門 的屏幕、地工紡織品、帳篷、鞋子之內鞋底、衣服、諸如 襪子、長褲、襯衫、制服、馬毯、蚊帳、農業及葡萄栽培 中的罩子；用於包裝之織物或網片、包裝袋；食物、種子 及飼料用之容器；紙張；建築材料、傢倶、皮革、乙烯樹 脂物件、電線及電纜。 Φ 最佳的是自聚酯製成之織物或網片，因爲聚酯網片具 有類似棉的感覺及低可燃性之故。此等也是爲何此等網片 係WHO偏愛之理由。於此方面，要強調本發明係針對 75、100或150丹尼（denier) 36條絲之第滅寧浸漬的聚 酯網片相關之應用（如Permanet 2.0 )的一具體實例。 與本發明有關的其他特別應用爲， -圍牆，諸如在WO〇3〇〇3 827中所揭示者， -殺害蟲的毯子，諸如在W003055307中所揭示者， φ -用於食物之保護性蓋子及水貯存容器，諸如在 W003090532中所揭示者， -空氣清淨罩子諸如在W02006024304中所揭示者， -帆布諸如在WO03/063 5 87中所揭示者。 昆蟲 本發明之目的控制及/或對抗各種害蟲，諸如壁蝨、 蟑螂、床舖臭蟲、蟎、跳蚤、虱子、水蛭、家蠅、蚊子、 白蟻、螞蟻、蛾、蜘蛛、蝗蟲、蟋蟀、蠢魚、及其他會飛 -16- 200845894 及爬行的昆蟲。 施用程序 殺蟲浸漬組成物之施用可經由壓染、深入洗滌、噴 霧、印刷等技術完成’例如轉印或如噴墨印刷。 【實施方式】 圖la圖解說明一種無生命物體1，其在基質3中有協 乘劑2 -在文體上以點2舉例示出，不過協乘劑2可在基質 中均勻地分布。該基質3係用含有殺蟲劑5的膜4塗覆-在文體上以三角形4舉例示出，不過該殺蟲劑可能在膜塗 層中均勻地分布。當基質3用此膜4塗覆時，協乘劑2會 遷移透過膜4至無生命物體1之表面6，其在圖ib中示 出。而且’殺蟲劑5會遷移至表面6，使得表面6含有殺 蟲劑5 ’和協乘劑2 ’供昆蟲攝取。此外，如圖1 b所示者， 若基質係可讓殺蟲劑5遷移者，則殺蟲劑5 ”可自膜4遷 移到基質3中。 圖2圖解說明一基質3，其呈用膜4塗覆的纖維之形 式。該圖式只示出原理且不按比例繪出。基質，諸如纖維 之塗層可能呈連續膜之形式，如圖2所示，或該塗層可成 片段形式，如圖5所示。若使用膜形成性組份時，此類片 段可呈膜形式。藉由，例如噴霧技術可達到此片段式的塗 層。 下面，要更詳細地說明產物及擠壓程序。圖3圖解說 -17- 200845894 明一擠壓機，其具有機殼8，其內活塞9沿著擠壓噴嘴l〇 方向朝前移動，因而使熔融聚合物基質4被推動擠壓產生 擠壓產物1 1，例如聚合物纖維。於噴嘴1 0上游短距離 處’導管12連接至機殼8用以從槽13送入協乘劑2。協 乘劑進入熔融聚合物4且從進入機殼8直到擠壓聚合物冷 卻下來所經期間內，都暴露於熔融聚合物之高溫。 應提及者，在此點上，使用活塞的擠壓原理可容易地 用可擠壓熔融聚合物的擠壓螺桿或其他工具予以取代。而 且，作爲替代者，導管12可爲噴嘴本身的一部分，唯一 要求者爲PBO進入熔融聚合物內且分布在其中。在此方 面，不一定要達到均勻地分布，只要PBO進入基質且蓄 積在此基質內使得可經由遷移透過該基質和膜到無生命材 料上而達到長期效用即可。 圖4中圖解說明該噴嘴之替代性原理。於此情況中， 該協乘劑係於環繞擠壓噴嘴1 〇之環型供給導管1 4中添加 至熔融聚合物中，其中協乘劑係從該導管且透過噴嘴2中 的許多注射孔沿著聚合物4流之周緣1 5添加至聚合物4。 此可能導致協乘劑2在擠壓纖維11內之不均勻分布。由 於協乘劑2之遷移，此不均勻地分布可能因協乘劑之梯度 支配遷移導致隨時間改變成爲更均勻分布。在某些情況 中，可能由此方法在最後產品，例如纖維接近表面處達到 相當高的濃度。若只有從基質透過周圍的膜之逐漸遷移導 致協乘劑之長期釋放時，此可爲可接受者。協乘劑在基質 內的不均勻分布，如圖4中藉由點之不均勻分布所示者’ -18- 200845894 於多數的協乘劑存在於擠壓產品的邊緣部分中之下，由於 擠壓物件1 1之外部1 6在擠壓後先冷卻之事實，此可能是 優點，其暗示協乘劑在基質邊緣部分16對高溫的暴露比 在基質中央部分1 7更短。因此，有相當高部分之協乘劑 在基質邊緣部分保留完整。此外，在噴嘴內的熔融聚合物 可能有溫度分布，使得聚合物流1 9的邊緣部分1 8具有比 聚合物4中央部分20更低的溫度。並且，此事實會降低 協乘劑由於高溫所致分解。爲了儘可能多地延遲協乘劑的 加熱，環狀導管14可藉由隔離材料21而與噴嘴2壁22 熱隔離。 在添加協乘劑與直到擠壓聚合物已冷卻到對協乘劑不 緊要的溫度之間的時間爲對於協乘劑的分解和溫度之關鍵 性因素。若該溫度係低於協乘劑分解之臨界溫度，則此時 間係根本無關緊要者。若該溫度係在協乘劑之臨界分解溫 度附近，必須小心將溫度暴露保持爲相當短。若該溫度遠 高於協乘劑之臨界溫度，則協乘劑暴露於溫度之時間必須 保持非常短。在擠壓機內之實驗期間，可驗證出可藉由擠 壓摻加多致70%的完整PBO到聚酯纖維內。由於熔融聚酯 之溫度爲290 °C，其遠高於經認爲是PBO之臨界分解溫 度，因此該結果是令人震驚者。已有提出將PBO摻加到 聚乙烯（polythene)基質之內者，因爲聚乙烯之熔化溫度 120°C矽頗爲低者。不過，在遠高於PBO的155°C沸點之 聚酯（聚對苯二甲酸乙二酯，PET ) 250 °C之熔化溫度下， 咸信PBO不能保留完整。此在理論與實際之間的矛盾對 -19- 200845894 於在聚酯中的協乘劑摻加不只是一項優點，而且對於在聚 乙烯中的協乘劑摻加也是一項優點，因爲儘可能多的聚乙 烯，時常，係在遠高於上述1 2 0 °c的溫度下擠壓。例如， 有實施過多個實驗，其中聚乙烯係在高於250 °C的溫度下 擠壓。如此，根據本發明之實驗證實可在高於1 6 0 °C，例 如高於180°C或甚至高於200°C之溫度下，將協乘劑，特 別是ΡΒ Ο，完整地摻加到聚合物基質內。 爲了將PBO的高溫暴露時間保持短，可將擠壓聚合 物積極地冷卻，例如藉由冷空氣注射，或藉由擠壓到冷卻 用液體內。 如上面所討論者，本發明方法可用於廣多種物體之構 製。不過，較佳的應用是用於製造殺蟲纖維或織物或，特 別地，殺蟲網片。在下文中，要說明殺蟲網片構製程序之 步驟。 網片之編織、清潔、著色、縫紉及包裝 拉製的組織化（texturised)聚酯纖維紗（DTY聚對 苯二甲酸乙二酯，PET )係從供應商以捲形式送到，其中 該纖維係由3 6條聚酯細絲組成。將該送達纖維織成連續 的網。在該網經隨意地著色，縫紉成正確的尺寸及包裝之 前，對彼等施以浸漬程序。 浸漬程序 在_*步驟程序a )中’將殺蟲劑’較佳者除蟲菊醋， -20- 200845894 特別者第滅寧，在溶劑中之溶液與醇或二醇（乙醇、丙二 醇、等）混合且將該織物或網片通過有殺蟲液體之浴，或 將殺蟲液體藉由噴霧、印刷或其他技術施加至織物或網 片。特別適合於工業製造者，爲減少程序中使用的溶劑之 量，將該織物或網片通過二個滾筒或抵緊一固定的表面之 一滾筒以榨出儘可能多之流體。在溶液中的除蟲菊酯濃度 係以在此程序後保留在織物中或網片上之溶液量來計算。 接著乾燥該織物或網片，例如藉由通過空氣流或在烤箱 內。織物及特別者網片在保持固定在此程序中以不改變形 狀或以施加某些形狀至該網片。在乾燥程序中使用之溫 度，必須爲在組成物本身中低於220 °C，且較佳者低於 1 00 °C。乾燥之後，將織物或網片通過第二浴、噴佈站、 印刷站、或類似者，於其中添加耐洗劑之溶液或乳液。可 添加交互黏合劑或催化劑。此具有聚氟碳之乳液在水蒸發 期間形成一連續的膜。 在一步驟程序b )中，其係較佳的方法，係將殺蟲劑 在溶劑中之溶液與醇或二醇（乙醇、丙二醇、等）混合。 然後將此混合物在攪拌下與防洗劑的有機溶液或水乳液？昆 合，隨意地加入催化劑或交互黏合劑及酸化劑。可添加清 潔劑使殺害蟲劑之有機溶液在水乳液中穩定化且使其容易 濕潤。在完全濕潤後，可將織物或網片通過一壓機，例如 包括二滾筒者，以減低所吸收的組成物之量。或者，可經 由離心移除過多的組成物。最後將織物或網片乾燥，如上 述者，或藉由通過溫熱表面乾燥，諸如越過溫熱滾筒。或 -21 - 200845894 者，可將織物部分的或完全地空氣乾燥，例如在真空下， 且接著通過介於一或二熱滾筒之間或滾筒與熱表面之間。 對於網片，乾燥程序期間之溫度必須選擇成使得殺蟲劑不 會分解。此在高溫程序的最後乾燥亦可用來加速防洗劑分 子之取向以形成均勻的防洗劑膜。此程序係常稱爲“固 化”。 用於蚊帳之浸漬程序 在一較佳具體實例中，特別是用於蚊帳者，將第滅寧 溶解/分散在溶劑，例如丙酮及乙醇中。將膜形成性組份 與安定劑/乳液一起溶解/分散在水中，其中也使用酸化 劑。將最後含殺蟲劑及膜形成劑的混合物藉由壓染施加於 網，於其中該網係在控制的速度下在滾筒上經過。對於如 PermaNet®之網，起始攝取重量係選擇成使得在乾燥後， 最後第滅寧淨含量爲5 5毫克/平方米。將網片乾燥且施以 在低於殺蟲劑以臨界速率分解的溫度之溫度下之固化程 序。於此情況中決定性者不宜一定是加熱介質之溫度，例 如滾筒或熱空氣加熱器，而是塗層中之溫度，因爲後述溫 度決定殺蟲劑的分解之故。因此，加熱器之溫度可高於殺 蟲劑之分解溫度，特別地只要該塗料不乾燥即可，因溶劑 /水之蒸發對殺蟲膜具有冷卻作用之故。 【圖式簡單說明】 本發明將參照圖式予以更詳細地解說，其中 -22- 200845894 圖1圖解說明一種在基質中具有協乘劑之聚合物基質 及具有殺蟲劑之塗層， . 圖2圖解說明一種纖維形式的塗覆基質 圖3圖解說明一種擠壓程序， 圖4圖解說明擠壓噴嘴的另一例子之更詳細圖形， 圖5圖解說明一種以片段膜塗覆的纖維形式之基質。 φ 【主要元件符號說明】 I :無生命物體a synergistic agent in the material, such as PBO, but without an insecticide in the matrix, and having an insecticidal coating on at least a portion of the surface of the polymer matrix 'eg, containing del tame t hr in . In this regard, it is necessary that the matrix be provided in the form of a non-insecticide but in the initial state with a co-aggregation agent. Thus, in another embodiment, the matrix of the inanimate material is free of insecticide until at least the coating procedure. Although the substrate is not doped with an insecticide in the initial state, it is still within the scope of the present invention that the insecticide can migrate from the coating to the polymer matrix after the subsequent coating step. Thus, in another embodiment, the substrate has an initial solid state free of insecticide containing at least one co-agent, and wherein it has a final solid state, which contains a pesticidal coating. In one embodiment, the substrate may contain one or more co-agents, such as PBO, but no pesticide, and the coating does not contain a co-agent but includes one or more insecticides, such as difenin. In a practical embodiment, the polymer matrix is formed by extruding a molten thermoplastic polymer through an extrusion nozzle. The synergistic agent is added to the molten polymer through a passage in or upstream of the extrusion nozzle. This may be critical in certain combinations, particularly if the substrate is made of polyester, a preferred material for fibers and webs. So this is because the melting temperature of the polyester is about 25 ° C, far exceeding the temperature at which the synergist such as PB 0 remains intact. However, the degree of decomposition of the synergistic agent, such as PB0, depends not only on the temperature, but also on the time at which P B 0 is exposed to the temperature, as the decomposition process is gradually carried out. Under this point of view, it has also been identified, and experimentally confirmed that the synergistic agent, such as PB0, can withstand high temperatures, such as 180 ° C or 200845894 high, higher than the commonly considered decomposition temperature, if the exposure remains short. Therefore, in order to reduce the time of exposure to high temperatures, the principle of a special extrusion nozzle. This principle has a short distance from the passage of the coupling agent added to the melt in the extrusion process. The term "short distance" refers to a distance which results in a synergistic temperature. The agent remains in the extruded matrix during the elapsed time. For example, the distance can be selected to add to the co-multiplier the maximum exposure time for which the temperature increase is increased and the maximum time is limited by the predetermined upper jaw. How much this “sufficient amount” depends on the synergy and degree. In some cases, a decomposition of 99% is acceptable, and in the case of an effective amount of agent that is resistant to pesticide resistance for a long period of time, a decomposition rate of less than 90% may be acceptable. Since the melting temperature of a square polymer incorporating a synergistic agent in a thermoplastic polymer far exceeds the decomposition experiment of the synergist, it is surprisingly found that for the polyester, there is still more than 50% regardless of the pressure temperature. The synergistic agent remains intact. In a preferred embodiment, the channel is mounted, for example, within a few millimeters or centimeters from the nozzle exit. This first receives the temperature of the polymer as it enters the nozzle. Surrounded by a ring-shaped multi-agent supply conduit that injects the entire edge of the polymer stream through a nozzle to a time at which it is melted at a temperature to infiltrate the polymer into the nozzle. In this context, the complete synergy of the increase and the full amount of temperature produces a maximum temperature increase, wherein the maximum temperature acceptable decomposition time is within 1% of the remaining synergy. Among other things, the present invention provides a method in which the temperature is not the case. At the side of the extrusion above 250 °C, it is suggested that when the co-agent is, for example, the nozzle may be synergistically substantially within the molten polymer. -9- 200845894 This also leads to the possibility of cooling the synergist before injection, so that the increase in the temperature of the synergistic agent caused by the heat uptake of the polymer accelerates the hardening and cooling of the polymer. In addition, the extruded polymer can be actively cooled shortly downstream of the extrusion nozzle, such as by cold air injection. The process, wherein the matrix is coated, can be achieved by impregnation of the fabric or web as disclosed in WO 0 1 /3 7662 to impart insecticidal and/or repellent properties, including: a) preparation comprising a solution or aqueous emulsion of an insecticide and/or an insect repellent and a film-forming component which can form a water-resistant and optionally oil-repellent film via a surface of the inanimate material, for example surrounding the fiber. And reducing the pesticide component to be washed away and degraded from the inanimate material; and applying the solution or emulsion to the inanimate material, or b) preparing a first solution or water containing an insecticide and/or an insect repellent An emulsion and a second solution or aqueous emulsion for preparing a film-forming component, the film-forming component being capable of reducing insecticide by forming a water-resistant and optionally oil-resistant film on the surface of the inanimate material, for example, surrounding the fiber The component is washed away and degraded from the inanimate material; and the solution or aqueous emulsion of the insecticide and/or insect repellent is applied to the inanimate material, and then the solution or emulsion of the film forming component is applied to The inanimate material, wherein the film is formed Groups ingredients comprise a polymer backbone component or a fixing agent selected from paraffin oil or overstep, silicon, silicon oil or Lap, and polyfluorocarbon, or a derivative thereof in the composition of the. In another embodiment, the film-forming component comprises a component selected from the group consisting of stone oil or strontium, sand, sand oil or wax, and polyfluorocarbon, or a derivative thereof, in the group of -10- 200845894 The mixture is preferably a mixture of agglomerated carbon and stone oil or a mixture of a polyfluoride and a polyoxane. For example, the sand oil or lanthanide polyoxyalkylene. In another embodiment, polyfluorocarbon, sarcophagus or hydrazine, eucalyptus or hydrazine, or a derivative thereof is attached to the polymer backbone. For example, the polymer backbone fixing agent is a resin, a polyurethane or a polyacrylic acid. In a preferred embodiment, the film-forming component comprises a polymeric matrix anchoring agent that polymerizes into a drying process or a curing process or a drying and curing process of the inanimate material to form a polymer on the polymer backbone. a film of a fluorocarbon side chain. a combined solution or emulsion in which the pesticide composition is incorporated into the washant prior to application to the inanimate material, which may be used as a composition for impregnation or as part of a composition for impregnation, to Mix other components. Such components may be other insecticides, synergists, anti-v agents, preservatives, detergents, sputum agents, impact modifiers, antifogging agents, foaming agents, clarifying agents, crystal nucleating agents, Coupling agents, conductivity improvers for antistatic, stabilizers such as antioxidants, carbon and oxygen radical scavengers and peroxide decomposers and the like, flame retardants, mold release agents, optical brighteners, spreading agents, Anti-blocking agent, anti-migration agent, migration promoter, foam forming agent, antifouling agent, antiscaling agent, thickener, other biocide, wetting agent, plasticizer, adhesive or anti-adhesive agent, aromatic Agents, pigments and dyes and other liquids include water or organic solvents. The impregnating composition can also be partially absorbed in the absorbent fabric, which can extend insecticidal activity and improve wash fastness. In the case where the fiber is a multifilament yarn, -11 - 200845894, the insecticide may be trapped between the filaments, resulting in higher washing durability of the trapped insecticide. The method of the invention can be used for hand soaking, however, it has proven to be particularly suitable for industrial production. The protective composition of the present invention relates to a one-component or multi-component mixture which gives water resistance or water and oil resistance. One or more cleaning agents may be added to increase the wettability of the agent to the fabric to stabilize the emulsion used or to increase the anchoring effect. A crosslinking agent or catalyst can be used to increase the anchoring effect. The pesticidal composition and protective composition can be added sequentially (method a) or in a procedure (method b). Improved finishing and curing can be achieved by final heating through a hot surface such as an iron or hot roller or with hot air. Polymer backbones are discussed in more detail in WO 0 1 /37662. Other insecticidal coatings which can be used in connection with the present invention are disclosed in WO 2006/092094 to Liu et al., relating to mesh/fabric coatings, containing insecticides, aqueous adhesives, such as aqueous polyamine-based adhesives. An acid ester latex or a polyacrylate latex, and a crosslinking agent such as an epoxy polymer crosslinking agent. A number of different blends - also relevant to the present invention - are disclosed in WO 2006/092094, which, more particularly, discloses a finishing liquid for repelling and killing mosquitoes/insects, the formulation of which (Based on mass percentage) including: Insecticides and/or insect repellents 0.05%-40.00% Adhesives 5.00%-40.00% Crosslinkers 0 · 0 2 5 % -1 . 5 0 % ; and the remainder are water, The total amount of all components is 100%. The insecticide according to WO 2006/092094 is an aqueous pesticide having an effective content of -12-200845894 1 - 50%, which is prepared from one or two of the following substances: , cyfluthrin, cyhalothrin, cis-cypermethrin, permethrin, and etofenpox; deworming in the WO 2006/092094 The agent is an aqueous insect repellent having an effective content of 1 - 50%, and the water repellent is prepared from one or two of the following materials: diethyltoluamide (DEET), phthalic acid Dimethyl Phthalate and Baishenning; the aqueous dosage form of the insecticide and insect repellent in WO 2006/092094 includes one or two of the following dosage forms: wettable powder, water dispersible powder, water dispersible Suspensions, water-dispersible tablets, aqueous emulsions, microcapsule suspensions, and water-dispersible granules; the adhesive of WO 2006/092094 is an aqueous adhesive having a solid content of 40-50%, Contains one or two of the following materials: polybutadiene latex, aqueous poly A urethane latex, a polyacrylic latex, a polyacrylate latex or a vinyl acetate latex; the crosslinking agent in WO 2006/092094 contains one or two of the following: epoxy polymer crosslinking agent, methyl group - Etherified hexamethylol melamine resin primary condensation crosslinker, polyfunctional aziridine crosslinker, various methylol crosslinkers, crosslinkers composed of hydroxyethyl and epoxy groups, and epoxy An acetate crosslinker of a polycondensate of chloropropane and hexamethylenediamine. Preferably, the insecticide associated with the present invention is a pyrethroid, preferably difenmethine or benzinone, but other pyrethroids may also be used, as in w〇•13- 200845894 01/37662 The form revealed in . However, the invention can also be used in the impregnation compositions in connection with urethane or organophosphates. A more extensive form of possible insecticides is found in WO 01/37662 or WO 06/128870 and contains examples of insect repellents. Further, the term insecticide is also applied to the insecticidal composition of the impregnating composition of the present invention. For example, in order to also combat resistant insects, pyrethroids can be combined with urethane or organophosphate. Moreover, two or more insecticides can be applied to different parts of the mesh or fabric, for example by printing or spraying techniques, without mixing and evenly using, which can be beneficial for toxicology and registration reasons. . Alternative or supplemental insecticides can also be sterilized insecticides when using mesh sheets for a large number of activities, thus inactivating mosquitoes and avoiding mosquito offspring. Such insecticides may be benzammonium or triterpenoids. Other possible combinations include metaflumizone as disclosed in WO 06/1 27407, N-aryloxime as disclosed in WO 0 6 1 2 8 8 7 0 or 1-phenyl as disclosed in WO 06128867 Triazoles, for example in combination with pyrethrins. In addition, or in the alternative, insecticides and co-agents may be combined in the coating, such as butyric acid, scorpion, Tropital, Bucarpolate, ethion , profenofos, or dimethoate, saponin, terpene, TPP, dimethyl maleate, NIA-16388 (NIA), s_421, MGK-264 (bicycloheptene) Bicycloheptenedicarboximide ), S, S, S. Tributyltrithiolate 200845894 Phosphate (DEF), -N-octyltriheptene dicarbonyl quinone imine, sesamin, sesame Other alternatives for sesamolin, or sesamex, coatings associated with the present invention are disclosed in US20070095 63, wherein the formulation of a solution according to various embodiments of the present invention comprises the following four parts: i•from Insecticides such as Dimethoate, Esfenvalerate, Efenin, biphenthrin, Baishenning and Xeronine, all of which are rapidly activating and have High boiling point. 2) A wire stabilizing agent such as perfluoroacrylate, a resin, an adhesive, and a polyacrylate. 3. Thickeners such as starch, gum, and titanium dioxide. 4 · Solvents, for example, water. Inanimate Materials In the following, a number of examples of inanimate materials in the context of the present invention are given: groups selected from the group consisting of yarns, fibers, fabrics, knits-commodities, non-woven fabrics, mesh materials, foils, and tarpaulins. In textile materials or plastic materials and coating compositions. The mesh material, for example, may be prepared by circular knitting or warp knitting, or by stitching a portion of the mesh to obtain a desired web. The textile or plastic material can be made from a variety of natural and synthetic fibers' and also in a woven or non-woven form of textile blend, knit, yarn or fiber. Materials for the synthetic fibers are, for example, polyamine, polyester, polyacrylonitrile, polyolefins such as polypropylene or polyethylene, and polytetrafluoroethylene (Tefl〇n). Polyamines, polyolefins and polyesters, such as polyethylene terephthalate, are preferred. -15- 200845894 Applications of textile materials or plastic materials include sheets, mattresses, pillows, mats, upholstery, curtains, wall coverings, carpets and windows, cupboards and door screens, geotextiles, tents, shoes Sole, clothing, such as socks, trousers, shirts, uniforms, horse blankets, mosquito nets, covers for agriculture and viticulture; fabrics or meshes for packaging, bags; containers for food, seeds and feed; paper; Building materials, furniture, leather, vinyl objects, wires and cables. Φ The most preferred is a fabric or mesh made of polyester because the polyester mesh has a cotton-like feel and low flammability. This is also the reason why these images are preferred by WHO. In this regard, it is emphasized that the present invention is directed to a specific example of a 75, 100 or 150 denier 36 filament denitrified impregnated polyester mesh application (e.g., Permanet 2.0). Other special applications relating to the invention are: a wall, such as those disclosed in WO 〇 3 〇〇 3 827, a worm-killing blanket, such as disclosed in W003055307, φ - a protective cover for food And a water storage container, such as that disclosed in WO 03090532, - an air cleaning cover such as disclosed in WO2006024304, - a canvas such as disclosed in WO 03/063 5 87. Insects The purpose of the present invention is to control and/or combat various pests such as ticks, ticks, bed bugs, crickets, fleas, scorpions, otters, house flies, mosquitoes, termites, ants, moths, spiders, locusts, crickets, stupid fish, and Others will fly -16-200845894 and crawling insects. Application Procedure Application of the pesticidal impregnating composition can be accomplished via techniques such as pressure dyeing, intensive washing, spraying, printing, etc.' such as transfer or such as ink jet printing. [Embodiment] Fig. 1a illustrates an inanimate object 1 having a co-agent 2 in a matrix 3 - exemplified by a point 2 on the body, but the synergistic agent 2 can be uniformly distributed in the matrix. The matrix 3 is coated with a film 4 containing an insecticide 5 - exemplified by a triangle 4 on the body, although the insecticide may be uniformly distributed in the film coating. When the substrate 3 is coated with the film 4, the synergist 2 will migrate through the film 4 to the surface 6 of the inanimate object 1, which is shown in Figure ib. Moreover, the insecticide 5 migrates to the surface 6, so that the surface 6 contains the insecticide 5' and the synergist 2' for insect uptake. Further, as shown in Fig. 1b, if the matrix is such that the insecticide 5 is migrating, the insecticide 5" can migrate from the membrane 4 into the matrix 3. Figure 2 illustrates a matrix 3 in which a film is used. The form of the coated fiber. The drawing is only for the purpose of illustration and not drawn to scale. The substrate, such as a coating of fibers, may be in the form of a continuous film, as shown in Figure 2, or the coating may be in the form of a segment. As shown in Figure 5. If a film-forming component is used, such a fragment may be in the form of a film. This fragmented coating can be achieved by, for example, a spray technique. Next, the product and extrusion will be described in more detail. Fig. 3 illustrates a press machine of -17-200845894, which has a casing 8 with an inner piston 9 moving forward along the direction of the extrusion nozzle, thereby causing the molten polymer matrix 4 to be pushed and squeezed. Extruding the product 1, for example a polymer fiber. At a short distance upstream of the nozzle 10, the conduit 12 is connected to the casing 8 for feeding the synergist 2 from the tank 13. The synergist enters the molten polymer 4 and enters The casing 8 is exposed to the high temperature of the molten polymer until the time during which the extruded polymer cools down. As mentioned, at this point, the extrusion principle of the piston can be easily replaced with an extrusion screw or other tool that can squeeze the molten polymer. Moreover, as an alternative, the conduit 12 can be part of the nozzle itself. The only requirement is that the PBO enters and is distributed within the molten polymer. In this regard, it is not necessary to achieve a uniform distribution as long as the PBO enters the matrix and accumulates within the matrix such that it can migrate through the matrix and membrane to the inanimate material. The long-term utility can be achieved. The alternative principle of the nozzle is illustrated in Fig. 4. In this case, the synergistic agent is added to the molten polymer in the annular supply conduit 14 surrounding the extrusion nozzle 1 Wherein the co-agent is added to the polymer 4 from the conduit and through a plurality of injection holes in the nozzle 2 along the periphery 15 of the polymer 4 stream. This may result in the co-multiplier 2 not being in the extruded fiber 11. Uniform distribution. Due to the migration of the multiplier 2, this uneven distribution may be more uniform over time due to the gradient-dominated migration of the synergistic agent. In some cases, it may be possible In the final product, for example, the fiber reaches a relatively high concentration near the surface. This can be acceptable if only the gradual migration from the substrate through the surrounding film results in long-term release of the synergistic agent. Uniform distribution, as shown by the uneven distribution of dots in Figure 4, is shown in -18-200845894. Most of the co-agents are present in the edge portion of the extruded product due to the external 1 6 of the extruded object 1 1 This may be an advantage of cooling first after extrusion, which suggests that the synergistic agent is exposed to high temperatures at the substrate edge portion 16 at a higher temperature than at the central portion of the substrate 17. Therefore, there is a relatively high portion of the synergistic agent in the matrix. The edge portion remains intact. Furthermore, the molten polymer within the nozzle may have a temperature profile such that the edge portion 18 of the polymer stream 19 has a lower temperature than the central portion 20 of the polymer 4. Moreover, this fact reduces the decomposition of the synergistic agent due to high temperatures. In order to delay the heating of the synergistic agent as much as possible, the annular conduit 14 can be thermally isolated from the wall 22 of the nozzle 2 by the insulating material 21. The time between the addition of the synergistic agent and the temperature until the extruded polymer has cooled to less than the synergistic agent is a critical factor for the decomposition and temperature of the synergistic agent. If the temperature is below the critical temperature at which the synergistic agent decomposes, then the time is not at all critical. If the temperature is near the critical decomposition temperature of the synergist, care must be taken to keep the temperature exposure fairly short. If the temperature is much higher than the critical temperature of the synergist, the time at which the synergist is exposed to temperature must be kept very short. During the experiment in the extruder, it was verified that 70% of the complete PBO could be incorporated into the polyester fiber by extrusion. Since the temperature of the molten polyester is 290 ° C, which is much higher than the critical decomposition temperature considered to be PBO, the result is shocking. It has been proposed to incorporate PBO into a polythene matrix because the melting temperature of polyethylene is quite low at 120 °C. However, at temperatures above 150 °C of PBO's 155 ° C boiling point (polyethylene terephthalate, PET) melting temperature, the salt PBO can not remain intact. This contradiction between theory and practice is not only an advantage for the addition of synergistic agents in polyesters, but also for the addition of synergistic agents in polyethylene. It is possible that a large amount of polyethylene, often, is extruded at a temperature much higher than the above 1 20 °c. For example, there have been a number of experiments in which polyethylene is extruded at temperatures above 250 °C. Thus, experiments according to the invention have demonstrated that the synergistic agent, in particular ruthenium, can be completely incorporated at temperatures above 160 ° C, for example above 180 ° C or even above 200 ° C. Within the polymer matrix. In order to keep the high temperature exposure time of the PBO short, the extruded polymer can be actively cooled, for example, by cold air injection, or by extrusion into a cooling liquid. As discussed above, the method of the present invention can be used to construct a wide variety of objects. However, a preferred application is for the manufacture of insecticidal fibers or fabrics or, in particular, insecticidal mesh sheets. In the following, the steps of the insecticidal mesh construction procedure are explained. Texturised polyester fiber yarn (DTY polyethylene terephthalate, PET) which is woven, cleaned, colored, sewn and packaged, which is fed from a supplier in the form of a roll, wherein the fiber It consists of 36 polyester filaments. The delivery fibers are woven into a continuous web. The web is subjected to an impregnation procedure before being randomly colored, sewn into the correct size and packaged. The impregnation procedure in the _* step procedure a) 'pesticide' is preferred, pyrethrum vinegar, -20- 200845894, especially the chlorhexidine, a solution in a solvent with an alcohol or a glycol (ethanol, propylene glycol, etc.) Mixing and passing the fabric or web through a bath with an insecticidal liquid, or applying the insecticidal liquid to the fabric or web by spraying, printing or other techniques. Particularly suitable for industrial manufacturers, to reduce the amount of solvent used in the process, the fabric or web is passed through two rollers or against a roller of a fixed surface to squeeze as much fluid as possible. The pyrethroid concentration in the solution is calculated as the amount of solution remaining in the fabric or on the web after this procedure. The fabric or web is then dried, for example by passing through a stream of air or in an oven. The fabric and the special mesh are held in this procedure so as not to change shape or to apply certain shapes to the web. The temperature used in the drying process must be less than 220 ° C in the composition itself, and preferably less than 100 ° C. After drying, the fabric or web is passed through a second bath, spray station, printing station, or the like, to which a detergent-resistant solution or emulsion is added. An interactive binder or catalyst can be added. This emulsion of polyfluorocarbon forms a continuous film during evaporation of water. In the one-step procedure b), a preferred method is to mix a solution of the insecticide in a solvent with an alcohol or a glycol (ethanol, propylene glycol, etc.). Then mix the mixture with an organic solution or an aqueous emulsion of the anti-detergent? Kunming, optionally add catalyst or interactive binder and acidifier. A cleaning agent may be added to stabilize the organic solution of the pesticide in the aqueous emulsion and to make it easy to wet. After being completely wetted, the fabric or web can be passed through a press, such as a two-roller, to reduce the amount of composition absorbed. Alternatively, excess composition can be removed by centrifugation. The fabric or web is finally dried, as described above, or by drying through a warm surface, such as over a heated roller. Or -21 - 200845894, the fabric may be partially or completely air dried, such as under vacuum, and then passed between one or two heated rollers or between the rollers and the heated surface. For mesh, the temperature during the drying process must be chosen such that the pesticide does not decompose. This final drying in the high temperature program can also be used to accelerate the orientation of the detergent molecules to form a uniform anti-detergent film. This program is often referred to as "curing." Immersion Procedure for Mosquito Nets In a preferred embodiment, particularly for mosquito nets, difenin is dissolved/dispersed in a solvent such as acetone and ethanol. The film-forming component is dissolved/dispersed in water together with a stabilizer/emulsion, wherein an acidulant is also used. The final mixture containing the insecticide and film former is applied to the web by press dyeing, wherein the web passes over the drum at a controlled rate. For a network such as PermaNet®, the initial ingestion weight is chosen such that after drying, the final content of the ninth inging is 5 5 mg/m2. The web is dried and subjected to a curing process at a temperature below the temperature at which the pesticide decomposes at a critical rate. In this case, the decisive person should not necessarily be the temperature of the heating medium, such as a drum or a hot air heater, but the temperature in the coating because the temperature described later determines the decomposition of the pesticide. Therefore, the temperature of the heater can be higher than the decomposition temperature of the insecticide, in particular, as long as the coating does not dry, the solvent/water evaporation has a cooling effect on the insecticidal membrane. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be explained in more detail with reference to the drawings, in which -22-200845894 Fig. 1 illustrates a polymer matrix having a synergistic agent in a matrix and a coating having an insecticide. 2 illustrates a coated substrate in the form of a fiber. FIG. 3 illustrates an extrusion process, FIG. 4 illustrates a more detailed pattern of another example of an extrusion nozzle, and FIG. 5 illustrates a matrix in the form of a fiber coated with a segment film. . Φ [Explanation of main component symbols] I : Inanimate objects
2, 2’，2” ：協乘齊U 3 :基質 4 ··膜 5, 5’，5” ：殺蟲劑 6 :表面 8 :機殼 • 9 :活塞 10 :擠壓噴嘴 II :擠壓產物 1 2 :導管 ' 13 :槽 1 3 :環狀導管 1 4 :環型供給導管 1 5 :周緣 1 6 :基質邊緣部分 -23- 2008458942, 2', 2": synergistic U 3 : matrix 4 · · film 5, 5', 5": insecticide 6 : surface 8 : casing • 9 : piston 10 : extrusion nozzle II : extrusion Product 1 2 : Catheter ' 13 : Tank 1 3 : Annular conduit 1 4 : Annular supply conduit 1 5 : Peripheral 1 6 : Matrix edge portion -23 - 200845894
17 :基質中央部分 1 8 :聚合物流邊緣部分 1 9 :聚合物流 20:聚合物中央部分 2 1 :隔離材料 2 2 :噴嘴壁 -2417: central portion of the matrix 1 8 : edge portion of the polymer stream 1 9 : polymer stream 20: central portion of the polymer 2 1 : spacer material 2 2 : nozzle wall -24