CN102202502A - 包含农药、有机uv光保护过滤剂和涂敷的金属氧化物纳米颗粒的农化配制剂 - Google Patents
包含农药、有机uv光保护过滤剂和涂敷的金属氧化物纳米颗粒的农化配制剂 Download PDFInfo
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- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
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Abstract
本发明涉及包含农药、有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的农化配制剂。本发明还涉及一种制备所述配制剂的方法。此外,本发明还涉及有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的混合物在农化配制剂中的用途以及本发明农化配制剂在稳定农药以防UV辐射中的用途。此外,本发明涉及一种防治有害昆虫和/或植物病原性真菌的方法,包括使植物、其中或其上有害昆虫和/或植物病原性真菌生长或可能生长的土壤或植物生长地、需要防止所述有害昆虫和/或植物病原性真菌侵袭或侵染的植物或土壤与有效量的本发明配制剂接触,涉及一种防止不希望的植物生长的方法,包括使除草有效量的所述配制剂作用于植物、其生长地上。
Description
本发明涉及包含农药、有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的农化配制剂。本发明还涉及一种制备所述配制剂的方法。此外,本发明涉及多组分成套包装,其以分开的组分包含在防止不希望的植物生长、有害昆虫和/或植物病原性真菌的方法中组合施用的A)包含UV光保护过滤剂和涂敷的纳米颗粒状金属氧化物的农化配制剂以及B)农药。本发明还涉及有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的混合物在农化配制剂中的用途以及本发明农化配制剂在稳定农药以防UV辐射中的用途。此外还涉及一种防治有害昆虫和/或植物病原性真菌的方法,包括使植物、其中或其上有害昆虫和/或植物病原性真菌生长或可能生长的土壤或植物生长地、需要防止所述有害昆虫和/或植物病原性真菌侵袭或侵染的植物或土壤与有效量的本发明配制剂接触,涉及一种防止不希望的植物生长的方法,包括使除草有效量的所述配制剂作用于植物或其生长地。优选实施方案与其他优选实施方案的组合在本发明范围内。
许多农药对阳光敏感且分解。分解可能在储存过程中或甚至在施用于环境之后已经发生。结果农药活性降低,必须施用更大量的农药,农药必须以更短间隔施用,或者最终产生有毒降解产物。
包含农药和有机UV光保护过滤剂的农化配制剂是已知的:Miskus等,J.Agr.Food Chem.1972,20,313-315公开了UV吸收剂和抗氧化剂在矿物油配制剂中的组合以稳定拟除虫菊酯(parethroid)杀虫剂。EP 0496106B1公开了包含不饱和胺衍生物、固体载体和任选的UV吸收剂的农化配制剂。此外,UV散射剂如二氧化钛任选用于该组合物中。EP 1719409A1公开了任选包含UV吸收剂或UV散射剂如二氧化钛的杀虫剂组合物。WO2006/077394公开了染料在保护微胶囊中所含活性组分以防UV降解中的用途。
在农业化学中使用二氧化钛是已知的:WO 2007/014826公开了含有UV辐射吸收性金属氧化物粉末和超级铺展剂的制剂在降低对有用植物的晒伤损害中的用途。EP 1139763B1公开了颗粒状材料如二氧化钛在不损害光合作用下降低植物生理学病害中的用途。WO 2005/072680公开了一种TiO2或ZnO颗粒,其已经掺杂有一种或多种其他元素而使掺杂剂在颗粒表面的浓度大于在颗粒核中的浓度。
尽管描述了二氧化钛对植物的正面效果,但已知二氧化钛的几个缺点:Topalov等,Water Research 1999,33,1371-1376公开了二氧化钛对于杀真菌剂甲霜灵(metalaxyl)分解的光催化活性。Kuer和Nunez,PestManagement Science,2007,63,491-494公开了使用二氧化钛作为光催化剂降解氮杂环-大量市售除草剂和杀真菌剂的基础结构单元。在JP2004323501的摘要中公开了二氧化钛作为分解农产品用残留农用化学品的光催化剂。
本发明的目的是提供包含农药的农化配制剂,其降低了农药因阳光,尤其是因紫外(UV)光的分解。另一目的是提高农药的农化配制剂在储存过程中和/或在施用于环境之后的稳定性。再一目的是提高农化配制剂在施用于环境之后的农药活性。
该目的由包含农药、有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的农化配制剂实现。
涂敷的金属氧化物纳米颗粒的平均粒度为1-1000nm,优选1-100nm,更优选10-20nm,借助X射线衍射光谱法测定。
术语“涂敷的金属氧化物纳米颗粒”涉及一种类型的所述化合物或几种不同类型的所述化合物的混合物。合适的金属氧化物例如为钛氧化物(无定形或金红石和/或锐钛矿型结晶)、铁氧化物、锌氧化物、锆氧化物或铈氧化物。对本发明而言,可提到的优选金属氧化物是二氧化钛和氧化锌,特别优选二氧化钛。
术语“涂敷的”或“涂层”指金属氧化物纳米颗粒已经用诸如氨基酸、蜂蜡、脂肪酸、脂肪醇、阴离子表面活性剂、卵磷脂,脂肪酸的钠、钾、锌、铁或铝盐,金属(例如钛或铝)醇盐、聚乙烯、聚硅氧烷、蛋白质(胶原蛋白或弹性蛋白)、链烷醇胺、硅氧化物、金属氧化物、六偏磷酸钠、氧化铝或甘油的化合物进行一次或多次化学、电子、机械化学和/或机械性质的表面处理。该表面处理得到金属氧化物纳米颗粒的涂层。
在优选实施方案中,金属氧化物纳米颗粒的涂层包含含硅聚合物和/或无机氧化物。更优选该涂层包含含硅聚合物或含硅聚合物和无机氧化物。尤其优选包含含硅聚合物和无机氧化物的涂层。
术语“含硅聚合物”指包含硅原子的合成聚合化合物,硅原子经由氧原子与聚合物连接且其中硅原子的残留价键被氢和/或有机残基饱和。含硅聚合物的实例是聚硅氧烷,如聚甲基硅氧烷或聚甲基硅氧烷和聚二甲基硅氧烷的共聚物。
术语“无机氧化物”指无机元素如硅(例如二氧化硅SiO2)、铝(例如氧化铝Al2O3,或氢氧化铝Al(OH)3)、锆或铁,优选铝和硅的氧化物和氢氧化物。优选的无机氧化物是氧化铝、氢氧化铝和二氧化硅。
在一个实施方案中,金属氧化物纳米颗粒的涂层包含含硅聚合物和无机氧化物。合适的实例包括但不限于涂敷的二氧化钛纳米颗粒,其用二氧化硅、氧化铝和聚硅氧烷表面处理(如Tayca公司的产品“MicrotitaniumDioxide MT 100 SAS”、“Microtitanium Dioxide MT 600 SAS”和“Microtitanium Dioxide MT 500 SAS”)或用氧化铝和聚硅氧烷表面处理(如Kemira公司的产品“UVT-M262”)。涂敷的二氧化钛纳米颗粒的其他实例可由BASF SE以T-Lite SF(涂敷氢氧化铝和聚二甲基硅氧烷/聚甲基硅氧烷共聚物的二氧化钛;二氧化钛含量79-89重量%)、T-Lite SF-S(涂敷水合二氧化硅、聚二甲基硅氧烷/聚甲基硅氧烷共聚物和氢氧化铝的二氧化钛;二氧化钛含量73-83重量%)或T-lite MAX(涂敷二甲氧基二苯基硅烷/三乙氧基辛酰基硅烷交联聚合物、水合二氧化硅和氢氧化铝的二氧化钛;二氧化钛含量69-73重量%)市购。上述T-Lite产品各自具有14-16nm的晶粒尺寸、50nm的平均颗粒长度和10nm的宽度。涂敷的氧化锌纳米颗粒的其他实例是以名称“Daitopersion ZN-30”和“Daitopersion ZN-50”由Daito公司销售的那些(在环聚甲基硅氧烷/氧乙烯化聚二甲基硅氧烷中的分散体,含有30%或50%被二氧化硅和聚甲基氢硅氧烷涂敷的纳米氧化锌),或以名称“Fuji ZNO-SMS-10”由Fuji Pigment公司销售的那些(被二氧化硅和聚甲基倍半硅氧烷涂敷的ZnO)。
在另一实施方案中,金属氧化物纳米颗粒的涂层包含含硅聚合物。该涂层可以包含至少一种含硅聚合物。优选它包含所述聚合物之一。合适的实例包括但不限于用辛基三甲基硅烷处理的二氧化钛纳米颗粒(如Degussa公司的“T 805”),用聚二甲基硅氧烷处理的二氧化钛纳米颗粒(如由Cardre公司以商标名“70250 Cardre UF TiO2SI3”销售的产品),用聚二甲基氢硅氧烷处理的二氧化钛纳米颗粒(如由Color Techniques公司以商标名“Microtitanium Dioxide USP Grade Hydrophobic”销售的产品)。其他实例是涂敷的氧化锌纳米颗粒的那些,其以名称“Zinc Oxide CS-5”由Toshibi公司销售(被聚甲基氢硅氧烷涂敷的ZnO)、以“SPD-Zl”由Shin-Etsu公司销售(被聚硅氧烷接枝的丙烯酸系聚合物涂敷的ZnO,分散于环二甲基硅氧烷中)。其他涂敷的氧化锌颗粒由BASF SE以Z-COTEHP1(98重量%氧化锌和2重量%三乙氧基辛酰基硅烷)或Z-COTEMAX(96-99重量%氧化锌和1-4重量%二甲氧基二苯基硅烷/三乙氧基辛酰基硅烷交联聚合物)市购。
在另一实施方案中,金属氧化物纳米颗粒的涂层包含无机氧化物。该涂层可以包含至少一种无机氧化物。优选它包含一种无机氧化物。合适的实例包括但不限于二氧化钛纳米颗粒,其用二氧化硅和氧化铝表面处理(如来自Tayca公司的产品“Micro-titanium Dioxide MT 500 SA”和“Microtitanium dioxide MT 100 SA”,以及来自Tioxide公司的产品“Tioveil Fin”、“Tioveil OP”、“Tioveil MOTG”和“Tioveil IPM”),用氧化铝和硬脂酸铝表面处理(如来自Tayca公司的产品“Microtitaniumdioxide MT 100 T”),用氧化铝和月桂酸铝表面处理(如来自Tayca公司的产品“Microtitanium dioxide MT 100 S”),用铁氧化物和硬脂酸铁表面处理(如来自Tayca公司的产品“Microtitanium dioxide MT 100 F”),用氧化铝和硬脂酸表面处理(如来自Kemira公司的产品“UVT-M160”),用氧化铝和甘油表面处理(如来自Kemira公司的产品“UVT-M212”)。
金属氧化物纳米颗粒可能已经进行一次或至少两次表面处理。优选纳米颗粒已经进行至少两次表面处理。因此,纳米颗粒可能具有单一或多个涂层(多涂层)。优选纳米颗粒具有多涂层。该涂层可以是无机氧化物,优选氧化铝,以及含硅聚合物,优选聚甲基硅氧烷或聚甲基硅氧烷和聚二甲基硅氧烷的共聚物(CAS No:68037-59-2)的多涂层。优选该涂层包含二氧化硅作为额外组分。术语聚甲基硅氧烷和聚二甲基硅氧烷分别表示甲基氢聚硅氧烷和二甲基聚硅氧烷。
特别优选的涂敷的金属氧化物纳米颗粒是其中颗粒被第一层金属氧化物(优选氧化铝或氧化铝和二氧化硅的混合物)和含硅聚合物外层(优选聚甲基硅氧烷和聚二甲基硅氧烷的共聚物)涂敷的那些。
本发明所用涂敷的金属氧化物颗粒例如可以如US 6,660.380(涂敷的氧化锌颗粒)、DE 3642794A1、EP 0603627A1或WO 1997/16156所述得到。
涂敷的金属氧化物纳米颗粒通常具有50-99.9重量%,优选60-99.9重量%,最优选70-99.5重量%的金属氧化物含量。在另一优选实施方案中,涂敷的二氧化钛颗粒具有70-92重量%,优选72-90重量%,特别优选73-83重量%的二氧化钛含量。在另一优选实施方案中,涂敷的二氧化锌颗粒具有70-99.9重量%,优选90-99.9重量%,特别优选95-99.5重量%的二氧化锌含量。重量百分数涉及相应涂敷的金属氧化物纳米颗粒的总重量。
涂敷的金属氧化物纳米颗粒通常具有0.1-20重量%,优选0.3-15重量%,最优选0.5-10重量%的含硅聚合物含量。涂敷的二氧化钛纳米颗粒通常具有1-15重量%,优选2-10重量%,特别优选3-8重量%的含硅聚合物含量。在优选实施方案中,涂敷的二氧化钛纳米颗粒具有3-10重量%,优选4-7重量%,特别优选4.5-6.5重量%的聚甲基硅氧烷或聚甲基硅氧烷/聚二甲基硅氧烷共聚物含量。二氧化锌颗粒通常具有0.1-15重量%,优选0.3-9重量%,特别优选0.5-5重量%的含硅聚合物含量。重量百分数涉及相应涂敷的金属氧化物纳米颗粒的总重量。
涂敷的金属氧化物纳米颗粒通常具有1-20重量%,优选3-15重量%,特别优选5-10重量%的无机氧化物含量。在优选实施方案中,涂敷的金属氧化物纳米颗粒具有4-10重量%,优选5-9重量%,特别优选6.5-8.5重量%的二氧化硅含量。在另一优选实施方案中,涂敷的金属氧化物纳米颗粒具有0.5-15重量%,优选1-10重量%,特别优选2-5重量%的氧化铝含量。二氧化钛颗粒通常具有4-10重量%,优选5-9重量%,特别优选6.5-8.5重量%的二氧化硅含量,其中百分数涉及涂敷的二氧化钛颗粒的总重量。二氧化钛颗粒通常具有1-10重量%,优选1-5重量%,特别优选2.5-4.5重量%的氧化铝含量,其中百分数涉及涂敷的二氧化钛颗粒的总重量。
涂敷的氧化铁颗粒例如由Arnaud公司以名称“Nanogard WCD2008(FE 45B FN)”、“Nanogard WCD 2009(FE 45B 556)”、“NanogardFE 45 BL 345”和“Nanogard FE 45 BL”销售或由BASF公司以名称“Transparent Iron Oxide”销售。
还可以提到金属氧化物的混合物,尤其是二氧化钛与二氧化铈的混合物,包括二氧化硅涂敷的二氧化钛和二氧化铈的等重量混合物,其由Ikeda公司以名称“Sunveil A”销售,以及氧化铝、二氧化硅和聚硅氧烷涂敷的二氧化钛和二氧化锌的混合物,如由Kemira公司销售的产品“M261”,或氧化铝、二氧化硅和甘油涂敷的二氧化钛和二氧化锌的混合物,如由Kemira公司销售的产品“M 211”。
在优选实施方案中,金属氧化物包含小于0.05mol%,优选小于0.01mol%,更优选小于0.005mol%的掺杂剂,尤其不包含掺杂剂。合适的掺杂剂例如由WO2005/072680第42页第2段已知。实例是锰、钒、铬或铁的阳离子。
涂敷的金属氧化物纳米颗粒在农化配制剂中的总量通常为0.5-20重量%,优选2-15重量%,更优选4-12重量%。
有机UV光保护过滤剂应理解为指能够吸收紫外射线并再次以更长波辐射如热放出吸收的能量的有机物质。术语“有机UV光保护过滤剂”涉及一种类型所述化合物或不同类型所述化合物的混合物。有机物质可以是油溶性的或水溶性的或者它们可以与聚合物结合。光保护过滤剂可以是UV-A和UV-B过滤剂,优选UV-B过滤剂。光保护过滤剂通常为无色至浅黄色化合物。优选光保护过滤剂不能在所施用浓度下肉眼检测。
可以使用的UV-B过滤剂例如为下列物质:
-3-亚苄基樟脑及其衍生物,例如3-(4-甲基亚苄基)樟脑;
-4-氨基苯甲酸衍生物,优选4-(二甲氨基)苯甲酸2-乙基己基酯、4-(二甲氨基)苯甲酸2-辛基酯和4-(二甲氨基)苯甲酸戊基酯;
-肉桂酸的酯,优选4-甲氧基肉桂酸2-乙基己基酯、4-甲氧基肉桂酸丙酯、4-甲氧基肉桂酸异戊酯、4-甲氧基肉桂酸异戊基酯、2-氰基-3-苯基肉桂酸2-乙基己基酯(奥克立林(otocrylene));
-水杨酸酯,优选水杨酸2-乙基己基酯、水杨酸4-异丙基苄基酯、水杨酸三甲环己酯;
-二苯甲酮衍生物,优选2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-4′-甲基二苯甲酮、2,2′-二羟基-4-甲氧基二苯甲酮;
-亚苄基丙二酸酯,优选4-甲氧基亚苄基丙二酸2-乙基己基酯;
-丙烷-1,3-二酮类,例如1-(4-叔丁基苯基)-3-(4′-甲氧基苯基)丙烷-1,3-二酮。
-2-苯基苯并咪唑-5-磺酸及其碱金属、碱土金属、铵、烷基铵、链烷醇铵和葡糖铵盐;
-二苯甲酮类的磺酸衍生物,优选2-羟基-4-甲氧基二苯甲酮-5-磺酸及其盐;
-3-亚苄基樟脑的磺酸衍生物,例如4-(2-氧代-3-亚冰片基甲基)苯磺酸和2-甲基-5-(2-氧代-3-亚冰片基)磺酸及其盐。
优选的UV-B过滤剂是二苯甲酮的衍生物。
合适的UV-A过滤剂是:
-苯甲酰基甲烷的衍生物,如1-(4′-叔丁基苯基)-3-(4′-甲氧基苯基)丙烷-1,3-二酮、4-叔丁基-4′-甲氧基二苯甲酰基甲烷或1-苯基-3-(4′-异丙基苯基)丙烷-1,3-二酮;
-二苯甲酮类的氨基羟基取代衍生物,例如N,N-二乙基氨基羟基苯甲酰基苯甲酸正己基酯。
UV-A和UV-B过滤剂当然还可以以混合物使用。
有机UV光保护过滤剂在农化配制剂中的总量通常为0.5-30重量%,优选2-20重量%,更优选5-15重量%。有机UV光保护过滤剂与涂敷的金属氧化物纳米颗粒的重量比通常为10∶1-1∶10,优选5∶1-1∶5,更优选3∶1-1∶2。
农药与有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的总质量的重量比通常为50∶1-1∶10,优选20∶1-1∶2,最优选10∶1-1∶1。
农化配制剂还可以包含一种或多种抗氧化剂。优选农化配制剂包含抗氧化剂。抗氧化剂例如为氨基酸(例如甘氨酸、组氨酸、酪氨酸、色氨酸)及其衍生物,咪唑和咪唑衍生物(例如尿刊酸),肽类,如D,L-肌肽、D-肌肽、L-肌肽及其衍生物(例如鹅肌肽),类胡萝卜素,胡萝卜素类(例如α-胡萝卜素、β-胡萝卜素、番茄红素)及其衍生物,硫辛酸及其衍生物(例如二氢硫辛酸),金硫葡糖,丙硫尿嘧啶和其他硫代化合物(例如硫甘油、硫代山梨醇、巯基乙酸、硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺及其糖基、N-乙酰基、甲基、乙基、丙基、戊基、丁基、月桂基、棕榈酰基、油基、γ-亚油基、胆甾烯基和甘油基酯)及其盐,硫代二丙酸二月桂基酯,硫代二丙酸二硬脂基酯,硫代二丙酸及其衍生物(酯、醚、肽、类脂、核苷酸、核苷和盐),以及非常低耐受剂量(例如pmol/kg至pmol/kg)的亚砜胺(sulfoximine)化合物(例如丁硫氨酸亚砜胺,高半胱氨酸亚砜胺,丁硫氨酸砜,戊硫堇(pentathionine)、己硫堇(hexathionine)、庚硫堇(heptathionine)亚砜胺),还有金属螯合剂(例如α-羟基脂肪酸,EDTA,EGTA,植酸,乳铁蛋白),α-羟基酸(例如柠檬酸、乳酸、苹果酸),腐殖酸,胆汁酸,胆汁提取物,没食子酸酯(例如没食子酸丙基、辛基和十二烷基酯),类黄酮,儿茶素,胆红素,胆绿素及其衍生物,不饱和脂肪酸及其衍生物(例如γ-亚麻酸、亚油酸、花生四烯酸、油酸),叶酸及其衍生物,氢醌及其衍生物(例如熊果苷),泛醌和泛醇及其衍生物,维生素C及其衍生物(例如抗坏血酰棕榈酸酯、硬脂酸酯、二棕榈酸酯、乙酸酯,抗坏血酰磷酸酯镁,抗坏血酸钠和镁,抗坏血酰磷酸酯和硫酸酯二钠,抗坏血酰生育酚磷酸酯钾,脱乙酰壳多糖抗坏血酸酯),异抗坏血酸及其衍生物,生育酚类及其衍生物(例如生育酚乙酸酯、亚油酸酯、油酸酯和琥珀酸酯,生育酚聚醚-5,生育酚聚醚-10,生育酚聚醚-12,生育酚聚醚-18,生育酚聚醚-50,水溶性维生素E(tocophersolan)),维生素A和衍生物(例如维生素A棕榈酸酯),苯偶姻树脂的苯甲酸松柏基酯,芸香苷,芸香亭酸及其衍生物,芸香亭基硫酸二钠,肉桂酸及其衍生物(例如阿魏酸、阿魏酸乙酯、咖啡酸),曲酸,脱乙酰壳多糖乙醇酸酯和水杨酸酯,丁羟基甲苯,丁羟基茴香醚,去甲二氢愈创酸(nordihydroguaiacic acid),去甲二氢愈创木酸,三羟基苯丁酮,尿酸及其衍生物,甘露糖及其衍生物,硒和硒衍生物(例如硒代蛋氨酸),茋和茋衍生物(例如氧化茋、反式-氧化茋)。根据本发明,可以使用合适的衍生物(盐、酯、糖类、核苷酸、核苷、肽和类脂)以及这些所述活性成分的混合物或包含这些抗氧化剂的植物提取物(例如茶树油、迷迭香提取物和迷迭香酸)。上述抗氧化剂的混合物通常是可能的。
优选的抗氧化剂为生育酚类、丁羟基甲苯和丁羟基茴香醚。
抗氧化剂在农化配制剂中的总量通常为0-20重量%,优选0.05-10重量%,尤其是0.1-5重量%,非常特别优选0.1-2重量%。
农化配制剂可以额外包含自由基清除剂。大多数抗氧化剂如丁羟基甲苯和丁羟基茴香醚通常也起自由基清除剂的作用。自由基清除剂的其他实例是所谓的受阻胺光稳定剂(HALS),例如N,N′-1,6-己二基二(N-(2,2,6,6-四甲基哌啶基甲酰胺)(以4050H由BASF SE市购),1-乙酰基-4-(3-十二烷基-2,5-二氧代-1-吡咯烷基)-2,2,6,6-四甲基哌啶(来自Clariant的3058 Liquid),癸二酸二(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)酯(可以123由Ciba市购),癸二酸二(1,2,2,6,6-五-甲基-4-哌啶基)酯(可以292由Ciba市购)。优选的自由基清除剂是受阻胺光稳定剂。
自由基清除剂在农化配制剂中的总量通常为0-20重量%,优选0.05-10重量%,尤其是0.1-5重量%。
任选地,农化配制剂可以额外包含未涂敷的金属氧化物颗粒。这些未涂敷的金属氧化物可以选自锌(例如ZnO)、铁(例如Fe2O3)、锆(例如ZrO2)、硅(例如SiO2)、锰(例如MnO)、铝(例如氧化铝A12O3)、铈(例如Ce2O3)的氧化物,相应金属的混合氧化物以及该类氧化物的混合物。优选氧化锌。未涂敷的金属氧化物颗粒在农化配制剂中的总量通常为0-30重量%,优选2-20重量%,更优选5-15重量%。在优选实施方案中,农化配制剂基本不含,优选不含未涂敷的金属氧化物颗粒。
本发明农化配制剂可以额外包含配制助剂。术语“配制助剂”在本发明含义内是适合配制农药的辅助剂,如其他溶剂和/或载体和/或表面活性剂(离子性或非离子性表面活性剂、助剂、分散剂)和/或防腐剂和/或消泡剂和/或防冻剂。
合适溶剂的实例是水,芳族溶剂(例如Solvesso产品,二甲苯),石蜡(例如矿物油馏分如煤油或柴油)、煤焦油以及植物或动物来源的油,脂族、环状和芳族烃类,例如甲苯、二甲苯、石蜡、四氢化萘、烷基化萘或其衍生物,醇类(例如甲醇、丁醇、戊醇、苄醇、环己醇),酮类(例如环己酮、γ-丁内酯),吡咯烷酮类(NMP,NEP,NOP),乙酸酯类(乙二醇二乙酸酯),二醇类,脂肪酸二甲基酰胺类,脂肪酸和脂肪酸酯,异佛尔酮和二甲亚砜。原则上还可以使用溶剂混合物。
合适的表面活性剂是木素磺酸、萘磺酸、苯酚磺酸、二丁基萘磺酸的碱金属、碱土金属和铵盐,烷基芳基磺酸盐,烷基硫酸盐,烷基磺酸盐,脂肪醇硫酸盐,脂肪酸和硫酸化脂肪醇乙二醇醚,此外还有磺化萘和萘衍生物与甲醛的缩合物,萘或萘磺酸与苯酚和甲醛的缩合物,聚氧乙烯辛基酚醚,乙氧基化异辛基酚、辛基酚、壬基酚,烷基酚聚乙二醇醚、三丁基苯基聚乙二醇醚、三硬脂基苯基聚乙二醇醚、烷基芳基聚醚醇、醇和脂肪醇/氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚,乙氧基化聚氧丙烯,月桂醇聚乙二醇醚缩醛,山梨醇酯,木素亚硫酸盐废液和甲基纤维素。
合适载体的实例是矿土如硅胶、硅酸盐、滑石、高岭土、活性粘土(attaclay)、石灰石、石灰、白垩、红玄武土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁、氧化镁,磨碎的合成材料,肥料如硫酸铵、磷酸铵、硝酸铵、脲类以及植物来源的产品,如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉,聚乙烯基吡咯烷酮和其他固体载体。
还可以向该配制剂中加入防冻剂如甘油、乙二醇、己二醇、丙二醇和杀菌剂。
合适的消泡剂例如为基于硬脂酸硅或镁的消泡剂。
合适的防腐剂例如为1,2-苯并异噻唑啉-3-酮和/或2-甲基-2H-异噻唑-3-酮或苯甲酸钠或苯甲酸。
术语“农药”在本发明含义内表示一种或多种化合物可以选自杀真菌剂、杀虫剂、杀线虫剂、除草剂和/或安全剂或生长调节剂,优选选自杀真菌剂、杀虫剂或杀线虫剂。还可以使用两种或更多种上述类别农药的混合物。熟练技术人员熟知该类农药,它们例如可以在the Pesticide Manual,第13版(2003),The British Crop Protection Council,London中找到。
下列农药用于说明可能的组合,但不施加任何限制:
杀真菌剂可以选自:
A)嗜球果伞素类:
腈嘧菌酯(azoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌酯(enestroburin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、pyribencarb、肟菌酯(trifloxystrobin)、2-(2-(6-(3-氯-2-甲基苯氧基)-5-氟嘧啶-4-基氧基)苯基)-2-甲氧亚氨基-N-甲基乙酰胺、3-甲氧基-2-(2-(N-(4-甲氧基苯基)环丙烷亚胺酰硫基甲基)苯基)丙烯酸甲酯、(2-氯-5-[1-(3-甲基苄氧亚氨基)乙基]苄基)氨基甲酸甲酯和2-(2-(3-(2,6-二氯苯基)-1-甲基亚烯丙基氨基氧甲基)苯基)-2-甲氧亚氨基-N-甲基乙酰胺;
B)羧酰胺类:
-羧酰苯胺类:苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M)、麦锈灵(benodanil)、bixafen、啶酰菌胺(boscalid)、萎锈灵(carboxin)、呋菌胺(fenfuram)、环酰菌胺(fenhexamid)、氟酰胺(flutolanil)、呋吡唑灵(furametpyr)、isopyrazam、异噻菌胺(isotianil)、kiralaxyl、丙氧灭绣胺(mepronil)、甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M(mefenoxam))、甲呋酰胺(ofurace)、霜灵(oxadixyl)、氧化萎锈灵(oxycarboxin)、吡噻菌胺(penthiopyrad)、叶枯酞(tecloftalam)、溴氟唑菌(thifluzamide)、噻酰菌胺(tiadinil)、2-氨基-4-甲基噻唑-5-甲酰苯胺、2-氯-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)烟酰胺、N-(2′,4′-二氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′,4′-二氯联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′,5′-二氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′,5′-二氯联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,5′-二氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′-氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′-氯联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′-氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′-氯联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,5′-二氯联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,4′,5′-三氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′,4′,5′-三氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-[2-(1,1,2,3,3,3-六氟丙氧基)苯基]-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-[2-(1,1,2,2-四氟乙氧基)苯基]-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(4′-三氟甲硫基联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2-(1,3-二甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺、N-(2-(1,3,3-三甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺、N-(4′-氯-3′,5′-二氟-联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(4′-氯-3′,5′-二氟-联苯-2-基)-3-三氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,4′-二氯-5′-氟-联苯-2-基)-3-三氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,5′-二氟-4′-甲基-联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,5′-二氟-4′-甲基-联苯-2-基)-3-三氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2-双环丙-2-基苯基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(顺式-2-双环丙-2-基苯基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(反式-2-双环丙-2-基苯基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-[1,2,3,4-四氢-9-(1-甲基乙基)-1,4-亚甲基萘-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰胺;
-羧酸吗啉化物:烯酰吗啉(dimethomorph)、氟吗啉(flumorph);
-苯甲酰胺类:氟联苯菌(flumetover)、氟吡菌胺(fluopicolide)、氟吡菌酰胺(fluopyram);
-其他羧酰胺类:氯环丙酰胺(carpropamid)、双氯氰菌胺(diclocymet)、双炔酰菌胺(mandipropamid)、土霉素(oxytetracyclin)、硅噻菌胺(silthiofarm)和N-(6-甲氧基吡啶-3-基)环丙烷甲酰胺;
C)唑类:
-三唑类:戊环唑(azaconazole)、双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、醚唑(difenoconazole)、烯唑醇(diniconazole)、烯唑醇M(diniconazole-M)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、喹唑菌酮(fluquinconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、酰胺唑(imibenconazole)、环戊唑醇(ipconazole)、环戊唑菌(metconazole)、腈菌唑(myclobutanil)、oxpoconazole、多效唑(paclobutrazole)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazole)、三唑酮(triadimefon)、唑菌醇(triadimenol)、戊叉唑菌(triticonazole)、烯效唑(uniconazole)、1-(4-氯苯基)-2-([1,2,4]三唑-1-基)环庚醇;
-咪唑类:氰霜唑(cyazofamid)、烯菌灵(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizol);
-苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole);
-其他:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole)和2-(4-氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2-炔基氧基乙酰胺;
D)含氮杂环化合物
-吡啶类:氟啶胺(fluazinam)、啶斑肟(pyrifenox)、3-[5-(4-氯苯基)-2,3-二甲基异唑烷-3-基]吡啶、3-[5-(4-甲基苯基)-2,3-二甲基异唑烷-3-基]吡啶、2,3,5,6-四氯-4-甲磺酰基吡啶、3,4,5-三氯吡啶-2,6-二甲腈、N-(1-(5-溴-3-氯吡啶-2-基)乙基)-2,4-二氯烟酰胺、N-((5-溴-3-氯吡啶-2-基)甲基)-2,4-二氯烟酰胺;
-嘧啶类:磺嘧菌灵(bupirimate)、环丙嘧啶(cyprodinil)、二氟林(diflumetorim)、异嘧菌醇(fenarimol)、嘧菌腙(ferimzone)、嘧菌胺(mepanipyrim)、氯草定(nitrapyrin)、氟苯嘧啶醇(nuarimol)、二甲嘧菌胺(pyrimethanil);
-哌嗪类:嗪氨灵(triforine);
-吗啉类:4-十二烷基-2,6-二甲基吗啉(aldimorph)、吗菌灵(dodemorph)、吗菌灵乙酸酯(dodemorph-acetate)、丁苯吗啉fenpropimorph)、克啉菌(tridemorph);
-哌啶类:苯锈啶(fenpropidin);
-二羧酰亚胺类:氟菌安(fluoroimid)、异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin);
-非芳族5员杂环:唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、异噻菌酮(octhilinone)、噻菌灵(probenazole)、5-氨基-2-异丙基-3-氧代-4-邻甲苯基-2,3-二氢吡唑-1-硫代甲酸S-烯丙基酯;
-其他:噻二唑素(acibenzolar-S-methyl)、amisulbrom、敌菌灵(anilazin)、灭瘟素(blasticidin-S)、敌菌丹(captafol)、克菌丹(captan)、灭螨蜢(chinomethionat)、棉隆(dazomet)、咪菌威(debacarb)、哒菌清(diclomezine)、野燕枯(difenzoquat)、野燕枯甲基硫酸酯(difenzoquat-methylsulfate)、氰菌胺(fenoxanil)、灭菌丹(folpet)、恶喹酸(oxolinicacid)、粉病灵(piperalin)、丙氧喹啉(proquinazid)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、唑菌嗪(triazoxide)、三环唑(tricyclazole)、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、5-氯-1-(4,6-二甲氧基嘧啶-2-基)-2-甲基-1H-苯并咪唑、5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶、6-(3,4-二氯苯基)-5-甲基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-(4-叔丁基苯基)-5-甲基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-甲基-6-(3,5,5-三甲基己基)-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-甲基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-甲基-5-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-乙基-5-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-乙基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-乙基-6-(3,5,5-三甲基己基)-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-辛基-5-丙基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-甲氧基甲基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-辛基-5-三氟甲基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺和5-三氟甲基-6-(3,5,5-三甲基己基)-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺;
E)氨基甲酸盐
-硫代-和二硫代氨基甲酸盐:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、威百亩(metam)、磺菌威(methasulfocarb)、代森联(metiram)、甲基代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram);
-氨基甲酸盐:苯噻菌胺(benthiavalicarb)、乙霉威(diethofencarb)、flubenthiavalicarb、异丙菌胺(iprovalicarb)、百维灵(propamocarb)、霜霉威盐酸盐(propamocarb hydrochlorid)、valiphenal和N-(1-(1-(4-氰基苯基)乙磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
F)其他活性物质
-胍类:胍、多果定(dodine)、多果定游离碱、双胍盐(guazatine)、双胍辛胺(guazatine-acetate)、双胍辛醋酸盐(iminoctadine)、双胍辛胺三乙酸盐(iminoctadine triacetate)、双八胍盐(iminoctadine tris(albesilate));
-抗生素类:春雷素(kasugamycin)、水合春雷素(kasugamycinhydrochloride-hydrate)、链霉素(streptomycin)、多氧霉素(polyoxine)、井冈霉素(validamycin A);
-硝基苯基衍生物:乐杀螨(binapacryl)、敌螨通(dinobuton)、敌螨普(dinocap)、异丙消(nitrothal-isopropyl)、四氯硝基苯(tecnazene);
-有机金属化合物:三苯锡基盐,例如薯瘟锡(fentin-acetate)、三苯锡氯(fentin chloride)或毒菌锡(fentin hydroxide);
-含硫杂环化合物:二噻农(dithianon)、稻瘟灵(isoprothiolane);
-有机磷化合物:克瘟散(edifenphos)、藻菌磷(fosetyl)、乙磷铝(fosetyl-aluminum)、异稻瘟净(iprobenfos)、亚磷酸及其盐、定菌磷(pyrazophos)、甲基立枯磷(tolclofos-methyl);
-有机氯化合物:百菌清(chlorothalonil)、抑菌灵(dichlofluanid)、双氯酚(dichlorophen)、磺菌胺(flusulfamide)、六氯苯(hexachlorobenzene)、戊菌隆(pencycuron)、五氯酚(pentachlorphenole)及其盐、四氯苯酞(phthalide)、五氯硝基苯(quintozene)、甲基托布津(thiophanate-methyl)、对甲抑菌灵(tolylfluanid)、N-(4-氯-2-硝基苯基)-N-乙基-4-甲基苯磺酰胺;
-无机活性物质:波尔多液(Bordeaux混合物)、醋酸铜、氢氧化铜、王铜(copper oxychloride)、碱式硫酸铜,硫;
-其他:联苯、拌棉醇(bronopol)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、二苯胺、苯菌酮(metrafenone)、米多霉素(mildiomycin)、喹啉铜(oxin-copper)、调环酸钙(prohexadione-calcium)、螺茂胺(spiroxamine)、对甲抑菌灵、N-(环丙基甲氧亚氨基-(6-二氟-甲氧基-2,3-二氟苯基)甲基)-2-苯基乙酰胺、N′-(4-(4-氯-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N′-(4-(4-氟-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N′-(2-甲基-5-三氟甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒和N′-(5-二氟甲基-2-甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒。
除草剂可以选自:
-乙酰胺类:乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、异丙甲草胺(metolachlor)、吡草胺(metazachlor)、草萘胺(napropamid)、萘丙胺(naproanilide)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、扑草胺(propachlor)、噻醚草胺(thenylchlor);
-氨基酸衍生物:双丙氨酰膦(bilanafos)、草甘膦(glyphosate)、草铵膦(glufosinate)、草硫膦(sulfosate);
-芳氧基苯氧基丙酸酯类:炔草酯(clodinafop)、氰氟草酯(cyhalofop-butyl)、唑禾草灵(fenoxaprop)、吡氟禾草灵(fluazifop)、吡氟氯禾灵(haloxyfop)、恶唑酰草胺(metamifop)、喔草酯(propaquizafop)、喹禾灵(quizalofop)、喹禾灵(四氢糠基酯)(quizalofop-P-tefuryl);
-联吡啶类:敌草快阳离子(diquat)、对草快阳离子(paraquat);
-(硫代)氨基甲酸酯类:黄草灵(asulam)、苏达灭(butylate)、长杀草(carbetamide)、异苯敌草(desmedipham)、哌草丹(dimepiperate)、扑草灭(eptam)(EPTC)、禾草畏(esprocarb)、草达灭(molinate)、坪草丹(orbencarb)、苯敌草(phenmedipham)、苄草丹(prosulfocarb)、稗草畏(pyributicarb)、杀草丹(thiobencarb)、野麦畏(triallate);
-环己二酮类:丁氧环酮(butroxydim)、烯草酮(clethodim)、噻草酮(cycloxydim)、环苯草酮(profoxydim)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim);
-二硝基苯胺类:氟草胺(benfluralin)、丁氟消草(ethalfluralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、氟乐灵(trifluralin);
-二苯基醚类:氟锁草醚(acifluorfen)、苯草醚(aclonifen)、治草醚(bifenox)、氯甲草(diclofop)、氯氟草醚(ethoxyfen)、氟黄胺草醚(fomesafen)、乳氟禾草灵(lactofen)、乙氧氟草醚(oxyfluorfen);
-羟基苄腈类:溴苯腈(bromoxynil)、敌草腈(dichlobenil)、碘苯腈(ioxynil);
-咪唑啉酮类:咪草酯(imazamethabenz)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr);
-苯氧基乙酸类:稗草胺(clomeprop)、2,4-二氯苯氧基乙酸(2,4-D)、2,4-DB、2,4-滴丙酸(dichlorprop)、MCPA、2甲4氯乙硫酯(MCPA-thioethyl)、MCPB、2甲4氯丙酸(mecoprop);
-吡嗪类:杀草敏(chloridazon)、氟哒嗪草酯(flufenpyr-ethyl)、达草氟(fluthiacet)、达草灭(norflurazon)、达草止(pyridate);
-吡啶类:氨草啶(aminopyralid)、二氯皮考啉酸(clopyralid)、吡氟草胺(diflufenican)、氟硫草定(dithiopyr)、氟草同(fluridone)、氟草烟(fluroxypyr)、毒莠定(picloram)、氟吡酰草胺(picolinafen)、噻氟啶草(thiazopyr);
-磺酰脲类:磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、氯嘧黄隆(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟吡磺隆(flucetosulfuron)、氟啶黄隆(flupyrsulfuron)、酰胺磺隆(foramsulfuron)、吡氯黄隆(halosulfuron)、啶咪黄隆(imazosulfuron)、甲基碘磺隆(iodosulfuron)、甲磺胺磺隆(mesosulfuron)、甲黄隆(metsulfuron-methyl)、烟嘧黄隆(nicosulfuron)、环丙氧黄隆(oxasulfuron)、氟嘧黄隆(primisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、乙黄黄隆(sulfosulfuron)、噻黄隆(thifensulfuron)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、三氟啶磺隆(trifloxysulfuron)、氟胺磺隆(triflusulfuron)、三氟甲磺隆(tritosulfuron)、1-((2-氯-6-丙基咪唑并[1,2-b]哒嗪-3-基)磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲;
-三嗪类:莠灭净(ametryn)、莠去津(atrazine)、草净津(cyanazine)、戊草津(dimethametryn)、乙嗪草酮(ethiozin)、六嗪同(hexazinone)、苯嗪草(metamitron)、赛克津(metribuzin)、扑草净(prometryn)、西玛津(simazine)、特丁津(terbuthylazine)、去草净(terbutryn)、苯氧丙胺津(triaziflam);
-脲类:绿麦隆(chlorotoluron)、香草隆(daimuron)、敌草隆(diuron)、伏草隆(fluometuron)、异丙隆(isoproturon)、利谷隆(linuron)、噻唑隆(methabenzthiazuron)、丁唑隆(tebuthiuron);
-其他乙酰乳酸合成酶抑制剂:双草醚钠盐(bispyribac-sodium)、氯酯磺草胺(cloransulam-methyl)、唑嘧磺胺(diclosulam)、双氟磺草胺(florasulam)、氟酮磺隆(flucarbazone)、氟唑啶草(flumetsulam)、唑草磺胺(metosulam)、嘧苯胺磺隆(ortho-sulfamuron)、五氟磺草胺(penoxsulam)、丙氧基卡巴腙(propoxycarbazone)、丙酯草醚(pyribambenz-propyl)、嘧苯草肟(pyribenzoxim)、环酯草醚(pyriftalid)、肟啶草(pyriminobac-methyl)、pyrimisulfan、嘧硫苯甲酸(pyrithiobac)、pyroxasulfone、甲氧磺草胺(pyroxsulam);
-其他:胺唑草酮(amicarbazone)、三唑胺(aminotriazole)、莎稗磷(anilofos)、beflubutamid、草除灵(benazolin)、bencarbazone、benfluresate、吡草酮(benzofenap)、噻草平(bentazone)、苯并双环酮(benzobicyclon)、除草定(bromacil)、溴丁酰草胺(bromobutide)、氟丙嘧草酯(butafenacil)、草胺磷(butamifos)、胺草唑(cafenstrole)、氟酮唑草(carfentrazone)、吲哚酮草酯(cinidon-ethyl)、敌草索(chlorthal)、环庚草醚(cinmethylin)、异恶草酮(clomazone)、苄草隆(cumyluron)、cyprosulfamide、麦草畏(dicamba)、苯敌快(difenzoquat)、二氟吡隆(diflufenzopyr)、稗内脐蠕孢菌(Drechslera monoceras)、敌草腈(endothal)、乙呋草黄(ethofumesate)、乙苯酰草(etobenzanid)、四唑酰草胺(fentrazamide)、氟烯草酸(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、胺草唑(flupoxam)、氟咯草酮(fluorochloridone)、呋草酮(flurtamone)、茚草酮(indanofan)、异恶草胺(isoxaben)、异氟草(isoxaflutole)、环草定(lenacil)、敌稗(propanil)、拿草特(propyzamide)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、硝草酮(mesotrione)、甲胂酸(methylarsonic acid)、抑草生(naptalam)、炔丙唑草(oxadiargyl)、恶草灵(oxadiazon)、氯嗪草(oxaziclomefone)、戊唑草(pentoxazone)、唑啉草酯(pinoxaden)、双唑草腈(pyraclonil)、吡草醚(pyraflufen-ethyl)、pyrasulfotole、苄草唑(pyrazoxyfen)、吡唑特(pyrazolynate)、灭藻醌(quinoclamine)、嘧啶肟草醚(saflufenacil)、磺草酮(sulcotrione)、磺胺草唑(sulfentrazone)、特草定(terbacil)、tefuryltrione、tembotrione、thiencarbazone、topramezone、4-羟基-3-[2-(2-甲氧基乙氧基甲基)-6-三氟甲基吡啶-3-羰基]双环[3.2.1]辛-3-烯-2-酮、(3-[2-氯-4-氟-5-(3-甲基-2,6-二氧代-4-三氟甲基-3,6-二氢-2H-嘧啶-1-基)苯氧基]吡啶-2-基氧基)乙酸乙酯、6-氨基-5-氯-2-环丙基嘧啶-4-甲酸甲酯、6-氯-3-(2-环丙基-6-甲基苯氧基)哒嗪-4-醇、4-氨基-3-氯-6-(4-氯苯基)-5-氟吡啶-2-甲酸、4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-甲酸甲酯和4-氨基-3-氯-6-(4-氯-3-二甲基氨基-2-氟苯基)吡啶-2-甲酸甲酯。
杀虫剂可以选自:
-有机(硫代)磷酸酯:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、毒虫畏(chlorfenvinphos)、二嗪农(diazinon)、敌敌畏(dichlorvos)、百治磷(dicrotophos)、乐果(dimethoate)、乙拌磷(disulfoton)、乙硫磷(ethion)、杀螟松(fenitrothion)、倍硫磷(fenthion)、异唑磷(isoxathion)、马拉硫磷(malathion)、甲胺磷(methamidophos)、杀扑磷(methidathion)、甲基对硫磷(methyl-parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸磷(oxydemeton-methyl)、对氧磷(paraoxon)、一六零五(parathion)、稻丰散(phenthoate)、伏杀硫磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、甲拌磷(phorate)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、丙硫磷(prothiofos)、田乐磷(sulprophos)、杀虫威(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(triazophos)、敌百虫(trichlorfon);
-氨基甲酸酯类:棉铃威(alanycarb)、涕灭威(aldicarb)、虫威(bendiocarb)、丙硫克百威(benfuracarb)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、双氧威(fenoxycarb)、呋线威(furathiocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、唑蚜威(triazamate);
-拟除虫菊酯类:丙烯除虫菊(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、(RS)氯氟氰菊酯(cyhalothrin)、苯醚氰菊酯(cyphenothrin)、氯氰菊酯(cypermethrin)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、氯氟氰菊酯(lambda-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊(pyrethrin)I和II、灭虫菊(resmethrin)、灭虫硅醚(silafluofen)、氟胺氰菊酯(tau-fluvalinate)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin)、丙氟菊酯(profluthrin)、四氟甲醚菊酯(dimefluthrin);
-昆虫生长调节剂:a)几丁质合成抑制剂:苯甲酰脲类:定虫隆(chlorfluazuron)、灭蝇胺(cyramazin)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron);噻嗪酮(buprofezin)、茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯唑(etoxazole)、四螨嗪(clofentazine);b)蜕皮激素拮抗剂:特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide)、艾扎丁(azadirachtin);c)保幼激素类似物:蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)、双氧威;d)类脂生物合成抑制剂:例如螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramate);
-烟碱受体激动剂/拮抗剂化合物:噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、吡虫清(acetamiprid)、噻虫啉(thiacloprid)、1-(2-氯噻唑-5-基甲基)-2-硝酰亚氨基(nitrimino)-3,5-二甲基-[1,3,5]三嗪烷(triazinane);
-GABA拮抗剂化合物:硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、5-氨基-1-(2,6-二氯-4-甲基苯基)-4-亚磺酰氨酰基(sulfinamoyl)-1H-吡唑-3-硫代甲酰胺;
-大环内酯杀虫剂:齐墩螨素(abamectin)、甲氨基阿维菌素(emamectin)、米尔螨素(milbemectin)、lepimectin、艾克敌105(spinosad)、spinetoram;
-线粒体电子传输抑制剂(METI)I杀螨剂:喹螨醚(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、嘧虫胺(flufenerim);
-METI II和III化合物:灭螨醌(acequinocyl)、fluacyprim、灭蚁腙(hydramethylnon);
-分离剂:氟唑虫清(chlorfenapyr);
-氧化磷酸化抑制剂:三环锡(cyhexatin)、杀螨硫隆(diafenthiuron)、杀螨锡(fenbutatin oxide)、克螨特(propargite);
-蜕皮(moulting)干扰剂化合物:灭蝇胺(cryomazine);
-混合功能氧化酶抑制剂:增效醚(piperonyl butoxide);
-其他:benclothiaz、联苯肼酯(bifenazate)、杀螟丹(cartap)、氟啶虫酰胺(flonicamid)、啶虫丙醚(pyridalyl)、拒嗪酮(pymetrozine)、硫、硫环杀(thiocyclam)、氟虫酰胺(flubendiamide)、氯虫酰胺(chlorantraniliprole)、cyazypyr(HGW86)、cyenopyrafen、吡氟硫磷(flupyrazofos)、丁氟螨酯(cyflumetofen)、amidoflumet、imicyafos、双三氟虫脲(bistrifluron)和pyrifluquinazon。
生长调节剂可以选自脱落酸(abscisic acid)、先甲草胺(amidochlor)、嘧啶醇(ancymidol)、苄胺基嘌呤(6-benzylaminopurine)、油菜素内酯(brassinolide)、地乐胺(butralin)、矮壮素阳离子(chlormequat)(矮壮素(chlormequat chloride))、氯化胆碱(cholin chloride)、环丙酸酰胺(cyclanilide)、丁酰肼(daminozide)、敌草克(dikegulac)、噻节因(dimethipin)、2,6-二甲基吡啶(2,6-dimethylpuridine)、乙烯利(ethephon)、抑芽敏(flumetralin)、呋嘧醇(flurprimidol)、达草氟(fluthiacet)、调吡脲(forchlorfenuron)、九二O(gibberellic acid)、抗倒胺(inabenfide)、吲哚-3-乙酸、抑芽丹(maleic hydrazide)、氟草磺(mefluidide)、助壮素阳离子(mepiquat)(助壮素(mepiquat chloride))、萘乙酸、N-6-苄基腺嘌呤、多效唑、调环酸(prohexadione)(调环酸钙)、茉莉酸丙酯(prohydrojasmon)、赛二唑素(thidiazuron)、抑芽唑(triapenthenol)、脱叶磷(tributylphosphorotrithioate)、2,3,5-三碘苯甲酸、抗倒酯(trinexapac-ethyl)和烯效唑(unicon azole)。
在优选实施方案中,农药对UV光敏感。敏感性可以通过简单试验检测,其中将农药暴露于UV光一定时间。然后可以对未分解的残留农药定量。
优选的除草剂是草萘胺、敌稗(proparnil)、噻草平、对草快(Paraquatdichloride)、噻草酮、稀禾定、丁氟消草、黄草消、胺硝草、氟乐灵、氟锁草醚(Acifluren)、苯草醚、氟黄胺草醚、乙氧氟草醚(oxyfluoren)、碘苯腈、咪草烟、灭草喹、杀草敏、达草灭、噻氟啶草、绿草定(Triclopyr)、氟硫草定、吡氟草胺、氟吡酰草胺、磺氨黄隆、草达灭、灭草猛(vernolate)、Promethon、赛克津、唑啶草酮(azafenidin)、氟酮唑草(Carfentrazone-ethyl)、磺胺草唑、甲氧隆(metoxuron)、绿谷隆(monolinuron)、氟消草(Fluchloralin)和抑草丁(Flurenol)。
优选的杀真菌剂是环丙嘧啶、麦穗宁、烯酰吗啉、丙氯灵、氟菌唑、克啉菌、克瘟散(edifenfos)、异嘧菌醇、氟苯嘧啶醇、乙嘧酚(ethirimol)、喹氧灵(quinoxylen)、二噻农、叉氨苯酰胺、肟菌酯、抑菌灵(Dichlofluamid)、糠菌唑(Bromuconnazol)和腈菌唑。
优选的杀虫剂是高灭磷、乙基谷硫磷(Azinphos-Ethyl)、谷硫磷、甲基异柳磷(Isofenphos)、甲基毒死蜱、甲基毒虫畏(dimethylvinphos)、甲拌磷、辛硫磷、丙硫磷、三环锡、棉铃威、杀虫丹(Ethiofencarb)、抗蚜威、硫双威、锐劲特、生物烯丙菊酯(bioallethrin)、生物苄呋菊酯(bioresmethin)、溴氰菊酯、甲氰菊酯(fenpropathin)、氟氰戊菊酯(Flucythrinate)、氟胺氰菊酯、氯氰菊酯、己体氯氰菊酯、灭虫菊(resmethin)、七氟菊酯、氯氟氰菊酯和灭蚁腙。在另一优选实施方案中,杀虫剂为氰氟虫胺或甲体氯氰菊酯。
农药最优选为氰氟虫胺或甲体氯氰菊酯,尤其是氰氟虫胺。
本发明农化配制剂由一种其中混合农药、有机UV过滤剂和涂敷的金属氧化物纳米颗粒的方法制备。通常可以将所述化合物在一步或多步混合中以任何顺序混合。农药、有机UV过滤剂和涂敷的金属氧化物纳米颗粒可以一起或单独加入任何制备农化配制剂的方法中。可以将所述化合物中的一种或多种加入农化配制剂并将残留化合物加入包含所述农化配制剂的桶混物中。
合适农化配制剂的实例是液体配制剂如EC(可乳化浓缩物)配制剂;SL或LS(可溶性浓缩物)配制剂;EW(水包油乳液)配制剂;ME(微乳液)配制剂;MEC(可微乳化浓缩物)配制剂;CS(胶囊悬浮液)配制剂;TK(母药)配制剂;OD(油基悬浮浓缩物)配制剂;SC(悬浮浓缩物)配制剂;SE(悬浮乳液)配制剂;ULV(超低体积液体)配制剂;SO(铺展油)配制剂;AL(任何其他液体)配制剂;LA(漆)配制剂;DC(分散性浓缩物)配制剂;或固体配制剂如WG(水分散性颗粒)配制剂;TB(片剂)配制剂;FG(细颗粒)配制剂;MG(微粒剂)配制剂;SG(可溶性颗粒)。优选的液体配制剂是EC、SL、LS、EW、ME、MEC、TK、OD、SC、SE、ULV、SO、AL、LA和DC。
优选的农化配制剂是液体配制剂。更优选该液体农化配制剂包含作为液滴溶解、乳化或作为基质颗粒悬浮的农药。甚至更优选该液体农化配制剂包含作为液滴溶解或乳化的农药。术语“基质颗粒”指其中农药均匀分布在整个颗粒中的颗粒。为了对比,在包封农药颗粒(不为基质颗粒)中,农药浓集在核中并因此通过被聚合物壁保护以防UV辐射。
上述配制剂可以借助喷雾、雾化、撒粉、撒播或浇灌直接使用或以由其制备的使用形式使用,例如以可直接喷雾溶液、粉末、悬浮液或分散体、乳液、油分散体、糊、可撒粉产品、撒播材料或颗粒形式使用。使用形式完全取决于意欲的目的;意欲确保在每种情况下农药和本发明聚合物的最佳可能分布。
含水使用形式还可以通过加入合适溶剂如水而由乳液浓缩物、糊或可湿性粉末(可喷雾粉末、油分散体)制备。
各组分可以单独或已经部分或完全相互混合而用于制备本发明组合物。还可以将它们作为结合组合物如多组分成套包装来包装和进一步使用。在本发明的一个实施方案中,成套包装可以包含一种或多种(包括所有)可以用于制备本发明农化组合物的组分。例如成套包装可以包含农药组分和/或有机UV光保护过滤剂组分和/或涂敷的金属氧化物纳米颗粒组分。一种或多种组分可能已经组合在一起或预配制。在其中两种以上组分提供在成套包装中的那些实施方案中,各组分可能已经组合在一起并直接包装在单独容器如罐、瓶、桶、袋、囊或箱中。在其他实施方案中,成套包装的两种或更多种组分可以分开包装,即不预配制。这样成套包装可以包含一个或多个分开的容器如罐、瓶、桶、袋、囊或箱,其中各容器含有农化组合物的单独组分。在两种形式中,成套包装的一种组分可以与其他组分分开或一起施用或者作为本发明结合组合物的组分用于制备本发明组合物。
在优选实施方案中,本发明涉及多组分成套包装,其以分开的组分包含在防止不希望的植物生长、有害昆虫和/或植物病原性真菌的方法中组合施用的如下组分:
A)包含有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的组合物,和
B)农药。
包含有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的组合物A)可以通过混合所述化合物而制备。任选可以加入配制助剂。所述组合物可以是固体或液体,优选液体。包含农药的组分B)通常存在于农化配制剂或稀释的农化配制剂中。优选在桶混物中合并分开的组分A)和B)。通常将所述组分同时或在48小时,优选24小时,更优选12小时,最优选6小时内施用于不希望的植物生长、有害昆虫和/或植物病原性真菌。优选同时施用它们。
上述施用的所有实施方案在下文中称为“本发明配制剂”。
本发明还涉及有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的混合物在农化配制剂中的用途。另一实施方案是本发明配制剂在农化配制剂中的用途。
本发明还涉及本发明配制剂在稳定农药以防UV辐射中的用途。
此外,本发明还涉及一种防治有害昆虫和/或植物病原性真菌的方法,包括使植物、其中或其上有害昆虫和/或植物病原性真菌生长或可能生长的土壤或植物生长地、需要防止所述有害昆虫和/或植物病原性真菌侵袭或侵染的植物或土壤与有效量的本发明配制剂接触。本发明配制剂因此可以用于防治在各种栽培植物上防治大量植物病原性真菌或昆虫或在例如小麦、黑麦、大麦、燕麦、稻、玉米、禾草、香蕉、棉花、大豆、咖啡、甘蔗、葡萄藤、水果和观赏植物以及蔬菜如黄瓜、菜豆、土豆、土豆和葫芦中防治杂草。
本发明还涉及一种防止不希望的植物生长的方法,包括使除草有效量的本发明配制剂作用于植物或其生长地。防止不希望的植物生长应理解为指破坏杂草。杂草在最宽意义上应理解为指所有在不希望的地方生长的那些植物。
因此,本发明配制剂可以用于在各种栽培植物上防治大量植物病原性真菌或昆虫或在例如小麦、黑麦、大麦、燕麦、稻、玉米、禾草、香蕉、棉花、大豆、咖啡、甘蔗、葡萄藤、水果和观赏植物以及蔬菜如黄瓜、菜豆、土豆、土豆和葫芦中以及这些植物的种子上防止杂草。
因此,本发明配制剂本发明组合物适合在有用植物,尤其是作物如燕麦、大麦、小米、玉米、稻、小麦、甘蔗、棉花、油籽油菜、亚麻、扁豆、糖用甜菜、烟草、向日葵和大豆中或在多年生作物中防止常见有害植物。
术语“栽培植物”应理解为包括已经通过育种、诱变或基因工程修饰的植物,包括但不限于上市销售或开发的农业生物技术产品(参见http://www.bio.org/speeches/pubs/er/agri_products.asp)。基因修饰植物是其基因材料通过使用在自然条件下不易通过杂交、突变或自然重组得到的重组DNA技术修饰的植物。通常将一个或多个基因整合到基因修饰植物的基因材料中以改善植物的某些性能。这类基因修饰还包括但不限于蛋白质、寡肽或多肽的靶向翻译后修饰,例如通过糖基化或聚合物加成如异戊二烯化、乙酰化或法呢基化结构部分或PEG结构部分。
已经通过育种、诱变或基因工程修饰的植物例如已经因常规育种或基因工程方法而耐受特殊类别的除草剂施用的植物,所述除草剂例如羟基苯基丙酮酸双加氧酶(HPPD)抑制剂;乙酰乳酸合成酶(ALS)抑制剂如磺酰脲类(例如参见US 6,222,100,WO 01/82685,WO 00/26390,WO97/41218,WO 98/02526,WO 98/02527,WO 04/106529,WO05/20673,WO 03/14357,WO 03/13225,WO 03/14356,WO 04/16073)或咪唑啉酮类(例如参见US 6,222,100,WO 01/82685,WO 00/26390,WO 97/41218,WO 98/02526,WO 98/02527,WO 04/106529,WO05/20673,WO 03/14357,WO 03/13225,WO 03/14356,WO04/16073);烯醇丙酮酰莽草酸3-磷酸合成酶(EPSPS)抑制剂如草甘膦(例如参见WO 92/00377);谷氨酰胺合成酶(GS)抑制剂如草铵膦(例如参见EP-A 242236,EP-A 242246)或oxynil除草剂(例如参见US 5,559,024)。几种栽培植物已经通过常规育种(诱变)方法而耐受除草剂,例如夏播油菜(Canola,德国BASF SE)耐受咪唑啉酮类如咪草啶酸。基因工程方法已经用于使栽培植物如大豆、棉花、玉米、甜菜和油菜耐受除草剂如草甘膦和草铵膦,它们中的一些可以以商标名(耐受草甘膦,Monsanto,U.S.A.)和(耐受草铵膦,德国BayerCropScience)市购。
此外,还包括通过使用重组DNA技术而能够合成一种或多种杀虫蛋白的植物,该蛋白尤其是由芽孢杆菌属(Bacillus)细菌已知的那些,特别是由苏云金芽孢杆菌(Bacillus thuringiensis)已知的那些,例如δ-内毒素如CryIA(b)、CryIA(c)、CryIF、CryIF(a2)、CryIIA(b)、CryIIIA、CryIIIB(b1)或Cry9c;无性杀虫蛋白(VIP)如VIP1、VIP2、VIP3或VIP3A;线虫定居细菌的杀虫蛋白如发光杆菌属(Photorhabdus)或致病杆菌属(Xenorhabdus);动物产生的毒素如蝎毒素、蜘蛛毒素、黄蜂毒素或其他昆虫特异性神经毒素;真菌产生的毒素如链霉菌属(Streptomycetes)毒素,植物凝集素如豌豆或大麦凝集素;凝集素;蛋白酶抑制剂如胰蛋白酶抑制剂、丝氨酸蛋白酶抑制剂、patatin、半胱氨酸蛋白酶抑制剂或木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP)如蓖麻蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽蛋白、皂草素或异株腹泻毒蛋白(bryodin);类固醇代谢酶如3-羟基类固醇氧化酶、蜕皮甾类-IDP糖基转移酶、胆固醇氧化酶、蜕皮激素抑制剂或HMG-CoA还原酶;离子通道阻断剂如钠通道或钙通道阻断剂;保幼激素酯酶;利尿激素受体(helicokinin受体);茋合成酶,联苄合成酶,壳多糖酶或葡聚糖酶。就本发明而言,这些杀虫蛋白或毒素还具体理解为前毒素、杂合蛋白、截短的或其他方面改性的蛋白。杂合蛋白的特征在于蛋白域的新型组合(例如参见WO 02/015701)。该类毒素或能够合成该类毒素的基因修饰植物的其他实例公开于例如EP-A 374753、WO 93/007278、WO 95/34656、EP-A 427529、EP-A 451878、WO 03/18810和WO 03/52073中。生产该类基因修饰植物的方法对本领域熟练技术人员通常是已知的且例如描述于上述出版物中。这些含于基因修饰植物中的杀虫蛋白赋予产生这些蛋白的植物以对来自所有昆虫分类学的害虫,尤其是甲虫(鞘翅目(Coeleropta))、双翅目昆虫(双翅目(Diptera))和蝶(鳞翅目(Lepidoptera))以及线虫(线虫纲(Nematoda))的耐受性。能合成一种或多种杀虫蛋白的基因修饰植物例如描述于上述出版物中,并且它们中的一些可市购,例如(产生Cry1Ab毒素的玉米栽培品种),Plus(产生Cry1Ab和Cry3Bb1毒素的玉米栽培品种),(产生Cry9c毒素的玉米栽培品种),RW(产生Cry34Ab1、Cry35Ab1和酶膦丝菌素-N-乙酰转移酶[PAT]的玉米栽培品种);33B(产生Cry1Ac毒素的棉花栽培品种),I(产生Cry1Ac毒素的棉花栽培品种),II(产生Cry1Ac和Cry2Ab2毒素的棉花栽培品种);(产生VIP毒素的棉花栽培品种);(产生Cry3A毒素的土豆栽培品种);法国Syngenta Seeds SAS的Bt11(例如CB)和Bt176(产生Cry1Ab毒素和PAT酶的玉米栽培品种),法国Syngenta Seeds SAS的MIR604(产生Cry3A毒素的修饰译本的玉米栽培品种,参见WO 03/018810),比利时Monsanto Europe S.A.的MON 863(产生Cry3Bb1毒素的玉米栽培品种),比利时Monsanto EuropeS.A.的IPC 531(产生Cry1Ac毒素的修饰译本的棉花栽培品种)和比利时Pioneer Overseas Corporation的1507(产生Cry1F毒素和PAT酶的玉米栽培品种)。
此外,还包括通过使用重组DNA技术而能够合成一种或多种蛋白以增加其对细菌、病毒或真菌病原体的抗性或耐受性的植物。这类蛋白的实例是所谓的“与发病机理相关的蛋白”(PR蛋白,例如参见EP-A 392225),植物病害抗性基因(例如表达针对来自野生墨西哥土豆Solanumbulbocastanum的致病疫霉(Phytophthora infestans)的抗性基因的土豆栽培品种)或T4溶菌酶(例如能够合成对细菌如Erwinia amylvora具有增强抗性的这些蛋白的土豆栽培品种)。生产这类基因修饰植物的方法通常为本领域熟练技术人员所已知且例如描述于上述出版物中。
此外,还包括通过使用重组DNA技术而能够合成一种或多种蛋白以提高产量(例如生物质产量、谷粒产量、淀粉含量、油含量或蛋白含量),对干旱、盐或其他限制生长的环境因素的耐受性或对害虫以及真菌、细菌或其病毒病原体的耐受性的植物。
此外,还包括通过使用重组DNA技术而含有改变量的物质含量或新物质含量以尤其改善人类或动物营养的植物,例如产生促进健康的长链ω-3脂肪酸或不饱和ω-9脂肪酸的油料作物(例如油菜,加拿大DOW Agro Sciences)。
术语植物病原性真菌包括但不限于下列属种:蔬菜、油菜、糖用甜菜以及水果和稻上的链格孢属(Alternaria)(例如土豆和其他植物上的早疫链格孢(A.solani)或链格孢(A.alternata));糖用甜菜和蔬菜上的丝囊霉属(Aphanomyces);玉米、禾谷类、稻和草坪上的平脐蠕孢属(Bipolaris)和内脐蠕孢属(Drechslera)(例如大麦上的大麦网斑内脐蠕孢(D.teres),小麦上的D.tritici-repentis);禾谷类上的小麦白粉菌(Blumeria graminis)(白粉病);草莓、蔬菜、花卉和葡萄藤上的灰葡萄孢(Botrytis cinerea)(灰霉病);莴苣上的莴苣盘梗霉(Bremia lactucae);玉米、大豆、稻和糖用甜菜上的尾孢属(Cercospora)(例如糖用甜菜上的甜菜生尾孢(C.beticola));玉米、禾谷类、稻上的旋孢腔菌属(Cochliobolus)(例如禾谷类上的禾旋孢腔菌(Cochliobolus sativus),稻上的宫部旋孢腔菌(Cochliobolus miyabeanus));大豆、棉花和其他植物上的剌盘孢属(Colletotricum)(例如各种植物上的尖孢炭疽(C.acutatum));由Phaeoacremonium chlamydosporium、Ph.Aleophilum和斑褐孔菌(Formitipora punctata(同义词Phellinus punctatus)引起的葡萄藤上的埃斯卡(Esca);玉米上的突脐蠕孢属(Exserohilum);葫芦上的二孢白粉菌(Erysiphe cichoracearum)和单丝壳白粉菌(Sphaerotheca fuliginea);各种植物上的镰孢霉属(Fusarium)和轮生菌属(Verticillium)(例如茄黄萎病菌(V.dahliae)(例如小麦上的禾本科镰孢(F.graminearum));禾谷类上的禾顶囊壳(Gaeumanomyces graminis);禾谷类和稻上的赤霉属(Gibberella)(例如稻上的藤仓赤霉(Gibberella fujikuroi));稻上的Grainstaining complex;玉米和稻上的长蠕孢属(Helminthosporium(例如H.graminicola));禾谷类上的雪霉叶枯菌(Michrodochium nivale);禾谷类、香蕉和花生上的球腔菌属(Mycosphaerella)(小麦上的禾生球腔菌(M.Graminicola),香蕉上的斐济球腔菌(M.Fijiesis));大豆上的豆薯层锈菌(Phakopsara pachyrhizi)和山马蟥层锈菌(Phakopsara meibomiae);大豆、向日葵和葡萄藤上的拟茎点霉属(Phomopsis)(葡萄藤上的葡萄黑腐病菌(P.viticola),向日葵上的褐色茎腐病(P.Helianthii));土豆和西红柿上的致病疫霉;葡萄藤上的葡萄生单轴霉(Plasmopara viticola);苹果上的苹果白粉病菌(Podosphaera leucotricha);禾谷类上的小麦基腐病菌(Pseudocercosporella herpotrichoides);啤酒花和葫芦上的假霜霉属(Pseudoperonospora(例如黄瓜上的古巴假霜霉(P.Cubenis));禾谷类、玉米和芦笋上的柄锈菌属(Puccinia)(小麦上的小麦柄锈菌(P.Triticina)和条形柄锈病(P.Striformis),芦笋上的天门冬属柄锈病(P.Asparagi));禾谷类上的核腔菌属(Pyrenophora);稻上的稻瘟病菌(Pyricularia oryzae)、笹木伏革菌(Corticium sasakii)、稻帚枝霉(Sarocladium oryzae)、S.Attenuatum、稻叶黑粉菌(Entyloma oryzae);草坪和禾谷类上的稻梨孢菌(Pyricularia grisea);草坪、稻、玉米、棉花、油菜、向日葵、糖用甜菜、蔬菜和其他植物上的的腐霉属(Pythium);棉花、稻、土豆、草坪、玉米、油菜、糖用甜菜、蔬菜和各种其他植物上的丝核菌属(Rhizoctonia)(例如立枯丝核菌(R.solani);例如黑麦和大麦上的黑麦喙孢(Rhynchosporium secalis);油菜、向日葵和其他植物上的核盘菌属(Sclerotinia)(例如核盘菌(S.sclerotiorum));小麦上的小麦壳针孢(Septoriatritici)和颖枯壳多孢(Stagonospora nodorum);葡萄藤上的葡萄钩丝壳(Erysiphe(同义词Uncinula)necator);玉米和草坪上的大斑病菌属(Setospaeria);玉米上的丝轴黑粉菌(Sphacelotheca reilinia);大豆和棉花上的上的根串珠霉属(Thievaliopsis);禾谷类上的腥黑粉菌属(Tilletia);禾谷类、玉米和糖用甜菜上的黑粉菌属(Ustilago);苹果和梨上的黑星菌属(Venturia)(黑星病)(例如梨上的苹果黑星病(V.inaequalis))。它们特别适合防治卵菌纲(Oomycetes)如霜霉属(Peronospora)、疫霉属(Phytophthora)、葡萄生单轴霉和Pseudoperonospora有害真菌。
此外,本发明还涉及一种在作物,尤其是燕麦、大麦、小米、玉米、稻、小麦、甘蔗、棉花、油菜、亚麻、扁豆、糖用甜菜、烟草、向日葵和大豆作物中或在多年生作物中防止不希望的植物生长的方法,包括使有效量的本发明农化配制剂作用于植物、其生长地或所述植物的种子上。
本发明进一步涉及一种在通过基因工程或育种而耐受一种或多种除草剂和/或杀真菌剂和/或耐受昆虫侵袭的作物中防止不希望的植物生长的方法,包括使有效量的本发明农化配制剂作用于植物、其生长地或所述植物的种子上。
不希望的植物生长的防治应理解为指破坏杂草。杂草从最宽意义上应理解为指所有在不希望的地方生长的那些植物,例如:
下列属的双子叶杂草:野芥属(Sinapis)、独行菜属(Lepidium)、猪殃殃属(Galium)、繁缕属(Stellaria)、母菊属(Matricaria)、春黄菊属(Anthemis)、牛膝菊属(Galinsoga)、藜属(Chenopodium)、荨麻属(Urtica)、千里光属(Senecio)、苋属(Amaranthus)、马齿苋属(Portulaca)、苍耳属(Xanthium)、旋花属(Convolvulus)、番薯属(Ipomoea)、蓼属(Polygonum)、田菁属(Sesbania)、豚草属(Ambrosia)、蓟属(Cirsium)、飞廉属(Carduus)、苣荬菜属(Sonchus)、茄属(Solanum)、蔊菜属(Rorippa)、节节菜属(Rotala)、母草属(Lindernia)、野芝麻属(Lamium)、婆婆纳属(Veronica)、苘麻属(Abutilon)、Emex、曼陀罗属(Datura)、堇菜属(Viola)、鼬瓣花属(Galeopsis)、罂粟属(Papaver)、矢车菊属(Centaurea)、车轴草属(Trifolium)、毛茛属(Ranunculus)、蒲公英属(Taraxacum)。下列属的单子叶杂草:稗属(Echinochloa)、狗尾草属(Setaria)、黍属(Panicum)、马唐属(Digitaria)、猫尾草属(Phleum)、早熟禾属(Poa)、羊茅属(Festuca)、穇属(Eleusine)、臂形草属(Brachiaria)、黑麦草属(Lolium)、雀麦属(Bromus)、野燕麦属(Avena)、莎草属(Cyperus)、高粱属(Sorghum)、冰草属(Agropyron)、狗牙根属(Cynodon)、雨久花属(Monochoria)、飘拂草属(Fimbristyslis)、慈姑属(Sagittaria)、荸荠属(Eleocharis)、藨草属(Scirpus)、雀稗属(Paspalum)、鸭嘴草属(Ischaemum)、尖瓣花属(Sphenoclea)、龙爪茅属(Dactyloctenium)、翦股颖属(Agrostis)、看麦娘属(Alopecurus)、阿披拉草属(Apera)。
本发明具有几个优点:降低了农药因阳光,尤其是紫外(UV)光的分解。提高了农药的农化配制剂在储存和/或施用于环境之后的稳定性。提高了农化配制剂在施用于环境之后的农药活性。无需包封农药以防止UV损害。甚至稳定了溶解的农药或悬浮的基质颗粒以防UV光。还无需金属氧化物纳米颗粒的复杂掺杂,这允许使用廉价的市售金属氧化物纳米颗粒。
通过下列实施例进一步说明但不限制本发明。
实施例:
乳化剂:聚(乙二醇-嵌段-丙二醇-嵌段-乙二醇),丙二醇嵌段摩尔质量为3250g/mol且总聚合物摩尔质量为约6500g/mol(例如由BASF SE以PE 10500市购)
二氧化钛:具有二甲氧基二苯基硅烷三乙氧基辛基硅烷交联聚合物、二氧化硅和氢氧化铝的涂层的二氧化钛颗粒;晶粒尺寸14-16nm;金红石晶体结构;比表面积BET 100m2/g;69-73重量%的二氧化钛含量(例如由BASF SE以T-MAX市购)。
氧化锌:具有二甲氧基二苯基硅烷-三乙氧基辛基硅烷交联聚合物、水合二氧化硅和氢氧化铝的涂层的氧化锌颗粒;96-99重量%微粉化氧化锌、1-4重量%涂层;粒度<0.2μm;BET面积12-24m2/g(例如由BASF SE以Z-MAX市购)。
消泡剂:包含20重量%非离子聚硅氧烷的聚硅氧烷基消泡乳液(例如由Wacker以Silifoam SRE市购)。
T150:乙基己基三嗪酮型光保护过滤剂(2,4,6-三苯胺基-对-(2′-乙基-1′-己氧甲酰基)-1,3,5-三嗪,CAS Nr.88122-99-0;例如由BASF SE以T150市购)。
实施例1:悬浮浓缩物
通过在中研磨(3000U/min下1小时)下列化合物而获得悬浮浓缩物(SC)C-1至C-3(不根据本发明)和A(根据本发明)。得到其中90%的固体颗粒具有小于5μm的粒度的均相、稳定悬浮液。
C-1:不含有机UV过滤剂,不含涂敷的二氧化钛
C-2:含有机UV过滤剂,不含涂敷的二氧化钛
C-3:不含有机UV过滤剂,含涂敷的二氧化钛
A:含有机UV过滤剂,含涂敷的二氧化钛
表1
a)有机光保护过滤剂
实施例2:生物学活性的改进
用实施例1的稀释悬浮浓缩物处理胡椒子(胡椒(piper nigrum)),其中农药浓度为300或500ppm。将植物保持在可透过阳光的UV辐射的温室中。在0和7天之后(DAT=0或7)将植物用桃蚜(Myzus persicae)侵染。侵染4天后测定死亡率。当使用组合物A时,逃蚜的死亡率与组合物C-1至C-3相比显著更高。
实施例3:对植物的损害/植物毒性
在侵染8天后对实施例2的胡椒子检测植物损害。植物基本不被组合物A或组合物C-1至C-3损害。
实施例4:悬浮浓缩物
通过用水将100g氰氟虫胺、70g丙二醇、167g乳化剂、20g分散剂、5g消泡剂、3g黄原胶、2g物杀伤剂、任选的有机UV光保护过滤剂和任选的涂敷的金属氧化物纳米颗粒的混合物填补至总体积为1000ml,然后混合并研磨(在上,在3000U/min下1小时)以形成均相悬浮液而得到悬浮浓缩物Comp-1至Comp-5(非本发明)。组合物Comp-1至Comp-5的细节列于表2中。通过以合适量混合样品Comp-1至Comp-5而制备样品1-12,使得达到表2所列浓度。TiO2指二氧化钛且ZnO指氧化锌。所有样品的粒度D(4;3)为约1.0μm。
样品1-12在储存时稳定且未观察到相分离。在54℃下储存两周的过程中观察粒度。没有发现粒度变化且没有形成聚集体。
表2
样品 | 金属氧化物 | 金属氧化物浓度[g/l] | 光保护过滤剂 | 光保护过滤剂浓度[g/l] |
Comp-1 | - | - | - | - |
Comp-2 | TiO2 | 50 | - | - |
Comp-3 | - | - | T150 | 50 |
Comp-4 | - | - | 3040 | 50 |
Comp-5 | ZnO | 50 | - | - |
1 | TiO2 | 35 | T150 | 15 |
2 | TiO2 | 35 | 3040 | 15 |
3 | TiO2 | 25 | T150 | 25 |
4 | TiO2 | 25 | 3040 | 25 |
5 | TiO2 | 15 | T150 | 35 |
6 | TiO2 | 15 | 3040 | 35 |
7 | ZnO | 35 | T150 | 15 |
8 | ZnO | 25 | T150 | 25 |
9 | ZnO | 15 | T150 | 35 |
10 | ZnO | 35 | 3040 | 15 |
11 | ZnO | 25 | 3040 | 25 |
12 | ZnO | 15 | 3040 | 35 |
实施例5:UV暴露之后的残留杀虫活性
在除去顶端和子叶之后将利马豆植物(2片真叶阶段)用于氰氟虫胺处理。为了模拟田间处理,在带有3喷嘴中耕作物喷杆的室内喷雾室中处理植物。施用量为300L/ha,并且为了与不同的配制剂对比,以10g/ha的施用率施用氰氟虫胺。在风干之后,在装有荧光和UV灯泡的组合的生长室中将被处理植物保持在26℃和恒定的24h/d光下。在UV室中,在39Watt/m2下测量300-400nm的UV范围内光的辐射强度。
在处理1、4、7和10天(DAT)之后,将被处理植物从进行昆虫生物分析的UV实验室中取出以测定氰氟虫胺的残留杀虫活性。首先从被处理植物上切割叶子并将各叶子放入顶侧朝上的塑料陪替氏皿中的水润湿滤纸上。然后将7只南部灰翅夜蛾(Spodoptera eridania)幼虫(3龄期)放入各皿中,并将盖子置于皿上以包围幼虫。将各皿备份,并且每个处理重复4次。将含有被处理叶子和南部灰翅夜蛾的皿于恒定荧光光照和26℃下保持在实验室中,并在3-4天后评价死亡率(死亡+垂死)和进食损伤(肉眼评估损伤的叶表面%)(表3)。
数据表明本发明组合物与不含二氧化钛、氧化锌或光保护过滤剂的参照组合物Comp-1相比在暴露于UV光之后具有更高的氰氟虫胺残留活性。
数据还表明当仅将二氧化钛(Comp-2)或氧化锌(Comp-5)加入Comp-1中时,与Comp-1相比对残留活性具有不利影响。
此外,本发明样品具有在15-35g/l范围内的相当低浓度的T150或3040。然而,这些样品的残留活性与均以50g/l的相当高浓度仅仅含有3040(Comp-3)或T150(Comp-5)的样品相比近乎一样高或甚至更高。
表3
样品 | 备注 | 1DAT | 4DAT | 7DAT | 10DAT | 累计 |
Comp-1 | - | 100 | 100 | 21 | 21 | 242 |
Comp-2 | 仅TiO2 | 100 | 86 | 11 | 21 | 218 |
Comp-3 | 仅T150 | 100 | 100 | 46 | 57 | 303 |
Comp-4 | 仅3040 | 100 | 100 | 32 | 21 | 253 |
Comp-5 | 仅ZnO | 100 | 86 | 18 | 36 | 240 |
1 | TiO2+T150 | 100 | 86 | 46 | 25 | 257 |
3 | TiO2+T150 | 100 | 100 | 61 | 64 | 325 |
2 | TiO2+3040 | 100 | 100 | 64 | 46 | 310 |
4 | TiO2+3040 | 100 | 64 | 57 | 57 | 278 |
6 | TiO2+3040 | 100 | 100 | 32 | 25 | 257 |
7 | ZnO+T150 | 100 | 89 | 68 | 32 | 289 |
8 | ZnO+T150 | 100 | 96 | 75 | 57 | 328 |
9 | ZnO+T150 | 100 | 93 | 71 | 71 | 335 |
10 | ZnO+3040 | 100 | 100 | 100 | 82 | 382 |
11 | ZnO+3040 | 100 | 82 | 68 | 50 | 300 |
12 | ZnO+3040 | 100 | 86 | 64 | 57 | 307 |
Claims (14)
1.包含农药、有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的农化配制剂。
2.根据权利要求1的农化配制剂,其中所述纳米颗粒的平均粒度为5-1000nm。
3.根据权利要求1或2的农化配制剂,其中所述金属氧化物为二氧化钛或氧化锌。
4.根据权利要求1-3中任一项的农化配制剂,其中所述涂层包含含硅聚合物和/或无机氧化物。
5.根据权利要求1-4中任一项的农化配制剂,其中所述有机UV光保护过滤剂选自3-亚苄基樟脑及其衍生物、4-氨基苯甲酸衍生物、肉桂酸酯、水杨酸酯、二苯甲酮衍生物、亚苄基丙二酸酯、三嗪衍生物、丙烷-1,3-二酮类、2-苯基苯并咪唑-5-磺酸及其盐、二苯甲酮类的磺酸衍生物、3-亚苄基樟脑的磺酸衍生物、2-甲基-5-(2-氧代-3-亚冰片基)磺酸及其盐、苯甲酰基甲烷的衍生物或二苯甲酮类的氨基羟基取代衍生物。
6.根据权利要求1-5中任一项的农化配制剂,其中所述有机UV光保护过滤剂与所述金属氧化物的重量比为10∶1-1∶10。
7.根据权利要求1-6中任一项的农化配制剂,其中所述农药与所述有机UV光保护过滤剂和所述金属氧化物的总质量的重量比为50∶1-1∶10。
8.根据权利要求1-7中任一项的农化配制剂,其中所述农药对UV光敏感。
9.一种制备根据权利要求1-8中任一项的组合物的方法,其中混合农药、有机UV过滤剂和涂敷的金属氧化物纳米颗粒。
10.多组分成套包装,以分开的组分包含在防止不希望的植物生长、有害昆虫和/或植物病原性真菌的方法中组合施用的如下组分:
A)包含有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的组合物,和
B)农药。
11.有机UV光保护过滤剂和涂敷的金属氧化物纳米颗粒的混合物在农化配制剂中的用途。
12.根据权利要求1-8中任一项的农化配制剂在稳定农药以防UV辐射中的用途。
13.一种防治有害昆虫和/或植物病原性真菌的方法,包括使植物、其中或其上有害昆虫和/或植物病原性真菌生长或可能生长的土壤或植物生长地、需要防止所述有害昆虫和/或植物病原性真菌侵袭或侵染的植物或土壤与有效量的如权利要求1-8中任一项所要求的农化配制剂接触。
14.一种防止不希望的植物生长的方法,包括使除草有效量的如权利要求1-8中任一项所要求的农化配制剂作用于植物或其生长地。
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EP08158664.6 | 2008-06-20 | ||
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PCT/EP2009/057329 WO2009153231A2 (en) | 2008-06-20 | 2009-06-15 | Agrochemical formulation comprising a pesticide, an organic uv photoprotective filter and coated metal oxide nanoparticles |
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EP (1) | EP2306818A2 (zh) |
JP (1) | JP5559777B2 (zh) |
KR (1) | KR20110043608A (zh) |
CN (1) | CN102202502A (zh) |
AR (1) | AR072260A1 (zh) |
AU (1) | AU2009259456A1 (zh) |
BR (1) | BRPI0914847A2 (zh) |
CA (1) | CA2727153A1 (zh) |
CR (1) | CR11833A (zh) |
EA (1) | EA201100029A1 (zh) |
IL (1) | IL209890A0 (zh) |
MA (1) | MA32476B1 (zh) |
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CN102499892A (zh) * | 2011-11-02 | 2012-06-20 | 中国科学院力学研究所 | 基于液滴表面张力驱动的药物封装方法及采用该方法制备的药物 |
CN105851057A (zh) * | 2011-11-17 | 2016-08-17 | 堺化学工业株式会社 | 表面处理氧化锌粉体、抗菌剂和抗菌性组合物 |
CN107075712A (zh) * | 2014-10-24 | 2017-08-18 | 巴斯夫欧洲公司 | 改变固体颗粒的表面电荷的非两性、可季化和水溶性聚合物 |
US10899932B2 (en) | 2014-10-24 | 2021-01-26 | Basf Se | Non-amphoteric, quaternisable and water-soluble polymers for modifying the surface charge of solid particles |
CN108207945A (zh) * | 2016-12-12 | 2018-06-29 | 住友化学株式会社 | 农业化学复合颗粒及其制造方法 |
CN107041244A (zh) * | 2017-04-05 | 2017-08-15 | 南京农业大学 | 一种提高草坪草抗旱性能的方法 |
EP3657944A4 (en) * | 2017-07-28 | 2020-07-08 | Dogatech Arastirma Gelistirme Tar.Ur.Gida Hay.San. Ve Tic.Ltd.Sti | SUN PROTECTION COMPOSITION FOR AGRICULTURAL PRODUCTS |
CN110283316A (zh) * | 2018-12-28 | 2019-09-27 | 杭州师范大学 | 一种有机硅增效剂的制备方法 |
CN110283316B (zh) * | 2018-12-28 | 2021-05-18 | 杭州师范大学 | 一种有机硅增效剂的制备方法 |
CN113040136A (zh) * | 2021-03-17 | 2021-06-29 | 湖南嘉诚农业科技有限公司 | 一种航空施药助剂及其制备方法和应用 |
CN113040136B (zh) * | 2021-03-17 | 2022-05-06 | 湖南嘉诚农业科技有限公司 | 一种航空施药助剂及其制备方法和应用 |
CN114698640A (zh) * | 2021-10-28 | 2022-07-05 | 上海生农生化制品股份有限公司 | 一种抗光解悬浮剂及其制备方法 |
CN114698640B (zh) * | 2021-10-28 | 2024-02-06 | 上海生农生化制品股份有限公司 | 一种抗光解悬浮剂及其制备方法 |
Also Published As
Publication number | Publication date |
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MA32476B1 (fr) | 2011-07-03 |
AU2009259456A1 (en) | 2009-12-23 |
BRPI0914847A2 (pt) | 2020-12-15 |
CR11833A (es) | 2011-02-16 |
EP2306818A2 (en) | 2011-04-13 |
EA201100029A1 (ru) | 2011-08-30 |
IL209890A0 (en) | 2011-02-28 |
US8404263B2 (en) | 2013-03-26 |
JP5559777B2 (ja) | 2014-07-23 |
MX2010013530A (es) | 2010-12-21 |
WO2009153231A3 (en) | 2010-09-16 |
US20110111957A1 (en) | 2011-05-12 |
WO2009153231A2 (en) | 2009-12-23 |
CA2727153A1 (en) | 2009-12-23 |
JP2011524874A (ja) | 2011-09-08 |
AR072260A1 (es) | 2010-08-18 |
KR20110043608A (ko) | 2011-04-27 |
ZA201100457B (en) | 2012-03-28 |
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