CN117241879A - 含有活性物质的新型微胶囊 - Google Patents
含有活性物质的新型微胶囊 Download PDFInfo
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- CN117241879A CN117241879A CN202280030623.6A CN202280030623A CN117241879A CN 117241879 A CN117241879 A CN 117241879A CN 202280030623 A CN202280030623 A CN 202280030623A CN 117241879 A CN117241879 A CN 117241879A
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Abstract
具有壳和核的微胶囊,其中所述核含有非水液体,所述非水液体为一种或多种液体(在21℃下)活性物质或者一种或多种溶于溶剂S中的活性物质,其中溶剂S与水不溶混并且其中所述壳含有i)至少一种总体带负电的蛋白质PR,ii)至少一种总体带正电的多糖PS以及iii)任选地,能够经由非共价键的形成交联组分蛋白质PR和多糖PS的无机盐IS。
Description
本发明涉及具有壳和核的微胶囊,其中所述核含有非水液体,所述非水液体为一种或多种液体(在21℃下)活性物质或者一种或多种溶于非水溶剂S中的活性物质,其中溶剂S与水不溶混并且其中所述壳含有:
i)至少一种总体带负电的蛋白质PR,
ii)至少一种总体带正电的多糖PS,和
iii)任选地,能够经由非共价键的形成交联组分蛋白质PR和多糖PS的无机盐IS。
进一步涉及制备该类微胶囊的方法及其使用方法以及该类微胶囊的配制剂和用途。
当在本文中提及“相互作用的”两种组分时,这应是指该两种组分通过形成非共价键而相互作用。
当在本文中提及无机盐经由非共价键的形成“交联”组分蛋白质PR和多糖PS时,这应具有与“经由非共价键的形成与组分蛋白质PR和多糖PS相互作用”相同的含义。
活性物质的包封已知长时间了。它相对于未包封配制剂提供了几个优点。例如,可以控制活性物质在配制剂中的释放特性。
已知的包封技术例如涉及在包封的活性物质周围形成聚合物壳或聚合物颗粒。通常用于该包封的聚合物包括丙烯酸系聚合物、聚脲或聚氨酯聚合物或氨基塑料聚合物。
上面所列包封技术的缺点是聚合物不易生物降解并且可能导致形成长期持续存在的小聚合物颗粒。该类持续存在的聚合物颗粒有时也称为微塑料。
因此,本发明的目的是要提供含有活性物质的微胶囊,它们具有优异的释放特性并形成稳定的配制剂,同时可以在环境条件下容易地降解并且不会形成微塑料。
该目的由具有壳和核的微胶囊实现,其中所述核含有非水液体,所述非水液体为一种或多种液体(在21℃下)活性物质或者一种或多种溶于溶剂S中的活性物质,其中溶剂S与水不溶混并且其中所述壳含有:
i)至少一种总体带负电的蛋白质PR,
ii)至少一种总体带正电的多糖PS,和
iii)任选地,能够经由非共价键的形成交联组分蛋白质PR和多糖PS的无机盐IS。
本发明的微胶囊在核中含有一种或多种活性物质。本文所用活性物质应是指用来在其释放时对目标物实现一定效果的任何化合物或化合物混合物。下面例举的活性物质可以单独或与其他活性物质组合包含在本发明微胶囊中。
根据本发明,本发明微胶囊中所含活性物质与水不溶混。
“与水不溶混”就此而言应指该类活性物质在水中具有的溶解度在21℃下小于10g/l,优选在21℃下小于1g/l。在一个实施方案中,水不溶混性活性物质在水中具有的溶解度在21℃下小于0.1g/l。
在一个实施方案中,活性物质选自农药、增效剂、辅助剂、植物保健剂、驱除剂、生物杀伤剂、相变材料、药物、化妆品成分(如香料、香水、维生素、精油、植物提取物)、营养素、食品添加剂(如植物油、鱼油、维生素、芳香剂、抗氧化剂、精油、植物提取物)、信息素、催化剂。
优选的活性物质选自农药、药物、化妆品成分(如香料、香水、维生素、精油、植物提取物)、营养素、食品添加剂(如植物油、鱼油、维生素、芳香剂、抗氧化剂、精油、植物提取物)、信息素和催化剂。
在一个实施方案中,活性物质选自农药、化妆品成分(如香料、香水、维生素、精油、植物提取物)、营养素、食品添加剂(如植物油、鱼油、维生素、芳香剂、抗氧化剂、精油、植物提取物)、信息素和催化剂。
在一个实施方案中,活性物质选自农药。
在一个实施方案中,活性物质选自增效剂。
在一个实施方案中,活性物质选自辅助剂。
在一个实施方案中,活性物质选自个人护理用活性成分。
在一个实施方案中,活性物质选自化妆品成分(如香料、香水、维生素、精油、植物提取物)。
在一个实施方案中,活性物质选自营养素。
在一个实施方案中,活性物质选自食品添加剂(如植物油、鱼油、维生素、芳香剂、抗氧化剂、精油、植物提取物)。
在一个实施方案中,活性物质选自信息素。
在一个实施方案中,活性物质选自催化剂。
在一个实施方案中,活性物质选自驱虫剂。
在一个实施方案中,活性物质选自生物杀伤剂。
在一个实施方案中,活性物质是用于食品和动物营养领域中的营养素,如亲脂性维生素,如生育酚、维生素A及其衍生物、维生素D及其衍生物、维生素K及其衍生物,维生素E、维生素F及其衍生物,或者饱和和不饱和脂肪酸以及还有其衍生物和化合物,天然和合成香料,芳香物质和香料以及亲脂性染料如类视黄醇、类黄酮或类胡萝卜素。
在一个实施方案中,活性物质是药物,如麻醉药和镇静剂,抗胆碱能药,抗抑郁药,精神兴奋药和精神抑制药,抗癫痫药,抗真菌药,消炎药,支气管扩张药,心血管药物,细胞抑制剂,充血药,抗高血脂药,解痉药,睾酮衍生物,止痛药或抗病毒药。
在一个实施方案中,活性物质是食品添加剂如植物油、鱼油、维生素、芳香剂、抗氧化剂、精油、植物提取物。
一种优选的活性成分是维生素A。
一种优选的活性成分是维生素E。
一种优选类型的活性成分是含有不饱和脂肪酸如ω-3脂肪酸或高度不饱和脂肪酸如二十二碳六烯酸或二十碳五烯酸的食用油(例如植物油或鱼油)。
在一个实施方案中,活性物质是用于个人护理领域(例如化妆品)中的物质,如芳香油、有机UV过滤剂、染料或护理物质,如泛醇。
在一个实施方案中,活性物质为可以在本发明胶囊中用作活性物质的优选染料,如批准用于营养或化妆品领域中的天然或合成染料,例如如WO 2005/009604 A1第9页第18-30行所述。
在一个实施方案中,活性物质是有机UV过滤剂。该类有机UV过滤剂的实例为下列市售UV过滤剂:PABA,胡莫柳酯(HMS),二苯甲酮-3(BENZ-3),丁基甲氧基二苯甲酰甲烷(BMDBM),奥克立林(OC),聚丙烯酰胺基甲基亚苄基樟脑,甲氧基肉桂酸乙基己酯(EMC,OMC),对甲氧基肉桂酸异戊酯(IMC),乙基己基三嗪酮(OT,ET),甲酚曲唑三硅氧烷,二乙基己基丁酰胺基三嗪酮(DBT),4-甲基亚苄基樟脑(MBC),3-亚苄基樟脑(BC),水杨酸乙基己酯(OS,ES),乙基己基二甲基PABA(OD-PABA,ED-PABA),二苯甲酮-4(BENZ-4),亚甲基双苯并三唑基四甲基丁基酚(双辛基三唑,BOT),双乙基己氧苯酚甲氧苯基三嗪(AT),聚硅氧烷15或二乙氨基羟苯甲酰基苯甲酸己酯以及这些UV过滤剂的混合物。同样可以使用其他UV过滤剂:2,4,6-三(联苯基)-1,3,5-三嗪(TBT)、1,1'-(1,4-哌嗪二基)二[1-[2-[4-(二乙氨基)-2-羟基苯甲酰基]苯基]]甲酮(CAS号919803-06-8)、1,1-二(羧基-(2',2'-二甲基丙基))-4,4-二苯基丁二烯、部花青衍生物或亚苄基丙二酸酯UVB过滤剂,还有这些UV过滤剂相互之间或者与UV过滤剂的混合物。
特别优选选自奥克立林、甲氧基肉桂酸乙基己酯、乙基己基三嗪酮、二乙氨基羟苯甲酰基苯甲酸己酯、亚甲基双苯并三唑基四甲基丁基酚或双乙基己氧苯酚甲氧苯基三嗪的UV过滤剂以及这些UV过滤剂的混合物。
适合作为活性物质的信息素包括下列:
在一个优选实施方案中,所述活性成分选自以下列举:(1S)-4,6,6-三甲基双环[3.1.1]庚-3-烯-2-酮;3,7-二甲基双环[3.1.1]庚-3-烯-2-醇;4,6,6-三甲基-[1S-(1a,2b,5a)]-2,6-辛二烯醛;(3,3-二甲基亚环己基)乙醛;(2Z)(3,3-二甲基亚环己基)乙醛和(2E)(3,3-二甲基亚环己基)乙醛的混合物;2-甲基-6-亚甲基-2,7-辛二烯-4-醇;(2E)2-(3,3-二甲基亚环己基)乙醇;顺式-1-甲基-2-(1-甲基乙烯基)-环丁烷乙醇;(2Z)-2-(3,3-二甲基亚环己基)乙醇;2-甲基-6-亚甲基-7-辛烯-4-醇;4-甲基-5-壬酮;(5E)-5-癸烯-1-醇;(5Z)-5-癸烯-1-醇;4-甲基-5-壬醇;(2E,4E,6Z)-2,4,6-癸三烯酸甲酯;(2E,4Z)-2,4-癸二烯酸甲酯;4,6-二甲基-7-羟基壬-3-酮;(4R,6S,7S)-(.+-.)-4,6-二甲基-7-羟基壬-3-酮和(4R,6R,7R)-(.+-.)-4,6-二甲基-7-羟基壬-3-酮的混合物;(8E,10E)-8,10-十二碳二烯-1-醇;(5E)-5-癸烯-1-醇乙酸酯;(3Z)-3-癸烯-1-醇乙酸酯;(5Z)-5-癸烯-1-醇乙酸酯;(7Z)-7-癸烯-1-醇乙酸酯;(8Z)-8-十二碳烯-1-醇;(9Z)-9-十二碳烯-1-醇;(8E,10E)-8,10-十二碳二烯-1-醇乙酸酯;(7E,9Z)-7,9-十二碳二烯-1-醇乙酸酯;11-十四碳烯醛;(11E)-11-十四碳烯醛和(11Z)-11-十四碳烯醛的混合物;(11Z)-11-十四碳烯醛;(9Z)-9-十四碳烯醛;(9Z,12E)-9,12-十四碳二烯-1-醇;(7Z)-7-十四碳烯-2-酮;11-十二碳烯-1-醇乙酸酯;(7E)-7-十二碳烯-1-醇乙酸酯;(8E)-8-十二碳烯-1-醇乙酸酯;(9E)-9-十二碳烯-1-醇乙酸酯;8-十二碳烯-1-醇-1-乙酸酯;(8E)-8-十二碳烯-1-醇-1-乙酸酯和(8Z)-8-十二碳烯-1-醇-1-乙酸酯的混合物;(5Z)-5-十二碳烯-1-醇乙酸酯;(7Z)-7-十二碳烯-1-醇乙酸酯;(8Z)-8-十二碳烯-1-醇乙酸酯;(9Z)-9-十二碳烯-1-醇乙酸酯;(11E)-11-十四碳烯-1-醇;(11Z)-11-十四碳烯-1-醇;(6E)-7,11-二甲基-3-亚甲基-1,6,10-十二碳三烯;4-十三碳烯-1-醇乙酸酯;(4E)-4-十三碳烯-1-醇乙酸酯和(4Z)-4-十三碳烯-1-醇乙酸酯的混合物;(4Z)-4-十三碳烯-1-醇乙酸酯;(11Z,13Z)-11,13-十六碳二烯醛;(9E,11E)-9,11-十四碳二烯-1-醇乙酸酯;(9Z,12E)-9,12-十四碳二烯-1-醇乙酸酯;(9Z,11E)-9,11-十四碳二烯-1-醇乙酸酯;(11Z)-11-十六碳烯醛;(9Z)-9-十六碳烯醛;(11Z)-11-十四碳烯-1-醇乙酸酯;(11E)-11-十四碳烯-1-醇乙酸酯;(9E)-9-十四碳烯-1-醇乙酸酯;(7Z)-7-十四碳烯-1-醇乙酸酯;(8Z)-8-十四碳烯-1-醇乙酸酯;(9Z)-9-十四碳烯-1-醇乙酸酯;(11E)-11-十六碳烯-1-醇;(11Z)-11-十六碳烯-1-醇;(8Z)-14-甲基-8-十六碳烯醛;6-乙酰氧基-5-十六烷内酯;(13Z)-13-十八碳烯醛;(11Z)-11-十六碳烯-1-醇乙酸酯;(11E)-11-十六碳烯-1-醇乙酸酯;2,13-十八碳二烯-1-醇乙酸酯;(2E,13Z)-2,13-十八碳二烯-1-醇乙酸酯和(3E,13Z)-2,13-十八碳二烯-1-醇乙酸酯的混合物;(7Z)-7-二十碳烯-11-酮;(13Z)-13-十八碳烯-1-醇乙酸酯;(6Z)-6-二十一碳烯-11-酮;(9Z)-9-二十三碳烯;3-甲基-2-环己烯-1-酮;1-辛烯-3-醇;(3R)-1-辛烯-3-醇;8-十二碳烯-1-醇乙酸酯和(8Z)-十二碳烯-1-醇的混合物;(8Z)-8-十二碳烯-1-醇乙酸酯、(8E)-8-十二碳烯-1-醇乙酸酯和(8Z)-8-十二碳烯-1-醇的混合物;5-癸烯-1-醇乙酸酯;(5E)-5-癸烯-1-醇乙酸酯和(5E)-5-癸烯-1-醇的混合物;(11E)-11-十四碳烯-1-醇乙酸酯和(9E,11E)-9,11-十四碳二烯-1-醇乙酸酯的混合物;具有CAS号[30820-22-5]、[26532-23-0]、[26532-24-1]和[26532-25-2]的化合物的混合物;(Z)-9-十六碳烯醛、(Z)-11-十六碳烯醛和(Z)-13-十八碳烯醛的混合物;L-香芹酮;柠檬醛;乙酸(E,Z)-7,9-十二碳二烯-1-基酯;甲酸乙酯;(E,Z)-2,4-癸二烯酸乙酯(梨酯);(Z,Z,E)-7,11,13-十六碳三烯醛;丁酸庚酯;肉豆蔻酸异丙酯;千里酸熏衣草酯;顺式-茉莉酮;2-甲基-1-丁醇;甲基丁香酚;茉莉酮酸甲酯;(E,Z)-2,13-十八碳二烯-1-醇;(E,Z)-2,13-十八碳二烯-1-醇乙酸酯;(E,Z)-3,13-十八碳二烯-1-醇;(R)-1-辛烯-3-醇;白蚁信息素(pentatermanone);乙酸(E,Z,Z)-3,8,11-十四碳三烯基酯;乙酸(Z,E)-9,12-十四碳二烯-1-基酯;(Z)-7-十四碳烯-2-酮;乙酸(Z)-9-十四碳烯-1-基酯;(Z)-11-十四碳烯醛;(Z)-11-十四碳烯-1-醇;土荆芥(Chenopodium ambrosiodes)的提取物;印楝油;皂树提取物或其混合物。
当使用不同异构体或不同信息素的混合物时,这些通常以1:100-100:1,优选1:10-10:1的质量比使用。
在三元或更高级混合物的情况下,该比率对于混合配对的各组合适用。
在一个实施方案中,所述活性成分选自L-香芹酮、柠檬醛、乙酸(E,Z)-7,9-十二碳二烯-1-基酯、甲酸乙酯、(E,Z)-2,4-癸二烯酸乙酯(梨酯)、(Z,Z,E)-7,11,13-十六碳三烯醛、丁酸庚酯、肉豆蔻酸异丙酯、千里酸熏衣草酯、顺式-茉莉酮、2-甲基-1-丁醇、甲基丁香酚、茉莉酮酸甲酯、(E,Z)-2,13-十八碳二烯-1-醇、(E,Z)-2,13-十八碳二烯-1-醇乙酸酯、(E,Z)-3,13-十八碳二烯-1-醇、(R)-1-辛烯-3-醇、白蚁信息素、乙酸(E,Z,Z)-3,8,11-十四碳三烯基酯、乙酸(Z,E)-9,12-十四碳二烯-1-基酯、(Z)-7-十四碳烯-2-酮、乙酸(Z)-9-十四碳烯-1-基酯、(Z)-11-十四碳烯醛、(Z)-11-十四碳烯-1-醇、土荆芥提取物、印楝油,皂树提取物或其混合物。
在一个实施方案中,所述活性成分选自L-香芹酮、柠檬醛、乙酸(E,Z)-7,9-十二碳二烯-1-基酯、甲酸乙酯、(E,Z)-2,4-癸二烯酸乙酯(梨酯)、(Z,Z,E)-7,11,13-十六碳三烯醛、丁酸庚酯、肉豆蔻酸异丙酯、千里酸熏衣草酯、顺式-茉莉酮、2-甲基-1-丁醇、甲基丁香酚、茉莉酮酸甲酯、(E,Z)-2,13-十八碳二烯-1-醇、(E,Z)-2,13-十八碳二烯-1-醇乙酸酯、(E,Z)-3,13-十八碳二烯-1-醇、(R)-1-辛烯-3-醇、白蚁信息素、乙酸(E,Z,Z)-3,8,11-十四碳三烯基酯、乙酸(Z,E)-9,12-十四碳二烯-1-基酯、(Z)-7-十四碳烯-2-酮、乙酸(Z)-9-十四碳烯-1-基酯、(Z)-11-十四碳烯醛、(Z)-11-十四碳烯-1-醇或其混合物。
在一个优选实施方案中,所述活性成分选自乙酸(E,Z)-7,9-十二碳二烯基酯;乙酸11-十二碳烯基酯;乙酸(E)-7-十二碳烯基酯;乙酸(E)-11-十四碳烯基酯;乙酸(E)-9-十四碳烯基酯;乙酸(E)-11-十六碳烯基酯;乙酸(Z,Z)-7,11-十六碳二烯基酯;乙酸(E,Z)-4,7-十三碳二烯基酯;乙酸(E,Z,Z)-4,7,10-十三碳三烯基酯;(Z,Z,E)-7,11,13-十六碳三烯醛;(Z,Z)-7,11-十六碳二烯醛;(Z)-11-十六碳烯醛;(Z)-11-十六碳烯-1-醇;乙酸(Z)-11-十六碳烯基酯;(Z)-7-十四碳烯醛;乙酸(Z,E)-7,11-十六碳二烯基酯;(Z,E)-7,11-十六碳二烯醛;(Z,E)-9,12-十四碳二烯-1-醇;(Z)-9-十四碳烯-1-醇;乙酸(Z,E)-9,12-十四碳二烯基酯;乙酸(E)-9-十四碳烯基酯;乙酸(Z)-7-十二碳烯基酯;乙酸(E)-9-十四碳烯基酯;乙酸(Z,E)-9,11-十四碳二烯基酯;(E,Z)-10,12-十六碳二烯醛;(E,E)-10,12-十六碳二烯醛;乙酸(E)-7-十二碳烯基酯;乙酸(E)-8-十二碳烯基酯;乙酸(Z)-8-十二碳烯基酯;乙酸(Z)-7-十二碳烯基酯;乙酸(E,Z,Z)-3,8,11-十四碳三烯基酯;乙酸(E,Z)-3,8-十四碳二烯基酯;(E,Z)-3,7,11-三甲基-2,6,10-十二碳三烯-1-醇;乙酸(Z)-3,7,11-三甲基-1,6,10-十二碳三烯-3-醇;(E)-3,7-二甲基-2,6-辛二烯-1-醇;3,7-二甲基-6-辛烯-1-醇;2-(3,3-二甲基亚环己基)-(2E)-乙醇;顺式-1-甲基-2-(1-甲基乙烯基)环丁烷乙醇;(2Z)-2-(3,3-二甲基亚环己基)乙醇;顺式-2-异丙烯基-1-甲基环丁烷乙醇;10-甲基十三烷-2-酮;丙酸8-甲基癸-2-基酯;丁酸丁酯;丁酸(E)-2-丁烯基酯;(Z,E)-4,4-(1,5-二甲基-4-亚庚烯基)-1-甲基环己烯;2-丙烯酸乙酯;4-羟基-3-甲氧基苯甲醛;(E)-2-癸醛;1-甲基-4-(1,5-二甲基-(Z)-1,4-己二烯基)环己烯;(1S,2R,4S)-4-(1,5-二甲基-(Z)-1,4-己二烯基)-1,2-环氧基-1-甲基环己烷;(1R,2S,4S)-4-(1,5-二甲基-(Z)-1,4-己二烯基)-1,2-环氧基-1-甲基环己烷;己酸己酯;己酸(E)-2-己烯基酯;丁酸辛酯;乙酸3-甲基-6-异丙烯基-9-癸烯基酯;乙酸(Z)-3-甲基-6-异丙烯基-3,9-癸二烯基酯;(E)-7,11-二甲基-3-亚甲基-1,6,10-十二碳三烯;(1S,2R,3S)-2-(1-甲酰基乙烯基)-5-甲基环戊烷甲醛;(1R,4aS,7S,7aR)-六氢-4,7-二甲基环戊二烯并[c]吡喃-1-醇;(4aS,7S,7aR)-四氢-4,7-二甲基环戊二烯并[c]吡喃酮;2-苯基乙腈;3-甲基-2-丁烯酸(S)-5-甲基-2-(丙-1-烯-2-基)己-4-烯基酯;3-甲基丁酸(S)-5-甲基-2-(丙-1-烯-2-基)己-4-烯基酯;(S)-5-甲基-2-(丙-1-烯-2-基)己-4-烯-1-醇;丙酸(Z)-3,7-二甲基-2,7-辛二烯基酯;丙酸(E)-3,7-二甲基-2,7-辛二烯基酯;丙酸3-亚甲基-7-甲基-7-辛烯基酯或其混合物。
在一个优选实施方案中,所述活性成分选自乙酸(E,Z)-7,9-十二碳二烯基酯;乙酸11-十二碳烯基酯;乙酸(E)-7-十二碳烯基酯;乙酸(E)-11-十四碳烯基酯;乙酸(E)-9-十四碳烯基酯;乙酸(E)-11-十六碳烯基酯;乙酸(Z,Z)-7,11-十六碳二烯基酯;乙酸(E,Z)-4,7-十三碳二烯基酯;乙酸(E,Z,Z)-4,7,10-十三碳三烯基酯;(Z,Z,E)-7,11,13-十六碳三烯醛;(Z,Z)-7,11-十六碳二烯醛;(Z)-11-十六碳烯醛;(Z)-11-十六碳烯-1-醇;乙酸(Z)-11-十六碳烯基酯;(Z)-7-十四碳烯醛;乙酸(Z,E)-7,11-十六碳二烯基酯;(Z,E)-7,11-十六碳二烯醛;(Z,E)-9,12-十四碳二烯-1-醇;(Z)-9-十四碳烯-1-醇;乙酸(Z,E)-9,12-十四碳二烯基酯;乙酸(E)-9-十四碳烯基酯;乙酸(Z)-7-十二碳烯基酯;乙酸(E)-9-十四碳烯基酯;乙酸(Z,E)-9,11-十四碳二烯基酯;(E,Z)-10,12-十六碳二烯醛;(E,E)-10,12-十六碳二烯醛;乙酸(E)-7-十二碳烯基酯;乙酸(E)-8-十二碳烯基酯;乙酸(Z)-8-十二碳烯基酯;乙酸(Z)-7-十二碳烯基酯;乙酸(E,Z,Z)-3,8,11-十四碳三烯基酯;乙酸(E,Z)-3,8-十四碳二烯基酯或其混合物。
作为活性物质的优选驱虫剂是丁基乙酰氨基丙酸乙酯、二乙基甲苯酰胺、派卡瑞丁、2-十一烷酮。
在一个实施方案中,活性物质是农药如杀虫剂、杀真菌剂、杀线虫剂、灭鼠剂、杀螺剂、生长调节剂、除草剂或生物杀伤剂。
在一个实施方案中,活性物质是农药如杀虫剂、杀真菌剂、杀线虫剂、灭鼠剂、杀螺剂、生长调节剂和除草剂。
优选的农药是杀虫剂、杀真菌剂和除草剂。
术语农药(或农业化学活性物质)涉及至少一种选自杀真菌剂、杀虫剂、杀线虫剂、除草剂、灭鼠剂、安全剂和/或生长调节剂的活性物质。优选的农药是杀真菌剂、杀虫剂、灭鼠剂和除草剂。还可以使用两种或更多种上述类别农药的混合物。本领域熟练技术人员熟知该类农药,它们例如可以在the Pesticide Manual,第14版(2006),The British CropProtection Council,London中找到。
农药:
美国环境保护局(EPA)将农药定义为“目的在于防止、破坏、驱除或减轻任何有害物的任何物质或物质混合物”。熟练技术人员熟知该类农药,它们例如可以在thePesticide Manual,第16版(2013),The British Crop Protection Council,London中找到。农药可以是用于对抗包括与人类争夺食物、破坏财产、传播疾病或者令人讨厌的昆虫、植物病原体、杂草、软体动物、鸟类、哺乳动物、鱼类、线虫(蛔虫)和微生物在内的有害物的化学物质或生物制剂(如病毒或细菌)。在下列实例中给出适合本发明农业化学组合物的农药。
杀真菌剂:杀真菌剂是用来防止真菌在花园和作物中传播的化合物。杀真菌剂也用来对抗真菌感染。杀真菌剂可以是接触或内吸杀真菌剂。接触杀真菌剂在喷雾于真菌表面时将其杀灭。内吸杀真菌剂必须在真菌死亡之前由其吸收。根据本发明合适的杀真菌剂的实例包括选自A)-L)组的下列化合物:
A)呼吸抑制剂
-Qo位点的配合物III抑制剂:腈嘧菌酯(azoxystrobin)(A.1.1)、甲香菌酯(coumethoxystrobin)(A.1.2)、丁香菌酯(coumoxystrobin)(A.1.3)、醚菌胺(dimoxystrobin)(A.1.4)、烯肟菌酯(enestroburin)(A.1.5)、烯肟菌胺(fenaminstrobin)(A.1.6)、fenoxystrobin/氟菌螨酯(flufenoxystrobin)(A.1.7)、氟嘧菌酯(fluoxastrobin)(A.1.8)、亚胺菌(kresoxim-methyl)(A.1.9)、mandestrobin(A.1.10)、叉氨苯酰胺(metominostrobin)(A.1.11)、肟醚菌胺(orysastrobin)(A.1.12)、啶氧菌酯(picoxystrobin)(A.1.13)、唑菌胺酯(pyraclostrobin)(A.1.14)、唑胺菌酯(pyrametostrobin)(A.1.15)、唑菌酯(pyraoxystrobin)(A.1.16)、肟菌酯(trifloxystrobin)(A.1.17)、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(A.1.18)、吡菌苯威(pyribencarb)(A.1.19)、氯啶菌酯(triclopyricarb)/chlorodincarb(A.1.20)、唑酮菌(famoxadone)(A.1.21)、咪唑菌酮(fenamidone)(A.1.21)、N-[2-[(1,4-二甲基-5-苯基吡唑-3-基)氧基甲基]苯基]-N-甲氧基氨基甲酸甲酯(A.1.22)、metyltetraprole(A.1.25)、(Z,2E)-5-[1-(2,4-二氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺(A.1.34)、(Z,2E)-5-[1-(4-氯苯基)吡唑-3-基]氧基-2-甲氧亚氨基-N,3-二甲基戊-3-烯酰胺(A.1.35)、嘧螨胺(pyriminostrobin)(A.1.36)、吡氟菌酯(bifujunzhi)(A.1.37)、2-(邻-((2,5-二甲基苯基氧亚甲基)苯基)-3-甲氧基丙烯酸甲酯(A.1.38);
-Qi位点的配合物III抑制剂:氰霜唑(cyazofamid)(A.2.1)、吲唑磺菌胺(amisulbrom)(A.2.2)、2-甲基丙酸[(6S,7R,8R)-8-苄基-3-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]-6-甲基-4,9-二氧代-1,5-二氧壬环-7-基]酯(A.2.3)、fenpicoxamid(A.2.4)、吡啶菌酰胺(florylpicoxamid)(A.2.5);(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(4-氟-2-甲基苯基)-1,3-二甲基丁基]酯、(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(2,4-二甲基苯基)-1,3-二甲基丁基]酯、(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(2,4-二氟苯基)-1,3-二甲基丁基]酯、(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(2-氟-4-甲基苯基)-1,3-二甲基丁基]酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(4-氟-2-甲基苯基)-1,3-二甲基丁基]酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(2,4-二甲基苯基)-1,3-二甲基丁基]酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(2,4-二氟苯基)-1,3-二甲基丁基]酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(2-氟-4-甲基苯基)-1,3-二甲基丁基]酯、2-甲基丙酸[2-[[(1S)-2-[(1S,2S)-2-(4-氟-2-甲基苯基)-1,3-二甲基丁氧基]-1-甲基-2-氧代乙基]氨基甲酰基]-4-甲氧基-3-吡啶基]氧基甲基酯、2-甲基丙酸[2-[[(1S)-2-[(1S,2S)-2-(2,4-二甲基苯基)-1,3-二甲基丁氧基]-1-甲基-2-氧代乙基]氨基甲酰基]-4-甲氧基-3-吡啶基]氧基甲基酯、2-甲基丙酸[2-[[(1S)-2-[(1S,2S)-2-(2,4-二氟苯基)-1,3-二甲基丁氧基]-1-甲基-2-氧代乙基]氨基甲酰基]-4-甲氧基-3-吡啶基]氧基甲基酯、2-甲基丙酸[2-[[(1S)-2-[(1S,2S)-2-(2-氟-4-甲基苯基)-1,3-二甲基丁氧基]-1-甲基-2-氧代乙基]氨基甲酰基]-4-甲氧基-3-吡啶基]氧基甲基酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-1-甲基-2-(邻甲苯基)丙基]酯、(2S)-2-[(4-甲氧基-3-丙酰氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-1-甲基-2-(邻甲苯基)丙基]酯、(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-1-甲基-2-(邻甲苯基)丙基]酯、2-甲基丙酸[4-甲氧基-2-[[(1S)-1-甲基-2-[(1S,2S)-1-甲基-2-(邻甲苯基)丙氧基]-2-氧代乙基]氨基甲酰基]-3-吡啶基]酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(2,4-二甲基苯基)-1-甲基丙基]酯、2-甲基丙酸[2-[[(1S)-2-[(1S,2S)-2-(2,4-二甲基苯基)-1-甲基丙氧基]-1-甲基-2-氧代乙基]氨基甲酰基]-4-甲氧基-3-吡啶基]酯、(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(2,4-二甲基苯基)-1-甲基丙基]酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(2,6-二甲基苯基)-1-甲基丙基]酯、2-甲基丙酸[2-[[(1S)-2-[(1S,2S)-2-(2,6-二甲基苯基)-1-甲基丙氧基]-1-甲基-2-氧代乙基]氨基甲酰基]-4-甲氧基-3-吡啶基]酯、(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(2,6-二甲基苯基)-1-甲基丙基]酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-[4-氟-2-三氟甲基苯基]-1-甲基丙基]酯、2-甲基丙酸[2-[[(1S)-2-[(1S,2S)-2-[4-氟-2-三氟甲基苯基]-1-甲基丙氧基]-1-甲基-2-氧代乙基]氨基甲酰基]-4-甲氧基-3-吡啶基]酯、(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-[4-氟-2-三氟甲基苯基]-1-甲基丙基]酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(4-氟-2-甲基苯基)-1-甲基丙基]酯、2-甲基丙酸[2-[[(1S)-2-[(1S,2S)-2-(4-氟-2-甲基苯基)-1-甲基丙氧基]-1-甲基-2-氧代乙基]氨基甲酰基]-4-甲氧基-3-吡啶基]酯、(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(4-氟-2-甲基苯基)-1-甲基丙基]酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-1-甲基-2-[2-三氟甲基苯基]丙基]酯、2-甲基丙酸[4-甲氧基-2-[[(1S)-1-甲基-2-[(1S,2S)-1-甲基-2-[2-三氟甲基苯基]丙氧基]-2-氧代乙基]氨基甲酰基]-3-吡啶基]酯、(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-1-甲基-2-[2-三氟甲基苯基]丙基]酯、(2S)-2-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(4-氟-2,6-二甲基苯基)-1-甲基丙基]酯、2-甲基丙酸[2-[[(1S)-2-[(1S,2S)-2-(4-氟-2,6-二甲基苯基)-1-甲基丙氧基]-1-甲基-2-氧代乙基]氨基甲酰基]-4-甲氧基-3-吡啶基]酯、(2S)-2-[(3-羟基-4-甲氧基吡啶-2-羰基)氨基]丙酸[(1S,2S)-2-(4-氟-2,6-二甲基苯基)-1-甲基丙基]酯;配合物II抑制剂:麦锈灵(benodanil)(A.3.1)、苯并烯氟菌唑(benzovindiflupyr)(A.3.2)、联苯吡菌胺(bixafen)(A.3.3)、啶酰菌胺(boscalid)(A.3.4)、萎锈灵(carboxin)(A.3.5)、呋菌胺(fenfuram)(A.3.6)、氟吡菌酰胺(fluopyram)(A.3.7)、氟酰胺(flutolanil)(A.3.8)、氟唑菌酰胺(fluxapyroxad)(A.3.9)、呋吡唑灵(furametpyr)(A.3.10)、异丙噻菌胺(isofetamid)(A.3.11)、吡唑萘菌胺(isopyrazam)(A.3.12)、丙氧灭绣胺(mepronil)(A.3.13)、氧化萎锈灵(oxycarboxin)(A.3.14)、氟唑菌苯胺(penflufen)(A.3.15)、吡噻菌胺(penthiopyrad)(A.3.16)、氟唑菌酰羟胺(pydiflumetofen)(A.3.17)、联苯吡嗪菌胺(pyraziflumid)(A.3.18)、氟唑环菌胺(sedaxane)(A.3.19)、叶枯酞(tecloftalam)(A.3.20)、溴氟唑菌(thifluzamide)(A.3.21)、inpyrfluxam(A.3.22)、pyrapropoyne(A.3.23)、氟茚唑菌胺(fluindapyr)(A.3.28)、N-[2-[2-氯-4-三氟甲基苯氧基]苯基]-3-二氟甲基-5-氟-1-甲基吡唑-4-甲酰胺(A.3.29)、(E)-2-[2-[(5-氰基-2-甲基苯氧基)甲基]苯基]-3-甲氧基丙-2-烯酸甲酯(A.3.30)、isoflucypram(A.3.31)、2-二氟甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺(A.3.32)、2-二氟甲基-N-[(3R)-1,1,3-三甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺(A.3.33)、2-二氟甲基-N-(3-乙基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺(A.3.34)、2-二氟甲基-N-[(3R)-3-乙基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺(A.3.35)、2-二氟甲基-N-(1,1-二甲基-3-丙基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺(A.3.36)、2-二氟甲基-N-[(3R)-1,1-二甲基-3-丙基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺(A.3.37)、2-二氟甲基-N-(3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基)吡啶-3-甲酰胺(A.3.38)、2-二氟甲基-N-[(3R)-3-异丁基-1,1-二甲基-2,3-二氢化茚-4-基]吡啶-3-甲酰胺(A.3.39);
-其他呼吸抑制剂:二氟林(diflumetorim)(A.4.1);硝基苯基衍生物:乐杀螨(binapacryl)(A.4.2)、敌螨通(dinobuton)(A.4.3)、敌螨普(dinocap)(A.4.4)、氟啶胺(fluazinam)(A.4.5)、消螨多(meptyldinocap)(A.4.6)、嘧菌腙(ferimzone)(A.4.7);有机金属化合物:三苯锡基盐,如薯瘟锡(fentin-acetate)(A.4.8)、三苯锡氯(fentinchloride)(A.4.9)或毒菌锡(fentinhydroxide)(A.4.10);唑嘧菌胺(ametoctradin)(A.4.11);硅噻菌胺(silthiofam)(A.4.12);
B)甾醇生物合成抑制剂(SBI杀真菌剂)
-C14脱甲基酶抑制剂:三唑类:戊环唑(azaconazole)(B.1.1)、双苯三唑醇(bitertanol)(B.1.2)、糠菌唑(bromuconazole)(B.1.3)、环唑醇(cyproconazole)(B.1.4)、醚唑(difenoconazole)(B.1.5)、烯唑醇(diniconazole)(B.1.6)、烯唑醇M(diniconazole-M)(B.1.7)、氧唑菌(epoxiconazole)(B.1.8)、腈苯唑(fenbuconazole)(B.1.9)、喹唑菌酮(fluquinconazole)(B.1.10)、氟硅唑(flusilazole)(B.1.11)、粉唑醇(flutriafol)(B.1.12)、己唑醇(hexaconazole)(B.1.13)、酰胺唑(imibenconazole)(B.1.14)、环戊唑醇(ipconazole)(B.1.15)、环戊唑菌(metconazole)(B.1.17)、腈菌唑(myclobutanil)(B.1.18)、恶咪唑(oxpoconazole)(B.1.19)、多效唑(paclobutrazole)(B.1.20)、戊菌唑(penconazole)(B.1.21)、丙环唑(propiconazole)(B.1.22)、丙硫菌唑(prothioconazole)(B.1.23)、硅氟唑(simeconazole)(B.1.24)、戊唑醇(tebuconazole)(B.1.25)、氟醚唑(tetraconazole)(B.1.26)、三唑酮(triadimefon)(B.1.27)、唑菌醇(triadimenol)(B.1.28)、戊叉唑菌(triticonazole)(B.1.29)、烯效唑(uniconazole)(B.1.30)、2-(2,4-二氟苯基)-1,1-二氟-3-(四唑-1-基)-1-[5-[4-(2,2,2-三氟乙氧基)苯基]-2-吡啶基]丙-2-醇(B.1.31)、2-(2,4-二氟苯基)-1,1-二氟-3-(四唑-1-基)-1-[5-[4-(三氟甲氧基)苯基]-2-吡啶基]丙-2-醇(B.1.32)、4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(5-硫烷基-1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苄腈(B.1.33)、伊芬三氟康唑(ipfentrifluconazole)(B.1.37)、氯氟醚菌唑(mefentrifluconazole)(B.1.38)、(2R)-2-[4-(4-氯苯氧基)-2-三氟甲基苯基]-1-(1,2,4-三唑-1-基)丙-2-醇、(2S)-2-[4-(4-氯苯氧基)-2-三氟甲基苯基]-1-(1,2,4-三唑-1-基)丙-2-醇、2-(氯甲基)-2-甲基-5-(对甲苯基甲基)-1-(1,2,4-三唑-1-基甲基)环戊醇(B.1.43);咪唑类:抑霉唑(imazalil)(B.1.44)、稻瘟酯(pefurazoate)(B.1.45)、丙氯灵(prochloraz)(B.1.46)、氟菌唑(triflumizol)(B.1.47);嘧啶类、吡啶类、哌嗪类:异嘧菌醇(fenarimol)(B.1.49)、啶斑肟(pyrifenox)(B.1.50)、嗪氨灵(triforine)(B.1.51)、[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)异唑-4-基]-(3-吡啶基)甲醇(B.1.52)、4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苄睛(B.1.53)、2-[6-(4-溴苯氧基)-2-三氟甲基-3-吡啶基]-1-(1,2,4-三唑-1-基)丙-2-醇(B.1.54)、2-[6-(4-氯苯氧基)-2-三氟甲基-3-吡啶基]-1-(1,2,4-三唑-1-基)丙-2-醇(B.1.55);
-Δ14-还原酶抑制剂:4-十二烷基-2,6-二甲基吗啉(aldimorph)(B.2.1)、吗菌灵(dodemorph)(B.2.2)、吗菌灵乙酸酯(dodemorph-acetate)(B.2.3)、丁苯吗啉(fenpropimorph)(B.2.4)、克啉菌(tridemorph)(B.2.5)、苯锈啶(fenpropidin)(B.2.6)、粉病灵(piperalin)(B.2.7)、螺茂胺(spiroxamine)(B.2.8);
-3-酮基还原酶抑制剂:环酰菌胺(fenhexamid)(B.3.1);
-其他甾醇生物合成抑制剂:氯苯肟唑(chlorphenomizole)(B.4.1);
C)核酸合成抑制剂
-苯基酰胺类或酰基氨基酸类杀真菌剂:苯霜灵(benalaxyl)(C.1.1)、精苯霜灵(benalaxyl-M)(C.1.2)、kiralaxyl(C.1.3)、甲霜灵(metalaxyl)(C.1.4)、精甲霜灵(metalaxyl-M)(C.1.5)、甲呋酰胺(ofurace)(C.1.6)、霜灵(oxadixyl)(C.1.7);
-其他核酸合成抑制剂:土菌消(hymexazole)(C.2.1)、异噻菌酮(octhilinone)(C.2.2)、恶喹酸(oxolinic acid)(C.2.3)、磺嘧菌灵(bupirimate)(C.2.4)、5-氟胞嘧啶(C.2.5)、5-氟-2-(对甲苯基甲氧基)嘧啶-4-胺(C.2.6)、5-氟-2-(4-氟苯基甲氧基)嘧啶-4-胺(C.2.7)、5-氟-2-(4-氯苯基甲氧基)嘧啶-4-胺(C.2.8);
D)细胞分裂和细胞骨架抑制剂
-微管蛋白抑制剂:苯菌灵(benomyl)(D.1.1)、多菌灵(carbendazim)(D.1.2)、麦穗宁(fuberidazole)(D1.3)、涕必灵(thiabendazole)(D.1.4)、甲基托布津(thiophanate-methyl)(D.1.5)、pyridachlometyl(D.1.6)、N-乙基-2-[(3-乙炔基-8-甲基-6-喹啉基)氧基]丁酰胺(D.1.8)、N-乙基-2-[(3-乙炔基-8-甲基-6-喹啉基)氧基]-2-甲硫基乙酰胺(D.1.9)、2-[(3-乙炔基-8-甲基-6-喹啉基)氧基]-N-(2-氟乙基)丁酰胺(D.1.10)、2-[(3-乙炔基-8-甲基-6-喹啉基)氧基]-N-(2-氟乙基)-2-甲氧基乙酰胺(D.1.11)、2-[(3-乙炔基-8-甲基-6-喹啉基)氧基]-N-丙基丁酰胺(D.1.12)、2-[(3-乙炔基-8-甲基-6-喹啉基)氧基]-2-甲氧基-N-丙基乙酰胺(D.1.13)、2-[(3-乙炔基-8-甲基-6-喹啉基)氧基]-2-甲硫基-N-丙基乙酰胺(D.1.14)、2-[(3-乙炔基-8-甲基-6-喹啉基)氧基]-N-(2-氟乙基)-2-甲硫基乙酰胺(D.1.15)、4-(2-溴-4-氟苯基)-N-(2-氯-6-氟苯基)-2,5-二甲基吡唑-3-胺(D.1.16);
-其他细胞分裂抑制剂:乙霉威(diethofencarb)(D.2.1)、噻唑菌胺(ethaboxam)(D.2.2)、戊菌隆(pencycuron)(D.2.3)、氟吡菌胺(fluopicolide)(D.2.4)、苯酰菌胺(zoxamide)(D.2.5)、苯菌酮(metrafenone)(D.2.6)、苯啶菌酮(pyriofenone)(D.2.7)、氰烯菌酯(phenamacril)(D.2.8);
E)氨基酸和蛋白质合成抑制剂
-蛋氨酸合成抑制剂:环丙嘧啶(cyprodinil)(E.1.1)、嘧菌胺(mepanipyrim)(E.1.2)、二甲嘧菌胺(pyrimethanil)(E.1.3);
-蛋白质合成抑制剂:灭瘟素(blasticidin-S)(E.2.1)、春雷素(kasugamycin)(E.2.2)、水合春雷素(kasugamycin hydrochloride-hydrate)(E.2.3)、米多霉素(mildiomycin)(E.2.4)、链霉素(streptomycin)(E.2.5)、土霉素(oxytetracyclin)(E.2.6);
F)信号转导抑制剂
-MAP/组氨酸激酶抑制剂:氟菌安(fluoroimid)(F.1.1)、异丙定(iprodione)(F.1.2)、杀菌利(procymidone)(F.1.3)、烯菌酮(vinclozolin)(F.1.4)、氟菌(fludioxonil)(F.1.5);
-G蛋白抑制剂:喹氧灵(quinoxyfen)(F.2.1);
G)类脂和膜合成抑制剂
-磷脂生物合成抑制剂:克瘟散(edifenphos)(G.1.1)、异稻瘟净(iprobenfos)(G.1.2)、定菌磷(pyrazophos)(G.1.3)、稻瘟灵(isoprothiolane)(G.1.4);
-类脂过氧化:氯硝胺(dicloran)(G.2.1)、五氯硝基苯(quintozene)(G.2.2)、四氯硝基苯(tecnazene)(G.2.3)、甲基立枯磷(tolclofos-methyl)(G.2.4)、联苯(G.2.5)、地茂散(chloroneb)(G.2.6)、氯唑灵(etridiazole)(G.2.7)、噻唑锌(zinc thiazole)(G.2.8);
-磷脂生物合成和细胞壁沉积:烯酰吗啉(dimethomorph)(G.3.1)、氟吗啉(flumorph)(G.3.2)、双炔酰菌胺(mandipropamid)(G.3.3)、丁吡吗啉(pyrimorph)(G.3.4)、苯噻菌胺(benthiavalicarb)(G.3.5)、异丙菌胺(iprovalicarb)(G.3.6)、霜霉灭(valifenalate)(G.3.7);
-影响细胞膜渗透性的化合物和脂肪酸:百维灵(propamocarb)(G.4.1);
-氧化甾醇结合蛋白抑制剂:氟噻唑吡乙酮(oxathiapiprolin)(G.5.1)、fluoxapiprolin(G.5.3)、4-[1-[2-[3-二氟甲基-5-甲基吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺(G.5.4)、4-[1-[2-[3,5-二(二氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺(G.5.5)、4-[1-[2-[3-二氟甲基-5-三氟甲基吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺(G.5.6)、4-[1-[2-[5-环丙基-3-二氟甲基吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺(G.5.7)、4-[1-[2-[5-甲基-3-三氟甲基吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺(G.5.8)、4-[1-[2-[5-二氟甲基-3-三氟甲基吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺(G.5.9)、4-[1-[2-[3,5-二(三氟甲基)吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺(G.5.10)、(4-[1-[2-[5-环丙基-3-三氟甲基吡唑-1-基]乙酰基]-4-哌啶基]-N-四氢萘-1-基吡啶-2-甲酰胺(G.5.11);
H)有多位点作用的抑制剂
-无机活性物质:波尔多液(Bordeaux混合物)(H.1.1)、铜(H.1.2)、醋酸铜(H.1.3)、氢氧化铜(H.1.4)、王铜(copper oxychloride)(H.1.5)、碱式硫酸铜(H.1.6)、硫(H.1.7);
-硫代-和二硫代氨基甲酸酯类:福美铁(ferbam)(H.2.1)、代森锰锌(mancozeb)(H.2.2)、代森锰(maneb)(H.2.3)、威百亩(metam)(H.2.4)、代森联(metiram)(H.2.5)、甲基代森锌(propineb)(H.2.6)、福美双(thiram)(H.2.7)、代森锌(zineb)(H.2.8)、福美锌(ziram)(H.2.9);
-有机氯化合物:敌菌灵(anilazine)(H.3.1)、百菌清(chlorothalonil)(H.3.2)、敌菌丹(captafol)(H.3.3)、克菌丹(captan)(H.3.4)、灭菌丹(folpet)(H.3.5)、抑菌灵(dichlofluanid)(H.3.6)、双氯酚(dichlorophen)(H.3.7)、六氯苯(H.3.8)、五氯酚(pentachlorphenole)(H.3.9)及其盐、四氯苯酞(phthalide)(H.3.10)、对甲抑菌灵(tolylfluanid)(H.3.11);
-胍类及其他:胍(H.4.1)、多果定(dodine)(H.4.2)、多果定游离碱(H.4.3)、双胍盐(guazatine)(H.4.4)、双胍辛胺(guazatine-acetate)(H.4.5)、双胍辛醋酸盐(iminoctadine)(H.4.6)、双胍辛胺三乙酸盐(iminoctadine-triacetate)(H.4.7)、双八胍盐(iminoctadine-tris(albesilate))(H.4.8)、二噻农(dithianon)(H.4.9)、2,6-二甲基-1H,5H-[1,4]二噻二烯并[2,3-c:5,6-c']联吡咯-1,3,5,7(2H,6H)-四酮(H.4.10);
I)细胞壁合成抑制剂
-葡聚糖合成抑制剂:井冈霉素(validamycin)(I.1.1)、多氧霉素(polyoxinB)(I.1.2);
-黑素合成抑制剂:咯喹酮(pyroquilon)(I.2.1)、三环唑(tricyclazole)(I.2.2)、氯环丙酰胺(carpropamid)(I.2.3)、双氯氰菌胺(dicyclomet)(I.2.4)、氰菌胺(fenoxanil)(I.2.5);
J)植物防御诱发剂
-噻二唑素(acibenzolar-S-methyl)(J.1.1)、噻菌灵(probenazole)(J.1.2)、异噻菌胺(isotianil)(J.1.3)、噻酰菌胺(tiadinil)(J.1.4)、调环酸钙(prohexadione-calcium)(J.1.5);膦酸酯类:藻菌磷(fosetyl)(J.1.6)、乙磷铝(fosetyl-aluminum)(J.1.7)、4-环丙基-N-(2,4-二甲氧基苯基)噻二唑-5-甲酰胺(J.1.10);
K)未知作用模式
-拌棉醇(bronopol)(K.1.1)、灭螨蜢(chinomethionat)(K.1.2)、环氟菌胺(cyflufenamid)(K.1.3)、清菌脲(cymoxanil)(K.1.4)、棉隆(dazomet)(K.1.5)、咪菌威(debacarb)(K.1.6)、双氯氰菌胺(diclocymet)(K.1.7)、哒菌清(diclomezine)(K.1.8)、野燕枯(difenzoquat)(K.1.9)、野燕枯甲基硫酸酯(difenzoquat-methylsulfate)(K.1.10)、二苯胺(K.1.11)、杀螟松(fenitropan)(K.1.12)、胺苯吡菌酮(fenpyrazamine)(K.1.13)、氟联苯菌(flumetover)(K.1.14)、磺菌胺(flusulfamide)(K.1.15)、氟噻唑菌腈(flutianil)(K.1.16)、超敏蛋白(harpin)(K.1.17)、磺菌威(methasulfocarb)(K.1.18)、氯定(nitrapyrin)(K.1.19)、异丙消(nitrothal-isopropyl)(K.1.20)、tolprocarb(K.1.21)、喹啉铜(oxin-copper)(K.1.22)、丙氧喹啉(proquinazid)(K.1.23)、tebufloquin(K.1.24)、叶枯酞(K.1.25)、唑菌嗪(triazoxide)(K.1.26)、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(K.1.27)、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(K.1.28)、N'-[4-[[3-[(4-氯苯基)甲基]-1,2,4-噻二唑-5-基]氧基]-2,5-二甲基苯基]-N-乙基-N-甲基甲脒(K.1.29)、N'-(5-溴-6-(2,3-二氢化茚-2-基)氧基-2-甲基-3-吡啶基)-N-乙基-N-甲基甲脒(K.1.30)、N'-[5-溴-6-[1-(3,5-二氟苯基)乙氧基]-2-甲基-3-吡啶基]-N-乙基-N-甲基甲脒(K.1.31)、N'-[5-溴-6-(4-异丙基环己氧基)-2-甲基-3-吡啶基]-N-乙基-N-甲基甲脒(K.1.32)、N'-[5-溴-2-甲基-6-(1-苯基乙氧基)-3-吡啶基]-N-乙基-N-甲基甲脒(K.1.33)、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(K.1.34)、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(K.1.35)、2-(4-氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2-炔氧基乙酰胺(K.1.36)、3-[5-(4-氯苯基)-2,3-二甲基异唑烷-3-基]吡啶(pyrisoxazole)(K.1.37)、3-[5-(4-甲基苯基)-2,3-二甲基异唑烷-3-基]吡啶(K.1.38)、5-氯-1-(4,6-二甲氧基嘧啶-2-基)-2-甲基-1H-苯并咪唑(K.1.39)、(Z)-3-氨基-2-氰基-3-苯基丙-2-烯酸乙酯(K.1.40)、四唑吡氨酯(picarbutrazox)(K.1.41)、N-[6-[[(Z)-[(1-甲基四唑-5-基)苯基亚甲基]氨基]氧基甲基]-2-吡啶基]氨基甲酸戊酯(K.1.42)、N-[6-[[(Z)-[(1-甲基四唑-5-基)苯基亚甲基]氨基]氧基甲基]-2-吡啶基]氨基甲酸丁-3-炔基酯(K.1.43)、ipflufenoquin(K.1.44)、quinofumelin(K.1.47)、噻霉酮(benziothiazolinone)(K.1.48)、溴菌腈(bromothalonil)(K.1.49)、2-(6-苄基-2-吡啶基)喹唑啉(K.1.50)、2-[6-(3-氟-4-甲氧基苯基)-5-甲基-2-吡啶基]喹唑啉(K.1.51)、dichlobentiazox(K.1.52)、N'-(2,5-二甲基-4-苯氧基苯基)-N-乙基-N-甲基甲脒(K.1.53)、aminopyrifen(K.1.54)、氟醚菌酰胺(fluopimomide)(K.1.55)、N'-[5-溴-2-甲基-6-(1-甲基-2-丙氧基乙氧基)-3-吡啶基]-N-乙基-N-甲基甲脒(K.1.56)、N'-[4-(4,5-二氯噻唑-2-基)氧基-2,5-二甲基苯基]-N-乙基-N-甲基甲脒(K.1.57)、N-(2-氟苯基)-4-[5-三氟甲基-1,2,4-二唑-3-基]苯甲酰胺(K.1.58)、N-甲基-4-[5-三氟甲基-1,2,4-二唑-3-基]硫代苯甲酰胺(K.1.59);
L)生物农药
L4)具有杀虫、杀螨、杀螺、信息素和/或杀线虫活性的生物化学农药:L-香芹酮、柠檬醛、乙酸(E,Z)-7,9-十二碳二烯-1-基酯、甲酸乙酯、(E,Z)-2,4-癸二烯酸乙酯(梨酯)、(Z,Z,E)-7,11,13-十六碳三烯醛、丁酸庚酯、肉豆蔻酸异丙酯、千里酸熏衣草酯、顺式-茉莉酮、2-甲基-1-丁醇、甲基丁香酚、茉莉酮酸甲酯、(E,Z)-2,13-十八碳二烯-1-醇、(E,Z)-2,13-十八碳二烯-1-醇乙酸酯、(E,Z)-3,13-十八碳二烯-1-醇、R-1-辛烯-3-醇、白蚁信息素、乙酸(E,Z,Z)-3,8,11-十四碳三烯基酯、乙酸(Z,E)-9,12-十四碳二烯-1-基酯、Z-7-十四碳烯-2-酮、乙酸Z-9-十四碳烯-1-基酯、Z-11-十四碳烯醛、Z-11-十四碳烯-1-醇、土荆芥提取物、印楝油、皂树提取物;
优选的杀真菌剂为下列:(3-乙氧基丙基)溴化汞、2-甲氧基乙基氯化汞、2-苯基苯酚、8-羟基喹啉硫酸盐、8-苯基汞氧喹啉、噻二唑素(acibenzolar)、酰基氨基酸类杀真菌剂、八九十混酸(acypetacs)、4-十二烷基-2,6-二甲基吗啉、脂族氮类杀真菌剂、烯丙醇、酰胺类杀真菌剂、氨丙膦酸(ampropylfos)、敌菌灵、酰替苯胺类杀真菌剂、抗菌素类杀真菌剂、芳族杀真菌剂、金色制霉素(aureofungin)、戊环唑、氧化福美双(azithiram)、腈嘧菌酯、多硫化钡、苯霜灵、精苯霜灵、麦锈灵、苯菌灵、敌菌腙(benquinox)、丙唑草隆(bentaluron)、苯噻菌胺、苯扎氯铵、benzamacril、苯甲酰胺类杀真菌剂、苯杂吗(benzamorf)、苯甲酰苯胺类杀真菌剂、苯并咪唑类杀真菌剂、苯并咪唑前体杀真菌剂、苯并咪唑基氨基甲酸酯杀真菌剂、苯并异羟肟酸、苯并噻唑类杀真菌剂、百杀辛(bethoxazin)、乐杀螨、联苯、双苯三唑醇、硫双二氯酚、灭瘟素、波尔多液、啶酰菌胺、桥接联苯类杀真菌剂、糠菌唑、磺嘧菌灵、Burgundy混合物、粉病定(buthiobate)、丁胺、多硫化钙、敌菌丹、克菌丹、氨基甲酸酯类杀真菌剂、吗菌威(carbamorph)、苯基氨基甲酸酯类杀真菌剂、多菌灵、萎锈灵、氯环丙酰胺、香芹酮、Cheshunt混合物、灭螨蜢、灭瘟唑(chlobenthiazone)、双胺灵(chloraniformethan)、氯醌(chloranil)、苯咪唑菌(chlorfenazole)、氯二硝萘、地茂散、氯化苦(chloropicrin)、百菌清、四氯喹啉(chlorquinox)、乙菌利(chlozolinate)、环吡酮(ciclopirox)、氯咪巴唑(climbazole)、克霉唑(clotrimazole)、康唑类杀真菌剂、康唑类杀真菌剂(咪唑类)、康唑类杀真菌剂(三唑类)、醋酸铜(II)、碱式碳酸铜(II)、铜杀真菌剂、氢氧化铜、环烷酸铜、油酸铜、王铜、硫酸铜(II)、碱式硫酸铜、铬酸铜锌、甲酚、硫杂灵(cufraneb)、福美铜氯(cuprobam)、氧化亚铜、氰霜唑、环糠酰胺(cyclafuramid)、环状二硫代氨基甲酸酯类杀真菌剂、放线菌酮(cycloheximide)、环氟菌胺、清菌脲、氰菌灵(cypendazole)、环唑醇、环丙嘧啶、棉隆、DBCP、咪菌威、癸磷锡(decafentin)、脱氢乙酸、二羧酰亚胺类杀真菌剂、抑菌灵、二氯萘醌(dichlone)、双氯酚、二氯苯、二羧酰亚胺类杀真菌剂、菌核利(dichlozoline)、苄氯三唑醇(diclobutrazol)、双氯氰菌胺、哒菌清、氯硝胺、乙霉威、焦碳酸二乙酯、醚唑、二氟林、甲菌定(dimethirimol)、烯酰吗啉、醚菌胺、烯唑醇、二硝基苯酚类杀真菌剂、敌螨通、敌螨普、二硝酯(dinocton)、硝戊酯(dinopenton)、硝辛酯(dinosulfon)、硝丁酯(dinoterbon)、二苯胺、吡菌硫(dipyrithione)、双硫仑(disulfiram)、灭菌磷(ditalimfos)、二噻农、二硫代氨基甲酸酯类杀真菌剂、二硝甲酚(DNOC)、吗菌灵、多敌菌(dodicin)、多果定、DONATODINE、敌菌酮(drazoxolon)、克瘟散、氧唑菌、乙环唑(etaconazole)、伊藤(etem)、噻唑菌胺、乙菌定(ethirimol)、促长啉(ethoxyquin)、乙汞硫丙二醇(ethylmercury 2,3-dihydroxypropyl mercaptide)、醋酸乙汞、溴化乙汞、氯化乙汞、磷酸乙汞、氯唑灵、唑酮菌、咪唑菌酮、地可松(fenaminosulf)、菌拿灵(fenapanil)、异嘧菌醇、腈苯唑、呋菌胺、环酰菌胺、杀螟松、氰菌胺、拌种咯(fenpiclonil)、苯锈啶、丁苯吗啉、三苯锡基(fentin)、福美铁、嘧菌腙、氟啶胺、氟菌、氟联苯菌、氟吗啉、氟吡菌胺、氟菌安、菌唑灵(fluotrimazole)、氟嘧菌酯、喹唑菌酮、氟硅唑、磺菌胺、氟酰胺、粉唑醇、灭菌丹、甲醛、藻菌磷、麦穗宁、呋氨丙灵(furalaxyl)、呋吡唑灵、糠酰胺类杀真菌剂、糠酰苯胺类杀真菌剂、灭菌胺(furcarbanil)、呋菌唑(furconazole)、呋醚唑(furconazole-cis)、糠醛、拌种胺(furmecyclox)、呋菌隆(furophanate)、果绿定(glyodin)、灰黄霉素(griseofulvin)、双胍盐、烯菌酯(halacrinate)、六氯苯、六氯丁二烯、六氯酚、己唑醇、环己硫磷(hexylthiofos)、萘磺汞(hydrargaphen)、土菌消、抑霉唑、酰胺唑、咪唑类杀真菌剂、双胍辛醋酸盐、无机杀真菌剂、无机汞类杀真菌剂、碘甲烷、环戊唑醇、异稻瘟净、异丙定、异丙菌胺、稻瘟灵、氯苯咪菌酮(isovaledione)、春雷素、亚胺菌、石硫合剂、锰铜混剂(mancopper)、代森锰锌、代森锰、灭锈胺(mebenil)、咪卡病西(mecarbinzid)、嘧菌胺、丙氧灭绣胺、升汞、氧化汞、甘汞、汞类杀真菌剂、甲霜灵、精甲霜灵、威百亩、肼叉唑酮(metazoxolon)、环戊唑菌、磺菌威、甲呋菌胺(methfuroxam)、溴甲烷、异硫氰酸甲酯、苯甲酸甲汞、氰胍甲汞(methylmercurydicyandiamide)、五氯酚甲汞(methylmercury pentachlorophenoxide)、代森联、叉氨苯酰胺、苯菌酮、噻菌胺(metsulfovax)、代森环(milneb)、吗啉类杀真菌剂、腈菌唑、甲菌利(myclozolin)、N-乙基汞-对甲苯磺酰苯胺、代森钠(nabam)、多马霉素(natamycin)、硫氰散(nitrostyrene)、异丙消、氟苯嘧啶醇(nuarimol)、OCH、异噻菌酮、甲呋酰胺、有机汞类杀真菌剂、有机磷类杀真菌剂、有机锡类杀真菌剂、肟醚菌胺、霜灵、氧硫杂环己二烯类杀真菌剂、唑类杀真菌剂、喹啉铜(oxine copper)、恶咪唑、氧化萎锈灵、稻瘟酯、戊菌唑、戊菌隆、五氯酚、吡噻菌胺、苯汞脲、赛力散(phenylmercury acetate)、氯化苯汞、邻苯二酚的苯汞衍生物、硝酸苯汞、水杨酸苯汞、苯基硫酰胺类杀真菌剂、双氯苯磷(phosdiphen)、四氯苯酞、邻苯二甲酰亚胺类杀真菌剂、啶氧菌酯、粉病灵、福代锌(polycarbamate)、聚合二硫代氨基甲酸酯类杀真菌剂、多氧霉素(polyoxins)、保粒霉素(polyoxorim)、多硫化物杀真菌剂、噻菌灵、丙氯灵、杀菌利、百维灵、丙环唑、甲基代森锌、丙氧喹啉、胺丙威(prothiocarb)、丙硫菌唑、比锈灵(pyracarbolid)、唑菌胺酯、吡唑类杀真菌剂、定菌磷、吡啶类杀真菌剂、病定清(pyridinitril)、啶斑肟、二甲嘧菌胺、嘧啶类杀真菌剂、咯喹酮、吡氧氯(pyroxychlor)、氯吡呋醚(pyroxyfur)、吡咯类杀真菌剂、喹菌(quinacetol)、酯菌腙(quinazamid)、唑喹菌酮(quinconazole)、喹啉类杀真菌剂、醌类杀真菌剂、喹喔啉类杀真菌剂、喹氧灵、五氯硝基苯、吡咪唑菌(rabenzazole)、水杨酰替苯胺、硅噻菌胺、硅氟唑、螺茂胺、链霉素、嗜球果伞素类(strobilurin)杀真菌剂、磺酰苯胺类杀真菌剂、硫、戊苯砜(sultropen)、TCMTB、戊唑醇、叶枯酞、四氯硝基苯、福代硫(tecoram)、氟醚唑、涕必灵、噻二氟(thiadifluor)、噻唑类杀真菌剂、噻菌腈(thicyofen)、溴氟唑菌、硫代氨基甲酸酯类杀真菌剂、苯菌胺(thiochlorfenphim)、水杨乙汞(thiomersal)、托布津(thiophanate)、甲基托布津、噻吩类杀真菌剂、克杀螨(thioquinox)、福美双、噻酰菌胺、硫氰苯甲酰胺(tioxymid)、tivedo、甲基立枯磷、托萘酯(tolnaftate)、对甲抑菌灵、醋酸甲苯汞、三唑酮、唑菌醇、三唑磷胺(triamiphos)、嘧菌醇(triarimol)、丁三唑(triazbutil)、三嗪类杀真菌剂、三唑类杀真菌剂、唑菌嗪、丁蜗锡(tributyltin oxide)、杨菌胺(trichlamide)、三环唑、克啉菌,肟菌酯、氟菌唑、嗪氨灵、氯氟醚菌唑、metyltetraprole、戊叉唑菌、未分类杀真菌剂、十一碳烯酸、烯效唑、脲类杀真菌剂、井冈霉素、缬氨酰胺类杀真菌剂、烯菌酮、氯菌胺(zarilamid)、环烷酸锌、代森锌、福美锌、苯酰菌胺及其混合物。
除草剂:除草剂是用来杀灭不想要的植物的农药。选择性除草剂杀灭特定目标物,同时使所需作物相对不受伤害。这些中的一些通过干扰杂草生长而起作用并且通常基于植物激素。用来清理荒地的除草剂是非选择性的并且杀灭与其接触的所有植物材料。除草剂广泛用于农业和景观草坪管理中。它们以用于公路和铁路养护的植被总量控制(TVC)方案施用。更小的量用于林业、牧业系统以及野生动物栖息地的管理。下文汇编了许多合适的除草剂:
在一个实施方案中,本发明的微胶囊或组合物可以含有大量其他组除草或生长调节活性物质—下文称为除草或或生长调节活性物质B)和C)—的代表或其混合物作为活性物质或者将这些一起施用。还可能的是微粒可以包含一种或多种包封在该微粒中的活性成分B)或C)。
B)b1)-b15)类除草剂:
b1)类脂生物合成抑制剂;
b2)乙酰乳酸合成酶抑制剂(ALS抑制剂);
b3)光合成抑制剂;
b4)原卟啉原-IX氧化酶抑制剂,
b5)漂白剂除草剂;
b6)烯醇丙酮酰莽草酸3-磷酸合成酶抑制剂(EPSP抑制剂);
b7)谷氨酰胺合成酶抑制剂;
b8)7,8-二氢蝶酸合成酶抑制剂(DHP抑制剂);
b9)有丝分裂抑制剂;
b10)非常长链脂肪酸合成抑制剂(VLCFA抑制剂);
b11)纤维素生物合成抑制剂;
b12)去偶剂除草剂;
b13)植物生长素除草剂;
b14)植物生长素输送抑制剂;和
b15)选自如下的其他除草剂:溴丁酰草胺(bromobutide)、氯甲丹(chlorflurenol)、氯甲丹(chlorflurenol-methyl)、环庚草醚(cinmethylin)、苄草隆(cumyluron)、茅草枯(dalapon)、棉隆、野燕枯、野燕枯甲基硫酸酯、噻节因(dimethipin)、甲胂钠(DSMA)、香草隆(dymron)、敌草腈(endothal)及其盐、乙苯酰草(etobenzanid)、氟燕灵(flamprop)、氟燕灵(flamprop-isopropyl)、甲氟燕灵(flamprop-methyl)、强氟燕灵(flamprop-M-isopropyl)、麦草伏(flamprop-M-methyl)、抑草丁(flurenol)、抑草丁(flurenol-butyl)、调嘧醇(flurprimidol)、膦铵素(fosamine)、茚草酮(indanofan)、茚嗪氟草胺(indaziflam)、抑芽丹(maleichydrazide)、氟草磺(mefluidide)、威百亩、甲硫唑草啉(methiozolin)、叠氮甲烷、溴甲烷、苯丙隆(methyl-dymron)、碘甲烷、甲胂一钠(MSMA)、油酸、氯嗪草(oxaziclomefone)、壬酸、稗草畏(pyributicarb)、灭藻醌(quinoclamine)、四氟络草胺(tetflupyrolimet)、苯氧丙胺津(triaziflam)、灭草环(tridiphane)和6-氯-3-(2-环丙基-6-甲基苯氧基)-4-哒嗪醇(CAS 499223-49-3)及其盐和酯;
包括其可农用盐或衍生物;以及
C)安全剂。
若本文所述的除草化合物B和/或安全剂C能够形成几何异构体,例如E/Z异构体,则可以在本发明组合物中使用纯异构体及其混合物二者。
若本文所述的除草化合物B和/或安全剂C具有一个或多个手性中心并且因此作为对映体或非对映体存在,则可以在本发明组合物中使用纯对映体和非对映体及其混合物二者。
本文所述具有羧基的除草化合物B和/或安全剂C可以以酸的形式、以如上所述可农用盐的形式或者以可农用衍生物的形式,例如作为酰胺,如单-和二-C1-C6烷基酰胺或芳基酰胺,作为酯,例如作为烯丙基酯、炔丙基酯、C1-C10烷基酯、烷氧基烷基酯、四氢呋喃基甲基((四氢呋喃-2-基)甲基)酯以及还有作为硫酯,例如作为C1-C10烷硫基酯使用。优选的单-和二-C1-C6烷基酰胺是甲基和二甲基酰胺。优选的芳基酰胺例如为酰替苯胺和2-氯酰替苯胺。优选的烷基酯例如为甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、甲基己基(1-甲基己基)、甲基庚基(1-甲基庚基)、庚基、辛基或异辛基(2-乙基己基)酯。优选的C1-C4烷氧基-C1-C4烷基酯是直链或支化C1-C4烷氧基乙基酯,例如2-甲氧基乙基、2-乙氧基乙基、2-丁氧基乙基(丁氧乙基)、2-丁氧基丙基或3-丁氧基丙基酯。直链或支化C1-C10烷硫基酯的实例是乙硫基酯。
根据本发明的第一个实施方案,组合物含有至少一种类脂生物合成抑制剂(除草剂b1)。这些是抑制类脂生物合成的化合物。可以通过抑制乙酰CoA羧化酶(下文称为ACC除草剂)或通过不同作用模式(下文称为非ACC除草剂)而进行类脂生物合成的抑制。ACC除草剂属于HRAC分类体系的A类,而非ACC除草剂属于HRAC分类的N类。
根据本发明的另一实施方案,组合物含有至少一种ALS抑制剂(除草剂b2)。这些化合物的除草活性基于乙酰乳酸合成酶的抑制并因此基于支链氨基酸生物合成的抑制。这些抑制剂属于HRAC分类体系的B类。
根据本发明的另一实施方案,组合物含有至少一种光合成抑制剂(除草剂b3)。这些化合物的除草活性基于植物中光合系统II的抑制(所谓的PSII抑制剂,HRAC分类的C1、C2和C3类)或基于使植物中光合系统I中的电子转移转向(所谓的PSI抑制剂,HRAC分类的D类)并因此基于光合成的抑制。其中优选PSII抑制剂。
根据本发明的另一实施方案,组合物含有至少一种原卟啉原-IX氧化酶抑制剂(除草剂b4)。这些化合物的除草活性基于原卟啉原-IX氧化酶的抑制。这些抑制剂属于HRAC分类体系的E类。
根据本发明的另一实施方案,组合物含有至少一种漂白剂除草剂(除草剂b5)。这些化合物的除草活性基于类胡萝卜素生物合成的抑制。这些包括通过抑制八氢番茄红素去饱和酶而抑制类胡萝卜素生物合成的化合物(所谓的PDS抑制剂,HRAC分类的F1类),抑制4-羟基苯基丙酮酸二加氧酶的化合物(HPPD抑制剂,HRAC分类的F2类),抑制DOX合成酶的化合物(HRAC分类的F4类)和通过未知作用方式抑制类胡萝卜素生物合成的化合物(漂白剂—未知目标,HRAC分类的F3类)。
根据本发明的另一实施方案,组合物含有至少一种EPSP合成酶抑制剂(除草剂b6)。这些化合物的除草活性基于烯醇丙酮酰莽草酸3-磷酸合成酶的抑制并且因此基于植物中氨基酸生物合成的抑制。这些抑制剂属于HRAC分类体系的G类。
根据本发明的另一实施方案,组合物含有至少一种谷氨酰胺合成酶抑制剂(除草剂b7)。这些化合物的除草活性基于谷氨酰胺合成酶的抑制并且因此基于植物中氨基酸生物合成的抑制。这些抑制剂属于HRAC分类体系的H类。
根据本发明的另一实施方案,组合物含有至少一种DHP合成酶抑制剂(除草剂b8)。这些化合物的除草活性基于7,8-二氢蝶酸合成酶的抑制。这些抑制剂属于HRAC分类体系的I类。
根据本发明的另一实施方案,组合物含有至少一种有丝分裂抑制剂(除草剂b9)。这些化合物的除草活性基于微管形成或组织化的扰乱或抑制并且因此基于有丝分裂的抑制。这些抑制剂属于HRAC分类体系的K1和K2类。其中优选K1类化合物,尤其是二硝基苯胺类。
根据本发明的另一实施方案,组合物含有至少一种VLCFA抑制剂(除草剂b10)。这些化合物的除草活性基于非常长链脂肪酸合成的抑制并且因此基于植物中细胞分裂的扰乱或抑制。这些抑制剂属于HRAC分类体系的K3类。
根据本发明的另一实施方案,组合物含有至少一种纤维素生物合成抑制剂(除草剂b11)。这些化合物的除草活性基于纤维素生物合成的抑制并且因此基于植物中细胞壁合成的抑制。这些抑制剂属于HRAC分类体系的L类。
根据本发明的另一实施方案,组合物含有至少一种去偶剂除草剂(除草剂b12)。这些化合物的除草活性基于细胞膜的干扰。这些抑制剂属于HRAC分类体系的M类。
根据本发明的另一实施方案,组合物含有至少一种植物生长素除草剂(除草剂b13)。这些包括模拟植物生长素,即植物激素并影响植物生长的化合物。这些化合物属于HRAC分类体系的O类。
根据本发明的另一实施方案,组合物含有至少一种植物生长素输送抑制剂(除草剂b14)。这些化合物的除草活性基于植物中植物生长素输送的抑制。这些化合物属于HRAC分类体系的P类。
对于活性物质的给定作用机理和分类,例如参见“HRAC,根据作用模式的除草剂分类”,http://www.plantprotection.org/hrac/MOA.html)。
优选那些包含至少一种选自除草剂类别b2、b3、b4、b5、b6、b9和b10的除草剂B的本发明组合物。
具体优选那些包含至少一种选自除草剂类别b4、b6、b9和b10的除草剂B的本发明组合物。
特别优选那些包含至少一种选自除草剂类别b4、b6和b10的除草剂B的本发明组合物。
可以与本发明组合物组合使用的除草剂B的实例为:
b1)选自如下的类脂生物合成抑制剂:ACC除草剂如枯杀达(alloxydim)、丁氧环酮(butroxydim)、烯草酮(clethodim)、炔草酯(clodinafop)、炔草酯(clodinafop-propargyl)、噻草酮(cycloxydim)、氰氟草酯(cyhalofop)、氰氟草酯(cyhalofop-butyl)、氯甲草(diclofop)、禾草灵(diclofop-methyl)、唑禾草灵(fenoxaprop)、唑禾草灵(fenoxaprop-ethyl)、高唑禾草灵(fenoxaprop-P)、高唑禾草灵(fenoxaprop-P-ethyl)、吡氟禾草灵(fluazifop)、吡氟禾草灵(fluazifop-butyl)、精吡氟禾草灵(fluazifop-P)、精吡氟禾草灵(fluazifop-P-butyl)、吡氟氯禾灵(haloxyfop)、吡氟氯禾灵(haloxyfop-methyl)、精吡氟氯禾灵(haloxyfop-P)、精吡氟氯禾灵(haloxyfop-P-methyl)、唑酰草胺(metamifop)、唑啉草酯(pinoxaden)、环苯草酮(profoxydim)、喔草酯(propaquizafop)、喹禾灵(quizalofop)、喹禾灵(quizalofop-ethyl)、喹禾灵(四氢糠基酯)(quizalofop-tefuryl)、精喹禾灵(quizalofop-P)、精喹禾灵(quizalofop-P-ethyl)、精喹禾灵(四氢糠基酯)(quizalofop-P-tefuryl)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim)、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS 1312337-72-6)、4-(2',4'-二氯-4-环丙基[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS 1312337-45-3)、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS 1033757-93-5)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-2,2,6,6-四甲基-2H-吡喃-3,5(4H,6H)-二酮(CAS 1312340-84-3)、5-乙酰氧基-4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS 1312337-48-6)、5-乙酰氧基-4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮、5-乙酰氧基-4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS 1312340-82-1)、5-乙酰氧基-4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS 1033760-55-2)、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1312337-51-1)、4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1312340-83-2)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1033760-58-5);以及非ACC除草剂如呋草黄(benfuresate)、苏达灭(butylate)、草灭特(cycloate)、茅草枯、哌草丹(dimepiperate)、扑草灭(EPTC)、禾草畏(esprocarb)、乙呋草黄(ethofumesate)、四氟丙酸(flupropanate)、草达灭(molinate)、坪草丹(orbencarb)、克草猛(pebulate)、苄草丹(prosulfocarb)、TCA、杀草丹(thiobencarb)、丁草威(tiocarbazil)、野麦畏(triallate)和灭草猛(vernolate);
b2)选自如下的ALS抑制剂:磺酰脲类,如磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、苄嘧黄隆(bensulfuron-methyl)、氯嘧黄隆(chlorimuron)、氯嘧黄隆(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、胺苯黄隆(ethametsulfuron)、胺苯黄隆(ethametsulfuron-methyl)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟吡磺隆(flucetosulfuron)、氟定黄隆(flupyrsulfuron)、甲酰氨磺隆(foramsulfuron)、吡氯黄隆(halosulfuron)、吡氯黄隆(halosulfuron-methyl)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、iofensulfuron、甲基二磺隆(mesosulfuron)、嗪吡嘧磺隆(metazosulfuron)、甲黄隆(metsulfuron)、甲黄隆(metsulfuron-methyl)、烟嘧黄隆(nicosulfuron)、嘧苯胺磺隆(orthosulfamuron)、环丙氧黄隆(oxasulfuron)、氟嘧黄隆(primisulfuron)、氟嘧黄隆(primisulfuron-methyl)、丙嗪嘧磺隆(propyrisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、吡嘧黄隆(pyrazosulfuron-ethyl)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、嘧黄隆(sulfometuron-methyl)、乙黄黄隆(sulfosulfuron)、噻黄隆(thifensulfuron)、噻黄隆(thifensulfuron-methyl)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、苯黄隆(tribenuron-methyl)、三氟啶磺隆(trifloxysulfuron)、氟胺磺隆(triflusulfuron)、氟胺磺隆(triflusulfuron-methyl)和三氟甲磺隆(tritosulfuron),咪唑啉酮类如咪草酯(imazamethabenz)、咪草酯(imazamethabenz-methyl)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)和咪草烟(imazethapyr),三唑并嘧啶类除草剂和磺酰苯胺类如唑嘧磺胺酸(cloransulam)、唑嘧磺胺盐(cloransulam-methyl)、唑嘧磺胺(diclosulam)、氟唑啶草(flumetsulam)、双氟磺草胺(florasulam)、唑草磺胺(metosulam)、五氟磺草胺(penoxsulam)、吡硫磺(pyrimisulfan)和啶磺草胺(pyroxsulam),嘧啶基苯甲酸酯类如双嘧苯甲酸(bispyribac)、嘧啶肟草醚(pyribenzoxim)、环酯草醚(pyriftalid)、肟啶草(pyriminobac)、肟啶草(pyriminobac-methyl)、嘧硫苯甲酸(pyrithiobac)、4-[[[2-[(4,6-二甲氧基-2-嘧啶基)氧基]苯基]甲基]氨基]苯甲酸1-甲基乙基酯(CAS 420138-41-6)、4-[[[2-[(4,6-二甲氧基-2-嘧啶基)氧基]苯基]甲基]氨基]苯甲酸丙基酯(CAS 420138-40-5)、N-(4-溴苯基)-2-[(4,6-二甲氧基-2-嘧啶基)氧基]苯甲胺(CAS 420138-01-8),磺酰氨基羰基三唑啉酮类除草剂如氟酮磺隆(flucarbazone)、丙苯磺隆(propoxycarbazone)、噻酮磺隆(thiencarbazone)和噻酮磺隆(thiencarbazone-methyl),以及氟酮磺草胺(triafamone);
其中本发明的优选实施方案涉及包含至少一种咪唑啉酮类除草剂的那些组合物;
b3)选自如下的光合成抑制剂:胺唑草酮(amicarbazone),光合系统II抑制剂,例如1-(6-叔丁基嘧啶-4-基)-2-羟基-4-甲氧基-3-甲基-2H-吡咯-5-酮(CAS 1654744-66-7)、1-(5-叔丁基异唑-3-基)-2-羟基-4-甲氧基-3-甲基-2H-吡咯-5-酮(CAS 1637455-12-9)、1-(5-叔丁基异唑-3-基)-4-氯-2-羟基-3-甲基-2H-吡咯-5-酮(CAS 1637453-94-1)、1-(5-叔丁基-1-甲基吡唑-3-基)-4-氯-2-羟基-3-甲基-2H-吡咯-5-酮(CAS1654057-29-0)、1-(5-叔丁基-1-甲基吡唑-3-基)-3-氯-2-羟基-4-甲基-2H-吡咯-5-酮(CAS 1654747-80-4)、4-羟基-1-甲氧基-5-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 2023785-78-4)、4-羟基-1,5-二甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS2023785-79-5)、5-乙氧基-4-羟基-1-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS1701416-69-4)、4-羟基-1-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 1708087-22-2)、4-羟基-1,5-二甲基-3-[1-甲基-5-三氟甲基吡唑-3-基]咪唑烷-2-酮(CAS2023785-80-8)、1-(5-叔丁基异唑-3-基)-4-乙氧基-5-羟基-3-甲基咪唑烷-2-酮(CAS1844836-64-1),三嗪类除草剂,包括氯代三嗪类、三嗪酮类、三嗪二酮类、甲硫基三嗪类和哒嗪酮类,如莠灭净(ametryn)、莠去津(atrazine)、杀草敏(chloridazone)、草净津(cyanazine)、敌草净(desmetryn)、戊草津(dimethametryn)、六嗪同(hexazinone)、赛克津(metribuzin)、扑灭通(prometon)、扑草净(prometryn)、扑灭津(propazine)、西玛津(simazine)、西草净(simetryn)、甲氧去草净(terbumeton)、特丁津(terbuthylazin)、去草净(terbutryn)和草达津(trietazin);芳基脲类如氯溴隆(chlorobromuron)、绿麦隆(chlorotoluron)、枯草隆(chloroxuron)、丁隆(dimefuron)、敌草隆(diuron)、伏草隆(fluometuron)、异丙隆(isoproturon)、异恶隆(isouron)、利谷隆(linuron)、苯嗪草(metamitron)、噻唑隆(methabenzthiazuron)、色满隆(metobenzuron)、甲氧隆(metoxuron)、绿谷隆(monolinuron)、草不隆(neburon)、环草隆(siduron)、丁唑隆(tebuthiuron)和赛二唑素(thiadiazuron),苯基氨基甲酸酯类如异苯敌草(desmedipham)、卡草灵(karbutilat)、苯敌草(phenmedipham)、乙苯敌草(phenmedipham-ethyl),腈类除草剂如杀草全(bromofenoxim)、溴苯腈(bromoxynil)及其盐和酯、碘苯腈(ioxynil)及其盐和酯,尿嘧啶类如除草定(bromacil)、环草定(lenacil)和特草定(terbacil)以及噻草平(bentazon)、达草止(pyridate)、pyridafol、蔬草灭(pentanochlor)和敌稗(propanil)以及光合系统I抑制剂如敌草快阳离子(diquat)、敌草快(diquat-dibromide)、对草快阳离子(paraquat)、对草快(paraquat-dichloride)和对草快(paraquat-dimetilsulfate)。其中本发明的优选实施方案涉及包含至少一种芳基脲类除草剂的那些组合物。其中本发明的优选实施方案同样涉及包含至少一种三嗪类除草剂的那些组合物。其中本发明的优选实施方案同样涉及包含至少一种腈类除草剂的那些组合物;
b4)选自如下的原卟啉原-IX氧化酶抑制剂:氟锁草醚(acifluorfen)、唑啶炔草(azafenidin)、苯唑磺隆(bencarbazone)、双苯嘧草酮(benzfendizone)、治草醚(bifenox)、氟丙嘧草酯(butafenacil)、氟酮唑草(carfentrazone)、氟酮唑草(carfentrazone-ethyl)、氯硝醚(chlomethoxyfen)、氯酞亚胺(chlorphthalim)、吲哚酮草酯(cinidon-ethyl)、cyclopyranil、异丙吡草酯(fluazolate)、氟哒嗪草酯(flufenpyr)、氟哒嗪草酯(flufenpyr-ethyl)、酰亚胺苯氧乙酸(flumiclorac)、酰亚胺苯氧乙酸戊酯(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、乙羧氟草醚(fluoroglycofen)、乙羧氟草醚(fluoroglycofen-ethyl)、达草氟(fluthiacet)、达草氟(fluthiacet-methyl)、氟黄胺草醚(fomesafen)、氟硝磺酰胺(halosafen)、乳氟禾草灵(lactofen)、炔丙唑草(oxadiargyl)、恶草灵(oxadiazon)、乙氧氟草醚(oxyfluorfen)、戊唑草(pentoxazone)、氟唑草胺(profluazol)、双唑草腈(pyraclonil)、氟唑草酯(pyraflufen)、氟唑草酯(pyraflufen-ethyl)、苯嘧磺草胺(saflufenacil)、磺胺草唑(sulfentrazone)、噻二唑胺(thidiazimin)、氟嘧硫草酯(tiafenacil)、[3-[2-氯-4-氟-5-(1-甲基-6-三氟甲基-2,4-二氧代-1,2,3,4-四氢嘧啶-3-基)苯氧基]-2-吡啶氧基]乙酸乙酯(CAS 353292-31-6;S-3100)、N-乙基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS452098-92-9)、N-四氢糠基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 915396-43-9)、N-乙基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 452099-05-7)、N-四氢糠基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 452100-03-7)、3-[7-氟-3-氧代-4-(丙-2-炔基)-3,4-二氢-2H-苯并[1,4]嗪-6-基]-1,5-二甲基-6-硫代-[1,3,5]三嗪烷(triazinan)-2,4-二酮(CAS 451484-50-7)、2-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[b][1,4]嗪-6-基)-4,5,6,7-四氢异吲哚-1,3-二酮(CAS 1300118-96-0)、1-甲基-6-三氟甲基-3-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]嗪-6-基)-1H-嘧啶-2,4-二酮(CAS1304113-05-0)、(E)-4-[2-氯-5-(4-氯-5-二氟甲氧基-1H-甲基吡唑-3-基)-4-氟苯氧基]-3-甲氧基丁-2-烯酸甲酯(CAS 948893-00-3)和3-[7-氯-5-氟-2-三氟甲基-1H-苯并咪唑-4-基]-1-甲基-6-三氟甲基-1H-嘧啶-2,4-二酮(CAS 212754-02-4)、2-[2-氯-5-[3-氯-5-三氟甲基-2-吡啶基]-4-氟苯氧基]-2-甲氧基乙酸甲酯(CAS 1970221-16-9)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]乙酸甲酯(CAS 2158274-96-3)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]乙酸乙酯(CAS 158274-50-9)、2-[[3-[2-氯-5-[4-二氟甲基-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟苯氧基]-2-吡啶基]氧基]乙酸甲酯(CAS 2271389-22-9)、2-[[3-[2-氯-5-[4-二氟甲基-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟苯氧基]-2-吡啶基]氧基]乙酸乙酯(CAS 2230679-62-4)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]乙酸甲酯(CAS 2158275-73-9)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]乙酸乙酯(CAS 2158274-56-5)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]-N-(甲基磺酰基)乙酰胺(CAS 2158274-53-2)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]-N-(甲基磺酰基)乙酰胺(CAS 2158276-22-1);
b5)选自如下的漂白剂除草剂:PDS抑制剂:氟丁酰草胺(beflubutamid)、吡氟草胺(diflufenican)、氟草同(fluridone)、氟咯草酮(flurochloridone)、呋草酮(flurtamone)、达草灭(norflurazon)、氟吡酰草胺(picolinafen)、4-(3-三氟甲基苯氧基)-2-(4-三氟甲基苯基)嘧啶(CAS 180608-33-7)和3-氯-2-[-3-二氟甲基异唑-5-基]苯基-5-氯嘧啶-2-基醚,HPPD抑制剂:苯并双环酮(benzobicyclon)、吡草酮(benzofenap)、氟吡草酮(bicyclopyrone)、异恶草酮(clomazone)、fenquinotrione、异氟草(isoxaflutole)、甲基磺草酮(mesotrione)、oxotrione(CAS 1486617-21-3)、磺酰草吡唑(pyrasulfotole)、吡唑特(pyrazolynate)、苄草唑(pyrazoxyfen)、磺草酮(sulcotrione)、呋喃磺草酮(tefuryltrione)、环磺酮(tembotrione)、tolpyralate、托普拉威(topramezone)、双唑草酮(bipyrazone)、苯唑氟草酮(fenpyrazone)、环吡氟草酮(cypyrafluone)、三唑磺草酮(tripyrasulfone)、喹草酮(benquitrione)、2-(3,4-二甲氧基苯基)-4-[2-羟基-6-氧代环己-1-烯-1-基)羰基]-6-甲基哒嗪-3(2H)-酮;漂白剂,未知目标:苯草醚(aclonifen)、杀草强(amitrole)、伏草隆(flumeturon)、2-氯-3-甲硫基-N-(1-甲基四唑-5-基)-4-三氟甲基苯甲酰胺(CAS 1361139-71-0)、二氯异草酮(bixlozone)和2-(2,5-二氯苯基)甲基-4,4-二甲基-3-异唑烷酮(CAS 81778-66-7);
b8)选自如下的DHP合成酶抑制剂:黄草灵(asulam);
b9)选自如下的有丝分裂抑制剂:K1组化合物:二硝基苯胺类如氟草胺(benfluralin)、地乐胺(butralin)、敌乐胺(dinitramine)、丁氟消草(ethalfluralin)、氟消草(fluchloralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)和氟乐灵(trifluralin),氨基磷酸酯类如胺草磷(amiprophos)、甲基胺草磷(amiprophos-methyl)和草胺磷(butamiphos),苯甲酸类除草剂如敌草索(chlorthal)、敌草索(chlorthal-dimethyl),吡啶类如氟硫草定(dithiopyr)和噻氟啶草(thiazopyr),苯甲酰胺类如拿草特(propyzamide)和丙戊草胺(tebutam),K2组化合物:长杀草(carbetamide)、氯苯胺灵(chlorpropham)、氟燕灵(flamprop)、氟燕灵(flamprop-isopropyl)、甲氟燕灵、强氟燕灵、麦草伏和苯胺灵(propham);其中优选K1组化合物,尤其优选二硝基苯胺类;
b10)选自如下的VLCFA抑制剂:氯乙酰胺类如乙草胺(acetochlor)、甲草胺(alachlor)、先甲草胺(amidochlor)、丁草胺(butachlor)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、精噻吩草胺(dimethenamid-P)、吡草胺(metazachlor)、异丙甲草胺(metolachlor)、S-异丙甲草胺(metolachlor-S)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、扑草胺(propachlor)、异丙草胺(propisochlor)和噻醚草胺(thenylchlor),羟基乙酰苯胺类(oxyacetanilide)如氟噻草胺(flufenacet)和苯噻草胺(mefenacet),乙酰苯胺类如草乃敌(diphenamid)、萘丙胺(naproanilide)、草萘胺(napropamide)和精草萘胺(napropamide-M),四唑啉酮类如四唑酰草胺(fentrazamide)以及其他除草剂如莎稗磷(anilofos)、唑草胺(cafenstrole)、苯磺唑草(fenoxasulfone)、三唑酰草胺(ipfencarbazone)、哌草磷(piperophos)、派罗克杀草砜(pyroxasulfone)、dimesulfazet以及式II.1、II.2、II.3、II.4、II.5、II.6、II.7、II.8和II.9的异唑啉化合物:
式(II)的异唑啉化合物在本领域中是已知的,例如由WO 2006/024820、WO2006/037945、WO 2007/071900和WO 2007/096576已知;
在VLCFA抑制剂中,优选氯代乙酰胺类和羟基乙酰胺类;
b11)选自如下的纤维素生物合成抑制剂:草克乐(chlorthiamid)、敌草腈(dichlobenil)、胺草唑(flupoxam)、茚嗪氟草胺、异恶草胺(isoxaben)、苯氧丙胺津和1-环己基-5-五氟苯氧基-14-[1,2,4,6]硫杂三嗪-3-基胺(CAS 175899-01-1);
b12)选自如下的去偶剂除草剂:地乐酚(dinoseb)、地乐消酚(dinoterb)以及二硝甲酚及其盐;
b13)选自如下的植物生长素除草剂:2,4-D及其酯,如氯酰草膦(clacyfos),2,4-DB及其酯,环丙嘧啶酸(aminocyclopyrachlor)及其酯,氨草啶(aminopyralid)及其酯,草除灵(benazolin),草除灵(benazolin-ethyl),草灭平(chloramben)及其酯,稗草胺(clomeprop),二氯皮考啉酸(clopyralid)及其酯,2,4-滴丙酸(dichlorprop)及其酯,高2,4-滴丙酸(dichlorprop-P)及其酯,氯氟吡啶酯(flopyrauxifen),氟草烟(fluroxypyr),氟草烟(fluroxypyr-butometyl),氟氯胺啶(fluroxypyr-meptyl),氟氯吡啶酯(halauxifen)及其酯(CAS 943832-60-8),MCPA及其酯,2甲4氯乙硫酯(MCPA-thioethyl),MCPB及其酯,2甲4氯丙酸(mecoprop)及其酯,高2甲4氯丙酸(mecoprop-P)及其酯,毒莠定(picloram)及其酯,二氯喹啉酸(quinclorac),喹草酸(quinmerac),TBA(2,3,6)及其酯,绿草定(triclopyr)及其酯,氯氟吡啶酯(florpyrauxifen),氯氟吡啶酯(florpyrauxifen-benzyl)(CAS 1390661-72-9)和4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶甲酸(CAS1629965-65-6);
b14)选自如下的植物生长素输送抑制剂:二氟吡隆(diflufenzopyr)、抑草生(naptalam);
b15)选自如下的其他除草剂:溴丁酰草胺、氯甲丹(chlorflurenol)、氯甲丹(chlorflurenol-methyl)、环庚草醚、苄草隆、cyclopyrimorate(CAS 499223-49-3)及其盐和酯、茅草枯、棉隆、野燕枯、野燕枯甲基硫酸酯、噻节因、甲胂钠、香草隆、敌草腈及其盐、乙苯酰草、抑草丁(flurenol)、抑草丁(flurenol-butyl)、调嘧醇、膦铵素、茚草酮、抑芽丹、氟草磺、威百亩、甲硫唑草啉、叠氮甲烷、溴甲烷、苯丙隆、碘甲烷、甲胂一钠、油酸、氯嗪草、壬酸、稗草畏、灭藻醌、四氟络草胺和灭草环。
可以与本发明组合物组合使用的优选除草剂B为:
b1)选自如下的类脂生物合成抑制剂:烯草酮、炔草酯、噻草酮、氰氟草酯、禾草灵、高唑禾草灵、精吡氟禾草灵、精吡氟氯禾灵、唑酰草胺、唑啉草酯、环苯草酮、喔草酯、精喹禾灵、精喹禾灵(四氢糠基酯)、稀禾定、醌肟草、肟草酮、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS 1312337-72-6)、4-(2',4'-二氯-4-环丙基[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS 1312337-45-3)、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS 1033757-93-5)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-2,2,6,6-四甲基-2H-吡喃-3,5(4H,6H)-二酮(CAS 1312340-84-3)、5-(乙酰氧基)-4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS1312337-48-6)、5-(乙酰氧基)-4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮、5-(乙酰氧基)-4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS 1312340-82-1)、5-(乙酰氧基)-4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS1033760-55-2)、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1312337-51-1)、4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1312340-83-2)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1033760-58-5)、呋草黄、哌草丹、扑草灭、禾草畏、乙呋草黄、草达灭、坪草丹、苄草丹、杀草丹和野麦畏;
b2)选自如下的ALS抑制剂:磺氨黄隆、四唑黄隆、苄嘧黄隆、氯嘧黄隆、绿黄隆、唑嘧磺胺盐、环丙黄隆、唑嘧磺胺、胺苯黄隆、乙氧嘧黄隆、啶嘧黄隆、双氟磺草胺、氟吡磺隆、氟唑啶草、甲酰氨磺隆、吡氯黄隆、咪草酯、咪草啶酸、甲基咪草烟、灭草烟、灭草喹、咪草烟、啶咪黄隆、碘黄隆、iofensulfuron、甲基二磺隆、嗪吡嘧磺隆、唑草磺胺、甲黄隆、烟嘧黄隆、嘧苯胺磺隆、环丙氧黄隆、五氟磺草胺、氟嘧黄隆、丙嗪嘧磺隆、氟丙黄隆、吡嘧黄隆、嘧啶肟草醚、吡硫磺、环酯草醚、肟啶草、啶磺草胺、玉嘧黄隆、嘧黄隆、乙黄黄隆、噻酮磺隆、噻黄隆、醚苯黄隆、苯黄隆、三氟啶磺隆、氟胺磺隆、三氟甲磺隆和氟酮磺草胺;
b3)选自如下的光合成抑制剂:莠灭净、胺唑草酮、莠去津、噻草平、溴苯腈及其盐和酯、杀草敏、绿麦隆、草净津、异苯敌草、敌草快、敌草隆、伏草隆、六嗪同、碘苯腈及其盐和酯、异丙隆、环草定、利谷隆、苯嗪草、噻唑隆、赛克津、对草快阳离子、对草快、苯敌草、敌稗、达草止、西玛津、去草净、特丁津、赛二唑素、1-(6-叔丁基嘧啶-4-基)-2-羟基-4-甲氧基-3-甲基-2H-吡咯-5-酮(CAS 1654744-66-7)、1-(5-叔丁基异唑-3-基)-2-羟基-4-甲氧基-3-甲基-2H-吡咯-5-酮(CAS 1637455-12-9)、1-(5-叔丁基异唑-3-基)-4-氯-2-羟基-3-甲基-2H-吡咯-5-酮(CAS 1637453-94-1)、1-(5-叔丁基-1-甲基吡唑-3-基)-4-氯-2-羟基-3-甲基-2H-吡咯-5-酮(CAS 1654057-29-0)、1-(5-叔丁基-1-甲基吡唑-3-基)-3-氯-2-羟基-4-甲基-2H-吡咯-5-酮(CAS 1654747-80-4)、4-羟基-1-甲氧基-5-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 2023785-78-4)、4-羟基-1,5-二甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 2023785-79-5)、5-乙氧基-4-羟基-1-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 1701416-69-4)、4-羟基-1-甲基-3-[4-三氟甲基-2-吡啶基]咪唑烷-2-酮(CAS 1708087-22-2)、4-羟基-1,5-二甲基-3-[1-甲基-5-三氟甲基吡唑-3-基]咪唑烷-2-酮(CAS 2023785-80-8)和1-(5-叔丁基异唑-3-基)-4-乙氧基-5-羟基-3-甲基-咪唑烷-2-酮(CAS 1844836-64-1);
b4)选自如下的原卟啉原-IX氧化酶抑制剂:苯唑磺隆、双苯嘧草酮、氟丙嘧草酯、氟酮唑草、吲哚酮草酯、cyclopyranil、氟哒嗪草酯、酰亚胺苯氧乙酸戊酯、氟嗪酮、乙羧氟草醚、达氟黄胺草醚、乳氟禾草灵、炔丙唑草、恶草灵、乙氧氟草醚、戊唑草、氟唑草酯(pyraflufen)、氟唑草酯(pyraflufen-ethyl)、苯嘧磺草胺、磺胺草唑、氟嘧硫草酯、[3-[2-氯-4-氟-5-(1-甲基-6-三氟甲基-2,4-二氧代-1,2,3,4-四氢嘧啶-3-基)苯氧基]-2-吡啶氧基]乙酸乙酯(CAS 353292-31-6;S-3100)、N-乙基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 452098-92-9)、N-四氢糠基-3-(2,6-二氯-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 915396-43-9)、N-乙基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 452099-05-7)、N-四氢糠基-3-(2-氯-6-氟-4-三氟甲基苯氧基)-5-甲基-1H-吡唑-1-甲酰胺(CAS 452100-03-7)、3-[7-氟-3-氧代-4-(丙-2-炔基)-3,4-二氢-2H-苯并[1,4]嗪-6-基]-1,5-二甲基-6-硫代-[1,3,5]三嗪烷-2,4-二酮(CAS 451484-50-7)、2-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]嗪-6-基)-4,5,6,7-四氢异吲哚-1,3-二酮(CAS 1300118-96-0)、1-甲基-6-三氟甲基-3-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]嗪-6-基)-1H-嘧啶-2,4-二酮(CAS 1304113-05-0)和3-[7-氯-5-氟-2-三氟甲基-1H-苯并咪唑-4-基]-1-甲基-6-三氟甲基-1H-嘧啶-2,4-二酮(CAS 212754-02-4)、2-[2-氯-5-[3-氯-5-三氟甲基-2-吡啶基]-4-氟苯氧基]-2-甲氧基乙酸甲酯(CAS 1970221-16-9)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]乙酸甲酯(CAS 2158274-96-3)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]乙酸乙酯(CAS 158274-50-9)、2-[[3-[2-氯-5-[4-二氟甲基-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟-苯氧基]-2-吡啶基]氧基]乙酸甲酯(CAS 2271389-22-9)、2-[[3-[2-氯-5-[4-二氟甲基-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟-苯氧基]-2-吡啶基]氧基]乙酸乙酯(CAS 2230679-62-4)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]乙酸甲酯(CAS 2158275-73-9)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]乙酸乙酯(CAS2158274-56-5)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]-N-(甲基磺酰基)乙酰胺(CAS 2158274-53-2)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]-N-(甲基磺酰基)乙酰胺(CAS 2158276-22-1);
b5)选自如下的漂白剂除草剂:苯草醚、杀草强、氟丁酰草胺、苯并双环酮、氟吡草酮、异恶草酮、环吡氟草酮、吡氟草胺、fenquinotrione、伏草隆、氟咯草酮、呋草酮、异氟草、甲基磺草酮、oxotrione(CAS 1486617-21-3)、达草灭、氟吡酰草胺、磺酰草吡唑、吡唑特、磺酰草吡唑、呋喃磺草酮、环磺酮、tolpyralate、托普拉威、4-(3-三氟甲基苯氧基)-2-(4-三氟甲基苯基)嘧啶(CAS 180608-33-7)、2-氯-3-甲硫基-N-(1-甲基四唑-5-基)-4-三氟甲基苯甲酰胺(CAS 1361139-71-0)、二氯异草酮、2-(2,5-二氯苯基)甲基-4,4-二甲基-3-异唑烷酮(CAS 81778-66-7)、氯-2-[-3-二氟甲基异唑-5-基]苯基-5-氯嘧啶-2-基醚和2-(3,4-二甲氧基苯基)-4-[2-羟基-6-氧代环己-1-烯-1-基)羰基]-6-甲基哒嗪-3(2H)-酮;
b8)选自如下的DHP合成酶抑制剂:黄草灵;
b9)选自如下的有丝分裂抑制剂:氟草胺、氟硫草定、丁氟消草、氟燕灵(flamprop)、氟燕灵(flamprop-isopropyl)、甲氟燕灵、强氟燕灵、麦草伏、黄草消、胺硝草、噻氟啶草和氟乐灵;
b10)选自如下的VLCFA抑制剂:乙草胺、甲草胺、先甲草胺、莎稗磷、丁草胺、唑草胺、噻吩草胺、精噻吩草胺、dimesulfazet、四唑酰草胺、氟噻草胺、苯噻草胺、吡草胺、异丙甲草胺、S-异丙甲草胺、萘丙胺、草萘胺、精草萘胺、丙草胺、苯磺唑草、三唑酰草胺、派罗克杀草砜、噻醚草胺以及如上所述式II.1、II.2、II.3、II.4、II.5、II.6、II.7、II.8和II.9的异唑啉化合物;
b11)选自如下的纤维素生物合成抑制剂:敌草腈、胺草唑、茚嗪氟草胺、异恶草胺、苯氧丙胺津和1-环己基-5-五氟苯氧基-14-[1,2,4,6]硫杂三嗪-3-基胺(CAS 175899-01-1);
b13)选自如下的植物生长素除草剂:2,4-D及其酯、环丙嘧啶酸及其酯、氨草啶及其酯、二氯皮考啉酸及其盐和酯、高2,4-滴丙酸及其盐和酯、氯氟吡啶酯、氟氯胺啶、氟氯吡啶酯(halauxifen)及其盐和酯(CAS 943832-60-8)、MCPA及其盐和酯、MCPB及其盐和酯、高2甲4氯丙酸及其盐和酯、毒莠定及其盐和酯、二氯喹啉酸、喹草酸、绿草定及其盐和酯、氯氟吡啶酯(florpyrauxifen)、氯氟吡啶酯(florpyrauxifen-benzyl)(CAS 1390661-72-9)和4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶甲酸(CAS 1629965-65-6);
b14)选自如下的植物生长素输送抑制剂:二氟吡隆;
b15)选自如下的其他除草剂:溴丁酰草胺、环庚草醚、苄草隆、cyclopyrimorate(CAS 499223-49-3)及其盐和酯、茅草枯、野燕枯、野燕枯甲基硫酸酯、甲胂钠、香草隆(=daimuron)、茚草酮、威百亩、溴甲烷、甲胂一钠、氯嗪草、稗草畏、四氟络草胺和灭草环。
可以与本发明组合物组合使用的特别优选除草剂B为:
b1)选自如下的类脂生物合成抑制剂:炔草酯、噻草酮、氰氟草酯、高唑禾草灵、唑啉草酯、环苯草酮、醌肟草、肟草酮、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS 1312337-72-6)、4-(2',4'-二氯-4-环丙基[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS 1312337-45-3)、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5-羟基-2,2,6,6-四甲基-2H-吡喃-3(6H)-酮(CAS 1033757-93-5)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-2,2,6,6-四甲基-2H-吡喃-3,5(4H,6H)-二酮(CAS 1312340-84-3)、5-(乙酰氧基)-4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS 1312337-48-6)、5-(乙酰氧基)-4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮、5-(乙酰氧基)-4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS 1312340-82-1)、5-(乙酰氧基)-4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-3,6-二氢-2,2,6,6-四甲基-2H-吡喃-3-酮(CAS 1033760-55-2)、4-(4'-氯-4-环丙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1312337-51-1)、4-(2',4'-二氯-4-环丙基-[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯、4-(4'-氯-4-乙基-2'-氟[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1312340-83-2)、4-(2',4'-二氯-4-乙基[1,1'-联苯]-3-基)-5,6-二氢-2,2,6,6-四甲基-5-氧代-2H-吡喃-3-基甲酸甲酯(CAS 1033760-58-5)、禾草畏、苄草丹、杀草丹和野麦畏;
b2)选自如下的ALS抑制剂:苄嘧黄隆、环丙黄隆、唑嘧磺胺、氟唑啶草、甲酰氨磺隆、咪草啶酸、甲基咪草烟、灭草烟、灭草喹、咪草烟、啶咪黄隆、碘黄隆、iofensulfuron、甲基二磺隆、嗪吡嘧磺隆、烟嘧黄隆、五氟磺草胺、丙嗪嘧磺隆、吡嘧黄隆、啶磺草胺、玉嘧黄隆、乙黄黄隆、噻酮磺隆、三氟甲磺隆和氟酮磺草胺;
b3)选自如下的光合成抑制剂:莠灭净、莠去津、敌草隆、伏草隆、六嗪同、异丙隆、利谷隆、赛克津、对草快阳离子、对草快、敌稗、去草净、特丁津、1-(5-叔丁基异唑-3-基)-2-羟基-4-甲氧基-3-甲基-2H-吡咯-5-酮(CAS 1637455-12-9)、1-(5-叔丁基异唑-3-基)-4-氯-2-羟基-3-甲基-2H-吡咯-5-酮(CAS 1637453-94-1)、1-(5-叔丁基异唑-3-基)-4-乙氧基-5-羟基-3-甲基-咪唑烷-2-酮(CAS 1844836-64-1);
b4)选自如下的原卟啉原-IX氧化酶抑制剂:cyclopyranil、氟嗪酮、乙氧氟草醚、氟唑草酯(pyraflufen)、氟唑草酯(pyraflufen-ethyl)、苯嘧磺草胺、磺胺草唑、[3-[2-氯-4-氟-5-(1-甲基-6-三氟甲基-2,4-二氧代-1,2,3,4-四氢嘧啶-3-基)苯氧基]-2-吡啶氧基]乙酸乙酯(CAS 353292-31-6;S-3100)、3-[7-氟-3-氧代-4-(丙-2-炔基)-3,4-二氢-2H-苯并[1,4]嗪-6-基]-1,5-二甲基-6-硫代-[1,3,5]三嗪烷-2,4-二酮(CAS 451484-50-7)、2-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]嗪-6-基)-4,5,6,7-四氢异吲哚-1,3-二酮(CAS 1300118-96-0)和1-甲基-6-三氟甲基-3-(2,2,7-三氟-3-氧代-4-丙-2-炔基-3,4-二氢-2H-苯并[1,4]嗪-6-基)-1H-嘧啶-2,4-二酮(CAS1304113-05-0)、2-[2-氯-5-[3-氯-5-三氟甲基-2-吡啶基]-4-氟苯氧基]-2-甲氧基乙酸甲酯(CAS 1970221-16-9)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]乙酸甲酯(CAS 2158274-96-3)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]乙酸乙酯(CAS 158274-50-9)、2-[[3-[2-氯-5-[4-二氟甲基-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟-苯氧基]-2-吡啶基]氧基]乙酸甲酯(CAS 2271389-22-9)、2-[[3-[2-氯-5-[4-二氟甲基-3-甲基-5-氧代-1,2,4-三唑-1-基]-4-氟-苯氧基]-2-吡啶基]氧基]乙酸乙酯(CAS 2230679-62-4)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]乙酸甲酯(CAS 2158275-73-9)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]乙酸乙酯(CAS 2158274-56-5)、2-[2-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]苯氧基]-N-(甲基磺酰基)乙酰胺(CAS 2158274-53-2)、2-[[3-[[3-氯-6-[3,6-二氢-3-甲基-2,6-二氧代-4-三氟甲基-1(2H)-嘧啶基]-5-氟-2-吡啶基]氧基]-2-吡啶基]氧基]-N-(甲基磺酰基)乙酰胺(CAS 2158276-22-1);
b5)选自如下的漂白剂除草剂:杀草强、氟吡草酮、异恶草酮、吡氟草胺、fenquinotrione、伏草隆、氟咯草酮、异氟草、甲基磺草酮、oxotrione(CAS 1486617-21-3)、氟吡酰草胺、磺酰草吡唑、呋喃磺草酮、环磺酮、tolpyralate、托普拉威、2-氯-3-甲硫基-N-(1-甲基四唑-5-基)-4-三氟甲基苯甲酰胺(CAS 1361139-71-0)、二氯异草酮、2-(2,5-二氯苯基)甲基-4,4-二甲基-3-异唑烷酮(CAS 81778-66-7)和氯-2-[-3-二氟甲基异唑-5-基]苯基-5-氯嘧啶-2-基醚;
b9)选自如下的有丝分裂抑制剂:胺硝草和氟乐灵;
b10)选自如下的VLCFA抑制剂:乙草胺、唑草胺、精噻吩草胺、四唑酰草胺、氟噻草胺、苯噻草胺、吡草胺、异丙甲草胺、S-异丙甲草胺、苯磺唑草、三唑酰草胺和派罗克杀草砜;同样优选如上所述的式II.1、II.2、II.3、II.4、II.5、II.6、II.7、II.8和II.9的异唑啉化合物;
b11)选自如下的纤维素生物合成抑制剂:茚嗪氟草胺、异恶草胺和苯氧丙胺津;
b13)选自如下的植物生长素除草剂:2,4-D及其盐和酯如氯酰草膦、环丙嘧啶酸及其盐和酯、氨草啶及其盐和其酯、二氯皮考啉酸及其盐和酯、氯氟吡啶酯、氟氯胺啶、氟氯吡啶酯(halauxifen)、氟氯吡啶酯(halauxifen-methyl)、二氯喹啉酸、喹草酸、氯氟吡啶酯(florpyrauxifen)、氯氟吡啶酯(florpyrauxifen-benzyl)(CAS 1390661-72-9)和4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶甲酸(CAS 1629965-65-6);
b14)选自如下的植物生长素输送抑制剂:二氟吡隆;
b15)选自如下的其他除草剂:环庚草醚、香草隆(dymon)(=daimuron)、茚
草酮、氯嗪草和四氟络草胺。
在本发明的另一实施方案中,本发明组合物包含至少一种安全剂C。
安全剂是防止或降低对有用植物的损害但不对本发明组合物的除草活性组分对不想要的植物的除草作用具有显著影响的化合物。它们可以在播种之前施用(例如在种子处理时、在嫩枝或秧苗上)或以有用植物的出苗前施用或出苗后施用方式施用。安全剂和本发明组合物和/或除草剂B可以同时或依次施用。
合适的安全剂例如是(喹啉-8-氧基)乙酸类、1-苯基-5-卤代烷基-1H-1,2,4-三唑-3-甲酸、1-苯基-4,5-二氢-5-烷基-1H-吡唑-3,5-二甲酸、4,5-二氢-5,5-二芳基-3-异唑甲酸、二氯乙酰胺类、α-肟基苯基乙腈类、苯乙酮肟类、4,6-二卤代-2-苯基嘧啶类、N-[[4-(氨基羰基)苯基]磺酰基]-2-苯甲酰胺类、1,8-萘二甲酸酐、2-卤代-4-卤代烷基-5-噻唑羧酸、硫代磷酸酯类和N-烷基-O-苯基氨基甲酸酯类及其可农用盐和其可农用衍生物如酰胺、酯和硫酯,条件是它们具有酸基。
优选安全剂C的实例是解草酮(benoxacor)、喹氧乙酸(cloquintocet)、抑害腈(cyometrinil)、环丙磺酰胺(cyprosulfamide)、抑害胺(dichlormid)、dicyclonon、增效磷(dietholate)、解草唑(fenchlorazole)、解草啶(fenclorim)、解草安(flurazole)、肟草安(fluxofenim)、解草呋(furilazole)、双苯唑酸(isoxadifen)、吡咯二酸(mefenpyr)、mephenate、萘二甲酸酐(naphthalic anhydride)、解草腈(oxabetrinil)、4-二氯乙酰基-1-氧杂-4-氮杂螺[4.5]癸烷(MON4660,CAS 71526-07-3)、2,2,5-三甲基-3-二氯乙酰基-1,3-唑烷(R-29148,CAS 52836-31-4)、metcamifen和BPCMS(CAS 54091-06-4)。
尤其优选的安全剂C为解草酮、喹氧乙酸、环丙磺酰胺、抑害胺、解草唑、解草啶、解草安、肟草安、解草呋、双苯唑酸、吡咯二酸、萘二甲酸酐、解草腈、4-(二氯乙酰基)-1-氧杂-4-氮杂螺[4.5]癸烷(MON4660,CAS 71526-07-3)、2,2,5-三甲基-3-(二氯乙酰基)-1,3-唑烷(R-29148、CAS 52836-31-4)和metcamifen。
特别优选的安全剂C为解草酮、喹氧乙酸、环丙磺酰胺、抑害胺、解草唑、解草啶、解草呋、双苯唑酸、吡咯二酸、萘二甲酸酐、4-(二氯乙酰基)-1-氧杂-4-氮杂螺[4.5]癸烷(MON4660,CAS 71526-07-3)、2,2,5-三甲基-3-(二氯乙酰基)-1,3-唑烷(R-29148,CAS52836-31-4)和metcamifen。
b1)-b15)组的活性化合物B和活性化合物C是已知的除草剂和安全剂,例如参见The Compendium of Pesticide Common Names(http://www.alanwood.net/pesticides/);Farm Chemicals Handbook 2000,第86卷,Meister Publishing Company,2000;B.Hock,C.Fedtke,R.R.Schmidt,Herbizide[除草剂],Georg Thieme Verlag,Stuttgart,1995;W.H.Ahrens,Herbicide Handbook,第7版,Weed Science Society ofAmerica,1994以及K.K.Hatzios,Herbicide Handbook,第7版增补,Weed Science Societyof America,1998。2,2,5-三甲基-3-二氯乙酰基-1,3-唑烷[CAS号52836-31-4]也称为R-29148。4-二氯乙酰基-1-氧杂-4-氮杂螺[4.5]癸烷[CAS号71526-07-3]也称为AD-67和MON 4660。
活性化合物的相应作用机理的归属基于现有知识。若几种作用机理适用于一种活性化合物,则该物质仅归属于一种作用机理。
具有羧基的活性化合物B和C在本发明组合物中可以如上所述以酸的形式、可农用盐形式或可农用衍生物的形式使用。
2,4-D的合适酯的实例是2,4-D丁氧基乙酯(2,4-D-butotyl)、2,4-D-2-丁氧基丙酯、2,4-D-3-丁氧基丙酯、2,4-D丁酯(2,4-D-butyl)、2,4-D乙酯(2,4-D-ethyl)、2,4-D乙基己基酯(2,4-D-ethylhexyl)、2,4-D异丁酯(2,4-D-isobutyl)、2,4-D异辛酯(2,4-D-isooctyl)、2,4-D异丙酯(2,4-D-isopropyl)、2,4-D甲基庚基酯(2,4-D-meptyl)、2,4-D甲酯(2,4-D-methyl)、2,4-D辛酯(2,4-D-octyl)、2,4-D戊酯(2,4-D-pentyl)、2,4-D丙酯(2,4-D-propyl)、2,4-D四氢呋喃酯(2,4-D-tefuryl)和氯酰草膦。
2,4-DB的合适酯例如为2,4-DB丁酯(2,4-DB-butyl)和2,4-DB异辛酯(2,4-DB-isoctyl)。
2,4-滴丙酸的合适酯的实例是2,4-滴丙酸丁氧基乙酯(dichlorprop-butotyl)和2,4-滴丙酸异辛酯(dichlorprop-isoctyl)。
MCPA的合适酯包括MCPA丁氧基乙酯(MCPA-butotyl)、MCPA丁酯(MCPA-butyl)、MCPA二乙醇胺(MCPA-diolamine)、MCPA乙酯(MCPA-ethyl)、2甲4氯乙硫酯、MCPA-2-乙基己基酯(MCPA-2-ethylhexyl)、MCPA异丁酯(MCPA-isobutyl)、MCPA异辛酯(MCPA-isoctyl)、MCPA异丙酯(MCPA-isopropyl)、MCPA甲酯(MCPA-methyl)、MCPA乙醇胺(MCPA-olamine)和MCPA三乙醇胺(MCPA三乙醇胺)。
MCPB的合适酯是MCPB乙酯(MCPB-ethyl)。
二氯皮考啉酸的合适酯的实例是二氯皮考啉酸甲酯。
氟草烟的合适酯的实例是是氟氯胺啶和氟草烟2-丁氧基-1-甲基乙基酯(fluroxypyr-2-butoxy-1-methylethyl),其中优选氟氯胺啶。
毒莠定的合适酯是毒莠定异辛酯(picloram-isoctyl)。
绿草定的合适酯例如是绿草定乙酯(triclopyr-ethyl)和绿草定丁氧基乙酯(triclopyr-butotyl)。
草灭平的合适酯包括草灭平二乙醇胺(chloramben-diolamine)、草灭平甲酯(chloramben-methyl)。
溴苯腈的合适盐和酯例如为溴苯腈丁酸酯(bromoxynil-butyrate)、溴苯腈庚酸酯(bromoxynil-heptanoate)、溴苯腈辛酸酯(bromoxynil-octanoate)。
碘苯腈(ioxonil)的合适盐和酯例如为碘苯腈辛酸酯(ioxonil-octanoate)。
2甲4氯丙酸的合适酯包括2甲4氯丙酸丁氧基乙酯(mecoprop-butotyl)、2甲4氯丙酸二乙醇胺(mecoprop-diolamine)、mecoprop-ethadyl、2甲4氯丙酸2-乙基己基酯(mecoprop-2-ethylhexyl)、2甲4氯丙酸异辛酯(mecoprop-isoctyl)、2甲4氯丙酸甲酯(mecoprop-methyl)和2甲4氯丙酸三乙醇胺(mecoprop-trolamine)。
环丙嘧啶酸的合适酯例如为环丙嘧啶酸甲酯。
根据本发明的优选实施方案,该组合物包含至少一种,优选正好一种除草剂B作为除草活性化合物B或组分B。
根据本发明的另一优选实施方案,该组合物包含至少两种,优选正好两种相互不同的除草剂B作为除草活性化合物B或组分B。
根据本发明的另一优选实施方案,该组合物包含至少三种,优选正好三种相互不同的除草剂B作为除草活性化合物B或组分B。
根据本发明的另一优选实施方案,该组合物包含至少一种,优选正好一种安全剂C作为安全组分C或组分C。
根据本发明的另一优选实施方案,该组合物包含至少一种,优选正好一种除草剂B作为组分B和至少一种,优选正好一种安全剂C作为组分C。
根据本发明的另一优选实施方案,该组合物包含至少两种,优选正好两种相互不同的除草剂B以及作为组分C的至少一种,优选正好一种安全剂C。
根据本发明的另一优选实施方案,该组合物包含至少三种,优选正好三种相互不同的除草剂B以及作为组分C的至少一种,优选正好一种安全剂C。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b1)组,尤其是选自烯草酮、炔草酯、噻草酮、氰氟草酯、唑禾草灵、高唑禾草灵、唑酰草胺、唑啉草酯、环苯草酮、稀禾定、醌肟草、肟草酮、禾草畏、乙呋草黄、草达灭、苄草丹、杀草丹和野麦畏的除草活性化合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b2)组,尤其是选自苄嘧黄隆、唑嘧磺胺盐、绿黄隆、氯嘧黄隆(clorimuron)、环丙黄隆、唑嘧磺胺、双氟磺草胺、氟唑啶草、甲酰氨磺隆、咪草啶酸、甲基咪草烟、灭草烟、灭草喹、咪草烟、啶咪黄隆、iofensulfuron、甲磺胺磺隆(mesosulfuron-methyl)、嗪吡嘧磺隆、甲黄隆、唑草磺胺、烟嘧黄隆、五氟磺草胺、吡嘧黄隆、嘧啶肟草醚、环酯草醚、啶磺草胺、丙嗪嘧磺隆、玉嘧黄隆、乙黄黄隆、噻酮磺隆、噻黄隆、苯黄隆、三氟甲磺隆和氟酮磺草胺的除草活性化合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b3)组,尤其是选自莠灭净、莠去津、噻草平、溴苯腈、溴苯腈辛酸酯、溴苯腈庚酸酯、敌草隆、伏草隆、六嗪同、异丙隆、利谷隆、苯嗪草、赛克津、对草快、敌稗、西玛津、去草净和特丁津的除草活性化合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b4)组,尤其是选自氟锁草醚、氟丙嘧草酯(butafencil)、氟酮唑草(carfenetrazone-ethyl)、氟嗪酮、达氟黄胺草醚、炔丙唑草、乙氧氟草醚、氟唑草酯(pyraflufen)、氟唑草酯(pyraflufen-ethyl)、苯嘧磺草胺、磺胺草唑、[3-[2-氯-4-氟-5-(1-甲基-6-三氟甲基-2,4-二氧代-1,2,3,4-四氢嘧啶-3-基)苯氧基]-2-吡啶氧基]乙酸乙酯(CAS 353292-31-6;S-3100)的除草活性化合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b5)组,尤其是选自杀草强、苯并双环酮、氟吡草酮、异恶草酮、吡氟草胺、fenquintrone、伏草隆、氟咯草酮、异氟草、甲基磺草酮、达草灭、oxotrione(CAS 1486617-21-3)、氟吡酰草胺、磺酰草吡唑、呋喃磺草酮、环磺酮、tolpyralate、托普拉威、2-氯-3-甲硫基-N-(1-甲基四唑-5-基)-4-三氟甲基苯甲酰胺(CAS 1361139-71-0)、二氯异草酮、2-(2,5-二氯苯基)甲基-4,4-二甲基-3-异唑烷酮(CAS 81778-66-7)和氯-2-[-3-二氟甲基异唑-5-基]苯基-5-氯嘧啶-2-基醚的除草活性化合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b9)组,尤其是选自胺硝草和氟乐灵的除草活性化合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b10)组,尤其是选自乙草胺、丁草胺、唑草胺、精噻吩草胺、四唑酰草胺、氟噻草胺、苯噻草胺、吡草胺、异丙甲草胺、S-异丙甲草胺、苯磺唑草、三唑酰草胺和派罗克杀草砜的除草活性化合物。
同样优选包含至少一种,尤其是正好一种选自b10)组,尤其是选自如上所定义的式II.1、II.2、II.3、II.4、II.5、II.6、II.7、II.8和II.9的异唑啉化合物的除草活性化合物的组合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b11)组,尤其是选自茚嗪氟草胺、异恶草胺和苯氧丙胺津的除草活性化合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b13)组,尤其是选自2,4-D、2,4-D异丁酯、环丙嘧啶酸、环丙嘧啶酸甲酯、氨草啶、氨草啶甲酯、二氯皮考啉酸、二氯皮考啉酸甲酯、二氯皮考啉酸乙醇胺、氯氟吡啶酯、氟草烟、氟氯胺啶、氟氯吡啶酯(halauxifen)、氟氯吡啶酯(halauxifen-methyl)、MCPA、MCPA-2-乙基己基酯、二氯喹啉酸、喹草酸、氯氟吡啶酯(florpyrauxifen)、氯氟吡啶酯(florpyrauxifen-benzyl)(CAS 1390661-72-9)和4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶甲酸(CAS1629965-65-6)的除草活性化合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b14)组,尤其是选自二氟吡隆、香草隆和茚草酮的除草活性化合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种选自b15)组,尤其是选自环庚草醚、香草隆(=daimuron)、茚草酮、氯嗪草和四氟络草胺的除草活性化合物。
根据本发明的另一优选实施方案,该组合物包含至少一种,尤其是正好一种安全剂C,尤其是选自解草酮、喹氧乙酸、环丙磺酰胺、抑害胺、解草唑、解草啶、解草呋、双苯唑酸、吡咯二酸、4-(二氯乙酰基)-1-氧杂-4-氮杂螺[4.5]癸烷(MON4660,CAS 71526-07-3)和2,2,5-三甲基-3-(二氯乙酰基)-1,3-唑烷(R-29148,CAS 52836-31-4)的安全剂C。
在两种活性化合物的二元组合物中,这些活性化合物的重量比通常在1:1000-1000:1,优选1:500-500:1,尤其是1:250-250:1,特别优选1:75-75:1范围内。
在包含除草活性成分成分B和至少一种安全剂C的二元组合物中,除草活性成分B:安全剂C的重量比通常在1:1000-1000:1,优选1:500-500:1,尤其是1:250-250:1,特别优选1:75-75:1范围内。
在包含两种除草活性化合物B和至少一种安全剂C的三元组合物中,除草组分B的相对重量比例通常在1:1000-1000:1,优选1:500-500:1,尤其是1:250-250:1,特别优选1:75-75:1范围内,各除草剂B:组分C的重量比通常在1:1000-1000:1,优选1:500-500:1,尤其是1:250-250:1,特别优选1:75-75:1范围内并且组分B:C的重量比通常在1:1000-1000:1,优选1:500-500:1,尤其是1:250-250:1,特别优选1:75-75:1范围内。
特别优选的除草剂B是如上所定义的除草剂B,尤其是下面在表B中所列的除草剂B.1-B.214:
表B:
作为组分C为本发明组合物的成分的特别优选安全剂C是如上所定义的安全剂C,尤其是下面在表C中所列的安全剂C.1-C.17:
表C
在下述优选混合物中各组分的重量比在上面所给限度内,尤其是在优选限度内。
作为活性物质的优选除草剂是下列或其混合物:
莠去津,一种用于玉米和高粱中以防治阔叶杂草和禾草的三嗪除草剂。它由于其低成本并且由于其在与其他除草剂使用时作为增效剂起作用而仍在使用,它是光合系统II抑制剂。
二氯皮考啉酸,一种主要用于草皮、牧场中以及用于防治有毒蓟的吡啶类阔叶除草剂。以其在堆肥中的持久性著称。它是合成植物生长素的另一实例。
灭草烟,一种用于防治宽范围杂草的非选择性除草剂,这些杂草包括陆生一年生和多年生禾草和阔叶杂草本植物、木本植物以及河岸和新兴水生植物。
甲基咪草烟,一种用于出苗前和出苗后防治一些一年生和多年生禾草以及一些阔叶杂草的选择性除草剂。甲基咪草烟通过抑制蛋白质合成和细胞生长所需的支链氨基酸(缬氨酸、亮氨酸和异亮氨酸)的产生而杀灭植物。
异丙甲草胺,一种广泛用于在玉米和高粱中防治一年生禾草的出苗前除草剂;对于这些用途它在很大程度上替代莠去津。
对草快阳离子,一种用于免耕焚毁以及空中销毁大麻和古柯种植的非选择性接触除草剂。比广泛商业使用的任何其他除草剂对人更具急性毒性。
毒莠定,一种主要用于在牧场和田野边缘防治不想要的树木的吡啶除草剂。它是另一合成植物生长素。
绿草定。
环庚草醚
苯嘧磺草胺
三氟草嗪(trifludimoxazin)
在一个实施方案中,活性物质是选自环庚草醚、精噻吩草胺、异恶草酮、氟吡酰草胺、吡草胺、S-异丙甲草胺(S-metalochlor)、乙草胺、胺硝草、苯嘧磺草胺、派罗克杀草砜、二氯异草酮、苄草丹、氟噻草胺、苯草醚、野麦畏、氟嗪酮、吡草胺、烯草胺、草萘胺、特丁津、异氟草、异恶草胺、苯嗪草、三氟草嗪、氟嘧硫草酯、磺胺草唑或其混合物的除草剂。
在一个实施方案中,活性物质是选自环庚草醚、精噻吩草胺、异恶草酮、氟吡酰草胺、吡草胺、S-异丙甲草胺、乙草胺、胺硝草、苯嘧磺草胺、派罗克杀草砜、二氯异草酮或其混合物的除草剂。
在一个实施方案中,活性成分是精噻吩草胺和异恶草酮的混合物。
在一个实施方案中,活性成分是环庚草醚和氟吡酰草胺的混合物。
在一个实施方案中,该活性成分为环庚草醚。
杀虫剂:杀虫剂为用于对抗所有发育形式的昆虫的农药。它们包括用于对抗昆虫卵和幼虫的杀卵剂和杀幼虫剂。杀虫剂用于农业、医药、工业和家庭中。下面提及合适的杀虫剂:
O)O.1-O.28类杀虫剂
O.1乙酰胆碱酯酶(AChE)抑制剂:涕灭威(aldicarb)、棉铃威(alanycarb)、虫威(bendiocarb)、丙硫克百威(benfuracarb)、丁酮威(butocarboxim)、丁酮氧威(butoxycarboxim)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、苯虫威(ethiofencarb)、仲丁威(fenobucarb)、抗螨脒(formetanate)、呋线威(furathiocarb)、异丙威(isoprocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、速灭威(metolcarb)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、久效威(thiofanox)、混杀威(trimethacarb)、XMC、灭杀威(xylylcarb)、唑蚜威(triazamate);高灭磷(acephate)、唑啶磷(azamethiphos)、乙基谷硫磷(azinphos-ethyl)、谷硫磷(azinphosmethyl)、硫线磷(cadusafos)、氯氧磷(chlorethoxyfos)、毒虫畏(chlorfenvinphos)、氯甲硫磷(chlormephos)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、蝇毒磷(coumaphos)、杀螟腈(cyanophos)、甲基内吸磷(demeton-S-methyl)、二嗪农(diazinon)、敌敌畏(dichlorvos/DDVP)、百治磷(dicrotophos)、乐果(dimethoate)、甲基毒虫畏(dimethylvinphos)、乙拌磷(disulfoton)、EPN、乙硫磷(ethion)、丙线磷(ethoprophos)、伐灭磷(famphur)、苯线磷(fenamiphos)、杀螟松(fenitrothion)、倍硫磷(fenthion)、噻唑硫磷(fosthiazate)、庚烯磷(heptenophos)、新烟碱类(imicyafos)、异丙胺磷(isofenphos)、O-(甲氧基氨基硫代磷酰基)水杨酸异丙酯、异唑磷(isoxathion)、马拉硫磷(malathion)、灭蚜磷(mecarbam)、甲胺磷(methamidophos)、杀扑磷(methidathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、二溴磷(naled)、氧乐果(omethoate)、砜吸磷(oxydemeton-methyl)、一六零五(parathion)、甲基对硫磷(parathion-methyl)、稻丰散(phenthoate)、甲拌磷(phorate)、伏杀磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、巴胺磷(propetamphos)、丙硫磷(prothiofos)、吡唑硫磷(pyraclofos)、哒嗪硫磷(pyridaphenthion)、喹硫磷(quinalphos)、治螟磷(sulfotep)、丁基嘧啶磷(tebupirimfos)、双硫磷(temephos)、特丁磷(terbufos)、杀虫威(tetrachlorvinphos)、甲基乙拌磷(thiometon)、三唑磷(triazophos)、敌百虫(trichlorfon)、蚜灭磷(vamidothion);
O.2GABA门控氯离子通道拮抗剂:硫丹(endosulfan)、氯丹(chlordane)、乙虫腈(ethiprole)、锐劲特(fipronil)、丁烯氟虫腈(flufiprole)、pyrafluprole、pyriprole;
O.3钠通道调节剂:氟丙菊酯(acrinathrin)、丙烯除虫菊(allethrin)、右旋丙烯菊酯(d-cis-trans allethrin)、右旋反式丙烯菊酯(d-transallethrin)、氟氯菊酯(bifenthrin)、κ-氟氯菊酯(kappa-bifenthrin)、生物烯丙菊酯(bioallethrin)、2-环戊烯基生物烯丙菊酯(bioallethrinS-cyclopentenyl)、生物苄呋菊酯(bioresmethrin)、乙氰菊酯(cycloprothrin)、氟氯氰菊酯(cyfluthrin)、高效氟氯氰菊酯(beta-cyfluthrin)、(RS)氯氟氰菊酯(cyhalothrin)、氯氟氰菊酯(lambda-cyhalothrin)、精高效氯氟氰菊酯(gamma-cyhalothrin)、氯氰菊酯(cypermethrin)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、高效反式氯氰菊酯(theta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、苯醚氰菊酯(cyphenothrin)、溴氰菊酯(deltamethrin)、烯炔菊酯(empenthrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、氟氰戊菊酯(flucythrinate)、氟氯苯菊酯(flumethrin)、氟胺氰菊酯(tau-fluvalinate)、溴氟醚菊酯(halfenprox)、七氟甲醚菊酯(heptafluthrin)、咪炔菊酯(imiprothrin)、氯氟醚菊酯(meperfluthrin)、甲氧苄氟菊酯(metofluthrin)、momfluorothrin、epsilon-momfluorothrin、氯菊酯(permethrin)、苯醚菊酯(phenothrin)、炔酮菊酯(prallethrin)、丙氟菊酯(profluthrin)、除虫菊酯(pyrethrin(除虫菊(pyrethrum)))、灭虫菊(resmethrin)、灭虫硅醚(silafluofen)、七氟菊酯(tefluthrin)、κ-七氟菊酯(kappa-tefluthrin)、四氟醚菊酯(tetramethylfluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin);DDT、甲氧滴滴涕(methoxychlor);
O.4烟碱型乙酰胆碱受体(nAChR)激动剂:吡虫清(acetamiprid)、噻虫胺(clothianidin)、环氧虫啶(cycloxaprid)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、硝胺烯啶(nitenpyram)、噻虫啉(thiacloprid)、噻虫嗪(thiamethoxam);4,5-二氢-N-硝基-1-(2-环氧乙烷基甲基)-1H-咪唑-2-胺、(2E-)-1-[(6-氯吡啶-3-基)甲基]-N'-硝基-2-亚戊基氨基胍;1-[(6-氯吡啶-3-基)甲基]-7-甲基-8-硝基-5-丙氧基-1,2,3,5,6,7-六氢咪唑并[1,2-a]吡啶;烟碱;氟啶虫胺腈(sulfoxaflor)、氟吡呋喃酮(flupyradifurone)、三氟苯嘧啶(triflumezopyrim)、(3R)-3-(2-氯噻唑-5-基)-8-甲基-5-氧代-6-苯基-2,3-二氢噻唑并[3,2-a]嘧啶-8--7-醇盐、(3S)-3-(6-氯-3-吡啶基)-8-甲基-5-氧代-6-苯基-2,3-二氢噻唑并[3,2-a]嘧啶-8--7-醇盐、(3S)-8-甲基-5-氧代-6-苯基-3-嘧啶-5-基-2,3-二氢噻唑并[3,2-a]嘧啶-8--7-醇盐、(3R)-3-(2-氯噻唑-5-基)-8-甲基-5-氧代-6-[3-三氟甲基苯基]-2,3-二氢噻唑并[3,2-a]嘧啶-8--7-醇盐;(3R)-3-(2-氯噻唑-5-基)-6-(3,5-二氯苯基)-8-甲基-5-氧代-2,3-二氢噻唑并[3,2-a]嘧啶-8--7-醇盐、(3R)-3-(2-氯噻唑-5-基)-8-乙基-5-氧代-6-苯基-2,3-二氢噻唑并[3,2-a]嘧啶-8--7-醇盐;
O.5烟碱型乙酰胆碱受体变构活化剂:艾克敌105(spinosad)、乙基多杀菌素(spinetoram);
O.6氯离子通道活化剂:齐墩螨素(abamectin)、甲氨基阿维菌素苯甲酸盐(emamectin benzoate)、伊维菌素(ivermectin)、雷皮菌素(lepimectin)、米尔螨素(milbemectin);
O.7保幼激素模拟物:蒙512(hydroprene)、烯虫炔酯(kinoprene)、蒙五一五(methoprene);双氧威(fenoxycarb)、蚊蝇醚(pyriproxyfen);
O.8其他非特异性(多位点)抑制剂:溴甲烷和其他烷基卤化物;氯化苦、磺酰氟、硼砂、酒石酸氧锑钾(tartar emetic);
O.9脊索神经器官TRPV通道调节剂:拒嗪酮(pymetrozine)、pyrifluquinazon;
O.10螨虫生长抑制剂:四螨嗪(clofentezine)、噻螨酮(hexythiazox)、氟螨嗪(diflovidazin);特苯唑(etoxazole);
O.11昆虫中肠膜的微生物干扰剂:苏云金芽孢杆菌(Bacillusthuringiensis)、球形芽孢杆菌(Bacillus sphaericus)以及它们产生的杀虫蛋白:苏云金芽孢杆菌以色列亚种(Bacillus thuringiensis subsp.israelensis)、球形芽孢杆菌、苏云金芽孢杆菌鲇泽亚种(Bacillusthuringiensis subsp.aizawai)、苏云金芽孢杆菌库斯塔克亚种(Bacillusthuringiensis subsp.kurstaki)、苏云金芽孢杆菌拟步行甲亚种菌株(Bacillusthuringiensis subsp.tenebrionis),Bt作物蛋白:Cry1Ab、Cry1Ac、Cry1Fa、Cry2Ab、mCry3A、Cry3Ab、Cry3Bb、Cry34/35Ab1;
O.12线粒体ATP合成酶抑制剂:杀螨硫隆(diafenthiuron);三唑锡(azocyclotin)、三环锡(cyhexatin)、杀螨锡(fenbutatin oxide)、克螨特(propargite)、三氯杀螨砜(tetradifon);
O.13经由质子梯度干扰的氧化磷酸化去偶剂:氟唑虫清(chlorfenapyr)、二硝甲酚、氟虫胺(sulfluramid);
O.14烟碱型乙酰胆碱受体(nAChR)通道阻断剂:杀虫磺(bensultap)、杀螟丹(cartap hydrochloride)、杀虫环(thiocyclam);
O.15类型0几丁质生物合成抑制剂:双三氟虫脲(bistrifluron)、定虫隆(chlorfluazuron)、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)、多氟虫酰脲(noviflumuron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron);
O.16类型1几丁质生物合成抑制剂:噻嗪酮(buprofezin);
O.17蜕皮干扰剂:灭蝇胺(cyromazine);
O.18蜕皮素受体激动剂:甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide)、特丁苯酰肼(halofenozide)、呋喃虫酰肼(fufenozide)、环虫酰肼(chromafenozide);
O.19章鱼胺受体激动剂(Octopamin receptor agonsit):双甲脒(amitraz);
O.20线粒体配合物III电子传输抑制剂:灭蚁腙(hydramethylnon)、灭螨醌(acequinocyl)、嘧螨酯(fluacrypyrim)、联苯肼酯(bifenazate);
O.21线粒体配合物I电子传输抑制剂:喹螨醚(fenazaquin)、唑螨酯(fenpyroximate)、嘧螨醚(pyrimidifen)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad);鱼藤酮(rotenone);
O.22电压依赖性钠通道阻断剂:二唑虫(indoxacarb)、氰氟虫胺(metaflumizone)、2-[2-(4-氰基苯基)-1-[3-三氟甲基苯基]亚乙基]-N-[4-(二氟甲氧基)苯基]氨基脲、N-(3-氯-2-甲基苯基)-2-[(4-氯苯基)-[4-[甲基(甲基磺酰基)氨基]苯基]亚甲基]氨基脲;
O.23乙酰CoA羧化酶抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramat)、spiropidion;
O.24线粒体配合物IV电子传输抑制剂:磷化铝、磷化钙、膦、磷化锌、氰化物;
O.25线粒体配合物II电子传输抑制剂:腈吡螨酯(cyenopyrafen)、丁氟螨酯(cyflumetofen);
O.26鱼尼汀(Ryanodine)受体调节剂:氟虫酰胺(flubendiamide)、氯虫酰胺(chlorantraniliprole)、氰虫酰胺(cyantraniliprole)、环溴虫酰胺(cyclaniliprole)、氟氰虫酰胺(tetraniliprole);(R)-3-氯-N1-{2-甲基-4-[1,2,2,2-四氟-1-三氟甲基乙基]苯基}-N2-(1-甲基-2-甲基磺酰基乙基)邻苯二甲酰胺、(S)-3-氯-N1-{2-甲基-4-[1,2,2,2-四氟-1-三氟甲基乙基]苯基}-N2-(1-甲基-2-甲基磺酰基乙基)邻苯二甲酰胺、2-[3,5-二溴-2-({[3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基]羰基}氨基)苯甲酰基]-1,2-二甲基肼甲酸甲酯;N-[4,6-二氯-2-[(二乙基-λ-4-亚硫烷基(sulfanylidene))氨基甲酰基]苯基]-2-(3-氯-2-吡啶基)-5-三氟甲基吡唑-3-甲酰胺;N-[4-氯-2-[(二乙基-λ-4-亚硫烷基)氨基甲酰基]-6-甲基苯基]-2-(3-氯-2-吡啶基)-5-三氟甲基吡唑-3-甲酰胺;N-[4-氯-2-[(二-2-丙基-λ-4-亚硫烷基)氨基甲酰基]-6-甲基苯基]-2-(3-氯-2-吡啶基)-5-三氟甲基吡唑-3-甲酰胺;N-[4,6-二氯-2-[(二-2-丙基-λ-4-亚硫烷基)氨基甲酰基]苯基]-2-(3-氯-2-吡啶基)-5-三氟甲基吡唑-3-甲酰胺;N-[4,6-二溴-2-[(二乙基-λ-4-亚硫烷基)氨基甲酰基]苯基]-2-(3-氯-2-吡啶基)-5-三氟甲基吡唑-3-甲酰胺;N-[2-(5-氨基-1,3,4-噻二唑-2-基)-4-氯-6-甲基苯基]-3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺;3-氯-1-(3-氯-2-吡啶基)-N-[2,4-二氯-6-[[(1-氰基-1-甲基乙基)氨基]羰基]苯基]-1H-吡唑-5-甲酰胺;四氯虫酰胺(tetrachlorantraniliprole);N-[4-氯-2-[[(1,1-二甲基乙基)氨基]羰基]-6-甲基苯基]-1-(3-氯-2-吡啶基)-3-氟甲氧基-1H-吡唑-5-甲酰胺;氯氟氰虫酰胺(cyhalodiamide);
O.27:脊索神经器官调节剂—未定义的目标位点:氟啶虫酰胺(flonicamid);
O.28.其他或未知或不确定作用模式的杀虫化合物:双丙环虫酯(afidopyropen)、afoxolaner、印楝素(azadirachtin)、磺胺螨酯(amidoflumet)、苯螨特(benzoximate)、溴虫氟苯双酰胺(broflanilide)、溴螨酯(bromopropylate)、灭螨蜢、冰晶石(cryolite)、dicloromezotiaz、三氯杀螨醇(dicofol)、嘧虫胺(flufenerim)、氟虫碳酸酯(flometoquin)、氟噻虫砜(fluensulfone)、fluhexafon、氟吡菌酰胺、fluralaner、虫酮(metoxadiazone)、增效醚(piperonyl butoxide)、pyflubumide、啶虫丙醚(pyridalyl)、tioxazafen、11-(4-氯-2,6-二甲基苯基)-12-羟基-1,4-二氧杂-9-氮杂二螺[4.2.4.2]-十四碳-11-烯-10-酮、3-(4'-氟-2,4-二甲基联苯-3-基)-4-羟基-8-氧杂-1-氮杂螺[4.5]癸-3-烯-2-酮、1-[2-氟-4-甲基-5-[(2,2,2-三氟乙基)亚磺酰基]苯基]-3-三氟甲基-1H-1,2,4-三唑-5-胺、坚强芽孢杆菌(Bacillus firmus)I-1582;flupyrimin;三氟咪啶酰胺(fluazaindolizine);4-[5-(3,5-二氯苯基)-5-三氟甲基-4H-异唑-3-基]-2-甲基-N-(1-氧代硫杂丁环-3-基)苯甲酰胺;氟唑酰胺(fluxametamide);5-[3-[2,6-二氯-4-(3,3-二氯烯丙氧基)苯氧基]丙氧基]-1H-吡唑;4-氰基-N-[2-氰基-5-[[2,6-二溴-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]苯基]氨基甲酰基]苯基]-2-甲基苯甲酰胺;4-氰基-3-[(4-氰基-2-甲基苯甲酰基)氨基]-N-[2,6-二氯-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]苯基]-2-氟苯甲酰胺;N-[5-[[2-氯-6-氰基-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]苯基]氨基甲酰基]-2-氰基苯基]-4-氰基-2-甲基苯甲酰胺;N-[5-[[2-溴-6-氯-4-[2,2,2-三氟-1-羟基-1-三氟甲基乙基]苯基]氨基甲酰基]-2-氰基苯基]-4-氰基-2-甲基苯甲酰胺;N-[5-[[2-溴-6-氯-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]苯基]氨基甲酰基]-2-氰基苯基]-4-氰基-2-甲基苯甲酰胺;4-氰基-N-[2-氰基-5-[[2,6-二氯-4-[1,2,2,3,3,3-六氟-1-三氟甲基丙基]苯基]氨基甲酰基]-苯基]-2-甲基苯甲酰胺;4-氰基-N-[2-氰基-5-[[2,6-二氯-4-[1,2,2,2-四氟-1-三氟甲基乙基]苯基]氨基甲酰基]苯基]-2-甲基苯甲酰胺;N-[5-[[2-溴-6-氯-4-[1,2,2,2-四氟-1-三氟甲基乙基]苯基]氨基甲酰基]-2-氰基苯基]-4-氰基-2-甲基苯甲酰胺;2-(1,3-二烷-2-基)-6-[2-(3-吡啶基)-5-噻唑基]吡啶;2-[6-[2-(5-氟-3-吡啶基)-5-噻唑基]-2-吡啶基]嘧啶;2-[6-[2-(3-吡啶基)-5-噻唑基]-2-吡啶基]嘧啶;N-甲基磺酰基-6-[2-(3-吡啶基)噻唑-5-基]吡啶-2-甲酰胺;N-甲基磺酰基-6-[2-(3-吡啶基)噻唑-5-基]吡啶-2-甲酰胺;1-[(6-氯-3-吡啶基)甲基]-1,2,3,5,6,7-六氢-5-甲氧基-7-甲基-8-硝基咪唑并[1,2-a]吡啶;1-[(6-氯吡啶-3-基)甲基]-7-甲基-8-硝基-1,2,3,5,6,7-六氢咪唑并[1,2-a]吡啶-5-醇;1-异丙基-N,5-二甲基-N-哒嗪-4-基吡唑-4-甲酰胺;1-(1,2-二甲基丙基)-N-乙基-5-甲基-N-哒嗪-4-基吡唑-4-甲酰胺;N,5-二甲基-N-哒嗪-4-基-1-(2,2,2-三氟-1-甲基乙基)吡唑-4-甲酰胺;1-[1-(1-氰基环丙基)乙基]-N-乙基-5-甲基-N-哒嗪-4-基吡唑-4-甲酰胺;N-乙基-1-(2-氟-1-甲基丙基)-5-甲基-N-哒嗪-4-基吡唑-4-甲酰胺;1-(1,2-二甲基丙基)-N,5-二甲基-N-哒嗪-4-基吡唑-4-甲酰胺;1-[1-(1-氰基环丙基)乙基]-N,5-二甲基-N-哒嗪-4-基吡唑-4-甲酰胺;N-甲基-1-(2-氟-1-甲基丙基]-5-甲基-N-哒嗪-4-基吡唑-4-甲酰胺;1-(4,4-二氟环己基)-N-乙基-5-甲基-N-哒嗪-4-基吡唑-4-甲酰胺;1-(4,4-二氟环己基)-N,5-二甲基-N-哒嗪-4-基吡唑-4-甲酰胺、N-(1-甲基乙基)-2-(3-吡啶基)-2H-吲唑-4-甲酰胺;N-环丙基-2-(3-吡啶基)-2H-吲唑-4-甲酰胺;N-环己基-2-(3-吡啶基)-2H-吲唑-4-甲酰胺;2-(3-吡啶基)-N-(2,2,2-三氟乙基)-2H-吲唑-4-甲酰胺;2-(3-吡啶基)-N-[(四氢-2-呋喃基)甲基]-2H-吲唑-5-甲酰胺;2-[[2-(3-吡啶基)-2H-吲唑-5-基]羰基]肼甲酸甲酯;N-[(2,2-二氟环丙基)甲基]-2-(3-吡啶基)-2H-吲唑-5-甲酰胺;N-(2,2-二氟丙基)-2-(3-吡啶基)-2H-吲唑-5-甲酰胺;2-(3-吡啶基)-N-(2-嘧啶基甲基)-2H-吲唑-5-甲酰胺;N-[(5-甲基-2-吡嗪基)甲基]-2-(3-吡啶基)-2H-吲唑-5-甲酰胺、tyclopyrazoflor;sarolaner、lotilaner、N-[4-氯-3-[[(苯基甲基)氨基]羰基]苯基]-1-甲基-3-(1,1,2,2,2-五氟乙基)-4-三氟甲基-1H-吡唑-5-甲酰胺;2-(3-乙基磺酰基-2-吡啶基)-3-甲基-6-三氟甲基咪唑并[4,5-b]吡啶、2-[3-乙基磺酰基-5-三氟甲基-2-吡啶基]-3-甲基-6-三氟甲基咪唑并[4,5-b]吡啶、异唑虫酰胺(isocycloseram)、N-[4-氯-3-(环丙基氨基甲酰基)苯基]-2-甲基-5-(1,1,2,2,2-五氟乙基)-4-三氟甲基吡唑-3-甲酰胺、N-[4-氯-3-[(1-氰基环丙基)氨基甲酰基]苯基]-2-甲基-5-(1,1,2,2,2-五氟乙基)-4-三氟甲基吡唑-3-甲酰胺;acynonapyr;苯嘧虫烷(benzpyrimoxan);tigolaner;氯-N-(1-氰基环丙基)-5-[1-[2-甲基-5-(1,1,2,2,2-五氟乙基)-4-三氟甲基吡唑-3-基]吡唑-4-基]苯甲酰胺、oxazosulfyl、N-[4-[1-[4-(三氟甲氧基)苯基]-1,2,4-三唑-3-基]苯基]氨基甲酸[(2S,3R,4R,5S,6S)-3,5-二甲氧基-6-甲基-4-丙氧基四氢吡喃-2-基]酯、N-[4-[1-[4-(三氟甲氧基)苯基]-1,2,4-三唑-3-基]苯基]氨基甲酸[(2S,3R,4R,5S,6S)-3,4,5-三甲氧基-6-甲基四氢吡喃-2-基]酯、N-[4-[1-[4-(1,1,2,2,2-五氟乙氧基)苯基]-1,2,4-三唑-3-基]苯基]氨基甲酸[(2S,3R,4R,5S,6S)-3,5-二甲氧基-6-甲基-4-丙氧基四氢吡喃-2-基]酯、N-[4-[1-[4-(1,1,2,2,2-五氟乙氧基)苯基]-1,2,4-三唑-3-基]苯基]氨基甲酸[(2S,3R,4R,5S,6S)-3,4,5-三甲氧基-6-甲基四氢吡喃-2-基]酯、(2Z)-3-(2-异丙基苯基)-2-[(E)-[4-[1-[4-(1,1,2,2,2-五氟乙氧基)苯基]-1,2,4-三唑-3-基]苯基]亚甲基亚肼基]噻唑烷-4-酮;2-(6-氯-3-乙基磺酰基咪唑并[1,2-a]吡啶-2-基)-3-甲基-6-三氟甲基咪唑并[4,5-b]吡啶、2-(6-溴-3-乙基磺酰基咪唑并[1,2-a]吡啶-2-基)-3-甲基-6-三氟甲基咪唑并[4,5-b]吡啶、2-(3-乙基磺酰基-6-碘咪唑并[1,2-a]吡啶-2-基)-3-甲基-6-三氟甲基咪唑并[4,5-b]吡啶、2-[3-乙基磺酰基-6-三氟甲基咪唑并[1,2-a]吡啶-2-基]-3-甲基-6-三氟甲基咪唑并[4,5-b]吡啶、2-(7-氯-3-乙基磺酰基咪唑并[1,2-a]吡啶-2-基)-3-甲基-6-三氟甲基咪唑并[4,5-b]吡啶、2-(3-乙基磺酰基-7-碘咪唑并[1,2-a]吡啶-2-基)-3-甲基-6-三氟甲基咪唑并[4,5-b]吡啶、3-乙基磺酰基-6-碘-2-[3-甲基-6-三氟甲基咪唑并[4,5-b]吡啶-2-基]咪唑并[1,2-a]吡啶-8-甲腈、2-[3-乙基磺酰基-8-氟-6-三氟甲基咪唑并[1,2-a]吡啶-2-基]-3-甲基-6-三氟甲基咪唑并[4,5-b]吡啶、2-[3-乙基磺酰基-7-三氟甲基咪唑并[1,2-a]吡啶-2-基]-3-甲基-6-(三氟甲基亚磺酰基)咪唑并[4,5-b]吡啶、2-[3-乙基磺酰基-7-三氟甲基咪唑并[1,2-a]吡啶-2-基]-3-甲基-6-三氟甲基咪唑并[4,5-c]吡啶、2-(6-溴-3-乙基磺酰基咪唑并[1,2-a]吡啶-2-基)-6-三氟甲基吡唑并[4,3-c]吡啶,
除虫菊提取物、羟哌酯(icaridin)、N,N-二乙基间甲苯甲酰胺(DEET)、对薄荷二醇(PMD)、甲氧苄氟菊酯、氯氟醚菊酯、dimeflluthrin、氯菊酯、氯氰菊酯、溴氰菊酯、七氟甲醚菊酯、d-七氟甲醚菊酯、胺菊酯、咪炔菊酯、饱和和/或不饱和脂肪酸、d-胺菊酯、d-苯醚菊酯、1R-反式苯醚菊酯、四氟菊酯、d-丙烯除虫菊、右旋反式丙烯菊酯75/25、炔酮菊酯、增效醚及其类似物/同系物。
优选的杀虫剂为下列:
ο氯化杀虫剂,如毒杀芬(Camphechlor)、六氯环己烷、γ-六氯环己烷、甲氧滴滴涕、五氯酚、TDE、艾氏剂(Aldrin)、氯丹、十氯酮(Chlordecone)、狄氏剂(Dieldrin)、硫丹、异狄氏剂(Endrin)、七氯(Heptachlor)、灭蚁灵(Mirex)及其混合物;
ο有机磷化合物,如高灭磷、谷硫磷(Azinphos-methyl)、地散磷(Bensulide)、氯氧磷、毒死蜱、甲基毒死蜱、二嗪农、敌敌畏(DDVP)、百治磷、乐果、乙拌磷、丙线磷(Ethoprop)、苯线磷、杀螟松、倍硫磷、噻唑硫磷、马拉硫磷、甲胺磷、杀扑磷、甲基对硫磷(Methyl-parathion)、速灭磷、二溴磷、氧乐果、砜吸磷、一六零五、甲拌磷、伏杀磷、亚胺硫磷、丁嘧硫磷(Phostebupirim)、虫螨磷、丙溴磷、特丁磷、杀虫威、脱叶磷(Tribufos)、敌百虫及其混合物;
ο合成除虫菊酯类,如丙烯除虫菊、氟氯菊酯、溴氰菊酯、氯菊酯、灭虫菊、聚醚菊酯(Sumithrin)、胺菊酯、四溴菊酯、四氟菊酯及其混合物;
ο植物毒素衍生化合物,如鱼藤(鱼藤酮)、除虫菊、印楝(印楝素)、烟碱、咖啡因及其混合物。
灭鼠剂:灭鼠剂是一类意欲杀灭啮齿动物的有害物控制化学品。在下文给出合适灭鼠剂的实例:
ο抗凝剂,例如敌拿鼠(difenacoum)、毒鼠强(brodifacoum)、氟鼠酮(floccumafen)、溴敌隆(bromadiolone)、噻鼠灵(difethialone)、杀鼠灵(warfarin)、杀鼠迷(coumatetralyl)、氯敌鼠(chlorophacinone)、敌鼠酮(diphacinone)、氯杀鼠灵(coumachlor)、克灭鼠(coumachlor)和杀鼠酮(pindone);
ο金属磷化物;
ο磷化物;或
ο高钙血,例如钙化醇(维生素D)、胆钙化醇(维生素D3)和麦角钙化醇(维生素D2)。
杀螨剂、杀贝剂和杀线虫剂:杀螨剂是杀灭螨虫的农药。抗菌素类杀螨剂、氨基甲酸酯类杀螨剂、甲脒类杀螨剂、螨虫生长调节剂、有机氯、氯菊酯和有机磷酸酯类杀螨剂全部属于该类别。杀贝剂是用于控制软体动物,如蛾、蛞蝓和蜗牛的农药。这些物质包括四聚乙醛、灭虫威和硫酸铝。杀线虫剂是一类用于杀灭寄生线虫(蠕虫门)的化学杀虫剂。杀线虫剂由印楝籽饼得到;后者为印楝籽在榨油之后的残留物。印楝在世界上已知有几个名称,但自古以来首次在印度种植。
该农药通常具有至多10g/l,优选至多5g/l,更优选至多1g/l的水溶性。
该农药在20℃下可以为固体或液体。
优选的农药是除草剂、杀虫剂和杀真菌剂。
在一个实施方案中,活性物质是除草剂。
在一个实施方案中,活性物质是杀真菌剂。
在一个实施方案中,活性物质是杀虫剂。
在一个实施方案中,活性成分是精噻吩草胺和异恶草酮的混合物。
在一个实施方案中,活性成分是环庚草醚和氟吡酰草胺的混合物。
尤其优选作为活性物质的农药是醌肟草、氟噻草胺、草萘胺、异恶草胺、精吡氟禾草灵、苯嗪草、拿草特、苯敌草、烯草酮、杀草敏、精噻吩草胺、胺硝草、毒死蜱、乐果、甲体氯氰菊酯、氯氰菊酯、噻虫胺、氟唑虫清、锐劲特、精噻吩草胺、异恶草酮、氟吡酰草胺、吡草胺、S-异丙甲草胺、乙草胺、胺硝草、苯嘧磺草胺、派罗克杀草砜、二氯异草酮、唑菌胺酯、精噻吩草胺、丁苯吗啉、苯嘧磺草胺、三氟草嗪和环庚草醚。
在一个实施方案中,活性物质是选自精噻吩草胺、异恶草酮、氟吡酰草胺、吡草胺、S-异丙甲草胺、乙草胺、胺硝草、苯嘧磺草胺、派罗克杀草砜、二氯异草酮、环庚草醚或其混合物的除草剂。
特别优选作为活性物质的农药是环庚草醚、唑菌胺酯、精噻吩草胺。
在一个实施方案中,活性物质选自除虫菊提取物、羟哌酯、N,N-二乙基间甲苯甲酰胺(DEET)、对薄荷二醇(PMD)、甲氧苄氟菊酯、氯氟醚菊酯、dimeflluthrin、氯菊酯、氯氰菊酯、溴氰菊酯、七氟甲醚菊酯、d-七氟甲醚菊酯、胺菊酯、咪炔菊酯、饱和和/或不饱和脂肪酸、d-胺菊酯、d-苯醚菊酯、1R-反式苯醚菊酯、四氟菊酯、d-丙烯除虫菊、右旋反式丙烯菊酯75/25、炔酮菊酯、增效醚及其类似物/同系物,精油及其组分,或者它们的混合物。
在一个实施方案中,活性物质选自除虫菊提取物、羟哌酯、N,N-二乙基间甲苯甲酰胺(DEET)、甲氧苄氟菊酯、氯氟醚菊酯、dimeflluthrin、氯菊酯、七氟甲醚菊酯、d-七氟甲醚菊酯、胺菊酯、饱和和/或不饱和脂肪酸、d-胺菊酯、d-苯醚菊酯、1R-反式苯醚菊酯、四氟菊酯、d-丙烯除虫菊、右旋反式丙烯菊酯75/25、炔酮菊酯、增效醚及其类似物/同系物,或者它们的混合物。
本发明微胶囊通常含有1-95重量%,优选10-90重量%,更优选30-85重量%所述一种或多种活性物质。
活性物质原则上在21℃下可以是液体或固体,其中固体本身也可以溶于水不溶混性溶剂S中而存在。
在一个实施方案中,用于本发明胶囊中的活性物质在21℃下是液体。
在一个实施方案中,用于本发明胶囊中的活性物质在21℃下是液体并且不溶于溶剂中而含于本发明微胶囊中。
在一个实施方案中,用于本发明胶囊中的活性物质在21℃下是液体并且作为纯物质含于本发明微胶囊中。
在一个实施方案中,活性物质作为在水不溶混性溶剂S中的溶液含于本发明微胶囊中。
有时活性物质也可以用作溶剂,或者溶剂也可以用作活性物质。
水不溶混性溶剂S在水中具有的溶解度在21℃下为1重量%或更低,优选在21℃下为0.1重量%或更低。
溶剂S包括:
中到高沸点的矿物油馏分,例如煤油、柴油;植物或动物来源的油;脂族、环状和芳族烃类,例如甲苯、石蜡、四氢萘、烷基化萘和沸点范围内为130-300℃的C8-C11芳族石油衍生物(芳族烃类);
植物油,如椰子油、棕榈仁油、棕榈油、大豆油、菜籽油、玉米油以及上述油的甲基或乙基酯,烃类如闪点为40-250℃且蒸馏范围为150-450℃的芳香族贫化烃类、线性链烷烃类、异链烷烃类、环链烷烃类;
酮类,例如苯乙酮;
碳酸酯类,例如碳酸二丁酯;
酯类,例如乙酸苄酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸丁酯、乳酸苄酯、丙酸2-苯氧基乙酯;
乳酸酯,例如乳酸2-乙基己基酯;
脂肪酸酯类,
脂肪酸类;
膦酸酯类;
脂肪酸胺类;
吡咯烷酮类,如N-丁基吡咯烷酮、N-辛基吡咯烷酮、N-乙基吡咯烷酮、N-十二烷基吡咯烷酮、羟乙基吡咯烷酮;
脂肪酸酰胺类,例如N,N-二甲基辛酰胺、N,N-二甲基壬酰胺、N,N-二甲基癸酰胺、N,N-二甲基-9-癸烯酰胺、N,N-二甲基月桂酰胺、N,N-二甲基月桂酰胺及其混合物。
本文中“C8二甲基酰胺”和“N,N-二甲基辛酰胺”应理解为是指“C8脂肪酸N,N-二甲基酰胺”(其他链长类似)。
“脂肪酸”在本文中应表示具有饱和或不饱和脂族链的线性或支化羧酸。
在一个实施方案中,溶剂S是油。短语“油“在本发明上下文中包括所有种类的油体或油组分,尤其是植物油如菜籽油、葵花油、大豆油、橄榄油等,改性植物油,例如烷氧基化葵花油或大豆油,合成甘油(三)酯如C6-C22脂肪酸甘油单酯、甘油二酯和甘油三酯的工业混合物,脂肪酸烷基酯,例如植物油的甲酯或乙酯(ME 18 RD-F、ME 18 SD-F、ME 12C-F、ME1270,全部为德国BASF SE的产品),基于所述C6-C22脂肪酸的脂肪酸烷基酯,矿物油及其混合物。在一种形式中,该油优选包含矿物油。
说明合适溶剂S的性质而不将本发明限于这些实例的实例为基于具有6-18个,优选8-10个碳原子的脂肪醇的格尔伯特醇,线性C6-C22脂肪酸与线性或支化C6-C22脂肪醇的酯或者支化C6-C13羧酸与线性或支化C6-C22脂肪醇的酯,如肉豆蔻醇肉豆蔻酸酯、肉豆蔻醇棕榈酸酯、肉豆蔻醇硬脂酸酯、肉豆蔻醇异硬脂酸酯、肉豆蔻醇油酸酯、肉豆蔻醇山萮酸酯、肉豆蔻醇芥酸酯、鲸蜡醇肉豆蔻酸酯、鲸蜡醇棕榈酸酯、鲸蜡醇硬脂酸酯、鲸蜡醇异硬脂酸酯、鲸蜡醇油酸酯、鲸蜡醇山萮酸酯、鲸蜡醇芥酸酯、硬脂醇肉豆蔻酸酯、硬脂醇棕榈酸酯、硬脂醇硬脂酸酯、硬脂醇异硬脂酸酯、硬脂醇油酸酯、硬脂醇山萮酸酯、硬脂醇芥酸酯、异硬脂醇肉豆蔻酸酯、异硬脂醇棕榈酸酯、异硬脂醇硬脂酸酯、异硬脂醇异硬脂酸酯、异硬脂醇油酸酯、异硬脂醇山萮酸酯、异硬脂醇油酸酯、油醇肉豆蔻酸酯、油醇棕榈酸酯、油醇硬脂酸酯、油醇异硬脂酸酯、油醇油酸酯、油醇山萮酸酯、油醇芥酸酯、山萮醇肉豆蔻酸酯、山萮醇棕榈酸酯、山萮醇硬脂酸酯、山萮醇异硬脂酸酯、山萮醇油酸酯、山萮醇山萮酸酯、山萮醇芥酸酯、瓢儿菜醇肉豆蔻酸酯、瓢儿菜醇棕榈酸酯、瓢儿菜醇硬脂酸酯、瓢儿菜醇异硬脂酸酯、瓢儿菜醇油酸酯、瓢儿菜醇山萮酸酯和瓢儿菜醇芥酸酯。还合适的是线性C6-C22脂肪酸与支化醇,尤其是2-乙基己醇的酯,C18-C38烷基羟基羧酸与线性或支化C6-C22脂肪醇的酯,尤其是苹果酸二辛酯,线性和/或支化脂肪酸与多元醇(例如丙二醇、二聚体二醇或三聚体三醇)和/或格尔伯特醇的酯,基于C6-C10脂肪酸的甘油三酯,基于C6-C18脂肪酸的液体甘油单酯/甘油二酯/甘油三酯混合物,C6-C22脂肪醇和/或格尔伯特醇与芳族羧酸,尤其是苯甲酸的酯,C2-C12二羧酸与具有1-22个碳原子的线性或支化醇或具有2-10个碳原子和2-6个羟基的多元醇的酯,植物油,支化伯醇,取代的环己烷类,线性和支化C6-C22脂肪醇碳酸酯,例如碳酸二辛酯(CC),基于具有6-18个,优选8-10个碳原子的脂肪醇的格尔伯特碳酸酯,苯甲酸与线性和/或支化C6-C22醇的酯,每个烷基具有6-22个碳原子的线性或支化、对称或不对称二烷基醚,如二辛基醚,环氧化脂肪酸酯与多元醇的开环产物,硅油(环聚二甲基硅氧烷、聚甲基硅氧烷品级等),脂族烃或环烷烃,如角鲨烷、角鲨烯或二烷基环己烷类,和/或矿物油。在一种形式中,该油优选包含脂族烃或环烷烃和/或矿物油。
在本发明上下文中,优选的溶剂S为基于具有6-18个,优选8-10个碳原子的脂肪醇的格尔伯特醇,线性C6-C22脂肪酸与线性或支化C6-C22脂肪醇的酯或支化C6-C13羧酸与线性或支化C6-C22脂肪醇的酯,如肉豆蔻醇肉豆蔻酸酯、肉豆蔻醇棕榈酸酯、肉豆蔻醇硬脂酸酯、肉豆蔻醇异硬脂酸酯、肉豆蔻醇油酸酯、肉豆蔻醇山萮酸酯、肉豆蔻醇芥酸酯、鲸蜡醇肉豆蔻酸酯、鲸蜡醇棕榈酸酯、鲸蜡醇硬脂酸酯、鲸蜡醇异硬脂酸酯、鲸蜡醇油酸酯、鲸蜡醇山萮酸酯、鲸蜡醇芥酸酯、硬脂醇肉豆蔻酸酯、硬脂醇棕榈酸酯、硬脂醇硬脂酸酯、硬脂醇异硬脂酸酯、硬脂醇油酸酯、硬脂醇山萮酸酯、硬脂醇芥酸酯、异硬脂醇肉豆蔻酸酯、异硬脂醇棕榈酸酯、异硬脂醇硬脂酸酯、异硬脂醇异硬脂酸酯、异硬脂醇油酸酯、异硬脂醇山萮酸酯、异硬脂醇油酸酯、油醇肉豆蔻酸酯、油醇棕榈酸酯、油醇硬脂酸酯、油醇异硬脂酸酯、油醇油酸酯、油醇山萮酸酯、油醇芥酸酯、山萮醇肉豆蔻酸酯、山萮醇棕榈酸酯、山萮醇硬脂酸酯、山萮醇异硬脂酸酯、山萮醇油酸酯、山萮醇山萮酸酯、山萮醇芥酸酯、瓢儿菜醇肉豆蔻酸酯、瓢儿菜醇棕榈酸酯、瓢儿菜醇硬脂酸酯、瓢儿菜醇异硬脂酸酯、瓢儿菜醇油酸酯、瓢儿菜醇山萮酸酯和瓢儿菜醇芥酸酯。
还优选的油是线性C6-C22脂肪酸与支化醇,尤其是2-乙基己醇的酯,C18-C38烷基羟基羧酸与线性或支化C6-C22脂肪醇的酯,线性或支化C6-C22脂肪醇,尤其是苹果酸二辛酯,线性和/或支化脂肪酸与多元醇(如丙二醇、二聚体二醇或三聚体三醇)和/或格尔伯特醇的酯,基于C6-C10脂肪酸的甘油三酯,基于C6-C18脂肪酸的液体甘油单酯/甘油二酯/甘油三酯混合物,C6-C22脂肪醇和/或格尔伯特醇与芳族羧酸,尤其是苯甲酸的酯,C2-C12二羧酸与具有1-22个碳原子的线性或支化醇或具有2-10个碳原子和2-6个羟基的多元醇的酯,植物油,支化伯醇,取代的环己烷类,线性和支化C6-C22脂肪醇碳酸酯,如碳酸二辛酯(CetiolTM CC),基于具有6-18个,优选8-10个碳原子的脂肪醇的格尔伯特碳酸酯,苯甲酸与线性和/或支化C6-C22醇的酯(例如FinsolvTM TN),每个烷基具有6-22个碳原子的线性或支化、对称或不对称二烷基醚,如二辛基醚(CetiolTM OE),环氧化脂肪酸酯与多元醇的开环产物,硅油(环聚二甲基硅氧烷、聚甲基硅氧烷品级等)和/或脂族烃或环烷烃,如角鲨烷、角鲨烯或二烷基环己烷类。
此外,在本发明上下文中可以将液体线性和/或支化和/或饱和或不饱和烃类或其任何所需混合物用作油。这些例如可以是具有4-22个,优选6-18个碳原子的链烷烃或其任何所需混合物。还合适的是具有4-22个碳原子的不饱和烃或具有相同碳原子数的不饱和烃以及这些烃类的任何所需混合物。环状烃类和芳烃类,例如甲苯及其混合物也可以是本发明上下文中的油。在另一优选形式中,该油包含芳烃类。还合适的是硅油。所有所述核材料的任何所需混合物。
化妆品中的常规油组分例如是石蜡油、甘油硬脂酸酯、肉豆蔻酸异丙酯、己二酸二异丙酯、己二酸二丁酯、鲸蜡硬脂醇2-乙基己酸酯、氢化聚异丁烯、凡士林、辛酸/癸酸甘油三酯、微晶蜡、羊毛脂核硬脂酸。然而,该列举是示例性的且并非穷举。
特别优选那些在用于构造本发明胶囊的壳的该水不溶性或微水溶性溶胶-凝胶前体中可溶或可悬浮的微水溶性或水不溶性有机活性物质。
尤其用于作为活性物质的农药的优选溶剂S是中到高沸点的矿物油馏分,例如煤油、柴油;植物或动物来源的油;脂族、环状和芳族烃类,例如甲苯、石蜡、四氢萘、烷基化萘和沸点范围内为130-300℃的C8-C11芳族石油衍生物(芳族烃类);植物油,如椰子油、棕榈仁油、棕榈油、大豆油、菜籽油、玉米油以及上述油的甲基或乙基酯,烃类如闪点为40-250℃且蒸馏范围为150-450℃的芳香族贫化烃类、线性链烷烃类、异链烷烃类、环链烷烃类;苯乙酮;碳酸二丁酯;乙酸苄酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸丁酯、乳酸苄酯、丙酸2-苯氧基乙酯;乳酸2-乙基己基酯;脂肪酸酯类;脂肪酸类;C8-C12脂肪酸二甲基酰胺类;及其混合物。
更优选的有机溶剂S是苯乙酮;碳酸二丁酯;乙酸苄酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸丁酯、乳酸苄酯、丙酸2-苯氧基乙酯;乳酸2-乙基己基酯;脂肪酸酯类;脂肪酸类;C8-C12脂肪酸二甲基酰胺类及其混合物。
C8-C12脂肪酸二甲基酰胺类包括且优选的C8-C12脂肪酸二甲基酰胺类为:C8二甲基酰胺(N,N-二甲基辛酰胺),C8/C10二甲基酰胺(N,N-二甲基辛酰胺和N,N-二甲基癸酰胺的混合物),C9二甲基酰胺(N,N-二甲基壬酰胺或N,N-二甲基异壬酰胺),C10二甲基酰胺(N-二甲基癸酰胺或N,N-二甲基-9-癸烯酰胺),C12二甲基酰胺(N,N-二甲基月桂酰胺),植物油如椰子油、棕榈仁油、棕榈油、大豆油、菜籽油、玉米油以及上述油的甲基或乙基酯。
尤其优选的有机溶剂S是植物油如椰子油、棕榈仁油、棕榈油、大豆油、菜籽油、玉米油以及上述油的甲基或乙基酯,乙酸苄酯,苯甲酸甲酯,C8-C12脂肪酸二甲基酰胺,芳族烃或其混合物。
特别优选的有机溶剂S是芳族烃,己二酸酯(例如己二酸二丁酯),植物油如椰子油、棕榈仁油、棕榈油、大豆油、菜籽油、玉米油以及上述油的甲基或乙基酯或其混合物。
在一个实施方案中,本发明微粒的核含有与选自脂族和/或芳族烃或植物油如椰子油、棕榈仁油、棕榈油、大豆油、菜籽油、玉米油以及上述油的甲基或乙基酯的溶剂S共混的农药。
本发明微胶囊含有包围该核的壳。
所述壳包含:
i)至少一种总体带负电的蛋白质PR,
ii)至少一种总体带正电的多糖PS,和
iii)任选地,能够经由非共价键的形成交联组分蛋白质PR和多糖PS的无机盐IS。
本发明微胶囊是仿生的,这意味着它们包含含有天然蛋白质和多糖或者该类天然蛋白质的衍生物、多糖和多官能矿物或无机盐的壳。
蛋白质是氨基酸的大分子,其含有许多潜在阴离子性官能基团(如羧酸基团)和潜在阳离子性基团(如氨基)。取决于条件,尤其是取决于pH,蛋白质可以总体带负电或者总体带正电。大多数蛋白质通常在充分碱性条件下(意味着在更高pH的含水介质中)总体带负电并且在充分酸性条件下(意味着在更低pH的含水介质中)总体带正电。在等电点—对各蛋白质而言特定的pH,该蛋白质总体呈中性。
当提及在微胶囊中总体带负电的蛋白质PR时,这应理解为是指蛋白质PR在本发明微胶囊的壳中或者在它们存在于壳中时或在形成该壳的过程中的条件下带负电。
在一个实施方案中,蛋白质PR是天然蛋白质或者衍生于天然蛋白质。
优选蛋白质PR是在pH高于4,优选高于5下总体带负电的蛋白质。
蛋白质PR需要至少部分呈水溶性。为了能够得到本发明微胶囊,蛋白质PR需要在制备微胶囊的反应条件下至少部分呈水溶性。蛋白质PR在21℃和pH为8下至少部分呈水溶性。
当在2.5重量%所述蛋白质在水中的混合物中在不存在其他组分下测量时,蛋白质PR在21℃和pH为8下通常具有至少20重量%的水可溶性部分。该可溶性部分可以通过制备含有水和2.5重量%蛋白质的混合物,分离(例如通过过滤),干燥并测定不溶性部分的重量而确定。
在一个优选实施方案中,蛋白质PR为素蛋白,意味着它不是源自任何动物或者使用任何动物得到。
优选蛋白质PR为植物基蛋白质。
在一个优选实施方案中,蛋白质PR选自豌豆蛋白、米蛋白、小麦蛋白、向日葵蛋白和大豆蛋白。
在一个优选实施方案中,蛋白质PR选自大豆蛋白、小麦蛋白、米蛋白和豌豆蛋白。
在一个优选实施方案中,蛋白质PR选自小麦蛋白、米蛋白和豌豆蛋白。
当提及蛋白质PR时,这应包括天然蛋白质以及该类蛋白质的水解产物。
在一个实施方案中,蛋白质PR以其天然形式使用。
在一个实施方案中,蛋白质PR以作为水解产物或天然蛋白质使用。
本文所用蛋白质的水解产物通过酶催皂化蛋白质而得到。因此,通过选择性皂化蛋白质中的某些酰胺键可以得到更小的蛋白质片段。
蛋白质PR的该类水解产物通常长具有500-5000g/mol的平均分子量。
本文所给蛋白质的平均分子量的所有值通过尺寸排阻色谱法与多角度光散射(MALS)联用根据Some,D.,Amartely,H.,Tsadok,A.,Lebendiker,M.Characterization ofProteins by Size-Exclusion Chromatography Coupled to Multi-Angle LightScattering(SEC-MALS).J.Vis.Exp.(148),e59615,doi:10.3791/59615(2019)中所公开的方法测定。
本发明微胶囊的壳进一步包含至少一种总体带正电的多糖PS。
多糖通常为含有通过糖苷键结合的单糖单元的大分子。多糖PS含有多个潜在阳离子性官能基团(如氨基)。取决于条件,尤其是取决于pH,多糖PS可以总体带正电。在充分酸性条件下,例如在pH小于7的含水介质中多糖PS通常总体带正电。多糖PS通常用于在pH为3-6,优选4-5下制备本发明微胶囊。
当提及在微胶囊中总体带正电的多糖PS时,这应理解为是指多糖PS在本发明微胶囊的壳中或者在它们存在于壳中时或在形成该壳的过程中的条件下带正电。
优选多糖PS含有氨基。
优选多糖PS选自壳聚糖和几丁质。壳聚糖含有氨基酸并且在本文中被认为是总体带正电的多糖。
本文所用术语几丁质应包括天然几丁质以及已经进行降解过程,例如通过NaOCl而得到具有更小分子量的几丁质的天然几丁质。类似地,术语壳聚糖应包括由天然几丁质得到的壳聚糖以及由已经进行该类降解过程,例如通过NaOCl而得到更小分子量的几丁质或壳聚糖得到的低分子量壳聚糖(“降解壳聚糖”)。该类得到具有更低分子量的壳聚糖的过程例如公开于Zheng等,“Low mass chitosan”,Bioresources 10(2),2015,第2338-2349页中。降解壳聚糖的其他过程对熟练技术人员而言是已知的,它们中的许多依赖于氧化还原过程。
本文所给几丁质和壳聚糖的平均分子量的所有值通过尺寸排阻色谱法根据Zheng等“Low mass chitosan”,Bioresources 10(2),2015,第2338-2349页所给方法测定。
在一个实施方案中,多糖PS选自几丁质。
在一个实施方案中,多糖PS选自壳聚糖。
壳聚糖由几丁质通过衍生而得到。壳聚糖通常通过几丁质的脱乙酰而得到。一种制备壳聚糖的常见方法是在含水介质中使用氢氧化钠的几丁质脱乙酰。在一个实施方案中,所述脱乙酰通过使用几丁质脱乙酰酶的酶催化进行。
优选脱乙酰程度为至少50%,优选70%,优选至少75%,更优选至少80%,甚至更优选至少85%或90%。乙酰化程度描述的是已经脱乙酰的乙酰基摩尔百分数(通过NMR测定,本文所给任何值根据Journal of Pharmaceutical and Biomedical Analysis,32(2003)1149-1158中所述的NMR方法测定)。
合适的壳聚糖通常具有1-2,000kDa的平均分子量MW。
在一个实施方案中,合适的壳聚糖具有10-1,000kDa的平均分子量MW。
在一个实施方案中,合适的壳聚糖具有50-800kDa的平均分子量MW。
在一个实施方案中,合适的壳聚糖具有3000-20,000Da的平均分子量MW。在一个实施方案中,合适的壳聚糖具有100-200kDa的平均分子量MW。在一个实施方案中,合适的壳聚糖具有350-1100kDa的平均分子量MW。
在一个实施方案中,合适的壳聚糖作为20重量%乙酸溶液在20℃下具有200mPas或更小的粘度(Brookfield)。
在一个实施方案中,合适的壳聚糖作为20重量%乙酸溶液在20℃下具有100mPas或更大的粘度(Brookfield)。
在一个实施方案中,多糖PS为由真菌、节肢动物(如昆虫或甲壳纲动物)、软体动物、头足类喙或鱼鳞得到的几丁质或壳聚糖。
在一个实施方案中,多糖PS为由真菌(例如蘑菇)或甲壳纲动物(意指甲壳纲动物的外骨骼)得到的几丁质或壳聚糖。
在一个实施方案中,多糖PS尤其为来自真菌的几丁质。
在一个实施方案中,多糖PS尤其为来自甲壳纲动物,例如虾的几丁质。
在一个实施方案中,多糖PS尤其为来自真菌的壳聚糖。
在一个实施方案中,多糖PS尤其为来自甲壳纲动物的壳聚糖。
本发明微胶囊通常以使得该胶囊中蛋白质PR与多糖PS的质量比为1:10-10:1,优选3:1-1:3的量含有多糖PS和蛋白质PR。
在一个实施方案中,本发明微胶囊含有能够经由非共价键的形成交联组分蛋白质PR和多糖PS的无机盐IS。
在一个实施方案中,本发明微胶囊含有能够经由非共价键的形成与至少一种组分(蛋白质PR和多糖PS)相互作用的无机盐IS。
在一个实施方案中,无机盐IS是水溶性的,这是指它在20℃下在水中具有的溶解度大于10g/l。
在一个实施方案中,无机盐IS每分子含有至少两个带电结构部分。
在一个实施方案中,无机盐IS每分子含有至少至少两个带电结构部分,尤其是磷酸根基团。
在一个实施方案中,无机盐IS为聚磷酸盐。
在一个实施方案中,无机盐IS为选自碱金属或铵聚磷酸盐的聚磷酸盐。
在一个实施方案中,无机盐IS为六聚偏磷酸钠。
在一个实施方案中,本发明微胶囊含有非离子表面活性剂。
非离子表面活性剂通常存在于该胶囊壳和水壳的界面处。还可能的是一定量的表面活性剂存在于该胶囊的核和水相中。
合适的非离子表面活性剂包括烷氧基化物、N-取代的脂肪酸酰胺、氧化胺、酯、糖基表面活性剂、聚合物表面活性剂及其混合物。烷氧基化物的实例是诸如已经1-50当量烷氧基化的醇、烷基酚、胺、酰胺、芳基酚、脂肪酸或脂肪酸酯的化合物。可以将氧化乙烯和/或氧化丙烯用于烷氧基化,优选氧化乙烯。N-取代的脂肪酸酰胺的实例是脂肪酸葡糖酰胺或脂肪酸链烷醇酰胺。酯的实例是脂肪酸酯、甘油酯或甘油单酯。糖基表面活性剂的实例是脱水山梨糖醇、乙氧基化脱水山梨糖醇、蔗糖和葡萄糖酯或烷基聚葡糖苷。聚合物表面活性剂的实例是乙烯基吡咯烷酮、乙烯醇或乙酸乙烯酯的均聚物或共聚物。
非离子表面活性剂的实例包括式(II)的中性表面活性化合物:
R'-(O-B)n-OH (II)
其中
R'为具有8-40个,更优选12-30个碳原子和任选一个氧原子的烃基,
B为C2-C4链烷-1,2-二基,如1,2-亚乙基、1,2-亚丙基或1,2-亚丁基或其组合,更优选1,2-亚乙基或其与1,2-亚丙基的组合,和
n为3-100,优选4-50,更优选5-40。
优选的非离子表面活性剂包括氧化乙烯(EO)和氧化丙烯(PO)的嵌段共聚物。该类嵌段共聚物例如可以具有结构R-(EO)x-(PO)y-(EO)z,其中R为H或C4-C30烷基残基且x、y、z独立地为2-100的数。
合适烃基R'的实例包括对R提及的基团。在本发明的优选实施方案中,基团R'为被一个C4-C18烷基取代的苯基。
非离子表面活性剂的其他优选实例是山梨酸酯分子的乙氧基化物。优选聚山梨酸酯的乙氧基化物,其带有与脂肪酸,如C6-C30,尤其是C12-C18脂肪酸的末端酯基团。
若存在的话,含有本发明微胶囊的配制剂基于该配制剂通常含有0.01-5重量%,优选0.1-1重量%或0.1-0.5重量%的非离子表面活性剂。
若存在的话,本发明微胶囊基于该微胶囊通常含有0.01-5重量%,优选0.05-0.5重量%的非离子表面活性剂。
本发明微胶囊的形状是任意的并且例如可以为不规则的或球形的,优选球形的。
本发明微胶囊通常具有0.1-20μm,优选0.5-10μm的平均直径d50。本文所给所有粒度通过使用Malvern Mastersizer 2000的统计激光散射根据欧洲标准ISO 13320EN测定。
本发明微胶囊通常不使用任何形成共价键的交联剂得到。本发明微胶囊尤其不含醛如脂族醛如戊二醛作为共价交联剂的加成产物。因此,本发明微胶囊通常在蛋白质PR和多糖PS,尤其是壳聚糖之间不包含任何共价键。本发明微胶囊通常在蛋白质PR和多糖PS,尤其是壳聚糖的不同结构部分之间也不含任何共价键,后者在形成微胶囊之后通过交联得到,例如通过与醛如脂族醛如戊二醛的化学反应得到。
在一个实施方案中,本发明涉及具有壳和核的微胶囊,其中所述核含有非水液体,所述非水液体为一种或多种液体(在21℃下)活性物质或者一种或多种溶于溶剂S中的活性物质,其中溶剂S与水不溶混,并且其中所述壳含有:
i)至少一种总体带负电的蛋白质PR,其中蛋白质PR是植物蛋白,
ii)至少一种壳聚糖,和
任选地,能够经由非共价键的形成交联组分蛋白质PR和多糖PS的无机盐IS。
在一个实施方案中,本发明涉及具有壳和核的微胶囊,其中所述核含有非水液体,所述非水液体为一种或多种液体(在21℃下)活性物质或者一种或多种溶于溶剂S中的活性物质,其中溶剂S与水不溶混,并且其中所述壳含有:
i)至少一种选自豌豆蛋白、米蛋白、小麦蛋白、向日葵蛋白和大豆蛋白的蛋白质,
ii)至少一种壳聚糖,和
任选地,能够经由非共价键的形成交联组分蛋白质PR和多糖PS的无机盐IS。
本发明的另一方面涉及制备微胶囊的方法,包括下列步骤:
A)提供至少一种蛋白质PR的水溶液,其中所述蛋白质PR在所述水溶液中总体带负电并且其中所述蛋白质PR至少部分溶于该水溶液中,
B)提供至少一种多糖PS的单独水溶液,其中所述多糖PS总体带正电并且其中所述多糖PS至少部分溶于该水溶液中,
C)在步骤A)下提供的水溶液中乳化液体活性物质或活性物质在溶剂S中的溶液,其中溶剂S与水不溶混,任选通过搅拌和/或表面活性剂支持,
D)将在步骤B)中得到的水溶液加入在步骤C)中得到的乳液中,
E)任选地,将至少一种无机盐加入在步骤D)中得到的混合物中,所述无机盐IS能够经由非共价键的形成交联蛋白质PR和多糖PS。
在一个实施方案中,在进行步骤D)之前将水溶液A)的pH调节至4或更高,优选5或更高,更优选5-9的值。
在一个实施方案中,在进行步骤D)之前将水溶液B)的pH调节至7或更低,优选6或更低,更优选4-5的值。
在一个实施方案中,步骤C)中所用表面活性剂为非离子表面活性剂。
在一个实施方案中,进行步骤C)以使得在步骤C)中得到水包油乳液。
当本文提及乳化通过“搅拌”支持时,这应理解为包括所有支持乳化的常规机械方式,如搅拌、施加超声、振摇等等。
在一个实施方案中,在步骤E)中加入所述无机盐以使得得到的所述混合物基于整个混合物包含0.001-5重量%,更优选0.002-1重量%,尤其优选0.005-0.1重量%的所述无机盐。
不限制本发明范围,据信胶囊壳在步骤E)中的非共价交联在蛋白质PR和多糖PS形成的离子性配合物上发生。
本发明的惊人结果是本发明制备微胶囊的方法—包括包封步骤和使用无机盐,尤其是磷酸盐交联—可以在室温下或者无需冷却反应混合物下进行。
本发明的另一方面是可以通过上面所述的本发明方法和所述实施方案得到的微胶囊。
本发明的另一方面是由上面所述的本发明方法和所述实施方案得到的微粒。
本发明的另一方面是包含本发明微胶囊或根据本发明方法制备的微胶囊的配制剂。
可以将本发明微胶囊或根据本发明方法制备的微胶囊转化成农业化学组合物的常规类型:悬浮液、粉剂、粉末、糊、颗粒、模压制品或其混合物。
在一个实施方案中,本发明含微胶囊的配制剂为液体配制剂,其中微胶囊作为分散颗粒存在于溶剂(即悬浮液),优选含水介质中。
该含水悬浮液可以通过本文所述制备微粒组合物的方法得到。它还可以通过将本文所述的固体微粒组合物再分散于含水介质中而得到。
术语“含水介质“表示该组合物的液相并且包含含水溶剂以及任选溶于其中的化合物,例如上述表面活性剂和若存在的话,一种或多种常规配制剂添加剂,如增稠剂或生物杀伤剂。该含水悬浮液的含水溶剂是水或其与水溶混性有机溶剂的混合物,该水溶混性有机溶剂如C1-C4链烷醇,如甲醇、乙醇、正丙醇、异丙醇、正丁醇、2-丁醇、异丁醇或叔丁醇,C2-C5链烷二醇和C3-C8链烷三醇,优选乙二醇、1,2-丙二醇、1,3-丙二醇、甘油和1,4-丁二醇。该含水溶剂中水的量基于该含水溶剂通常为至少50重量%,尤其是至少80重量%或至少90重量%。该含水溶剂可以主要由水构成,即水占该悬浮液中存在的溶剂总量的至少95重量%。该含水溶剂还可以是上述水溶混性有机溶剂和水的混合物。在后一情况下,水与水溶混性有机溶剂在该含水溶剂中的重量比优选在99:1-1:1,更优选50:1-3:1,最优选20:1-4:1范围内。以不同方式表达的话,有机溶剂的量基于该含水溶剂的总重量可以为1-50重量%,更优选2-25重量%,最优选5-20重量%。
本发明配制剂可以在微胶囊外包含一种或多种其他活性成分。该类其他活性成分例如可以溶于溶剂介质,优选水相中,或者可以作为分散于溶剂介质,优选水相中的固体颗粒存在。
在一个实施方案中,本发明配制剂基于该配制剂包含1-50重量%,优选5-45重量%,更优选10-40重量%所述一种或多种活性物质。
若存在的话,表面活性剂在该含水悬浮液中的浓度基于微粒的含水悬浮液的总重量通常在0.01-10重量%,尤其是0.05-5重量%范围内。
本发明的含水组合物还可以包含常规配制助剂。助剂的实例包括通常用于含水配制剂活性成分的如粘度改性添加剂(增稠剂)、消泡剂、防腐剂、缓冲剂、无机分散剂、固体载体或填料、表面活性剂、分散剂、乳化剂、润湿剂、辅助剂、增溶剂、渗透促进剂、保护性胶体、粘附剂、保湿剂、驱除剂、引诱剂、进食刺激剂、相容剂、杀菌剂、防冻剂、消泡剂、着色剂、增粘剂和粘合剂等。
助剂的量通常不超过该配制剂总重量的10重量%,尤其是5重量%。
该类助剂可以在如本文所述的微胶囊形成过程中或者在形成本文所述的微胶囊之后掺入该含水悬浮液中。添加剂的量通常不超过该配制剂总重量的10重量%,尤其是5重量%。
适合防止微粒凝集的无机分散剂—也称为抗结块剂是二氧化硅(例如来自Degussa的22),氧化铝,碳酸钙等。在本发明上下文中,二氧化硅是优选的无机分散剂。无机分散剂在最终悬浮液中的浓度基于最终悬浮液的总重量通常不超过2重量%,并且若存在的话,基于最终配制剂的总重量优选在0.01-2重量%,特别是0.02-1.5重量%,尤其是0.1-1重量%范围内。
合适的增稠剂是影响悬浮浓缩物的流动行为并且可能有助于稳定微粒的含水悬浮液以防结块的化合物。就此而言例如可以提及基于多糖的市售增稠剂,如甲基纤维素、羧甲基纤维素、羟丙基纤维素(品级),黄原胶(例如作为品级由Kelco市购或者作为品级由Rhodia市购),合成聚合物,如丙烯酸聚合物(品级),聚乙烯醇(例如来自Kuraray的和品级)或聚乙烯基吡咯烷酮,硅酸或页硅酸盐,如可以疏水化的蒙脱石和膨润土(作为品级和品级由BASF SE市购;或者作为品级和Van品级由R.T.Vanderbilt市购)。在本发明上下文中,黄原胶是优选的增稠剂。增稠剂在该含水悬浮液中的浓度基于该含水悬浮液的总重量通常不超过2重量%,优选分别基于该含水悬浮液或最终配制剂的总重量在0.01-2重量%,特别是0.02-1.5重量%,尤其是0.1-1重量%范围内。
适合本发明组合物的消泡剂例如为聚硅氧烷乳液(例如来自Wacker的SiliconeSRE-PFL或来自Bluestar Silicones的),聚硅氧烷和改性聚硅氧烷,包括聚硅氧烷嵌段聚合物,如BASF SE的SI和ST产品,长链醇,脂肪酸,有机氟化合物及其混合物。
适合防止本发明组合物的微生物腐坏的防腐剂包括甲醛,对羟基苯甲酸的烷基酯,苯甲酸钠,2-溴-2-硝基-1,3-丙二醇,邻苯基苯酚,噻唑啉酮类,如苯并异噻唑啉酮、5-氯-2-甲基-4-异噻唑啉酮,五氯苯酚,2,4-二氯苄醇及其混合物。基于异噻唑啉酮类的市售防腐剂例如以商标(Arch Chemical),MBS(Thor Chemie)和MK(Rohm&Haas)销售。
合适的话,本发明配制剂,尤其是含水悬浮液可以包含调节pH的缓冲剂。缓冲剂的实例是弱无机或有机酸如磷酸、硼酸、乙酸、丙酸、柠檬酸、富马酸、酒石酸、草酸和琥珀酸的碱金属盐。
此外,本发明组合物,尤其是含水悬浮液可以用常规粘合剂,例如聚合物水分散体,水溶性树脂,例如水溶性醇酸树脂,或蜡配制。
本发明组合物还可以含有一种或多种辅助剂。合适的辅助剂对熟练人员而言是已知的并且包括表面活性剂、作物油浓缩物、粘展剂、润湿剂和渗透剂。在其他特殊组的实施方案中,该微粒组合物呈固体组合物形式。该固体组合物含有本发明微粒,任选一种或多种表面活性剂以及任选惰性固体载体材料。固体组合物例如可以是可再分散粉末、水分散性颗粒、可湿性粉末等。
固体载体例如包括矿土,如硅石、硅胶、硅酸盐、滑石、高岭土、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,例如硫酸铵、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,纤维素粉末或其他固体载体。
合适的表面活性剂是表面活性化合物,如阴离子、阳离子、非离子和两性表面活性剂,嵌段聚合物,聚电解质及其混合物。该类表面活性剂可以用作乳化剂、分散剂、增溶剂、润湿剂、渗透促进剂、保护性胶体或辅助剂。表面活性剂的实例列于McCutcheon's,第1卷:Emulsifiers&Detergents,McCutcheon's Directories,Glen Rock,USA,2008(International Ed.或North American Ed.)中。
合适的阴离子表面活性剂是磺酸、硫酸、磷酸、羧酸的碱金属、碱土金属或铵盐及其混合物。磺酸盐的实例是烷基芳基磺酸盐、二苯基磺酸盐、α-烯烃磺酸盐、木素磺酸盐、脂肪酸和油的磺酸盐、乙氧基化烷基酚的磺酸盐、烷氧基化芳基酚的磺酸盐、缩合萘的磺酸盐、十二烷基-和十三烷基苯的磺酸盐、萘和烷基萘的磺酸盐、磺基琥珀酸盐或磺基琥珀酰胺酸盐。硫酸盐的实例是脂肪酸和油的硫酸盐、乙氧基化烷基酚的硫酸盐、醇的硫酸盐、乙氧基化醇的硫酸盐或脂肪酸酯的硫酸盐。磷酸盐的实例是磷酸盐酯。羧酸盐的实例是烷基羧酸盐以及羧化醇或烷基酚乙氧基化物。
合适的非离子表面活性剂是烷氧基化物、N-取代的脂肪酸酰胺、氧化胺、酯、糖基表面活性剂、聚合物表面活性剂及其混合物。烷氧基化物的实例是诸如已经1-50当量烷氧基化的醇、烷基酚、胺、酰胺、芳基酚、脂肪酸或脂肪酸酯的化合物。可以将氧化乙烯和/或氧化丙烯,优选氧化乙烯用于烷氧基化。N-取代的脂肪酸酰胺的实例是脂肪酸葡糖酰胺或脂肪酸链烷醇酰胺。酯的实例是脂肪酸酯、甘油酯或甘油单酯。糖基表面活性剂的实例是脱水山梨糖醇、乙氧基化脱水山梨糖醇、蔗糖和葡萄糖酯或烷基聚葡糖苷。聚合物表面活性剂的实例是乙烯基吡咯烷酮、乙烯醇或乙酸乙烯酯的均聚物或共聚物。
合适的阳离子表面活性剂是季型表面活性剂,例如具有1或2个疏水性基团的季铵化合物,或长链伯胺的盐。合适的两性表面活性剂是烷基甜菜碱和咪唑啉类。合适的嵌段聚合物是包含聚氧乙烯和聚氧丙烯的嵌段的A-B或A-B-A类型嵌段聚合物,或包含链烷醇、聚氧乙烯和聚氧丙烯的A-B-C类型嵌段聚合物。合适的聚电解质是聚酸或聚碱。聚酸的实例是聚丙烯酸的碱金属盐或聚酸梳状聚合物。聚碱的实例是聚乙烯基胺或聚乙烯胺。
合适的辅助剂是本身具有可忽略的农药活性或者本身甚至没有农药活性且改善化合物I对目标物的生物学性能的化合物。实例是表面活性剂,矿物油或植物油以及其他助剂。其他实例由Knowles,Adjuvants and additives,Agrow Reports DS256,T&F InformaUK,2006,第5章列出。
合适的增稠剂是多糖(例如黄原胶、羧甲基纤维素)、无机粘土(有机改性或未改性的)、聚羧酸盐和硅酸盐。
合适的杀菌剂是拌棉醇和异噻唑啉酮衍生物如烷基异噻唑啉酮类和苯并异噻唑啉酮类。
合适的防冻剂是乙二醇、丙二醇、尿素和甘油。
合适的消泡剂是聚硅氧烷、长链醇和脂肪酸盐。
合适的着色剂(例如着红色、蓝色或绿色)是低水溶性颜料和水溶性染料。实例是无机着色剂(例如氧化铁、氧化钛、六氰合铁酸铁)和有机着色剂(例如茜素着色剂、偶氮着色剂和酞菁着色剂)。
合适的增粘剂或粘合剂是聚乙烯基吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇、聚丙烯酸酯、生物或合成蜡和纤维素醚。
本发明固体组合物还可以包含通常用于活性物质的固体配制剂中的常规配制助剂,如消泡剂、防腐剂、缓冲剂、无机分散剂等。该类助剂可以在固体配制剂的制备方法的任何常规阶段掺入其中。添加剂的量通常不超过该固体组合物总重量的10重量%,尤其是5重量%。
本发明的另一方面是本发明微粒或配制剂或者根据本发明方法制备的微粒在农业化学应用(例如作物保护、农业非作物应用、种子处理),药物应用,个人护理应用(例如化妆品应用),纺织品应用,人类或动物营养应用,化学工艺应用,粘合剂和密封剂,油漆和涂料,建筑和结构材料,自修复材料,烟草工业,家庭应用中的用途。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于作物保护中。
本发明微胶囊和含有农药作为活性物质的配制剂在防治各种栽培植物和植物繁殖材料如种子,以及这些植物的作物材料上的多种植物病原性真菌、不希望的植物生长、昆虫或线虫中特别重要,这些栽培植物如禾谷类,如小麦、黑麦、大麦、小黑麦、燕麦或稻;甜菜,例如糖用甜菜或饲用甜菜;水果如梨果、核果或浆果,例如苹果、梨、李、桃、杏仁、樱桃、草莓、山莓、黑莓或醋栗;豆科植物,如兵豆、豌豆、苜蓿或大豆;油料植物,如油菜、芥菜、橄榄、向日葵、椰子、可可豆、蓖麻油植物、油棕、花生或大豆;葫芦,如笋瓜、黄瓜或甜瓜;纤维植物,如棉花、亚麻、大麻或黄麻;柑桔类水果,如橙、柠檬、葡萄柚或桔;蔬菜,如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、西红柿、土豆、葫芦或辣椒;月桂类植物,如鳄梨、肉桂或樟脑;能源和原料植物,如玉米、大豆、油菜、甘蔗或油棕;玉米;烟草;坚果;咖啡;茶叶;香蕉;葡萄藤(鲜食葡萄和榨汁用葡萄);啤酒花;草皮;甜叶菊(也称为甜菊(Stevia));天然橡胶植物或观赏植物和森林植物,如花、灌木、阔叶树或常绿树(例如针叶树)。
优选的作物是落花生(Arachis hypogaea)、甜菜(Beta vulgarisspec.altissima)、欧洲油菜(Brassica napus var.napus)、羽衣甘蓝(Brassicaoleracea)、柠檬(Citrus limon)、甜橙(Citrus sinensis)、小果咖啡(Coffea arabica)(中果咖啡(Coffea canephora)、大果咖啡(Coffea liberica))、狗牙根(Cynodondactylon)、大豆(Glycine max)、陆地棉(Gossypium hirsutum)(树棉(Gossypiumarboreum)、草棉(Gossypium herbaceum)、Gossypium vitifolium)、向日葵(Helianthusannuus)、大麦(Hordeum vulgare)、核桃(Juglans regia)、兵豆(Lens culinaris)、亚麻(Linum usitatissimum)、番茄(Lycopersicon lycopersicum)、苹果属(Malus spec.)、紫苜蓿(Medicago sativa)、烟草(Nicotiana tabacum)(黄花烟草(N.rustica))、油橄榄(Olea europaea)、稻(Oryza sativa)、金甲豆(Phaseolus lunatus)、菜豆(Phaseolusvulgaris)、开心果(Pistacia vera)、荷兰豆(Pisum sativum)、扁桃(Prunus dulcis)、甘蔗(Saccharum officinarum)、黑麦(Secale cereale)、土豆(Solanum tuberosum)、两色蜀黍(Sorghum bicolor)(高粱(S.vulgare))、小黑麦(Triticale)、普通小麦(Triticumaestivum)、硬粒小麦(Triticum durum)、蚕豆(Vicia faba)、葡萄(Vitis vinifera)和玉蜀黍(Zea mays)。
尤其优选的作物是禾谷类作物、玉米、大豆、稻、油籽油菜、棉花、土豆、花生或多年生作物。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于非作物应用如家和花园,草坪和便利设施中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于种子处理中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于药物应用中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于公共卫生应用(疾病防控、病媒控制)中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于个人护理应用中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于化妆品应用中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于纺织品应用中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于人类或动物营养应用中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于化学工艺应用中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于粘合剂和密封剂中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于油漆和涂料中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于建筑和结构材料中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于自修复材料中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于烟草工业中。
在一个实施方案中,将本发明的微粒或配制剂或根据本发明方法制备的微粒用于家庭应用中。
本发明的另一方面是控制植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法,其中使在每种情况下含有一种或多种农药作为活性物质的本发明微粒或根据本发明方法制备的微粒或本发明配制剂作用于特定有害物、其栖息地或者待保护以防特定有害物的植物、土壤和/或不希望的植物和/或有用植物和/或其生长地上。
本发明的另一方面是含有本发明微胶囊或根据本发明制备的微胶囊的种子。
在每种情况下含有一种或多种农药作为活性物质的本发明微粒或者根据本发明方法制备的微粒或本发明配制剂在一个实施方案中作为悬浮乳液(SE)、可流动浓缩物(FS)、干处理用粉末(DS)、淤浆处理用水分散性粉末(WS)、水溶性粉末(SS)和凝胶(GF)的一部分用于处理植物繁殖材料,特别是种子。所述配制剂在稀释2-10倍后在即用制剂中给出0.01-60重量%,优选0.1-40重量%的活性物质浓度。施用可在播种之前或期间进行。微胶囊在植物繁殖材料,尤其是种子上的施用方法包括繁殖材料的拌种、包衣、造粒、撒粉、浸泡和犁沟内施用方法。优选通过不诱发萌发的方法,例如通过拌种、造粒、包衣和撒粉将化合物I或其组合物分别施用于植物繁殖材料上。
当用于植物保护中时,活性物质的施用量取决于所需的效果类型为0.001-2kg/ha,优选为0.005-2kg/ha,更优选为0.05-0.9kg/ha,特别为0.1-0.75kg/ha。
在植物繁殖材料如种子例如通过撒粉、包衣或浸透种子的处理中,通常要求活性物质的量为0.1-1000g/100kg,优选为1-1000g/100kg,更优选为1-100g/100kg,最优选为5-100g/100kg植物繁殖材料(优选种子)。
当用于保护材料或储存产品中时,活性物质的施用量取决于施用区域的类型和所需的效果。在材料保护中常用的施用量为0.001g-2kg,优选为0.005g-1kg活性物质/立方米被处理材料。
可向微胶囊或包含它们的配制剂中作为预混物加入或者合适的话在紧临使用前加入(桶混合)各种类型的油、润湿剂、辅助剂、肥料或微量营养素和其他农药(例如除草剂、杀虫剂、杀真菌剂、生长调节剂、安全剂)。这些试剂可以以1:100-100:1,优选1:10-10:1的重量比与本发明组合物混合。
用户通常从预剂量装置、背包式喷雾器、喷雾罐、喷雾飞机或灌溉系统施用本发明组合物。通常将该农业化学组合物用水、缓冲剂和/或其他助剂配制至所需的施用浓度,由此得到即用喷雾液或本发明农业化学组合物。每公顷农业利用区通常施用20-2000升,优选50-400升即用喷雾液。
根据一个实施方案,用户可以自己在喷雾罐中混合本发明组合物的各组分如成套包装的各部分或二元或三元混合物的各部分并且合适的话可以加入其他助剂。
本发明提供了下列优点:
本发明微胶囊是环境友好的。
本发明微胶囊在壳中仅含有天然聚合物或者受自然启发的聚合物。
本发明微胶囊不形成微塑料。
本发明微胶囊易于降解,例如在环境条件下易于降解。
本发明微胶囊含有基于天然材料的壳。
本发明微胶囊在没有任何共价交联下得到。它们不要求使用反应性交联剂。因此,它们具有有利的EHS特性并且易于生产。
本发明微胶囊允许活性物质的控制释放。可以根据应用要求调节该释放特性和挥发性。可以提供活性物质非常容易释放的胶囊。可以提供活性物质非常缓慢释放的胶囊。可以提供活性物质具有良好挥发性的胶囊。
本发明微胶囊可以用于宽范围的应用如农业化学应用(例如作物保护、农业非作物应用、种子处理),药物应用,公共卫生,个人护理应用(例如化妆品应用),纺织品应用,人类或动物营养应用,化学工艺应用,粘合剂和密封剂,油漆和涂料,建筑和结构材料,自修复材料,烟草工业,家庭应用中。
本发明微胶囊对于控制植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长显示出高生物活性。
本发明微胶囊的制备容易且经济。它们不要求复杂的设备。它们可以在室温下形成并且在其制备过程中不要求冷却。它们可以大量制备并且可以扩大其制造方法。
本发明微胶囊和配制剂储存稳定。
本发明微胶囊和配制剂与宽范围的其他活性物质相容并且可以用宽范围的其他活性物质配制。
实施例
粒度分布(PSD)通过使用Malvern Mastersizer 2000的统计激光散射统根据欧洲标准ISO 13320EN测定。根据Mie理论通过Malvern Instruments提供的使用“通用模型”的软件处理数据。重要的参数是n=10、50和90的dn值。
所用材料:
蛋白质A:由Roquette以豌豆蛋白S85XF得到的豌豆蛋白(蛋白质含量约85%,干燥损失约10%)。
蛋白质B:来自Roquette的水解小麦蛋白Nutralys W(蛋白质含量约85%,干燥损失约<8%)
蛋白质C:小麦蛋白,在21℃和pH 7下可溶性部分大于95重量%且粘度(Brookfield A1540方法)为2000-12 000mPas(来自Syral的Solpro050),蛋白质含量约82%,干燥损失约<7%
蛋白质D:来自BASF的水解米蛋白蛋白质含量>75%
多糖A:壳聚糖,粘度<200mPa.s,1%乙酸溶液(20℃ Brookfield A1540方法),乙酰化程度(由NMR测定,根据Journal of Pharmaceutical and Biomedical Analysis 32(2003),1149-1158,DOI 10.1016/S0731-7085(03)00155-9中所述方法):>75%(来自SigmaAldrich的壳聚糖LV)
表面活性剂A聚山梨酸月桂基酯乙氧基化物
溶剂A甲基化大豆油
溶剂B Solvesso 200ND
实施例1
用ULTRA-TURRAX 25在22 500rpm下将环庚草醚液体tgai(65.44g)乳化到豌豆蛋白水溶液(94.31水,3.35g蛋白质A,0.5g表面活性剂A)中达3分钟。
将pH为4.65(用乙酸调节)的壳聚糖溶液(2.46g壳聚糖在59.26g水)中加入该乳液中。
将该混合物用螺旋桨搅拌器在250rpm下搅拌30分钟。
然后加入六聚偏磷酸钠(0.02g在24.94g DI水中)。
将该混合物在室温下搅拌2小时。
所得胶囊悬浮液的平均d50为6.4μm且d90为29.5μm。
将如此制备的胶囊与可乳化浓缩物(EC)和聚脲胶囊悬浮液(PU CS)配制剂相比较。它们在温室和大田条件下在防治ALOMY、LOLRI、LOLMU、GALAP杂草中显示出优异的效力,但对冬小麦和大麦也显示出良好的作物耐受性。如此制备的胶囊还显示出比EC好得多的挥发性能,惊人地非常类似于PU CS。
实施例2
用ULTRA-TURRAX DF 25在21 000rpm下将环庚草醚液体tgai(400.101g)乳化到605.87g水解小麦蛋白水溶液(含有3.35重量%蛋白质B和0.5重量%表面活性剂A,pH 5.4)中达3分钟。
将370.82g壳聚糖水溶液(含有4重量%多糖A)在pH 4.65(用乙酸调节)下加入该乳液中。加入该溶液的时间:20分钟。
将该混合物用螺旋桨搅拌器在250rpm下搅拌30分钟。
然后加入154g六聚偏磷酸钠水溶液(含有0.1重量%六聚偏磷酸钠,pH 7.4)。
将该混合物在室温下搅拌1小时30分钟。
反应结束时pH为4.7。
所得胶囊悬浮液的平均d50为3μm且d90为10μm。
实施例3
用ULTRA-TURRAX DF 25在21 000rpm下将环庚草醚液体tgai(400.97g)乳化到606.18g小麦蛋白水溶液(含有3.40重量%蛋白质C和0.5重量%表面活性剂A,pH 6.3)中达3分钟。
将370.30g壳聚糖水溶液(含有4重量%多糖A)在pH 4.65(用乙酸调节)下加入该乳液中。加入该壳聚糖溶液的时间:20分钟。
将该混合物用螺旋桨搅拌器在250rpm下搅拌30分钟。
然后加入153g六聚偏磷酸钠水溶液(含有0.1重量%六聚偏磷酸钠,pH 7.4)。
将该混合物在室温下搅拌1小时30分钟。
反应结束时pH为4(用乙酸调节)。
所得胶囊悬浮液的平均d50为3μm且d90为8μm。
实施例4
用ULTRA-TURRAX DF 25在21 000rpm下将环庚草醚液体tgai(161.52g)乳化到242.86g水解米蛋白水溶液(含有3.40重量%蛋白质D和0.5重量%表面活性剂A,pH 8.9)中达2分钟。
将148.47g壳聚糖水溶液(含有4重量%多糖A)在pH 4.65(用乙酸调节)下加入该乳液中。加入该壳聚糖溶液的时间:20分钟。
将该混合物用螺旋桨搅拌器在250rpm下搅拌30分钟。
然后加入66g六聚偏磷酸钠水溶液(含有0,1重量%六聚偏磷酸钠,pH7.4)。
将该混合物在室温下搅拌1小时30分钟。
反应结束时pH为4(用乙酸调节)。
所得胶囊悬浮液的平均d50为9μm且d90为57μm。
实施例5
扩大生产规模:
用三级在线转子-定子将环庚草醚液体(3.9kg)连续乳化到豌豆蛋白水溶液(5.7kg水,0.2kg蛋白质A,30g表面活性剂A)中,其中活性成分和其他组分之间的比例如实施例1。
在乳化之后将该壳聚糖溶液(在1.5kg水中的0.147kg多糖A)连续加入来自连续乳化的搅拌产物容器中。将该混合物用锚式搅拌器搅拌60分钟。
然后将六聚偏磷酸钠(1.2g在1.5kg去离子水中的溶液)加入该混合物中并搅拌2小时。
所得放大胶囊悬浮液的平均d50为3.9μm且d90为8.5μm.
实施例6
用ULTRA-TURRAX DF 25在18 000rpm下将精噻吩草胺液体tgai(123.97g)、异恶草酮粘稠液体tgai(15.50g)和溶剂B(108.47g)混合,然后乳化到227.8g小麦蛋白水溶液(含有2.96重量%蛋白质C和0.44重量%表面活性剂A,pH 6.3)中达3分钟。
将124.23g壳聚糖水溶液(含有4重量%多糖A)在pH 4.65(用乙酸调节)下加入该乳液中。加入该壳聚糖溶液的时间:45分钟。
将该混合物用螺旋桨搅拌器在150rpm下搅拌60分钟。
然后在15分钟内加入20.06g聚磷酸铵水溶液(AP 420)(含有0.25重量%聚磷酸铵)。
将该混合物在室温下搅拌1小时。
所得胶囊悬浮液的平均d50为4.5μm且d90为11.6μm。
将如此制备的胶囊与精噻吩草胺可乳化浓缩物(EC)和异恶草酮聚脲胶囊悬浮液(PU CS)的桶混物以及精噻吩草胺和异恶草酮共聚脲胶囊悬浮液相比较。胶囊实施例6在温室条件下在防治SETFA、STEME杂草上显示出优异的效力。
实施例7
用ULTRA-TURRAX DF 25在18 000rpm下将精噻吩草胺液体tgai(107.8g)和溶剂B(107.8g)混合,然后乳化到198.08g小麦蛋白水溶液(含有2.96重量%蛋白质C和0.44重量%表面活性剂A,pH 6.3)中达3分钟。
将108.01g壳聚糖水溶液(含有4重量%多糖A)在pH 4.65(用乙酸调节)下加入该乳液中。加入该壳聚糖溶液的时间:45分钟。
将该混合物用螺旋桨搅拌器在150rpm下搅拌60分钟。
然后在15分钟内加入17.43g含有0.25重量%聚磷酸铵的聚磷酸铵水溶液(AP 420)。
将该混合物在室温下搅拌1小时。
所得胶囊悬浮液的平均d50为2.7μm且d90为7μm。
将如此制备的胶囊与精噻吩草胺可乳化浓缩物(EC)相比较。它们在温室条件下在防治CAPBP、GALAP、STEME、VIDAR、LAMPU杂草,还有SETVI、ECHCG、DIGSA禾草上显示出优异的效力。
当与EC相比较时,在大田中如此制备的胶囊对大豆和棉花显示出良好的处理、更好的作物耐受性和类似的杂草防治。
实施例8
用ULTRA-TURRAX DF 25在18 000rpm下将S-异丙甲草胺液体tgai(179g)和溶剂B(89g)混合,然后乳化到207.73g小麦蛋白水溶液(含有3.23重量%蛋白质C和0.49重量%表面活性剂A,pH 6.3)中达3分钟。
将124.62g壳聚糖水溶液(含有4.3重量%多糖A)在pH 4.65(用乙酸调节)下加入该乳液中。加入该壳聚糖溶液的时间:45分钟。
将该混合物用螺旋桨搅拌器在150rpm下搅拌60分钟。
然后在15分钟内加入20.05g含有0.25重量%聚磷酸铵的聚磷酸铵水溶液(AP 420)。
将该混合物在室温下搅拌1小时00分。最后加入0.61g 2-苯氧基乙醇并将该混合物在室温下搅拌额外10分钟。
所得胶囊悬浮液的平均d50为3.8μm且d90为8.9μm。
实施例9
用ULTRA-TURRAX DF 25在18 000rpm下将乙草胺液体tgai(247.94g)乳化到247.94g小麦蛋白水溶液(含有2.72重量%蛋白质C和0.41重量%表面活性剂A,pH 6.3)中达3分钟。
将124.96g壳聚糖水溶液(含有4重量%多糖A)在pH 4.65(用乙酸调节)下加入该乳液中。加入该壳聚糖溶液的时间:45分钟。
将该混合物用螺旋桨搅拌器在150rpm下搅拌60分钟。
然后在15分钟内加入20.05g含有0.25重量%聚磷酸铵的聚磷酸铵水溶液(AP 420)。
将该混合物在室温下搅拌1小时00分。最后加入0.64g 2-苯氧基乙醇并将该混合物在室温下搅拌额外10分钟。
所得胶囊悬浮液的平均d50为9.5μm并且d90为21μm。
Claims (26)
1.具有壳和核的微胶囊,其中所述核含有非水液体,所述非水液体为一种或多种液体(在21℃下)活性物质或者一种或多种溶于溶剂S中的活性物质,其中溶剂S与水不溶混并且其中所述壳含有:
i)至少一种总体带负电的蛋白质PR,其中蛋白质PR是植物蛋白,
ii)至少一种壳聚糖,和
iii)任选地,能够经由非共价键的形成交联组分蛋白质PR和多糖PS的无机盐IS。
2.根据权利要求1的微胶囊,其中蛋白质PR和壳聚糖不用脂族醛交联。
3.根据权利要求1或2的微胶囊,其中所述蛋白质PR是在4以上,优选5以上的pH下总体带负电的蛋白质。
4.根据权利要求1或2的微胶囊,其中所述蛋白质PR是素蛋白。
5.根据权利要求1-3中任一项的微胶囊,其中所述蛋白质PR选自豌豆蛋白、米蛋白、小麦蛋白、向日葵蛋白和大豆蛋白。
6.根据权利要求1-4中任一项的微胶囊,其中所述蛋白质PR以其天然形式或者作为水解产物应用。
7.根据权利要求1-5中任一项的微胶囊,其中所述多糖PS含有氨基。
8.根据权利要求1-6中任一项的微胶囊,其中所述壳聚糖由蘑菇或甲壳纲动物得到。
9.根据权利要求1-7中任一项的微胶囊,其中所述无机盐IS每分子含有至少两个带电结构部分,尤其是磷酸盐基团。
10.根据权利要求1-8中任一项的微胶囊,其中所述无机盐IS为聚磷酸盐,优选选自碱金属(如六聚偏磷酸钠)或铵聚磷酸盐。
11.根据权利要求1-9中任一项的微胶囊,进一步包含非离子表面活性剂。
12.根据权利要求1-11中任一项的微胶囊,其中蛋白质PR与多糖PS的质量比为1:10-10:1,优选3:1-1:3。
13.根据权利要求1-12中任一项的微胶囊,其中所述微胶囊具有0.1-20μm,优选0.5-10μm的平均直径d50。
14.根据权利要求1-13中任一项的微胶囊,其中所述微胶囊含有1-95重量%,优选10-90重量%,更优选30-85重量%所述一种或多种活性物质。
15.根据权利要求1-13中任一项的微粒,其中所述一种或多种活性物质选自农药、增效剂、辅助剂、植物保健剂、驱除剂、生物杀伤剂、相变材料、药物、化妆品成分(如香料、香水、维生素、精油、植物提取物)、营养素、食品添加剂(如植物油、鱼油、维生素、芳香剂、抗氧化剂、精油、植物提取物)、信息素、催化剂。
16.制备微胶囊的方法,包括下列步骤:
A)提供至少一种蛋白质PR的水溶液,其中所述蛋白质PR在所述水溶液中总体带负电并且其中所述蛋白质PR至少部分溶于所述水溶液中,
B)提供至少一种多糖PS的单独水溶液,其中所述多糖PS总体带正电并且其中所述多糖PS至少部分溶于所述水溶液中,
C)在步骤A)下提供的水溶液中乳化液体活性物质或活性物质在溶剂S中的溶液,其中溶剂S与水不溶混,任选通过搅拌和/或表面活性剂支持,D)将在步骤B)中得到的水溶液加入在步骤C)中得到的乳液中,E)任选地,将至少一种无机盐加入在步骤D)中得到的混合物中,所述无机盐IS能够经由非共价键的形成交联蛋白质PR和多糖PS。
17.根据权利要求15的方法,其中在进行步骤D)之前将水溶液A)的pH调节至4或更高,优选5或更高,更优选5-9的值。
18.根据权利要求15或16的方法,其中在进行步骤D)之前将水溶液B)的pH调节至7或更低,优选6或更低,更优选4-5的值。
19.根据权利要求15-17中任一项的方法,其中在步骤C)中使用的所述表面活性剂是非离子表面活性剂。
20.根据权利要求15-18中任一项的方法,其中进行步骤C)以使得在步骤C)中得到水包油乳液。
21.根据权利要求15-19中任一项的方法,其中在步骤E)中加入所述无机盐以使得所得到的所述混合物基于整个混合物包含0.001-5重量%,更优选0.002-1重量%,尤其优选0.005-0.1重量%所述无机盐。
22.包含根据权利要求1-14中任一项或者根据权利要求15-20中任一项制备的微胶囊的配制剂,其中所述微胶囊作为分散颗粒存在于含水介质中。
23.根据权利要求22的配制剂,其中所述配制剂包含1-50重量%,优选5-45重量%,更优选10-40重量%所述一种或多种活性物质。
24.根据权利要求1-14中任一项或者根据权利要求15-21中任一项制备的微粒或者根据权利要求22或23的配制剂在农业化学应用(例如作物保护、农业非作物应用、种子处理),药物应用,公共卫生,个人护理应用(例如化妆品应用),纺织品应用,人类或动物营养应用,化学工艺应用,粘合剂和密封剂,油漆和涂料,建筑和结构材料,自修复材料,烟草工业,家庭应用中的用途。
25.一种控制植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法,其中使根据权利要求1-14中任一项的微胶囊或者根据权利要求15-21中任一项的配制剂或者根据权利要求22或23的配制剂—在每种情况下含有一种或多种农药作为活性物质—作用于特定有害物、其栖息地或者待保护以防特定有害物的植物、土壤和/或不希望的植物和/或有用植物和/或其生长地上。
26.含有根据权利要求1-14中任一项或者根据权利要求15-21中任一项制备的微胶囊的种子。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP21159155.7A EP4049749A1 (en) | 2021-02-25 | 2021-02-25 | New microcapsules containing active substances |
EP21159155.7 | 2021-02-25 | ||
PCT/EP2022/053802 WO2022179911A1 (en) | 2021-02-25 | 2022-02-16 | New microcapsules containing active substances |
Publications (1)
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CN117241879A true CN117241879A (zh) | 2023-12-15 |
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CN202280030623.6A Pending CN117241879A (zh) | 2021-02-25 | 2022-02-16 | 含有活性物质的新型微胶囊 |
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US (1) | US20240058782A1 (zh) |
EP (2) | EP4049749A1 (zh) |
JP (1) | JP2024509096A (zh) |
CN (1) | CN117241879A (zh) |
AR (1) | AR124969A1 (zh) |
AU (1) | AU2022224956A1 (zh) |
CA (1) | CA3209161A1 (zh) |
WO (1) | WO2022179911A1 (zh) |
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WO2024126450A1 (en) * | 2022-12-14 | 2024-06-20 | Firmenich Sa | Protein-based microcapsules |
WO2024149991A1 (en) * | 2023-01-10 | 2024-07-18 | Delsys Technology Limited | Agrochemical compositions |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CA2458392A1 (en) * | 2001-10-03 | 2003-04-17 | Unilever Plc | Carbohydrate binding domain containing fusion proteins for delivery of therapeutic and other agents, and compositions containing them |
EP1371410A1 (en) * | 2002-06-14 | 2003-12-17 | NIZO food research | Complex coacervates containing whey proteins |
CA2533406C (en) | 2003-07-31 | 2013-01-22 | Sol-Gel Technologies Ltd. | Microcapsules loaded with active ingredients and a method for their preparation |
BRPI0514880A (pt) | 2004-09-03 | 2008-06-24 | Syngenta Ltd | composto, processo para a preparação do mesmo, composição herbicida, e, método para controlar gramas e ervas daninhas em culturas de plantas úteis |
ATE450517T1 (de) | 2004-10-05 | 2009-12-15 | Syngenta Ltd | Isoxazolinderivate und ihre verwendung als herbizide |
JP4782458B2 (ja) * | 2005-03-31 | 2011-09-28 | 森下仁丹株式会社 | 植物根寄生植物の防除方法 |
GB0526044D0 (en) | 2005-12-21 | 2006-02-01 | Syngenta Ltd | Novel herbicides |
GB0603891D0 (en) | 2006-02-27 | 2006-04-05 | Syngenta Ltd | Novel herbicides |
WO2007120500A2 (en) * | 2006-04-07 | 2007-10-25 | Ocean Nutrition Canada Ltd. | Emulsions and microcapsules with substances having low interfacial tension, methods of making and using thereof |
-
2021
- 2021-02-25 EP EP21159155.7A patent/EP4049749A1/en not_active Withdrawn
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2022
- 2022-02-16 AU AU2022224956A patent/AU2022224956A1/en active Pending
- 2022-02-16 JP JP2023551699A patent/JP2024509096A/ja active Pending
- 2022-02-16 CA CA3209161A patent/CA3209161A1/en active Pending
- 2022-02-16 US US18/278,064 patent/US20240058782A1/en active Pending
- 2022-02-16 WO PCT/EP2022/053802 patent/WO2022179911A1/en active Application Filing
- 2022-02-16 EP EP22708868.9A patent/EP4297892A1/en active Pending
- 2022-02-16 CN CN202280030623.6A patent/CN117241879A/zh active Pending
- 2022-02-24 AR ARP220100409A patent/AR124969A1/es unknown
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EP4297892A1 (en) | 2024-01-03 |
CA3209161A1 (en) | 2022-09-01 |
EP4049749A1 (en) | 2022-08-31 |
US20240058782A1 (en) | 2024-02-22 |
JP2024509096A (ja) | 2024-02-29 |
AR124969A1 (es) | 2023-05-24 |
WO2022179911A1 (en) | 2022-09-01 |
AU2022224956A1 (en) | 2023-09-07 |
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