除草活性剂的制作方法

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专利名称:除草活性剂的制作方法
技术领域
本发明涉及植物保护组合物技术领域,尤其是包含磺酰脲/安全剂组合(活性物质-解毒剂-组合)并且高度适用于控制有用作物中竞争性有害植物的除草活性组合物。
背景技术
抑制乙酰乳酸合酶(ALS)的除草剂和安全剂的组合是已知的。如此,EP 0 492 367 A2描述了不同ALS抑制剂与不同安全剂的组合。然而,该文献中特别公开的组合在选择性和活性谱方面不总是足够的。

发明内容
因此,本发明的任务是提供对于重要作物具有提高的选择性,并且同时对于有害植物具有高活性的除草活性组合物。出人意外地,该任务是通过本发明的除草活性组合物解决的。
因此,本发明提供一种除草活性组合物,其包含(A)一种或多种选自下组的磺酰脲类化合物甲磺隆、噻吩磺隆、苯磺隆、氯磺隆及其盐和酯,优选以除草有效量存在,和(B)一种或多种选自下组的安全剂吡咯二酸、双苯唑酸、喹氧乙酸、解草唑及其盐和酯,优选以解毒有效量存在,优选吡咯二酸、双苯唑酸、喹氧乙酸及其盐和酯,尤其优选吡咯二酸、喹氧乙酸及其盐和酯,尤其特别优选吡咯二酸及其盐和酯。
磺酰脲A)和安全剂B)也可以以其盐的形式存在,例如以具有无机和有机抗衡离子的盐存在。所述盐为例如金属盐,尤其是碱金属盐或碱土金属盐,尤其是钠盐和钾盐,或铵盐或与有机胺形成的盐。盐的形成也可以通过酸与碱基如氨基和烷基氨基形成加合物来进行。对此适宜的酸为强无机酸和有机酸,例如HCl、HBr、H2SO4或HNO3。优选的盐为碱金属盐,例如钠盐和钾盐。磺酰脲A)可以例如形成盐,其中-SO2-NH-基团的氢通过农业上适宜的阳离子被取代,例如金属离子如碱金属离子,优选钠离子或钾离子。
磺酰脲A)和安全剂B)也可以以其酯的形式存在,尤其以其烷基酯的形式,例如C1-C10-烷基酯。对于磺酰脲A)来说,甲酯和乙酯是尤其优选的。对于安全剂B)来说,甲酯、乙酯和甲基己基酯是尤其优选的。
磺酰脲(A)优选选自下组化合物甲磺隆-甲酯(A1.1)、噻吩磺隆-甲酯(A2.1)、苯磺隆-甲酯(A3.1)和氯磺隆(A4.1),包括农业上常规的盐,例如钠盐,甲磺隆-甲酯-钠盐(A1.2)、噻吩磺隆-甲酯-钠盐(A2.2)、苯磺隆-甲酯-钠盐(A3.2)和氯磺隆-钠盐(A4.2)。此外,优选的是甲磺隆(A1.3)、甲磺隆-钠盐(A1.4)、噻吩磺隆(A2.3)、噻吩磺隆-钠盐(A2.4)、苯磺隆(A3.3)和苯磺隆-钠盐(A3.4)。尤其优选的磺酰脲(A)是甲磺隆-甲酯(A1.1)、噻吩磺隆-甲酯(A2.1)、苯磺隆-甲酯(A3.1)和氯磺隆(A4.1)。
安全剂(B)优选选自下组化合物1-(2,4-二氯苯基)-5-(乙氧基羰基)-5-甲基-2-吡唑啉-3-羧酸乙酯(B1,吡咯二酸-二乙酯)、5,5-二苯基-2-异唑啉-3-羧酸乙酯(B2,双苯唑酸-乙酯)、(5-氯-8-喹啉氧基)乙酸-(-1-甲基己基)-酯(B3,解毒喹)、吡咯二酸-二甲酯(B4)、吡咯二酸(B5)、双苯唑酸(B6)和喹氧乙酸(B7)、1-(2,4-二氯苯基)-5-三氯甲基-(1H)-1,2,4-三唑-3-甲酸乙酯(B8,解草唑-乙酯)和解草唑(B9),包括农业上常规的盐,例如钠盐。优选的安全剂为(B1)、(B2)、(B3)和(B8),尤其是(B1)、(B2)和(B3)。尤其优选的安全剂为(B1)和(B2),并且尤其特别优选吡咯二酸-二乙酯(B1)。
对于本发明而言,除草有效量是足以对植物生长具有不利作用的一种或多种除草剂的量。
对于本发明而言,解毒有效量是足以至少部分地使得除草剂或除草剂混合物对有用植物的毒性作用失效的一种或多种安全剂的量。
化合物(A)和(B)还包括所有的立体异构体,其具有相同的原子拓扑连接,及其混合物。这类化合物包含一种或多种不对称的碳原子或双键,这没有在结构式中具体示出。由该特定空间形状定义的可能的立体异构体如对映异构体、非对映异构体、Z-和E-异构体可以通过常规方法从立体异构体的混合物中获得,或另外通过与使用立体化学纯初始物质相结合的立体选择反应来制得。
磺酰脲(A)是商购可得的并且已知于例如“The Pesticide Manual(农药手册)”,第12版(2000),The British Crop ProtectionAssociation,以及已知于US 4,370,480、EP 30138、US 4,701,535、EP 30142、EP 202830和US 4,127,405,其中包含了制备过程和初始物质方面的详细信息。将这些出版物特别地引入本说明书以作参考。
安全剂(B)是商购可得的并且已知于例如“The Pesticide Manual(农药手册)”,第12版(2000),The British Crop ProtectionAssociation,以及已知于WO 91/7874、WO 95/7897、EP-A-94349和EP-A-174562,其中包含了制备过程和初始物质方面的详细信息。将这些出版物特别地引入本说明书以作参考。
本发明磺酰脲(A)和安全剂(B)的优选组合的实例为(A1.1)+(B1),(A1.1)+(B2),(A1.1)+(B3),(A1.1)+(B8),(A2.1)+(B1),(A2.1)+(B2),(A2.1)+(B3),(A2.1)+(B8),(A3.1)+(B1),(A3.1)+(B2),(A3.1)+(B3),(A3.1)+(B8),(A4.1)+(B1),(A4.1)+(B2),(A4.1)+(B3),(A4.1)+(B8),(A1.2)+(B1),(A1.2)+(B2),(A1.2)+(B3),(A1.2)+(B8),(A2.2)+(B1),(A2.2)+(B2),(A2.2)+(B3),(A2.2)+(B8),(A3.2)+(B1),(A3.2)+(B2),(A3.2)+(B3),(A3.2)+(B8),(A4.2)+(B1),(A4.2)+(B2),(A4.2)+(B3),(A4.2)+(B8),(A1.3)+(B1),(A1.3)+(B2),(A1.3)+(B3),(A1.3)+(B8),(A2.3)+(B1),(A2.3)+(B2),(A2.3)+(B3),(A2.3)+(B8),(A3.3)+(B1),(A3.3)+(B2),(A3.3)+(B3),(A3.3)+(B8),(A1.4)+(B1),(A1.4)+(B2),(A1.4)+(B3),(A1.4)+(B8),(A2.4)+(B1),(A2.4)+(B2),(A2.4)+(B3),(A2.4)+(B8),(A3.4)+(B1),(A3.4)+(B2),(A3.4)+(B3),(A3.4)+(B8);(A1.1)+(A1.2)+(B1),(A1.1)+(A2.1)+(B1),(A1.1)+(A2.2)+(B1),(A1.1)+(A3.1)+(B1),(A1.1)+(A3.2)+(B1),(A1.1)+A4.1)+(B1),(A1.1)+(A4.2)+(B1);(A1.2)+(A2.1)+(B1),(A1.2)+(A2.2)+(B1),(A1.2)+(A3.1)+(B1),(A1.2)+(A3.2)+(B1),(A1.2)+(A4.1)+(B1),(A1.2)+(A4.2)+(B1);
(A2.1)+(A2.2)+(B1),(A2.1)+(A3.1)+(B1),(A2.1)+(A3.2)+(B1),(A2.1)+(A4.1)+(B1),(A2.1)+(A4.2)+(B1);(A2.2)+(A3.1)+(B1),(A2.2)+(A3.2)+(B1),(A2.2)+(A4.1)+(B1),(A2.2)+(A4.2)+(B1);(A3.1)+(A3.2)+(B1),(A3.1)+(A4.1)+(B1),(A3.1)+(A4.2)+(B1);(A3.2)+(A4.1)+(B1),(A3.2)+(A4.2)+(B1),(A4.1)+(A4.2)+(B1);(A1.1)+(A1.2)+(B2),(A1.1)+(A2.1)+(B2),(A1.1)+(A2.2)+(B2),(A1.1)+(A3.1)+(B2),(A1.1)+(A3.2)+(B2),(A1.1)+(A4.1)+(B2),(A1.1)+(A4.2)+(B2);(A1.2)+(A2.1)+(B2),(A1.2)+(A2.2)+(B2),(A1.2)+(A3.1)+(B2),(A1.2)+(A3.2)+(B2),(A1.2)+(A4.1)+(B2),(A1.2)+(A4.2)+(B2);(A2.1)+(A2.2)+(B2),(A2.1)+(A3.1)+(B2),(A2.1)+(A3.2)+(B2),(A2.1)+(A4.1)+(B2),(A2.1)+(A4.2)+(B2);(A2.2)+(A3.1)+(B2),(A2.2)+(A3.2)+(B2),(A2.2)+(A4.1)+(B2),(A2.2)+(A4.2)+(B2);(A3.1)+(A3.2)+(B2),(A3.1)+(A4.1)+(B2),(A3.1)+(A4.2)+(B2);(A3.2)+(A4.1)+(B2),(A3.2)+(A4.2)+(B2),(A4.1)+(A4.2)+(B2);(A1.1)+(A1.2)+(B3),(A1.1)+(A2.1)+(B3),(A1.1)+(A2.2)+(B3),(A1.1)+(A3.1)+(B3),(A1.1)+(A3.2)+(B3),(A1.1)+(A4.1)+(B3),(A1.1)+(A4.2)+(B3);(A1.2)+(A2.1)+(B3),(A1.2)+(A2.2)+(B3),(A1.2)+(A3.1)+(B3),(A1.2)+(A3.2)+(B3),(A1.2)+(A4.1)+(B3),(A1.2)+(A4.2)+(B3);(A2.1)+(A2.2)+(B3),(A2.1)+(A3.1)+(B3),(A2.1)+(A3.2)+(B3),(A2.1)+(A4.1)+(B3),(A2.1)+(A4.2)+(B3);(A2.2)+(A3.1)+(B3),(A2.2)+(A3.2)+(B3),(A2.2)+(A4.1)+(B3),(A2.2)+(A4.2)+(B3);(A3.1)+(A3.2)+(B3),(A3.1)+(A4.1)+(B3),(A3.1)+(A4.2)+(B3);(A3.2)+(A4.1)+(B3),(A3.2)+(A4.2)+(B3),(A4.1)+(A4.2)+(B3);(A1.1)+(A1.2)+(B8),(A1.1)+(A2.1)+(B8),(A1.1)+(A2.2)+(B8),(A1.1)+(A3.1)+(B8),(A1.1)+(A3.2)+(B8),(A1.1)+(A4.1)+(B8),(A1.1)+(A4.2)+(B8);(A1.2)+(A2.1)+(B8),(A1.2)+(A2.2)+(B8),(A1.2)+(A3.1)+(B8),(A1.2)+(A3.2)+(B8),(A1.2)+(A4.1)+(B8),(A1.2)+(A4.2)+(B8);(A2.1)+(A2.2)+(B8),(A2.1)+(A3.1)+(B8),(A2.1)+(A3.2)+(B8),(A2.1)+(A4.1)+(B8),(A2.1)+(A4.2)+(B8);
(A2.2)+(A3.1)+(B8),(A2.2)+(A3.2)+(B8),(A2.2)+(A4.1)+(B8),(A2.2)+(A4.2)+(B8);(A3.1)+(A3.2)+(B8),(A3.1)+(A4.1)+(B8),(A3.1)+(A4.2)+(B8);(A3.2)+(A4.1)+(B8),(A3.2)+(A4.2)+(B8),(A4.1)+(A4.2)+(B8)。
组(B)的安全剂(解毒剂)减少或防止了当将除草活性物质(A)用于有用作物时会出现的植物毒性作用,而对该除草活性物质控制有害植物的活性无实质上的负面影响。这使常规作物保护产品的应用范围得到十分显著地扩展,并且扩展至例如作物如小麦、大麦、玉米、水稻和迄今不能、或仅可能有限使用除草剂(也就是说以低用量受限制的防治谱来使用除草剂)的其它作物。
本发明的磺酰脲/安全剂组合的磺酰脲(A)和安全剂(B)可以一起施用(例如以成品配料剂或桶混法)或以任意顺序先后施用。安全剂∶磺酰脲的重量比可以在较大范围内变化,其优选范围为1∶100至100∶1,尤其优选1∶10至10∶1。磺酰脲和安全剂的各自最佳用量取决于所使用磺酰脲或安全剂的类型和待处理植物的种类,并且可以通过简单的标准前试验对各情形进行测定。
本发明的除草活性组合物的主要施用领域优选为谷类作物(例如小麦、黑麦、大麦、燕麦),水稻、玉米、高粱、棉花和大豆,优选谷类、水稻和玉米。
根据其性质,本发明除草活性组合物所包含的安全剂可以用于预处理作物种子(例如拌种),或在播种前混入种子犁沟,或在苗前或苗后与除草剂尤其是磺酰脲(A)一起施用。苗前处理包括在播种前处理种植区域,以及处理已经播种但尚未出苗的种植区域。与除草剂一起施用是优选的。对此,可以使用桶混物或成品配制剂。
根据指示和所使用的除草活性物质,安全剂的所需施用量可以在较大范围内变化,其常规范围为每公顷0.001至5kg,优选0.005至0.5kg的活性物质。
本发明的除草组合物或磺酰脲/安全剂组合还可以视需要包含其它组分(C)一种或多种溶剂,优选有机溶剂,(D)一种或多种磺基丁二酸酯(盐),(E)一种或多种不同于(A)和(B)的农业化学活性物质,和/或(F)常规助剂和添加剂。
作为任选地包含的有机溶剂(组分C)为,例如1)烃类,其可以是未经取代或经取代的,例如1a)芳族烃类,例如●经单或多烷基取代的苯,例如甲苯、二甲苯、均三甲苯、乙苯,或●经单或多烷基取代的萘,例如1-甲基萘、2-甲基萘或二甲基萘,或●其它衍生自苯的芳烃,例如茚满或Tetralin,或●它们的混合物1b)脂族烃类,例如●直链或分支的脂肪族化合物,例如通式CnH2n+2化合物,例如戊烷、己烷、辛烷、2-甲基丁烷或2,2,4-三甲基戊烷,或●环状的,任选地经烷基取代的脂肪族化合物,例如环己烷或甲基环戊烷,或●它们的混合物,例如ExxsolD-系列、Isopar-系列或Bayol-系列例如Bayol82(ExxonMobil Chemicals)或IsaneIP-系列或HydrosealG-系列(TotalFinaElf)的溶剂,1c)芳烃和脂族烃的混合物,如Solvesso-系列的溶剂,例如Solvesso100、Solvesso150或Solvesso200(ExxonMobil Chemicals),Solvarex/Solvaro-系列(TotalFinaElf)或Caromax-系列的溶剂,例如Caromax28(Petrochem Carless),或1d)卤代烃类,例如卤代芳烃和脂族烃,例如氯苯或二氯甲烷,或2)非质子极性溶剂,例如醚类,可以是单-、二-或多官能团的C1-C9-链烷酸的酯,例如其与C1-C18-烷基醇形成的单-、二-或三酯,具有低互变倾向的酮类,磷酸酯,酰胺,腈或砜,例如己二酸二异丁酯,RhodiasolvRPDE(Rhodia),环己酮,JeffsolPC(Huntsman),γ-丁内酯,N-甲基吡咯烷酮,二甲亚砜,乙腈,Tributylphosphatam或HostarexPO-系列(Clariant),或3)脂肪酸酯,例如天然源的如天然油类,例如动物油或植物油,或合成源的如Edenor-系列,例如EdenorMEPa或EdenorMESU,或AgniqueME-系列或AgniqueAE-系列(Cognis),SalimME-系列(Salim),Radia-系列,例如Radia30167(ICI),Prilube-系列,例如Prilube1530(Petrofina),StepanC-系列(Stepan)或Witconol23-系列(Witco)。脂肪酸酯优选C10-C22-、更优选C12-C20-脂肪酸的酯。C10-C22-脂肪酸酯为例如不饱和或饱和C10-C22-脂肪酸的酯,尤其是具有偶数碳原子的脂肪酸如芥子酸、月桂酸、棕榈酸的酯,和尤其是C18-脂肪酸如硬脂酸、油酸、亚油酸或亚麻酸的酯。
脂肪酸酯如C10-C22-脂肪酸酯的实例为脂肪酸如C10-C22-脂肪酸的丙三醇和乙二醇酯,或其酯交换产物,例如脂肪酸烷基酯如C10-C22-脂肪酸C1-C20-烷基酯,其例如可以通过将上述丙三醇-或乙二醇-脂肪酸酯如C10-C22-脂肪酸酯与C1-C20-醇(例如甲醇、乙醇、丙醇或丁醇)进行酯交换来获得。可以通过已知方法来进行酯交换,所述方法描述于例如Rmpp Chemie Lexikon,第9版,第2卷,第1343页,Thieme VerlagStuttgart。
优选的脂肪酸烷基酯如C10-C22-脂肪酸C1-C20-烷基酯为甲酯、乙酯、丙酯、丁酯、2-乙基-己酯和十二烷基酯。优选的乙二醇和丙三醇脂肪酸酯如C10-C22-脂肪酸酯是单一或混合的C10-C22-脂脂肪酸的乙二醇酯和丙三醇酯,优选具有偶数碳原子的脂肪酸如芥子酸、月桂酸、棕榈酸的酯,尤其是C18-脂肪酸如硬脂酸、油酸、亚油酸或亚麻酸的酯。
动物油通常是已知的并且是商购可得的。对于本发明而言,术语“动物油”应理解为指例如源于动物的油如鲸油、鱼肝油、麝香油或貂油。
植物油通常是已知的并且是商购可得的。对于本发明而言,术语“植物油”应理解为指例如产油植物品种的油,例如大豆油、菜籽油、玉米油、葵花油、棉籽油、亚麻子油、椰子油、棕榈油、红花油、核桃油、花生油、橄榄油或蓖麻油,优选菜籽油,其中植物油还包括其酯交换产物例如烷基酯如菜籽油甲酯或菜籽油乙酯。
植物油优选C10-C22-、更优选C12-C20-脂肪酸的酯。C10-C22-脂肪酸酯为例如不饱和或饱和C10-C22-脂肪酸的酯,尤其是具有偶数碳原子的脂肪酸如芥子酸、月桂酸、棕榈酸的酯,尤其是C18-脂肪酸如硬脂酸、油酸、亚油酸或亚麻酸的酯。
植物油的实例为与C10-C22-脂肪酸形成的丙三醇或乙二醇的C10-C22-脂肪酸酯,或C10-C22-脂肪酸-C1-C20-烷基酯,其可例如通过将上述丙三醇-或乙二醇-C10-C22-脂肪酸酯与C1-C20-醇(例如甲醇、乙醇、丙醇或丁醇)酯交换获得。酯交换反应可采用如Rmpp Chemie Lexikon[Rmpp′s dictionary of chemistry],第9版,第2卷,1343页,ThiemeVerlag Stuttgart中所述的已知方法进行。
植物油可以例如以商购可得的植物油形式,尤其是菜籽油,例如菜籽油甲酯,例如PhytorobB(Novance,法国),EdenorMESU和Agnique-ME系列(Cognis,德国)Radia-系列(ICI),Prilube-系列(Petrofina),或生物柴油,或以商购可得含有植物油的制剂添加剂形式,尤其是基于菜籽油,例如菜籽油甲酯的制剂添加剂,例如Hasten(Victoria Chemical Company,澳大利亚,下文称其为Hasten,主要成分菜籽油乙酯),ActirobB(Novance,法国,下文称其为ActirobB,主要成分菜籽油甲酯),Rako-Binol(Bayer AG,德国,下文称其为Rako-Binol,主要成分菜籽油),Renol(Stefes,德国,下文称其为Renol,植物油成分菜籽油甲酯)或Stefes Mero(Stefes,德国,下文指Mero,主要成分菜籽油甲酯)的形式被包含在混合物中。
合成脂肪酸酯的实例为例如源自具有奇数碳原子的脂肪酸的酯,例如C11-C21-脂肪酸酯。
优选的有机溶剂是芳族烃类、脂族烃类和脂肪酸酯例如植物油,例如具有10至22个碳原子的脂肪酸的甘油三酯,其可以是饱和的或不饱和的,直链或分支的,并且其任选地带有其它的功能基团,例如玉米油、菜籽油、葵花籽油、棉籽油、亚麻子油、大豆油、椰子油、棕榈油、红花油或蓖麻油,及其酯交换产物如脂肪酸烷基酯,及其混合物。
该溶剂可以是单独或包含于混合物中。所使用的溶剂或溶剂混合物优选具有低弱的溶解所使用的一种或多种磺酰脲(组分A)的能力。
本发明除草组合物中的溶剂总比例通常介于0和95重量%之间,优选范围为20至80重量%。极性溶剂如非质子极性溶剂的比例通常低于20重量%,优选范围为0至10重量%。
任选存在于本发明除草组合物中的磺基丁二酸酯(盐)(组分D)可以为例如磺基丁二酸的单-或二酯,优选下式(III)化合物R1-(X1)n-O-CO-CH2-CH(SO3M)-CO-O-(X2)m-R2(III)其中R1为H或未经取代或经取代的C1-C30-烃基,例如C1-C30-烷基或C7-C30-烷基芳基,R2为H或未经取代或经取代的C1-C30-烃基,例如C1-C30-烷基或C7-C30-烷基芳基,或阳离子,例如金属阳离子如碱金属或碱土金属阳离子,或铵阳离子如NH4、烷基-、烷基芳基-或聚(芳基烷基)苯基铵阳离子,X1,X2相同或不同,并且各自独立地为间隔单元,例如聚醚单元或聚酯单元,n,m相同或不同,并且各自独立地为0或1,优选为0,和M为阳离子,例如金属阳离子如碱金属或碱土金属阳离子,或铵阳离子如NH4、烷基-、烷基芳基-或聚(芳基烷基)苯基铵阳离子。
优选的式(III)磺基丁二酸酯(盐)是其中R1和R2相同或不同,并且各自独立地为直链、分支的或环状,饱和或不饱和的C1-C20-、优选C4-C18-烷基,例如甲基、乙基、丁基、己基、环己基、辛基如2-乙基己基、癸基、十三烷基或十八烷基,或R1和R2为C7-C20-烷基芳基,例如壬基苯基、2,4,6-三-仲-丁基苯基、2,4,6-三-(1-苯基乙基)-苯基、烷基苄基或氢化肉桂基(Hydrozimtrest),X1和X2相同或不同,并且各自独立地为聚醚单元,例如聚乙二醇-(C2H4O)p-或聚丙二醇-(C3H6O)p-,其中p=1至p=20,优选p=1至p=12,或聚酯单元,例如多羟基丁酸-(CH[CH3]-CH2-COO)q-或聚乳酸-(CH[CH3]-COO)q-,其中q=1至q=15,优选q=1至q=8,n,m相同或不同,并且各自独立地为0或1,优选为0,并且M为阳离子,例如金属阳离子,例如碱金属或碱土金属阳离子,或可以经烷基取代的铵阳离子。
优选包含的磺基丁二酸酯(盐)的实例为a1)用直链、环状或分支的脂族、脂环族和/或芳族醇酯化一次或两次的磺基丁二酸酯,该醇的烷基部分例如具有1-22个碳原子,优选用甲醇、乙醇、(异)丙醇、(异)丁醇、(异)戊醇、(异)己醇、环己醇、(异)庚醇、(异)辛醇(特别是乙基己醇)、(异)壬醇、(异)癸醇、(异)十一烷醇、(异)十二烷醇或(异)十三烷醇酯化一次或两次的磺基丁二酸单或二碱金属盐,特别是磺基丁二酸单或二钠盐,a2)用醇的(聚)环氧烷加成物酯化一次或两次的磺基丁二酸酯,该醇的烷基部分例如具有1-22个碳原子和(聚)环氧烷部分含1-200、优选2-200个环氧烷单元,优选用十二烷基/十四烷基醇加2-5摩尔环氧乙烷或异十三烷基醇加3摩尔环氧乙烷酯化一次或两次的磺基丁二酸单或二碱金属盐,特别是磺基丁二酸单或二钠盐,a3)与一当量的胺或其烷基部分例如具有1-22个碳原子的醇、胺、脂肪酸、酯或酰胺的氨基封端(聚)环氧烷加成物反应且随后经磺化的马来酸酐的二碱金属盐,优选二钠盐,(聚)环氧烷部分含1-200个、优选2-200个环氧烷单元,优选与一当量的椰油脂肪胺反应且随后经磺化的马来酸酐的二钠盐,a4)与一当量的酰胺或酰胺的(聚)环氧烷加成物反应且随后经磺化的马来酸酐的二碱金属盐,优选二钠盐,该酰胺的烷基例如含1-22个碳原子、(聚)环氧烷部分含1-200个、优选2-200个环氧烷单元,优选与一当量的油基酰胺加2摩尔环氧乙烷反应且随后经磺化的马来酸酐的二钠盐,和/或a5)N-(1,2-二羧基乙基-)-N-十八烷基磺基-丁二酸四碱金属盐,优选四钠盐。
商购可得的且在本发明范围内优选的组a1)至a5)的磺基丁二酸酯(盐)的实例如下所示a1)二烷基磺基丁二酸钠,例如二-(C4-C18)烷基磺基丁二酸钠,例如二异辛基磺基丁二酸钠,优选二-(2-乙基己基)磺基丁二酸钠,例如以Aerosol-商标(Cytec),Agrilan-或Lankropol-商标(AkzoNobel),Empimin-商标(Albright&Wilson),Cropol-商标(Croda),Lutensit-商标(BASF),Triton-商标(Union Carbide),Geropon-商标(Rhodia)或Imbirol,Madeol-或Polirol-商标(Cesalpinia)的形式商购可得,a2)醇聚乙二醇醚磺基丁二酸钠,例如以GeroponACR商标(Rhodia)的形式商购可得,a3)醇聚乙二醇醚半磺基丁二酸二钠,例如以Aerosol-商标(Cytec),Marlinat-或Sermul-商标(Condea),Empicol-商标(Albright&Wilson),Secosol-商标(Stepan),Geropon-商标(Rhodia),Disponil-或Texapon-商标(Cognis)或Rolpon-商标(Cesalpinia)的形式商购可得,a4)N-烷基磺基丁二酸二钠,例如以Aerosol-商标(Cytec),Rewopol-或Rewoderm-商标(Rewo),Empimin-商标(Albright&Wilson),Geropon-商标(Rhodia)或Polirol-商标(Cesalpinia)商购可得,a5)脂肪酸酰胺聚乙二醇醚半磺基丁二酸二钠,例如以Elfanol-或Lankropol-商标(Akzo Nobel),Rewoderm-、Rewocid-或Rewopol-商标(Rewo),Emcol-商标(Witco),Standapol-商标(Cognis)或Rolpon-商标(Cesalpinia)商购可得,和a6)N-(1,2-二羧基乙基)-N-十八烷基磺基丁二酸四钠,例如以Aerosol 22-(Cytec)形式商购可得。
磺基丁二酸盐例如以Aerosol-(Cytec)、Agrilan-或Lankropol-(Akzo Nobel)、Empimin-(Huntsman)、Cropol-(Croda)、Lutensit-(BASF)、TritonGR-系列(UnionCarbide)、Imbirol-/Madeol-/Polirol-(Cesalpinia);GeroponAR-系列或GeroponSDS(Rhodia)商购可得。
优选的磺基丁二酸盐为,例如二(烷基)磺基丁二酸的钠、钾和铵盐,其中烷基可以相同或不同,并且包含4至16个碳原子,并且优选丁基、己基、辛基如2-乙基己基,或癸基,它们可以是直链或分支的。
本发明除草组合物中的磺基丁二酸酯(盐)或多种磺基丁二酸酯(盐)的总比例通常介于0和60重量%之间,优选范围为0.5至30重量%。
对于本发明除草组合物而言,任选包含的不同于(A)和(B)的农业化学活性物质(E)为例如已知活性物质如除草剂、杀虫剂或杀真菌剂,例如描述于Weed Research(杂草研究)26,441-445(1986),或“The Pesticide Manual(农药手册)”,第12版,The British CropProtection Council,2000,及其所引用的文献,例如以混合制剂或用于桶混的组分形式。作为文献已知的除草剂可以包含于本发明的除草组合物中的有例如下列活性物质。所述化合物以国际标准化组织(ISO)的“通用名”或化学名称来表示,视需要与常用编码一起表示,并且总是包括所有可能的使用形式,例如酸、盐、酯和异构体如立体异构体和光学异构体乙草胺(acetochlor)、三氟羧草醚(acifluorfen)、苯草醚(aclonifen)、AKH 7088,即[[[1-[5-[2-氯-4-(三氟甲基)-苯氧基]-2-硝基苯基]-2-甲氧基亚乙基]-氨基]-氧基]-乙酸及其甲酯、甲草胺(alachlor)、禾草灭(alloxydim)、莠灭净(ametryn)、酰嘧磺隆(amidosulfuron)、杀草强(amitrol)、AMS(即氨基磺酸铵)、莎稗磷(anilofos)、磺草灵(asulam)、莠去津(atrazin)、唑啶草酮(azafenidine)(DPX-R6447)、四唑嘧磺隆(azimsulfurone)(DPX-A8947)、叠氮津(aziprotryn)、燕麦灵(barban)、BAS 516H(即5-氟-2-苯基-4H-3,1-苯并嗪-4-酮)、草除灵(bena zolin)、氟草胺(benfluralin)、呋草黄(benfuresate)、苄嘧磺隆(bensulfuron-methyl)、地散磷(bensulide)、灭草松(bentazone)、氟磺胺草(benzofluor)、新燕灵(benzoylprop-ethyl)、噻草隆(benzthiazuron)、双丙氨酰膦(bialaphos)、治草醚(bifenox)、双嘧苯甲酸(bispyribac-sodium)(KIH-2023)、除草定(bromacil)、溴丁酰草胺(bromobutide)、杀草全(bromofenoxim)、溴苯腈(bromoxynil),尤其是溴苯腈-辛醇酯和溴苯腈-庚醇酯,丁草胺(butachlor)、特克草(butamifos)、丁草胺(butenachlor)、草噻咪(buthidazole)、地乐胺(butralin)、丁苯草酮(butroxydim)(ICI-0500)、苏达灭(butylate)、唑酰草胺(cafenstrole)(CH-900)、双酰草胺(carbetamide)、唑酮草酯(cafentrazone)、CDAA(即2-氯-N,N-二-2-丙烯基乙酰胺)、CDEC(即2-氯烯丙基二乙基二硫代氨基甲酸酯)、氯硝醚(chlomethoxyfen)、草灭平(chloramben)、cloransulam-methyl(XDE-565)、炔禾灵丁酯(chlorazifop-butyl)、氯溴隆(chlorbromuron)、氯草灵(chlorbufam)、伐草克(chlorfenac)、氯甲丹(chlorflurenol-methyl)、杀草敏(chloridazon)、氯嘧黄隆(chlorimuron ethyl)、草枯醚(chlornitrofen)、绿麦隆(chlorotoluron)、枯草隆(chloroxuron)、氯苯胺灵(chlorpropham)、敌草索二甲酯(chlorthal-dimethyl)、草克乐(chlorthiamid)、吲哚酮草酯(cinidon-ethyl)、环庚草醚(cinmethylin)、醚黄隆(cinosulfuron)、烯草酮(clethodim)、炔草酯(clodinafop)及其酯衍生物(例如炔草丙酯)、异草松(clomazone)、稗草胺(clomeprop)、环己烯草酮(cloproxydim)、二氯吡啶酸(clopyralid)、cumyluron(JC 940)、草净津(cyanazine)、草灭特(cycloate)、环丙黄隆(cyclosulfamuron)(AC 014)、噻草酮(cycloxydim)、环莠隆(cycluron)、氰氟草酯(cyhalofop)及其酯衍生物(例如丁酯,DEH-112)、莎草快(cyperquat)、环草津(cyprazine)、环唑草胺(cyprazole)、2,4-D、2,4-DB、茅草枯(dalapon)、甜菜安(desmedipham)、敌草净(desmetryn)、燕麦敌(di-allate)、麦草畏(dicamba)、敌草腈(dichlobenil)、2,4-滴丙酸(dichlorprop)、禾草灵(diclofop)及其酯类(如禾草灵甲酯)、双氯磺草胺(diclosulam)(XDE-564)、乙酰甲草胺(diethatyl)、枯莠隆(difenoxuron)、野燕枯(difenzoquat)、吡氟酰草胺(diflufenican)、氟吡草腙(diflufenzopyr-sodium)(SAN-835H)、唑隆(dimefuron)、二甲草胺(dimethachlor)、异戊乙净(dimethametryn)、噻吩草胺(dimethenamid)(SAN-582H)、dimidazone、5-(4,6-二甲基嘧啶-2-基-氨基甲酰基氨磺酰基)-1-(2-吡啶基)-吡唑-4-羧酸甲酯(NC-330)、三嗪氟草胺(triaziflam)(IDH-1105)、cinosulfon、噻节因(dimethipin)、敌乐胺(dinitramine)、地乐酚(dinoseb)、特乐酚(dinoterb)、双甲酰草胺(diphenamid)、异丙净(dipropetryn)、草乃敌(diquat)、氟硫草定(dithiopyr)、敌草隆(diuron)、DNOC、草止津(eglinazine-ethyl)、EL 177(即5-氰基-1-(1,1-二甲基乙基)-N-甲基-1H-吡唑-4-羧酰胺)、草藻灭(endothal)、茚草酮(indanofan)(MK-243)、EPTC、禾草畏(esprocarb)、丁氟消草(ethalfluralin)、胺苯黄隆(ethametsulfuron-methyl)、噻二唑隆(ethidimuron)、嗪丁草(ethiozin)、乙呋草黄(ethofumesate)、F5231(即N-[2-氯-4-氟-5-[4-(3-氟丙基)-4,5-二氢-5-氧代-1H-四唑-1-基]-苯基]-乙基磺酰胺、氯氟草醚(ethoxyfen)及其酯(例如乙酯,HN-252)、乙氧嘧磺隆(ethoxysulfuron)(来自EP 342569)、乙氧苯草胺(etobenzanid(HW52))、3-(4-乙氧基-6-乙基-1,3,5-三嗪-2-基)-1-(2,3-二氢-1,1-二氧代-2-甲基苯并[b]噻吩-7-磺酰基)脲(EP-A 079 683)、3-(4-乙基-6-甲氧基-1,3,5-三嗪-2-基)-1-(2,3-二氢-1,1-二氧代-2-甲基苯并[b]噻吩-7-磺酰基)脲(EP-A 079 683)、2,4,5-涕丙酸(fenoprop)、异草松(clomazone)、唑禾草灵(fenoxaprop)及精唑禾草灵及其酯(例如精唑禾草灵乙酯和唑禾草灵乙酯)、丁苯草酮(butroxydim)、非草隆(fenuron)、氟燕灵(flamprop-methyl)、啶嘧黄隆(flazasulfuron)、氟噻草胺(flufenacet)(BAY-FOE-5043)、吡氟禾草灵(fluazifop)和精吡氟禾草灵及其酯类(例如吡氟禾草灵丁酯和精吡氟禾草灵丁酯)、双氟磺草胺(florasulam)(DE-570)、氯乙氟灵(fluchloralin)、氟唑啶草(flumetsulam)、fluometuron、酰亚胺苯氧乙酸(flumiclorac)及其酯类(例如戊酯,S-23031)、丙炔氟草胺(flumioxazin)(S-482)、flumipropyn、氟胺草唑(flupoxam)(KNW-739)、三氟硝草醚(fluorodifen)、乙羧氟草醚(fluoroglycofen(-ethyl))、flupropacil(UBIC-4243)、氟啶嘧磺隆钠盐(sodium flupyrsulfuron-methyl)(DPX-KE459)、氟草酮(fluridone)、氟咯草酮(flurochloridone)、氯氟吡氧乙酸(fluroxypyr)、呋草酮(flurtamone)、达草氟(fluthiacet-methyl)(KIH-9201)、氟黄胺草醚(fomesafen)、膦铵素(fosamine)、呋氧草醚(furyloxyfen)、草铵膦(glufosinate)、草甘膦(glyphosate)、氟硝磺酰胺(halosafen)、吡氯黄隆(halosulfuron)及其酯(例如甲酯,NC-319)、吡氟氯禾灵(haloxyfop)及其酯、精吡氟氯禾灵(即R-吡氟氯禾灵)及其酯、环嗪酮(hexazinone)、咪草酸甲酯(imazamethabenz-methyl)、甲氧咪草烟(imazamox)(AC-299263)、咪唑盐酸(imazapyr)、咪唑喹啉酸(imazaquin)及盐类如铵盐、imazapic、咪唑乙烟酸(imazethapyr)、咪唑磺隆(imazosulfuron)、碘甲磺隆钠盐(iodosulfuron-methyl-sodium)(4-碘代-2-[3-(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)脲基磺酰基]-苯甲酸甲酯,其钠盐,WO 92/13845)、碘苯腈(ioxynil)、丁环隆(isocarbamid)、异乐灵(isopropalin)、异丙隆(isoproturon)、异隆(isouron)、异酰草胺(isoxaben)、异草醚(isoxapyrifop)、特胺灵(karbutilate)、乳氟禾草灵(lactofen)、环草定(lenacil)、利谷隆(linuron)、2甲4氯(MCPA)、2甲4氯丁酸(MCPB)、2甲4氯丙酸(mecoprop)、苯噻草胺(mefenacet)、氟草磺(mefluidid)、苯嗪草酮(metamitron)、吡唑草胺(metazachlor)、甲基苯噻隆(methabenzthiazuron)、噻唑隆(metam)、灭草唑(methazole)、去草酮(methoxyphenone)、甲基杀草隆(methyldymron)、吡喃隆(metobenzuron)、甲磺胺磺隆(mesosulfuron-methyl)(WO 95/10507)、溴谷隆(metobromuron)、异丙甲草胺(metolachlor)、异丙甲草胺(S-metolachlor)、唑草磺胺(metosulam)(XRD 511)、甲氧隆(metoxuron)、嗪草酮(metribuzin)、抑芽丹(maleic hydrazide)、禾草敌(molinate)、杀草利(monalide)、单脲硫酸二氢酯(monocarbamide dihydrogensulfate)、绿谷隆(monolinuron)、灭草隆(monuron)、MT 128(即6-氯-N-(3-氯-2-丙烯基)-5-甲基-N-苯基-3-哒嗪胺)、MT 5950(即N-[3-氯代-4-(1-甲基乙基)-苯基]-2-甲基戊酰胺)、甲酰氨磺隆(foramsulfuron)(WO 95/01344)、萘丙胺(naproanilide)、敌草胺(napropamide)、萘草胺(naptalam)、NC 310(即4-(2,4-二氯苯甲酰基)-1-甲基-5-苄氧基吡唑)、草不隆(neburon)、烟嘧黄隆(nicosulfuron)、氟氯草胺(nipyraclofen)、磺乐灵(nitralin)、除草醚(nitrofen)、硝氟草醚(nitrofluorfen)、达草灭(norflurazon)、坪草丹(orbencarb)、氨磺乐灵(oryzalin)、丙炔草酮(oxadiargyl)(RP-020630)、草酮(oxadiazon)、嗪草酮(oxaziclomefone)(MY-100)、乙氧氟草醚(oxyfluorfen)、环氧嘧磺隆(oxasulfuron)(CGA-277476)、百草枯(paraquat)、克草猛(pebulate)、二甲戊灵(pendimethalin)、环戊草酮(pentoxazone)(KPP-314)、氟草磺胺(perfluidone)、棉胺宁(phenisopham)、苯敌草(phenmedipham)、氨氯吡啶酸(picloram)、派草磷(piperophos)、稗草畏(pyributicarb)、pirifenop-butyl、丙草胺(pretilachlor)、氟嘧黄隆(primisulfuron-methyl)、环氰津(procyazine)、氨基丙氟灵(prodiamine)、环丙氟灵(profluralin)、甘扑津(proglinazine-ethyl)、扑灭通(prometon)、扑草净(prometryn)、毒草安(propachlor)、敌稗(propanil)、草酸(propaquizafop)及其酯、扑草津(propazine)、苯胺灵(propham)、异丙草胺(propisochlor)、嘧草醚propoxycarbazone-sodium、炔苯酰草胺(propyzamide)、磺亚胺草(prosulfalin)、苄草丹(prosulfocarb)、氟磺隆(prosulfuron)(CGA-152005)、丙炔草胺(prynachlor)、氟唑草酯(pyraflufen-ethyl)(ET-751)、氯草敏(chloridazon)、吡嘧黄隆(pyrazosulfuron-ethyl)、苄草唑(pyrazoxyfen)、嘧啶肟草醚(pyribenzoxim)、哒草特(pyridate)、嘧草醚(pyriminobac-methyl)(KIH-6127)、嘧草硫醚(pyrithiobac)(KIH-2031)、pyroxofop及其酯(例如炔丙酯)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、喹禾灵(quizalofop)和精喹禾灵及其酯衍生物例如喹禾灵乙酯、精喹禾灵四氢糠基酯和精喹禾灵乙酯、砜嘧黄隆(rimsulfuron)(DPX-E 9636)、S 275(即2-[4-氯-2-氟-5-(2-丙炔基氧基)-苯基]-4,5,6,7-四氢-2H-吲唑)、仲丁通(secbumeton)、烯禾啶(sethoxydim)、环草隆(siduron)、西玛津(simazine)、西草净(simetryn)、SN 106279(即2-[[7-[2-氯-4-(三氟-甲基)-苯氧基]-2-萘基]-氧基]-丙酸及其甲酯)、磺胺草唑(sulfentrazone)(FMC-97285,F-6285)、sulfazuron、嘧黄隆(sulfometuron-methyl)、草硫磷(glyphosate-trimesium)(ICI-A0224)、磺酰磺隆(sulfosulfuron)(MON-37500)、TCA、牧草胺(tebutam)(GCP-5544)、丁噻隆(tebuthiuron)、tepraloxydim(BAS-620H)、特草定(terbacil)、特草灵(terbucarb)、仲丁草胺(terbuchlor)、特丁通(terbumeton)、特丁津(terbuthylazine)、去草净(terbutryn)、TFH 450(即N,N-二乙基-3-[(2-乙基-6-甲基苯基)-磺酰基]-1H-1,2,4-三唑-1-羧酰胺)、噻醚草胺(thenylchlor)(NSK-850)、噻氟隆(thiazafluron)、噻唑烟酸(thiazopyr)(Mon-13200)、噻二唑草胺(thidiazimin)(SN-124085)、杀草丹(thiobencarb)、仲草丹(tiocarbazil)、三甲苯草酮(tralkoxydim)、野麦畏(tri-allate)、醚苯黄隆(triasulfuron)、triazofenamide、三氯吡氧乙酸(triclopyr)、灭草环(tridiphane)、草达津(trietazine)、氟乐灵(trifluralin)、氟胺黄隆(triflusulfuron)及酯(例如甲酯,DPX-66037)、三甲隆(trimeturon)、tsitodef、灭敌草(vernolate)、WL 110547(即5-苯氧基-1-[3-(三氟甲基)-苯基]-1H-四唑、UBH-509、D-489、LS 82-556、KPP-300、KPP-421、MT-146、NC-324、丁烯草胺(butenachlor)(KH-218)、DPX-N8189、氟吡禾灵(haloxyfop-etotyl)(DOWCO-535)、DK-8910、丙炔氟草胺(flumioxazin)(V-53482)、PP-600、MBH-001,氨唑草酮(amicarbazone)、aminopyralid、氟丁酰草胺(beflubutamid)、benzobicyclon、吡草酮(benzofenap)、双苯嘧草酮(benzfendizone)、butafenacil、燕麦酯(chlorfenprop)、调果酸(cloprop)、杀草隆(daimuron)、精2,4-滴丙酸(dichlorprop-P)、dimepipeate、精噻吩草胺(dimethenamid-P)、四唑酰草胺(fentrazamide)、强氟燕灵(flamprop-M)、fluazolate、flucarbazone、flucetosulfuron、甲酰氨磺隆(foramsulfuron)、茚草酮(indanofan)、异氯草酮(isoxachlortole)、异唑草酮(isoxaflutole)、2甲4氯-硫代乙酯(MCPA-thioethyl)、精2甲4氯丙酸(mecoprop-P)、甲磺胺磺隆(mesosulfuron)、mesotrione、metamifop、orthosulfamuron(IR-5878)、penoxsulam、pethoxamid、picolinafen、pinoxaden、氟唑草胺(profluazol)、profoxydim、propoxycarbazone、双唑草腈(pyraclonil)、吡唑特(pyrazolynate)、pyridafol、环酯草醚(pyriftalid)、pyrimisulfan、磺草酮(sulcotrione)、噻苯隆(thidiazuron)、topramezone、三氟啶磺隆(trifloxysulfuron)、三氟甲磺隆(tritosulfuron)。
混合组分E)、磺酰脲A)和安全剂B)可以一起施用(作为成品配制剂或桶混物)或以任何顺序先后施用。
优选的混合组分E)为以其所有使用形式的溴苯腈(E1),包括盐和酯,例如溴苯腈-辛酸酯(E1.1)、溴苯腈-庚酸酯(E1.2)、溴苯腈-丁酸酯(E1.3)、溴苯腈-钠盐(E1.4)和溴苯腈-钾盐(E1.5);以其所有使用形式的2,4-D(E2),包括盐和酯,例如2,4-D-Butotyl(E2.1)、2,4-D-丁酯(E2.2)、2,4-D-二甲基铵盐(E2.3)、2,4-D-二乙醇胺(E2.4)、2,4-D-2-乙基己酯(E2.5)、2,4-D-异辛酯(E2.6)、2,4-D-异丙酯(E2.7)、2,4-D-钠盐(E2.8)和2,4-D-三乙醇胺(E2.9);以其所有使用形式的麦草畏(E3),包括盐和酯,例如麦草畏-钠盐(E3.1)、麦草畏-钾盐(E3.2)和麦草畏-二甲基铵盐(E3.3);以其所有使用形式的唑禾草灵(E4),包括酯,例如唑禾草灵-乙酯(E4.1)和精唑禾草灵-乙酯(E4.2);以其所有使用形式的氯氟吡氧乙酸(E5),包括盐和酯,例如氟草烟(E5.1)和氯氟吡氧乙酸-2-丁氧基-1-甲基乙基(E5.2);以其所有使用形式的2甲4氯(E6),包括盐和酯,例如2甲4氯-钠盐(E6.1),2甲4氯-钾盐(E6.2),2甲4氯-2-乙基己酯(E6.3),2甲4氯-butotyl(E6.4)和2甲4氯-二甲基铵盐(E6.5);以其所有使用形式的碘磺隆(E7),包括盐和酯,例如碘磺隆-甲酯(E7.1)和碘磺隆-甲基-钠盐(E7.2);以其所有使用形式的甲磺胺磺隆(E8),包括盐和酯,例如甲磺胺磺隆-甲酯(E8.1)和甲磺胺磺隆-甲基-钠盐(E8.2);以其所有使用形式的丙氧基缩二氨基脲(E9),包括盐和酯,例如丙氧基缩二氨基脲-钠盐(E9.1)。
本发明优选的组合(A)、(B)、(E)为,例如(E1)+(A1.1)+(B1),(E1)+(A1.1)+(B2),(E1)+(A1.1)+(B3),(E1)+A2.1)+(B1),(E1)+(A2.1)+(B2),(E1)+(A2.1)+(B3),(E1)+(A3.1)+(B1),(E1)+(A3.1)+(B2),(E1)+(A3.1)+(B3),(E1)+(A4.1)+(B1),(E1)+(A4.1)+(B2),(E1)+A4.1)+(B3),(E1)+(A1.2)+(B1),(E1)+(A1.2)+(B2),(E1)+(A1.2)+(B3),(E1)+(A2.2)+(B1),(E1)+(A2.2)+(B2),(E1)+(A2.2)+(B3),(E1)+(A3.2)+(B1),(E1)+(A3.2)+(B2),(E1)+(A3.2)+(B3),(E1)+(A4.2)+(B1),(E1)+(A4.2)+(B2),(E1)+(A4.2)+(B3),(E1)+(A1.1)+(A1.2)+(B1),(E1)+(A1.1)+(A2.1)+(B1),(E1)+(A1.1)+(A2.2)+(B1),(E1)+(A1.1)+(A3.1)+(B1),(E1)+(A1.1)+(A3.2)+(B1),(E1)+(A1.1)+(A4.1)+(B1),(E1)+(A1.1)+(A4.2)+(B1);(E1)+(A1.2)+(A2.1)+(B1),(E1)+(A1.2)+(A2.2)+(B1),(E1)+(A1.2)+(A3.1)+(B1),(E1)+(A1.2)+(A3.2)+(B1),(E1)+(A1.2)+(A4.1)+(B1),(E1)+(A1.2)+(A4.2)+(B1);(E1)+(A2.1)+(A2.2)+(B1),(E1)+A2.1)+(A3.1)+(B1),(E1)+(A2.1)+(A3.2)+(B1),(E1)+(A2.1)+(A4.1)+(B1),(E1)+(A2.1)+(A4.2)+(B1);(E1)+(A2.2)+(A3.1)+(B1),(E1)+(A2.2)+(A3.2)+(B1),(E1)+(A2.2)+(A4.1)+(B1),(E1)+(A2.2)+(A4.2)+(B1);(E1)+(A3.1)+(A3.2)+(B1),(E1)+(A3.1)+(A4.1)+(B1),(E1)+(A3.1)+(A4.2)+(B1);(E1)+(A3.2)+(A4.1)+(B1),(E1)+(A3.2)+(A4.2)+(B1),(E1)+(A4.1)+(A4.2)+(B1);(E1)+(A1.1)+(A1.2)+(B2),(E1)+(A1.1)+(A2.1)+(B2),(E1)+(A1.1)+(A2.2)+(B2),(E1)+(A1.1)+(A3.1)+(B2),(E1)+(A1.1)+(A3.2)+(B2),(E1)+(A1.1)+(A4.1)+(B2),(E1)+(A1.1)+(A4.2)+(B2);(E1)+(A1.2)+(A2.1)+(B2),(E1)+(A1.2)+(A2.2)+(B2),(E1)+(A1.2)+(A3.1)+(B2),(E1)+(A1.2)+(A3.2)+(B2),(E1)+(A1.2)+(A4.1)+(B2),(E1)+(A1.2)+(A4.2)+(B2);(E1)+(A2.1)+(A2.2)+(B2),(E1)+(A2.1)+(A3.1)+(B2),(E1)+(A2.1)+(A3.2)+(B2),(E1)+(A2.1)+(A4.1)+(B2),(E1)+(A2.1)+(A4.2)+(B2);(E1)+(A2.2)+(A3.1)+(B2),(E1)+(A2.2)+(A3.2)+(B2),(E1)+(A2.2)+(A4.1)+(B2),(E1)+(A2.2)+(A4.2)+(B2);(E1)+(A3.1)+(A3.2)+(B2),(E1)+(A3.1)+(A4.1)+(B2),(E1)+(A3.1)+(A4.2)+(B2);(E1)+(A3.2)+(A4.1)+(B2),(E1)+(A3.2)+(A4.2)+(B2),(E1)+(A4.1)+(A4.2)+(B2);(E1)+(A1.1)+(A1.2)+(B3),(E1)+(A1.1)+(A2.1)+(B3),(E1)+(A1.1)+(A2.2)+(B3),(E1)+(A1.1)+(A3.1)+(B3),(E1)+(A1.1)+(A3.2)+(B3),(E1)+(A1.1)+(A4.1)+(B3),(E1)+(A1.1)+(A4.2)+(B3);(E1)+(A1.2)+(A2.1)+(B3),(E1)+(A1.2)+(A2.2)+(B3),(E1)+(A1.2)+(A3.1)+(B3),(E1)+(A1.2)+(A3.2)+(B3),(E1)+(A1.2)+(A4.1)+(B3),(E1)+(A1.2)+(A4.2)+(B3);(E1)+(A2.1)+(A2.2)+(B3),(E1)+(A2.1)+(A3.1)+(B3),(E1)+(A2.1)+(A3.2)+(B3),(E1)+(A2.1)+(A4.1)+(B3),(E1)+(A2.1)+(A4.2)+(B3);(E1)+(A2.2)+(A3.1)+(B3),(E1)+(A2.2)+(A3.2)+(B3),(E1)+(A2.2)+(A4.1)+(B3),(E1)+(A2.2)+(A4.2)+(B3);(E1)+(A3.1)+(A3.2)+(B3),(E1)+(A3.1)+(A4.1)+(B3),(E1)+(A3.1)+(A4.2)+(B3);(E1)+(A3.2)+(A4.1)+(B3),(E1)+(A3.2)+(A4.2)+(B3),(E1)+(A4.1)+(A4.2)+(B3);
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(E8.2)+(A2.2)+(A3.1)+(B1),(E8.2)+(A2.2)+(A3.2)+(B1),(E8.2)+(A2.2)+(A4.1)+(B1),(E8.2)+(A2.2)+(A4.2)+(B1);(E8.2)+(A3.1)+(A3.2)+(B1),(E8.2)+(A3.1)+(A4.1)+(B1),(E8.2)+(A3.1)+(A4.2)+(B1);(E8.2)+(A3.2)+(A4.1)+(B1),(E8.2)+(A3.2)+(A4.2)+(B1),(E8.2)+(4.1)+(A4.2)+(B1);(E8.2)+(A1.1)+(A1.2)+(B2),(E8.2)+(A1.1)+(A2.1)+(B2),(E8.2)+(A1.1)+(A2.2)+(B2),(E8.2)+(A1.1)+(A3.1)+(B2),(E8.2)+(A1.1)+(A3.2)+(B2),(E8.2)+(A1.1)+(A4.1)+(B2),(E8.2)+(A1.1)+(A4.2)+(B2);(E8.2)+(A1.2)+(A2.1)+(B2),(E8.2)+(A1.2)+(A2.2)+(B2),(E8.2)+(A1.2)+(A3.1)+(B2),(E8.2)+(A1.2)+(A3.2)+(B2),(E8.2)+(A1.2)+(A4.1)+(B2),(E8.2)+(A1.2)+(A4.2)+(B2);(E8.2)+(A2.1)+(A2.2)+(B2),(E8.2)+(A2.1)+(A3.1)+(B2),(E8.2)+(A2.1)+(A3.2)+(B2),(E8.2)+(A2.1)+(A4.1)+(B2),(E8.2)+(A2.1)+(A4.2)+(B2);(E8.2)+(A2.2)+(A3.1)+(B2),(E8.2)+(A2.2)+(A3.2)+(B2),(E8.2)+(A2.2)+(A4.1)+(B2),(E8.2)+(A2.2)+(A4.2)+(B2);(E8.2)+(A3.1)+(A3.2)+(B2),(E8.2)+(A3.1)+(A4.1)+(B2),(E8.2)+(A3.1)+(A4.2)+(B2);(E8.2)+(A3.2)+(A4.1)+(B2),(E8.2)+(A3.2)+(A4.2)+(B2),(E8.2)+(A4.1)+(A4.2)+(B2);(E8.2)+(A1.1)+(A1.2)+(B3),(E8.2)+(A1.1)+(A2.1)+(B3),(E8.2)+(A1.1)+(A2.2)+(B3),(E8.2)+(A1.1)+(A3.1)+(B3),(E8.2)+(A1.1)+(A3.2)+(B3),(E8.2)+(A1.1)+(A4.1)+(B3),(E8.2)+(A1.1)+(A4.2)+(B3);(E8.2)+(A1.2)+(A2.1)+(B3),(E8.2)+(A1.2)+(A2.2)+(B3),(E8.2)+(A1.2)+(A3.1)+(B3),(E8.2)+(A1.2)+(A3.2)+(B3),(E8.2)+(A1.2)+(A4.1)+(B3),(E8.2)+(A1.2)+(A4.2)+(B3);(E8.2)+(A2.1)+(A2.2)+(B3),(E8.2)+(A2.1)+(A3.1)+(B3),(E8.2)+(A2.1)+(A3.2)+(B3),(E8.2)+(A2.1)+(A4.1)+(B3),(E8.2)+(A2.1)+(A4.2)+(B3);(E8.2)+(A2.2)+(A3.1)+(B3),(E8.2)+(A2.2)+(A3.2)+(B3),(E8.2)+(A2.2)+(A4.1)+(B3),(E8.2)+(A2.2)+(A4.2)+(B3);(E8.2)+(A3.1)+(A3.2)+(B3),(E8.2)+(A3.1)+(A4.1)+(B3),(E8.2)+(A3.1)+(A4.2)+(B3);(E8.2)+(A3.2)+(A4.1)+(B3),(E8.2)+(A3.2)+(A4.2)+(B3),(E8.2)+(A4.1)+(A4.2)+(B3);(E9)+(A1.1)+(B1),(E9)+(A1.1)+(B2),(E9)+(A1.1)+(B3),(E9)+(A2.1)+(B1),(E9)+(A2.1)+(B2),(E9)+(A2.1)+(B3),(E9)+(A3.1)+(B1),(E9)+(A3.1)+(B2),(E9)+(A3.1)+(B3),(E9)+(A4.1)+(B1),(E9)+(A4.1)+(B2),(E9)+(A4.1)+(B3),(E9)+(A1.2)+(B1),(E9)+(A1.2)+(B2),(E9)+(A1.2)+(B3),(E9)+(A2.2)+(B1),(E9)+(A2.2)+(B2),(E9)+(A2.2)+(B3),(E9)+(A3.2)+(B1),(E9)+(A3.2)+(B2),(E9)+(A3.2)+(B3),(E9)+(A4.2)+(B1),(E9)+(A4.2)+(B2),(E9)+(A4.2)+(B3),(E9)+(A1.1)+(A1.2)+(B1),(E9)+(A1.1)+(A2.1)+(B1),(E9)+(A1.1)+(A2.2)+(B1),(E9)+(A1.1)+(A3.1)+(B1),(E9)+(A1.1)+(A3.2)+(B1),(E9)+(A1.1)+(A4.1)+(B1),(E9)+(A1.1)+(A4.2)+(B1);(E9)+(A1.2)+(A2.1)+(B1),(E9)+(A1.2)+(A2.2)+(B1),(E9)+(A1.2)+(A3.1)+(B1),(E9)+(A1.2)+(A3.2)+(B1),(E9)+(A1.2)+(A4.1)+(B1),(E9)+(A1.2)+(A4.2)+(B1);(E9)+(A2.1)+(A2.2)+(B1),(E9)+(A2.1)+(A3.1)+(B1),(E9)+(A2.1)+(A3.2)+(B1),(E9)+(A2.1)+(A4.1)+(B1),(E9)+(A2.1)+(A4.2)+(B1);(E9)+(A2.2)+(A3.1)+(B1),(E9)+(A2.2)+(A3.2)+(B1),(E9)+(A2.2)+(A4.1)+(B1),(E9)+(A2.2)+(A4.2)+(B1);(E9)+(A3.1)+(A3.2)+(B1),(E9)+(A3.1)+(A4.1)+(B1),(E9)+(A3.1)+(A4.2)+(B1);(E9)+(A3.2)+(A4.1)+(B1),(E9)+(A3.2)+(A4.2)+(B1),(E9)+(A4.1)+(A4.2)+(B1);(E9)+(A1.1)+(A1.2)+(B2),(E9)+(A1.1)+(A2.1)+(B2),(E9)+(A1.1)+(A2.2)+(B2),(E9)+(A1.1)+(A3.1)+(B2),(E9)+(A1.1)+(A3.2)+(B2),(E9)+(A1.1)+(A4.1)+(B2),(E9)+(A1.1)+(A4.2)+(B2);(E9)+(A1.2)+(A2.1)+(B2),(E9)+(A1.2)+(A2.2)+(B2),(E9)+(A1.2)+(A3.1)+(B2),(E9)+(A1.2)+(A3.2)+(B2),(E9)+(A1.2)+(A4.1)+(B2),(E9)+(A1.2)+(A4.2)+(B2);(E9)+(A2.1)+(A2.2)+(B2),(E9)+(A2.1)+(A3.1)+(B2),(E9)+(A2.1)+(A3.2)+(B2),(E9)+(A2.1)+(A4.1)+(B2),(E9)+(A2.1)+(A4.2)+(B2);(E9)+(A2.2)+(A3.1)+(B2),(E9)+(A2.2)+(A3.2)+(B2),(E9)+(A2.2)+(A4.1)+(B2),(E9)+(A2.2)+(A4.2)+(B2);(E9)+(A3.1)+(A3.2)+(B2),(E9)+(A3.1)+(A4.1)+(B2),(E9)+(A3.1)+(A4.2)+(B2);(E9)+(A3.2)+(A4.1)+(B2),(E9)+(A3.2)+(A4.2)+(B2),(E9)+(A4.1)+(A4.2)+(B2);(E9)+(A1.1)+(A1.2)+(B3),(E9)+(A1.1)+(A2.1)+(B3),(E9)+(A1.1)+(A2.2)+(B3),(E9)+(A1.1)+(A3.1)+(B3),(E9)+(A1.1)+(A3.2)+(B3),(E9)+(A1.1)+(A4.1)+(B3),(E9)+(A1.1)+(A4.2)+(B3);(E9)+(A1.2)+(A2.1)+(B3),(E9)+(A1.2)+(A2.2)+(B3),(E9)+(A1.2)+(A3.1)+(B3),(E9)+(A1.2)+(A3.2)+(B3),(E9)+(A1.2)+(A4.1)+(B3),(E9)+(A1.2)+(A4.2)+(B3);(E9)+(A2.1)+(A2.2)+(B3),(E9)+(A2.1)+(A3.1)+(B3),(E9)+(A2.1)+(A3.2)+(B3),(E9)+(A2.1)+(A4.1)+(B3),(E9)+(A2.1)+(A4.2)+(B3);(E9)+(A2.2)+(A3.1)+(B3),(E9)+(A2.2)+(A3.2)+(B3),(E9)+(A2.2)+(A4.1)+(B3),(E9)+(A2.2)+(A4.2)+(B3);(E9)+(A3.1)+(A3.2)+(B3),(E9)+(A3.1)+(A4.1)+(B3),(E9)+(A3.1)+(A4.2)+(B3);(E9)+(A3.2)+(A4.1)+(B3),(E9)+(A3.2)+(A4.2)+(B3),(E9)+(A4.1)+(A4.2)+(B3);(E9.1)+(A1.1)+(B1),(E9.1)+(A1.1)+(B2),(E9.1)+(A1.1)+(B3),(E9.1)+(A2.1)+(B1),(E9.1)+(A2.1)+(B2),(E9.1)+(A2.1)+(B3),(E9.1)+(A3.1)+(B1),(E9.1)+(A3.1)+(B2),(E9.1)+(A3.1)+(B3),(E9.1)+(A4.1)+(B1),(E9.1)+(A4.1)+(B2),(E9.1)+(A4.1)+(B3),(E9.1)+(A1.2)+(B1),(E9.1)+(A1.2)+(B2),(E9.1)+(A1.2)+(B3),(E9.1)+(A2.2)+(B1),(E9.1)+(A2.2)+(B2),(E9.1)+(A2.2)+(B3),(E9.1)+(A3.2)+(B1),(E9.1)+(A3.2)+(B2),(E9.1)+(A3.2)+(B3),(E9.1)+(A4.2)+(B1),(E9.1)+(A4.2)+(B2),(E9.1)+(A4.2)+(B3),(E9.1)+(A1.1)+(A1.2)+(B1),(E9.1)+(A1.1)+(A2.1)+(B1),(E9.1)+(A1.1)+(A2.2)+(B1),(E9.1)+(A1.1)+(A3.1)+(B1),(E9.1)+(A1.1)+(A3.2)+(B1),(E9.1)+(A1.1)+(A4.1)+(B1),(E9.1)+(A1.1)+(A4.2)+(B1);(E9.1)+(A1.2)+(A2.1)+(B1),(E9.1)+(A1.2)+(A2.2)+(B1),(E9.1)+(A1.2)+(A3.1)+(B1),(E9.1)+(A1.2)+(A3.2)+(B1),(E9.1)+(A1.2)+(A4.1)+(B1),(E9.1)+(A1.2)+(A4.2)+(B1);(E9.1)+(A2.1)+(A2.2)+(B1),(E9.1)+(A2.1)+(A3.1)+(B1),(E9.1)+(A2.1)+(A3.2)+(B1),(E9.1)+(A2.1)+(A4.1)+(B1),(E9.1)+(A2.1)+(A4.2)+(B1);(E9.1)+(A2.2)+(A3.1)+(B1),(E9.1)+(A2.2)+(A3.2)+(B1),(E9.1)+(A2.2)+(A4.1)+(B1),(E9.1)+(A2.2)+(A4.2)+(B1);(E9.1)+(A3.1)+(A3.2)+(B1),(E9.1)+(A3.1)+(A4.1)+(B1),(E9.1)+(A3.1)+(A4.2)+(B1);(E9.1)+(A3.2)+(A4.1)+(B1),(E9.1)+(A3.2)+(A4.2)+(B1),(E9.1)+(A4.1)+(A4.2)+(B1);
(E9.1)+(A1.1)+(A1.2)+(B2),(E9.1)+(A1.1)+(A2.1)+(B2),(E9.1)+(A1.1)+(A2.2)+(B2),(E9.1)+(A1.1)+(A3.1)+(B2),(E9.1)+(A1.1)+(A3.2)+(B2),(E9.1)+(A1.1)+(A4.1)+(B2),(E9.1)+(A1.1)+(A4.2)+(B2);(E9.1)+(A1.2)+(A2.1)+(B2),(E9.1)+(A1.2)+(A2.2)+(B2),(E9.1)+(A1.2)+(A3.1)+(B2),(E9.1)+(A1.2)+(A3.2)+(B2),(E9.1)+(A1.2)+(A4.1)+(B2),(E9.1)+(A1.2)+(A4.2)+(B2);(E9.1)+(A2.1)+(A2.2)+(B2),(E9.1)+(A2.1)+(A3.1)+(B2),(E9.1)+(A2.1)+(A3.2)+(B2),(E9.1)+(A2.1)+(A4.1)+(B2),(E9.1)+(A2.1)+(A4.2)+(B2);(E9.1)+(A2.2)+(A3.1)+(B2),(E9.1)+(A2.2)+(A3.2)+(B2),(E9.1)+(A2.2)+(A4.1)+(B2),(E9.1)+(A2.2)+(A4.2)+(B2);(E9.1)+(A3.1)+(A3.2)+(B2),(E9.1)+(A3.1)+(A4.1)+(B2),(E9.1)+(A3.1)+(A4.2)+(B2);(E9.1)+(A3.2)+(A4.1)+(B2),(E9.1)+(A3.2)+(A4.2)+(B2),(E9.1)+(A4.1)+(A4.2)+(B2);(E9.1)+(A1.1)+(A1.2)+(B3),(E9.1)+(A1.1)+(A2.1)+(B3),(E9.1)+(A1.1)+(A2.2)+(B3),(E9.1)+(A1.1)+(A3.1)+(B3),(E9.1)+(A1.1)+(A3.2)+(B3),(E9.1)+(A1.1)+(A4.1)+(B3),(E9.1)+(A1.1)+(A4.2)+(B3);(E9.1)+(A1.2)+(A2.1)+(B3),(E9.1)+(A1.2)+(A2.2)+(B3),(E9.1)+(A1.2)+(A3.1)+(B3),(E9.1)+(A1.2)+(A3.2)+(B3),(E9.1)+(A1.2)+(A4.1)+(B3),(E9.1)+(A1.2)+(A4.2)+(B3);(E9.1)+(A2.1)+(A2.2)+(B3),(E9.1)+(A2.1)+(A3.1)+(B3),(E9.1)+(A2.1)+(A3.2)+(B3),(E9.1)+(A2.1)+(A4.1)+(B3),(E9.1)+(A2.1)+(A4.2)+(B3);(E9.1)+(A2.2)+(A3.1)+(B3),(E9.1)+(A2.2)+(A3.2)+(B3),(E9.1)+(A2.2)+(A4.1)+(B3),(E9.1)+(A2.2)+(A4.2)+(B3);(E9.1)+(A3.1)+(A3.2)+(B3),(E9.1)+(A3.1)+(A4.1)+(B3),(E9.1)+(A3.1)+(A4.2)+(B3);(E9.1)+(A3.2)+(A4.1)+(B3),(E9.1)+(A3.2)+(A4.2)+(B3),(E9.1)+(A4.1)+(A4.2)+(B3).
上述所有的组合还可以包含更多农业化学活性物质(E),尤其是两种或三种活性物质(E),优选选自下组化合物(E1),(E1.1),(E1.2),(E1.3),(E1.4),(E1.5),(E2),(E2.1),(E2.2),(E2.3),(E2.4),(E2.5),(E2.6),(E2.7),(E2.8),(E2.9),(E3),(E3.1),(E3.2),(E3.3),(E4),(E4.1),(E4.2),(E5),(E5.1),(E5.2),(E6),(E6.1),(E6.2),(E6.3),(E6.4),(E6.5),(E7),(E7.1),(E7.2),(E8),(E8.1),(E8.2),(E9),(E9.1)。与两种或三种活性物质(E)的优选组合(A),(B),(E)包含作为组分(E)的(E1.1)+(E1.2),(E1.1)+(E1.2)+(E6.3),(E1.1)+(E1.2)+(E2.6)或(E5.1)+(E6.3)。特别优选的是,包含在上述组合中的组分(A)和(B)与组分(E),即与(E1.1)+(E1.2),(E1.1)+(E1.2)+(E6.3),(E1.1)+(E1.2)+(E2.6)或(E5.1)+(E6.3)相组合。
还可以包含在本发明除草组合物中用作常规助剂和添加剂(组分F)为例如表面活性剂,例如乳化剂和分散剂,增稠剂和触变剂,湿润剂、抗漂浮剂,粘合剂,渗透剂,防腐剂和防冻剂,抗氧化剂,增溶剂,填料,载体和着色剂,消泡剂,肥料,蒸发抑制剂以及影响pH和粘度的制剂。
适宜的乳化剂和分散剂为,例如非离子型乳化剂和分散剂,例如1)聚烷氧基化的,优选聚乙氧基化的饱和和不饱和脂肪醇类,●在烷基中具有8至24个碳原子的脂肪醇类,其源自相应的脂肪酸或源自石油化工产品,和●具有1至100,优选2至50个环氧乙烷单元(EO)的脂肪醇类,其自由羟基可以进行烷氧基化,●例如以GenapolX-和GenapolO-系列(Clariant),CrovolM-系列(Croda)或以Lutensol-系列(BASF)商购可得的,2)聚烷氧基化的,优选聚乙氧基化的芳基烷基酚类,例如,平均乙氧基化度介于10和80之间,优选16至40的2,4,6-三-(1-苯基乙基)酚(三苯乙烯基酚),例如SoprophorBSU(Rhodia)或HOE S 3474(Clariant),
3)聚烷氧基化的,优选聚乙氧基化的烷基酚类,其具有一个或多个烷基,例如壬基酚或三-仲-丁基酚,且乙氧化度介于2和40之间,优选4至15,例如ArkopalN-系列或SapogenatT-系列(Clariant),4)聚烷氧基化的,优选聚乙氧基化的羟基脂肪酸或含有羟基脂肪酸的甘油酯类,例如蓖麻碱或蓖麻油,其乙氧化度介于10和80之间,优选25至40,例如EmulsogenEL-系列(Clariant)或AgniqueCSO-系列(Cognis),5)聚烷氧基化的,优选聚乙氧基化的脱水山梨糖醇酯,例如Atplus309F(Uniqema)或Alkamuls-系列(Rhodia),6)二和三嵌段共聚物,例如由环氧烷如环氧乙烷和环氧丙烷构成,其平均摩尔量介于200和10000之间,优选1000至4000g/mol,其聚乙氧基化嵌段的质量比例在10和80%之间变化,例如GenapolPF-系列(Clariant),Pluronic-系列(BASF),或SynperonicPE-系列(Uniqema)。
优选的非离子型乳化剂和分散剂为例如含有羟基脂肪酸的聚乙氧基化醇类,聚乙氧基化甘油三酯类和环氧乙烷-环氧丙烷嵌段共聚物。
本发明除草组合物中的非离子型乳化剂和分散剂的总比例通常介于0和20重量%之间。若非离子型乳化剂和分散剂除其乳化/分散性能外,还用于增强生物效力,例如作为渗透剂或粘合剂,则其在本发明除草组合物中的比例可以增至高达60重量%。
也考虑的离子型乳化剂和分散剂,例如1)聚烷氧基化的,优选聚乙氧基化的乳化剂/分散剂(参见组分e),其是离子改性的,例如通过将聚环氧乙烷嵌段的末端自由羟基官能团转化成硫酸酯或磷酸酯(例如作为碱金属和碱土金属盐),例如GenapolLRO或分散剂3618(Clariant),Emulphor(BASF)或CrafolAP(Cognis),2)具有直链或分支的烷基链的烷基芳基磺酸的碱金属和碱土金属盐,例如苯基磺酸盐CA或苯基磺酸盐CAL(Clariant),Atlox3377BM(ICI),或EmpiphosTM-系列(Huntsman),
3)聚电解质,例如木素磺酸盐、萘磺酸盐和甲醛的缩合物、聚苯乙烯磺酸盐或磺化不饱和或芳族聚合物(聚苯乙烯、聚丁二烯或聚萜烯),例如Tamol-系列(BASF)、MorwetD425(Witco)、Kraftsperse-系列(Westvaco)或Borresperse-系列(Borregard)。
优选的离子型乳化剂/分散剂为例如烷基芳基磺酸盐和由萘磺酸盐和甲醛聚缩构成的聚电解质。
本发明除草组合物中的离子型乳化剂和分散剂的总比例通常介于0和20重量%之间,优选介于0和8重量%之间。
作为增稠剂和触变剂例如考虑1)改性的天然硅酸盐,例如化学改性的膨润土、锂蒙脱石、硅镁土、蒙脱土、蒙脱石或其它的硅酸盐矿物,例如Bentone(Elementis),Attagel(Engelhard),Agsorb(Oil-Dri Corporation)或Hectorite(Akzo Nobel),2)合成硅酸盐,例如Sipernat,Aerosil-或Durosil-系列(Degussa),CAB-O-SIL-系列(Cabot)或Van Gel-系列(R.T.Vanderbilt)的硅酸盐,3)基于合成聚合物的增稠剂,例如Thixin-或Thixatrol-系列(Elementis)的增稠剂,4)基于天然聚合物和天然油的增稠剂,例如源于Thixin-或Thixatrol-系列(Elementis)。
优选的增稠剂和触变剂为,例如改性的层状硅酸盐和基于合成聚合物的增稠剂。
本发明除草组合物中的增稠剂和触变剂的比例通常介于0和5重量%之间,优选介于0.2和3重量%之间。
本发明的除草活性组合物或磺酰脲/安全剂组合可以通过已知的常规方法制得,例如借助搅拌器、摇动器、研磨机或(静态)混合机将不同组分进行混合。在此,为了达到完全溶解所包含的所有组分,任选地短时间加热混合物是有利的。
优选的本发明除草活性组合物包含
A)0.1至30重量%的一种或多种选自下组的磺酰脲类(A1.1),(A1.2),(A1.3),(A1.4),(A2.1),(A2.2),(A2.3),A2.4),(A3.1),(A3.2),(A3.3),(A3.4),(A4.1),(A4.2),优选选自下组的磺酰脲类(A1.1),(A2.1),(A3.1),(A4.1),B)2至40重量%的一种或多种选自下组的安全剂(B1),(B2),(B3),(B4),(B5),(B6),(B7),(B8),(B9),优选选自下组(B1),(B2),(B3),(B8),尤其优选(B1),(B2),(B3),尤其特别优选(B1),(B2),特别是(B1),C)20至80重量%的一种或多种溶剂,优选选自脂肪烃类,芳烃和脂肪烃的混合物,以及植物油,例如菜籽油甲酯,D)0.5至30重量%的一种或多种磺基丁二酸盐类,优选选自二(C4-C18)烷基磺基丁二酸碱金属盐类,例如二(C4-C18)烷基磺基丁二酸钠盐,E)1至20重量%的一种或多种不同于A)和B)的农业化学活性物质,F)0至40重量%的常规助剂和添加剂,优选0至20重量%的一种或多种非离子型乳化剂和分散剂,0至8重量%的一种或多种离子型乳化剂和分散剂,以及0至3重量%的一种或多种增稠剂和触变剂。
本发明还提供一种方法,其特征在于,本发明除草活性组合物的组分(A)和(B)一并或分别施用至有害植物、作物、植物种子或植物生长区域,视需要与其它组分例如一并或分别与组分(C)、(D)、(E)和(F)联合。其中一种或多种组(B)的安全剂(优选以解毒有效量存在)可以在磺酰脲类(A)之前、之后或同时施用至植物、植物种子或植物生长区域。
本发明的除草活性组合物也可用于控制已知或仍在开发中的基因工程改良植物中的有害植物。通常转基因植物以特别有利的特性而著称,例如对于特定植物保护剂的耐受性、对于植物疾病或植物疾病病原物如特定的昆虫或微生物如真菌、细菌或病毒的抵抗力。其它特别的特性涉及例如收成物的量、品质、储藏期、组成和特定内容物。因此转基因植物以具有提高的淀粉含量或改良淀粉品质,或收成物具有不同的脂肪酸组成而被人们所认知。
本发明组合优选在经济重要性的有用植物和观赏植物的转基因作物中应用,例如谷物(如小麦、大麦、黑麦、燕麦)、小米、水稻、木薯和玉米或还有作物甜菜、棉花、大豆、油菜、马铃薯、西红柿、豌豆和其它蔬菜种类。
当将本发明的组合用于转基因作物时,除了在其它作物中观察到的针对有害植物的效果外,还常常观察到对于在所述各种转基因作物中施用的特定效果,例如改良的或特别扩展的可控制杂草谱,可用于施用的改善的施用量,优选与转基因作物对其有抗性的除草剂的良好结合性,以及对转基因作物的生长和产量的影响。
因此本发明还涉及将本发明的除草活性组合物用于控制在转基因作物或通过选择育种而耐受的作物中有害植物的用途。
视其生物和/或化学物理参数而定,组(B)的安全剂和磺酰脲(A)可以视需要与其它组分例如组分(C)、(D)、(E)和(F)以各种方式联合一起或分别进行配制。作为配制可能性考虑可湿性粉剂(WP)、乳油(EC)、水溶性粉剂(SP)、水溶性浓缩物(SL)、浓缩性乳液(BW)例如水包油和油包水乳液、可喷洒溶液或乳液,胶囊悬浮剂(CS)、油或水基分散液(SC)、悬乳液、悬浮剂、粉剂(DP)、油溶混性溶液(OL)、拌种剂、以微粒、喷洒颗粒、涂覆颗粒和吸附性颗粒形式的粒剂(GR)、土壤施用或播散粒剂、水溶性粒剂(SG)、水分散性粒剂(WG)、ULV-制剂、微型胶囊类和蜡类。
上述各种制剂类型基本上是已知的,并例如在Winnacker-Küchler,“Chemische Technologie[化学技术]”,第7册,C.HauserVerlag München,第四版,1986;Wade van Valkenburg,“PesticideFormulations(农药制剂)”,Marcel Dekker N.Y.,1973;K.Martens,“Spray Drying Handbook(喷雾干燥手册)”,第三版,1979,G.GoodwinLtd.London中有描述。
所需配制助剂,例如惰性材料、表面活性剂、溶剂和其它添加剂同样是已知的并例如在“Handbook of Insecticide Dust Diluentsand Carrier(杀虫粉尘稀释液和载体手册)”,第二版,Darland Books,Caldwell N.J.;H.v.Olphen,“Introduction to Clay ColloidChemistry(粘土胶体化学入门)”,第二版,J.Wiley & Sons,N.Y.;C.Marsden,“Solvents Guide(溶剂指南)”,第二版,Interscience,N.Y.1963;McCutcheon′s,“Detergents and Emulsifiers Annual”,MC Publ.Corp.,Ridgewood N.J.;Sisley and Wood,“Encyclopediaof Surface Active Agents(表面活性剂百科全书)”,Chem.Publ.Co.Inc.,N.Y.1964;Schnfeldt,“Grenzflchenaktivethylenoxidaddukte[表面活性的环氧乙烷加成物]”,WissVerlagsgesell.,Stuttgart 1976;Winnacker-küchler,“ChemischeTechnologie”,第7册,C.Hauser Verlag München,第四版,1986中有描述。
以这些配制剂为基础,还可以制备具有其它农业化学活性物质,例如作为植物保护剂有效的物质如杀昆虫剂、杀螨剂、除草剂、杀真菌剂,或具有安全剂、肥料和/或生长调节剂的组合物,例如以成品配制或桶混的形式。
可湿性粉剂是均匀分散在水中的制剂,其除了活性物质,以及稀释剂或惰性物质外,还含有离子型或非离子型表面活性剂(润湿剂、分散剂),例如聚乙氧基化的烷基酚类、聚乙氧基化的脂肪醇类、聚乙氧基化的脂肪胺类、脂肪醇聚乙二醇醚硫酸酯、烷磺酸酯类、烷基苯磺酸酯类、木质素磺酸钠、2,2'-二萘甲烷-6,6′-二磺酸钠、二丁基萘磺酸钠或油酰甲基牛磺酸钠。为制备可湿性粉剂,将活性物质例如除草活性物质和/或安全剂磨细,例如在常用装置中如锤磨机、鼓风磨机和喷气磨机中磨细,同时或随后与助剂混合。
乳油是通过将活性物质例如除草活性物质和/或安全剂溶解在有机溶剂中,如丁醇、环己酮、二甲基甲酰胺、二甲苯或其它沸点较高烃类如芳烃、饱和或不饱和脂族烃或脂环族物质,或这些有机溶剂的混合物,并添加一种或多种离子型和/或非离子型表面活性剂(乳化剂)制备的。可以用作乳化剂的实例是(C16-C18)-烷基芳基磺酸钙如十二烷基苯磺酸钙,或非离子型乳化剂,如脂肪酸聚乙二醇酯、(C2-C18)-烷基芳基聚乙二醇醚、脂肪醇聚乙二醇醚、环氧丙烷/环氧乙烷缩合产物、烷基聚醚、脱水山梨糖醇酯例如脱水山梨糖醇脂肪酸酯或聚氧乙烯脱水山梨糖醇酯,例如聚氧乙烯脱水山梨糖醇脂肪酸酯。
粉剂是将活性物质例如除草活性物质和/或安全剂用细分布的固体物质加以磨碎而得,所述固体物质例如滑石、天然粘土(如高岭土、膨润土和叶蜡石)或硅藻土。
悬浮剂可为水基或油基。该制剂可以例如借助商购可得的球磨机通过湿磨制得,视需要添加例如在上述其它制剂类型中例举的表面活性剂。
乳液例如水包油乳液(EW)可以利用含水的有机溶剂,借助搅拌器、胶体研磨器和/或静态混合器来制得,并且视需要加入例如在上述其它制剂类型中例举的表面活性剂。
粒剂的制备可以通过将活性物质例如除草活性物质和/或安全剂喷洒在吸附性粒状的惰性物质上,或将活性物质浓缩物借助粘合剂(如聚乙烯醇,聚丙烯酸钠或矿物油)涂敷在载体(如砂、高岭土或粒状惰性物质)的表面上。适宜的活性物质还可以使用制造肥粒颗料的常规方法并视需要与肥料混合一同粒化。水分散性粒剂通常是利用常规方法如喷雾式干燥法、流化床式制粒法、碟式制粒法、用高速搅拌器混合法混合和无固体惰性物质的挤压制备而成。
对于碟式、流化床、挤压机和喷撒颗粒剂的制备方法,参见例如“Spray-Drying Handbook”(喷雾干燥手册)第3版,1979年,G.Goodwin Ltd.,London;J.E.Browning,“Agglomeration”(团聚作用),Chemical and Engineering(化学和工程)1967,第147页及其后;“Perry’s Chemical Engineer’s Handbook”(Perry’s化学工程师手册),第5版,McGraw-Hill,New York 1973,第8-57页。
对于更详细的植物保护剂的配制参见,例如G.C.Klingman,“WeedControl as a Science”(杂草控制科学),John Wiley and Sons,Inc.,New York,1961,第81-96页和J.D.Freyer,S.A.Evans,“Weed Control Handbook”(杂草控制手册),第5版,BlackwellScientific Publications,Oxford,1968,第101-103页。
优选制剂为液体制剂,例如油悬浮液、油悬浮剂、悬乳液、悬乳剂、乳液如W/O-或O/W基的,乳液浓缩物、微乳液、微乳剂、乳油,以及由此获得的喷雾液,优选水喷雾液。
尤其优选的液体制剂类型为油悬浮剂,即基于有机溶剂的悬浮剂,以及通过稀释由此获得的制剂如溶液、乳液、悬乳液和悬浮液。在油悬浮剂中,一种或多种活性物质悬浮在有机溶剂中;其它活性物质可以溶解在有机溶剂中。在优选的油悬浮剂中,除草剂(A)以悬浮形式存在于有机溶剂中。这表示主比例(以重量%表示)的磺酰胺以不溶解的高分散形式存在,较少比例的磺酰胺可以溶解地存在。在各情形下,基于本发明油悬浮剂中的磺酰胺的总量,优选地,大于80重量%,尤其优选大于90重量%的磺酰胺悬浮于有机溶剂中。
通常,农业化学配制剂包含0.1至99重量%,优选0.1至95重量%的活性物质,例如活性安全剂化合物(B),或磺酰脲(A),或含有磺酰脲(A)和活性安全剂化合物(B)的本发明除草剂/安全剂活性物质混合物,以及1至99.9重量%、优选5至99.8重量%的固体或液体添加剂,以及0至25重量%、优选0.1至25重量%的表面活性剂。
可湿性粉剂中,活性物质的浓度例如为约10~90重量%,至100重量%的余量由常规制剂组分构成。在乳油中,活性物质的浓度为约1~80重量%。粉剂形式的制剂通常含有1~20重量%的活性物质,而可喷雾型溶液含有约0.2~20重量%的活性物质。在粒剂如水分散颗粒剂中,活性物质的含量部分取决于活性物质是否以液态或固态形式存在。通常,水分散颗粒剂中的活性物质介于10和90重量%之间。
此外,上述活性物质制剂可视需要分别包含常用粘合剂、润湿剂、分散剂、乳化剂、渗透剂、防腐剂、防冻剂、溶剂、填料、载体、着色剂、消泡剂、蒸发抑制剂、影响pH和粘度的制剂。
对于施用而言,例如在可湿性粉剂、乳油、分散剂和水分散颗粒剂的情形下,商购可得的制剂任选用水以常规方式进行稀释。用水稀释的优选制剂为例如液体制剂例如油悬浮液、油悬浮剂、悬乳液、悬乳剂、乳液例如W/O-或O/W-基的,乳液浓缩物、微乳液、微乳剂、乳油。粉剂、土壤颗粒剂、撒布的颗粒剂和可喷雾溶液形式的制剂通常在使用前不用任何其它惰性物质稀释。
除草剂(A)的所需施用量随着外部环境而变化,例如尤其是温度、湿度和所采用除草剂的种类。该施用量可以在宽范围内变化,例如介于0.001和10.0kg/ha之间或更多的除草剂,但是优选介于0.005和5kg/ha之间。
具体实施例方式
采用如下实施例来说明本发明A制剂实施例a)粉剂的制备是将10重量份的磺酰脲(A)或安全剂(B)或磺酰脲(A)和安全剂(B)的活性物质混合物与90重量份的滑石(作为惰性物质)加以混合,将该混合物在锤磨机中粉碎。
b)在水中易于分散的可湿性粉剂的制备是将25重量份的磺酰脲(A)或安全剂(B)或磺酰脲(A)和安全剂(B)的活性物质混合物,64重量份的含高岭土的石英作为惰性物质,10重量份的木质素磺酸钾和1重量份的油酰甲基牛磺酸钠作为润湿剂和分散剂加以混合,并在栓型碟式磨粉机中研磨。
c)在水中易于分散或悬浮的浓缩物的制备是将20重量份的磺酰脲(A)或安全剂(B)或磺酰脲(A)和安全剂(B)的活性物质混合物、6重量份的烷基酚聚乙二醇醚(Triton X 207)、3重量份的异十三烷醇聚乙二醇醚(8EO)和71重量份的链烷烃矿物油(沸点范围例如为约255至277℃以上)加以混合,并且在球磨机上研磨该混合物至小于5微米的细度。
d)乳油是由下列物质获得15重量份的磺酰脲(A)或安全剂(B)或磺酰脲(A)和安全剂(B)的活性物质混合物,75重量份的环己酮作为溶剂和10重量份的氧乙基化的壬酚作为乳化剂。
e)水分散颗粒剂是利用下列方式制得将75重量份 的磺酰脲(A)或安全剂(B)或磺酰脲(A)和安全剂(B)的活性物质混合物,10重量份的 木质素磺酸钙,5重量份的 月桂基硫酸钠,3重量份的 聚乙烯醇和7重量份的 高岭土加以混合,将该混合物在栓型碟式磨粉机中磨成细粉,并将粉末在流化床中通过喷洒作为粒化液体的水以使之粒化。
f)水分散颗粒剂也可通过在胶体磨中将下列物质均质化和预先粉碎25重量份的 磺酰脲(A)或安全剂(B)或磺酰脲(A)和安全剂(B)的活性物质混合物,5重量份的 2,2′-二萘基甲烷-6,6′-二磺酸钠,2重量份的 油酰甲基牛磺酸钠,1重量份的 聚乙烯醇,17重量份的 碳酸钙和50重量份的 水,随后在球磨机中磨成细粉,在喷雾塔中利用单物质喷嘴将如此得到的悬浮液加以雾化和干燥。
g)油悬浮剂是例如通过混合各组分来制得的,例如任选将磺基丁二酸酯(盐)D)溶解于溶剂C)中,并且任选将其它助剂和添加剂F)加至该溶液中来制得预混物。随后将任选地使用的可溶的安全剂B)和农业化学活性物质E)溶解于预混物中。在溶解步骤结束后,将固态磺酰脲A)和任选地使用的不溶的安全剂B)和农业化学活性物质E)悬浮于该混合物中。视需要在预研磨后将粗粒悬浮液进行细研磨。
在制备油悬浮剂的另一个实施方式中,所使用的固态磺酰脲A)和任选地使用的不溶组分B)、E)和F)悬浮于溶剂C)中,该溶剂任选包含磺基丁二酸酯(盐)D),并进行研磨。在研磨后,加入任选地使用的可溶活性物质B)和E),以及无需研磨或对于研磨步骤非必要的助剂和添加剂F)。
在制备油悬浮剂的另一个实施方式中,其中增稠剂用作助剂和添加剂F),将增稠剂首先与溶剂C)相混合。随后加入活性物质A)、B)和任选地E)以及视需要的其它的助剂和添加剂F)和磺基丁二酸酯(盐)D),并且将混合物在例如研磨机中进行研磨。
h)制备特定的油悬浮剂将Solvesso200 ND、Bentone34和碳酸丙二醇酯加入研磨机中,并进行剧烈混合直至获得糊料。随后在搅拌下先后加入其它组分(助剂和添加剂和活性物质),并随后借助球磨机将所得混合物进行均质化。下表显示以该方法制得的油悬浮剂配方中各组分的比例(重量%)。表

注TritonGR-7M-E为二-2-乙基己基磺基丁二酸-钠,EmulsogenEL 400为具有40个环氧乙烷单元的乙氧基化蓖麻油,Etocas10为具有10个环氧乙烷单元的乙氧基化蓖麻油,GenapolPF 10为聚合的表面活性剂(环氧乙烷和环氧丙烷的嵌段共聚物),MorwetD 425为聚合的阴离子分散剂,Bentone34为增稠剂(基于改性层状硅酸盐),Rhodorsil454为有机硅消泡剂,Solvesso200ND为高沸点的芳族溶剂。
B.生物实施例1.损害计算根据0至100%的范围,与对照植物相比,目测评价对植物的损害0%=与未处理植物相比,未观察到效果,100%=处理植物死亡2.苗后除草作用将单子叶和双子叶杂草和作物的种子置于塑料盒中的砂壤土中,并覆上土壤,并于温室中在良好的生长条件下栽培。
播种3周后,在3至4叶阶段时处理试验植物。在换算为300升水/公顷的施用量下,将不同用量的以乳液浓缩物配制的本发明各活性物质单个或混合喷洒至植物绿色部分,待试验植物在置于理想的生长条件下的温室中3周后,目测记录与未处理对照组相比的制剂效果。如实施例所示,本发明磺酰脲和安全剂的组合能有效控制广谱杂草,并且与单独使用磺酰脲而无安全剂相比,显著地减少了对作物的损害。
对作物的试验结果总结于下表。其中显示了对作物的各损害度以及本发明除草剂/安全剂组合与单独施用所述除草剂相比所引起损害的减少以百分比给出。
表1玉米,栽培品种“Lorenzo”

除草剂A1.1甲磺隆-甲酯;除草剂A2.1噻吩磺隆-甲酯;除草剂A3.1苯磺隆-甲酯;除草剂A4.1氯磺隆;安全剂B2双苯唑酸-乙酯表2大麦,栽培品种“Baronesse”

除草剂A1.1甲磺隆-甲酯;除草剂A4.1氯磺隆;安全剂B1吡咯二酸二乙酯;安全剂B2双苯唑酸-乙酯;安全剂B3解毒喹表3大麦,栽培品种“Duett”

除草剂A2.1噻吩磺隆-甲酯;安全剂B1吡咯二酸二乙酯;安全剂B3解毒喹表4小麦,栽培品种“Triso”

除草剂A1.1甲磺隆-甲酯;安全剂B1吡咯二酸二乙酯;安全剂B2双苯唑酸-乙酯;
表5小麦,栽培品种“Kanzler”

除草剂A1.1甲磺隆-甲酯;除草剂A2.1噻吩磺隆-甲酯;除草剂A3.1苯磺隆-甲酯;安全剂B1吡咯二酸二乙酯;安全剂B2双苯唑酸-乙酯;安全剂B3解毒喹。
权利要求
1.除草活性组合物,其包含(A)一种或多种选自下组的磺酰脲类化合物甲磺隆、噻吩磺隆、苯磺隆、氯磺隆及其盐和酯,和(B)一种或多种选自下组的安全剂吡咯二酸、双苯唑酸、喹氧乙酸、解草唑及其盐和酯。
2.根据权利要求1的除草活性组合物,其中磺酰脲(A)选自下组甲磺隆-甲酯、噻吩磺隆-甲酯、苯磺隆-甲酯、氯磺隆及其碱金属盐类。
3.根据权利要求1或2的除草活性组合物,其中安全剂(B)选自下组吡咯二酸-二乙酯、双苯唑酸-乙酯、解毒喹和解草唑-乙酯。
4.根据权利要求1至3一项或多项所述的除草活性组合物,其中除草剂与安全剂的重量比为1∶100至100∶1。
5.根据权利要求1至4一项或多项所述的除草活性组合物,还包含(C)一种或多种溶剂,优选有机溶剂,(D)一种或多种磺基丁二酸酯或盐,(E)一种或多种不同于(A)和(B)的农业化学活性物质,和/或(F)常规助剂和添加剂。
6.根据权利要求1至5一项或多项所述的除草活性组合物,其是液体制剂形式。
7.液体制剂,其包含(A)一种或多种选自下组的磺酰脲类化合物甲磺隆、噻吩磺隆、苯磺隆、氯磺隆及其盐和酯,(B)一种或多种选自下组的安全剂吡咯二酸、双苯唑酸、喹氧乙酸、解草唑及其盐和酯,(C)一种或多种溶剂,优选有机溶剂,(D)任选地一种或多种磺基丁二酸酯或盐,(E)任选地一种或多种不同于(A)和(B)的农业化学活性物质,和(F)任选地常规助剂和添加剂。
8.根据权利要求7的液体制剂,其包含除草有效量的一种或多种磺酰脲(A)和解毒有效量的一种或多种安全剂(B)。
9.根据权利要求8的液体制剂,其以油悬浮液、油悬浮剂、悬乳液、悬乳剂、乳液、乳液浓缩物、微乳液、微乳剂、乳油或由此获得的喷雾液。
10.控制作物中有害植物的方法,该方法包括将权利要求1至6一项或多项所述的除草活性组合物的组分或权利要求7至9所述的液体制剂的组分一并或分别施用至有害植物、作物、植物种子或植物生长区域。
11.根据权利要求10的方法,其中作物选自下组玉米、小麦、黑麦、大麦、燕麦、水稻、高粱、棉花和大豆。
12.根据权利要求10或11的方法,其中作物是转基因的或由于选择育种具有耐受性。
13.将权利要求1至6一项或多项所述的除草活性组合物或权利要求7至9所述的液体制剂用于控制作物中有害植物的用途。
14.制备权利要求1至6一项或多项所述的除草活性组合物或权利要求7至9所述的液体制剂的方法,其中将各组分互相混合。
15.磺酰脲/安全剂的组合,其包含(A)一种或多种选自下组的磺酰脲类化合物甲磺隆、噻吩磺隆、苯磺隆、氯磺隆及其盐和酯,和(B)一种或多种选自下组的安全剂吡咯二酸、双苯唑酸、喹氧乙酸、解草唑及其盐和酯。
16.根据权利要求15的磺酰脲/安全剂的组合,其中磺酰脲(A)选自下组甲磺隆-甲酯、噻吩磺隆-甲酯、苯磺隆-甲酯、氯磺隆及其碱金属盐类。
17.根据权利要求15或16的磺酰脲/安全剂的组合,其中安全剂(B)选自下组吡咯二酸-二乙酯、双苯唑酸-乙酯、解毒喹和解草唑-乙酯。
18.根据权利要求15至17一项或多项的磺酰脲/安全剂的组合,还包含一种或多种不同于(A)和(B)的农业化学活性物质(E)。
全文摘要
除草活性组合物,其包含(A)一种或多种选自下组的磺酰脲类化合物甲磺隆、噻吩磺隆、苯磺隆、氯磺隆及其盐和酯,和(B)一种或多种选自下组的安全剂吡咯二酸、双苯噁唑酸、喹氧乙酸、解草唑及其盐和酯。
文档编号A01N43/653GK1886051SQ200480035470
公开日2006年12月27日 申请日期2004年10月21日 优先权日2003年11月3日
发明者F·齐默, G·施纳贝尔, D·哈泽, R·德克韦尔, C·洛斯格尔, D·菲斯特 申请人:拜尔作物科学有限公司
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