CN102355819A - 用包封农药处理作物的方法 - Google Patents
用包封农药处理作物的方法 Download PDFInfo
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- CN102355819A CN102355819A CN2010800119453A CN201080011945A CN102355819A CN 102355819 A CN102355819 A CN 102355819A CN 2010800119453 A CN2010800119453 A CN 2010800119453A CN 201080011945 A CN201080011945 A CN 201080011945A CN 102355819 A CN102355819 A CN 102355819A
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- agricultural chemicals
- methyl
- sealing
- corn
- acid
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
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Abstract
本发明涉及一种对最终生长高度为至少140cm的作物进行农药处理的方法,包括在作物生长高度至多为120cm时,用包封农药进行处理。本发明进一步涉及一种包含包封农药的组合物,以及一种包含包封农药与未包封的其他农药的混合物的组合物。最后,本发明还涉及包封农药在作物生长高度小于120cm时对最终生长高度为至少140cm的作物进行农药处理中的用途。
Description
本发明涉及一种对最终生长高度为至少140cm的作物实施农药处理的方法,包括在作物生长高度至多为120cm时用包封农药进行处理。本发明进一步涉及一种包含包封农药的组合物以及包含包封农药与未包封的其他农药的混合物的组合物。最后,本发明还涉及包封农药在作物生长高度小于120cm时对最终生长高度为至少140cm的作物实施农药处理中的用途。优选实施方案与其他优选实施方案的组合也处于本发明的范围之内。
WO2008/059053公开了通过用农药,例如唑菌胺酯(pyraclostrobin)处理植物而提高植物干生物质的方法。合适的植物为玉米。在生长阶段BBCH30至70期间对植物进行处理。
WO2008/155097公开了改善植物生长的方法,包括向植物施用微胶囊,所述微胶囊本身包含聚合物壳以及包含分散固体活性成分的核的。合适的活性成分为嗜球果伞素(strobilurin)类且合适的植物为玉米或向日葵。
WO2008/021800公开了延迟或防止具有结晶倾向的物质在水相中结晶的方法,其包括制备所述物质的特定胶囊。合适的物质为杀真菌剂,例如唑菌胺酯。所述胶囊包含脲甲醛预聚物。
技术信息简报“Fungicide Corn”(由BASF公司于2008年出版)公开了可在营养阶段VE至V10或在VT阶段或更晚阶段将杀真菌剂(唑菌胺酯的可乳化浓缩物)施用于玉米。其公开了最佳施用时间为玉米VT阶段至R2阶段或在病害发作之前。
在商业上通常将农药配制成浓缩物、乳液或悬浮液。尽管它们具有各种优点,但在一些情形下它们的应用具有一些缺点:一些农药的最佳施用时间为植株高于120cm的相当晚的生长阶段。例如,建议在VT(对应于BBCH GS 55)至R2(对应于BBCH GS 71)生长阶段将唑菌胺酯的乳液浓缩物施用至玉米以获得最佳产量响应。这仅可通过相当昂贵的空中施用或特殊的高架式牵引车实现,因为在作物已生长至约80-120cm高度后通过普通牵引车进行地面施用会对作物造成伤害。
本发明的目的为开发一种用农药处理作物的方法,其避免了现有技术有关的问题。该方法应可在较早生长阶段利用标准设备通过地面处理而应用,同时仍提供与在较晚生长阶段的最佳时间点相当的产量益处。另一目的为开发可用于所述方法的农药组合物。
该目的通过一种对最终生长高度为至少140cm的作物实施农药处理的方法而实现,所述方法包括在作物生长高度至多为120cm时用包封农药进行处理。
术语“最终生长高度”是指某种作物的平均最高生长高度。通常在收获时达到该生长高度。该最终生长高度在文献中是公知的(Carter,JackF.(编辑),“Sunflower Science and Technology”,Madison/Wisconsin:American Society of Agronomy,1978(Agronomy;第19卷);Cheers,Gordon,“Botanica:das Abc der Pflanzen:10.000 Arten in Text und Bild”,Cologne: 1998;Cramer,Nils.“Raps:Anbau undVerwertung”,Stuttgart:Ulmer,1990;Sprecher v.Bernegg,Andreas:“Tropische und subtropische Weltwirtschaftspflanzen,ihre Geschichte,Kultur und volkswirtschaftliche Bedeutung,Teil 1(XV):Zuckerpflanzen”,1929;Zscheischler,Johannes:“Handbuch Mais:Umweltgerechter Anbau,wirtschaftliche Verwertung”,第4版,Frankfurt/M.:DL.)。最终生长高度通常在无任何生长调节剂的情况下测定且是指在自然条件下的平均生长高度。在最终生长高度取决于局部条件的情况下,最终生长高度是指该局部区域中的生长高度。
最终生长高度为至少140cm的合适作物是公知的。典型实例为(括号中为最终生长高度)玉米(200-300cm)、向日葵(最高500cm)、油菜籽油菜(最高200cm)、甘蔗(300-400cm)、高粱(最高500cm)或芒属(miscanthus)(最高350cm)。一些作物物种可包括最终生长阶段小于140cm的品种和最终生长阶段至少为140cm的品种。根据本发明,只有最终生长高度为至少140cm的那些品种才落入本发明的范围之内。
优选作物为玉米、向日葵、油菜籽油菜、甘蔗、高粱或芒属。更优选为玉米、向日葵和油菜籽油菜,更优选为玉米和向日葵,最优选为玉米。在另一优选实施方案中,优选作物为如下品种:玉米、向日葵、油菜籽油菜、甘蔗、高粱或芒属,其最终生长高度为至少140cm,优选至少160cm。
术语“作物”应理解为包括已通过育种、诱变或基因工程修饰的植物,包括但不限于市场销售或开发中的农业生物技术产品。基因修饰植物是其遗传物质已利用DNA重组技术加以修饰且在自然环境下无法由杂交育种、诱变或自然重组容易地获得的植物。通常将一个或多个基因整合到基因改性植物的遗传物质中以改善植物的某些性能。这类基因修饰同样包括但不限于蛋白质、寡肽或多肽的靶向翻译后修饰,例如通过糖基化或聚合物加成如异戊二烯化、乙酰化或法呢基化结构部分或PEG结构部分。
例如,由于育种或基因工程的常规方法,已赋予通过育种、诱变或基因工程修饰的植物对特定类别除草剂施用的耐受性,所述除草剂例如为羟基苯基丙酮酸二加氧酶(HPPD)抑制剂;乙酰乳酸合酶(ALS)抑制剂,例如磺酰脲类(参见例如US6,222,100、WO01/82685、WO00/26390、WO97/41218、WO98/02526、WO98/02527、WO04/106529、WO05/20673、WO03/14357、WO03/13225、WO03/14356、WO04/16073)或咪唑啉酮类(参见例如US6,222,100、WO01/82685、WO00/026390、WO97/41218、WO98/002526、WO98/02527、WO04/106529、WO05/20673、WO03/014357、WO03/13225、WO03/14356、WO04/16073);烯醇丙酮酰莽草酸3-磷酸合酶(EPSPS)抑制剂,如草甘膦(glyphosate)(参见例如WO92/00377);谷氨酰胺合酶(GS)抑制剂,如草铵膦(glufosinate)(参见例如EP-A242236,EP-A242246)或oxynil除草剂(参见例如US5,559,024)。已通过常规育种(诱变)方法赋予数种栽培植物对除草剂的耐受性,例如夏季油菜(Canola,BASF SE,德国)对咪唑啉酮类如咪草啶酸(imazamox)具有耐受性。基因工程方法已用于赋予栽培植物如大豆、棉花、玉米、甜菜和油菜对除草剂如草甘膦和草铵膦的耐受性,其中一些可以以商品名(草甘膦耐受型,Monsanto,美国)和(草铵膦耐受型,Bayer CropScience,德国)商购获得。
此外,还涵盖通过利用DNA重组技术而能合成一种或多种杀虫蛋白的植物,所述杀虫蛋白尤其是由芽孢杆菌属(Bacillus)细菌,特别是由苏云金芽孢杆菌(Bacillus thuringiensis)已知的那些,例如δ-内毒素如CryIA(b)、CryIA(c)、CryIF、CryIF(a2)、CryIIA(b)、CryIIIA、CryIIIB(b1)或Cry9c;或无性杀虫蛋白(VIP),例如VIP1、VIP2、VIP3或VIP3A;线虫定居细菌的杀虫蛋白,例如发光杆菌属(Photorhabdus)或致病杆菌属(Xenorhabdus);动物产生的毒素如蝎毒素、蜘蛛毒素、黄蜂毒素或其他昆虫特异性神经毒素;由真菌例如链霉菌属(Streptomycetes)产生的毒素;植物凝集素,如豌豆或大麦凝集素;凝集素;蛋白酶抑制剂,如胰蛋白酶抑制剂、丝氨酸蛋白酶抑制剂、马铃薯块茎储藏蛋白(patatin)抑制剂、半胱氨酸蛋白酶抑制剂或木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP),如蓖麻蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽蛋白、皂草素或异株腹泻毒蛋白(bryodin);类固醇代谢酶,如3-羟基类固醇氧化酶、蜕皮甾类-IDP糖基转移酶、胆固醇氧化酶、蜕皮激素抑制剂或HMG-CoA还原酶;离子通道阻断剂,例如钠通道或钙通道阻断剂;保幼激素酯酶;利尿激素受体(helicokinin受体);茋合酶,联苄合酶,壳多糖酶和葡聚糖酶。在本发明上下文中,这些杀虫蛋白或毒素也可明确理解为前毒素、杂合蛋白、截短或改性的蛋白。杂合蛋白的特征在于蛋白域的新组合(例如参见WO2002/015701)。该类毒素或能合成该类毒素的基因修饰植物的其他实例例如公开于EP-A 374 753、WO93/07278、WO95/34656、EP-A 427 529、EP-A451 878、WO03/18810和WO 03/52073中。生产这些基因修饰植物的方法对本领域技术人员而言是公知的且例如描述于上述出版物中。基因修饰植物中所含的这些杀虫蛋白赋予产生这些蛋白的植物对所有分类学上为节肢动物的害虫,尤其是甲虫(鞘翅目(Coeleropta))、双翅目昆虫(双翅目(Diptera))和蛾(鳞翅目(Lepidoptera))以及线虫(线虫纲(Nematoda))的耐受性。能合成一种或多种杀虫蛋白的基因修饰植物例如描述于上述出版物中,且它们中的一些可商购获得,例如(产生毒素Cry1Ab的玉米栽培品种),Plus(产生毒素Cry1Ab和Cry3Bb1的玉米栽培品种),(产生毒素Cry9c的玉米栽培品种),RW(产生毒素Cry34Ab1、Cry35Ab1和酶膦丝菌素-N-乙酰转移酶[PAT]的玉米栽培品种);33B(产生毒素Cry1Ac的棉花栽培品种),I(产生毒素Cry1Ac的棉花栽培品种),II(产生毒素Cry1Ac和Cry2Ab2的棉花栽培品种);(产生VIP毒素的棉花栽培品种);(产生毒素Cry3A的土豆栽培品种); Bt11(例如CB)和法国Syngenta Seeds SAS的Bt176(产生毒素Cry1Ab和PAT酶的玉米栽培品种),法国Syngenta SeedsSAS的MIR604(产生毒素Cry3A的修饰译本的玉米栽培品种,参见WO03/018810),比利时Monsanto Europe S.A.的MON 863(产生毒素Cry3Bb1的玉米栽培品种),比利时Monsanto Europe S.A.的IPC 531(产生毒素Cry1Ac的修饰译本的棉花栽培品种)和比利时Pioneer OverseasCorporation的1507(产生毒素Cry1F和PAT酶的玉米栽培品种)。
此外,还涵盖通过利用DNA重组技术能合成一种或多种提高对细菌、病毒或真菌病原体的耐受性的蛋白质的植物。这类蛋白质的实例为所谓的“与发病机理相关的蛋白”(PR蛋白,参见EP-A 392 225),抗植物病害基因(例如表达出对来自野生墨西哥土豆Solanum bulbocastanum的致病疫霉(Phytophthora infestans)的抗性基因的土豆栽培品种)或T4溶菌酶(例如能合成这些蛋白质以提高对细菌如梨火疫病菌(Erwinia amylovora)的耐受性的马铃薯栽培品种)。生产这类基因修饰植物的方法通常是本领域技术人员所公知的且例如描述于上述公开文献中。
此外,还涵盖通过利用DNA重组技术而能合成一种或多种蛋白质以提高生产能力(例如生物质生产、谷粒产量、淀粉含量、油含量或蛋白质含量),对干旱、盐度或其他生长限制性环境因素的耐受性或对害虫以及真菌、细菌和病毒病原体的耐受性的那些植物。
此外,还涵盖通过利用DNA重组技术而含有改善量的内含物或新内含物,尤其是改善人类或动物营养的内含物的植物,例如产生有助于健康的长链ω-3脂肪酸或不饱和ω-9脂肪酸的油料作物(例如油菜,DOWAgro Sciences,加拿大)。
用包封农药处理通常在作物生长高度小于120cm,优选小于115cm,更优选小于110cm,甚至更优选小于100cm时进行。用包封农药处理通常在作物生长高度高于10cm,优选高于30cm,更优选高于50cm时进行。农场主可通过用卷尺测量从地面至作物顶端的生长高度而容易地确定作物的生长高度。通常,必须进行处理的田间作物植株至少70%,优选至少80%,更优选至少90%具有上述生长高度。
术语“生长阶段”是指如“Growth stages of mono-and dicotyledonousplants”(第二版,2001年,由来自Federal Biological Research Centre forAgriculture and Forestry的Uwe Meier编辑)中的BBCH代码所定义的生长阶段。BBCH代码是对所有单子叶和双子叶植物物种的物候学类似生长阶段进行统一编码的广为接受的体系。在一些国家,已知特定作物的相关代码。这类代码可能与BBCH代码相关,如Harell等,Agronomy J.1998,90,235-238所例示。玉米通常以营养阶段分级[VE(出苗)、V1(第一叶期)、V2(第二叶期)、V3(第三叶期)、V(n)(第n叶期)、VT(抽穗期)]和生殖阶段[R1(吐丝期)、R2(泡状期)、R3(乳熟期)、R4(糊熟期)、R5(齿状期)、R6(生理成熟期)]。
在优选实施方案中,所述作物为在生长阶段BBCH 10至51进行处理的玉米;在生长阶段BBCH 10至BBCH 69进行处理的向日葵;在生长阶段BBCH 10至69进行处理的油菜籽油菜;在生长阶段BBCH 10至51进行处理的高粱;或在生长阶段BBCH 11至49进行处理的甘蔗。
更优选所述作物为在生长阶段BBCH 13至39进行处理的玉米;在生长阶段BBCH 13至BBCH 57进行处理的向日葵;在生长阶段BBCH 13至59进行处理的油菜籽油菜;在生长阶段BBCH 13至39进行处理的高粱;或在生长阶段BBCH 29至49进行处理的甘蔗。
甚至更优选地,作物为在生长阶段BBCH 30至39进行处理的玉米;在生长阶段BBCH 37至BBCH 55进行处理的向日葵;在生长阶段BBCH 30至59进行处理的油菜籽油菜;在生长阶段BBCH 30至39进行处理的高粱;或在生长阶段BBCH 31至39进行处理的甘蔗。
在优选实施方案中,玉米通常在其生长阶段BBCH 10(从胚芽鞘中长出第一叶)至51(开始抽穗),优选13(第三叶展开)至39(可检测到9个或更多节),尤其为30(茎开始伸长)至39(可检测到9个或更多节),最优选32(可检测到2个节)至39(可检测到9个或更多节)阶段进行处理。在另一优选实施方案中,在生长高度至多为120cm,优选至多为115cm,更优选至多为100cm的生长阶段对玉米进行处理。
在另一优选实施方案中,向日葵通常在其生长阶段BBCH 10(子叶完全展开)至69(开花结束),优选13(第三叶展开)至59(在苞叶间可看到伞形小花),更优选37(7个明显伸长的节间)至55(花序从最幼小的营养叶中分离出来),尤其在39(9个或更多个明显伸长的节间)至53(花序从最幼小的叶中分离出来,苞叶可与营养叶区分开)阶段进行处理。在另一优选实施方案中,在作物高度至多为120cm,优选至多为100cm,更优选至多为80cm的生长阶段对向日葵进行处理。
在另一优选实施方案中,油菜籽油菜通常在其生长阶段BBCH 10(子叶完全展开)至69(开花结束),优选13(第三叶展开)至59(可看到第一片花瓣),更优选30(茎开始伸长)至59(可看到第一片花瓣),尤其在50(出现花芽)至59(可看到第一片花瓣)阶段进行处理。在另一优选实施方案中,在作物高度至多为120cm,优选至多为100cm,更优选至多为80cm的生长阶段对油菜籽油菜进行处理。
在另一优选实施方案中,甘蔗通常在其生长阶段BBCH 11(第一叶展开)至49(可收获的营养植物部分已达到最终尺寸),优选29(分蘖结束)至49(可收获的营养植物部分已达到最终尺寸),更优选31(开始拔节,可观测到1个节)至39(拔节结束,茎达到最终长度),尤其在31(开始拔节,可观测到1个节)至37(拔节,可观测到7个节)阶段进行处理。在另一优选实施方案中,在高度至多为120cm,优选至多为100cm,更优选至多为80cm的生长阶段对甘蔗进行处理。
在另一优选实施方案中,高粱通常在其生长阶段BBCH 10(从胚芽鞘中长出第一叶)至51(开始抽穗),优选13(第三叶展开)至39(可观测到9个或更多节),尤其是30(茎开始伸长)至39(可观测到9个或更多节),最优选35(可观测到5个节)至39(可观测到9个或更多节)阶段进行处理。在另一优选实施方案中,在作物高度至多为120cm,优选至多为100cm,更优选至多为80cm的生长阶段对高粱进行处理。
术语“农药”是指至少一种选自杀真菌剂、杀昆虫剂、杀线虫剂、除草剂、安全剂和/或生长调节剂的农药。也可使用上述种类中两种或多种农药的混合物。本领域技术人员熟知这些农药,其可参见Pesticide Manual,第14版(2006),The British Crop Protection Council,London。
合适的杀真菌剂为:
A)嗜球果伞素类(strobilurin):
腈嘧菌酯(azoxystrobin)、醚菌胺(dimoxystrobin)、enestroburin、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、pyribencarb、肟菌酯(trifloxystrobin)、2-(2-(6-(3-氯-2-甲基苯氧基)-5-氟嘧啶-4-基氧基)苯基)-2-甲氧基亚氨基-N-甲基乙酰胺、3-甲氧基-2-(2-(N-(4-甲氧基苯基)环丙烷甲酰亚氨基(carboximidoyl)硫基甲基)苯基)丙烯酸甲酯、(2-氯-5-[1-(3-甲基苄氧基亚氨基)乙基]苄基)氨基甲酸甲酯和2-(2-(3-(2,6-二氯苯基)-1-甲基亚烯丙基氨基氧基甲基)苯基)-2-甲氧基亚氨基-N-甲基乙酰胺;
B)羧酰胺类;
-羧酰苯胺类:苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M)、麦锈灵(benodanil)、bixafen、啶酰菌胺(boscalid)、萎锈灵(carboxin)、呋菌胺(fenfuram)、环酰菌胺(fenhexamid)、氟酰胺(flutolanil)、fluxapyroxad、呋吡唑灵(furametpyr)、isopyrazam、异噻菌胺(isotianil)、kiralaxyl、丙氧灭绣胺(mepronil)、甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M)(mefenoxam)、甲呋酰胺(ofurace)、霜灵(oxadixyl)、氧化萎锈灵(oxycarboxin)、penflufen、penthiopyrad、sedaxane、叶枯酞(tecloftalam)、溴氟唑菌(thifluzamide)、噻酰菌胺(tiadinil)、2-氨基-4-甲基噻唑-5-甲酰苯胺、2-氯-N-(1,1,3-三甲基茚满-4-基)烟碱酰胺、N-(2′,4′-二氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′,4′-二氯联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′,5′-二氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′,5′-二氯联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,5′-二氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′-氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′-氯联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′-氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2′-氯联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,5′-二氯联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,4′,5′-三氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺(对应于下式I的1-甲基吡唑-4-基羧酰苯胺;也称为fluxapyroxad)、N-(2′,4′,5′-三氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-[2-(1,1,2,3,3,3-六氟丙氧基)苯基]-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-[2-(1,1,2,2-四氟乙氧基)苯基]-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(4′-三氟甲基硫代联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2-(1,3-二甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺、N-(2-(1,3,3-三甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺、N-(4′-氯-3′,5′-二氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(4′-氯-3′,5′-二氟联苯-2-基)-3-三氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,4′-二氯-5′-氟联苯-2-基)-3-三氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,5′-二氟-4′-甲基联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(3′,5′-二氟-4′-甲基联苯-2-基)-3-三氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-[1,2,3,4-四氢-9-(1-甲基乙基)-1,4-亚甲基萘-5-基]-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、式I的1-甲基吡唑-4-基羧酰苯胺:
其中各取代基定义如下:
R1为C1-C4烷基或C1-C4卤代烷基;
R2为氢;
R3、R4和R5彼此独立地为氰基、硝基、卤素、C1-C4烷基、C1-C4卤代烷基、C1-C4烷氧基、C1-C4卤代烷氧基或C1-C4烷硫基;
-羧酰吗啉类:烯酰吗啉(dimethomorph)、氟吗啉(flumorph)、pyrimorph;
-苯甲酰胺类:氟联苯菌(flumetover)、氟吡菌胺(fluopicolide)、fluopyram、苯酰菌胺(zoxamide)、N-(3-乙基-3,5,5-三甲基环己基)-3-甲酰氨基-2-羟基苯甲酰胺;
-其它羧酰胺类:氯环丙酰胺(carpropamid)、双氯氰菌胺(dicylomet)、双炔酰菌胺(mandiproamid)、土霉素(oxytetracyclin)、硅噻菌胺(silthiofam)、N-(6-甲氧基吡啶-3-基)环丙烷甲酰胺;
C)唑类:
-三唑类:戊环菌(azaconazole)、双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、醚唑(difenoconazole)、烯唑醇(diniconazole)、精烯唑醇(diniconazole-M)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、腈苯唑(fluquinconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、酰胺唑(imibenconazole)、环戊唑醇(ipconazole)、环戊唑菌(metconazole)、腈菌唑(myclobutanil)、oxpoconazole、多效唑(paclobutrazole)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazole)、三唑酮(triadimefon)、唑菌醇(triadimenol)、戊叉唑菌(triticonazole)、烯效唑(uniconazole)、1-(4-氯苯基)-2-([1,2,4]三唑-1-基)环庚醇;
-咪唑类:氰霜唑(cyazofamid)、烯菌灵(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizole);
-苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole);
-其它:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole)和2-(4-氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2-炔氧基乙酰胺;
D)杂环化合物:
-吡啶类:氟啶胺(fluazinam)、啶斑肟(pyrifenox)、3-[5-(4-氯苯基)-2,3-二甲基异唑烷-3-基]吡啶、3-[5-(4-甲基苯基)-2,3-二甲基异唑烷-3-基]吡啶、2,3,5,6-四氯-4-甲磺酰基吡啶、3,4,5-三氯吡啶-2,6-二甲腈、N-(1-(5-溴-3-氯吡啶-2-基)乙基)-2,4-二氯烟碱酰胺、N-[(5-溴-3-氯-吡啶-2-基)甲基)]-2,4-二氯烟碱酰胺;
-嘧啶类:磺嘧菌灵(bupirimate)、环丙嘧啶(cyprodinil)、氟嘧菌胺(diflumetorim)、异嘧菌醇(fenarimol)、嘧菌腙(ferimzone)、嘧菌胺(mepanipyrim)、氯定(nitrapyrin)、氯苯嘧啶醇(nuarimol)、二甲嘧菌胺(pyrimethanil);
-哌嗪类:嗪氨灵(triforine);
-吗啉类:aldimorph、吗菌灵(dodemorph)、吗菌灵乙酸酯(dodemorphacetate)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph);
-哌啶类:苯锈啶(fenpropidin);
-二羧酰亚胺类:fluorimide、异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin);
-3-氧代-4-邻甲苯基-2,3-二氢吡唑-1-硫代甲酸S-烯丙基酯;
-其它:噻二唑素-S-甲基(acibenzolar-S-methyl)、amisulbrom、敌菌灵(anilazin)、灭瘟素(blasticidin-S)、敌菌丹(captafol)、克菌丹(captan)、灭螨锰(chinomethionat)、棉隆(dazomet)、双乙氧咪唑威(debacarb)、哒菌清(diclomezine)、苯敌快(difenzoquat)、苯敌快甲基硫酸酯(difenzoquatmethylsulfate)、氰菌胺(fenoxanil)、灭菌丹(folpet)、喹菌酮(oxolinic acid)、粉病灵(piperalin)、丙氧喹啉(proquinazid)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、唑菌嗪(triazoxide)、三环唑(tricyclazole)、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、5-氯-1-(4,6-二甲氧基嘧啶-2-基)-2-甲基-1H-苯并咪唑、5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶、6-(3,4-二氯苯基)-5-甲基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-(4-叔丁基苯基)-5-甲基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-甲基-6-(3,5,5-三甲基己基)-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-甲基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-甲基-5-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-乙基-5-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-乙基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-乙基-6-(3,5,5-三甲基己基)-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-辛基-5-丙基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-甲氧基甲基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-辛基-5-三氟甲基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺和5-三氟甲基-6-(3,5,5-三甲基己基)-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺;
E)氨基甲酸酯类
-硫代和二硫代氨基甲酸酯类:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、威百亩(metam)、methasulphocarb、代森联(metiram)、代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram);-氨基甲酸酯类:苯噻菌胺(benthiavalicarb)、乙霉威(diethofencarb)、异丙菌胺(iprovalicarb)、百维灵(propamocarb)、百维灵盐酸盐(propamocarb hydrochloride)、valiphenal、N-(1-(1-(4-氰基苯基)乙磺酰基)丁-2-基)氨基甲酸4-氟苯酯;
F)其它活性物质
-胍类:胍、多果定(dodine)、多果定游离碱、双胍盐(guazatine)、双胍乙酸盐(guazatine acetate)、双胍辛乙酸盐(iminoctadine)、双胍辛乙酸盐(iminoctadine triacetate)、双胍辛乙酸三(苯磺酸盐)(iminoctadinetris(albesilate));
-抗生素:春雷素(kasugamycin)、春雷素盐酸盐水合物(kasugamycinhydrochloride hydrate)、链霉素(streptomycin)、多氧霉素(polyoxin)、井冈霉素(validamycin A);
-硝基苯基衍生物:乐杀螨(binapacryl)、敌螨通(dinobuton)、敌螨普(dinocap)、异丙消(nitrothal-isopropyl)、四氯硝基苯(tecnazen);
-有机金属化合物:毒菌锡(fentin salt),如毒菌锡乙酸盐(fentin acetate)、毒菌锡氯(fentin chloride)、毒菌锡氢氧化物(fentin hydroxide);
-含硫杂环化合物:二噻农(dithianon)、稻瘟灵(isoprothiolane);
-有机磷化合物:稻瘟光(edifenphos)、藻菌磷(fosetyl)、藻菌磷铝(fosetyl-aluminum)、异稻瘟净(iprobenfos)、亚磷酸及其盐、定菌磷(pyrazophos)、甲基立枯磷(tolclofos-methyl);
-有机氯化合物:百菌清(chlorothalonil)、抑菌灵(dichlofluanid)、双氯酚(dichlorphen)、磺菌胺(flusulfamide)、六氯苯(hexachlorobenzene)、戊菌隆(pencycuron)、五氯酚(pentachlorphenole)及其盐、四氯苯酞(phthalide)、五氯硝基苯(quintozene)、甲基托布津(thiophanate-methyl)、对甲抑菌灵(tolylfluanid)、N-(4-氯-2-硝基苯基)-N-乙基-4-甲基苯磺酰胺;
-无机活性化合物:波尔多液(Bordeaux混合剂)、乙酸铜、氢氧化铜、王铜、碱式硫酸铜、硫;
-其它:联苯、溴硝丙二醇(bronopol)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、二苯胺(diphenylamine)、苯菌酮(metrafenone)、米多霉素(mildiomycin)、喹啉铜(oxin-copper)、调环酸钙(prohexadione-calcium)、螺茂胺(spiroxamine)、对甲抑菌灵(tolylfluanid)、N-(环丙基甲氧基亚氨基-(6-二氟甲氧基-2,3-二氟苯基)甲基)-2-苯基乙酰胺、N′-(4-(4-氯-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N′-(4-(4-氟-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N′-(2-甲基-5-三氟甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒、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、2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸甲基-(1,2,3,4-四氢化萘-1-基)酰胺、2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸甲基-(R)-1,2,3,4-四氢化萘-1-基酰胺、乙酸6-叔丁基-8-氟-2,3-二甲基喹啉-4-基酯和甲氧基乙酸6-叔丁基-8-氟-2,3-二甲基-喹啉-4-基酯。
合适的生长调节剂为:
-脱落酸(abscisic acid)、先甲草胺(amidochlor)、嘧啶醇(ancymidol)、6-苄基氨基嘌呤、油菜素内酯(brassinolide)、地乐胺(butralin)、矮壮素(chlormequat)(氯化矮壮素(chlormequat chloride))、胆碱盐酸盐(cholinechloride)、环丙酸酰胺(cyclanilide)、丁酰肼(daminozide)、敌草克(dikegulac)、噻节因(dimethipin)、2,6-二甲基吡啶、乙烯利(ethephon)、氟节胺(flumetralin)、调嘧醇(flurprimidol)、达草氟(fluthiacet)、调吡脲(forchlorfenuron)、赤霉酸(gibberellic acid)、抗倒胺(inabenfide)、吲哚-3-乙酸、马来酰肼、氟草磺(mefluidide)、助壮素(mepiquat)(氯化助壮素(mepiquat chloride)或矮壮素五硼酸盐(mepiquat pentaborate))、萘乙酸、N-6-苄基腺嘌呤、多效唑(paclobutrazol)、调环酸(调环酸钙)、茉莉酸诱导体(prohydrojasmon)、赛二唑素(thidiazuron)、抑芽唑(triapenthenol)、三硫代磷酸三丁酯、2,3,5-三碘苯甲酸、抗倒酯(trinexapac-ethyl)和烯效唑(uniconazole);
-乙烯调节剂:
抑制S-腺苷-L-甲硫氨酸转化为1-氨基环丙烷-1-甲酸(ACC)的乙烯生物合成抑制剂,例如乙烯基甘氨酸衍生物、羟基胺、肟醚衍生物;
阻断ACC转化为乙烯的乙烯生物合成抑制剂,选自:呈植物可利用形式的Co++或Ni++离子;酚型自由基清除剂如没食子酸正丙酯;多元胺,如腐胺、精胺或亚精胺;ACC的结构类似物,如α-氨基异丁酸或L-氨基环丙烯-1-甲酸;水杨酸或噻二唑素-S-甲基;用作ACC氧化酶抑制剂的抗坏血酸结构类似物,如调环酸钙或抗倒酯;
乙烯作用抑制剂,选自:乙烯结构类似物(例如环丙烯)及其衍生物(即,美国专利5518988、6194350)、四烯雌酮(aviglycine)、四烯雌酮盐酸盐(aviglycine hydrochloride)、2,5-降冰片二烯和3-氨基-1,2,4-三唑或Ag2+离子,尤其1-甲基环丙烯。
合适的除草剂为:
-乙酰胺类:乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、异丙甲草胺(metolachlor)、吡草胺(metazachlor)、草萘胺(napropamide)、萘丙胺(naproanilide)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、毒草安(propachlor)、噻醚草胺(thenylchlor);-氨基酸衍生物:双丙氨酰膦(bilanafos)、草甘膦(glyphosate)、草铵膦(glufosinate)、草硫膦(sulfosate);
-芳氧基苯氧基丙酸酯类:炔草酯(clodinafop)、氰氟草酯(cyhalofop-butyl)、唑禾草灵(fenoxaprop)、吡氟禾草灵(fluazifop)、吡氟氯禾灵(haloxyfop)、metamifop、喔草酯(propaquizafop)、喹禾灵(quizalofop)、精喹禾灵(quizalofop-P-tefuryl);
-联吡啶类:敌草快(diquat)、对草快(paraquat);
-(硫代)氨基甲酸酯类:黄草灵(asulam)、苏达灭(butylate)、长杀草(carbetamide)、异苯敌草(desmedipham)、哌草丹(dimepiperate)、扑草灭(eptam)(EPTC)、禾草畏(esprocarb)、草达灭(molinate)、坪草丹(orbencarb)、苯敌草(phenmedipham)、苄草丹(prosulfocarb)、稗草畏(pyributicarb)、杀草丹(thiobencarb)、野麦畏(triallate);
-环己二酮类:丁氧环酮(butroxydim)、烯草酮(clethodim)、噻草酮(cycloxydim)、profoxydim、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim);
-二硝基苯胺类:氟草胺(benfluralin)、丁氟消草(ethalfluralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、氟乐灵(trifluralin);
-二苯醚类:氟锁草醚(acifluorfen)、苯草醚(aclonifen)、治草醚(bifenox)、氯甲草(diclofop)、氯氟草醚(ethoxyfen)、氟黄胺草醚(fomesafen)、乳氟禾草灵(lactofen)、氟硝草醚(oxyfluorfen);
-羟基苄腈类:溴苯腈(bromoxynil)、敌草腈(dichlobenil)、碘苯腈(ioxynil);
-咪唑啉酮类:咪草酯(imazamethabenz)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr);
-苯氧基乙酸类:稗草胺(clomeprop)、2,4-二氯苯氧基乙酸(2,4-D)、2,4-滴丁酸(2,4-DB)、2,4-滴丙酸(dichlorprop)、2甲4氯(MCPA)、MCPA-硫乙基、2甲4氯丁酸(MCPB)、2甲4氯丙酸(mecoprop);
-吡嗪类:杀草敏(chloridazon)、氟哒嗪草酯(flufenpyr-ethyl)、达草氟(fluthiacet)、达草灭(norflurazon)、达草止(pyridate);
-吡啶类:氯氨吡啶酸(aminopyralid)、二氯皮考啉酸(clopyralid)、吡氟草胺(diflufenican)、氟硫草定(dithiopyr)、氟草同(fluridone)、氟草烟(fluroxypyr)、毒莠定(picloram)、picolinafen、噻氟啶草(thiazopyr);
-磺酰脲类:磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、氯嘧黄隆(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟吡磺隆(flucetosulfuron)、氟啶黄隆(flupyrsulfuron)、甲酰胺黄隆(foramsulfuron)、吡氯黄隆(halosulfuron)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、甲磺胺黄隆(mesosulfuron)、精甲磺胺黄隆(metsulfuron-methyl)、烟黄隆(nicosulfuron)、环丙氧黄隆(oxasulfuron)、氟嘧黄隆(primisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、乙黄黄隆(sulfosulfuron)、噻黄隆(thifensulfuron)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、三氟啶黄隆(trifloxysulfuron)、氟胺黄隆(triflusulfuron)、三氟甲黄隆(tritosulfuron)、1-((2-氯-6-丙基咪唑并[1,2-b]哒嗪-3-基)磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲;
-三嗪类:莠灭净(ametryn)、莠去津(atrazine)、草净津(cyanazine)、戊草津(dimethametryn)、乙嗪草酮(ethiozin)、六嗪同(hexazinone)、苯嗪草(metamitron)、赛克津(metribuzin)、扑草净(prometryn)、西玛津(simazine)、特丁津(terbuthylazine)、去草净(terbutryn)、苯氧丙胺津(triaziflam);
-脲类:绿麦隆(chlortoluron)、香草隆(daimuron)、敌草隆(diuron)、伏草隆(fluometuron)、异丙隆(isoproturon)、利谷隆(linuron)、噻唑隆(methabenzthiazuron)、丁唑隆(tebuthiuron);
-其它乙酰乳酸合酶抑制剂:双嘧苯甲酸钠(bispyribac-sodium)、唑嘧磺胺盐(cloransulam-methyl)、唑嘧磺胺(diclosulam)、双氟磺草胺(florasulam)、氟酮黄隆(flucarbazone)、氟唑啶草(flumetsulam)、唑草磺胺(metosulam)、ortho-sulfamuron、五氟磺草胺(penoxsulam)、丙苯磺隆(propoxycarbazone)、pyribambenz-propyl、嘧苯草肟(pyribenzoxim)、pyriftalide、肟啶草(pyriminobac-methyl)、pyrimisulfan、嘧硫苯甲酸(pyrithiobac)、pyroxasulfone、吡唑磺草胺(pyroxsulam);
-其它:氨唑草酮(amicarbazone)、杀草强(aminotriazole)、莎稗磷(anilofos)、氟丁酰草胺(beflubutamid)、草除灵(benazolin)、bencarbazone、呋草磺(benfluresate)、吡草酮(benzofenap)、噻草平(bentazone)、benzobicyclon、除草定(bromacil)、溴丁酰草胺(bromobutide)、氟丙嘧草酯(butafenacil)、草胺磷(butamifos)、唑草胺(cafenstrole)、氟酮唑草(carfentrazone)、吲哚酮草酯(cinidon-ethyl)、敌草索(chlorthal)、环庚草醚(cinmethylin)、异恶草酮(clomazone)、苄草隆(cumyluron)、cyprosulfamide、麦草畏(dicamba)、苯敌快(difenzoquat)、二氟吡隆(diflufenzopyr)、稗内脐蠕孢菌(Drechslera monoceras)、草藻灭(endothal)、乙呋草黄(ethofumesate)、乙苯酰草(etobenzanid)、四唑草胺(fentrazamide)、酰亚胺苯氧乙酸(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、胺草唑(flupoxam)、氟咯草酮(fluorochloridone)、呋草酮(flurtamone)、茚草酮(indanofan)、异恶草胺(isoxaben)、异氟草(isoxaflutole)、环草定(lenacil)、敌稗(propanil)、拿草特(propyzamide)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、硝磺酮(mesotrione)、甲砷酸(methyl arsenic acid)、抑草生(naptalam)、炔丙唑草(oxadiargyl)、恶草灵(oxadiazon)、氯嗪草(oxaziclomefone)、戊唑草(pentoxazone)、pinoxaden、双唑草腈(pyraclonil)、氟唑草酯(pyraflufen-ethyl)、pyrasulfotole、苄草唑(pyrazoxyfen)、吡唑特(pyrazolynate)、灭藻醌(quinoclamine)、saflufenacil、磺草酮(sulcotrione)、磺胺草唑(sulfentrazone)、特草定(terbacil)、tefuryltrione、tembotrione、thiencarbazone、吡草磺(topramezone)、4-羟基-3-[2-(2-甲氧基乙氧基甲基)-6-三氟甲基吡啶-3-羰基]二环[3.2.1]辛-3-烯-2-酮、(3-[2-氯-4-氟-5-(3-甲基-2,6-二氧代-4-三氟甲基-3,6-二氢-2H-嘧啶-1-基)苯氧基]吡啶-2-基氧基)乙酸乙酯、6-氨基-5-氯-2-环丙基嘧啶-4-甲酸甲酯、6-氯-3-(2-环丙基-6-甲基苯氧基)哒嗪-4-醇、4-氨基-3-氯-6-(4-氯苯基)-5-氟-吡啶-2-甲酸、4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-甲酸甲酯以及4-氨基-3-氯-6-(4-氯-3-二甲基氨基-2-氟苯基)吡啶-2-甲酸甲酯。
合适的杀昆虫剂为:
-有机(硫代)磷酸酯类:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、毒虫畏(chlorfenvinphos)、二嗪农(diazinon)、敌敌畏(dichlorvos)、百治磷(dicrotophos)、乐果(dimethoate)、乙拌磷(disulfoton)、乙硫磷(ethion)、杀螟松(fenitrothion)、倍硫磷(fenthion)、异唑磷(isoxathion)、马拉硫磷(malathion)、甲胺磷(methamidophos)、杀扑磷(methidathion)、甲基一六零五(methyl-parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸磷(oxydemeton-methyl)、对氧磷(paraoxon)、一六零五(parathion)、稻丰散(phenthoate)、伏杀硫磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、甲拌磷(phorate)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、丙硫磷(prothiofos)、乙丙硫磷(sulprophos)、四氯烯磷(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(triazophos)、敌百虫(trichlorfon);
-氨基甲酸酯类:棉铃威(alanycarb)、涕灭威(aldicarb)、虫威(bendiocarb)、丙硫克百威(benfuracarb)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、双氧威(fenoxycarb)、呋线威(furathiocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、唑蚜威(triazamate);
-拟除虫菊酯类:丙烯除虫菊酯(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、氯氟氰菊酯(cyhalothrin)、苯醚氰菊酯(cyphenothrin)、氯氰菊酯(cypermethrin)、α-氯氰菊酯(alpha-cypermethrin)、β-氯氰菊酯(beta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、λ-氯氟氰菊酯(lambda-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊酯I和II(pyrethrin I and II)、吡咪唑菌(resmethrin)、灭虫硅醚(silafluofen)、τ-氟胺氰菊酯(tau-fluvalinat)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin)、profluthrin、dimefluthrin;
-昆虫生长抑制剂:a)几丁质合成抑制剂:苯甲酰脲类:定虫隆(chlorfluazuron)、灭蝇胺(cyramazin)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron);噻嗪酮(buprofezin)、茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯唑(etoxazole)、四螨嗪(clofentezine);b)蜕皮激素拮抗剂:特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide)、艾扎丁(azadirachtin);c)保幼激素类似物:蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)、双氧威(fenoxycarb);d)类脂生物合成抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramat);
-烟碱受体激动剂/拮抗剂化合物:噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、吡虫清(acetamiprid)、噻虫啉(thiacloprid)、1-(2-氯噻唑-5-基甲基)-2-硝亚氨基-3,5-二甲基[1,3,5]六氢化三嗪(triazinane);
-GABA拮抗剂化合物:硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、5-氨基-1-(2,6-二氯-4-甲基苯基)-4-胺亚磺酰基(sulfinamoyl)-1H-吡唑-3-硫代羧酰胺;
-大环内酯杀虫剂:齐墩螨素(abamectin)、甲氨基阿维菌素(emamectin)、米尔螨素(milbemectin)、lepimectin、艾克敌105(spinosad)、spinetoram;
-线粒体电子传递抑制剂(METI)I杀螨剂:喹螨醚(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、flufenerim;
-METI II和III化合物:灭螨醌(acequinocyl)、fluacyprim、灭蚁腙(hydramethylnon);
-解偶联剂:氟唑虫清(chlorfenapyr);
-氧化磷酸化抑制剂:三环锡(cyhexatin)、杀螨硫隆(diafenthiuron)、杀螨锡(fenbutatin oxide)、克螨特(propargite);
-蜕皮干扰化合物:灭蝇胺(cyromazine);
-混合功能氧化酶抑制剂:增效醚(piperonyl butoxide);
-其它:benclothiaz、联苯肼酯(bifenazate)、杀螟丹(cartap)、氟啶虫酰胺(flonicamid)、啶虫丙醚(pyridalyl)、拒嗪酮(pymetrozine)、硫磺(sulfur)、硫环杀(thiocyclam)、氟虫酰胺(flubendiamide)、chlorantraniliprole、cyazypyr(HGW86)、cyenopyrafen、flupyrazofos、丁氟螨酯(cyflumetofen)、磺胺螨酯(amidoflumet)、imicyafos、双三氟虫脲(bistrifluron)和新喹唑啉(pyrifluquinazon)。
优选所述包封农药包含至少一种上述农药。更优选所述包封农药包含杀真菌剂、安全剂和/或生长调节剂。甚至更优选所述包封农药包含杀真菌剂和/或生长调节剂。尤其优选所述包封农药包含杀真菌剂如嗜球果伞素类、三唑类或羧酰胺类。最特别地优选所述包封农药包含唑菌胺酯或式I的1-甲基吡唑-4-基甲酰苯胺,优选唑菌胺酯。在包封农药包含生长调节剂的情况下,该生长调节剂优选为阻断ACC转化成乙烯的乙烯生物合成抑制剂、乙烯作用抑制剂、水杨酸、噻二唑素-S-甲基、调环酸钙、抗倒酯、环丙烯及其衍生物,更优选为水杨酸、噻二唑素-S-甲基、调环酸钙、抗倒酯或1-甲基环丙烯。
在另一优选实施方案中,包封农药在芳族烃溶剂中(优选在馏程为232-278℃的芳族烃中,例如获自Exxon的200)在20℃下的溶解度为至少5g/l,更优选至少50g/l,甚至更优选至少150g/l,尤其优选至少200g/l,最优选至少300g/l。
在优选实施方案中,本发明方法包括用包封农药与未包封的其他农药的混合物进行处理。所述其他农药可选自上述农药。所述未包封的其他农药可呈溶解、悬浮和/或乳化形式存在。优选所述未包封的其他农药呈溶解形式存在。所述未包封的其他农药可包含杀真菌剂、除草剂、杀昆虫剂或生长调节剂。合适的杀真菌剂可为嗜球果伞素类、三唑类或羧酰胺类,更优选为三唑类。合适的除草剂可为氨基酸衍生物、环己二酮类、咪唑啉酮类或麦草畏,优选为草甘膦、草铵膦、噻草酮、咪唑啉酮类或麦草畏。合适的杀昆虫剂可为拟除虫菊酯类或烟碱受体激动剂/拮抗剂化合物,更优选为拟除虫菊酯,尤其为α-氯氰菊酯。合适的生长调节剂可为氯化矮壮素、氯化助壮素、水杨酸、噻二唑素-S-甲基、调环酸钙、抗倒酯、环丙烯及其衍生物,更优选为氯化矮壮素、水杨酸、噻二唑素-S-甲基、调环酸钙、抗倒酯或1-甲基环丙烯。
在更优选的实施方案中,所述包封农药包含杀真菌剂,且所述未包封的其他农药包含杀真菌剂,其中所述杀真菌剂可相同或不同。优选包封农药包含嗜球果伞素类或羧酰胺类,且未包封的其他农药包含三唑类或羧酰胺类。在尤其优选的实施方案中,包封农药包含唑菌胺酯,且未包封的其他农药包含氧唑菌、环戊唑菌、啶酰菌胺或式I的1-甲基吡唑-4-基甲酰苯胺。在另一尤其优选的实施方案中,包封农药包含式I的1-甲基吡唑-4-基甲酰苯胺,且未包封的其他农药包含氧唑菌或环戊唑菌。在尤其优选实施方案中,包封农药包含唑菌胺酯,且未包封的其他农药包含氧唑菌、环戊唑菌、啶酰菌胺或fluxapyroxad。
在另一更优选的实施方案中,包封农药包含唑菌胺酯且未包封的其他农药包含草甘膦、草铵膦、麦草畏、咪草啶酸、灭草烟或咪草烟。
在又一更优选的实施方案中,包封农药包含唑菌胺酯且未包封的其他农药包含氯化矮壮素、氯化助壮素、助壮素五硼酸盐或调环酸钙。
在又一更优选的实施方案中,包封农药包含唑菌胺酯且未包封的其他农药包含α-氯氰菊酯或锐劲特。
本发明的方法尤其适于防止以下植物病害:
向日葵(例如婆罗门参白锈菌(A.tragopogonis))和油菜(白锈菌(A.candida))上的白锈菌属(Albugo);油菜(芸苔生链格孢(A.brassicola)或芸苔链格孢(A.brassicae))和向日葵(向日葵链格孢(A.Helianth))上的链格孢属(Alternaria);平脐蠕孢属(Bipolaris)和内脐蠕孢属(Drechslera)(有性型:旋孢腔菌属(Cochliobolus)),例如玉米上的叶斑病(玉蜀黍平脐蠕孢(D.maydis)和玉米生离蠕孢(B.zeicola));玉米上的玉米北方炭疽病(Aureobasidium zeae)(同义词:玉蜀黍球梗孢(Kabatiella zeae));油菜上的灰葡萄孢(Botrytis cinerea)(有性型:灰葡萄孢霉(Botryotinia fuckeliana):灰霉病);玉米(例如灰斑病:玉米尾孢菌(C.zeae-maydis))、甘蔗(例如大豆灰斑病菌(C.sojina)或大豆紫斑病菌(C.kikuchii))上的尾孢属(Cercospora)(尾孢叶斑病);玉米上的草芽枝孢(Cladosporium herbarum);玉米(灰色长蠕孢(C.carbonum))上的旋孢腔菌属(无性型:长蠕孢属(Helminthosporium)或平脐蠕孢属)(叶斑病);玉米(例如禾生炭疽病菌(C.graminicola):炭疽茎腐病)上的剌盘孢属(Colletotrichum)(有性型:围小丛壳菌属(Glomerella))(炭疽病);玉米上的内脐蠕孢属(同义词长蠕孢属,有性型:核腔菌属(Pyrenophora));油菜(例如十字花科白粉菌(E.Cruciferarum))上的半知菌附球菌属(Epicoccum);玉米(例如玉米大斑病菌(E.turcicum))上的突脐蠕孢属(Exserohilum)(同义词长蠕孢属);各种植物上的镰孢霉属(Fusarium)(有性型:赤霉属(Gibberella))(枯萎病,根腐病或茎腐病),例如玉米上的串珠镰孢菌(F.moniliforme)、再育镰孢菌(F.proliferatum)、胶孢镰孢菌(F.subglutinans)、轮枝镰孢菌(F.Verticillioides)和玉蜀黍镰孢菌(F.Zeae)(禾谷镰孢菌(Fusarium graminearum));玉米上的禾顶囊壳(Gaeumannomyces graminis)(全蚀病);玉米上的长蠕孢属(同义词内脐蠕孢,有性型:旋孢腔菌属);玉米上的菜豆壳球孢(Macrophominaphaseolina);玉米眼斑病(玉蜀黍梗孢(kabatiella zeae));油菜(例如寄生霜霉(P.parasitica))上的霜霉属(Peronospora)(霜霉病);油菜上的黑胫茎点霉(Phoma lingam)(根腐病和茎腐病)和向日葵上的茎点霉黑茎病(Phomamacdonaldii);向日葵上的拟茎点霉属(Phomopsis);玉米上的玉米褐斑病菌(Physoderma maydis)(褐斑病);油菜上的芸苔根肿菌(Plasmodiophorabrassicae)(根肿病);霜霉属(Plasmopara),向日葵上的霍尔斯单轴霉(P.halstedii),向日葵中的向日葵柄锈菌(Puccinia helianthi),玉米、油菜和向日葵上的腐霉属(Pythium)(立枯病);玉米、油菜上的丝核菌属(Rhizoctonia);田间作物例如油菜和向日葵(例如核盘菌(S.sclerotiorum))上的核盘菌属(Sclerotinia)(茎腐病或白绢病);玉米(例如玉米大斑病菌(S.turcicum),同义词大斑凸脐蠕孢(Helminthosporium turcicum))上的毛球腔菌属(Setosphaeria)(叶斑病);玉米(例如丝轴黑粉菌(S.reiliana):丝黑穗病)上的轴黑粉菌属(Sphacelotheca)(黑穗病);玉米上的大孢狭壳柱孢(Stenocarpella macrospora);例如玉米(例如玉蜀黍黑粉菌(U.maydis):玉米黑穗病)和甘蔗上的黑粉菌属(Urocystis);以及各种植物例如田间作物上的轮枝孢菌属(Verticillium)(枯萎病),例如油菜上的大丽轮枝孢(V.dahliae);玉米(高粱柄锈菌(P.Sorghi)和多堆柄锈菌(P.Polysora))、向日葵(向日葵柄锈菌(P.helianthi))、甘蔗(屈恩柄锈菌(P.Kuehnii)和黑顶柄锈菌(P.melanocephela))上的柄锈菌属(Puccinia)。在另一实施方案中,本发明尤其适于防治油菜籽油菜中的核盘菌和芸苔链格孢。
本发明方法可用于改善作物健康。术语“植物健康”应理解为表示植物和/或其产物的状况,其由数种指标单独或彼此组合决定,所述指标如产量(例如提高的生物质和/或提高的有价值成分的含量)、植物活力(例如改善的植物生长和/或更绿的叶子(“绿化效果”))、品质(例如改善的某些成分的含量或组成)、对非生物和/或生物逆境的耐受性以及生产效率(提高收获效率)。上述植物健康状况的指标可相互独立或可互为因果。
所述包封农药可配制成农业化学组合物。农业化学组合物包含农药有效量的农药。术语“有效量”表示足以防治对栽培植物有害的害物且不会对所处理的植物造成实质性损害的农药的量。该量可在宽范围内变化且取决于各种因素如待防治的真菌种属、处理的栽培植物、气候条件和所用的具体农药。
所述农业化学组合物也可包含农业化学组合物中常用的助剂。所用助剂分别取决于具体施用形式和活性物质。合适助剂的实例为溶剂、固体载体、分散剂或乳化剂(例如其他增溶剂、保护性胶体、表面活性剂和粘合剂)、有机及无机增稠剂、杀菌剂、防冻剂或消泡剂。
合适的溶剂为水;有机溶剂,例如中至高沸点的矿物油馏分如煤油和柴油,此外还有煤焦油,以及植物或动物来源的油,脂族、环状和芳族烃类,例如甲苯、二甲苯、石蜡、四氢化萘、烷基化萘或其衍生物,醇类如甲醇、乙醇、丙醇、丁醇和环己醇,二醇类,酮类如环己酮和γ-丁内酯,二甲基脂肪酰胺,脂肪酸和脂肪酸酯以及强极性溶剂,例如胺类如N-甲基吡咯烷酮。
合适的表面活性剂(助剂、润湿剂、增粘剂、分散剂或乳化剂)为芳族磺酸如木素磺酸(类型,挪威Borregaard)、苯酚磺酸、萘磺酸(类型,Akzo Nobel,美国)和二丁基萘磺酸(类型,德国BASF)以及脂肪酸的碱金属、碱土金属和铵盐,烷基磺酸盐和烷基芳基磺酸盐,烷基硫酸盐,月桂基醚硫酸化物,脂肪醇硫酸盐,以及硫酸化十六-、十七-和十八烷醇,硫酸化的脂肪醇乙二醇醚盐,此外还有萘或萘磺酸与苯酚和甲醛的缩合物,聚氧乙烯辛基苯基醚,乙氧基化异辛基酚,辛基酚,壬基酚,烷基苯基聚乙二醇醚,三丁基苯基聚乙二醇醚,三硬脂基苯基聚乙二醇醚、烷基芳基聚醚醇,醇和脂肪醇/氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚,乙氧基化聚氧丙烯,月桂醇聚乙二醇醚乙缩醛,山梨醇酯,木素亚硫酸盐废液,以及蛋白质,变性蛋白,多糖(例如甲基纤维素),疏水改性淀粉,聚乙烯醇(类型,Clariant,瑞士),聚羧酸盐(类型,BASF,德国),聚烷氧基化物,聚乙烯胺(类型,BASF,德国),聚乙烯基吡咯烷酮及其共聚物。
增稠剂(即赋予组合物以改进的流动性能,即静止状态下的高粘度和搅动过程中的低粘度的化合物)的实例为多糖及有机和无机粘土,例如黄原胶(CP Kelco,美国)、23(Rhodia,法国)、(R.T.Vanderbilt,美国)或(Engelhard公司,NJ,美国)。可添加杀菌剂以保存并稳定所述组合物。合适杀菌剂的实例为基于双氯酚和苄醇半缩甲醛的那些(ICI的或Thor Chemie的RS和Rohm&Haas的MK),以及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(Thor Chemie的MBS)。合适防冻剂的实例为乙二醇、丙二醇、尿素和甘油。消泡剂实例为聚硅氧烷乳液(例如SRE,德国Wacker或Rhodia,法国),长链醇,脂肪酸,脂肪酸盐,有机氟化合物及其混合物。
合适的话,可在即将使用(桶混)之前向所述农药或包含所述农药的组合物中添加各种油、润湿剂、辅助剂、除草剂、杀菌剂、其他杀真菌剂和/或农药。这些试剂可与本发明组合物以1∶100-100∶1、优选1∶10-10∶1的重量比混合。可使用的辅助剂尤其为聚醚改性的聚硅氧烷如BreakS240;脂肪醇烷氧基化物,如LF 120(BASF)和ON30(BASF);EO/PO嵌段聚合物,例如RPE 2035和Genapol B,醇乙氧基化物,例如Lutensol XP琥珀酸二辛酯磺酸钠,如Leophen聚乙烯醇,例如LF 240(BASF)。尤其优选辅助剂为脂肪醇烷氧基化物和聚醚改性的聚硅氧烷。
用包封农药处理作物可通过经由地面或空中施用,优选经由地面施用来施用所述农药而进行。合适的施用装置为前给药式装置(predosagedevice)、背负式喷雾器、喷雾桶或喷雾飞机。优选通过地面施用,例如借助前给药式装置、背负式喷雾器或喷雾桶进行处理。地面施用可通过使用者在作物田间行走或借助机动车辆,优选借助机动车辆而进行。所述机动车辆可具有标准离地间隙,例如至多为100cm,优选至多85cm,尤其是至多70cm。通常,每公顷农业有效面积施用50-500升,优选80-400升即用型喷雾液。取决于所需效果的类型,施用的农药量通常为0.001-3kg/ha,优选0.005-2kg/ha,更优选0.05-0.9kg/ha,尤其为0.1-0.75kg/ha。
本发明方法通常有助于避免农药的区域性施用。因此,本发明方法可用于在封闭建筑物(例如温室)外和/或在人工生长盆(例如由塑料制成的生长盆、泥炭盆、育苗盘)外处理作物。优选作物直接生长于农田耕作土壤中。这意味着作物不在人工生长盆中生长。
术语“包封农药”是指包含核和包封材料的任意种类的胶囊,其中所述核包含至少一种农药。优选所述核包含至少一种农药和至少一种有机溶剂(有机溶剂的实例将于下文给出)。在尤其优选的实施方案中,所述核包含溶于至少一种有机溶剂中的至少一种农药。通常,在25℃下核中至少80重量%,优选至少90重量%的农药溶于所述有机溶剂中。包封农药的包封材料优选包含聚氨酯或聚(甲基)丙烯酸酯。
聚(甲基)丙烯酸酯为已知的包封材料,例如由WO2008/071649、EP0457154或DE 10 2007 055 813已知。聚(甲基)丙烯酸酯通常包含呈聚合形式的丙烯酸和/或甲基丙烯酸的C1-C24烷基酯、丙烯酸、甲基丙烯酸和/或马来酸。更优选聚(甲基)丙烯酸酯包含甲基丙烯酸甲酯和甲基丙烯酸。聚(甲基)丙烯酸酯也可包含呈聚合形式的一种或多种二官能或多官能单体。聚(甲基)丙烯酸酯可进一步包含其他单体。
更优选聚(甲基)丙烯酸酯聚合物由以下物质合成:
30-100重量%,基于单体总重量,一种或多种选自丙烯酸和/或甲基丙烯酸的C1-C24烷基酯、丙烯酸、甲基丙烯酸和马来酸的单体(单体I),
10-70重量%,基于单体总重量,一种或多种二官能或多官能单体(单体II),和
0-40重量%,基于单体总重量,一种或多种其他单体(单体III)。
所述胶囊通常包含农药囊核和聚合物囊壁。囊核主要由(达大于95重量%的程度)农药构成。取决于温度,所述囊核可为固体或液体。
通常在囊壁中掺入保护性胶体,因此其同样为囊壁成分。一般而言,更具体地聚合物表面具有保护性胶体。因此,可存在以微胶囊总重量计至多为10重量%的保护性胶体。
胶囊的平均粒度(借助光散射法获得的z均值;优选D4,3平均值)为0.5-50μm,优选0.5-8μm,更优选1-5μm,尤其为1-3μm。在另一优选实施方案中,胶囊的平均粒度D90(借助光散射法测定)为0.5-50μm,优选1-15μm,更优选3-9μm,尤其为4.5-7.5μm。囊核与囊壁的重量比通常为50∶50-95∶5。优选核/壁比为70∶30-93∶7。
囊壁的聚(甲基)丙烯酸酯通常包含呈共聚形式的以单体总重量计为至少30重量%,在优选形式中为至少40重量%,在尤其优选形式中为至少50重量%,更特别地为至少60重量%,极其优选为至少70重量%,且至多为100重量%,优选不超过90重量%,更特别地为不超过85重量%,极其优选为不超过80重量%的至少一种选自丙烯酸和/或甲基丙烯酸的C1-C24烷基酯、丙烯酸、甲基丙烯酸和马来酸的单体(单体I)。
此外,囊壁的聚(甲基)丙烯酸酯优选包含呈共聚形式的以单体总重量计为至少10重量%,优选至少15重量%,优选至少20重量%,且通常不超过70重量%,优选不超过60重量%,尤其优选不超过50重量%的一种或多种二官能或多官能单体(单体II)。在另一优选实施方案中,囊壁的聚(甲基)丙烯酸酯优选包含呈共聚形式的以单体总重量计为至少10重量%,优选至少15重量%,且通常不超过50重量%,优选不超过40重量%的一种或多种多官能单体(单体II)。
此外,聚(甲基)丙烯酸酯也可包含呈共聚形式的至多为40重量%,优选至多30重量%,更特别地为至多20重量%的其他单体III。囊壁优选仅由组I和II单体合成。
合适的单体I为丙烯酸和/或甲基丙烯酸的C1-C24烷基酯以及C3和C4不饱和羧酸,例如丙烯酸、甲基丙烯酸以及马来酸。合适的单体I为丙烯酸异丙酯、丙烯酸异丁酯、丙烯酸仲丁酯和丙烯酸叔丁酯以及相应的甲基丙烯酸酯,且尤其优选丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯和丙烯酸正丁酯以及相应的甲基丙烯酸酯。通常优选甲基丙烯酸酯和甲基丙烯酸。
根据一个优选实施方案,微胶囊壁包含呈共聚形式的以单体总量计为25-75重量%的马来酸、甲基丙烯酸和/或丙烯酸,更特别地为甲基丙烯酸。
合适的单体II为二官能或多官能单体。二官能或多官能单体意指具有至少两个非共轭烯属双键的化合物。主要包括二乙烯基单体和多乙烯基单体。在聚合过程中,所述单体使囊壁交联。在另一优选实施方案中,合适的单体II为多官能单体。
合适的二乙烯基单体为二乙烯基苯和二乙烯基环己烷。优选二乙烯基单体为二醇与丙烯酸或甲基丙烯酸的二酯、以及这些二醇的二烯丙基醚和二乙烯基醚。例如可提及乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、甲基烯丙基甲基丙烯酰胺、丙烯酸烯丙基酯和甲基丙烯酸烯丙酯。尤其优选丙二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、戊二醇二丙烯酸酯和己二醇二丙烯酸酯以及相应的甲基丙烯酸酯。
优选多乙烯基单体为多元醇与丙烯酸和/或甲基丙烯酸的聚酯、以及这些多元醇的聚烯丙基醚和聚乙烯基醚、三乙烯基苯和三乙烯基环己烷。尤其优选三羟甲基丙烷三丙烯酸酯和三羟甲基丙烷三甲基丙烯酸酯、季戊四醇三烯丙基醚、季戊四醇四烯丙基醚、季戊四醇三丙烯酸酯和季戊四醇四丙烯酸酯及其工业级混合物。
单体III包括不同于单体I和II的其他单体,例如乙酸乙烯酯、丙酸乙烯酯、乙烯基吡啶及苯乙烯或α-甲基苯乙烯。尤其优选衣康酸、乙烯基膦酸、马来酸酐、丙烯酸2-羟乙酯和甲基丙烯酸2-羟乙酯、丙烯酰胺基-2-甲基丙磺酸、甲基丙烯腈、丙烯腈、甲基丙烯酰胺、N-乙烯基吡咯烷酮、N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、甲基丙烯酸二甲基氨基乙酯和甲基丙烯酸二乙基氨基乙酯。
微胶囊的制备方法为所谓的原位聚合法。微胶囊的形成原理基于由单体、自由基引发剂、保护性胶体和待包封的亲脂性物质制备稳定的水包油乳液。随后通过加热引发单体聚合,并且如果合适的话通过进一步提高温度进行控制,所得聚合物形成包封所述亲脂性物质的囊壁。该一般原理例如描述于DE A 101 39 171中,以引用方式将其明确并入本文。
具有包含聚氨酯的包封材料的胶囊是公知的且可以通过类似于现有技术的方式制备。其优选通过合适的聚合物壁形成材料的界面聚合方法制备。界面聚合通常在核材料的含水油包水乳液或悬浮液中进行,所述乳液或悬浮液包含溶于其中的至少一部分聚合物壁形成材料。在聚合过程中,所述聚合物与核材料分离至核材料与水的界面处,由此形成微胶囊壁。由此获得微胶囊材料的含水悬浮液。用于制备含农药化合物的微胶囊的界面聚合方法的合适方法已公开于现有技术中,例如US3,577,515、US4,280,833、US5,049,182、US5,229,122、US5,310,721、US5,705,174、US5,910,314、WO95/13698、WO00/10392、WO01/68234、WO03/099005、EP619,073或EP1,109,450,所述专利全部被引用。
聚氨酯胶囊的合适壁形成材料优选包括2组分或3组分体系,如:
-多官能异氰酸酯/多官能醇,
-多官能异氰酸酯/多官能胺,和
-多官能异氰酸酯+多官能酸或酰基氯/多官能胺。
优选聚氨酯包含呈聚合形式的多官能异氰酸酯(也称为多异氰酸酯)和多官能胺(也称为多元胺)。
也已知异氰酸酯基团可与水反应生成氨基甲酸基团,所述氨基甲酸基团又可脱除二氧化碳而最终获得胺基团。
在又一实施方案中,可通过使多官能异氰酸酯与水反应制备2组分体系多官能异氰酸酯/多官能胺。
在本发明极其优选的实施方案中,聚合壁材料为聚氨酯。聚氨酯通常通过任选在多官能酰基氯存在下使具有至少两个异氰酸酯基团的多异氰酸酯与具有至少两个伯氨基的多元胺反应以形成聚脲壁材料而形成。多异氰酸酯可单独或以两种或更多种两种多异氰酸酯的混合物形式使用。适用的多异氰酸酯包括二异氰酸酯和三异氰酸酯,其中异氰酸酯基团连接于脂族或脂环族结构部分(脂族异氰酸酯)或连接于芳族结构部分(芳族异氰酸酯)。合适的脂族二异氰酸酯实例包括四亚甲基二异氰酸酯、五亚甲基二异氰酸酯和六亚甲基二异氰酸酯以及脂环族异氰酸酯如异佛尔酮二异氰酸酯、1,4-双异氰酸酯基环己烷和双-(4-异氰酸酯基环己基)甲烷。合适的芳族异氰酸酯包括甲苯二异氰酸酯(TDI:2,4-异构体与2,6-异构体的混合物)、二苯基亚甲基-4,4′-二异氰酸酯(MDI)、多亚甲基多苯基异氰酸酯、2,4,4′-二苯基醚三异氰酸酯、3,3′-二甲基-4,4′-二苯基二异氰酸酯、3,3′-二甲氧基-4,4′-二苯基二异氰酸酯、1,5-亚萘基二异氰酸酯和4,4′,4″-三苯基甲烷三异氰酸酯。合适的还有上述二异氰酸酯的高级低聚物,如上述二异氰酸酯的异氰脲酸酯和缩二脲(biurethe)及其与上述二异氰酸酯的混合物。
在另一优选实施方案中,所述多异氰酸酯为低聚异氰酸酯。这类低聚异氰酸酯可包含呈低聚形式的上述脂族二异氰酸酯和/或芳族异氰酸酯。低聚异氰酸酯的平均官能度为2.0-4.0,优选2.1-3.2,更优选2.3-3.0。这些低聚异氰酸酯的粘度(按照DIN 53018测定)通常为20-1000mPas,更优选80-500mPas,尤其为150-320mPas。这类低聚异氰酸酯例如可以以商品名M10、M20、M50、M70、M200、MM103由BASF SE购得或以A270由Bayer AG购得。
同样合适的还有二异氰酸酯与多元醇如乙二醇、甘油和三羟甲基丙烷的加合物,所述加合物通过在二异氰酸酯的摩尔数与相应醇及其混合物的羟基摩尔数相等的情况下,使每摩尔多元醇与述二异氰酸酯加合而获得。以此方式,若干二异氰酸酯分子经由氨基甲酸酯基团连接至所述多元醇,从而形成高分子量聚异氰酸酯。尤其合适的此类产物L(Bayer公司,Pittsburgh)可通过使3摩尔甲苯二异氰酸酯与1摩尔2-乙基甘油(1,1-双羟甲基丙烷)反应而制备。其他合适的产物通过使六亚甲基二异氰酸酯或异佛尔酮二异氰酸酯与乙二醇或甘油加合而获得。
优选多异氰酸酯为异佛尔酮二异氰酸酯、二苯基甲烷-4,4′-二异氰酸酯、甲苯二异氰酸酯。在另一实施方案中,优选多异氰酸酯为低聚异氰酸酯。
在本发明范围内合适的多元胺应理解为通常意指分子中含有两个或更多个氨基的那些化合物,所述氨基可与脂族或芳族结构部分连接。合适的脂族多元胺实例为式H2N-(CH2)n-NH2的α,ω-二胺,其中n为2-6的整数。这类二胺的实例为乙二胺、亚丙基-1,3-二胺、四亚甲基二胺、五亚甲基二胺和六亚甲基二胺。优选二胺为六亚甲基二胺。
其他合适的脂族多元胺为式H2N-(CH2-CH2-NH)n-H的聚乙烯亚胺,其中n为2-5的整数。这类聚乙烯亚胺的代表性实例为二亚乙基三胺、三亚乙基四胺、四亚乙基五胺和五亚乙基六胺。其他合适的脂族多元胺为二氧杂烷烃-α,ω-二胺,例如式H2N-(CH2)3O-(CH2)4O-(CH2)3-NH2的4,9-二氧杂十二烷-1,12-二胺。
合适的芳族多元胺实例为1,3-苯二胺、2,4-甲苯二胺和2,6-甲苯二胺、4,4′-二氨基二苯基甲烷、1,5-二氨基萘、1,3,5-三氨基苯、2,4,6-三氨基甲苯、1,3,6-三氨基萘、2,4,4′-三氨基二苯基醚、3,4,5-三氨基-1,2,4-三唑和1,4,5,8-四氨基蒽醌。不溶于或不能充分溶于水的那些多元胺可以以其盐酸盐形式使用。
多元胺(如上文所述的那些)可单独或以两种或更多种多元胺的混合物形式使用。
各互补壁形成组分的相对量随其当量而变化。通常优选大约为化学计量量,尽管也可使用过量的一种组分,尤其是过量的多异氰酸酯。壁形成组分的总量大致对应于聚合物壁形成材料的总量。
本发明还涉及一种包含包封农药的组合物,其中所述农药嗜球果伞素类且所述包封农药的包封材料包含聚氨酯。这类组合物尤其适用于本发明的方法和本发明的用途。优选嗜球果伞素为腈嘧菌酯、醚菌胺、enestroburin、氟嘧菌酯、亚胺菌、叉氨苯酰胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、pyribencarb、肟菌酯。更优选嗜球果伞素为唑菌胺酯。合适的聚氨酯包封材料及其制备如上文所述。聚氨酯通常包含呈聚合形式的多官能异氰酸酯和多官能胺。优选多异氰酸酯为异佛尔酮二异氰酸酯、二苯基甲烷-4,4′-二异氰酸酯和甲苯二异氰酸酯。在另一优选实施方案中,多异氰酸酯包括芳族多异氰酸酯,如甲苯二异氰酸酯(TDI:2,4-异构体和2,6-异构体的混合物)、二苯基甲烷-4,4′-二异氰酸酯(MDI),优选MDI。在另一优选实施方案中,多异氰酸酯包括上文所述的低聚异氰酸酯。优选多官能胺为脂族多元胺,如式H2N-(CH2)n-NH2的α,ω-二胺,其中n为2-6的整数。这类二胺的实例为乙二胺、亚丙基-1,3-二胺、四亚甲基二胺、五亚甲基二胺和六亚甲基二胺。优选二胺为六亚甲基二胺。
包含包封农药(其中所述农药为嗜球果伞素且包封农药的包封材料包含聚氨酯)的组合物优选包含10-450g/l包封的嗜球果伞素,50-450g/l有机溶剂,1-100g/l表面活性剂(非离子型和/或阴离子型表面活性剂)以及补足至1.0L的水。更优选所述组合物包含100-350g/l包封的嗜球果伞素,150-400g/l有机溶剂,10-60g/l表面活性剂以及补足至1.0L的水。在另一优选实施方案中,所述组合物包含10-300g/l多异氰酸酯和0.5-30g/l多元胺。更优选所述组合物包含50-150g/l多异氰酸酯和1-10g/l多元胺。合适的有机溶剂实例为中至高沸点矿物油馏分如煤油或柴油,此外还有煤焦油以及植物或动物来源的油,脂族、环状和芳族烃类,例如甲苯、二甲苯、石蜡、四氢化萘、烷基化萘或其衍生物。优选所述包封农药的核包含至少一种嗜球果伞素和至少一种有机溶剂(如脂族、环状和芳族烃类)。在尤其优选的实施方案中,包封农药的核包含溶于至少一种有机溶剂中的至少一种嗜球果伞素。合适的表面活性剂如上文所列的那些。优选使用至少两种不同表面活性剂的混合物。更优选所述表面活性剂为非离子型表面活性剂与离子型表面活性剂的混合物。所述组合物也可包含农业化学组合物中常用的助剂。合适助剂的实例为溶剂、固体载体、分散剂或乳化剂(例如其他增溶剂、保护性胶体、表面活性剂和粘合剂)、有机及无机增稠剂、杀菌剂、防冻剂或消泡剂。这类助剂的合适实例如上文所列的那些。
本发明还涉及一种包含包封农药的组合物,其中所述农药为溶于至少一种有机溶剂中的农药,且所述包封农药的包封材料包含聚氨酯。这类组合物尤其适用于本发明的方法及本发明的用途。所述有机溶剂优选为非质子有机溶剂,更优选为中至高沸点矿物油馏分如煤油或柴油,此外还有煤焦油以及植物或动物来源的油,脂族、环状及芳族烃类,例如甲苯、二甲苯、石蜡、四氢化萘、烷基化萘或其衍生物。最优选地,有机溶剂优选为脂族、环状及芳族烃类。优选溶于至少一种有机溶剂中的农药为嗜球果伞素,例如腈嘧菌酯、醚菌胺、enestroburin、氟嘧菌酯、亚胺菌、叉氨苯酰胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、pyribencarb、肟菌酯。更优选所述嗜球果伞素为唑菌胺酯。合适的聚氨酯包封材料及其制备如上文所述。聚氨酯通常包含呈聚合形式的多官能异氰酸酯和多官能胺。优选多异氰酸酯为异佛尔酮二异氰酸酯、二苯基甲烷-4,4′-二异氰酸酯和甲苯二异氰酸酯。在另一优选实施方案中,所述多异氰酸酯包括芳族多异氰酸酯,如甲苯二异氰酸酯(TDI:2,4-异构体与2,6-异构体的混合物)、二苯基甲烷-4,4′-二异氰酸酯(MDI),优选MDI。在另一优选实施方案中,所述多异氰酸酯包括上文所述的低聚异氰酸酯。优选多官能胺为脂族多元胺,例如式H2N-(CH2)n-NH2的α,ω-二胺,其中n为2-6的整数。这类二胺的实例为乙二胺、亚丙基-1,3-二胺、四亚甲基二胺、五亚甲基二胺和六亚甲基二胺。优选二胺为六亚甲基二胺。
包含包封农药(其中所述农药为溶于至少一种有机溶剂中的农药,且包封农药的包封材料包含聚氨酯)的组合物优选包含10-450g/l包封农药(例如嗜球果伞素),50-450g/l有机溶剂,1-100g/l表面活性剂(非离子型和/或阴离子型表面活性剂)以及补足至1.0L的水。更优选所述组合物包含100-350g/l包封农药(例如嗜球果伞素),150-400g/l有机溶剂,10-60g/l表面活性剂以及补足至1.0L的水。在另一优选实施方案中,所述组合物包含10-300g/l多异氰酸酯和0.5-30g/l多元胺。更优选所述该组合物包含50-150g/l多异氰酸酯和1-10g/l多元胺。合适的有机溶剂实例为中至高沸点矿物油馏分如煤油或柴油,此外还有煤焦油以及植物或动物来源的油,脂族、环状及芳族烃类,例如甲苯、二甲苯、石蜡、四氢化萘、烷基化萘或其衍生物。优选所述包封农药的核包含至少一种嗜球果伞素和至少一种有机溶剂(如脂族、环状及芳族烃类)。合适的表面活性剂如上文所列。优选使用至少两种不同表面活性剂的混合物。更优选所述表面活性剂为非离子型表面活性剂与离子型表面活性剂的混合物。所述组合物也可包含农业化学组合物中常用的助剂。合适的助剂实例为溶剂、固体载体、分散剂或乳化剂(例如其他增溶剂、保护性胶体、表面活性剂和粘合剂)、有机及无机增稠剂、杀菌剂、防冻剂或消泡剂。这些助剂的合适实例如上文所列。
本发明进一步涉及一种包含包封的农药与未包封的其他农药的混合物的组合物,其中所述包封的农药包含嗜球果伞素类或羧酰胺类,且所述未包封的其他农药包含三唑类或羧酰胺。这类组合物尤其适用于本发明方法及本发明用途。在优选实施方案中,所述包封的农药包括唑菌胺酯,且所述未包封的其他农药包括氧唑菌、环戊唑菌、啶酰菌胺或式I的1-甲基吡唑-4-基甲酰苯胺。在另一优选实施方案中,所述包封的农药包括式I的1-甲基吡唑-4-基甲酰苯胺,且所述未包封的其他农药包括氧唑菌或环戊唑菌。所述包封农药的包封材料通常包括聚氨酯或聚(甲基)丙烯酸酯。合适的聚氨酯或聚(甲基)丙烯酸酯如上文所述。所述包封农药的核优选包含至少一种农药和至少一种有机溶剂(例如脂族、环状及芳族烃类)。在尤其优选的实施方案中,所述包封农药的核包含溶于至少一种有机溶剂中的至少一种农药。所述组合物优选包含10-450g/l包封的农药,50-450g/l有机溶剂,1-100g/l表面活性剂(非离子型和/或阴离子型表面活性剂)以及补足至1.0L的水。更优选所述组合物包含100-350g/l包封的农药,150-400g/l有机溶剂,10-60g/l表面活性剂以及补足至1.0L的水。在另一优选实施方案中,所述组合物包含10-300g/l多异氰酸酯和0.5-30g/l多元胺。更优选所述组合物包含50-150g/l多异氰酸酯和1-10g/l多元胺。所述组合物也可包含农业化学组合物中常用的助剂。合适助剂的实例为表面活性剂、溶剂、固体载体、分散剂或乳化剂(例如其他增溶剂、保护性胶体、表面活性剂和粘合剂)、有机及无机增稠剂、杀菌剂、防冻剂或消泡剂。这些助剂的合适实例如上文所列。合适的表面活性剂如上文所列。优选使用至少两种不同表面活性剂的混合物。更优选所述表面活性剂为非离子型表面活性剂与离子型表面活性剂的混合物。
本发明还涉及包封农药在于作物生长高度至多为120cm时对最终生长高度为至少140cm的作物进行农药处理中的用途。优选所述作物为玉米、向日葵、油菜籽油菜、甘蔗、高粱或芒属。在另一优选实施方案中,所述用途用于经由地面施用的农药处理。合适的农药、包封材料、最终生长高度、作物的生长高度和农药处理如上文所述。
本发明具有若干优点:可比通常所实施的处理更早对作物进行处理,同时仍提供与在较晚生长阶段的最佳时间点进行处理相当的产量。因此,在施用时作物植株较小且不仅可通过空中施用,还可借助标准设备从地面进行处理。更少的施用次数(尤其是在玉米中)使得作物保护更经济且耗时更少。农场主可使用其自有设备,因而节约了成本且施用时间可由种植者决定。因可用于作物处理的飞机数量之故,尤其是在美国可借助空中施用设备处理的面积有限。空中施用并非世界大多数国家的选择,因此目前种植者必须借助常规设备在并非最佳的时间点施用至作物,从而使得产量响应比在较晚施用时间可获得的小。另一优点是在作物植株较小的较早生长阶段进行处理对作物造成的损害较少。因为其能使本发明方法具有上述优点,因此本发明组合物在用于本发明方法和用途时尤其有利。当从包装中流出时,本发明组合物也显示出极佳的流出性质,从而允许农场主安全且有效地进行处理。本发明的组合物,尤其是包含包封农药的组合物允许对极高浓度的农药进行包封,从而使组合物具有高农药负载量。
以下本发明实例进一步对本发明进行阐述,然而本发明并限于这些实施例。
实施例
M20S:基于4,4′-二苯基甲烷二异氰酸酯(MDI)的无溶剂多异氰酸酯,平均官能度为2.7,NCO含量为31.8g/100g(ASTM D 5155-96A),以HCl计算的酸度为150mg/kg(ASTM D 1638-74)(购自Elastogran)。
多异氰酸酯C:基于4,4′-二苯基甲烷二异氰酸酯(MDI)的无溶剂多异氰酸酯,平均官能度为2.5-2.8,NCO含量为30-35g/100g(通过ASTM D5155-96A测定)。
40 88:部分水解的聚乙烯醇,粘度为38-42mPas(DIN 53015)(购自Kuraray)。
Pyraclo-SC:包含唑菌胺酯的悬浮液浓缩物。
Pyraclo-WP:包含唑菌胺酯的可润湿粉末。
MMA甲基丙烯酸甲酯
MAS甲基丙烯酸
BDA1,4-丁二醇二丙烯酸酯
PETIA季戊四醇三丙烯酸酯与季戊四醇四丙烯酸酯的工业级混合物PMMA聚甲基丙烯酸甲酯
实施例1A-唑菌胺酯的PMMA胶囊
使用表1中所汇总的浓度[g/l]制备表1的四种PMMA胶囊。制备包含水、保护性胶体和亚硝酸钠的水相。油相通过在升高的温度下将唑菌胺酯溶于Solvesso 200而制备,并在搅拌同时将其添加至水相中。然后添加单体MMA、MAS、BDA和PETIA。将两相混合物在70℃下搅拌30分钟并冷却至50℃。在搅拌的同时向所得乳液中添加过氧化新戊酸叔丁酯并在2小时内加热至高达70℃,随后在85℃下加热1.5小时。然后,在60分钟内添加叔丁基过氧化氢和抗坏血酸,同时冷却至20℃。粒度在Malvern Mastersizer上借助光散射以z均测定。蒸发后的残余物通过将胶囊在105℃下加热2小时并随后在130℃下加热1小时而测定。固含量通过将胶囊悬浮液在105℃下加热2小时而测定。PMMA胶囊CWF和CXF制备的其他细节描述于EP09177493.5中(尤其是在实施例8中)。
表1:PMMA胶囊的配方(浓度以g/l计)
实施例1B-唑菌胺酯的聚氨酯(PU)胶囊
使用如表2中所汇总的浓度[g/l;指总悬浮液中的浓度]制备表2A和2B的PU胶囊悬浮液。在氮气气氛下制备包含水、保护性胶体(例如Mowiol、Culminal、分散剂)的水相。在剧烈搅拌下添加溶于Solvesso中的二异氰酸酯与唑菌胺酯的混合物并在40℃下于水相中分散15分钟。然后,在搅拌的同时在1小时内添加二胺,在60℃下加热1小时,并在80℃下加热2小时。粒度在Malvern Mastersizer上借助光散射以z均测定。表2B中所列胶囊的粒度D90为4.0-6.0μm且D4,3为2.0-2.5μm。蒸发后的残余物通过将胶囊在105℃下加热2小时并随后在130℃下加热1小时而测定。固含量通过将胶囊悬浮液在105℃下加热2小时而测定。
表2A:PU胶囊的配方(浓度以g/l计)
表2B:PU胶囊的配方(浓度以g/l计)
实施例2-玉米产量(美国)
玉米生长于美国的15块不同田地中。玉米于2008年4月至5月左右种植。在生长阶段V8至V10(对应于BBCH 32/35;生长高度为约100-115cm)通过喷雾150g/ha实施例1的唑菌胺酯处理田地。为了进行比较,每块田地都有一部分未经处理且一部分在VT至R1(对应于BBCH 55至61;生长高度为约200-250cm)用处理。成熟时收获玉米并测定作物的谷物产量。表1列出了以未经处理田地百分比计算的13次田间试验的平均产量,其中未经处理的对照例对应于100%产量。
所述田间试验显示用包封农药对玉米进行早期处理获得了与在玉米较晚的生长阶段用未包封农药进行常规处理相当的产量。
表1
农药配制剂 | 玉米产量[对照例的%] |
未经处理的对照例a) | 100 |
Headlinea) | 104 |
PU-1 | 101 |
PU-2 | 103 |
CTF | 101 |
CVF | 104 |
CWF | 106 |
CXF | 102 |
a)未按照本发明
实施例3-玉米的真菌防治
玉米如实施例2中所述生长。在营养期期间该作物受到真菌高粱柄锈菌(Puccinia sorghi)(PUCCSO)、玉米尾孢菌(Cercospora zea maydis)(CERCZM)和玉米褐斑病菌(Physoderma maydis)(PHYDMA)的自然侵染。在生长阶段V8至V10(BBCH 32/35;生长高度为约100-120cm)借助CO2喷雾器用150g/ha实施例1的唑菌胺酯处理所述玉米。为了进行比较,一部分田地未经处理且一部分在生长阶段VT/R1(BBCH 55/61;生长高度为约200-250cm)用处理。在生长阶段R4至R5(BBCH 75/82)通过评估每块地十株随机选定植株的侵染叶面积而确定侵染程度。根据Abbott′s公式[E=1-侵染对照/侵染处理*100]计算功效。表2列出了4次高粱柄锈菌防治田间试验、14次玉米尾孢菌防治田间试验和3次玉米褐斑病菌防治田间试验的平均功效水平。
所述田间试验显示用包封农药对玉米进行早期处理获得了与在玉米较晚生长阶段用未包封农药进行常规处理相当的真菌防治效果。
表2
a)未按照本发明
实施例4-玉米产量(欧洲)
玉米生长在德国和法国的3块不同田地中。玉米于2008年5月种植。在生长阶段BBCH 32/34(生长高度为约80-115cm)借助喷雾用110g/ha实施例1的唑菌胺酯处理所述田地。此外,将110g/ha唑菌胺酯作为存在于含40g呈市售配制剂形式的环戊唑菌杀真菌剂桶混剂中的PU-1配制剂施用。为了进行比较,每次都使所述田地一部分未经处理且一部分在生长阶段BBCH 55/57(抽穗;生长高度为约175-200cm)借助喷雾用110g/ha处理。成熟时收获玉米并测定作物的谷物产量。表3列出了以未经处理田地的百分比计算的3次田间试验的平均产量,其中未经处理的对照例对应于100%。
所述田间试验显示用包封农药对玉米进行早期处理获得了与在玉米较晚生长阶段用未包封农药进行常规处理相当的产量。
表3
农药配制剂 | 玉米产量[%] |
未经处理的对照例a) | 100.0 |
Headlinea) | 98.7 |
PU-1 | 103.4 |
PU-2 | 106.0 |
CTF | 100.6 |
CVF | 105.2 |
PU-1+Caramba | 106.6 |
a)未按照本发明
实施例5-玉米的真菌防治(欧洲)
玉米如实施例4中所述生长。在于法国进行的试验中在生长阶段73-82时玉米作物显示受到真菌长蠕孢圆锥菌(Helminthosporium turgidum)的自然侵染。在生长阶段BBCH 32/34(生长高度为约80-115cm)时借助喷雾用110g/ha实施例1的唑菌胺酯处理所述玉米。此外,将110g/ha唑菌胺酯作为存在于含40g呈市售配制剂形式的环戊唑菌杀真菌剂桶混剂中的PU-1配制剂施用。为了进行比较,使所述田地一部分未经处理且一部分在生长阶段BBCH 55/57(生长高度为约175-200cm)借助喷雾用处理。通过评估每块地十株随机选定植株的侵染叶面积而确定侵染程度。根据Abbott′s公式[E=1-侵染对照/侵染处理*100]计算功效。表4列出了在法国进行的田间试验的平均功效。
所述田间试验显示用包封农药对玉米进行早期处理获得了甚至比在玉米较晚生长阶段用未包封农药进行常规处理更好的真菌防治效果。
表4
a)未按照本发明
Claims (15)
1.一种对最终生长高度为至少140cm的作物进行农药处理的方法,包括在该作物生长高度至多为120cm时用包封农药进行处理。
2.如权利要求1的方法,其中所述包封农药的包封材料包含聚氨酯或聚(甲基)丙烯酸酯。
3.如权利要求1或2的方法,其中所述聚(甲基)丙烯酸酯包含呈聚合形式的甲基丙烯酸甲酯和甲基丙烯酸。
4.如权利要求1或2的方法,其中所述聚氨酯包含呈聚合形式的多官能异氰酸酯和多官能胺。
5.如权利要求1-4中任一项的方法,其中所述处理通过地面施用而进行。
6.如权利要求1-5中任一项的方法,其中所述作物为玉米、向日葵、油菜籽油菜、甘蔗、高粱或芒属(Miscanthus)。
7.如权利要求6的方法,其中所述作物为在其生长阶段BBCH 10至51进行处理的玉米、在其生长阶段BBCH 10至BBCH 69进行处理的向日葵、在其生长阶段BBCH 10至69进行处理的油菜籽油菜、在其生长阶段BBCH10至51进行处理的高粱或在其生长阶段BBCH 11至49进行处理的甘蔗。
8.如权利要求1-7中任一项的方法,包括用所述包封农药与未包封的其他农药的混合物进行处理。
9.如权利要求8的方法,其中所述包封农药包括嗜球果伞素类或羧酰胺类,且所述未包封的其他农药包括三唑类或羧酰胺类。
10.一种包含包封农药的组合物,其中所述农药为溶于至少一种有机溶剂中的农药,且所述包封农药的包封材料包含聚氨酯。
11.如权利要求10的组合物,其中所述农药为嗜球果伞素类。
12.一种组合物,其包含包封农药与未包封的其他农药的混合物,其中所述包封农药包括嗜球果伞素类或羧酰胺类,且所述未包封的其他农药包括三唑类或羧酰胺类。
14.如权利要求13的组合物,其中所述包封农药包括如权利要求11的式I的1-甲基吡唑-4-基甲酰苯胺,且所述未包封的其他农药包括氧唑菌或环戊唑菌。
15.如权利要求11-14中任一项的组合物,其中所述包封农药的包封材料包含聚氨酯或聚(甲基)丙烯酸酯。
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BRPI1006238B1 (pt) | 2017-11-14 |
EA201101335A1 (ru) | 2012-04-30 |
WO2010105971A2 (en) | 2010-09-23 |
US20120009238A1 (en) | 2012-01-12 |
KR20120014241A (ko) | 2012-02-16 |
AU2010225016A1 (en) | 2011-10-13 |
CN102355819B (zh) | 2016-03-02 |
ZA201107577B (en) | 2013-02-27 |
EP2408298B1 (en) | 2016-06-29 |
CA2753984A1 (en) | 2010-09-23 |
MX2011009120A (es) | 2011-09-26 |
EA026108B1 (ru) | 2017-03-31 |
AR076139A1 (es) | 2011-05-18 |
WO2010105971A3 (en) | 2011-06-03 |
HUE030498T2 (en) | 2017-05-29 |
BRPI1006238A2 (pt) | 2015-09-15 |
CR20110545A (es) | 2011-11-03 |
PL2408298T3 (pl) | 2016-12-30 |
CA2753984C (en) | 2017-04-18 |
EP2408298A2 (en) | 2012-01-25 |
TW201038195A (en) | 2010-11-01 |
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