CN102480937B - 悬浮乳液农药组合物 - Google Patents
悬浮乳液农药组合物 Download PDFInfo
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- CN102480937B CN102480937B CN201080033214.9A CN201080033214A CN102480937B CN 102480937 B CN102480937 B CN 102480937B CN 201080033214 A CN201080033214 A CN 201080033214A CN 102480937 B CN102480937 B CN 102480937B
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Classifications
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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
- A01N25/02—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
-
- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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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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- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pretreatment Of Seeds And Plants (AREA)
Abstract
本发明涉及至少包含如下组分的配制剂:(i)溶解于乳酸酯中的两种农药化合物A和B,并且其中a)A和B都具有低于900C的熔点,b)A和B都选自下列物质:唑菌胺酯、甲霜灵、精甲霜灵、肟菌酯、烯菌灵、丙氯灵和环戊唑醇,条件是A和B不同,(ii)至少一种以固体颗粒形式存在且熔点为900C和更高的农药化合物C,它们作为种子处理配制剂的用途,以及它们在植物保护,包括种子和作物保护中的用途。
Description
本发明涉及含有至少三种杀真菌活性化合物的悬浮乳液(suspo-emulsion)(SE)含水配制剂,它们作为种子处理配制剂的用途,以及它们在植物保护,包括种子和作物保护中的用途。
农药化合物通常以稀含水组合物形式施用以获得目标生物如植物、真菌和昆虫之间的良好相互作用。然而,用作农药的大部分活性化合物,尤其是杀真菌活性化合物在水中仅微溶或甚至不溶,即它们通常具有不大于50g/l的水溶性。
因此,配制者就在可容易地长期储存且直至最终使用仍具有高稳定性和有效活性的稳定配制剂中配制农药化合物方面常常面临困难。如果组合物中存在两种以上活性化合物,则尤其会出现该问题。
WO 03/075657涉及乳酸酯在施用过程中作为结晶抑制剂的用途。使用乳酸酯以在施用过程中抑制农药组合物中固体颗粒的存在,由此确保通过将液体组合物喷雾至植物上的较好流动性。
WO 07/028538涉及不同乳酸酯在不同农业农药配制剂中在改善农业农药对植物水平的作用中的用途。
WO 2005/074685涉及尤其包含乳酸2-乙基己酯的植物保护组合物在水稻作物中防治有害生物中的用途。
上述专利集中在乳酸酯对于改善配制剂适用性的功能上。
在许多的多组分配方中,尤其是当高熔点活性成分需要与低熔点活性物质组合时,悬浮乳液为唯一可行的配制剂类型。该悬浮乳液可以包含溶解于选定有机溶剂中的两种杀真菌剂A和B以及同时以固体颗粒形式存在的第三农药活性化合物C,其中所有组分以稳定形式共存。悬浮乳液的一个关键方面为溶剂的选择,因为该溶剂面临几个要求。一方面溶剂应溶解低熔点活性物质,另一方面它不可以造成高熔点活性物质的奥斯特瓦尔德熟化。
我们现已惊人地发现乳酸酯非常适合于该配制剂类型,尤其是当需要配制一种以上低熔点活性物质时。
本发明涉及包含如下组分的悬浮乳液农药组合物:
(i)溶解于乳酸酯中的两种农药化合物A和B,并且其中
a)A和B都具有低于90℃的熔点
b)A和B都选自下列物质:唑菌胺酯(pyraclostrobin)、甲霜灵(metalaxyl)、精甲霜灵(mefenoxam)、肟菌酯(trifloxystrobin)、烯菌灵(imazalil)、丙氯灵(prochloraz)和环戊唑醇(ipconazole),条件是A和B不同,
(ii)至少一种以固体颗粒形式存在且熔点为90℃和更高的农药化合物C,
(iii)水,
(iv)以及任选配制助剂。
已惊人地发现本发明组合物提供含有作为连续相的水、溶解于作为有机溶剂的乳酸酯中的两种杀真菌活性化合物A和B以及呈分散颗粒形式的第三农药活性化合物C的悬浮乳液(SE)配制剂,其能够改善所述组合物的杀真菌活性。
本文所用“农药化合物”或“活性化合物”或“化合物”为直接产生生物学相关作用,优选农药作用,更优选杀真菌作用的化合物。
本发明进一步涉及组合物在处理种子中的用途,防治植物病原性真菌的方法,防止不希望的植物生长的方法和基于上述组合物改善植物健康的方法。
已惊人地发现如下的组合物:在作为化合物A和B的溶解剂的选定有机溶剂,作为连续相的水,维持疏水颗粒悬浮于水中的分散剂中包含特征在于熔点低于90℃的杀真菌化合物A、B,呈固体形式且熔点等于或高于90℃的第三杀真菌活性化合物C,其形成化合物C颗粒在含有溶解的杀真菌活性化合物A和B的乳液中的稳定悬浮液。
根据本发明合适的有机溶剂必须能够在溶解两种杀真菌组分A和B时防止结晶形成并且同时必须不溶解第三组分C,其需要以固体颗粒形式存在于组合物中。该选定溶剂因此必须首先在乳液液滴中完全溶解组分A和B并且进一步确保含有呈固体形式的分散第三组分C的最终悬浮乳液配制剂的稳定性。
已惊人地发现根据本发明合适的有机溶剂为乳酸酯。本发明乳酸酯显示出液滴速率和粒度在乳液中随着温度变化而稳定分布并且甚至在长期储存时也如此。通过使用本发明乳酸酯,本发明配制剂组合物的储存稳定性提高。使用本发明乳酸酯允许获得如下的组合物:其中两种杀真菌化合物与以固体形式存在的第三农药化合物共存应使得来自溶解于乳酸酯中的两种杀真菌化合物的液滴的分布和第三杀真菌化合物固体颗粒均匀分布于悬浮乳液组合物中。
已进一步发现在长期储存之后维持活性成分的物理状态,由此提供含有溶解于乳酸酯中的化合物A和B以及第三杀真菌活性化合物C细粒的可喷雾液体。
当在整个说明书中使用术语乳酸酯时,乳酸酯意指包括两种光学异构体及其混合物。
根据本发明的优选实施方案,对于实施本发明优选的乳酸酯为C4-C12饱和及不饱和烷基乳酸酯,C4-C12饱和及不饱和环状乳酸酯、C4-C12饱和及不饱和支化烷基乳酸酯及其混合物。
特别优选的乳酸酯为乳酸2-乙基己酯、乳酸环己酯、乳酸2-甲基环己酯、乳酸庚酯、乳酸辛酯及其混合物。
更特别优选的乳酸酯为乳酸2-乙基己酯(EHL),其为2-乙基己醇与乳酸,优选L-(+)-乳酸的酯,例如可由Purac Bioquimica(Gran Vial 19-25,08160 Montmelo-Barcelona,西班牙)或Purac Biochem(Gorinchem,荷兰)以EHL获得。
本发明化合物A和B为选定的杀真菌活性化合物。化合物A和B为选自唑菌胺酯、甲霜灵、精甲霜灵、肟菌酯、烯菌灵、丙氯灵和环戊唑醇的杀真菌剂,条件是A和B不同。
本发明化合物C为农药活性化合物。具体而言,化合物C为选自下列物质的杀真菌剂。本发明化合物可与其组合使用的下列活性化合物C意欲阐述可能组合,但不限制它们。下列物质可以提及作为化合物C的实例:
腈嘧菌酯(azoxystrobin),啶酰菌胺(boScalid)或下组化合物:
a)唑类:
-三唑类:戊环唑(azaconazole)、双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、醚唑(difenoconazole)、烯唑醇(diniconazole)、烯唑醇M(diniconazole-M)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、喹唑菌酮(fluq uinconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、酰胺唑(imibenconazole)、环戊唑醇、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、稻瘟酯(pefurazoate)、丙氯灵、氟菌唑(triflumizol);
-苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole);
-其他:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole)和2-(4-氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2-炔氧基乙酰胺;
b)杂环化合物
-吡啶类:氟啶胺(fluazinam)、啶斑肟(pyrifenox)、3-[5-(4-氯苯基)-2,3-二甲基异唑烷-3-基]吡啶、3-[5-(4-甲基苯基)-2,3-二甲基异唑烷-3-基]吡啶、2,3,5,6-四氯-4-甲磺酰基吡啶、3,4,5-三氯吡啶-2,6-二甲腈、N-(1-(5-溴-3-氯吡啶-2-基)乙基)-2,4-二氯烟酰胺、N-[(5-溴-3-氯吡啶-2-基)甲基]-2,4-二氯烟酰胺;
-嘧啶类:磺嘧菌灵(bupirimate)、环丙嘧啶(cyprodinil)、二氟林(diflumetorim)、异嘧菌醇(fenarimol)、嘧菌腙(ferimzone)、嘧菌胺(mepanipyrim)、氯草定(nitrapyrin)、氟苯嘧啶醇(nuarimol)、二甲嘧菌胺(pyrimethanil);
-哌嗪类:嗪氨灵(triforine);
-吡咯类:拌种咯(fenpiclonil)、氟菌(fludioxonil);
-吗啉类:4-十二烷基-2,6-二甲基吗啉(aldimorph)、吗菌灵(dodemorph)、吗菌灵乙酸酯(dodemorph-acetate)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph);
-哌啶类:苯锈啶(fenpropidin);
-二羧酰亚胺类:氟菌安(fluoroimid)、异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin);
-非芳族5员杂环:唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、flutianil、异噻菌酮(octhilinone)、噻菌灵(probenazole)、5-氨基-2-异丙基-3-氧代-4-邻甲苯基-2,3-二氢吡唑-1-硫代甲酸S-烯丙基酯;
-其他:噻二唑素(acibenzolar-S-methyl)、amisulbrom、敌菌灵(anilazin)、灭瘟素(blasticidin-S)、敌菌丹(captafol)、克菌丹(captan)、灭螨蜢(chinomethionat)、棉隆(dazomet)、咪菌威(debacarb)、哒菌清(diclomezine)、野燕枯(difenzoquat)、野燕枯甲基硫酸酯(difenzoquat-methylsulfate)、氰菌胺(fenoxanil)、灭菌丹(folpet)、恶喹酸(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]嘧啶和5-乙基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺。
本发明特别优选的化合物C为腈嘧菌酯或啶酰菌胺或唑类化合物如戊叉唑菌、氟菌。
本发明组合物为至少三元混合物,即本发明组合物包含一种杀真菌化合物A(组分1)、第一其他杀真菌活性化合物B(组分2)和第二其他农药活性化合物C(组分3)。
特别优选如下的悬浮乳液组合物:包含作为组分1的化合物A,其为唑菌胺酯,作为组分2的化合物B,其选自甲霜灵、精甲霜灵、肟菌酯、烯菌灵、丙氯灵和环戊唑醇,以及作为组分3的化合物C,其选自腈嘧菌酯或啶酰菌胺或戊叉唑菌或氟菌。
特别优选如下的悬浮乳液组合物:包含作为组分1的化合物A,其为唑菌胺酯,作为组分2的化合物B,其选自甲霜灵、精甲霜灵、肟菌酯、烯菌灵和环戊唑醇,以及作为组分3的化合物C,其选自腈嘧菌酯或啶酰菌胺或戊叉唑菌或氟菌。
特别优选如下的配制剂组合物:包含作为组分1的化合物A,其为唑菌胺酯,作为组分2的化合物B,其为甲霜灵,以及作为组分3的化合物C,其选自腈嘧菌酯或啶酰菌胺或戊叉唑菌或氟菌。
因此,在更优选的实施方案中,本发明进一步涉及如下的组合物:包含作为组分1的化合物A,其为唑菌胺酯,作为组分2的化合物B,其为甲霜灵,以及作为组分3的化合物C,其为腈嘧菌酯。
因此,在更优选的实施方案中,本发明进一步涉及如下的组合物:包含作为组分1的化合物A,其为唑菌胺酯,作为组分2的化合物B,其为甲霜灵,以及作为组分3的化合物C,其为氟菌。
因此,在更优选的实施方案中,本发明进一步涉及如下的组合物:包含作为组分1的化合物A,其为唑菌胺酯,作为组分2的化合物B,其为甲霜灵,以及作为组分3的化合物C,其为啶酰菌胺。
因此,在更优选的实施方案中,本发明进一步涉及如下的组合物:包含作为组分1的化合物A,其为唑菌胺酯,作为组分2的化合物B,其为甲霜灵,以及作为组分3的化合物C,其为戊叉唑菌。
称为组分1或2或3的活性化合物、其制备及其对有害真菌的活性是已知的(参见http://www.alanwood.net/pesticides/);这些物质可市购。由IUPAC命名法所述的化合物、其制备及其杀真菌活性也是已知的(参见Can.J.Plant Sci.48(6),587-94,1968;EP 141317;EP 152031;EP 226917;EP 243970;EP 256503;EP 428941;EP 532022;EP 1028125;EP 1035122;EP 1201648;EP 1122244,JP 2002316902;DE 19650197;DE 10021412;DE 102005009458;US 3,296,272;US 3,325,503;WO 98/46608;WO99/14187;WO 99/24413;WO 99/27783;WO 00/29404;WO 00/46148;WO 00/65913;WO 01/54501;WO 01/56358;WO 02/22583;WO 02/40431;WO 03/10149;WO 03/11853;WO 03/14103;WO 03/16286;WO 03/53145;WO 03/61388;WO 03/66609;WO 03/74491;WO 04/49804;WO 04/83193;WO 05/120234;WO 05/123689;WO 05/123690;WO 05/63721;WO05/87772;WO 05/87773;WO 06/15866;WO 06/87325;WO 06/87343;WO 07/82098;WO 07/90624)。
本发明组合物可以任选含有其他配制助剂如乳化剂分散剂、防冻剂、消泡剂、增稠剂和在施用于种子情况下的粘合剂。
在优选的实施方案中,能够维持疏水颗粒悬浮于水中的特定分散剂为Atlox 4913。
术语配制助剂涉及其本身不产生生物学相关作用,但支持活性化合物作用的化合物或所述化合物的组合。这些配制助剂对本领域熟练技术人员是已知的且例如描述于“农业活性有机化合物的晶体复合物(crystallinecomplexes of agriculturally active organic compounds)”(WO 2008/096005)中。
存在的话,配制助剂优选占至少0.5%,基于本发明组合物总量。
本发明配制剂组合物可按如下制备:
首先将化合物A和B溶解于乳酸酯,优选EHL中以形成溶液S。该溶液S通过将其与水和乳化剂混合且施加剪切以得到液滴尺寸<10μm的乳液E而在水中乳化。化合物C通过与分散剂和水混合且在珠磨机上研磨至小于10μm,优选小于2μm的中等粒度以形成分散体D而分散于水中。最后,乳液E和分散体D通过搅拌混合并且可以加入其他助剂如防冻剂、增稠剂、粘合剂等。
本发明悬浮乳液组合物中乳酸酯溶剂的量通常取决于化合物A和B的量。乳酸酯溶剂与化合物A和B一起的重量比通常为1∶1-10∶1。乳酸酯总量基于配制剂总重量通常为2-40重量%,尤其是5-20重量%。
在特别优选的实施方案中,本发明悬浮乳液组合物中EHL的量通常取决于化合物A和B的量。EHL与化合物A和B一起的重量比通常为1∶1-10∶1。EHL总量基于配制剂总重量通常为2-40重量%,尤其是5-20重量%。
乳酸酯溶剂与化合物C的重量比通常为1∶1-50∶1。
在本发明的优选实施方案中,EHL与化合物C的重量比为1∶1-50∶1。
化合物A(组分1)与化合物B(组分2)的重量比为1∶50-50∶1,尤其是1∶10-10∶1,并且化合物A(组分1)与化合物C(组分3)的重量比优选为1∶50-50∶1,尤其是1∶10-10∶1。
即用组合物配制剂中全部农药活性化合物A、B和C浓度可在相当大范围内变化。它们基于制剂总重量通常为0.01-80重量%,常常为0.1-50重量%,优选0.5-20重量%。
除非另有说明,以重量%表示的全部量涉及全部组合物(或配制剂)的重量。
根据另一特定实施方案,本发明组合物为种子处理配制剂。本发明组合物显示出活性化合物A、B和C与种子的良好附着并且用本发明组合物处理的种子显示出良好的流动性。被处理种子的发芽不受影响。
本发明还涉及本文所定义组合物在处理种子中的用途。
本发明还涉及用本文所述组合物处理种子的方法,其包括将有效量的本文所定义组合物施加至大量种子上。
包含粘合剂、填料和/或增塑剂的种子悬浮乳液组合物在本领域中是熟知的。种子悬浮乳液组合物例如尤其公开于美国专利号5,939,356、5,882,713、5,876,739、5,849,320、5,834,447、5,791,084、5,661,103、5,622,003、5,580,544、5,328,942、5,300,127、4,735,015、4,634,587、4,383,391、4,372,080、4,339,456、4,272,417和4,245,432中。
包括在本发明种子悬浮乳液组合物中的活性化合物A、B和C的量取决于种子类型而变化,但悬浮乳液组合物含有农药有效量的活性化合物。悬浮乳液组合物中活性化合物的量通常为总重量的约0.005-约75%。活性化合物的更优选范围为约0.01-约40%;更优选约0.05-约20%。
包括在悬浮乳液组合物中的活性化合物的实际量必须不抑制种子发芽且在其中会对种子或植物造成损害的目标害虫生命周期过程中应有效保护种子和/或植物。悬浮乳液在播种之后通常有效约0-120天,优选约0-60天。
本文所用术语“种子”是指与植物的无性阶段物理分离和/或可以长期储存和/或可以用于再生长相同物种的另一植物个体的任何植物休眠阶段。本文术语“休眠”是指其中植物在适当期限内维持存活的状态,尽管不存在无性(即非种子)状态需要的光、水和/或养料。该术语尤其是指真正种子,但不包括植物繁殖体如侧枝芽、球茎、球根、果实、块茎、谷粒、插条和茎切段(cut shoot)。
本文所用术语“植物”是指整个植物或其部分。术语“整个植物”是指呈其无性,即非种子阶段的完整植物个体,其特征在于存在根、枝和叶的配置,取决于植物发育阶段还有花和/或果实,其全部物理连接而形成个体,该个体在适当条件下能存活而无需人工措施。该术语还可以指直接收获的整个植物。
术语“植物部分”是指根、枝、叶、花或植物无性阶段的其他部分,其当自剩余部分移走或分离时不能存活,除非有人工措施支撑,或能够再生长出缺失部分以形成整个植物。本文所用果实也认为是植物部分。
本文所用术语“根”是指通常为了完成其生理机能而位于土壤表面以下的植物部分。该术语优选指位于种子以下且直接由种子,或由其他根,但不由枝或叶长出的植物部分。
本文所用植物的“枝和叶”应理解为指嫩枝、茎、枝条、叶子以及植物的茎和枝条在种子发芽之后的其他附枝,但不包括植物的根。植物的枝和叶优选应理解为已由种子生长且位于距长出它们的种子至少一英寸处(种子区之外)的那些植物非根部分,更优选应理解为处于土壤表面或土壤表面上方的植物非根部分。
本文所用“果实”是指含种子和/或用于种子分散,和/或可以由植物取走而不影响其存活性的植物部分。
根据本发明,种子处理包括将本发明组合物施用于种子。虽然本发明方法可以应用于呈任何生理状态的种子,但优选种子处于充分稳定的状态使得它在处理方法期间不遭受显著的损害。该种子通常为由大田收获,由植物取走,和/或由果实和任何芯、荚果、梗、外壳和周围果肉或其他非种子植物物质分离的种子。该种子还优选以处理不对种子造成生理损害的程度而在生理上稳定。在一个实施方案中,例如可对已收获、清洗且干燥至低于约15重量%湿含量的种子施加处理。在另一实施方案中,该种子可以为已干燥,随后用水和/或另一材料灌注,并且然后在用本发明组合物处理之前或期间再干燥的种子。
根据本发明的优选实施方案,待处理种子由此为基本上干燥的。“基本上干燥的”种子包括具有的湿含量应允许种子在大气中在20-30℃和30-90%相对湿度如在25℃和50%相对湿度下平衡的种子。
本文的“种子处理”是指使种子和本发明组合物相互接触的所有方法并且“拌种”是指提供具有一定量的活性化合物的种子,即产生包含活性化合物的种子的种子处理方法。该处理原则上可以在从收获种子至播种的任何时间施加于种子。该种子可以在紧临播种之前或在播种期间例如使用“种子箱(hopper-box)”或“种植箱(planter-box)”方法处理。然而,该处理还可以在播种之前例如以拌种处理形式进行数周或数月如高达12个月而观察不到显著降低的效力。
该处理方便地施加于未播种的种子。本文所有术语“未播种的种子”是指包括在从收获种子至在土地里为了植物发芽和生长目的而播种的任何时间的种子。该种子优选不为催芽种子如催芽稻种。
当提到未播种的种子被“处理”时,该处理不意指包括其中将农药施用于土壤而不是直接施用于种子的那些做法。
通过在播种之前对种子施加处理而简化操作。种子例如可以此方式在中心位置处理并且然后分散用于播种。这使得播种者避免操作和使用活性化合物而是仅以对正常未处理种子而言常规的方式操作和播种经处理的种子,这降低了人体暴露。
具体而言,该种子处理进行以下程序:将种子暴露于具体所需量的本发明所限定农药组合物配制剂。施加的本发明组合物为即用农药配制剂。对于大部分类型的施用设备无需进一步用水稀释。另一方面,需要的话,可以与其他种子处理产品桶混和或用水稀释。
包含化合物A、B、C的本发明组合物适合作为杀真菌剂。它们的特征在于对宽范围的植物病原性真菌[包括尤其源于根肿菌纲(Plasmodiophoromycetes)、Peronosporomycetes(同义词卵菌纲(Oomycetes))、壶菌纲(Chytridiomycetes)、接合菌纲(Zygomycetes)、子囊菌纲(Ascomycetes)、担子菌纲(Basidiomycetes)和半知菌纲(Deuteromycetes)(同义词不完全菌纲(Fungi imperfecti))的土传真菌]具有显著的效力。它们中的一些内吸有效并且可以作为叶面杀真菌剂、拌种用杀真菌剂和土壤杀真菌剂用于作物保护中。此外,它们适合防治尤其存在于木材或植物根部中的有害真菌。
包含化合物A、B、C的本发明组合物对于在各种栽培植物如禾谷类,例如小麦、黑麦、大麦、小黑麦、燕麦或稻;甜菜,例如糖用甜菜或饲料甜菜;水果如仁果、核果或浆果,例如苹果、梨、李、桃、杏仁、樱桃、草莓、悬钩子、黑莓或鹅莓;豆科植物,例如扁豆、豌豆、苜蓿或大豆;油料植物,例如油菜、芥菜、橄榄、向日葵、椰子、可可豆、蓖麻油植物、油棕、花生或大豆;葫芦科植物,例如南瓜、黄瓜或甜瓜;纤维植物,例如棉花、亚麻、大麻或黄麻;柑桔类水果,例如橙子、柠檬、葡萄柚或橘;蔬菜植物,例如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、西红柿、土豆、葫芦或柿子椒;月桂类植物,例如鳄梨、肉桂或樟脑;能量和原料植物,例如玉米、大豆、油菜、甘蔗或油棕;玉米;烟草;坚果;咖啡;茶;香蕉;葡萄藤(食用葡萄和酿酒用葡萄);啤酒花;草坪;天然橡胶植物或观赏和森林植物,例如花卉、灌木、阔叶树或常绿树如针叶树,以及植物繁殖材料如种子和这些植物的作物材料上防治大量植物病原性真菌特别重要。
优选将包含化合物A、B、C的本发明组合物用于在农作物,例如土豆、糖用甜菜、烟草、小麦、黑麦、大麦、燕麦、稻、玉米、棉花、大豆、油菜、豆科植物、向日葵、咖啡或甘蔗;水果;葡萄藤;观赏植物或蔬菜如黄瓜、西红柿、菜豆或南瓜上防治大量真菌。
术语“植物繁殖材料”应理解为表示植物的所有繁殖部分如种子,以及可以用于繁殖植物的无性植物部分如插条和块茎(例如土豆)。这包括种子、根、果实、块茎、球茎、地下茎、枝、芽和其他植物部分,包括在发芽后或出苗后由土壤移植的秧苗和幼苗。这些幼苗还可以在移植之前通过经由浸渍或浇灌的完全或部分处理而保护。
优选将本发明组合物及其组合物对植物繁殖材料的处理分别用于在禾谷类作物如小麦、黑麦、大麦和燕麦;稻、玉米、棉花和大豆中防治大量真菌。
术语“栽培植物”应理解为包括已经通过育种、诱变或基因工程修饰的植物,包括但不限于上市销售或开发的农业生物技术产品(参见http://www.bio.org/speeches/pubs/er/agri_products.asp)。基因修饰植物是其基因材料通过使用在自然条件下不易通过杂交、突变或自然重组得到的重组DNA技术修饰的植物。通常将一个或多个基因整合到基因修饰植物的遗传材料中以改善植物的某些性能。这类基因修饰还包括但不限于蛋白质、寡肽或多肽的翻译后修饰,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。
通过育种、诱变或基因工程修饰的植物,例如因常规育种或基因工程方法而耐受特殊类别除草剂施用的植物,这些除草剂如羟基苯基丙酮酸二加氧酶(HPPD)抑制剂,乙酰乳酸合成酶(ALS)抑制剂,例如磺酰脲类(例如参见US 6,222,100,WO 01/82685,WO 00/26390,WO 97/41218,WO98/02526,WO 98/02527,WO 04/106529,WO 05/20673,WO 03/14357,WO 03/13225,WO 03/14356,WO 04/16073)或咪唑啉酮类(例如参见US6,222,100,WO 01/82685,WO 00/026390,WO 97/41218,WO 98/002526,WO 98/02527,WO 04/106529,WO 05/20673,WO 03/014357,WO03/13225,WO 03/14356,WO 04/16073),烯醇丙酮酰莽草酸3-磷酸合成酶(EPSPS)抑制剂,例如草甘膦(例如参见WO 92/00377),谷氨酰胺合成酶(GS)抑制剂,例如草铵膦(例如参见EP-A 242236,EP-A 242246)或oxynil除草剂(例如参见US 5,559,024)。几种栽培植物已经通过常规育种(诱变)方法而耐受除草剂,例如耐受咪唑啉酮类如咪草啶酸的夏播油菜(Canola,德国BASF SE)。使用基因工程方法使栽培植物如大豆、棉花、玉米、甜菜和油菜耐受除草剂如草甘膦和草铵膦,它们中的一些可以以商标名(耐受草甘膦,Monsanto,U.S.A.)和(耐受草铵膦,德国Bayer CropScience)得到。
此外,还包括通过使用重组DNA技术能够合成一种或多种杀虫蛋白,尤其是由芽孢杆菌属(Bacillus)细菌菌株,特别是苏云金芽孢杆菌(Bacillusthuringiensis)已知的那些的植物,所述杀虫蛋白如δ-内毒素,例如CryIA(b)、CryIA(c)、CryIF、CryIF(a2)、CryIIA(b)、CryIIIA、CryIIIB(b1)或Cry9c;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子毒素、蜘蛛毒素、黄蜂毒素或其他昆虫特异性神经毒素;真菌产生的毒素,例如链霉菌属(Streptomycetes)毒素;植物凝集素,例如豌豆或大麦凝集素;凝集素,蛋白酶抑制剂,例如胰蛋白酶抑制剂,丝氨酸蛋白酶抑制剂,patatin,半胱氨酸蛋白酶抑制剂或木瓜蛋白酶抑制剂,核糖体失活蛋白(RIP),例如蓖麻蛋白、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,例如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);茋合成酶,联苄合成酶,壳多糖酶或葡聚糖酶。在本发明上下文中,这些杀虫蛋白或毒素还应具体理解为前毒素、杂合蛋白或截短的或其他方面改性的蛋白。杂合蛋白的特征在于不同蛋白域的新型组合(例如参见WO02/015701)。该类毒素或能够合成这些毒素的基因修饰植物的其他实例例如公开于EP A374753、WO 93/007278、WO 95/34656、EP A427529、EPA451878、WO 03/18810和WO 03/52073中。生产这些基因修饰植物的方法对本领域熟练技术人员通常是已知的且例如公开于上述出版物中。这些含于基因修饰植物中的杀虫蛋白赋予产生这些蛋白的植物以对所有分类学上为节肢动物的害虫,尤其是甲虫(鞘翅目(Coeloptera))、双翅目昆虫(双翅目(Diptera))和蝴蝶(鳞翅目(Lepidoptera))以及线虫(线虫纲(Nematoda))的耐受性。能够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,它们中的一些可市购,例如(产生毒素Cry1Ab的玉米品种),Plus(产生毒素Cry1Ab和Cry3Bb1的玉米品种),
(产生毒素Cry9c的玉米品种),RW(产生毒素Cry34Ab1、Cry35Ab1和酶膦丝菌素-N-乙酰转移酶[PAT]的玉米品种);33B(产生毒素Cry1Ac的棉花品种),I(产生毒素Cry1Ac的棉花品种),II(产生毒素Cry1Ac和Cry2Ab2的棉花品种);(产生VIP毒素的棉花品种);(产生毒素Cry3A的土豆品种);Bt11(例如CB)和法国Syngenta Seeds SAS的Bt176(产生毒素Cry1Ab和PAT酶的玉米品种),法国Syngenta Seeds SAS的MIR604(产生毒素Cry3A的修饰译本的玉米品种,参见WO 03/018810),比利时Monsanto Europe S.A.的MON 863(产生毒素Cry3Bb1的玉米品种),比利时Monsanto Europe S.A.的IPC 531(产生毒素Cry1Ac的修饰译本的棉花品种)和比利时Pioneer Overseas Corporation的1507(产生毒素Cry1F和PAT酶的玉米品种)。
此外,还包括通过使用重组DNA技术能够合成一种或多种对细菌、病毒或真菌病原体的抵抗性或耐受性增强的蛋白质的植物。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,例如参见EP A392225),植物病害抗性基因(例如表达对来自野生墨西哥土豆Solanumbulbocastanum的致病疫霉(Phytophthora infestans)起作用的抗性基因的土豆栽培品种)或T4溶菌酶(例如能够合成这些蛋白而对细菌如Erwiniaamylvora具有提高的耐受性的土豆栽培品种)。生产这类基因修饰植物的方法通常为本领域熟练技术人员所已知并且例如描述于上述出版物中。
此外,还包括通过使用重组DNA技术能够合成一种或多种蛋白质以提高产量(例如生物质产生、谷粒产量、淀粉含量、油含量或蛋白质含量),对干旱、盐或其他生长限制环境因素的耐受性或对害虫以及真菌、细菌或那些植物的病毒病原体的耐受性的植物。
此外,还包括尤其为了改善人类或动物营养而通过使用重组DNA技术含有改变量的物质含量或新物质含量的植物,例如产生促进健康的长链ω-3脂肪酸或不饱和ω-9脂肪酸的油料植物(例如油菜,加拿大DOW Agro Sciences)。
此外,还包括尤其为了改进原料生产而通过使用重组DNA技术含有改变量的物质含量或新物质含量的植物,例如产生增加量的支链淀粉的土豆(例如土豆,德国BASF SE)。
本发明组合物特别适合防治下列植物病害:观赏植物、蔬菜作物(例如白锈菌(A.candida))和向日葵(例如婆罗门参白锈菌(A.tragopogonis))上的白锈菌属(Albugo)(白锈病);蔬菜、油菜(芸苔生链格孢(A.brassicola)或芸苔链格孢(A.brassicae))、糖用甜菜(A.tenuis)、水果、稻、大豆、土豆(例如早疫链格孢(A.solani)或链格孢(A.alternata))、西红柿(例如早疫链格孢或链格孢)和小麦上的链格孢属(Alternaria)(链格孢叶斑病);糖用甜菜和蔬菜上的丝囊霉属(Aphanomyces);禾谷类和蔬菜上的壳二孢属(Ascochyta),例如小麦上的A.tritici(炭疽病)和大麦上的大麦壳二孢(A.hordei);平脐蠕孢属(Bipolaris)和内脐蠕孢属(Drechslera)(有性型:旋孢腔菌属(Cochliobolus)),例如玉米上的小斑病(玉蜀黍平脐蠕孢(D.maydis))或大斑病(玉米生离蠕孢(B.zeicola)),例如禾谷类上的斑枯病(麦根腐平脐蠕孢(B.sorokiniana))以及例如稻和草坪上的稻平脐蠕孢(B.oryzae);禾谷类(例如小麦或大麦)上的小麦白粉菌(Blumeria(旧名:Erysiphe)graminis)(白粉病);水果和浆果(例如草莓)、蔬菜(例如莴苣、胡萝卜、根芹菜和卷心菜)、油菜、花卉、葡萄藤、森林植物和小麦上的灰葡萄孢(Botrytis cinerea)(有性型:灰葡萄孢霉(Botryotinia fuckeliana):灰霉病);莴苣上的莴苣盘梗霉(Bremia lactucae)(霜霉病);阔叶树和常绿树上的长喙壳属(Ceratocystis)(同义词线嘴壳属(Ophiostoma))(腐烂病或枯萎病),例如榆树上的榆枯萎病菌(C.ulmi)(荷兰榆病);玉米(例如灰叶斑:玉米灰斑病菌(C.zeae-maydis))、稻、糖用甜菜(例如甜菜生尾孢(C.beticola))、甘蔗、蔬菜、咖啡、大豆(例如大豆灰斑病菌(C.sojina)或大豆紫斑病菌(C.kikuchii))和稻上的尾孢属(Cercospora)(尾孢叶斑病);西红柿(例如番茄叶霉菌(C.fulvum):叶霉病)和禾谷类(例如小麦上的草芽枝孢(C.herbarum)(穗腐病))上的枝孢属(Cladosporium);禾谷类上的麦角菌(Claviceps purpurea)(麦角病);玉米(灰色长蠕孢(C.carbonum))、禾谷类(例如禾旋孢腔菌(C.sativus),无性型:麦根腐平脐蠕孢)和稻(例如宫部旋孢腔菌(C.miyabeanus),无性型:水稻长蠕孢(H.oryzae))上的旋孢腔菌属(无性型:长蠕孢属(Helminthosporium)或平脐蠕孢属)(叶斑病);棉花(例如棉炭疽病菌(C.gossypii))、玉米(例如禾生炭疽病菌(C.graminicola):炭疽茎腐病)、浆果、土豆(例如西瓜炭疽病菌(C.coccodes):黑点病)、菜豆(例如菜豆炭疽病菌(C.lindemuthianum))和大豆(例如大豆炭疽病菌(C.truncatum)或C.gloeosporioides)上的剌盘孢属(Colletotrichum)(有性型:围小丛壳菌属(Glomerella))(炭疽病);伏革菌属(Corticium),例如稻上的笹木伏革菌(C.sasakii)(纹枯病);大豆和观赏植物上的黄瓜褐斑病菌(Corynespora cassiicola)(叶斑病);锈斑病菌属(Cycloconium),例如橄榄树上的C.oleaginum;果树、葡萄藤(例如C.liriodendri,有性型:Neonectria liriodendri:乌脚病)和观赏植物上的人参生柱隔孢属(Cylindrocarpon)(例如果树腐烂病或葡萄藤乌脚病,有性型:丛赤壳属(Nectria)或杓兰菌根菌属(Neonectria));大豆上的白纹羽菌(Dematophora(有性型:Rosellinia)necatrix)(根腐病和茎腐病);北茎溃疡菌属(Diaporthe),例如大豆上的大豆北茎溃疡病菌(D.phaseolorum)(立枯疡);玉米、禾谷类如大麦(例如大麦网斑内脐蠕孢(D.teres),网斑病)和小麦(例如D.tritici-repentis:褐斑病)、稻和草坪上的内脐蠕孢属(同义词长蠕孢属,有性型:核腔菌属(Pyrenophora));由斑褐孔菌(Formitiporia(同义词Phellinus)punctata)、F.mediterranea、Phaeomoniellachlamydospora(旧名为Phaeoacremonium chlamydosporum)、Phaeoacremonium aleophilum和/或葡萄座腔菌(Botryosphaeria obtusa)引起的葡萄藤上的埃斯卡(Esca)(葡萄藤枯萎病,干枯病);仁果(E.pyri)、浆果(覆盆子痂囊腔菌(E.veneta):炭疽病)和葡萄藤(葡萄痂囊腔菌(E.ampelina):炭疽病)上的痂囊腔菌属(Elsinoe);稻上的稻叶黑粉菌(Entyloma oryzae)(叶黑粉病);小麦上的附球菌属(Epicoccum)(黑穗病);糖用甜菜(甜菜白粉菌(E.betae))、蔬菜(例如豌豆白粉菌(E.pisi))如葫芦(例如二孢白粉菌(E.cichoracearum))、卷心菜、油菜(例如E.cruciferarum)上的白粉菌属(Erysiphe)(白粉病);果树、葡萄藤和观赏树上的侧弯孢菌(Eutypa lata)(Eutypa溃疡病或枯萎病,无性型:Cytosporina lata,同义词Libertella blepharis);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),例如禾谷类(例如小麦或大麦)上的禾本科镰孢(F.graminearum)或大刀镰孢(F.culmorum)(根腐病、痂病或银尖病),西红柿上的尖镰孢(F.oxysporum),大豆上的茄镰孢(F.solani)和玉米上的轮枝镰孢(F.verticillioides);禾谷类(例如小麦或大麦)和玉米上的禾顶囊壳(Gaeumannomyces graminis)(全蚀病);禾谷类(例如玉蜀黍赤霉(G.zeae))和稻(例如藤仓赤霉(G.fujikuroi):恶苗病)上的赤霉属;葡萄藤、仁果和其他植物上的苹果炭疽病菌(Glomerella cingulata)以及棉花上的棉炭疽病菌(G.gossypii);稻上的Grainstaining complex;葡萄藤上的葡萄黑腐病菌(Guignardia bidwellii)(黑腐病);蔷薇科植物和刺柏上的锈菌属(Gymnosporangium),例如梨上的G.sabinae(锈病);玉米、禾谷类和稻上的长蠕孢属(同义词内脐蠕孢属,有性型:旋孢腔菌属);驼孢锈菌属(Hemileia),例如咖啡上的咖啡驼孢锈菌(H.vastatrix)(咖啡叶锈病);葡萄藤上的褐斑拟棒束孢(Isariopsis clavispora)(同义词Cladosporium vitis);大豆和棉花上的菜豆壳球孢(Macrophomina phaseolina(同义词phaseoli))(根腐病和茎腐病);禾谷类(例如小麦或大麦)上的雪霉叶枯菌(Microdochium(同义词Fusarium)nivale(雪霉病);大豆上的扩散叉丝壳(Microsphaera diffusa)(白粉病);丛梗孢属(Monilinia),例如核果和其他蔷薇科植物上的核果链核盘菌(M.laxa)、桃褐腐菌(M.fructicola)和M.fructigena(花腐病和枝腐病,褐腐病);禾谷类、香蕉、浆果和花生上的球腔菌属(Mycosphaerella),例如小麦上的禾生球腔菌(M.graminicola)(无性型:小麦壳针孢(Septoria tritici),壳针孢叶斑病)或香蕉上的斐济球腔菌(M.fijiensis)(Sigatoka黑斑病);卷心菜(例如芸苔霜霉(P.brassicae))、油菜(例如寄生霜霉(P.parasitica))、洋葱(例如大葱霜霉(P.destructor))、烟草(烟草霜霉(P.tabacina))和大豆(例如大豆霜霉病菌(P.manshurica))上的霜霉属(Peronospora)(霜霉病);大豆上的豆薯层锈菌(Phakopsorapachyrhizi)和山马蟥层锈菌(P.meibomiae)(大豆锈病);例如葡萄藤(例如P.Tracheiphila和P.tetraspora)和大豆(例如大豆茎褐腐病菌(P.gregata):茎腐病)上的瓶霉菌属(Phialophora);油菜和卷心菜上的黑胫茎点霉(Phoma lingam)(根腐病和茎腐病)以及糖用甜菜上的甜菜茎点霉(P.betae)(根腐病、叶斑病和立枯病);向日葵、葡萄藤(例如葡萄黑腐病菌(P.viticola):蔓割病和叶斑病)和大豆(例如茎腐病:P.phaseoli,有性型:大豆北茎溃疡病菌(Diaporthe phaseolorum))上的拟茎点霉属(Phomopsis);玉米上的玉米褐斑病菌(Physoderma maydis)(褐斑病);各种植物如柿子椒和葫芦(例如辣椒疫霉(P.capsici))、大豆(例如大豆疫霉(P.megasperma),同义词P.sojae)、土豆和西红柿(例如致病疫霉(P.infestans):晚疫病)和阔叶树(例如栎树猝死病菌(P.ramorum):橡树急死病)上的疫霉属(Phytophthora)(枯萎病,根腐病,叶腐病,茎腐病和果树腐烂病);卷心菜、油菜、小萝卜和其他植物上的芸苔根肿菌(Plasmodiophorabrassicae)(根肿病);霜霉属(Plasmopara),例如葡萄藤上的葡萄生单轴霉(P.viticola)(葡萄藤霜霉病)和向日葵上的霍尔斯单轴霉(P.halstedii);蔷薇科植物、啤酒花、仁果和浆果上的叉丝单囊壳属(Podosphaera)(白粉病),例如苹果上的苹果白粉病菌(P.leucotricha);例如禾谷类如大麦和小麦(禾谷多粘菌(P.graminis))以及糖用甜菜(甜菜多粘菌(P.betae))上的多粘菌属(Polymyxa)以及由此传播的病毒病害;禾谷类如小麦或大麦上的小麦基腐病菌(Pseudocercosporella herpotrichoides)(眼斑病,有性型:Tapesiayallundae);各种植物上的假霜霉属(Pseudoperonospora)(霜霉病),例如葫芦科植物上的古巴假霜霉(P.cubensis)或啤酒花上的葎草假霜(P.humili);葡萄藤上的Pseudopezicula tracheiphila(葡萄角斑叶焦病菌或‘rotbrenner’,无性型:瓶霉属(Phialophora));各种植物上的柄锈菌属(Puccinia)(锈病),例如禾谷类如小麦、大麦或黑麦上的小麦柄锈菌(P.triticina)(小麦褐锈病或叶锈病),条形柄锈病(P.striiformis)(条锈病或黄锈病),大麦柄锈病(P.hordei)(大麦黄矮叶锈病),禾柄锈菌(P.graminis)(茎锈病或黑锈病)或小麦叶锈菌(P.recondita)(褐锈病或叶锈病),以及芦笋(例如P.asparagi);小麦上的小麦黄斑叶枯病菌(Pyrenophora(无性型:Drechslera)tritici-repentis)(黄斑病)或大麦上的大麦网斑内脐蠕孢(P.teres)(网斑病);梨孢属(Pyricularia),例如稻上的稻瘟病菌(P.oryzae)(有性型:Magnaporthe grisea,稻瘟病)以及草坪和禾谷类上的稻梨孢菌(P.grisea);草坪、稻、玉米、小麦、棉花、油菜、向日葵、大豆、糖用甜菜、蔬菜和各种其他植物(例如终极腐霉菌(P.ultimum)或瓜果腐霉(P.aphanidermatum))上的腐霉属(Pythium)(立枯病);柱隔孢属(Ramularia),例如大麦上的R.collo-cygni(柱隔孢叶斑病,生理叶斑病)和糖用甜菜上的甜菜叶斑病菌(R.Beticola);棉花、稻、土豆、草坪、玉米、油菜、土豆、糖用甜菜、蔬菜和各种其他植物上的丝核菌属(Rhizoctonia),例如大豆上的立枯丝核菌(R.solani)(根腐病和茎腐病),稻上的R.solani(纹枯病)或小麦或大麦上的禾谷丝核菌(R.Cerealis)(丝核菌小麦纹枯病);草莓、胡萝卜、卷心菜、葡萄藤和西红柿上的葡枝根霉(Rhizopus stolonifer)(黑霉病,软腐病);大麦、黑麦和小黑麦上的黑麦喙孢(Rhynchosporium secalis)(叶斑病);稻上的稻帚枝霉(Sarocladiumoryzae)和S.attenuatum(叶鞘腐败病);蔬菜和农作物如油菜、向日葵(例如核盘菌(S.sclerotiorm))和大豆(例如S.rolfsii或核盘菌)上的核盘菌属(Sclerotinia)(茎腐病或白绢病);各种植物上的壳针孢属(Septoria),例如大豆上的大豆壳针孢(S.glycines)(褐斑病),小麦上的小麦壳针孢(S.tritici)(壳针孢叶斑病)和禾谷类上的颖枯壳多孢(S.(同义词Stagonospora)nodorum)(壳多孢斑枯病);葡萄藤上的葡萄钩丝壳(Uncinula(同义词Erysiphe)necator)(白粉病,无性型:Oidium tuckeri);玉米(例如玉米大斑病菌(S.turcicum),同义词大斑凸脐蠕孢(Helminthosporium turcicum))和草坪上的大斑病菌属(Setosphaeria)(叶斑病);玉米(例如丝轴黑粉菌(S.reiliana):丝黑穗病)、高粱和甘蔗上的轴黑粉菌属(Sphacelotheca)(黑穗病);葫芦科植物上的单丝壳白粉菌(Sphaerotheca fuliginea)(白粉病);土豆上的粉痂菌(Spongospora subterranea)(粉痂病)以及由此传播的病毒病害;禾谷类上的壳多孢属(Stagonospora),例如小麦上的颖枯壳多孢(S.nodorum)(壳多孢斑枯病,有性态:颖枯球腔菌(Leptosphaeria[同义词Phaeosphaeria]nodorum));土豆上的马铃薯癌肿病菌(Synchytriumendobioticum)(土豆癌肿病);外囊菌属(Taphrina),例如桃上的畸形外囊菌(T.deformans)(缩叶病)和李上的李外囊菌(T.pruni)(囊果李);烟草、仁果、蔬菜、大豆和棉花上的根串珠霉属(Thielaviopsis)(黑色根腐病),例如黑色根腐病菌(T.basicola)(同义词Chalara elegans);禾谷类上的腥黑粉菌属(Tilletia)(腥黑穗病或光腥黑穗病),例如小麦上的T.tritici(同义词T.caries,小麦腥黑穗病)和T.controversa(矮腥黑穗病);大麦或小麦上的肉孢核瑚菌(Typhula incarnata)(灰雪腐病);条黑粉菌属(Urocystis),例如黑麦上的隐条黑粉菌(U.occulta)(条黑粉病);蔬菜如菜豆(例如疣顶单胞锈菌(U.appendiculatus),同义词U.phaseoli)和糖用甜菜(例如甜菜锈病菌(U.betae))上的单孢锈属(Uromyces)(锈病);禾谷类(例如麦散黑粉菌(U.nuda)和U.avaenae)、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(Ustilago)(黑穗病);苹果(例如苹果黑星病(V.inaequalis))和梨上的黑星菌属(Venturia)(黑星病);以及各种植物如果树和观赏植物、葡萄藤、浆果、蔬菜和农作物上的轮生菌属(Verticillium)(枯萎病),例如草莓、油菜、土豆和西红柿上的茄黄萎病菌(V.dahliae)。
本发明组合物还适合防治有害真菌以保护储藏的产品或收获品以及保护材料。术语“保护材料”应理解为表示保护工业和非活体材料,如粘合剂、胶、木材、纸张和纸板、纺织品、皮革、漆分散体、塑料、冷却润滑剂(colling lubricant)、纤维或织物以防有害微生物如真菌和细菌侵染和破坏。对于木材和其他材料的保护,特别应注意下列有害真菌:子囊菌纲真菌,例如线嘴壳属,长喙壳属,出芽短梗霉(Aureobasidium pullulans),Sclerophoma spp.,毛壳属(Chaetomium spp.),腐质霉属(Humicola spp.),彼得壳属(Petriella spp.),毛束霉属(Trichurus spp.);担子菌纲真菌,例如粉孢革菌属(Coniophora spp.),革盖菌属(Coriolus spp.),粘褶菌属(Gloeophyllum spp.),香菇属(Lentinus spp.),侧耳属(Pleurotus spp.),卧孔属(Poria spp.),干朽菌属(Serpula spp.)和干酪菌属(Tyromyces spp.),半知菌纲真菌,例如曲霉属(Aspergillus spp.),枝孢属,青霉属(Penicilliumspp.),木霉属(Trichoderma spp.),链格孢属,拟青霉属(Paecilomyces spp.)和接合菌纲(Zygomycetes)真菌,例如毛霉属(Mucor spp.),此外在储存产品和收获品的保护中应注意下列酵母真菌:假丝酵母属(Candida spp.)和酿酒酵母(Saccharomyces cerevisae)。
本发明通过以下实施例阐述,而不限于这些。
1-稳定性
测量本发明组合物在使用乳酸酯下的稳定性得到下文归纳的结果:
在该实施例中,EHL为乳酸乙基己酯,RME为油酸甲酯且BC为碳酸亚丁酯。湿筛为检验粒度保持恒定的标准试验(筛目大小=150μm)。储存制度如下:
8W-5/+30=在温度循环为-5℃至+30℃之间的人工气候室中储存8周
2W-10/+10=在温度循环为-10℃至+10℃之间的人工气候室中储存2周
以上试验结果显示出EHL通过在限定的观察时间内(2-8周)改变储存温度稳定本发明SE的粒度分布的能力,相比于其他溶剂(REM和BC)。
2-配制实施例
实施例1a:制备溶液S:在EHL中的化合物A和B
在40℃下向1000g EHL中加入419,3g纯度为95,4%的唑菌胺酯、240g纯度为100%的甲霜灵、100g Atlas G-5000和80g Atlox 4914,直到获得1839,3g澄清溶液S。
实施例1b:制备乳液E
将492g水加入Silverson高剪切混合器中。在3000rpm下剪切时,加入368g来自实施例1a的溶液S以得到860g乳白色的自由流动的乳液E。实施例1c:制备分散体D:
向175g水中加入274g纯度为91%的戊叉唑菌、10g Soprophor 4D384、35g Atlox 4913和30g甘油。将该混合物首先在机械磨(商标名PUC)上,然后在珠磨机(Bachofen的KDL-Dynomill)上研磨,直到90%颗粒的尺寸<4μm,其通过激光散射测量。在研磨之后,收回499g乳白色产物并且用1,4g有机硅消泡剂、28,5g的2%黄原胶溶液和1g抗微生物剂Acticide MBS补充而得到546g分散体D。
实施例1:制备悬浮乳液:
向860g实施例1b中获得的乳液E中加入185g来自实施例1c的分散体D以得到1045g乳白色的自由流动的悬浮乳液。
Claims (13)
1.一种包含如下组分的悬浮乳液农药组合物:
(i)溶解于乳酸酯中的两种农药化合物A和B,并且其中
a)A和B都具有低于90℃的熔点
b)A和B都选自下列物质:唑菌胺酯、甲霜灵、精甲霜灵、肟菌酯、烯菌灵、丙氯灵和环戊唑醇,条件是A和B不同,
(ii)至少一种以固体颗粒形式存在且熔点为90℃和更高的农药化合物C,其中化合物C选自下列三唑类:戊环唑、双苯三唑醇、糠菌唑、环唑醇、醚唑、烯唑醇、烯唑醇M、氧唑菌、腈苯唑、喹唑菌酮、氟硅唑、粉唑醇、己唑醇、酰胺唑、环戊唑菌、腈菌唑、oxpoconazole、多效唑、戊菌唑、丙环唑、丙硫菌唑、硅氟唑、戊唑醇、氟醚唑、三唑酮、唑菌醇、戊叉唑菌、烯效唑、1-(4-氯苯基)-2-([1,2,4]三唑-1-基)环庚醇,
(iii)水,
(iv)以及任选配制助剂,
其中所述乳酸酯选自包含C4-C12饱和及不饱和环烷基乳酸酯和C4-C12饱和及不饱和支化烷基乳酸酯及其混合物的组,
其中所述乳酸酯与化合物C的重量比为1:1-50:1。
2.根据权利要求1的悬浮乳液组合物,其中化合物A为唑菌胺酯且化合物B为甲霜灵。
3.根据权利要求1的悬浮乳液组合物,其中化合物C为戊叉唑菌。
4.根据权利要求2的悬浮乳液组合物,其中化合物C为戊叉唑菌。
5.根据权利要求1-4中任一项的悬浮乳液组合物,其中所述乳酸酯选自乳酸2-乙基己酯、乳酸环己酯、乳酸2-甲基环己酯、乳酸庚酯和乳酸辛酯。
6.根据权利要求5的悬浮乳液组合物,其中所述乳酸酯为乳酸2-乙基己酯。
7.根据权利要求1-4中任一项的悬浮乳液组合物,其中所述乳酸酯与化合物A和B之和的重量比为1:1-10:1。
8.根据权利要求5的悬浮乳液组合物,其中所述乳酸酯与化合物A和B之和的重量比为1:1-10:1。
9.一种制备根据权利要求1-8中任一项的悬浮乳液农药组合物的方法,其包括以下步骤:
a)将化合物A和B溶解于乳酸酯中而得到预制溶液S
b)以及混合S与化合物C、水和需要的话配制助剂。
10.根据权利要求1-8中任一项的悬浮乳液组合物在处理植物或种子中的用途。
11.一种防治或防护植物病原性真菌的方法,其包括使植物繁殖材料与根据权利要求1-8中任一项的悬浮乳液接触。
12.一种防治植物病原性真菌和/或改善植物健康的方法,其包括使植物、种子、土壤或植物生长地与根据权利要求1-8中任一项的悬浮乳液组合物接触。
13.一种处理种子的方法,其包括使种子与有效量的根据权利要求1-8中任一项的悬浮乳液组合物接触。
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2010
- 2010-07-20 CN CN201080033214.9A patent/CN102480937B/zh active Active
- 2010-07-20 CA CA2767283A patent/CA2767283C/en active Active
- 2010-07-20 US US13/387,273 patent/US8703649B2/en active Active
- 2010-07-20 WO PCT/EP2010/060463 patent/WO2011012493A2/en active Application Filing
- 2010-07-20 MX MX2012000421A patent/MX2012000421A/es active IP Right Grant
- 2010-07-20 EP EP10734491A patent/EP2458981A2/en not_active Withdrawn
- 2010-07-20 BR BR112012001595-8A patent/BR112012001595B1/pt active IP Right Grant
- 2010-07-20 AU AU2010277783A patent/AU2010277783A1/en not_active Abandoned
- 2010-07-20 UA UAA201201890A patent/UA108206C2/ru unknown
- 2010-07-20 EA EA201200187A patent/EA020385B1/ru not_active IP Right Cessation
- 2010-07-27 AR ARP100102722A patent/AR077775A1/es active IP Right Grant
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CA2767283A1 (en) | 2011-02-03 |
AU2010277783A1 (en) | 2012-03-08 |
CA2767283C (en) | 2017-06-20 |
WO2011012493A2 (en) | 2011-02-03 |
MX2012000421A (es) | 2012-02-08 |
EA201200187A1 (ru) | 2012-08-30 |
EP2458981A2 (en) | 2012-06-06 |
UA108206C2 (xx) | 2015-04-10 |
US8703649B2 (en) | 2014-04-22 |
CN102480937A (zh) | 2012-05-30 |
EA020385B1 (ru) | 2014-10-30 |
BR112012001595B1 (pt) | 2018-06-05 |
ZA201201381B (en) | 2013-05-29 |
AR077775A1 (es) | 2011-09-21 |
BR112012001595A2 (pt) | 2015-09-01 |
US20120122682A1 (en) | 2012-05-17 |
WO2011012493A3 (en) | 2011-10-13 |
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