CN102215679B - 包含hppd-抑制剂的除草组合物和在草皮草中防治杂草的方法 - Google Patents
包含hppd-抑制剂的除草组合物和在草皮草中防治杂草的方法 Download PDFInfo
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Classifications
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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
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- 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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
-
- 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
Abstract
本发明涉及用包含除草有效量的HPPD抑制剂和安全剂的组合物在草坪中防治杂草而不导致草皮草显著损伤的方法。
Description
本发明涉及在草坪中用包含除草有效量的HPPD抑制剂和安全剂的组合物防治杂草而不导致草皮草的显著损伤的方法。
例如，对于草坪、高尔夫球场、运动场所和路旁来说高品质、健康的草皮是不可或缺的。由于草皮草植物与杂草之间的颜色和质地差异，杂草能够降低草坪品质。此外，杂草还与草皮草植物竞争现有的水和养料，这通常引起希望草皮草覆盖变得稀疏。因此，需要新的方法来增强草皮草品质从而提供高品质、健康的草坪。
HPPD抑制剂已知对各种作物中的杂草是有效的除草剂。然而，其能够导致对某些草皮草种类的植物毒性，包括缺绿病、灼伤和矮化。在将HPPD抑制剂施用至暖季草皮草的情况下，植物毒性则特别严重。相应地，需要降低HPPD抑制剂对草皮草特别是暖季草皮草的植物毒性。
WO2007/011847公开硝磺草酮的颗粒剂配制剂，其能够帮助降低硝磺草酮对草皮草的植物毒性。然而，希望进一步改善硝磺草酮的草坪安全性。
令人惊讶地，目前发现在与某些安全剂组合施用至草皮草的情况下能够进一步降低HPPD抑制剂的植物毒性效果，而不损失除草效力。尤其是，已发现在与某些安全剂组合施用的情况下硝磺草酮、或其盐或金属螯合物的植物毒性效果能够被进一步降低，而不损失除草效力。
硝磺草酮与各种其它除草剂和植物生长调节剂、任选与安全剂组合的混合物已知于例如WO08/011506，WO08/011509，WO08/011511，WO08/011283，GB2452374，GB2452375，GB2452376，GB2452377，WO09/019431，WO09/019432，WO09/027032，WO09/027029，WO09/027033，WO09/027030，WO09/027034，WO09/027031，WO09/027028，和WO09/027027。
根据本发明，提供在草皮草中防治杂草而不导致草皮草的显著损伤的方法，包括向草皮草施用组合物，该组合物包含除草有效量的除式I化合物外的HPPD抑制剂
和选自环丙磺酰胺(cyprosulfamide)和式IV化合物的安全剂化合物
条件是组合物不由下述组成：硝磺草酮，莠去津和式IV化合物；硝磺草酮，二氯吡啶酸和式IV化合物；硝磺草酮，乙氧呋草黄和式IV化合物；硝磺草酮，噁唑禾草灵-乙酯和式IV化合物；硝磺草酮，咪唑喹啉酸和式IV化合物；硝磺草酮，噁草酮和式IV化合物；硝磺草酮，二甲戊灵和式IV化合物；硝磺草酮，氟嘧磺隆和式IV化合物；至少一种HPPD抑制剂，至少一种植物生长调节剂和式IV化合物；硝磺草酮，莠去津和环丙磺酰胺；硝磺草酮，二氯吡啶酸和环丙磺酰胺；硝磺草酮，乙氧呋草黄和环丙磺酰胺；硝磺草酮，噁唑禾草灵-乙酯和环丙磺酰胺；硝磺草酮，咪唑喹啉酸和环丙磺酰胺；硝磺草酮，噁草酮和环丙磺酰胺；硝磺草酮，二甲戊灵和环丙磺酰胺；硝磺草酮，氟嘧磺隆和环丙磺酰胺；或者至少一种HPPD抑制剂，至少一种植物生长调节剂和环丙磺酰胺。
在本发明方法的备择实施方式中，组合物不包含硝磺草酮，莠去津和式IV化合物；硝磺草酮，二氯吡啶酸和式IV化合物；硝磺草酮，乙氧呋草黄和式IV化合物；硝磺草酮，噁唑禾草灵-乙酯和式IV化合物；硝磺草酮，咪唑喹啉酸和式IV化合物；硝磺草酮，噁草酮和式IV化合物；硝磺草酮，二甲戊灵和式IV化合物；硝磺草酮，氟嘧磺隆和式IV化合物；至少一种HPPD抑制剂，至少一种植物生长调节剂和式IV化合物；硝磺草酮，莠去津和环丙磺酰胺；硝磺草酮，二氯吡啶酸和环丙磺酰胺；硝磺草酮，乙氧呋草黄和环丙磺酰胺；硝磺草酮，噁唑禾草灵-乙酯和环丙磺酰胺；硝磺草酮，咪唑喹啉酸和环丙磺酰胺；硝磺草酮，噁草酮和环丙磺酰胺；硝磺草酮，二甲戊灵和环丙磺酰胺；硝磺草酮，氟嘧磺隆和环丙磺酰胺；或至少一种HPPD抑制剂，至少一种植物生长调节剂和环丙磺酰胺。
在本发明的另一实施方式中，提供在草皮草中防治杂草而不导致草皮草的显著损伤的方法，包括向草皮草施用组合物，其基本上由除草有效量的除式I化合物外的HPPD抑制剂
和选自环丙磺酰胺和式IV化合物的安全剂组成。适宜地，组合物由除草有效量的除式I化合物外的HPPD抑制剂，和选自环丙磺酰胺和式IV化合物的安全剂组成。
HPPD抑制剂是选择性的除草剂，其抑制4-羟基苯基-丙酮酸加双氧酶并且通过影响类胡萝卜素生物合成起作用。按照本发明方法可以使用除式I化合物外的任意HPPD抑制剂。例如，所述HPPD抑制剂可以选自三酮类，异噁唑类，吡唑类，双环磺草酮和ketospiradox。属于三酮类，异噁唑类和吡唑类的单独化合物的进一步细节可以参见PCT公开号WO2005/053407(将其公开通过援引并入本文)，但仍可提及硝磺草酮，磺草酮，异噁唑草酮，异噁氯草酮，吡草酮，吡唑特和苄草唑。用于本发明的其它适宜HPPD抑制剂包括苄草酮(tembotrione)，苯唑草酮(topramezone)，和任意上述化合物的全部互变异构体形式。全部可商购HPPD抑制剂的完整列表可以参见The Pesticide Manual(由英国作物保护委员会(British Crop Protection Council)出版，第14版)。
在本发明的一种实施方式中，所述HPPD抑制剂选自硝磺草酮，苄草酮和苯唑草酮。在本发明的另一实施方式中，所述HPPD抑制剂是苄草酮。在本发明的又一实施方式中，所述HPPD抑制剂是苯唑草酮。在本发明的又一实施方式中，所述HPPD抑制剂是硝磺草酮。
硝磺草酮(2-(2’-硝基-4’-甲基磺酰基苯甲酰基)-1，3-环己烷二酮)是三酮类HPPD抑制剂的成员。在酸形式中，其结构可以表示为：
除了上述酸形式，硝磺草酮还形成盐和金属螯合物，例如铜螯合物。这些金属螯合物尤其公开于美国专利No.5,912,207(通过援引将其公开并入本文)，其中它们在某些环境中与未螯合的硝磺草酮相比显示具有出人意料的优异稳定性。
当在玉米和草皮草上苗后施用时，硝磺草酮在宽范围的生长阶段防治广谱阔叶杂草的能力最为人所知。其通常以低比率使用(100-225克活性成分每公顷，取决于施用时的除草剂配制剂)从而防治施用时就存在及其之后多至四周内出苗的杂草。一经施用，硝磺草酮即被叶子、芽孢、根和种子快速吸收。在易感杂草中，它中断类胡萝卜素生物合成(植物生长的关键过程)，这导致植物死亡。与杂草不同，玉米植物和某些草皮草物种能够通过将活性化合物快速分解为无活性化合物从而耐受硝磺草酮。
如本文所用，名称‘硝磺草酮’包括硝磺草酮的盐和螯合形式，以及酸形式，还包括任何可以导致几何异构体的烯醇互变异构形式。此外，在某些情况下，各种取代基和/或螯合形式可以引起光学异构和/或立体异构。所有这些互变异构形式、外消旋混合物和异构体都包括在本发明的范围内。
在本发明的一种实施方式中，硝磺草酮以酸形式存在。在另外的实施方式中，硝磺草酮作为盐或金属螯合物存在。
硝磺草酮的适宜盐包括在农业或园艺用途的成盐技术领域中已知且接受的阳离子或阴离子的盐。该盐可以例如使用胺、碱金属碱、碱土金属碱和季铵碱来形成。
包括硝磺草酮的2-(经取代的苯甲酰基)-1，3-环己二酮化合物的金属螯合物尤其描述于美国专利No.5,912,207中。在一种实施方式中，硝磺草酮的适宜金属螯合物具有下述通式：
其中M代表二-或三价金属离子。
适宜地，所述二-或三价金属离子可以是Cu2+、Co2+、Zn2+、Ni2+、Ca2+、Al3+、Ti3+或Fe3+离子。更适宜地，所述金属离子可以是二价过渡金属离子比如Cu2+、Ni2+、Zn2+和Co2+。更适宜地所述金属离子可以是Cu2+和Zn2+而最适宜地是Cu2+。
本发明中使用的除草用硝磺草酮金属螯合物可以通过前述美国专利中所描述的方法或者通过应用或调整在化学文献中使用或描述的已知方法来制备。具体来说，任何可以作为二-或三价金属离子来源的合适盐都可以用来形成根据本发明的二酮化合物的金属螯合物。特别适宜的盐包括盐酸盐、硫酸盐、硝酸盐、碳酸盐、磷酸盐和乙酸盐。
短语“不导致草皮草的显著损伤”意指不引起无法接受的草皮草的植物毒性、漂白或矮化水平，和/或无法接受的草皮草颜色减少和品质降低。草皮草颜色和品质是基于1至9等级的工业标准评价，其中9级表示深绿色草坪也即最高品质。草皮草品质的评价基于数种因素，包括草坪群丛的矮化、均匀性和密度。6级或更低的草皮草品质视为无法接受。
短语“施用至草皮草”如本文所用包括直接施用至草皮草本身，施用至草皮草处所，施用至草皮草中生长的杂草，和施用至草皮草种子，以及施用至草皮草种子已被或将要播种的裸露地面。“处所”意在包括土壤、种子和幼苗以及建立的植物。
术语“除草有效量”指出能够对植物生长产生控制或改变效果的HPPD抑制剂的量。防治或改变效果包括所有对自然发育的偏离，例如：灭除，阻滞，叶灼伤，白化，矮化等。例如未被杀死的植物通常是低矮的并伴随开花被破坏是非竞争性的。术语“植物”是指植物的所有物理部分，包括种子、幼苗、幼树、根、块茎、茎、秆、叶和果实。
术语“安全剂”如本文所用意指化合物，其降低除草剂对草皮草的植物毒性效果。因此，安全剂(或解毒剂)具有通过降低或消除其对草皮草的潜在植物毒性来增强除草剂选择性的效果。术语“解毒有效量”描述某种程度地消除有益作物对除草剂的植物毒性应答的安全剂化合物的量。
在本发明的一种实施方式中，所述安全剂是环丙磺酰胺。在本发明的又一实施方式中，所述安全剂是式IV化合物。
在一种实施方式中，组合物是液体。液态组合物包括比如溶液，悬浮液或乳液等的配制剂类型。
在又一实施方式中，组合物是固体。固体组合物包括比如颗粒剂，粉末，粉剂，板，片剂，棒剂等的配制剂类型。例如，配制剂可以是颗粒剂。按照本发明可以使用任意适宜的颗粒剂，包括肥料颗粒剂和惰性载体颗粒剂。在一种实施方式中，颗粒剂是肥料颗粒剂。
HPPD抑制性除草剂与安全剂的比率可以取决于除草剂的选择，安全剂的选择，配制剂类型和组合物将向其施用的草皮草品种而变化。本领域技术人员熟悉如何确定任意给定方案的适当比率。一般地，除草剂与安全剂的比率为约50∶1至1∶50重量。在一种实施方式中，除草剂与安全剂的比率为20∶1至1∶1重量。
如果希望，本发明包括多于一种HPPD抑制除草剂的混合物的用途，例如增强杂草防治谱的用途。也可能与本发明结合使用多于一种安全剂的混合物，从而例如增强选择性(也即提供除草组合物对较宽范围的希望草皮草种类降低的损伤)。
尤其是，在本发明方法中可以使用下述HPPD抑制除草剂和安全剂的混合物：硝磺草酮和环丙磺酰胺；硝磺草酮和式IV化合物；苄草酮和环丙磺酰胺；苄草酮和式IV化合物；苯唑草酮和环丙磺酰胺；以及苯唑草酮和式IV化合物。
在本发明的一种实施方式中，所述HPPD抑制剂是硝磺草酮而所述安全剂是环丙磺酰胺。在本发明的另一实施方式中，所述HPPD抑制剂是硝磺草酮而所述安全剂是式IV化合物。
本发明组合物的施用量取决于待防治杂草的具体类型，所需的防治程度，草皮草种类以及施用时机和方法。通常，本发明组合物能够以0.005千克活性成分/公顷(kg/公顷)至约5.0kg活性成分/公顷的施用率施用。优选约0.1kg活性成分/公顷至约3.0kg活性成分/公顷的施用率，特别优选约0.5kg活性成分/公顷至1.2kg活性成分/公顷的施用率。
本发明组合物可以用来防治大量农业经济学上重要的杂草，包括单子叶杂草和双子叶杂草。
例如本发明的组合物可以用于防治双子叶杂草如苘麻属(Abutilonspp.)，豚草属(Ambrosia spp.)，苋属(Amaranthus spp.)，藜属(Chenopodium spp.)，糖芥属(Erysimum spp.)，大戟属(Euphorbiaspp.)，何首乌属(Fallopia spp.)，猪殃殃属(Galium spp.)，天胡荽属(Hydrocotyle spp.)，番薯属(Ipomoea spp.)，野芝麻属(Lamium spp.)，苜蓿属(Medicago spp.)，酢浆草属(Oxalis spp.)，车前草属(Plantagospp.)，蓼属(Polygonum spp.)，墨苜蓿属(Richardia spp.)，黄花稔属(Sida spp.)，白芥属(Sinapis spp.)，茄属(Solanum spp.)，繁缕属(Stellaria spp.)，蒲公英属(Taraxacum spp.)，车轴草属(Trifoliumspp.)，婆婆纳属(Veronica spp.)，堇菜属(Viola spp.)和苍耳属(Xanthium spp.)。
本发明也可以用来防治单子叶杂草，比如剪股颖属(Agrostis spp.)、看麦娘属(Alopecurus spp.)、阿披拉草属(Apera spp.)、燕麦属(Avenaspp.)、臂形草属(Brachiaria spp.)、雀麦属(Bromus spp.)、马唐属(Digitaria spp.)、稗属(Echinochloa spp.)、属(Eleusine spp.)、野黍属(Eriochloa spp.)、千金子属(Leptochloa spp.)、黑麦草属(Loliumspp.)、半颖黍属(Ottochloa spp.)、稷属(Panicum spp.)、雀稗属(Paspalum spp.)、虉草属(Phalaris spp.)、早熟禾属(Poa spp.)、筒轴茅属(Rottboellia spp.)、狗尾草属(Setaria spp.)、蜀黍属(Sorghumspp.)，这些禾本科杂草的任何内在敏感生物型以及抗性(例如ACCase和/或ALS抗性)生物型，以及阔叶单子叶杂草比如鸭跖草属(Commelinaspp.)、雨久花属(Monochoria spp.)、慈姑属(Sagittaria spp.)和苔草(sedge)，比如莎草属(Cyperus spp.)和藨草属(Scirpus spp.)。
更特别地，在可以通过本发明组合物防治的杂草中尤其可以提及单子叶杂草，比如稗(Echinochloa crus-galli)，马唐(Digitaria sanguinalis)和止血马唐(Digitaria ischaemum)，牛筋草(Eleusine indica)，翦股颖属(Agrostis spp.)，金色狗尾草(Setaria glauca)，油莎草(CyperusEsculentus)，轮生虎尾草(Chloris verticillata)和乱子草(Muhlenbergiaschreberi)，和双子叶杂草比如蒲公英属(Taraxacum spp.)，白色车轴草和红色车轴草(车轴草属(Trifolium spp.))，繁缕(Stellaria media)，宝盖草(Lamium amplexicaule)，直立婆婆纳(Veronica arvensis)，酢浆草属(Oxalis spp.)，长叶车前草(Plantago lanceolata)和车前草(Plantagomajor)，伞花天胡荽(Hydrocotyle umbellata)，佛罗里达马齿苋(FLpusley)(墨苜蓿(Richardia scabra))，藜属(Chenopodium spp.)，蓼(何首乌属(Fallopia spp.))，豚草(Ambrosia artemisiifolia)，野生紫罗兰(堇菜属(Viola spp.))，藜(pigweed)(苋属(Amaranthus spp.))，天蓝苜蓿(Medicago lupulina)，钻果大蒜芥(Erysimum officinale)，欧毛茛(Ranunculus sardous)，种梭粟米草(Mollugo verticillata)，皱叶酸模(Rumex cripsus))，弗罗里达水苏(Stachys floridana)，牛滕菊(Galinsoga)(睫毛牛膝属(Galinsoga ciliata))，欧活血丹(Glechoma hederacea)，夏枯草(Prunella vulgaris)，草坪刺果杂草(Saliva sessilis)，小白酒草(Conyzacanadensis)，马齿苋(Portulaca oleracea)，荠菜(Capsella bursa-pastoris)，苦苣菜(Sanchus oleraceus)，臭荠(Coronopus didymus)，丝路蓟(Cirsiumarvense)，马鞭草(Verbena)(戟叶马鞭草(Verbena hastata))和野胡萝卜(Daucus carota)。
出于本发明目的，术语‘杂草’包括不希望的作物种比如自生作物。例如，在草皮草作物比如高尔夫球场的环境中，如果在管理不同品种草的平坦球道区发现有匍匐剪股颖轻击区草皮，则可以认为其是“自生的”。当在不适当的地方发现时，以下列举的草可被类似地视为杂草。
在施用组合物以在已稳固生长的草皮草中灭除杂草的情况下，本发明的益处体现得最明显。本发明可以施用至冷季草皮草和暖季草皮草。
冷季草皮草包括，例如：早熟禾属(Poa L.)，比如草地早熟禾(Poapratensis L.)，普通早熟禾(Poa trivialis L.)，加拿大早熟禾(Poa compressaL.)和早熟禾(Poa annua L.)；剪股颖属(Agrostis L.)，比如匍匐翦股颖(Agrostis palustris Huds.)，细弱翦股颖(Agrostis tenius Sibth.)，普通翦股颖(Agrostis canina L.)和小糠草(Agrostis alba L.)；羊茅属(Festuca L.)，比如紫羊茅(Festuca rubra L.)，丛生型紫羊茅(Festuca rubra var.Commutata Gaud.)，绵羊羊茅(Festuca ovina L.)，长叶羊茅(Festucalongifolia)，苇状羊茅(Festuca arundinacea Schreb.)，牛尾草(Festucaelatior L.)；黑麦草属(Lolium L.)，比如多年黑麦草(Lolium perenne L.)，多花黑麦草(Lolium multiflorum Lam.)；冰草属(Agropyron Gaertn.)，比如冰草(Agropyron cristatum(L.)Gaertn.)，蓝茎冰草(Agropyronsmithii Rydb.)；无芒雀麦(Bromus inermis Leyss.)；和梯牧草属(PhleumL.)。
暖季草皮草的实例是狗芽根(Cynodon L.C.Rich)，结缕草属(ZoysiaWilld.)，偏序钝叶草(Stenotaphrum secundatum(Walt.)Kuntze)，假俭草(Eremochloa ophiuroides(Munro.)Hack.)，地毯草属(AxonopusBeauv.)，百喜草(Paspalum notatum Flugge.)，铺地狼尾草(Pennisetumclandestinum Hochst.ex Chiov.)，野牛草(Buchloe dactyloides(Nutt.)Engelm.)，蜈蚣草属(Eremochloa spp)，结缕草属(Zoysia spp.)和海雀稗(Paspalum vaginatum swartz)。
暖季草皮草比冷季草皮草更易受施用HPPD抑制剂的损伤。在一种实施方式中，组合物施用至暖季草皮草。
本发明可以施用至作为常规育种方法或基因工程改造的结果已使其耐受病虫害和农药，包括除草剂或多类除草剂(并且，适宜地包括HPPD抑制除草剂)的草皮草。对除草剂的耐受意指与常规草皮草相比对特定除草剂所引起的损害有所降低的易感性。能够改造或培育草皮草以耐受例如HPPD抑制剂比如硝磺草酮，EPSPS抑制剂比如草甘膦或耐受草铵膦酸(glufosinate)。应注意玉米天然耐受硝磺草酮。在本发明的一种实施方式中，草皮草是HPPD耐受的。
取决于向其上施用组合的作物，通过将本发明的组合物苗前或苗后施用于需要防治的处所以用来防治不希望的植物生长。因此，在一种实施方式中本发明的除草组合物作为苗前施用来施用。在又一种实施方式中，本发明的除草组合物作为苗后施用来施用。
本发明的HPPD抑制性化合物和所述安全剂可以同时地或以任意次序按顺序地施用。如果按顺序地给予，所述组分可以以任意次序在适宜时间范围内给予，例如，给予第一组分的时间和给予最后组分的时间之间不超过24小时。适宜地，全部组分在数小时比如一小时的时间范围内给予。如果同时给予各组分，可以分开给予它们或者将其作为桶混或作为预配制的全部组分的混合物给予。在一种实施方式中，本发明的混合物或组合物可以在种植前作为种子处理施用至作物。
在本发明方法是指向草皮草施用共配制的HPPD抑制剂和安全剂的组合物的情况下，则组合物包含HPPD抑制性化合物和所述安全剂。例如，可以将HPPD抑制性化合物和所述安全剂与全部其它配制剂组分一起均匀地混合。然后可以将组分压缩、挤出或造粒以形成固体配制剂。另选地，可以一起混合所述HPPD抑制性化合物和所述安全剂，并施用至预先形成的固体配制剂的表面作为包衣或者施用于待吸收入颗粒剂的溶剂中。另选地，所述HPPD抑制性化合物可以与其它配制剂组分混合以形成固体配制剂，并随后将所述安全剂施用至所述固体配制剂的表面；反之亦然。另选地，所述HPPD抑制性化合物和所述安全剂可以是包封以形成‘固态’组合物的液体形式。
在本发明方法是指分开施用(同时地或按顺序地)一种包含HPPD抑制剂而另一种包含安全剂的两种组合物至草皮草的情况下，所述组合物之一或两者可以是固态配制剂。
在实践中，本发明方法中所用的组合物作为含有本领域已知或使用的各种助剂和载体的配制剂来施用。
乳油是在水中或其它液体中可分散的匀质液体组合物并可以完全由活性化合物与液体或固体乳化剂组成，或者还可以含有液体载体比如二甲苯、重芳族的石脑油、异佛尔酮和其它非挥发性有机溶剂。在使用中，将上述乳油分散在水或其它液体中并通常作为喷雾施用至待处理区域。活性成分的量可以在乳油的约0.5％至约95％的范围内。
对于除草施用的其它有用配制剂包括活性成分在溶剂比如丙酮、烷基化萘、二甲苯和其它有机溶剂中的简单溶液，其中所述活性成分以希望浓度完全溶解。还可以使用加压喷雾器，其中由于低沸点分散剂溶剂载体的汽化导致活性成分以细分形式分散。
观察到在HPPD抑制剂和安全剂的配制剂作为固体配制剂施用的情况下，一般在暖季草皮草上实现更佳水平的草皮草安全性。因此，可以将本发明组合物配制为颗粒剂(和，适宜地作为稳定化的颗粒剂)、可湿性粉剂、粉剂或尘剂、胶悬剂，或控释形式比如微胶囊。这些配制剂可以包含少至约0.5重量％到多至约95重量％或更多的活性成分。对于任何给定的化合物的最佳量取决于配制剂、施用设备和待防治的植物的性质。
可湿性粉剂是在水中或其它液体载体中易于分散的细分颗粒形式。所述颗粒包含保留在固体基质中的活性成分。典型的固体基质包括漂白土、高岭土、硅土和其它易于润湿的有机或无机固体。可湿性粉剂通常含有约5％至约95％的活性成分，以及少量的润湿剂、分散剂或乳化剂。
颗粒状配制剂包括挤出物和相对粗的颗粒，并且通常不经稀释地施用至需要抑制植物的区域。用于颗粒状配制剂的典型载体包括肥料、沙、漂白土、凹凸棒石粘土、膨润土、蒙脱土、蛭石、珍珠岩、碳酸钙、砖、浮石、叶蜡石、高岭土、白云石、灰泥、木屑、玉米轴、花生壳、糖、氯化钠、硫酸钠、硅酸钠、硼酸钠、氧化镁、云母、氧化铁、氧化锌、氧化钛、氧化锑、冰晶石、石膏、硅藻土、硫酸钙和其它吸收活性化合物或可以用活性化合物涂覆的有机或无机物质。特别适合的是肥料颗粒载体。颗粒状配制剂通常含有约5％至约25％的活性成分，其可以包含表面活性剂如重芳族石脑油、煤油和其它石油馏分，或植物油；和/或粘合剂如糊精、胶水或合成树脂。适宜地，颗粒剂配制剂可以是稳定化的组合物，其包含至少一种颗粒剂基底物质，该基底物质含有至少一种硝磺草酮金属螯合物和安全剂。所述颗粒剂基底物质可以是上述典型载体之一和/或可以是肥料物质例如脲/甲醛肥料，脲，氯化钾，铵化合物，磷化合物，硫，相似的植物养分和微量营养素和其混合物或组合。硝磺草酮的金属螯合物和所述安全剂可以均匀地分布在整个颗粒剂中或者可以在形成颗粒剂之后喷雾浸渍或吸收在颗粒剂基底上。
粉尘剂是活性成分与细分固体的自由流动性混合物，所述细分固体是比如滑石、粘土、面粉和其它充当分散剂和载体的有机和无机固体。
微囊剂典型地是包封在惰性多孔壳中的活性物质的小滴或颗粒，所述惰性多孔壳允许被包封的物质以受控速率释放到周围环境中。包囊粒剂通常是具有密封颗粒孔口的多孔膜的多孔颗粒，活性成分以液体形式保留在颗粒孔中。颗粒剂直径典型为1毫米至1厘米，优选1至2毫米。颗粒剂通过挤出、团聚或喷射造粒形成或是天然形成。这种材料的实例为蛭石、烧结粘土、高岭土、凹凸棒石粘土、锯屑和颗粒状碳。壳或膜材料包括天然或合成橡胶、纤维质材料、苯乙烯-丁二烯共聚物、聚丙烯腈、聚丙烯酸类、聚酯、聚酰胺、聚脲、聚氨酯和淀粉黄原酸酯。
上述这些配制剂中的许多包括润湿剂、分散剂或乳化剂。实例为烷基与烷基芳基磺酸酯和硫酸酯以及它们的盐、多羟基醇；聚乙氧基化的醇、酯和脂肪胺。在使用时，这些试剂通常占配制剂重量的0.1％至15％。
本领域技术人员熟知在适用于将本发明所用组合物配制为上述配制剂类型的农业助剂和载体。不同类别的适宜实例见于下述非限制性列表。
可以采用的液体载体包括水，甲苯，二甲苯，石脑油，植物油，丙酮，甲乙酮，环己酮，乙酸酐，乙腈，苯乙酮，乙酸戊酯，2-丁酮，氯苯，环己烷，环己醇，乙酸烷基酯，二丙酮醇，1，2-二氯丙烷，二乙醇胺，对-二乙基苯，二乙二醇，二乙二醇松香酸酯，二乙二醇丁醚，二乙二醇乙醚，二乙二醇甲醚，N，N-二甲基甲酰胺，二甲亚砜，1，4-二噁烷，二丙二醇，二丙二醇甲醚，二丙二醇二苯甲酸酯，diproxitol，烷基吡咯烷酮，乙酸乙酯，2-乙基己醇，碳酸亚乙酯，1，1，1-三氯乙烷，2-庚酮，α蒎烯，d-苧烯，乙二醇，乙二醇丁醚，乙二醇甲醚，γ-丁内酯，甘油，甘油二乙酸酯，甘油单乙酸酯，甘油三乙酸酯，十六烷，己二醇，乙酸异戊酯，乙酸异冰片酯，异辛烷，异佛尔酮，异丙基苯，肉豆蔻酸异丙酯，乳酸，月桂胺，异亚丙基丙酮，甲氧基-丙醇，甲基异戊基酮，甲基异丁基酮，月桂酸甲酯，辛酸甲酯，油酸甲酯，二氯甲烷，间二甲苯，正己烷，正辛胺，十八烷酸，乙酸辛胺，油酸，油胺，邻二甲苯，苯酚，聚乙二醇(PEG400)，丙酸，丙二醇，丙二醇单甲醚，对二甲苯，甲苯，磷酸三乙酯，三甘醇，二甲苯磺酸，石蜡，矿物油，三氯乙烯，全氯乙烯，乙酸乙酯，乙酸戊酯，乙酸丁酯，甲醇，乙醇，异丙醇，以及较高分子量的醇如戊醇、四氢糠醇、己醇、辛醇等，乙二醇，丙二醇，甘油，N-甲基-2-吡咯烷酮等。水通常是用于稀释浓缩物的所选载体。
适合的固体载体包括滑石，二氧化钛，叶蜡石粘土，硅土，凹凸棒石粘土，硅藻土，白垩，硅藻土(diatomaxeous earth)，石灰，碳酸钙、膨润土，漂白土，肥料，棉子壳，小麦粉，大豆粉，浮石，木粉，胡桃壳粉，木质素等。
可将宽范围的表面活性剂用于组合物中。表面活性剂的性质可以是阴离子、阳离子、非离子或高分子型并且能够用作乳化剂、润湿剂、助悬剂或其它意图。典型的表面活性剂包括烷基硫酸酯盐，如月桂基硫酸酯二乙醇铵盐；烷基芳基磺酸盐，如十二烷基苯磺酸钙；烷基酚-环氧烷烃加成产物，如壬酚-C.sub.18乙氧基化物；醇-环氧烷烃加成产物，如十三烷基醇-C.sub.16乙氧基化物；皂，如硬脂酸钠；烷基萘磺酸盐，如二丁基萘磺酸钠；磺基琥珀酸二烷基酯盐，如二(2-乙基己基)磺基琥珀酸钠；山梨糖醇酯，如山梨糖醇油酸酯；季胺，如月桂基三甲基氯化铵；脂肪酸聚乙二醇酯，如聚乙二醇硬脂酸酯；环氧乙烷与环氧丙烷嵌段共聚物；以及单烷基和二烷基磷酸酯盐。
农业组合物中一般运用的其它助剂包括色素，抗氧化剂，起泡剂，遮光剂，增容剂，螯合剂，中和剂和缓冲剂，缓蚀剂，染料，增香剂，铺展剂，助渗剂，微量营养素，软化剂，润滑剂，粘着剂，等。还能够将组合物与粒状肥料载体比如硝酸铵、脲等一起配制。
根据本发明，提供包含硝磺草酮和式IV安全剂化合物的除草组合物，条件是所述组合物不由下述组成：硝磺草酮，莠去津和式IV化合物；硝磺草酮，二氯吡啶酸和式IV化合物；硝磺草酮，乙氧呋草黄和式IV化合物；硝磺草酮，噁唑禾草灵-乙酯和式IV化合物；硝磺草酮，咪唑喹啉酸和式IV化合物；硝磺草酮，噁草酮和式IV化合物；硝磺草酮，二甲戊灵和式IV化合物；硝磺草酮，氟嘧磺隆和式IV化合物；或者硝磺草酮，至少一种植物生长调节剂(比如抗倒酯、调环酸钙、多效唑、烯效唑、甲哌鎓和矮壮素)和式IV化合物。
根据本发明，也提供包含硝磺草酮和式IV安全剂化合物的除草组合物，条件是所述组合物不包含：硝磺草酮，莠去津和式IV化合物；硝磺草酮，二氯吡啶酸和式IV化合物；硝磺草酮，乙氧呋草黄和式IV化合物；硝磺草酮，噁唑禾草灵-乙酯和式IV化合物；硝磺草酮，咪唑喹啉酸和式IV化合物；硝磺草酮，噁草酮和式IV化合物；硝磺草酮，二甲戊灵和式IV化合物；硝磺草酮，氟嘧磺隆和式IV化合物；或硝磺草酮，至少一种植物生长调节剂和式IV化合物。
根据本发明，提供基本上由作为活性成分的硝磺草酮和式IV安全剂化合物组成的除草组合物。适宜地，所述除草组合物由作为活性成分的硝磺草酮和式IV安全剂化合物组成。
根据本发明，提供包含硝磺草酮和式IV安全剂化合物的颗粒剂组合物。
此外进一步地，其它杀生物活性成分或组合物也可以与本发明的除草组合物相组合。例如，组合物除了HPPD抑制剂和安全剂之外还可以含有其它除草剂、杀昆虫剂、杀真菌剂、杀菌剂、杀螨剂、杀线虫剂和/或植物生长调节剂，以便拓宽活性谱。尤其是，本发明组合物还包含选自草甘膦，草铵膦酸，麦草畏，精异丙甲草胺，乙草胺和2，4-滴的除草剂。
上述每种配制剂都可以制备为包含除草剂与配制剂的其它成分(稀释剂、乳化剂、表面活性剂等)的包装。
这些配制剂可以通过常规方法施用于需要防治的区域。例如，将颗粒剂配制剂施用至已稳固生长的草皮草可以是经由手持式展布器、推式展布器或连接至拖拉机的展布器进行分布。能够通过常规手段比如灌溉、圆盘耕地、平地或混合操作将施用至其中已经或将要播种草皮草的土壤表面的尘剂或颗粒剂组合物分布在土壤表面之下。
本发明能够用于其中希望杂草防治的任意情况中，例如农业中、高尔夫球场、运动场或其它专业管理的草皮草区域上或园地中。本发明特别适于在草皮草中选择性防治杂草。包覆在肥料颗粒剂上或浸渍于其中的硝磺草酮与安全剂的混合物特别有用。
下述实施例仅用于解释目的。所述实施例并非旨在作为所有经实施测试的必然代表，并且不意欲以任何方式限制本发明。正如本领域技术人员所熟知，在除草试验中大量不易控制的因素会影响单个试验的结果并使得它们不能重现。例如，所述结果可以取决于环境因素，尤其是比如光照量和水量、土壤类型、土壤pH、温度和湿度而变化。同样，栽种深度，单独和组合除草剂的施用量，安全剂的施用量，单独除草剂与安全剂的比率，和测试的作物或杂草的性质能够影响试验结果。结果可以在草皮草物种间以及在草皮草变种内变化。
实施例
实施例1
通过喷雾施用以下表中所示的各种用量将硝磺草酮的液体配制剂施用至狗牙根(Cynodon dactylon x C.dactylon)和沟叶结缕草(Zoysia matrella)，加和不加安全剂。在施用之后7、14和21天进行评价，以确定百分比生长抑制、百分比毒性(缺绿病和/或灼伤)。
表1：狗牙根
表2：沟叶结缕草
这些结果显示在向暖季草皮草施用与式IV化合物或环丙磺酰胺组合的硝磺草酮液体配制剂的情况下实现安全效果。使用式IV化合物则观察到特别良好的安全效果。
Claims (11)
1.在草皮草中防治杂草而不导致草皮草的显著损伤的方法，包括向草皮草施用组合物，该组合物包含除草有效量的硝磺草酮,
和选自由环丙磺酰胺或式IV化合物组成的组的安全剂化合物
条件是所述组合物不由下述组成：硝磺草酮，莠去津和式IV化合物；硝磺草酮，二氯吡啶酸和式IV化合物；硝磺草酮，乙氧呋草黄和式IV化合物；硝磺草酮，噁唑禾草灵-乙酯和式IV化合物；硝磺草酮，咪唑喹啉酸和式IV化合物；硝磺草酮，噁草酮和式IV化合物；硝磺草酮，二甲戊灵和式IV化合物；硝磺草酮，氟嘧磺隆和式IV化合物；至少一种HPPD抑制剂，至少一种植物生长调节剂和式IV化合物；硝磺草酮，莠去津和环丙磺酰胺；硝磺草酮，二氯吡啶酸和环丙磺酰胺；硝磺草酮，乙氧呋草黄和环丙磺酰胺；硝磺草酮，噁唑禾草灵-乙酯和环丙磺酰胺；硝磺草酮，咪唑喹啉酸和环丙磺酰胺；硝磺草酮，噁草酮和环丙磺酰胺；硝磺草酮，二甲戊灵和环丙磺酰胺；硝磺草酮，氟嘧磺隆和环丙磺酰胺；或至少一种HPPD抑制剂，至少一种植物生长调节剂和环丙磺酰胺。
2.根据权利要求1的方法，其中所述安全剂是环丙磺酰胺。
3.根据权利要求1的方法，其中所述安全剂是式IV化合物。
4.根据权利要求1的方法，其中所述组合物是液体。
5.根据权利要求1的方法，其中所述组合物是固体。
6.根据权利要求5的方法，其中所述组合物是惰性颗粒剂或肥料颗粒剂。
7.根据权利要求1的方法，其中所述草皮草是暖季草皮草。
8.根据权利要求1的方法，其中所述草皮草是HPPD耐受的。
9.根据权利要求1的方法，其中除草剂与安全剂的比率是20：1至1：1。
10.包含硝磺草酮和式IV安全剂化合物的除草组合物，条件是所述组合物不由下述组成：硝磺草酮，莠去津和式IV化合物；硝磺草酮，二氯吡啶酸和式IV化合物；硝磺草酮，乙氧呋草黄和式IV化合物；硝磺草酮，噁唑禾草灵-乙酯和式IV化合物；硝磺草酮，咪唑喹啉酸和式IV化合物；硝磺草酮，噁草酮和式IV化合物；硝磺草酮，二甲戊灵和式IV化合物；硝磺草酮，氟嘧磺隆和式IV化合物；或者硝磺草酮，至少一种植物生长调节剂和式IV化合物。
11.包含硝磺草酮和式IV安全剂化合物的除草组合物，条件是所述组合物不包含：硝磺草酮，莠去津和式IV化合物；硝磺草酮，二氯吡啶酸和式IV化合物；硝磺草酮，乙氧呋草黄和式IV化合物；硝磺草酮，噁唑禾草灵-乙酯和式IV化合物；硝磺草酮，咪唑喹啉酸和式IV化合物；硝磺草酮，噁草酮和式IV化合物；硝磺草酮，二甲戊灵和式IV化合物；硝磺草酮，氟嘧磺隆和式IV化合物；或者硝磺草酮，至少一种植物生长调节剂和式IV化合物。
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| CN103221409B (zh) | 2010-10-01 | 2016-03-09 | 巴斯夫欧洲公司 | 除草的苯并*嗪酮类 |
| WO2012080239A1 (en) | 2010-12-15 | 2012-06-21 | Basf Se | Herbicidal compositions |
| JP6121998B2 (ja) | 2011-07-22 | 2017-04-26 | ライステック アクチェンゲゼルシャフト | Ａｃｃアーゼ阻害性除草剤に対して抵抗性のイネを生成するための方法および組成物 |
| US9303270B2 (en) | 2011-07-22 | 2016-04-05 | Ricetec Aktiengesellschaft | Rice resistant to HPPD and accase inhibiting herbicides |
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| GB201301976D0 (en) * | 2013-02-04 | 2013-03-20 | Syngenta Participations Ag | New safening method |
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| CN105050401B (zh) * | 2013-03-25 | 2018-04-27 | 先正达参股股份有限公司 | 改进的杂草控制方法 |
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| CN104351236A (zh) * | 2014-10-17 | 2015-02-18 | 王龙潮 | 一种可用于甜玉米的除草组合物 |
| CN104663696A (zh) * | 2015-02-12 | 2015-06-03 | 海利尔药业集团股份有限公司 | 一种含有硝磺草酮与氟胺磺隆的除草组合物 |
| KR20170117431A (ko) * | 2015-02-20 | 2017-10-23 | 다우 아그로사이언시즈 엘엘씨 | 할라욱시펜 또는 4-아미노-3-클로로-5-플루오로-6-(4-클로로-2-플루오로-3-메톡시페닐)피리딘-2-카르복실산을 함유하는 안전해진 제초제 조성물 및 잔디에서의 그 사용 방법 |
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| CA2738413C (en) | 2016-10-25 |
| CN102215679A (zh) | 2011-10-12 |
| ES2443297T3 (es) | 2014-02-18 |
| WO2010040485A1 (en) | 2010-04-15 |
| KR101657164B1 (ko) | 2016-09-13 |
| EP2337451A1 (en) | 2011-06-29 |
| EP2337451B1 (en) | 2013-11-20 |
| JP2012504567A (ja) | 2012-02-23 |
| PL2337451T3 (pl) | 2014-04-30 |
| JP5600109B2 (ja) | 2014-10-01 |
| AU2009301406A1 (en) | 2010-04-15 |
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| ZA201102125B (en) | 2012-08-29 |
| CA2738413A1 (en) | 2010-04-15 |
| PT2337451E (pt) | 2014-01-28 |
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