CN104381250A - 拌种方法 - Google Patents
拌种方法 Download PDFInfo
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- CN104381250A CN104381250A CN201410541734.0A CN201410541734A CN104381250A CN 104381250 A CN104381250 A CN 104381250A CN 201410541734 A CN201410541734 A CN 201410541734A CN 104381250 A CN104381250 A CN 104381250A
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- methyl
- acid
- seed
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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
-
- 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
- A01N3/00—Preservation of plants or parts thereof, e.g. inhibiting evaporation, improvement of the appearance of leaves or protection against physical influences such as UV radiation using chemical compositions; Grafting wax
-
- 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
- A01N25/24—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 ingredients to enhance the sticking of the active ingredients
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Toxicology (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及一种方法,其包括用至少选自特定丙烯酸酯共聚物的粘着剂处理植物繁殖材料;还涉及包含这类粘着剂的拌种配制剂,以及用这类粘着剂包衣的植物繁殖材料。
Description
本申请是申请日为2010年1月26日,申请号为201080005553.6,发明名称为“拌种方法”的发明专利申请的分案申请。
用包含农药的配制剂处理植物繁殖材料所带来的一个问题是形成粉尘,这可引起环境问题。
植物繁殖材料在干燥后运动——即在植物繁殖材料包装时,植物繁殖材料处理和运输过程中以及播种过程中运动,会一直产生粉尘。除了来自植物繁殖材料(在处理过程中被擦掉)的部分以及在植物繁殖材料清洁过程中未被完全清除的其他植物部分(如斯卑尔脱小麦(spelt)部分)之外,粉尘也可能包含一部分在经处理的植物繁殖材料操作期间被擦掉的存在于种子处理配制剂中的农药。
为了避免或减少包含农药的粉尘形成,种子处理配制剂经常包含特定聚合物(粘着剂)以确保将农药粘着至各植物繁殖材料。
此外,粘着剂可能对对客户而言是重要的经处理的种子的性质,如植物繁殖材料部分的不希望的聚结(团聚)产生不利影响,这直接影响植物繁殖材料的流动性。
对流动性的不利影响的潜在后果是在工厂对植物繁殖材料进行处理(运输,包装,例如用于谷物的加工)时会产生问题和/或降低“播种能力”,即,降低使用现有技术的机械(如用于中耕作物如玉米、大豆或向日葵的气动式播种机)的种植精确度。后一部分对中耕作物极其重要,而对谷物而言,植物繁殖材料于工厂中的流动性问题更为重要。
另一问题是限制了可施用于植物繁殖材料的液体量。因此,需要在低剂量施用率下具有高性能的粘着剂。
粘着剂可能导致的另一问题是配制剂不仅粘着在植物繁殖材料,而且粘着在用于种子处理的机器上,从而需要在机器清洗时付出更多努力。
粘着剂可能导致的另一问题是其对种子生命力具有不利影响。种子生 命力(活力)本身以各种形式表现。植物生命力的表现形式的实例为:
(a)整体目视外观;
(b)根生长和/或根发育;
(c)叶面积大小;
(d)叶显绿强度;
(e)在地面附近的死叶数量;
(f)植株高度;
(g)植株重量;
(h)生长速率;
(i)植株林分密度;
(j)萌芽行为;
(k)出苗行为;
(l)嫩枝数量;
(m)嫩枝类型(质量和繁殖力);
(n)植株韧性,例如抗生物或非生物应力;
(o)坏死的存在;
(p)衰老行为。
优选地,术语“种子生命力(活力)”是指植株林分密度,种子可储存性和/或萌芽行为。
在作物保护中,各种努力的另一目的是提高植物产量。“产量”应理解为由植物,如谷物、适当定义的果实、蔬菜、核果、谷粒、种子、木材(例如在造林植物的情况下)或者甚至花卉(例如在园林植物、观赏植物的情况下)所产生的具有经济价值的任何植物产品。此外,所述植物产品还可在收获后进一步利用和/或加工。
根据本发明,植物,尤其是农业、造林和/或园艺植物,优选农业植物的“提高的产量”意指与在相同条件,但不施用本发明混合物的情况下所获得的相同植物产品的产量相比,各植物产品的产量具有可测量量的提高。
提高的产量尤其可通过以下植物性质的改善加以表征:
·提高的植株重量
·提高的植株高度
·提高的生物量,如更高的总新鲜重量(FW)
·更高的谷物产量
·更多的分蘖
·更大的叶子
·改善的嫩枝生长
·提高的蛋白质含量
·提高的油含量
·提高的淀粉含量
·提高的色素含量。
根据本发明,产量提高至少2%,优选至少4%,更优选至少8%,甚至更优选至少16%。
尽管现有技术描述了若干种可部分满足这些要求的粘着剂(参见例如US20080103044),仍一直需要改善种子处理配制剂的整体性能。
因此,本发明的目的是提供包含粘着剂的种子处理配制剂,其能减少粉尘,同时保持或改善种子生命力(活力)——尤其是植株林分密度、种子可储存性和/或萌芽行为——和/或具有令人满意的流动性和/或所得配制剂很少粘着在种子处理过程中所用的机器上和/或降低剂量施用率和/或提高产量。
该目的提高一种包括用下文所定义的至少一种粘着剂处理植物繁殖材料,优选种子的方法而实现。
该方法使粉尘得以减少。优选地,除减少粉尘以外,所述方法也优选提供:
1)保持或改善种子生命力(活力),尤其是植株林分密度、种子可储存性和/或萌芽行为,和/或
2)保持经处理的种子的流动性和/或
3)减少所得配制剂在种子处理过程中所用机器上的粘着和/或
4)与目前标准相比,减少粘着剂的剂量施用率;和/或
5)提高植物产量。
所述粘着剂优选与至少一种农药组合施用。此时,所述粘着剂与所述至少一种农药同时(即共同或分开)或依次施用。
所述粘着剂包含呈聚合形式的:
a)至少一种选自丙烯酸、甲基丙烯酸或丙烯酰胺的共聚单体a);和
b)至少一种选自甲基丙烯酸甲酯、丙烯酸甲酯或苯乙烯的共聚单体b);和
c)至少一种选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c)。
粘着剂的该实施方案在下文中称为“粘着剂I”。
在优选实施方案中,所述粘着剂包含呈聚合形式的:
a)选自甲基丙烯酸或丙烯酰胺、或丙烯酸与丙烯酰胺混合物的共聚单体a);和
b)选自甲基丙烯酸甲酯、丙烯酸甲酯或苯乙烯的共聚单体b);和
c)选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c)。
该实施方案在下文中称为“粘着剂II”。
在另一优选实施方案中,所述粘着剂包含呈聚合形式的:
a)选自丙烯酸或甲基丙烯酸的共聚单体a);和
b)选自甲基丙烯酸甲酯或丙烯酸甲酯的共聚单体b);和
c)选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c)。
该实施方案在下文中称为“粘着剂III”。
在更优选的实施方案中,所述粘着剂包含呈聚合形式的:
a)选自甲基丙烯酸或丙烯酰胺、或丙烯酸与丙烯酰胺混合物的共聚单体a);和
b)选自甲基丙烯酸甲酯或丙烯酸甲酯的共聚单体b);和
c)选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c),其中共聚单体c)优选为丙烯酸正丁酯。
该实施方案在下文中称为“粘着剂IV”。
在另一更优选的实施方案中,所述粘着剂包含呈聚合形式的:
a)选自丙烯酰胺、或丙烯酸与丙烯酰胺混合物的共聚单体a);和
b)作为共聚单体b)的苯乙烯;和
c)选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c),其中共聚单体c) 优选为丙烯酸正丁酯。
该实施方案在下文中称为“粘着剂V”。
在另一更优选的实施方案中,所述粘着剂包含呈聚合形式的:
a)选自丙烯酸的共聚单体a);和
b)选自甲基丙烯酸甲酯和丙烯酸甲酯,优选丙烯酸甲酯的共聚单体b);和c)选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c),其中共聚单体c)优选为丙烯酸正丁酯。
该实施方案在下文中称为“粘着剂VI”。
粘着剂I、II、III、IV、V和VI的玻璃化转变温度(Tg)优选为-30℃至+30℃,更优选为-15℃至+30℃,尤其是-12℃至+28℃。聚合物的玻璃化转变温度由差示扫描量热计(DSC)确定。将所有试样在110℃下干燥1小时,以消除水/溶剂对共聚物Tg的影响。DSC试样尺寸为约10-15mg。所述测量通常在N2气氛下,于-100℃至100℃下,以20℃/分钟进行。Tg由转变区的中点确定。
在最优选的实施方案中,所述粘着剂包含呈聚合形式的:
a)作为共聚单体a)的丙烯酸与丙烯酰胺的混合物;和
b)作为共聚单体b)的苯乙烯;和
c)作为共聚单体c)的丙烯酸正丁酯;
且具有优选为-30℃至+30℃,更优选为-20℃至28℃,尤其是+15℃至+28℃的Tg。
该实施方案在下文中称为“粘着剂VII”。
在最优选的实施方案中,所述粘着剂包含呈聚合形式的:
a)作为共聚单体a)的甲基丙烯酸;和
b)作为共聚单体b)的甲基丙烯酸甲酯;和
c)作为共聚单体c)的丙烯酸正丁酯;
且具有优选为-30℃至+30℃,更优选为-20℃至+28℃,尤其是-15℃至+10℃的Tg。
该实施方案在下文中称为“粘着剂VIII”。
粘着剂I、粘着剂II、粘着剂III、粘着剂IV、粘着剂V、粘着剂VI、粘 着剂VII和粘着剂VIII在下文称为“本发明粘着剂”。
优选地,本发明粘着剂包含0.05-20重量%,优选0.1-10重量%,尤其是0.5-8重量%的共聚单体a)。
优选地,本发明粘着剂包含10-90重量%,优选15-70重量%,更优选18-55重量%,尤其是20-55重量%的共聚单体b)。
优选地,本发明粘着剂包含10-90重量%,优选40-85重量%的共聚单体c)。
上文所述的粘着剂的所有实施方案在下文中称为“本发明粘着剂”。
本发明粘着剂可按照现有技术中已知的方法制备,例如类似于EP1077237A、EP0810274A或US6790272中所述的方法。
本发明还涉及本发明粘着剂在种子处理中的用途。
在优选实施方案中,所述粘着剂以含水分散体形式存在。由于其制备方法所致,以含水分散体形式存在的粘着剂通常含有用于在所述含水分散体中稳定聚合物颗粒的乳化剂。因此,其可包含至少一种阴离子乳化剂和/或至少一种非离子乳化剂。合适的乳化剂为通常用于这些目的的化合物。合适乳化剂的综述可参见Houben-Weyl,Methoden der organischen Chemie,第XIV/1卷,Makromolekulare Stoffe[大分子物质],Georg-Thieme-Verlag,Stuttgart,1961,第192-208页。
优选阴离子乳化剂包括如下物质的碱金属盐和铵盐,尤其是钠盐:烷基硫酸酯(其中所述烷基为C8-C20烷基)、乙氧基化链烷醇的硫酸单酯(平均乙氧基化度:2-50,烷基:C10-C20)、以及式I的单-和二-(C4-C24烷基)二苯基醚二磺酸盐:
其中R1和R2为氢或C4-C24烷基,优选C8-C16烷基,但不同时为氢,且X和Y可为碱金属离子和/或铵离子。通常使用含有50-90重量%比例的单烷基化产物的工业混合物,实例为2A1(R1=C12烷基;DOW CHEMICAL)。化合物I是公知的,例如由美国专利4,269,749已知,且可商购获得。
其他优选的阴离子乳化剂为硫酸C10-C18烷基酯、乙氧基化度≤5的乙氧基化C10-C20链烷醇的硫酸酯,以及单-和二-(C8-C16)二苯基醚二磺酸盐。
所述含水分散体通常可包含占粘合剂总重量0.1-5重量%,优选0.5-3重量%,尤其是约1-2重量%的阴离子乳化剂。
优选非离子乳化剂为脂族非离子乳化剂,实例为乙氧基化的长链醇(平均乙氧基化度:3-50,烷基:C8-C36)和聚氧化乙烯/聚氧化丙烯嵌段共聚物。优选长链链烷醇的乙氧基化物(烷基:C10-C22,平均乙氧基化度:3-50),这些中尤其优选基于具有直链或支化C12-C18烷基且乙氧基化度为8-50的天然存在的醇或羰基合成醇的那些。尤其优选非离子乳化剂为具有支化C10-C16烷基且平均乙氧基化度为8-20的羰基合成醇的乙氧基化物,以及具有直链C14-C18烷基且平均乙氧基化度为10-30的脂肪醇乙氧基化物。非离子乳化剂通常以基于粘合剂总重量为0.1-5重量%,特别是0.3-3重量%,尤其是0.5-2重量%的量使用。阴离子和非离子乳化剂的总量优选不超过粘合剂总重量的5重量%,尤其为0.5-4重量%。
粘着剂(若以本文所述的分散体形式存在)的粒度为重均粒度,如可通过动态光散射法确定。该方法为本领域技术人员所熟知,例如由H.Wiese in D.Distler,Polymerdispersionen[含水聚合物分散体],Wiley-VCH,1999,第4.2.1章,第40页及随后各页以及本文所引述的文献,和H.Auweter与D.Horn,J.Colloid Interf.Sci.,105(1985),399,D.Lilge与D.Horn,Colloid Polym.Sci.,269(1991),704或H.Wiese与D.Horn,J.Chem.Phys.,94(1991),6429已知。本发明粘着剂的粒度为5-800nm,优选10-200nm。
术语“植物繁殖材料”应理解为是指可用于植物繁殖的所有植物有性生殖部分如种子,以及无性生殖植物材料如插条和块茎(例如马铃薯)。这包括种子、根、果实、块茎、球茎、根茎、嫩枝、新芽和其他植物部分(包括萌芽后或自土壤出苗后可移植的幼苗和秧苗)。这些秧苗也可在移植前通过全部或部分浸渍或浇灌处理而加以保护。优选术语植物种子表示种子。
各种栽培植物的种子均可用于本发明,例如禾谷类,如小麦、黑麦、大麦、小黑麦、燕麦或稻;甜菜,例如糖用甜菜或饲用甜菜;水果如梨果、核果或浆果,例如苹果、梨、李子、桃、杏仁、樱桃、草莓、山莓、黑莓或醋栗;豆科植物,如兵豆、豌豆、苜蓿或大豆;油料植物,如油菜、油菜籽油菜/卡诺拉、芥末、橄榄、向日葵、椰子、可可豆、蓖麻油植物、油棕、花生或大豆;葫芦,如南瓜、黄瓜或甜瓜;纤维植物,如棉花、亚麻、大麻或黄麻;柑桔类水果,如橙、柠檬、葡萄柚或桔;蔬菜,如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、西红柿、马铃薯、葫芦或辣椒;月桂科植物,如鳄梨、肉桂或樟脑;能源及原料植物,如玉米、大豆、油菜、甘蔗或油棕;玉米;烟草;核果;咖啡;茶叶;香蕉;藤本植物(鲜食葡萄藤和榨汁用葡萄藤);啤酒花;草皮;天然橡胶植物或观赏用植物及森林植物,如花、灌木、阔叶树或常绿树(例如针叶树);优选玉米,向日葵,禾谷类如小麦、黑麦、大麦、黑小麦、燕麦或稻,大豆,棉花,油菜籽油菜/卡诺拉;更优选玉米,向日葵,大豆,禾谷类如小麦、黑麦、大麦、黑小麦、燕麦或稻。
术语“栽培植物”应理解为包括通过繁育、诱变或基因工程改造的植物,包括但不限于市场上或研发中的农业生物技术产品(参见http://www.bio.org/speeches/pubs/er/agri_products.asp)。转基因植物是其遗传物质已通过使用DNA重组技术改良且在自然条件下无法轻易通过杂交繁育、诱变或自然重组而获得的植物。通常将一个或多个基因整合至转基因植物的遗传物质中,以改善所述植物的某些性质。这类转基因改造也包括但不限于蛋白质、寡肽或多肽的靶向翻译后修饰法(例如糖基化法)或聚合物加成法,如异戊烯基化、乙酰化或法尼基化(farnesylated)的结构部分或PEG结构部分。
已通过繁育、诱变或基因工程改造的植物,例如已赋予对特定类别除草剂施用的耐受性,所述除草剂如羟基苯基丙酮酸酯二氧酶(HPPD)抑制剂;乙酰乳酸合酶(ALS)抑制剂,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);烯醇丙酮酰基莽草酸-3-磷酸酯合酶(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-A 242236、EP-A 242246)或苯腈(oxynil)类除草剂(参见例如US5,559,024),这是常规繁育或基因工程方法的结果。若干栽培植物已通过常规繁育(诱变)方法而赋予对除草剂的耐受性,例如 夏季油菜(Canola,BASF SE,德国),其具有对咪唑啉酮类(例如咪草啶酸(imazamox))的耐受性。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,美国,Monsanto)和 (草铵膦耐受型,德国,Bayer CropScience)商购获得。
此外,植物也涵盖可通过使用DNA重组技术合成一种或多种杀虫蛋白质,尤其是已知来自杆菌属(Bacillus)的细菌,特别是来自苏云金杆菌(Bacillus thuringiensis)的那些,如δ-内毒素,例如CryIA(b)、CryIA(c)、CryIF、CryIF(a2)、CryIIA(b)、CryIIIA、CryIIIB(b1)或Cry9c;营养期杀虫蛋白质(VIP),例如VIP1、VIP2、VIP3或VIP3A;细菌定殖线虫杀虫蛋白质,例如发光杆菌(Photorhabdus spp.)或嗜线虫杆菌(Xenorhabdus spp.);由动物产生的毒素,如蝎毒素、蜘蛛毒素、黄蜂毒素,或其他昆虫特异性神经毒素;由真菌制造的毒素,如链霉菌毒素、植物外源凝集素如豌豆或大麦外源凝集素;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、马铃薯储藏蛋白酶抑制剂、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),如蓖麻毒蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽毒蛋白、皂毒素或异株腹泻毒蛋白;类固醇新陈代谢酶,如3-羟基类固醇氧化酶、蜕皮类固醇-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,如钠或钙通道阻断剂;保幼激素酯酶;利尿激素受体(螺旋激肽(helicokinin)受体);二苯乙烯合酶、联苄合酶、壳多糖酶或葡聚糖酶。本发明上下文中,这些杀虫蛋 白质或毒素也可明确理解为前毒素、杂合蛋白质、截短或修饰的蛋白质。杂合蛋白质的特征在于蛋白质结构域的重新组合(参见例如WO02/015701)。这些毒素或可合成这些毒素的转基因植物的其他实例例如公开于EP A 374 753、WO93/007278、WO95/34656、EP A 427 529、EP A 451 878、WO03/18810和WO03/52073中。这类转基因植物的生产方法通常为本领域技术人员所已知且描述于(例如)上文所述的公开文献中。转基因植物中所含的这些杀虫蛋白质赋予产生这些蛋白质的植物对所有节肢动物分类组的害虫,尤其是甲虫(鞘翅目)、双翼昆虫(双翅目)和蛾(鳞翅目)的耐受性以及对线虫(线虫纲)的耐受性。能合成一种或多种杀虫蛋白质的转基因植物例如描述于上文所述的公开文献中,且其中一些可商购获得,如 (产生Cry1Ab毒素的玉米栽培品种)、Plus(产生Cry1Ab和Cry3Bb1毒素的玉米栽培品种)、(产生Cry9c毒素的玉米栽培品种)、RW(产生Cry34Ab1、Cry35Ab1和磷丝菌素(Phosphinothricin)-N-乙酰转移酶[PAT]酶的玉米栽培品种)、33B(产生Cry1Ac毒素的棉花栽培品种)、I(产生Cry1Ac毒素的棉花栽培品种)、II(产生Cry1Ac与Cry2Ab2毒素的棉花栽培品种)、 (产生VIP毒素的棉花栽培品种)、(产生Cry3A毒素的马铃薯栽培品种),来自法国Syngenta Seeds SAS的 Bt11(例如CB)和Bt176(产生Cry1Ab毒素和PAT酶的玉米栽培品种),来自法国Syngenta Seeds SAS的MIR604(产生修饰形式的Cry3A毒素的玉米栽培品种,参见WO03/018810),来自比利时Monsanto Europe S.A.的MON 863(产生Cry3Bb1毒素的玉米栽培品种),来自比利时Monsanto Europe S.A.的IPC 531(产生修饰形式的Cry1Ac毒素的棉花栽培品种)以及来自比利时Pioneer Overseas Corporation的1507(产生Cry1F毒素和PAT酶的玉米栽培品种)。
此外,植物也涵盖可通过使用DNA重组技术合成一种或多种蛋白质以提高那些植物对细菌、病毒或真菌病原体的抗性或耐受性的植物。这类蛋白质的实例是所谓的“病程相关的蛋白质”(PR蛋白质,参见例如EP-A 392225)、植物病害抵抗基因(例如马铃薯栽培品种,其表达的抵抗基因对衍生 自墨西哥野生马铃薯Solanum bulbocastanum的致病疫霉(Phytophthora infestans)具有抗性作用)或T4-溶菌酶(例如可合成对诸如梨火疫病菌(Erwinia amylvora)的细菌具有提高的抗性的这些蛋白质的马铃薯栽培品种)。这些转基因植物的生产方法是本领域技术人员所公知的且描述于(例如)上述公开文献中。
此外,植物也涵盖可通过使用DNA重组技术合成一种或多种蛋白质以提高那些植物的生产力(例如生物量生产、谷物产量、淀粉含量、油含量或蛋白质含量),对干旱、盐度或其他限制生长的环境因素的耐受性或对害虫和真菌、细菌或病毒病原体的耐受性的植物。
此外,植物也涵盖通过使用DNA重组技术而含有改善的物质含量或新物质含量,尤其是改善人类或动物营养的植物,例如产生有益于健康的长链ω-3脂肪酸或不饱和ω-9脂肪酸(例如油菜,加拿大DOW Agro Sciences)的油料作物。
此外,植物也涵盖通过使用DNA重组技术而含有改善的物质含量或新物质含量,尤其是改善原料产量的植物,例如提高支链淀粉含量的马铃薯(例如马铃薯,德国BASF SE)。
本发明粘着剂可单独使用或可与至少一种农药和配制剂助剂一起转化为常规配制剂或可存于包括以下各组分的成套包装中:
a)作为组分I的本发明粘着剂,和
b)作为组分II的包含至少一种农药,但不包含本发明粘着剂的农业化学配制剂。
或者,本发明粘着剂可与包含至少一种农药,但不包含本发明粘着剂的农业化学配制剂一起使用。此时,可将本发明粘着剂加入市售农业化学配制剂中,或与配制的农药一起施用于种子。此时,可将所述粘着剂和存在于市售农业化学配制剂中的至少一种农药同时(即共同或分开)或依次施用于种子。
可用于种子处理领域的常规配制剂的实例例如为溶液、乳液和悬浮液。
此外,本发明还包括包含至少一种农药和至少一种粘着剂的农业化学配制剂,其中所述粘着剂为:
(a)粘着剂II,优选粘着剂IV或V;
(b)粘着剂III,优选粘着剂VI。
最优选地,本发明还包括包含至少一种农药和至少一种粘着剂的农业化学配制剂,其中所述粘着剂为:
(c)粘着剂VIII;或
(d)粘着剂VII。
本发明的另一实施方案为多组分成套包装,包含:
a)作为组分I的粘着剂II或III,和
b)作为组分II的包含至少一种农药,但不包含粘着剂II或III的农业化学配制剂;
该多组分成套包装中的所述粘着剂优选为:
(a)粘着剂IV或V;或
(b)粘着剂VI;
该多组分成套包装中的所述粘着剂最优选为:
(c)粘着剂VIII;或
(d)粘着剂VII。
此外,所述多组分成套包装也可任选包含作为组分III(或IV或V)的一种或多种包含至少一种农药,但不包含本发明粘着剂II或III的农业化学配制剂。
各配制剂以已知方式制备(参见US 3,060,084、EP-A 707445(对于液体浓缩物),Browning:“Agglomeration”,Chemical Engineering,1967年12月4日,147-48,Perry's Chemical Engineer's Handbook,第4版,McGraw-Hill,New York,1963,S.8-57及随后各页以及参见WO91/13546、US4,172,714、US4,144,050、US3,920,442、US5,180,587、US5,232,701、US5,208,030、GB2,095,558、US3,299,566,Klingman:Weed Control as a Science(J.Wiley&Sons,New York,1961),Hance等:Weed Control Handbook(第8版,Blackwell Scientific,Oxford,1989)和Mollet,H.与Grubemann,A.:Formulation technology(Wiley VCH Verlag,Weinheim,2001))。
除本发明粘着剂以外,这些配制剂也可包含农业化学配制剂中常见的其他助剂。所用助剂分别取决于具体施用形式和农药。合适的助剂实例为溶剂、载体、表面活性剂(如分散剂、乳化剂、其他增溶剂和粘合剂)、保护性胶体、有机和无机增稠剂、杀菌剂、防冻剂、消泡剂和合适的话着色剂。
合适的溶剂为水;有机溶剂如中至高沸点的矿物油馏分,例如煤油或柴油;此外还有煤焦油和来源于植物或动物的油;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;脂肪酸二甲胺、脂肪酸和脂肪酸酯以及强极性溶剂,例如胺如N-甲基吡咯烷酮。
载体为矿土如硅酸盐、硅胶、滑石、高岭土、石灰石、石灰、白垩、红玄武土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁、氧化镁、经研磨的合成材料,肥料如硫酸铵、磷酸铵、硝酸铵、尿素,以及来源于植物的产物如谷物粉、树皮粉、木粉和核果壳粉、纤维素粉以及其他固体载体。
合适的表面活性剂(助剂、润湿剂、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,美国Akzo Nobel)、二丁基萘磺酸(类型,德国BASF),以及脂肪酸、烷基磺酸、烷基芳基磺酸,烷基硫酸,月桂基醚硫酸和脂肪醇硫酸,以及硫酸化十六-、十七-和十八烷醇、硫酸化脂肪醇二醇醚的碱金属、碱土金属和铵盐;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、乙氧基化的异辛基苯酚、辛基苯酚、壬基苯酚、烷基苯基聚二醇醚、三丁基苯基聚二醇醚、三硬脂基苯基聚二醇醚、烷基芳基聚醚醇、醇和脂肪醇/氧化乙烯缩合物、乙氧基化的蓖麻油、聚氧乙烯烷基醚、乙氧基化的聚氧化丙烯、月桂醇聚二醇醚乙缩醛、山梨糖醇酯、木素亚硫酸盐废液和蛋白质、变性蛋白质、多醣类(例如甲基纤维素)、疏水改性的淀粉、聚乙烯醇(型,瑞士Clariant)、聚羧酸酯(型,德国BASF)、聚烷氧基化物、聚乙烯胺类(型,德国BASF)、聚乙烯基吡咯烷酮及其共聚物。
增稠剂(即赋予配制剂改善的流动性,即在静止状态下具有高粘度而在搅拌过程中具有低粘度的化合物)的实例为多醣以及有机和无机粘土,如黄原胶(美国CP Kelco)、23(法国Rhodia)、(美国R.T.Vanderbilt)或(美国Engelhard Corp.,NJ)。
可加入杀菌剂以防腐及稳定配制剂。合适的杀菌剂实例为基于二氯芬和苄醇半缩甲醛(来自ICI的或来自Thor Chemie的RS和来自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(来自Thor Chemie的MBS)的那些。
合适的防冻剂实例为乙二醇、丙二醇、尿素和甘油。
合适的消泡剂实例为聚硅氧烷乳液(如SRE,德国Wacker或 法国Rhodia)、长链醇、脂肪酸、脂肪酸盐、氟化有机化合物及其混合物。
合适的着色剂为低水溶性颜料和水溶性染料。可提及的实例和牌号为若丹明B、溶剂红1、颜料蓝15:4、颜料蓝15:3、颜料蓝15:2、颜料蓝15:1、颜料蓝80、颜料黄1、颜料黄13、颜料红112、颜料红48:2、颜料红48:1、颜料红57:1、颜料红53:1、颜料橙43、颜料橙34、颜料橙5、颜料绿36、颜料绿7、颜料白6、颜料棕25、碱性紫10、碱性紫49、酸性红51、酸性红52、酸性红14、酸性蓝9、酸性黄23、碱性红10、碱性红108、酸性红18=食品红7、食品红1。
配制剂类型,尤其是用于种子处理的配制剂类型包括但不限于可溶性浓缩物(LS)、乳液(ES)、悬浮液(FS)、水分散性粉剂和水溶性粉剂(WS)以及可撒粉粉剂(DS)。
配制剂中的农药量取决于配制剂类型。原则上,所述农业化学配制剂通常包含0.01-95重量%,优选0.1-90重量%,最优选0.5-90重量%的农药。
例如在液体配制剂(如上所述)中,所述至少一种农药的量通常为2-70重量%。
在固体配制剂(如上所述)中,所述至少一种农药的量通常占该固体配制剂总重量的10-70重量%,尤其是15-50重量%。
配制剂助剂的总量取决于所用配制剂的类型。其通常基于该配制剂总 重量为30-90重量%,尤其是85-50重量%。
特别地,表面活性剂的量根据配制剂类型而变化。其通常基于该配制剂总重量为0.1-20重量%,尤其是0.2-15重量%,特别优选为0.5-10重量%。
载体与溶剂的量根据配制剂类型而变化。其通常基于该配制剂总重量为1-90重量%,尤其是10-60重量%,特别优选为15-50重量%。
其余配制剂助剂(粘度改进添加剂(增稠剂)、消泡剂、防冻剂、pH调节剂、稳定剂、防结块剂和生物杀伤剂(防腐剂)、着色剂、粘着剂、填料和增塑剂)的量根据配制剂类型而变化。其通常基于该配制剂总重量为0.1-60重量%,尤其是0.5-40重量%,特别优选为1-20重量%。
粘着剂的量通常不超过配制剂的40重量%,优选以该配制剂总重量计为1-40重量%,尤其是5-30重量%。粘着剂与农药的重量比优选为1:10-2:1,更优选为1:5-1.5:1。
这些配制剂(经稀释或未经稀释)可施用于植物繁殖材料,尤其是种子。所述组合物在稀释2-10倍后,得到农药浓度为0.01-60重量%,优选0.1-40重量%的即用型制剂。可在播种前或播种过程中施用。分别在植物繁殖材料,尤其是种子上施用或处理农业化学化合物及其组合物的方法是现有技术所已知的,包括繁殖材料的拌种、包衣、造粒、撒粉和浸泡施用方法(也包括沟畦处理)。在优选实施方案中,本发明粘着剂或包含本发明粘着剂的配制剂通过不引发萌芽的方法,例如通过拌种、造粒、包衣和撒粉,分别施用于植物繁殖材料上。
在处理植物繁殖材料(优选种子)时,本发明粘着剂的施用率通常为10-500g/100kg植物繁殖材料(优选种子),优选为20-200g/100kg植物繁殖材料(优选种子)。
本发明还涉及包含(即包覆有和/或含有)本发明粘着剂的植物繁殖材料(优选种子),其中所述粘着剂为:
(a)粘着剂II,优选粘着剂IV或V;或
(b)粘着剂III,优选粘着剂VI;
最优选所述粘着剂为:
(c)粘着剂VIII;或
(d)粘着剂VII。
本发明还涉及包含(即包覆有和/或含有)本发明粘着剂的植物繁殖材料(优选种子),其中所述粘着剂为:
(a)粘着剂II,优选粘着剂IV或V;或
(b)粘着剂III,优选粘着剂VI;
最优选所述粘着剂为:
(c)粘着剂VIII;或
(d)粘着剂VII;
和至少一种农药。
所述植物繁殖材料(优选种子)包含0.1g-10kg/100kg植物繁殖材料(优选种子),优选0.1g-1kg/100kg植物繁殖材料(优选种子)的量的所述至少一种农药。
在其中超过两种组分(本发明粘着剂、农药和其他配制剂助剂)以如上所定义的多组分成套包装形式提供的那些实施方案中,各组分中的一些可先组合在一起,并以这种形式包装(作为常规配制剂)在一个容器中,如管瓶、瓶、罐、袋或小罐、桶。
在其他实施方案中,成套包装的两种或更多种组分可分开包装,即未经预先配制。如此,所述成套包装可包含两个或更多个独立的容器,如管瓶、罐、瓶、袋或小罐,其中各容器含有农业化学组合物的独立组分。
在这两种形式中,可将所述成套包装的组分与其他组分分开施用或与其一起施用,或作为本发明组合物的组合组分以制备本发明组合物。
根据一个实施方案,可先将包含本发明粘着剂的成套包装与至少一种常规配制剂混合,然后再将它们施用于植物繁殖材料(优选种子);或可逐步施用,其中首先用所述配制剂处理植物繁殖材料(优选种子),然后施用所述粘着剂(如果合适的话,任选与其他助剂一起施用),或与此相反,即先施用粘着剂,然后施用配制剂;或者若使用超过一种农业化学配制剂,则依次处理(即先施用配制剂,然后施用粘着剂,接着施用配制剂;先施用配制剂,接着施用配制剂II,接着施用粘着剂,粘着剂,接着施用配制剂I、II等)。
在本发明含义范围内,术语“至少一种农药”表示一种或多种可选自杀真菌剂、杀昆虫剂、杀线虫剂、除草剂和/或安全剂或生长调节剂,优选选自杀真菌剂、杀昆虫剂或杀线虫剂的化合物。还可使用两种或更多种上述类别的农药的混合物。本领域技术人员熟知这些农药,其可例如参见Pesticide Manual,第13版(2003),The British Crop Protection Council,London。
下文所列农药旨在阐述可能的组合,而非加以限制:
杀真菌剂,包括:
A)嗜球果伞素类
腈嘧菌酯(azoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌酯(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)环丙烷羧酰亚氨基(carboximidoyl)硫基甲基)苯基)丙烯酸甲酯、(2-氯-5-[1-(3-甲基苄氧亚氨基)乙基]苄基)氨基甲酸甲酯、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)、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)、吡噻菌胺(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-2,3-二氢化茚-4-基)烟酰胺、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、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;
-羧酸吗啉化物: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)、氟吡菌酰胺(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-羟基苯甲酸;
-其他羧酰胺类:氯环丙酰胺(carpropamid)、双氯氰菌胺(diclocymet)、双炔酰菌胺(mandipropamid)、土霉素(oxytetracyclin)、硅噻菌胺(silthiofarm)、N-(6-甲氧基吡啶-3-基)环丙烷甲酰胺;
C)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(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)、抑霉唑(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);
-其他:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole)、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元杂环类: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-S-甲基(acibenzolar-S-methyl)、amisulbrom、敌菌灵(anilazine)、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(difenzoquat methylsulfate)、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
-硫代及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和N-(1-(1-(4-氰基苯基)乙磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
F)其他活性物质
-胍类:胍、多果定(dodine)、多果定游离碱、双胍盐(guazatine)、双胍乙酸盐(guazatine acetate)、双胍辛醋酸盐(iminoctadine)、双胍辛醋酸盐(iminoctadine triacetate)、双胍辛醋酸三(苯磺酸盐)(iminoctadine tris(albesilate));
-抗生素:春雷素(kasugamycin)、春雷素盐酸盐水合物(kasugamycin hydrochloride hydrate)、链霉素(streptomycin)、多氧霉素(polyoxine)、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)、nitrthal-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)或毒菌锡氢氧化物(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(chlorthalonil)、抑菌灵(dichlofluanid)、双氯酚(dichlorphen)、磺菌胺(flusulfamide)、六氯苯(hexachlorobenzene)、戊菌隆(pencycuron)、五氯酚(pentachlorophenole)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;
-无机活性物质:波尔多液(Bordeaux混合剂)、乙酸铜、氢氧化铜、王铜、碱性硫酸铜、硫;
-其他:联苯、溴硝丙二醇(bronopol)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、二苯胺(diphenylamin)、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;
G)生长调节剂:
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)、矮壮素阳离子(chlormequat)(氯化矮壮素(chlormequat chloride))、胆碱盐酸盐(choline chloride)、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)、助壮素阳离子(mepiquat)(氯化助壮素(mepiquat chloride))、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);
H)除草剂,包括:
-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、草铵膦、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、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);
-其他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)、pyriftalid、肟啶草(pyriminobac-methyl)、pyrimisulfan、嘧硫苯甲酸(pyrithiobac)、pyroxasulfone、吡唑磺草胺(pyroxsulam);
-其他: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(benfuresate)、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。
I)选自如下组的杀昆虫剂或杀螨剂或杀线虫剂:
M.1.有机(硫代)磷酸酯类:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷乙酯(azinphos-ethyl)、谷硫磷甲酯(azinphos-methyl)、壤虫氯磷(chlorethoxyfos)、毒虫畏(chlorfenvinphos)、氯甲磷(chlormephos)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、蝇毒磷(coumaphos)、杀螟腈(cyanophos)、甲基一O五九(demeton-S-methyl)、二嗪农(diazinon)、敌敌畏(dichlorvos/DDVP)、百治磷(dicrotophos)、乐果(dimethoate)、甲基毒虫畏(dimethylvinphos)、乙拌磷(disulfoton)、苯硫磷(EPN)、乙硫磷(ethion)、灭克磷(ethoprophos)、氨磺磷(famphur)、克线磷(fenamiphos)、杀螟松(fenitrothion)、倍硫磷(fenthion)、吡氟硫磷(flupyrazophos)、噻唑酮磷(fosthiazate)、庚虫磷(heptenophos)、异唑磷(isoxathion)、马拉硫磷(malathion)、灭蚜磷(mecarbam)、甲胺磷(methamidophos)、杀扑磷(methidathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、二溴磷(naled)、氧化乐果(omethoate)、砜吸磷(oxydemeton-methyl)、一六零五(parathion)、甲基一六零五(parathion-methyl)、稻丰散(phenthoate)、甲拌磷(phorate)、伏杀磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、烯虫磷(propetamphos)、丙硫磷(prothiofos)、吡唑硫磷(pyraclofos)、打杀磷(pyridaphenthion)、 喹恶磷(quinalphos)、硫特普(sulfotep)、嘧丙磷(tebupirimfos)、硫甲双磷(temephos)、特丁磷(terbufos)、杀虫畏(tetrachlorvinphos)、甲基乙拌磷(thiometon)、三唑磷(triazophos)、敌百虫(trichlorfon)、蚜灭多(vamidothion);
M.2.氨基甲酸酯类:涕灭威(aldicarb)、棉铃威(alanycarb)、虫威(bendiocarb)、丙硫克百威(benfuracarb)、丁叉威(butocarboxim)、氧丁叉威(butoxycarboxim)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、苯虫威(ethiofencarb)、丁苯威(fenobucarb)、伐虫脒(formetanate)、呋线威(furathiocarb)、异丙威(isoprocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、速灭威(metolcarb)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、特氨叉威(thiofanox)、混杀威(trimethacarb)、二甲威(XMC)、灭杀威(xylylcarb)、唑蚜威(triazamate);
M.3.拟除虫菊酯类:氟酯菊酯(acrinathrin)、丙烯除虫菊(allethrin)、d-顺-反丙烯除虫菊、d-反丙烯除虫菊、氟氯菊酯(bifenthrin)、反丙烯除虫菊(bioallethrin)、反丙烯除虫菊S-环戊烯基(bioallethrin S-cylclopentenyl)、右旋反灭虫菊酯(bioresmethrin)、乙氰菊脂(cycloprothrin)、氟氯氰菊酯(cyfluthrin)、β-氟氯氰菊酯、(RS)氯氟氰菊酯(cyhalothrin)、λ-(RS)氯氟氰菊酯、γ-(RS)氯氟氰菊酯、氯氰菊酯(cypermethrin)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、辛体氯氰菊酯(theta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、苯醚氰菊酯(cyphenothrin)、溴氰菊酯(deltamethrin)、烯炔菊酯(empenthrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、氟氰戊菊酯(flucythrinate)、氟氯苯菊酯(flumethrin)、T-氟氯苯菊酯(tau-flumethrin)、卤醚菊酯(halfenprox)、咪炔菊酯(imiprothrin)、甲氧苄氟菊酯(metofluthrin)、氯菊酯(permethrin)、苯醚菊酯(phenothrin)、炔酮菊酯(prallethrin)、丙氟菊酯(profluthrin)、除虫菊(pyrethrin(pyrethrum))、灭虫菊(resmethrin)、灭虫硅醚(silafluofen)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、四溴菊酯 (tralomethrin)、四氟菊酯(transfluthrin);
M.4.拟保幼激素(juvenile hormone mimics):蒙五一二(hydroprene)、蒙七七七(kinoprene)、蒙五一五(methoprene)、双氧威(fenoxycarb)、蚊蝇醚(pyriproxyfen);
M.5.烟碱受体激动剂/拮抗剂化合物:吡虫清(acetamiprid)、杀虫磺(bensultap)、巴丹(cartap hydrochloride)、噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、烟碱(nicotine)、艾克敌105(spinosad)(变构激动剂)、spinetoram(变构激动剂)、噻虫啉(thiacloprid)、硫环杀(thiocyclam)、杀虫双(thiosultap-sodium)和AKD1022;
M.6.GABA门控氯离子通道拮抗剂化合物:氯丹(chlordane)、硫丹(endosulfan)、林丹(gamma-HCH(lindane))、acetoprole、乙虫清(ethiprole)、锐劲特(fipronil)、pyrafluprole、pyriprole;
M.7.氯离子通道活化剂:齐墩螨素(abamectin)、甲氨基阿维菌素苯甲酸盐(emamectin benzoate)、米尔螨素(milbemectin)、lepimectin;
M.8.METI I化合物:喹螨醚(fenazaquin)、唑螨酯(fenpyroximate)、嘧胺苯醚(pyrimidifen)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、flufenerim、鱼藤酮(rotenone);
M.9.METI II和III化合物:灭螨醌(acequinocyl)、fluacyprim、灭蚁腙(hydramethylnon);
M.10.氧化磷酸化去偶剂:氟唑虫清(chlorfenapyr),二硝甲酚(DNOC);
M.11.氧化磷酸化抑制剂:唑环锡(azocyclotin)、三环锡(cyhexatin)、杀螨硫隆(diafenthiuron)、杀螨锡(fenbutatin oxide)、克螨特(propargite)、三氯杀螨砜(tetradifon);
M.12.蜕皮干扰剂:灭蝇胺(cyromazine)、chromafenozide、特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide);
M.13.增效剂:增效醚(piperonyl butoxide)、脱叶磷(tribufos);
M.14.钠通道阻断剂化合物:二唑虫(indoxacarb)、氰氟虫胺(metaflumizone);
M.15.熏蒸剂:甲基溴、氯化苦(chloropicrin)、磺酰氟(sulfuryl fluoride);
M.16.选择性进食阻断剂:氟铝酸钠(cryolite)、拒嗪酮(pymetrozine)、氟啶虫酰胺(flonicamid);
M.17.螨虫生长抑制剂:四螨嗪(clofentezine)、噻螨酮(hexythiazox)、特苯 唑(etoxazole);
M.18.甲壳素合成抑制剂:噻嗪酮(buprofezin)、双三氟虫脲(bistrifluron)、定虫隆(chlorfluazuron)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、多氟脲(noviflumuron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron);
M.19.类脂生物合成抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramat);
M.20.章鱼胺激动剂:虫螨脒(amitraz);
M.21.鱼尼汀(ryanodine)受体调节剂:氟虫酰胺(flubendiamide),(R)-、(S)-3-氯-N1-{2-甲基-4-[1,2,2,2-四氟-1-(三氟甲基)乙基]苯基}-N2-(1-甲基-2-甲基磺酰基乙基)邻苯二甲酰胺(M21.1);
M.22.其它:磷化铝、磺胺螨酯(amidoflumet)、benclothiaz、苯螨特(benzoximate)、联苯肼酯(bifenazate)、硼砂、溴螨酯(bromopropylate)、氰化物、cyenopyrafen、丁氟螨酯(cyflumetofen)、灭螨猛(chinomethionate)、开乐散(dicofol)、氟乙酸酯、膦、啶虫丙醚(pyridalyl)、pyrifluquinazon、硫、有机硫化合物、吐酒石(tartar emetic)、sulfoxaflor、4-丁-2-炔氧基-6-(3,5-二甲基哌啶-1-基)-2-氟嘧啶(M22.1)、3-苯甲酰基氨基-N-[2,6-二甲基-4-(1,2,2,2-四氟-1-三氟甲基乙基)苯基]-2-氟苯甲酰胺(M22.2)、4-[5-(3,5-二氯苯基)-5-三氟甲基-4,5-二氢异唑-3-基]-2-甲基-N-吡啶-2-基甲基苯甲酰胺(M22.3)、4-[5-(3,5-二氯苯基)-5-三氟甲基-4,5-二氢异唑-3-基]-2-甲基-N-(2,2,2-三氟乙基)苯甲酰胺(M22.4)、4-[5-(3,5-二氯苯基)-5-三氟甲基-4,5-二氢异唑-3-基]-2-甲基-N-噻唑-2-基甲基苯甲酰胺(M22.5)、4-[5-(3,5-二氯苯基)-5-三氟甲基-4,5-二氢异唑-3-基]-2-甲基-N-(四氢呋喃-2-基甲基)苯甲酰胺(M22.6)、4-{[(6-溴吡啶-3-基)甲 基](2-氟乙基)氨基}呋喃-2(5H)-酮(M22.7)、4-{[(6-氟吡啶-3-基)甲基](2,2-二氟乙基)氨基}呋喃-2(5H)-酮(M22.8)、4-{[(2-氯-1,3-噻唑-5-基)甲基](2-氟乙基)氨基}呋喃-2(5H)-酮(M22.9)、4-{[(6-氯吡啶-3-基)甲基](2-氟乙基)氨基}呋喃-2(5H)-酮(M22.10)、4-{[(6-氯吡啶-3-基)甲基](2,2-二氟乙基)氨基}呋喃-2(5H)-酮(M22.11)、4-{[(6-氯-5-氟吡啶-3-基)甲基](甲基)氨基}呋喃-2(5H)-酮(M22.12)、4-{[(5,6-二氯吡啶-3-基)甲基](2-氟乙基)氨基}呋喃-2(5H)-酮(M22.13)、4-{[(6-氯-5-氟吡啶-3-基)甲基](环丙基)氨基}呋喃-2(5H)-酮(M22.14)、4-{[(6-氯吡啶-3-基)甲基](环丙基)氨基}呋喃-2(5H)-酮(M22.15)、4-{[(6-氯吡啶-3-基)甲基](甲基)氨基}呋喃-2(5H)-酮(M22.16)、环丙烷乙酸、1,1'-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-环丙基乙酰基)氧基]甲基]-1,3,4,4a,5,6,6a,12,12a,12b-十氢-12-羟基-4,6a,12b-三甲基-11-氧代-9-(3-吡啶基)-2H,11H-萘并[2,1-b]吡喃并[3,4-e]吡喃-3,6-二基]酯(M22.17)、8-(2-环丙基甲氧基-4-甲基苯氧基)-3-(6-甲基-哒嗪-3-基)-3-氮杂-双环[3.2.1]辛烷(M22.18);
M.23.N-R'-2,2-二卤代-1-R″-环丙烷甲酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)腙或N-R'-2,2-二(R″')丙酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)腙,其中R'为甲基或乙基,卤素为氯或溴,R″为氢或甲基且R″'为甲基或乙基;
M.24.邻氨基苯甲酰胺类:chloranthraniliprole、cyantraniliprole、5-溴-2-(3-氯吡啶-2-基)-2H-吡唑-3-甲酸[4-氰基-2-(1-环丙基乙基氨基甲酰基)-6-甲基苯基]酰胺(M24.1)、5-溴-2-(3-氯吡啶-2-基)-2H-吡唑-3-甲酸[2-氯-4-氰基-6-(1-环丙基乙基氨基甲酰基)苯基]酰胺(M24.2)、5-溴-2-(3-氯吡啶-2-基)-2H-吡唑-3-甲酸[2-溴-4-氰基-6-(1-环丙基乙基氨基甲酰基)苯基]酰胺(M24.3)、5-溴-2-(3-氯吡啶-2-基)-2H-吡唑-3-甲酸[2-溴-4-氯-6-(1-环丙基乙基氨基甲酰基)苯基]酰胺(M24.4)、5-溴-2-(3-氯吡啶-2-基)-2H-吡唑-3-甲酸[2,4-二氯-6-(1-环丙基乙基氨基甲酰基)苯基]酰胺(M24.5)、5-溴-2-(3-氯吡啶-2-基)-2H-吡唑-3-甲酸[4-氯-2-(1-环丙基乙基氨基甲酰基)-6-甲基苯基]酰胺(M24.6);
M.25.丙二腈类化合物:CF2HCF2CF2CF2CH2C(CN)2CH2CH2CF3(2-(2,2,3,3,4,4,5,5-八氟戊基)-2-(3,3,3-三氟丙基)丙二腈)、 CF2HCF2CF2CF2CH2C(CN)2CH2CH2CF2CF3(2-(2,2,3,3,4,4,5,5-八氟戊基)-2-(3,3,4,4,4-五氟丁基)丙二腈);
M.26.微生物干扰剂:苏云金杆菌以色列亚种(Bacillus thuringiensis subsp.Israelensi)、球形芽孢杆菌(Bacillus sphaericus)、苏云金杆菌鲇泽亚种(Bacillus thuringiensis subsp.Aizawai)、苏云金杆菌库斯塔克亚种(Bacillus thuringiensis subsp.Kurstaki)、苏云金芽胞杆菌拟步行甲亚种(Bacillus thuringiensis subsp.Tenebrionis);
式M6.1的硫代酰胺及其制备已描述于WO98/28279中。Lepimectin由Agro Project,PJB Publications Ltd,2004年11月已知。Benclothiaz及其制备已描述于EP-A1454621中。杀扑磷和对氧磷(Paraoxon)及其制备已描述于Farm Chemicals Handbook,第88卷,Meister Publishing Company,2001中。氰氟虫胺及其制备已描述于EP-A1462456中。Flupyrazofos已描述于Pesticide Science 54,1988,第237-243页和US4822779中。Pyrafluprole及其制备已描述于JP2002193709和WO01/00614中。Pyriprole及其制备已描述于WO98/45274和US6335357中。磺胺螨酯及其制备已描述于US6221890和JP21010907中。Flufenerim及其制备已描述于WO03/007717和WO03/007718中。AKD 1022及其制备已描述于US6300348中。Chloranthraniliprole已描述于WO01/70671、WO03/015519和WO05/118552中。邻氨基苯甲酰胺类M24.1至M24.6已描述于WO2008/72743和WO200872783中。邻苯二甲酰胺M21.1由WO2007/101540已知。丁氟螨酯及其制备已描述于WO04/080180中。氨基喹唑啉酮化合物pyrifluquinazon已描述于EP A 1097932中。炔基醚化合物M22.1描述于例如JP2006131529中。有机硫化合物已描述于WO2007060839中。羧酰胺化合物M22.2由WO2007/83394中已知。唑啉化合物M22.3至M22.6已描述于WO2007/074789中。呋喃酮化合物M22.7至M22.16已描述于例如WO2007/115644中。pyripyropene衍生物M22.17已描述于WO2008/66153和WO2008/108491中。哒嗪化合物M22.18已描述于JP2008/115155中。丙二腈化合物已描述于WO02/089579、WO02/090320、WO02/090321、WO04/006677、WO05/068423、WO05/068432和WO05/063694中。
若将除草剂用于种子处理,则优选将所述除草剂施用于各除草剂耐受性植物上。耐受除草剂的合适转基因植物实例为上文所述的那些。
为防止除草剂被种子处理法损害,可将各除草剂与合适的安全剂组合,以防止受到除草剂的植物毒性损害。合适的安全剂可选自下列:8-喹啉氧基乙酸(如喹氧乙酸(cloquintocet-mexyl))、1-苯基-5-卤代烷基-1,2,4-三唑-3-羧酸(如解草唑(fenchlorazole)和解草唑乙酯(fenchlorazole-ethyl))、1-苯基-5-烷基-2-吡唑啉-3,5-二羧酸(如吡咯二酸(mefenpyr)和吡咯二酸二乙酯(mefenpyr-diethyl))、4,5-二氢-5,5-二芳基-1,2-唑-3-羧酸(如双苯恶唑酸(isoxadifen)和双苯恶唑酸乙酯(isoxadifen-ethyl))、二氯乙酰胺类(如抑害胺(dichlormid)、解草呋(furilazole)、dicyclonon和解草酮(benoxacor))、α-(烷氧基亚氨基)苯乙腈(如抑害腈(cyometrini)和解草腈(oxabetrinil))、苯乙酮肟类(如肟草安(fluxofenim))、4,6-二卤代-2-苯基嘧啶类(如解草啶(fenclorim))、N-((4-烷基氨基甲酰基)苯基磺酰基)-2-苯甲酰胺类(如cyprosulfamide)、1,8-萘二甲酸酐、2-卤代-4-卤代烷基-1,3-噻唑-5-羧酸类与2-卤代-4-卤代烷基-1,3-噻唑-5-羧酸酯类(如解草安(flurazole))、N-烷基-O-苯基氨基甲酸酯类(如mephenate)、N-烷基-N'-芳基脲类(如香草隆(daimuron)和苄草隆(cumyluron))、S-烷基-N-烷基-硫代氨基甲酸酯类(如哌草丹(dimepiperate))和硫代磷酸酯类(如dietholate);以及它们的可农用盐及其可农用衍生物,如就本发明的羧酸官能团而言的酰胺、酯和硫代酯。
或者,可事先用不含活性物质的聚合物膜包覆种子材料。合适方法为本领域技术人员所知晓。例如WO04/049778描述了一种方法,其中在第一步中,用不含活性物质的聚合物膜包覆种子材料,然后施加拌种配制剂。此外,对所述除草剂可使用囊封技术,以避免潜在植物毒性影响。
用于各具有耐受性的植物繁殖材料上的优选除草剂为氨基酸衍生物,如双丙氨酰膦、草甘膦、草铵膦、草硫膦,更优选为草甘膦和草铵磷,最优选为草甘膦。
优选杀昆虫剂为sulfoxaflor、吡虫清、甲体氯氰菊酯、噻虫胺、锐劲特、吡虫啉、艾克敌105、七氟菊酯、噻虫嗪、氰氟虫胺、β-氟氯氰菊酯、chlorantraniliprole(rynaxypyr)、cyantraniliprole(cyazapyr)、sulfoxaflor 和氟虫酰胺;更优选为吡虫清、噻虫胺、吡虫啉、噻虫嗪、艾克敌105、氰氟虫胺、锐劲特、chlorantraniliprole(rynaxypyr)和cyantraniliprole(cyazapyr)。
优选杀真菌剂选自:甲霜灵、精甲霜灵、二甲嘧菌胺、氧唑菌、fluquiconazole、粉唑醇、土菌消、抑霉唑、环戊唑菌、丙氯灵、戊唑醇、戊叉唑菌、异丙定、代森联、福美双、啶酰菌胺、多菌灵、硅噻菌胺(silthiofam)、氟菌、腈嘧菌酯、亚胺菌、肟醚菌胺、唑菌胺酯、肟菌酯、甲基托布津、戊唑醇、丙硫菌唑、醚唑、唑菌醇、唑菌嗪、氟嘧菌酯、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、N-[2-(4'-三氟甲硫基)联苯基]-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、bixafen、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、sedaxane、isopyrazam和吡噻菌;更优选为甲霜灵、精甲双灵、氧唑菌、fluquiconazole、丙氯灵、戊叉唑菌、异丙定、福美双、戊唑醇、啶酰菌胺、多菌灵、硅噻菌胺、氟菌、腈嘧菌酯、肟醚菌胺、唑菌胺酯、肟菌酯、甲基托布津、戊唑醇、丙硫菌唑、醚唑、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、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、sedaxane和吡噻菌胺。
本发明包括一种防治有害生物(意指动物害物和/或有害真菌或杂草)的方法,其中使用本发明粘着剂和至少一种杀真菌剂或杀昆虫剂对植物繁殖材料(优选种子)进行处理,其中优选所述粘着剂选自:
(a)粘着剂II,优选粘着剂IV或V;
(b)粘着剂III,优选粘着剂VI;且
最优选粘着剂为:
(c)粘着剂VIII;或
(d)粘着剂VII。
本发明进一步包括一种调节植物生长和/或控制不希望的植物生长(意指动物害虫和/或有害真菌或杂草)的方法,其中使用本发明粘着剂和至少一种除草剂对植物繁殖材料(优选种子)进行处理,其中优选所述粘着剂选自:
(a)粘着剂II,优选粘着剂IV或V;
(b)粘着剂III,优选粘着剂VI;且
最优选所述粘着剂选自:
(c)粘着剂VIII;或
(d)粘着剂VII。
在本文中,本发明粘着剂和所述至少一种农药同时(即共同或单独)或依次施用。
本发明进一步由以下实施例所阐述,但并非对其加以限制:
实施例
本发明的所有聚合物分散体根据EP810274A中所述方法合成。
单体组成和玻璃化温度示于下表I中。
表I | b) | c) | b) | a) | a) | a) | |
Tg | MMA(1) | BA(2) | S(3) | AAM(4) | AA(5) | MMA(5) | |
聚合物1 | -12 | 35-40 | 60-65 | 2-5 | |||
聚合物2 | 17 | 45-50 | 45-50 | 1 | 1 | ||
聚合物3 | 5 | 40 | 60 | 1-2 | 1-2 | ||
聚合物4 | -3 | 60 | 40 | 2 | |||
聚合物5 | 24 | 50 | 50 | 1-2 | 2-3 | ||
聚合物6 | 17 | 45-50 | 45-50 | 1-2 | 3-5 |
(1)甲基丙烯酸甲酯
(2)丙烯酸丁酯
(3)苯乙烯
(4)丙烯酰胺
(5)丙烯酸
(6)甲基丙烯酸
用通过将40g包含作为农药的500g/L锐劲特的市售FS配制剂与10g粘着剂混合并将所得混合物稀释至100mL而制备的浆液进行处理。
种子处理组合物
即用型处理浆液通过将市售FS配制剂(例如包含500g/L锐劲特作为农药的市售FS配制剂)与10mL粘着剂混合,并用水将所得混合物稀释至 100mL而制备。
种子处理实验采用所述浆液,通过在获自SATEC的分批式处理机中将20g浆液施用于2kg未经处理的玉米上而进行。在处理之前,将所述种子在20℃和50%相对湿度下于调节箱中储存24小时。所述分批式处理机依照转子定子原理使种子移动。通过旋转盘将所述浆液施用于种子上,借助蠕动泵剂量添加。处理开始30秒钟之后,从该处理机排出经处理的种子。
粉尘测量
在进行上述处理一天后,在同一SATEC分批式处理机中测量粉尘。将经处理的种子在20℃和50%相对湿度下于调节箱内储存24小时。处理机的转速和空气流动速率与处理期间相同。处理机的调节通过使空处理机运转10分钟而进行。将预先称重的滤料(Fisherbrand玻璃纤维滤料,38mm,产品号FB59403)置于连接至真空泵且位于该处理机盖体内的真空吸滤器中。所述泵抽吸一部分被吹至该处理机内空气(包含可能通过该滤料的粉尘)。在运行的处理机中装填1kg经处理的种子。30秒钟后停泵,再次称重滤料,并计算每100kg种子的粉尘。
测试结果与由Heubach粉尘计(Heubach GmbH)的测量结果非常吻合。
结果示于下表II中。
种植精准度
用于分析播种行为(即经处理种子的种植精准度)的测试标准基于装配有光-视觉传感器和计算机的市售John Deere气动式播种机单元。由分布图程序分析种子传送、播种精准度和种子放置。
在测试前,必须选择适于所述经处理种子的尺寸和形状的正确播种盘,并将其置于所述设备内。播种机单元的进口装配有漏斗,其中填充待测试的种子。
每次重复各试验时使用1000格,这理想地可传送1000粒种子。记录每1000格实际传送的种子数,丢失的(略过)种子的格数,以及出现两粒或更多粒(=两倍、三倍等)种子的格数。此外,除了记录在沟中精确地以正确的间距传送的种子数以外,也记录与最佳种子放置处的偏差。由这些数据可确定正确放置的种子百分比。每种处理重复3次,除非出现高偏差。 结果示于下表II中。
聚合物 | 粉尘测量[g/100kg] | 播种精准度% |
聚合物1 | 0.09 | 91.4 |
聚合物2 | 0.14 | 94.1 |
聚合物3 | 0.21 | 91.6 |
聚合物4 | 0.12 | 83.4 |
聚合物5 | 0.08 | 93.1 |
聚合物6 | 0.01 | 92.2 |
Claims (15)
1.一种用至少一种粘着剂处理种子的方法,所述粘着剂包含呈聚合形式的:
a)至少一种选自丙烯酰胺或丙烯酸与丙烯酰胺的混合物的共聚单体a);和b)至少一种选自甲基丙烯酸甲酯或丙烯酸甲酯的共聚单体b);和
c)至少一种选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c);
或者包含呈聚合形式的:
a)至少一种选自丙烯酰胺的共聚单体a);和
b)至少一种选自苯乙烯的共聚单体b);和
c)至少一种选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c)。
2.如权利要求1的方法,其中所述粘着剂包含呈聚合形式的:
a)选自丙烯酰胺或丙烯酸与丙烯酰胺的混合物的共聚单体a);和
b)选自甲基丙烯酸甲酯或丙烯酸甲酯的共聚单体b);和
c)选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c)。
3.如权利要求1的方法,其中所述粘着剂包含呈聚合形式的:
a)至少一种选自丙烯酰胺的共聚单体a);和
b)至少一种选自苯乙烯的共聚单体b);和
c)至少一种选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c)。
4.如权利要求1的方法,其中所述粘着剂包含呈聚合形式的:
a)选自丙烯酰胺或丙烯酸与丙烯酰胺的混合物的共聚单体a);和
b)选自甲基丙烯酸甲酯的共聚单体b);和
c)选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c)。
5.如权利要求1的方法,其中所述粘着剂包含呈聚合形式的:
a)选自丙烯酰胺的共聚单体a);和
b)选自甲基丙烯酸甲酯或丙烯酸甲酯的共聚单体b);和
c)选自丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚单体c)。
6.如权利要求1的方法,其中所述粘着剂包含呈聚合形式的:
a)选自丙烯酰胺的共聚单体a);和
b)选自甲基丙烯酸甲酯的共聚单体b);和
c)选自丙烯酸正丁酯的共聚单体c)。
7.如权利要求1的方法,其中所述粘着剂的Tg为-30℃至30℃。
8.如权利要求1的方法,其中所述粘着剂包含0.05-20重量%的共聚单体a)。
9.如权利要求1-8中任一项的方法,其中所述粘着剂包含10-90重量%的共聚单体b)。
10.如权利要求1-8中任一项的方法,其中所述粘着剂包含10-90重量%的共聚单体c)。
11.如权利要求1-10中任一项所定义的粘着剂在减少粉尘中的应用。
12.一种拌种配制剂,包含:
(1)如权利要求1-10中任一项所定义的粘着剂;和
(2)至少一种农药。
13.一种包含多组分的多组分成套包装,包含:
a)如权利要求1-10中任一项所定义的粘着剂;和
b)作为组分II的农业化学配制剂,所述配制剂包含至少一种农药,但不包
含如权利要求1-10中任一项所定义的粘着剂。
14.用权利要求1-10中任一项所定义的粘着剂包衣或含有所述粘着剂的种子。
15.一种防治有害生物的方法,所述方法包括用权利要求1-10中任一项所定义的粘着剂和至少一种农药处理有用植物的种子。
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CN104381250B (zh) | 2017-04-12 |
ES2524819T3 (es) | 2014-12-12 |
AR075166A1 (es) | 2011-03-16 |
CA2749223A1 (en) | 2010-08-05 |
UY32400A (es) | 2010-07-30 |
CN102300456A (zh) | 2011-12-28 |
US20140075602A1 (en) | 2014-03-13 |
EP2837286A1 (en) | 2015-02-18 |
EP2391206A2 (en) | 2011-12-07 |
EA021068B1 (ru) | 2015-03-31 |
EA201101112A1 (ru) | 2012-03-30 |
WO2010086303A2 (en) | 2010-08-05 |
US20110281926A1 (en) | 2011-11-17 |
WO2010086303A3 (en) | 2011-04-21 |
TW201036542A (en) | 2010-10-16 |
MX2011007403A (es) | 2011-08-03 |
AU2010209778A1 (en) | 2011-08-18 |
BRPI1005366A2 (pt) | 2020-10-27 |
CA2749223C (en) | 2017-07-04 |
CN102300456B (zh) | 2014-11-12 |
EP2391206B1 (en) | 2014-10-08 |
BRPI1005366B1 (pt) | 2022-02-08 |
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