CN114430657A - 邻氨基苯甲酰胺组合物 - Google Patents
邻氨基苯甲酰胺组合物 Download PDFInfo
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- CN114430657A CN114430657A CN202080067680.2A CN202080067680A CN114430657A CN 114430657 A CN114430657 A CN 114430657A CN 202080067680 A CN202080067680 A CN 202080067680A CN 114430657 A CN114430657 A CN 114430657A
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- component
- certain embodiments
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- chlorantraniliprole
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- -1 alkyl naphthalene sulfonate Chemical compound 0.000 claims abstract description 98
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- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
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- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000008103 glucose Substances 0.000 claims description 4
- DSOOGBGKEWZRIH-UHFFFAOYSA-N nereistoxin Chemical class CN(C)C1CSSC1 DSOOGBGKEWZRIH-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
本披露内容提供了一种农用化学组合物,其包含杀有害生物活性成分、增强剂(包含二烷基磺基琥珀酸盐、十二烷基硫酸盐、十二烷基苯磺酸盐、脂肪醇衍生物、烷基萘磺酸盐、或烷基萘硫酸盐、或其混合物)、以及分散剂(包括聚羧酸盐、酚磺酸缩合物、聚氧丙烯‑聚氧乙烯嵌段共聚物、或萘磺酸缩合物、或其混合物)。本发明还提供了一种用于防治作物中有害生物的方法,该方法包括将农业上有效量的所述组合物施加到有需要的作物或其环境。
Description
相关申请的交叉引用
本申请要求于2019年9月27日提交的美国临时申请号62/906801的权益。
技术领域
本披露内容涉及一种包含邻氨基苯甲酰胺的新颖组合物以及一种包括施加所述组合物用于防治有害生物的方法。
背景技术
邻氨基苯甲酰胺(也被认为是邻氨基苯甲酸二酰胺)是重要的影响钙稳态的合成类杀昆虫剂,其对昆虫兰尼碱受体相对于哺乳动物受体有高选择性。其中,氯虫苯甲酰胺是该类中使用最广泛的杀昆虫剂。它对属于鳞翅目(Lepidoptera)和一些鞘翅目(Coleoptera)、双翅目(Diptera)和等翅目(Isoptera)物种的有害生物具有高生物活性,并且对非靶标节肢动物具有非常低的毒性。氯虫苯甲酰胺主要地通过摄食以及次要地通过接触对咀嚼有害生物昆虫有活性。
通常地,已研制的氯虫苯甲酰胺制剂类型包括悬浮剂(SC)、水分散粒剂(WDG)、悬浮种衣剂(FS)、以及颗粒剂(GR)。这些杀有害生物制剂通常通过喷雾施加。手动喷施作为水溶液或悬浮液的杀有害生物剂是劳动密集型和耗费时间的。当前节省劳力的技术,诸如超低量(ULV)和飞行器喷施受限于需要较高的技术技能和设备成本,因此对于标准的种植者施加不总是可行的。ULV和飞行器喷施也可能与风漂移的问题相关联,这取决于喷施时的天气条件,杀有害生物剂可能潜在地进入环境中。因此,非常需要研制这样的新颖的杀有害生物剂制剂:易于种植者和农民施加、并且展现高水平有害生物防治效果的同时具有减少的环境负荷。
发明内容
本披露内容的诸位发明人已经发现,当将作为活性成分的邻氨基苯甲酰胺与一种或多种分散剂和一种或多种增强剂的合适的组合配制时,该制剂实现期望的在不使用设备的情况下均匀分散的效果,从而将农民从耗费时间和耗费劳力的手动喷雾中解脱出来。本文提供一种新颖组合物(例如,以片剂的形式),该组合物当被直接投掷例如至稻田中时均匀地分散,并且在推荐剂量下获得有害生物防治的更高功效。
在一个方面中,本披露内容提供一种包含组合物的制剂,该组合物包括:
(a)杀有害生物活性成分;
(b)增强剂,其中该增强剂包括二烷基磺基琥珀酸盐、十二烷基硫酸盐、十二烷基苯磺酸盐、脂肪醇衍生物、烷基萘磺酸盐、或烷基萘硫酸盐、或其混合物;
(c)分散剂,其中该分散剂包括聚羧酸盐、酚磺酸缩合物、聚氧丙烯-聚氧乙烯嵌段共聚物、或萘磺酸缩合物、或其混合物;
(d)粘结剂;以及
(e)任选地填料。
在一个方面中,本披露内容提供一种包含组合物的制剂,该组合物包含基于该组合物的总重量按重量计的以下项:
(a)约0.1%至约20%的杀有害生物活性成分;
(b)约0.1%至约5%的至少一种增强剂,其中该增强剂包括二烷基磺基琥珀酸盐、十二烷基硫酸盐、十二烷基苯磺酸盐、脂肪醇衍生物、烷基萘磺酸盐、或烷基萘硫酸盐、或其混合物;
(c)约0.1%至约10%的至少一种分散剂,其中该分散剂包括聚羧酸盐、酚磺酸缩合物、聚氧丙烯-聚氧乙烯嵌段共聚物、或萘磺酸缩合物、或其混合物;
(d)约0.1%至约20%的至少一种粘结剂;以及
(e)约0.1%至约50%的至少一种填料。
在某些实施例中,该组合物是以片剂的形式。
在某些实施例中,该杀有害生物活性成分是除草剂或杀昆虫剂。在某些实施例中,该杀有害生物活性成分是二酰胺、新烟碱、或沙蚕毒素类似物杀昆虫剂,或其混合物。在某些实施例中,该杀有害生物活性成分是二酰胺。
在某些实施例中,该组合物进一步包含基于该组合物总重量按重量计的组分(f)约0.1%至约40%的至少一种酸和/或(g)约0.1%至约40%的至少一种碱。
在某些实施例中,该增强剂包括二烷基磺基琥珀酸钠、十二烷基硫酸钠、十二烷基苯磺酸钠、脂肪醇衍生物、烷基萘磺酸钠、二辛基硫代琥珀酸钠、或烷基萘硫酸钠、或其混合物。
在一个方面中,本披露内容提供一种片剂组合物,其包含基于该组合物的总重量按重量计的以下项:
(a)约0.1%至约20%的包含一种或多种邻氨基苯甲酰胺的杀有害生物活性成分;
(b)约0.1%至约5%的至少一种增强剂,其中该增强剂包括二烷基磺基琥珀酸盐、十二烷基硫酸盐、十二烷基苯磺酸盐、脂肪醇衍生物、烷基萘磺酸盐、或烷基萘硫酸盐、或其混合物;
(c)约0.1%至约10%的至少一种分散剂,其中该分散剂包括聚羧酸盐、酚磺酸缩合物、聚氧丙烯-聚氧乙烯嵌段共聚物、或萘磺酸缩合物、或其混合物;
(d)约0.1%至约20%的至少一种粘结剂;以及
(e)约0.1%至约50%的至少一种填料。
在某些实施例中,该杀有害生物活性成分是除草剂或杀昆虫剂。在某些实施例中,该杀有害生物活性成分是二酰胺、新烟碱、或沙蚕毒素类似物杀昆虫剂,或其混合物。
在某些实施例中,该组分(a)包含氯虫苯甲酰胺、溴氰虫酰胺、四唑虫酰胺、环溴虫酰胺、氯氟氰虫酰胺、四氯虫酰胺、噻虫嗪、噻虫胺、噻虫啉、杀虫单、或杀虫双、或其混合物。在某些实施例中,该组分(a)包含氯虫苯甲酰胺。
在某些实施例中,该组分(a)是按重量计该组合物的约1%至约10%、约1%至约8%、约1%至约7%、约1%至约6%、约1%至约5.5%、约1%,约2.5%或约5%。
在某些实施例中,该增强剂包括二烷基磺基琥珀酸钠、十二烷基硫酸钠、十二烷基苯磺酸钠、脂肪醇衍生物、烷基萘磺酸钠、二辛基硫代琥珀酸钠、或烷基萘硫酸钠、或其混合物。在某些实施例中,该增强剂包括二辛基磺基琥珀酸盐。
在某些实施例中,该组分(b)包含SDS、OT-B、或OT-75、或其混合物。在某些实施例中,该组分(b)是一种选自由SDS、OT-B、和OT-75组成的组的物质。在某些实施例中,该组分(b)包括Geropon SDS。在某些实施例中,该组分(b)是SDS。
在某些实施例中,该组分(b)是按重量计该组合物的约0.1%至约4%、约0.1%至约3%、约0.1%至约2%、约0.2%至约2%、约0.3%至约2%、约0.3%至约1.8%、约0.3%至约1.5%、约0.3%至约1.2%、约0.3%至约1%、约0.5%至约1%、约0.6%至约1%、约0.7%至约1%、或约0.8%。
在某些实施例中,该组分(c)包含2700、Atlox metasperseTM 550S、Ultrasperse、D-205、或T/36、或其混合物。在某些实施例中,该组分(c)是一种选自由2700、Atlox metasperseTM 550S、Ultrasperse、D-205、和T/36组成的组的物质。在某些实施例中,该组分(c)包含2700。在某些实施例中,该组分(c)是2700。
在某些实施例中,该组分(c)是按重量计该组合物的约0.5%至约10%、约0.5%至约8%、约0.5%至约7%、约0.5%至约6%、约0.5%至约5%、约0.8%至约5%、约1%至约5%、约1.2%至约5%、约1.5%至约5%、约1.7%至约5%、约2%至约5%、约2%至约4.5%、约2%至约4%、约2%至约3.5%、约2%至约3%、约2.2%至约2.8%、约2.4%至约2.6%、或约2.5%。
在某些实施例中,该组合物进一步包含组分(f)约0.1%至约40%的至少一种酸和/或(g)约0.1%至约40%的至少一种碱。
在某些实施例中,该组分(f)包含至少一种选自由柠檬酸、丙二酸酯、己二酸、马来酸和D,L-酒石酸组成的组的物质。在某些实施例中,该组分(f)包含D,L-酒石酸。在某些实施例中,该组分(f)是D,L-酒石酸。
在某些实施例中,该组分(f)是按重量计该组合物的约0.5%至约25%、约1%至约25%、约5%至约25%、约10%至约25%、约15%至约25%、约16%至约25%、约17%至约25%、约18%至约25%、约19%至约25%、约20%至约25%、约20%至约24%、约20%至约23%、约20%至约22%、或约21%。
在某些实施例中,该组分(g)包含至少一种选自由碳酸氢盐和碳酸盐组成的组的物质。在某些实施例中,该组分(g)包含至少一种选自由碳酸氢钠、碳酸氢钾、碳酸钠、和碳酸钾组成的组的物质。在某些实施例中,该组分(g)包含碳酸氢钠和碳酸钠的混合物。在某些实施例中,该组分(g)是碳酸氢钠和碳酸钠的混合物。
在某些实施例中,按重量计碳酸氢钠和碳酸钠的比率、或者碳酸氢钾和碳酸钾的比率是约1:10-10:1、约1:5-10:1、约1:3-10:1、约1:2-10:1、约1:1-10:1、约2:1-10:1、约3:1-10:1、约3:1-9:1、约3:1-8:1、约3:1-7:1、约3:1-6:1、约3:1-5:1、约3:1-4:1、约3.5:1-4:1、或约3.7:1。
在某些实施例中,该组分(g)包含碳酸氢钠和碳酸钠的混合物,其中该碳酸氢钠是按重量计该组合物的约0.5%至约40%、约1%至约40%、约5%至约40%、约10%至约40%、约15%至约40%、约20%至约40%、约25%至约40%、约25%至约35%、约27%至约33%、或约30%,并且该碳酸钠是按重量计该组合物的约1%至约40%、约1%至约30%、约1%至约20%、约2%至约20%、约3%至约20%、约3%至约18%、约3%至约15%、约3%至约12%、约3%至约10%、约5%至约10%、约6%至约10%、约7%至约10%、或约8%。
在某些实施例中,该组分(g)包含碳酸氢钾和碳酸钾的混合物,其中该碳酸氢钾是按重量计该组合物的约0.5%至约40%、约1%至约40%、约5%至约40%、约10%至约40%、约15%至约40%、约20%至约40%、约25%至约40%、约25%至约35%、约27%至约33%、或约30%,并且该碳酸钾是按重量计该组合物的约1%至约40%、约1%至约30%、约1%至约20%、约2%至约20%、约3%至约20%、约3%至约18%、约3%至约15%、约3%至约12%、约3%至约10%、约5%至约10%、约6%至约10%、约7%至约10%、或约8%。
在某些实施例中,该组分(g)是按重量计该组合物的约0.5%至约40%、约1%至约40%、约5%至约40%、约10%至约40%、约15%至约40%、约20%至约40%、约25%至约40%、约30%至约40%、约35%至约40%、或约38%。
在某些实施例中,该组分(d)包含至少一种选自由以下项组成的组的物质:聚乙二醇(PEG)、麦芽糖、海藻糖、山梨醇、麦芽糖醇、聚乙烯基吡咯烷酮、磷酸氢钙、蔗糖、葡萄糖、玉米(玉蜀黍)淀粉、改性纤维素、海藻酸、羧甲基纤维素钠、和共聚维酮。在某些实施例中,该组分(d)包含PEG。在某些实施例中,该组分(d)是PEG。在某些实施例中,该PEG是选自由PEG2000、PEG4000、PEG6000、PEG8000和PEG10000组成的组的一个。在某些实施例中,该PEG是PEG 6000。
在某些实施例中,该组分(d)是按重量计该组合物的约1%至约15%、约1%至约10%、约1%至约8%、约1%至约7%、约1%至约6%、约1%至约5.5%、约2%至约5.5%、约3%至约5.5%、约3%、或约5.5%。
在某些实施例中,该组分(e)包含至少一种选自由以下各项组成的组的物质:乳糖、乳糖一水合物、甘露醇、蔗糖、滑石、麦芽糊精、糊精、麦芽糖醇、山梨醇、木糖醇、粉末状纤维素、纤维素胶、微晶纤维素、淀粉、或磷酸钙。在某些实施例中,该组分(e)包含滑石、或麦芽糊精,或其混合物。在某些实施例中,该组分(e)包含滑石和麦芽糊精的混合物。在某些实施例中,该组分(e)包含按重量计该组合物约1%至约15%、约1%至约10%、约1%至约8%、约2%至约8%、约3%至约8%、约4%至约8%、约5%至约8%、约6%至约8%、或约6%的滑石,以及按重量计该组合物1%至约40%、约1%至约30%、约5%至约30%、约8%至约30%、约10%至约30%、约15%至约30%、约18%至约30%、约18%至约27%、或约20%至约27%的麦芽糊精。
在某些实施例中,该组分(e)是按重量计该组合物的约0.5%至约50%、约1%至约50%、约5%至约50%、约10%至约50%、约15%至约50%、约20%至约50%、约20%至约45%、约20%至约40%、约20%至约35%、约25%至约35%、约26%至约33%、约26%、约29%或约33%。
在某些实施例中,该组合物进一步包含组分(h):按重量计该组合物约0.1%至约5%的至少一种润滑剂。
在某些实施例中,该组分(h)包含至少一种选自由以下各项组成的组的物质:白炭黑、滑石粉、硬脂酸镁、硬脂酸钙、硬脂酸钠、硬脂酸锌、硬脂酸、金属硬脂酸盐、硬脂富马酸钠、脂肪酸、脂肪醇、脂肪酸酯、山萮酸甘油酯、菜籽油(canola oil)、矿物油、植物油、硬脂酸棕榈酸甘油酯、氢化植物油、氢化植物油、氧化镁、泊洛沙姆、石蜡、亮氨酸、丙二醇脂肪酸酯、聚乙烯醇苯甲酸钠、十二烷基硫酸钠、硬脂富马酸钠、聚乙二醇、聚丙二醇、和聚亚烷基二醇。在某些实施例中,该组分(h)包含硬脂酸盐。在某些实施例中,该组分(h)是硬脂酸盐。在某些实施例中,该组分(h)包含硬脂酸镁。在某些实施例中,该组分(h)是硬脂酸镁。
在某些实施例中,该组分(h)是按重量计该组合物的约0.1%至约4.5%、约0.1%至约4.0%、约0.1%至约3.5%、约0.1%至约3.0%、约0.1%至约2.5%、约0.1%至约2.0%、约0.1%至约1.5%、约0.1%至约1.0%、约0.5%至约1.0%、约0.5%至约0.7%、约0.5%、或约0.7%。
在某些实施例中,该组合物进一步包含组分(i):按重量计该组合物约0.01%至约5%的至少一种苦味剂。
在某些实施例中,该组分(i)包含至少一种选自由苯并二氮杂卓、地那铵、蔗糖八乙酸酯、槲皮素、番木鳖碱和苦木素组成的组的物质。在某些实施例中,该组分(i)包含地那铵苯甲酸盐。
在某些实施例中,该组分(i)是按重量计该组合物的约0.01%至约4.5%、约0.01%至约4.0%、约0.01%至约3.5%、约0.01%至约3.0%、约0.01%至约2.5%、约0.01%至约2.0%、约0.01%至约1.5%、约0.01%至约1.0%、约0.01%至约0.5%、约0.01%至约0.4%、约0.01%至约0.3%、约0.01%至约0.2%、约0.01%至约0.1%、约0.01%至约0.05%、约0.05%、约0.1%。
在某些实施例中,该组合物进一步包含组分(j):按重量计该组合物约0.1%至约1.5%的至少一种分散剂。
在某些实施例中,该组分(j)包含至少一种选自由dysperse 131、polyfon H、disperse 132、和disperse 140组成的组的物质。在某些实施例中,该组分(i)包含polyfonH。
在某些实施例中,该组分(j)是按重量计该组合物的约0.1%至约至约4.0%、约0.1%至约3.5%、约0.1%至约3.0%、约0.1%至约2.5%、约0.1%至约2.0%、约0.1%至约1.5%、约0.1%至约1.0%、约0.1%至约0.5%、约0.1%至约0.4%、约0.1%至约0.3%、约0.1%至约0.2%、约0.1%至约0.1%、约0.1%至约0.5%、约0.5%、约1.0%。
在一个方面中,本披露内容提供一种片剂组合物,其包含基于该组合物的总重量按重量计的以下项:
(a)约0.1%至约20%的氯虫苯甲酰胺、或溴氰虫酰胺、或其混合物;
(d)约0.1%至约20%的PEG-6000;
(e)约0.1%-50%的包含滑石和麦芽糊精的混合物;
(f)约0.1%-40%的D,L-酒石酸;以及
(g)约0.1%至约40%的包含碳酸氢钠和碳酸钠的混合物。
在一个方面中,本披露内容提供一种片剂组合物,其包含基于该组合物的总重量按重量计的以下项:
(a)约1%-5.5%的氯虫苯甲酰胺、或溴氰虫酰胺、或其混合物;
(d)约1%-8%的PEG-6000;
(e)约3%-8%的滑石和约20%-30%的麦芽糊精;
(f)约15%-25%的D,L-酒石酸;以及
(g)约20%-40%的碳酸氢钠和约5%-10%的碳酸钠。
在某些实施例中,该组合物进一步包含(h):约0.5%至约0.7%的硬脂酸镁。在某些实施例中,该组合物进一步包含(i):约0.04%至约0.06%的地那铵苯甲酸盐。在某些实施例中,该组合物进一步包含(i):约0.06%至约0.12%的地那铵苯甲酸盐。在某些实施例中,该组合物进一步包含组分(j):按重量计该组合物约0.1%至约1.5%的至少一种分散剂。
在一个方面中,本披露内容提供一种片剂组合物,其包含基于该组合物的总重量按重量计的以下项:
(a)约1.05%的氯虫苯甲酰胺;
(d)约3.0%的PEG-6000;
(e)约6.0%的滑石和约27.1%的麦芽糊精;
(f)约21%的D,L-酒石酸;以及
(g)约30%的碳酸氢钠和约8%的碳酸钠。
在某些实施例中,该组合物进一步包含(h):约0.5%的硬脂酸镁。在某些实施例中,该组合物进一步包含(i):约0.05%的地那铵苯甲酸盐。在一些实施例中,该组合物进一步包含(i):约0.1%的地那铵苯甲酸盐。在某些实施例中,该组合物进一步包含组分(j):约1.0%的polyfon H。
在一个方面中,本披露内容提供一种片剂组合物,其包含基于该组合物的总重量按重量计的以下项:
(a)约2.6%的氯虫苯甲酰胺;
(d)约5.5%的PEG-6000;
(e)约6.0%的滑石和约22.85%的麦芽糊精;
(f)约21%的D,L-酒石酸;以及
(g)约30%的碳酸氢钠和约8%的碳酸钠。
在某些实施例中,该组合物进一步包含(h):约0.7%的硬脂酸镁。在某些实施例中,该组合物进一步包含(i):约0.05%的地那铵苯甲酸盐。在某些实施例中,该组合物进一步包含(i):约0.1%的地那铵苯甲酸盐。在某些实施例中,该组合物进一步包含组分(j):约1.0%的polyfon H。
在一个方面中,本披露内容提供一种片剂组合物,其包含基于该组合物的总重量按重量计的以下项:
(a)约5.1%的氯虫苯甲酰胺;
(d)约5.5%的PEG-6000;
(e)约6.0%的滑石和约20.35%的麦芽糊精;
(f)约21%的D,L-酒石酸;以及
(g)约30%的碳酸氢钠和约8%的碳酸钠。
在某些实施例中,该组合物进一步包含(h):约0.7%的硬脂酸镁。在某些实施例中,该组合物进一步包含(i):约0.05%的地那铵苯甲酸盐。在某些实施例中,该组合物进一步包含(i):约0.1%的地那铵苯甲酸盐。在某些实施例中,该组合物进一步包含组分(j):约1.0%的polyfon H。
在另一个方面中,本披露内容提供一种用于防治作物中有害生物的方法,该方法包含将农业上有效量的本文提供的制剂或组合物施加到有需要的作物或其环境。
在某些实施例中,以比率每公顷10克活性成分(gai/ha)至约10,000gai/ha、约10至约5,000gai/ha、约10至约1,000gai/ha、约10至约500gai/ha、约10至约200gai/ha、约10至约100gai/ha、约10至约90gai/ha、约10至约80gai/ha、约10至约70gai/ha、约10至约60gai/ha、约10至约50gai/ha、约20至约50gai/ha、约30至约50gai/ha、或约40gai/ha施加该制剂或组合物。
在某些实施例中,本披露内容的单一片剂包含约0.0004g至约1g、约0.001g至约0.5g、约0.002g至约0.4g、约0.003g至约0.3g、约0.004g至约0.2g、约0.005g至约0.2g、约0.01g至约0.3g、约0.05g至约0.3g、约0.07g至约0.3g、约0.1g至约0.3g、约0.1g至约0.25g、约0.1g至约0.2g、约0.0034g、约0.0775g、或约0.15g的组分(a)。
在某些实施例中,该作物选自由稻、蔬菜和玉米组成的组。在某些实施例中,该作物是稻。在某些实施例中,该作物是稻并且将该制剂或组合物施加到稻田。
附图说明
图1示出了收集活性成分用于检查片剂分布概况的采样位置。
图2示出了采样位置中活性成分的含量。
图3示出了杀有害生物剂施加后3天和20天稻茎中吸收的氯虫苯甲酰胺的浓度。
图4示出了在与施加点不同距离处收集的稻茎中吸收的氯虫苯甲酰胺的浓度。
具体实施方式
如本文所用,术语“包含(comprises)”、“包含(comprising)”、“包括(includes)”、“包括(including)”、“具有(has)”、“具有(having)”或其任何其他变型均旨在涵盖非排他性的包含。例如,包含一系列要素的组合物、混合物、工艺、方法、制品、或设备不必仅限于这些要素,而是可以包括其他未明确列出的要素或此类组合物、混合物、工艺、方法、制品或设备固有的要素。此外,除非明确相反地指出,否则“或”是指包含性的或而非排他性的或。例如,条件A或B由以下任一条件满足:A为真(或存在)且B为假(或不存在)、A为假(或不存在)且B为真(或存在)以及A和B皆为真(或存在)。
而且,使用“一个/一种(a/an)”来描述本发明的要素和组分。这样做仅仅是为了方便并且给出本发明的一般意义。该描述应被解读为包括一个/种或至少一个/种,并且单数形式也包括复数形式,除非其明确地另有具体说明。
当引用数值的范围时,应当假定整个范围包括陈述的终端值。还应理解,本文列举的任何数值范围包括从下限值到上限值的所有值。例如,如果将重量比率范围指定为1:50,则预期本说明书中明确地列举了如2:40、10:30、或1:3等值。这些仅是特殊预期的实例,并在所列举的最低值与最高值之间(并且包括其最低值和最高值)的数值的所有可能的组合将有待考虑清楚地陈述在本申请中。
如本文所使用的,术语“约”是指该值的增减10%。
在一个方面中,本披露内容提供一种包含组合物的制剂,该组合物包括:杀有害生物活性成分;增强剂,其中该增强剂包括二烷基磺基琥珀酸盐、十二烷基硫酸盐、十二烷基苯磺酸盐、脂肪醇衍生物、烷基萘磺酸盐、或烷基萘硫酸盐、或其混合物;分散剂,其中该分散剂包括聚羧酸盐、酚磺酸缩合物、聚氧丙烯-聚氧乙烯嵌段共聚物、或萘磺酸缩合物、或其混合物;粘结剂;以及任选地填料。
在另一个方面中,本披露内容提供一种包含组合物的制剂,该组合物包含基于该组合物的总重量按重量计的以下项:约0.1%至约20%的杀有害生物活性成分;约0.1%至约5%的至少一种增强剂,其中该增强剂包括二烷基磺基琥珀酸盐、十二烷基硫酸盐、十二烷基苯磺酸盐、脂肪醇衍生物、烷基萘磺酸盐、或烷基萘硫酸盐、或其混合物;约0.1%至约10%的至少一种分散剂,其中该分散剂包括聚羧酸盐、酚磺酸缩合物、聚氧丙烯-聚氧乙烯嵌段共聚物、或萘磺酸缩合物、或其混合物;约0.1%至约20%的至少一种粘结剂;以及约0.1%至约50%的至少一种填料。
在另一个方面中,本披露内容提供一种片剂制剂,其包含基于该组合物的总重量按重量计的以下项:约0.1%至约20%的杀有害生物活性成分;约0.1%至约5%的至少一种增强剂,其中该增强剂包括二烷基磺基琥珀酸盐、十二烷基硫酸盐、十二烷基苯磺酸盐、脂肪醇衍生物、烷基萘磺酸盐、或烷基萘硫酸盐、或其混合物;约0.1%至约10%的至少一种分散剂,其中该分散剂包括聚羧酸盐、酚磺酸缩合物、聚氧丙烯-聚氧乙烯嵌段共聚物、或萘磺酸缩合物、或其混合物;约0.1%至约20%的至少一种粘结剂;以及约0.1%至约50%的至少一种填料。
农业应用中无人机或无人驾驶飞行器(UAVs)的使用(诸如以化学产品用于田间处理)正在迅速扩展。
在本发明的一个方面中,本文披露的组合物和制剂可用于通过无人机或无人驾驶飞行器(UAVs)递送。
本文使用的术语“杀有害生物活性成分”涵括选自以下类的那些(包括其混合物):除草剂、杀真菌剂、杀细菌剂、杀昆虫剂、杀线虫剂、杀螨剂、和生长调节剂。
可用于本发明中的杀昆虫剂是:杀昆虫剂,诸如阿巴汀、乙酰甲胺磷、灭螨醌、啶虫脒、氟丙菊酯、酰基壬吡喃(acynonapyr)、双丙环虫酯([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(环丙基羰基)氧基]-1,3,4,4a,5,6,6a,12,12a,12b-十氢-6,12-二羟基-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-4-基]甲基环丙烷甲酸酯)、磺胺螨酯、双甲脒、阿维菌素、印楝素、保棉磷、丙硫克百威、杀虫磺、苯并嘧啶烷(benzpyrimoxan)、联苯菊酯、R-联苯菊酯、联苯肼酯、双三氟虫脲、硼酸盐、溴虫氟苯双酰胺(broflanilide)、噻嗪酮、硫线磷、甲萘威、克百威、杀螟丹、伐虫脒、氯虫苯甲酰胺、溴虫腈、氟啶脲、右旋反式氯炔丙菊酯(chloroprallethrin)、毒死蜱、毒死蜱-e、甲基毒死蜱、环虫酰肼、四螨嗪、右旋反式氯炔丙菊酯(chloroprallethrin)、噻虫胺、溴氰虫酰胺、(3-溴-1-(3-氯-2-吡啶基)-N-[4-氰基-2-甲基-6-[(甲基氨基)羰基]苯基]-1H-吡唑-5-甲酰胺)、环溴虫酰胺(3-溴-N-[2-溴-4-氯-6-[[(1-环丙基乙基)氨基]羰基]苯基]-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺)、乙氰菊酯、环氧虫啶((5S,8R)-1-[(6-氯-3-吡啶基)甲基]-2,3,5,6,7,8-六氢-9-硝基-5,8-环氧基-1H-咪唑并[1,2-a]氮杂卓)、腈吡螨酯(cyenopyrafen)、丁氟螨酯、氟氯氰菊酯、高效氟氯氰菊酯、氯氟氰虫酰胺(cyhalodiamide)、三氟氯氰菊酯、精高效氯氟氰菊酯、高效氯氟氰菊酯、氯氰菊酯、顺式氯氰菊酯、ζ-氯氰菊酯、灭蝇胺、溴氰菊酯、丁醚脲、二嗪磷、二氯噻吡嘧啶(dicloromesotiaz)、狄氏剂、除虫脲、四氟甲醚菊酯、杀虫双、乐果、嗪虫唑酰胺(dimpropyridaz)、呋虫胺、苯虫醚、甲氨基阿维菌素、甲氨基阿维菌素苯甲酸盐(emamectinbenzoate)、硫丹、高氰戊菊酯、乙虫腈、醚菊酯、ε-甲氧苄氟菊酯(epsilon-metofluthrin)、乙螨唑、苯丁锡、杀螟硫磷、苯硫威、苯氧威、甲氰菊酯、氰戊菊酯、氟虫腈、氟麦托醌(2-乙基-3,7-二甲基-6-[4-(三氟甲氧基)苯氧基]-4-喹啉基甲基碳酸酯)、氟啶虫酰胺、三氟咪啶酰胺(fluazaindolizine)、氟虫双酰胺、氟氰戊菊酯、嘧虫胺、氟虫脲、氟菌螨酯((αE)-2-[[2-氯-4-(三氟甲基)苯氧基]甲基]-α-(甲氧基亚甲基)苯乙酸甲酯)、联氟砜(5-氯-2-[(3,4,4-三氟-3-丁烯-1-基)磺酰基]噻唑)、氟己芬、氟吡菌酰胺、氟吡罗(flupiprole)(1-[2,6-二氯-4-(三氟甲基)苯基]-5-[(2-甲基-2-丙烯-1-基)氨基]-4-[(三氟甲基)亚磺酰基]-1H-吡唑-3-甲腈)、氟吡呋喃酮(4-[[(6-氯-3-吡啶基)甲基](2,2-二氟乙基)氨基]-2(5H)-呋喃酮)、氟吡利明(flupyrimin)、氟胺氰菊酯、氟胺氰戊菊酯、氟恶唑酰胺(fluxametamide)、地虫硫磷、伐虫脒、噻唑膦、精高效氯氟氰菊酯(gamma-cyhalothrin)、氯虫酰肼、七氟甲醚菊酯([2,3,5,6-四氟-4-(甲氧基甲基)苯基]甲基2,2-二甲基-3-[(1Z)-3,3,3-三氟-1-丙烯-1-基]环丙烷羧酸酯)、氟铃脲、噻螨酮、氟蚁腙、吡虫啉、茚虫威、杀虫肥皂、异丙胺磷、异噁唑虫酰胺(isocycloseram)、R-七氟菊酯(kappa-tefluthrin)、高效氯氟氰菊酯(lambda-cyhalothrin)、虱螨脲、马拉硫磷、氯氟醚菊酯([2,3,5,6-四氟-4-(甲氧基甲基)苯基]甲基(1R,3S)-3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷甲酸酯)、氰氟虫腙、四聚乙醛、甲胺磷、杀扑磷、甲硫威、灭多威、烯虫酯、甲氧滴滴涕、甲氧苄氟菊酯、甲氧虫酰肼、ε-甲氧苄氟菊酯、ε-甲氟菊酯(epsilon-momfluorothrin)、久效磷、单氟菊酯([2,3,5,6-四氟-4-(甲氧基甲基)苯基]甲基3-(2-氰基-1-丙烯-1-基)-2,2-二甲基环丙烷羧酸酯)、烟碱、烯啶虫胺、硝虫噻嗪、氟酰脲、多氟脲、杀线威、噁唑塞福(oxazosulfyl)、对硫磷、甲基对硫磷、氯菊酯、甲拌磷、伏杀硫磷、亚胺硫磷、磷胺、抗蚜威、丙溴磷、丙氟菊酯、炔螨特、丙苯烃菊酯、吡氟丁酰胺(1,3,5-三甲基-N-(2-甲基-1-氧丙基)-N-[3-(2-甲基丙基)-4-[2,2,2-三氟-1-甲氧基-1-(三氟甲基)乙基]苯基]-1H-吡唑-4-甲酰胺)、吡蚜酮、啶吡唑虫胺、除虫菊素、哒螨灵、啶虫丙醚、吡氟喹虫唑、嘧螨胺((αE)-2-[[[2-[(2,4-二氯苯基)氨基]-6-(三氟甲基)-4-嘧啶基]氧基]甲基]-α-(甲氧基亚甲基)苯乙酸甲酯)、吡唑虫啶、吡丙醚、鱼藤酮、兰尼碱、氟硅菊酯、乙基多杀菌素、多杀菌素、螺螨酯、螺甲螨酯、甲氧哌啶乙酯(spiropidion)、螺虫乙酯、硫丙磷、氟啶虫胺腈(N-[甲基氧化物[1-[6-(三氟甲基)-3-吡啶基]乙基]-λ4-亚磺胺基]氰胺)、虫酰肼、吡螨胺、氟苯脲、七氟菊酯、R-七氟菊酯、特丁硫磷、四氯虫酰胺(tetrachlorantraniliprole)、杀虫畏、胺菊酯、四氟醚菊酯([2,3,5,6-四氟-4-(甲氧基甲基)苯基]甲基2,2,3,3-四甲基环丙烷甲酸酯)、四唑虫酰胺、噻虫啉、噻虫嗪、硫双威、杀虫双、噻唑沙芬(3-苯基-5-(2-噻吩基)-1,2,4-噁二唑)、唑虫酰胺、四溴菊酯、唑蚜威、敌百虫、三氟苯嘧啶(2,4-二氧代-1-(5-嘧啶基甲基)-3-[3-(三氟甲基)苯基]-2H-吡啶并[1,2-a]嘧啶内盐)、杀铃脲、泰克罗吡亚唑氟罗(tyclopyrazoflor)、zeta-氯氰菊酯(zeta-cypermethrin)、苏云金芽孢杆菌δ-內毒素、昆虫病原细菌、昆虫病原病毒或昆虫病原真菌。
可用于本发明中的除草剂是:选自以下项的除草剂:(b1)光系统II抑制剂,(b2)乙酰羟酸合酶(AHAS)抑制剂,(b3)乙酰辅酶A羧化酶(ACCase)抑制剂,(b4)生长素模拟物,(b5)5-烯醇-丙酮酸莽草酸-3-磷酸酯(EPSP)合酶抑制剂,(b6)光系统I电子转向剂,(b7)原卟啉原氧化酶(PPO)抑制剂,(b8)谷氨酰胺合成酶(GS)抑制剂,(b9)极长链脂肪酸(VLCFA)延长酶抑制剂,(b10)生长素转运抑制剂,(b11)八氢番茄红素脱氢酶(PDS)抑制剂,(b12)4-羟基苯基-丙酮酸双加氧酶(HPPD)抑制剂,(b13)尿黑酸茄呢基转移酶(HST)抑制剂,(b14)纤维素生物合成抑制剂,(b15)其他除草剂,包括有丝分裂干扰剂、有机含砷化合物、磺草灵、溴丁酰草胺、环庚草醚、苄草隆、棉隆、野燕枯、杀草隆、乙氧苯草胺、抑草丁、调节膦、杀木膦、海丹托西丁、威百亩、甲基杀草隆、油酸、噁嗪草酮、壬酸和稗草畏,和(b16)除草剂安全剂;以及(b1)至(b16)的化合物的盐。
“光系统II抑制剂(b1)”是在QB结合位置处结合到D1蛋白质上并因此在叶绿体类囊体膜中阻断电子从QA传输至QB的化学化合物。由穿过光系统II被阻断的电子通过一系列反应转移以形成毒性化合物,这些毒性化合物破坏细胞膜并造成叶绿体溶胀、膜渗漏,并最终造成细胞破裂。QB结合位置具有三个不同的结合位点:结合位点A结合三嗪如莠去津、三嗪酮如环嗪酮、以及尿嘧啶如除草定,结合位点B结合苯基脲如敌草隆,并且结合位点C结合苯并噻二唑如灭草松、腈如溴苯腈以及苯基哒嗪如哒草特。光系统II抑制剂的实例包括莠灭净、氨唑草酮、莠去津、灭草松、除草定、杀草全、溴苯腈、氯溴隆、杀草敏、绿麦隆、枯草隆、苄草隆、草净津、杀草隆、甜菜安、敌草净、噁唑隆、异戊净、敌草隆、磺噻隆、非草隆、伏草隆、环嗪酮、碘苯腈、异丙隆、异噁隆、环草定、利谷隆、苯嗪草酮、甲基苯噻隆、溴谷隆、甲氧隆、嗪草酮、绿谷隆、草不隆、甲氯酰草胺、苯敌草、扑灭通、扑草净、敌稗、扑灭津、氯苯哒醇(pyridafol)、哒草特、环草隆、西玛津、西草净、特丁噻草隆、特草定、特丁通、特丁津、去草净和草达津。
“AHAS抑制剂(b2)”是抑制乙酰羟酸合酶(AHAS)(也称为乙酰乳酸合酶(ALS))的化学化合物,并因此通过抑制蛋白质合成和细胞生长所需的支链脂族氨基酸诸如缬氨酸、亮氨酸和异亮氨酸的生产来杀死植物。AHAS抑制剂的实例包括酰嘧磺隆、四唑嘧磺隆、苄嘧磺隆、双草醚钠盐、氯酯磺草胺、氯嘧磺隆、氯磺隆、醚磺隆、环丙嘧磺隆、双氯磺草胺、胺苯磺隆、乙氧嘧磺隆、啶嘧磺隆、双氟磺草胺、氟酮磺隆、唑嘧磺草胺、氟啶嘧磺隆、氟啶嘧磺隆钠、甲酰胺磺隆、氯吡嘧磺隆、咪草酸、甲氧咪草烟、甲咪唑烟酸、灭草烟、灭草喹、咪草烟、唑吡嘧磺隆、甲基碘磺隆(包括钠盐)、碘嗪磺隆(iofensulfuron)(2-碘-N-[[(4-甲氧基-6-甲基-1,3,5-三嗪-2-基)氨基]羰基]苯磺酰胺)、甲磺胺磺隆、嗪吡嘧磺隆(3-氯-4-(5,6-二氢-5-甲基-1,4,2-二噁嗪-3-基)-N-[[(4,6-二甲氧基-2-嘧啶基)氨基]羰基]-1-甲基-1H-吡唑-5-磺酰胺)、磺草唑胺、甲磺隆、烟嘧磺隆、环氧嘧磺隆、五氟磺草胺、氟氯磺隆、丙苯磺隆钠、丙嗪嘧磺隆(2-氯-N-[[(4,6-二甲氧基-2-嘧啶基)氨基]羰基]-6-丙基咪唑并[1,2-b]哒嗪-3-磺酰胺)、氟磺隆、吡嘧磺隆、嘧啶肟草醚、环酯草醚、嘧草醚、嘧硫草醚钠、砜嘧磺隆、甲嘧磺隆、磺酰磺隆、噻酮磺隆、噻吩磺隆、氟酮磺草胺(N-[2-[(4,6-二甲氧基-1,3,5-三嗪-2-基)羰基]-6-氟苯基]-1,1-二氟-N-甲基甲磺酰胺)、醚苯磺隆、苯磺隆、三氟啶磺隆(包括钠盐)、氟胺磺隆和三氟甲磺隆。
“ACCase抑制剂(b3)”是抑制乙酰辅酶A羧化酶的化学化合物,该酶负责催化植物中脂质和脂肪酸合成的早期步骤。脂质是细胞膜的主要组分,并且没有脂质,则不能产生新细胞。乙酰辅酶A羧化酶的抑制和后续脂质生产的缺乏导致细胞膜完整性丧失,尤其是在活跃生长区域如分生组织中。最终幼苗和根茎生长停止,并且幼苗分生组织和根茎芽开始枯死。ACCase抑制剂的实例包括禾草灭、丁苯草酮、烯草酮、炔草酯、噻草酮、氰氟草酯、禾草灵、噁唑禾草灵、吡氟禾草灵、吡氟氯禾灵、唑啉草酯、环苯草酮、喔草酯、喹禾灵、稀禾定、得杀草和肟草酮,包括经解析形式,诸如精噁唑禾草灵、精吡氟禾草灵、精吡氟氯禾灵和精喹禾灵以及酯形式如炔草酯、氰氟草酯、禾草灵和精噁唑禾草灵。
生长素是调节许多植物组织的生长的植物激素。“生长素模拟物(b4)”是模拟植物生长激素生长素的化合物,因此导致不受控制和无序的生长,从而导致易感物种的植物死亡。生长素模拟物的实例包括环丙嘧啶酸(6-氨基-5-氯-2-环丙基-4-嘧啶羧酸)及其甲基和乙基酯及其钠盐和钾盐、氯氨吡啶酸、草除灵-乙酯、草灭平、氯酰草膦、稗草胺、二氯吡啶酸、麦草畏、2,4D、2,4DB、滴丙酸、氯氟吡氧乙酸、氟氯吡啶酯(halauxifen)(4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)-2-吡啶羧酸)、氟氯吡啶甲酯(halauxifen-methyl)(4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)-2-吡啶羧酸甲酯)、MCPA、MCPB、2-甲-4-氯丙酸、毒莠定、二氯喹啉酸、氯甲喹啉酸、2,3,6TBA、绿草定、以及4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)-5-氟-2-吡啶羧酸甲酯。
“EPSP合酶抑制剂(b5)”是抑制酶5-烯醇丙酮酰莽草酸-3-磷酸酯合酶的化学化合物,该酶参与芳族氨基酸诸如酪氨酸、色氨酸和苯丙氨酸的合成。EPSP抑制剂除草剂易于通过植物叶吸收并在韧皮部中易位至生长点。草甘膦是属于该组的相对非选择性苗后除草剂。草甘膦包括酯和盐,诸如铵盐、异丙基铵盐、钾盐、钠盐(包括倍半钠盐)和三甲基锍盐(可替代地称为草硫膦)。
“光系统I电子转向剂(b6)”是从光系统I中接收电子,并在数次循环之后产生羟基自由基的化合物。这些自由基极具反应性并易于破坏不饱和脂质,包括膜脂肪酸和叶绿素。这破坏细胞膜完整性,使得细胞和细胞器“渗漏”,从而导致快速叶片萎蔫和干枯,并最终导致植物死亡。该第二类型的光合成抑制剂的实例包括敌草快和百草枯。
“PPO抑制剂(b7)”是抑制酶原卟啉原氧化酶的化合物,其迅速地导致在植物中形成破坏细胞膜的高反应性化合物,从而导致细胞液渗出。PPO抑制剂的实例包括三氟羧草醚钠、唑啶草酮、双苯嘧草酮、甲羧除草醚、氟丙嘧草酯、唑酮草酯、三唑酮草酯、甲氧除草醚、吲哚酮草酯、异丙吡草酯、氟哒嗪草酯、氟胺草酯、丙炔氟草胺、乙羧氟草醚、氟噻甲草酯、氟磺胺草醚、氟硝磺酰胺(halosafen)、乳氟禾草灵、丙炔噁草酮、噁草酮、乙氧氟草醚、环戊噁草酮、氟唑草胺、双唑草腈、吡草醚、苯嘧磺草胺、甲磺草胺、噻二唑草胺、三氟草嗪(trifludimoxazin)(二氢-1,5-二甲基-6-硫基-3-[2,2,7-三氟-3,4-二氢-3-氧代-4-(2-丙炔-1-基)-2H-1,4-苯并噁嗪-6-基]-1,3,5-三嗪-2,4(1H,3H)-二酮)和氟嘧硫草酯(N-[2-[[2-氯-5-[3,6-二氢-3-甲基-2,6-二氧代-4-(三氟甲基)-1(2H)-嘧啶基]-4-氟苯基]硫基]-1-氧代丙基]-β-丙氨酸甲酯)。
“GS抑制剂(b8)”是抑制谷氨酰胺合成酶的活性的化合物,植物使用该酶以将氨转化为谷氨酰胺。因此,氨累积并且谷氨酰胺水平降低。由于氨毒性和其他代谢过程所需的氨基酸的缺乏的联合效应,植物损害可能出现。GS抑制剂包括草胺磷及其酯和盐,诸如草胺磷和其他草胺瞵衍生物、草胺磷P((2S)-2-氨基-4-(羟基甲基氧膦基)丁酸)和双丙氨膦(bilanaphos)。
“VLCFA延长酶抑制剂(b9)”是具有各种化学结构的除草剂,其抑制延长酶。延长酶是位于叶绿体中或附近的酶之一,其在VLCFA的生物合成中被涉及。在植物中,极长链脂肪酸是疏水聚合物的主要成分,其防止叶表面处的干燥并提供花粉粒的稳定性。此类除草剂包括乙草胺、甲草胺、莎稗磷、丁草胺、苯酮唑、二甲草胺、噻吩草胺、双苯酰草胺、异噁苯砜(fenoxasulfone)(3-[[(2,5-二氯-4-乙氧基苯基)甲基]磺酰基]-4,5-二氢-5,5-二甲基异噁唑)、四唑酰草胺、氟噻草胺、茚草酮、苯噻草胺、吡唑草胺、异丙甲草胺、萘丙胺、敌草胺、敌草胺-M((2R)-N,N-二乙基-2-(1-萘氧基)丙酰胺)、烯草胺(pethoxamid)、哌草磷、丙草胺、毒草胺、异丙草胺、罗克杀草砜(pyroxasulfone)和甲氧噻草胺,包括经解析形式诸如精异丙甲草胺和氯乙酰胺和氧乙酰胺。
“生长素传输抑制剂(b10)”是抑制植物中生长素传输的化学物质,诸如通过与生长素载体蛋白质结合。生长素传输抑制剂的实例包括氟吡草腙、萘草胺(也称为N-(1-萘基)-邻氨甲酰基苯甲酸和2-[(1-萘基氨基)羰基]苯甲酸)。
“PDS抑制剂(b11)”是在八氢番茄红素去饱和酶步骤时抑制类胡萝卜素生物合成途径的化合物。PDS抑制剂的实例包括m-氟丁酰草胺、氟丁酰草胺、吡氟酰草胺、氟啶草酮、氟咯草酮、呋草酮、氟草敏(norflurzon)和氟吡酰草胺。
“HPPD抑制剂(b12)”是抑制4羟基苯基-丙酮酸酯双加氧酶合成的生物合成的化学物质。HPPD抑制剂的实例包括双环磺草酮、吡草酮、氟吡草酮(4-羟基-3-[[2-[(2-甲氧基乙氧基)甲基]-6-(三氟甲基)-3-吡啶基]羰基]双环[3.2.1]辛-3-烯-2-酮)、芬奎诺酮(2-[[8-氯-3,4-二氢-4-(4-甲氧基苯基)-3-氧代-2-喹喔啉基]羰基]-1,3-环己二酮)、异噁氯草酮、异噁唑草酮、甲基磺草酮、磺酰草吡脱、吡唑特、苄草唑、磺草酮、特呋三酮、环磺酮、托比拉特(tolpyralate)(1-[[1-乙基-4-[3-(2-甲氧基乙氧基)-2-甲基-4-(甲基磺酰基)苯甲酰基]-1H-吡唑-5-基]氧基]乙基甲基碳酸酯)、苯吡唑草酮、5-氯-3-[(2-羟基-6-氧代-1-环己烯-1-基)羰基]-1-(4-甲氧基苯基)-2(1H)-喹喔啉酮、4-(2,6-二乙基-4-甲基苯基)-5-羟基-2,6-二甲基-3(2H)-哒嗪酮、4-(4-氟苯基)-6-[(2-羟基-6-氧代-1-环己烯-1-基)羰基]-2-甲基-1,2,4-三嗪-3,5(2H,4H)-二酮、5-[(2-羟基-6-氧代-1-环己烯-1-基)羰基]-2-(3-甲氧基苯基)-3-(3-甲氧基丙基)-4(3H)-嘧啶酮、2-甲基-N-(4-甲基-1,2,5-噁二唑-3-基)-3-(甲基亚磺酰基)-4-(三氟甲基)苯甲酰胺和2-甲基-3-(甲基磺酰基)-N-(1-甲基-1H-四唑-5-基)-4-(三氟甲基)苯甲酰胺。
“HST抑制剂(b13)”破坏植物将尿黑酸转化成2-甲基-6-茄尼基-1,4-苯并醌的能力,从而破坏类胡萝卜素生物合成。HST抑制剂的实例包括氟啶草、氯草定、3-(2-氯-3,6-二氟苯基)-4-羟基-1-甲基-1,5-萘啶-2(1H)-酮、7-(3,5-二氯-4-吡啶基)-5-(2,2-二氟乙基)-8-羟基吡咯并[2,3-b]吡嗪-6(5H)-酮和4-(2,6-二乙基-4-甲基苯基)-5-羟基-2,6-二甲基-3(2H)-哒嗪酮。
HST抑制剂还包括式A和B的化合物。
其中Rd1是H、Cl或CF3;Rd2是H、Cl或Br;Rd3是H或Cl;Rd4是H、Cl或CF3;Rd5是CH3、CH2CH3或CH2CHF2;并且Rd6是OH、或-OC(=O)-i-Pr;并且Re1是H、F、Cl、CH3或CH2CH3;Re2是H或CF3;Re3是H、CH3或CH2CH3;Re4是H、F或Br;Re5是Cl、CH3、CF3、OCF3或CH2CH3;Re6是H、CH3、CH2CHF2或C≡CH;Re7是OH、-OC(=O)Et、-OC(=O)-i-Pr或-OC(=O)-t-Bu;并且Ae8是N或CH。
“纤维素生物合成抑制剂(b14)”抑制某些植物中的纤维素的生物合成。当对幼嫩或快速生长的植物出苗前施用或出苗后早期施用时,它们是最有效的。纤维素生物合成抑制剂的实例包括草克乐、敌草腈、氟胺草唑、三嗪茚草胺(N2-[(1R,2S)-2,3-二氢-2,6-二甲基-1H-茚-1-基]-6-(1-氟乙基)-1,3,5-三嗪-2,4-二胺)、异噁酰草胺和三嗪氟草胺。
“其他除草剂(b15)”包括通过多种不同作用模式起作用的除草剂,诸如有丝分裂干扰剂(例如,高效麦草氟甲酯和高效麦草氟异丙酯)、有机含砷化合物(例如,DSMA和MSMA)、7,8-二氢叶酸合成酶抑制剂、叶绿体类异戊二烯合成抑制剂和细胞壁生物合成抑制剂。其他除草剂包括具有未知作用模式或不落入(b1)至(b14)列出的具体类别中或通过以上列出的作用模式的组合起作用的那些除草剂。其他除草剂的实例包括苯草醚、磺草灵、杀草强、比克罗宗(bixlozone)、溴丁酰草胺、环庚草醚、异噁草酮、苄草隆、环哒草特(cyclopyrimorate)(6-氯-3-(2-环丙基-6-甲基苯氧基)-4-哒嗪基4-吗啉羧酸酯)、杀草隆、野燕枯、乙氧苯草胺、伏草隆、抑草丁、调节膦、调节膦-铵、棉隆、杀草隆、三唑酰草胺(1-(2,4-二氯苯基)-N-(2,4-二氟苯基)-1,5-二氢-N-(1-甲基乙基)-5-氧代-4H-1,2,4-三唑-4-甲酰胺)、威百亩、甲基杀草隆、油状物酸、噁嗪草酮、壬酸、稗草畏和5-[[(2,6-二氟苯基)甲氧基]甲基]-4,5-二氢-5-甲基-3-(3-甲基-2-噻吩基)异噁唑以及特氟吡罗利米特(tetflupyrolimet)。
可用于本发明中的杀真菌剂是:杀真菌剂,诸如苯并噻二唑、二甲基吗啉、唑嘧菌胺、氨吡芬(aminopyrifen)、吲唑磺菌胺、敌菌灵、阿扎康唑、嘧菌酯、苯霜灵(benalaxyl,包括精苯霜灵(benalaxyl-M))、麦锈灵、苯菌灵、苯噻菌胺(benthiavalicarb,包括苯噻菌胺(benthiavalicarb-isopropyl)、苯并烯氟菌唑、百杀辛(bethoxazin)、乐杀螨、联苯、联苯三唑醇、联苯吡菌胺、灭瘟素(blasticidin-S)、啶酰菌胺(boscalid)、糠菌唑、乙嘧酚磺酸酯(bupirimate)、丁硫啶、萎锈灵、环丙酰亚胺、敌菌丹、克菌丹、多菌灵、地茂散(chloroneb)、百菌清、乙菌利(chlozolinate)、氢氧化铜、王铜、硫酸铜、丁香菌酯、赛座灭(cyazofamid)、环氟菌胺、霜脲氰、环唑醇、嘧菌环胺、二氯苯塞佐斯(dichlobentiazox)、抑菌灵、双氯氰菌胺(diclocymet)、哒菌酮(diclomezine)、氯硝胺(dicloran)、乙霉威(diethofencarb)、苯醚甲环唑、氟嘧菌胺(diflumetorim)、甲菌定(dimethirimol)、烯酰吗啉、醚菌胺、烯唑醇(diniconazole,包括高效烯唑醇(diniconazole M))、敌螨普、敌派美创(dipymetitrone)、二噻农(dithianon)、二噻茂烷、十二环吗啉、多果定、益康唑、乙环唑、克瘟散、烯肟菌酯(enoxastrobin,也称为烯肟菌酯(enestroburin))、氟环唑、噻唑菌胺(ethaboxam)、乙菌定(ethirimol)、土菌灵(etridiazole)、噁唑菌酮、咪唑菌酮(fenamidone)、烯肟菌胺、氯苯嘧啶醇、腈苯唑、甲呋酰胺、环酰菌胺(fenhexamide)、稻瘟酰胺(fenoxanil)、拌种咯、苯吡克咪徳(fenpicoxamid)、苯锈啶(fenpropidine)、丁苯吗啉、胺苯吡菌酮、三苯基乙酸锡、三苯基氢氧化锡、福美铁、嘧菌腙(ferimzone)、氟麦托醌、吡啶菌酰胺(florylpicoxamid)、氟醚菌酰胺、氟啶胺(fluazinam)、氟苯醚酰胺(flubeneteram)、咯菌腈、氟菌螨酯、氟茚唑菌胺(fluindapyr)、氟吗啉、氟吡菌胺(fluopicolide)、氟吡菌酰胺、氟噁哌若灵(fluoxapiprolin)、氟嘧菌酯、氟喹唑、氟硅唑、磺菌胺(flusulfamide)、氟噻唑菌腈、氟酰胺(flutolanil)、粉唑醇、氟唑菌酰胺、灭菌丹、稻瘟酞(fthalide,也称为苯酞(phthalide)、麦穗宁、呋霜灵(furalaxyl)、呋吡菌胺、己唑醇、土菌消(hymexazole)、双胍辛盐(guazatine)、抑霉唑、亚胺唑、烷苯磺酸盐(iminoctadine albesilate)、双胍辛胺乙酸盐(iminoctadine triacetate)、茚吡氟胺(inpyrfluxam)、硫双威、种菌唑、依普芬三氟康纳唑(ipfentrifluconazole)、依普氟芬诺喹(ipflufenoquin)、异丙噻菌胺、异稻瘟净(iprobenfos)、异菌脲、丙森锌、异氟普仑(isoflucypram)、稻瘟灵(isoprothiolane)、吡唑萘菌胺(isopyrazam)、异噻菌胺、春雷霉素、醚菌酯、兰考曲酮(lancotrione)、代森锰锌、双炔酰菌胺(mandipropamid)、曼德斯宾(mandestrobin)、代森锰、嘧菌胺(mapanipyrin)、氯氟醚菌唑、灭锈胺、消螨多(meptyldinocap)、甲霜灵(包括高效甲霜灵(metalaxyl-M)/精甲霜灵(mefenoxam))、叶菌唑、磺菌威(methasulfocarb)、代森联、苯氧菌胺、美特尔特特拉普罗(metyltetraprole)、苯菌酮、腈菌唑、萘替芬(naftitine)、甲胂铁铵(甲基胂酸铁(ferric methanearsonate))、氟苯嘧啶醇、辛噻酮、呋酰胺、肟醚菌胺、恶霜灵(oxadixyl)、噻哌菌灵(oxathiapiprolin)、奥索利酸、噁咪唑(oxpoconazole)、氧化萎锈灵、土霉素、戊菌唑、戊菌隆(pencycuron)、氟唑菌苯胺、吡噻菌胺(penthiopyrad)、稻痕酯(perfurazoate)、亚磷酸(包括其盐,例如,乙磷铝(fosetyl-aluminm))、啶氧菌酯、哌丙灵(piperalin)、多氧霉素(polyoxin)、噻菌灵、咪鲜胺、腐霉利(procymidone)、霜霉威(propamocarb)、丙环唑、甲基代森锌、碘喹唑酮(proquinazid)、硫菌威(prothiocarb)、丙硫菌唑、氟唑菌酰羟胺唑菌胺酯、唑胺菌酯、吡拉吡波尼(pyrapropoyne)、唑菌酯、联苯吡嗪菌胺(pyraziflumid)、吡菌磷、吡菌苯威、吡布塔威(pyributacarb)、哒氯美蒂(pyridachlometyl)、啶斑肟(pyrifenox)、苯啶菌酮(pyriofenone)、皮里索萨唑(perisoxazole)、嘧霉胺(pyrimethanil)、啶斑肟、硝吡咯菌素(pyrrolnitrin)、咯喹酮(pyroquilon)、氟喹唑、灭螨猛(quinmethionate)、喹氟密灵(quinofumelin)、喹氧灵、五氯硝基苯、硅噻菌胺(silthiofam)、氟唑环菌胺(sedaxane)、硅氟唑(simeconazole)、螺环菌胺、链霉素、硫、戊唑醇、异丁乙氧喹啉、叶枯酞(teclofthalam)、叶枯酞、四氯硝基苯、特比萘芬、氟醚唑、噻苯达唑、噻呋酰胺、托布津、甲基托布津、塞仑、噻酰菌胺、甲基立枯磷、三氟甲氧威(tolprocarb)、甲苯氟磺胺、三唑酮、三唑醇、嘧菌醇、咪唑嗪(triazoxide)、碱式硫酸铜(tribasic copper sulfate)、氯啶菌酯、十三吗啉、肟菌酯、氟菌唑、三莫嘧三环唑(trimoprhamide tricyclazole)、肟菌酯、嗪氨灵、灭菌唑、烯效唑(uniconazole)、有效霉素、缬菌胺(valifenalate,也称为缬菌胺(valifenal))、乙烯菌核利(vinclozoline)、代森锌、福美锌、苯酰菌胺(zoxamide)和1-[4-[4-[5-(2,6-二氟苯基)-4,5-二氢-3-异噁唑基]-2-噻唑基]-1-哌啶基]-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮;杀线虫剂,诸如氟吡菌酰胺、螺虫乙酯、硫双威、噻唑膦、阿巴汀、异菌脲、联氟砜、二甲基二硫化物、噻唑沙芬、1,3-二氯丙烯(1,3-D)、威百亩(钠和钾)、棉隆、氯化苦、苯线磷(fenamiphos)、灭线磷、硫线磷(cadusaphos)、特丁硫磷、咪唑环磷(imicyafos)、杀线威、克百威、噻唑沙芬(tioxazafen)、坚强芽孢杆菌和西泽巴斯德氏菌;杀细菌剂,诸如链霉素;杀螨剂,诸如双甲脒、灭螨猛、乙酯杀螨醇、三环锡(cyhexatin)、三氯杀螨醇、除螨灵、乙螨唑、喹螨醚、苯丁锡、甲氰菊酯、唑螨酯、噻螨酮、克螨特、哒螨灵和吡螨胺。
在某些实施例中,该杀有害生物活性成分是杀昆虫剂。
如本文使用的术语“杀昆虫剂”涵括对昆虫生长具有防治或改变效果(包括但不限于杀死、伤害、减缓、阻碍生长、定向障碍、抑制繁殖等)的所有试剂。
在某些实施例中,该杀有害生物活性成分是二酰胺、新烟碱、或沙蚕毒素类似物杀昆虫剂,或其混合物。在一些实施例中,该杀有害生物活性成分是氯虫苯甲酰胺、溴氰虫酰胺、四唑虫酰胺、环溴虫酰胺、氯氟氰虫酰胺、四氯虫酰胺、溴虫苯甲酰胺、双氯虫酰胺(dichlorantraniliprole)、噻虫嗪、噻虫胺、噻虫啉、杀虫单、或杀虫双、或其混合物。
在某些实施例中,该杀有害生物活性成分是邻氨基苯甲酰胺。
本文使用的术语“邻氨基苯甲酰胺”是指针对众多经济上重要的农学和非农学无脊椎有害生物具有杀昆虫活性的羧酰胺类杀节肢动物剂。邻氨基苯甲酰胺通过与兰尼碱受体(一类细胞内钙离子通道)结合影响钙稳态。一经其结合,打开钙离子通道并释放钙离子至细胞质中。钙离子储量的减少导致昆虫麻痹和死亡。邻氨基苯甲酰胺的化学特征在于分子结构包含与芳环(典型地是苯环)碳原子键合的相邻羧酰胺取代基,其中一个羧酰胺部分通过羰基碳键合,并且另一个羧酰胺部分通过氮原子键合。
在一些实施例中,邻氨基苯甲酰胺选自具有式I的化合物、N-氧化物、及其盐
其中X是N、CF、CCl、CBr或Cl;R1是H、CH3、Cl、Br或F;R2是H、F、Cl、Br或-CN;R3是F、Cl、Br、C1-C4卤代烷基或C1-C4卤代烷氧基;R4a是H、C1-C4烷基、环丙基甲基或1-环丙基乙基;R4b是H或CH3;R5是H、F、Cl或Br;并且R6是H、F、Cl或Br。
在一些实施例中,邻氨基苯甲酰胺是氯虫苯甲酰胺、溴氰虫酰胺、四唑虫酰胺、环溴虫酰胺、氯氟氰虫酰胺、溴虫苯甲酰胺、双氯虫酰胺、或四氯虫酰胺、或其混合物。其他邻氨基苯甲酰胺以及用于它们的制备的方法在美国专利号6,747,047、WO 2003/015519、WO2004/067528、WO 2006/062978和WO 2008/069990中详细描述,将这些专利通过援引并入本文。
在一些实施例中,邻氨基苯甲酰胺是氯虫苯甲酰胺、或溴氰虫酰胺、或其混合物。
氯虫苯甲酰胺是邻氨基苯甲酸二酰胺类的杀昆虫剂,且具有化学名称5-溴-N-[4-氯-2-甲基-6-(甲基氨基甲酰基)苯基]-2-(3-氯吡啶-2-基)吡唑-3-甲酰胺,并且由FMC公司注册商标为氯虫苯甲酰胺是兰尼碱受体激动剂,并且被用于保护多种作物,包括玉米、棉、葡萄、稻和马铃薯。暴露于氯虫苯甲酰胺的昆虫一般表现为嗜睡和肌肉麻痹随后最终死亡。发现表明氯虫苯甲酰胺表现出对昆虫兰尼碱受体相对于哺乳动物兰尼碱受体极好的特异性的选择性。该选择性很可能是使用氯虫苯甲酰胺中观察到的哺乳动物安全性的主要贡献因素。
溴氰虫酰胺具有化学名称3-溴-1-(3-氯-2-吡啶基)-N-[4-氰基-2-甲基-6-[(甲基氨基)羰基]苯基]-1H-吡唑-5-甲酰胺,并且由FMC公司注册商标为溴氰虫酰胺是羧酰胺,其为连在苯环的氯原子被氰基代替的氯虫苯甲酰胺。溴氰虫酰胺可作为杀昆虫剂使用用来防治作物(诸如洋葱、马铃薯和番茄)中的粉虱、蓟马、蚜虫、果蝇、和果虫。它起到兰尼碱受体激动剂的作用。
在某些实施例中,本文提供的组合物包含按重量计该组合物约1%至约10%、约1%至约8%、约1%至约7%、约1%至约6%、约1%至约5.5%、约1%、约2.5%或约5%的邻氨基苯甲酰胺。在某些实施例中,该邻氨基苯甲酰胺是氯虫苯甲酰胺。
由于活性成分的功效和化学稳定性以及所配制的组合物的物理稳定性可能会受到制剂中惰性成分影响,因此合适的惰性成分应当不造成活性成分分解、不造成在施加时本质上降低其活性、或者在长期贮存下不造成可感知的沉淀或晶体形成。此外,惰性成分应当是无植物毒性的且对环境是安全的。在某些制剂中,惰性成分甚至可以通过促进渗透或吸收到植物或节肢动物有害生物中或者通过提高对洗除的耐受性来增强活性成分的生物学性能。
在某些实施例中,该增强剂包括二烷基磺基琥珀酸钠、十二烷基硫酸钠、十二烷基苯磺酸钠、脂肪醇衍生物、烷基萘磺酸钠、二辛基硫代琥珀酸钠、或烷基萘硫酸钠、或其混合物。
在某些实施例中,该增强剂包括SDS、MA-80I、OT系列、MULTIWETTMMO-85P、EFW、BEROLTM790A、DS 10、DF-90、TergitolTMW-610、L WET F、L WET P、1004、1010、AA、IP、WP、或HRB、或其混合物。
在某些实施例中,本文提供的组合物包含按总重量计约0.1%至约5%的至少一种包含二烷基磺基琥珀酸钠的增强剂。
本文使用的术语“包含二烷基磺基琥珀酸钠的增强剂”是指任何含有二烷基磺基琥珀酸钠和任选地一种或多种其他物质的增强剂,无论二烷基磺基琥珀酸钠是否是该增强剂的主要组分,只要该增强剂可以促进活性成分被作物或牧草有效吸收到有效防治有害生物的水平。在某些实施例中,二烷基磺基琥珀酸钠是该增强剂的主要组分。在某些实施例中,该增强剂包括按重量计大于约50%、55%、60%、65%、70%、75%、80%、85%、90%、95%或98%的二烷基磺基琥珀酸钠。在某些实施例中,该增强剂在与组合物其他组分混合后是以固体形式的。在某些实施例中,该增强剂在与组合物任何组分混合前是以固体形式的。
在某些实施例中,该增强剂是OT-B或OT-75。OT-B和OT-75是多用途阴离子表面活性剂(诸如润湿剂、乳化剂、抗静电/软化剂),其可被用于降低表面张力以及提高吸收性和渗透性、并且可以为界面提供非常快速的迁移。
在某些实施例中,该增强剂是按重量计该组合物的约0.1%至约4%、约0.1%至约3%、约0.1%至约2%、约0.2%至约2%、约0.3%至约2%、约0.3%至约1.8%、约0.3%至约1.5%、约0.3%至约1.2%、约0.3%至约1%、约0.5%至约1%、约0.6%至约1%、约0.7%至约1%、或约0.8%。
在某些实施例中,该分散剂包括T/36、TA-72、SC-213、Ultrasperse、D-205、D-305、D-518、2500、2700、Atlox metasperseTM 550S、TamolTM 731 SD、TamolTM DN、YUS-TXC、PE 10400、MORWETTM D-360、MORWETTM D-110、D-425、TamolTMFB P1、或TamolTM NN8906。
在某些实施例中,本文披露的组合物包含按总重量计约0.1%至约10%的至少一种包含聚羧酸盐的分散剂。
本文使用的术语“包含聚羧酸盐的分散剂”是指任何含有聚羧酸盐和任选地一种或多种其他物质的分散剂,无论聚羧酸盐是否是该分散剂的主要组分,只要该分散剂可以促进活性成分在液体中扩散和均匀分布。在某些实施例中,聚羧酸盐是该分散剂的主要组分。在某些实施例中,该分散剂包括按重量计大于约50%、55%、60%、65%、70%、75%、80%、85%、90%、95%或98%的聚羧酸盐。在某些实施例中,该分散剂在与组合物其他组分混合后是以固体形式的。在某些实施例中,该分散剂在与组合物任何组分混合前是以固体形式的。
本文使用的分散剂可以促进活性成分在液体中扩散和均匀分布,诸如冷、硬水(例如,含有大于约300ppm的碳酸钙,向其中施用该组合物,特别是当组合物分散不均匀时)。
合适的包含聚羧酸盐的分散剂是已知的,并且包括但不限于T/36、TA-72、SC-213、Ultrasperse、D-205、D-305、D-518、2500、2700、Atlox metasperseTM 550S、和TamolTM 731SD。
在某些实施例中,该分散剂是按重量计该组合物的约0.5%至约10%、约0.5%至约8%、约0.5%至约7%、约0.5%至约6%、约0.5%至约5%、约0.8%至约5%、约1%至约5%、约1.2%至约5%、约1.5%至约5%、约1.7%至约5%、约2%至约5%、约2%至约4.5%、约2%至约4%、约2%至约3.5%、约2%至约3%、约2.2%至约2.8%、约2.4%至约2.6%、或约2.5%。
增强剂和分散剂的优选范围可以在扩散性或渗透性方面改善含有氯虫苯甲酰胺的片剂组合物的功效。在某些实施例中,该增强剂与该分散剂之间的比率可以在按重量计约1:1-1:5、1:1-1:4、1:2-1:4或1:3-1:4的范围中。在某些实施例中,该比率是按重量计约8:25。在某些实施例中,该比率是按重量计约1:3。
在某些实施例中,本文提供的组合物进一步包含约0.1%至约40%的至少一种酸;以及约0.1%至约40%的至少一种碱。
本文使用的酸和碱通常共同作用以与水接触生成气体,促进组合物的崩解和活性成分的扩散。在某些实施例中,该组合物包括能够与组合物的碳酸盐组分反应释放二氧化碳的固体酸。该酸可以是水溶性酸性物质,尤其是多元有机酸,如琥珀酸、D,L-酒石酸、L-酒石酸、酒石酸、碱金属酸式硫酸盐、乳酸、己二酸、柠檬酸、碱金属酸式柠檬酸盐、碱金属酸式磷酸盐、碱金属酸式邻苯二甲酸盐和对甲苯磺酸、苹果酸、马来酸、丙二酸以及草酸等。在某些实施例中,该酸是D,L-酒石酸。
在某些实施例中,本文提供的组合物包含按重量计该组合物约0.5%至约25%、约1%至约25%、约5%至约25%、约10%至约25%、约15%至约25%、约16%至约25%、约17%至约25%、约18%至约25%、约19%至约25%、约20%至约25%、约20%至约24%、约20%至约23%、约20%至约22%、或约21%的酸。
碱是与该酸反应以提供二氧化碳源的无机碱。在这些盐中,优选为钠和钾的盐,归因于其良好的溶解性和低成本。该碱可以是碱金属或碱土金属碳酸盐,如碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、碳酸钙、和碳酸氢钙。
在某些实施例中,本文提供的组合物包含按重量计该组合物约0.5%至约40%、约1%至约40%、约5%至约40%、约10%至约40%、约15%至约40%、约20%至约40%、约25%至约40%、约30%至约40%、约35%至约40%、或约38%的碱。
在某些实施例中,该碱是碳酸氢盐和碳酸盐的混合物,例如,碳酸氢钠和碳酸钠、或碳酸氢钾和碳酸钾的混合物。按重量计碳酸氢盐和碳酸盐之间的比率可以在约1:10-10:1、约1:5-10:1、约1:3-10:1、约1:2-10:1、约1:1-10:1、约2:1-10:1、约3:1-10:1、约3:1-9:1、约3:1-8:1、约3:1-7:1、约3:1-6:1、约3:1-5:1、约3:1-4:1、约3.5:1-4:1、或约3.7:1的范围中。
在某些实施例中,该碳酸氢盐和碳酸盐分别是碳酸氢钠和碳酸钠,其中该碳酸氢钠是按重量计该组合物的约0.5%至约40%、约1%至约40%、约5%至约40%、约10%至约40%、约15%至约40%、约20%至约40%、约25%至约40%、约25%至约35%、约27%至约33%、约30%,并且该碳酸钠是按重量计该组合物的约1%至约40%、约1%至约30%、约1%至约20%、约2%至约20%、约3%至约20%、约3%至约18%、约3%至约15%、约3%至约12%、约3%至约10%、约5%至约10%、约6%至约10%、约7%至约10%、或约8%。在某些实施例中,该碳酸氢盐和碳酸盐分别是碳酸氢钾和碳酸钾,其中该碳酸氢钾是按重量计该组合物的约0.5%至约40%、约1%至约40%、约5%至约40%、约10%至约40%、约15%至约40%、约20%至约40%、约25%至约40%、约25%至约35%、约27%至约33%、约30%,并且该碳酸钾是按重量计该组合物的约1%至约40%、约1%至约30%、约1%至约20%、约2%至约20%、约3%至约20%、约3%至约18%、约3%至约15%、约3%至约12%、约3%至约10%、约5%至约10%、约6%至约10%、约7%至约10%、或约8%。
碳酸氢盐和/或碳酸盐与酸的比率可以在宽泛的限制内变化。例如,本文描述的组合物可以含有每当量碳酸氢盐和/或碳酸盐从0.05至2(例如,0.1、0.2、0.3、0.4、0.5、0.55、0.6、0.7、0.8、0.9、1、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、或1.9)当量的水溶性酸性物质。
术语“当量”在本文是以酸-碱意义使用的,1克分子重量的固体酸被当作为1克分子重量NaHCO3、或0.5克分子重量Na2CO3的当量。但是,可以使用更少的量,并且这些量不是关键。对于每当量的碳酸氢盐,只需要大于约0.05当量的酸。也就是说,当碱金属碳酸盐是碳酸氢盐时,每当量碳酸氢盐超过0.05当量的任何量的酸都足够造成该组合物有些泡腾。
本文披露的组合物包含按总重量计约0.1%至约20%(例如,约1%至约15%、约1%至约10%、约1%至约8%、约1%至约7%、约1%至约6%、约1%至约5.5%、约2%至约5.5%、约3%至约5.5%、约3%、或约5.5%)的至少一种粘结剂。粘结剂将该组合物的不同组分结合在一起以协助组合物的完整性,并减少该组合物制造、包装、运输和递送过程中粉末的产生。合适的粘结剂包括聚乙二醇(PEG)、麦芽糖、海藻糖、山梨醇、麦芽糖醇、聚乙烯基吡咯烷酮(PVP)、聚乙烯基吡咯烷酮交联剂(PVPP)、磷酸氢钙、蔗糖、葡萄糖、玉米(玉蜀黍)淀粉、改性纤维素、海藻酸、羧甲基纤维素钠(hydroxyl sodium methylcellulose)、羟甲基纤维素钠、或共聚维酮、或其混合物。在某些实施例中,该粘结剂包含PEG。在某些实施例中,该粘结剂包含选自由PEG200、PEG1000、PEG2000、PEG4000、PEG6000、PEG8000和PEG10000组成的组的至少一种。在某些实施例中,该粘结剂包含PEG6000。
本文披露的组合物包含按总重量计约0.1%至约50%(例如,约0.1%至约45%、约0.5%至约45%、约1%至约45%、1%至约40%、约1%至约35%、约1%至约30%、约5%至约30%、约8%至约30%、约10%至约30%、约15%至约30%、约20%至约30%、约25%至约30%、约5%至约25%、约5%至约20%、约5%至约15%、或约5%至约10%)的至少一种填料。
如本文所使用的,术语“填料”是指添加到组合物以增加该组合物的重量和/或尺寸的物质。数种合适的填料是已知的,并且包括但不限于硫酸钠、硫酸铵、淀粉、膨润土、硅藻土、高岭土、糊精、麦芽糊精、葡萄糖、纤维素、微晶纤维素、壳聚糖、乳糖、乳糖一水合物、甘露醇、蔗糖、滑石、麦芽糖醇、山梨醇、木糖醇、粉末状纤维素、纤维素胶、淀粉、或磷酸钙。
在某些实施例中,本文提供的组合物包含至少两种填料。在某些实施例中,第一填料与第二填料之间的比率可以在按重量计约1:10至10:1(例如1:9、1:8、1:7、1:6、1:5、1:4.5、1:4、1:3.5、1:3、1:2、1:1、2:1、3:1、3.5:1、4:1、4.5:1、5:1、6:1、7:1、7:1、8:1、或9:1)的范围内变化。
在某些实施例中,该填料包含滑石或麦芽糊精,或其混合物。在某些实施例中,该填料包含滑石和麦芽糊精的混合物。在某些实施例中,滑石与麦芽糊精之间的比率是在按重量计约1:1-1:10、1:1-1:9、1:1-1:8、1:1-1:7、1:2-1:7、1:2-1:6、1:3-1:6、1:3-1:5、1:3-1:4、1:4-1:5、1:5、1:4.5、1:4、1:3.5、1:3、或1:2的范围中。在一些实施例中,滑石与麦芽糊精之间的比率是按重量计约1:3.3。在一些实施例中,滑石与麦芽糊精之间的比率是按重量计约1:4.5。
可以向本披露内容的组合物添加不同的次要成分,但是不必要。这样的次要成分实例是:润滑剂,诸如硬脂酸镁;苦味剂;香料;光学增亮剂;染料;羧甲基纤维素钠。若需要,该组合物还可以以水溶性膜(如聚乙烯醇膜)涂膜。
可使用润滑剂以增强片剂从其形成的设备上释放,例如通过防止粘接在上冲头(“拾取”)或下冲头(“黏附”)的表面。合适的润滑剂包括,例如,白炭黑、滑石粉、硬脂酸镁、硬脂酸钙、硬脂酸钠、硬脂酸锌、硬脂酸、硼酸、金属硬脂酸盐、硬脂富马酸钠、脂肪酸、脂肪醇、脂肪酸酯、山萮酸甘油酯、菜籽油(canola oil)、矿物油、植物油、硬脂酸棕榈酸甘油酯、氢化植物油、氢化植物油、氧化镁、泊洛沙姆、石蜡、亮氨酸、丙二醇脂肪酸酯、聚乙烯醇苯甲酸钠、十二烷基硫酸钠、硬脂富马酸钠、聚乙二醇、聚丙二醇、和聚亚烷基二醇。优选地,该润滑剂包含硬脂酸和其盐,如硬脂酸钙、硬脂酸镁和硬脂酸铝。在某些实施例中,该润滑剂包含硬脂酸镁。在一个实施例中,包括按重量计该组合物约0.1%至约5%(例如,约0.1%至约4.5%、约0.1%至约4.0%、约0.1%至约3.5%、约0.1%至约3.0%、约0.1%至约2.5%、约0.1%至约2.0%、约0.1%至约1.5%、约0.1%至约1.0%、约0.5%至约1.0%、约0.5%至约0.7%、约0.5%、或约0.7%)的量的作为润滑剂的硬脂酸镁。
也可以将苦味剂作为厌恶剂用于本文提供的组合物中,以阻止人类或非靶标动物的不恰当摄食。合适的苦味剂包括但不限于苯并二氮杂卓、地那铵、蔗糖八乙酸酯、槲皮素、番木鳖碱和苦木素。在某些实施例中,该苦味剂包含地那铵苯甲酸盐。在某些实施例中,该苦味剂是地那铵苯甲酸盐。在一个实施例中,包括按重量计该组合物约0.01%至约5%(约0.01%至约4.5%、约0.01%至约4.0%、约0.01%至约3.5%、约0.01%至约3.0%、约0.01%至约2.5%、约0.01%至约2.0%、约0.01%至约1.5%、约0.01%至约1.0%、约0.01%至约0.5%、约0.01%至约0.4%、约0.01%至约0.3%、约0.01%至约0.2%、约0.01%至约0.1%、约0.01%至约0.05%、约0.05%、约0.1%)的量的作为苦味剂的地那铵苯甲酸盐。
在某些实施例中,本文提供的组合物基本上不含有任何无机溶剂,例如,量少于按重量计该组合物的10%、5%、3%、1%、0.5%、0.2%、0.1%、0.05%、0.01%、0.001%、0.0001%、0.00001%、或0.000001%。
在某些实施例中,在片剂中该组合物基本上不含有尘粉剂,例如,量少于按重量计该组合物的10%、5%、3%、1%、0.5%、0.2%、0.1%、0.05%、0.01%、0.001%、0.0001%、0.00001%、或0.000001%。
在某些实施例中,该组合物可任选地进一步含有一种或多种选自除草剂、杀真菌剂、杀细菌剂、杀昆虫剂、杀线虫剂、杀螨剂、和生长调节剂的活性成分。
在某些实施例中,本文提供的组合物可被配制为片剂组合物。在某些实施例中,每个单一片剂含有从约0.0004g至约1g、约0.001g至约0.5g、约0.002g至约0.4g、约0.003g至约0.3g、约0.004g至约0.2g、约0.005g至约0.2g、约0.01g至约0.3g、约0.05g至约0.3g、约0.07g至约0.3g、约0.1g至约0.3g、约0.1g至约0.25g、约0.1g至约0.2g、约0.0034g、约0.0775g、或约0.15g的活性成分组分(a)。
如在制药领域众所周知的,本文使用的术语“片剂组合物”是指可以通过将粉末在压片机上成型或压实制备的固体形式。
本披露内容的片剂组合物既可以是均质的、也可以是异质的。本文使用的术语“均质的”是指通过单一颗粒组合物的成型或压实生产的片剂,但是并不意味着该组合物的所有颗粒都将有必要是相同的组合物。本文使用的术语“异质的”是指有多个离散区域的片剂,例如插入物周围具有层、插入物或涂膜。
片剂可使用常规的片剂制作设备制备,且可以是任何合适的尺寸和形状,例如圆形、椭圆形、多边形或枕形,并且任选地可以带有非功能性的表面标识。可将本发明的片剂包装在容器中,随附包装说明书提供相关信息诸如,例如,剂量和施加信息、浓度、预防措施、药物相互作用和不良反应。
本文提供的组合物可以通过已知的常规方法制造,优选地涉及混合成分、过筛和压型。典型地,粉末共混物通过混合至均匀来制备,将其通过具有筛目尺寸主要从约70至200目的网筛,并且在压片机(例如,5000至10000磅的力的液压机)中压型成所期望的片剂尺寸和密度。
在某些实施例中,本文提供的组合物具有比水的密度更大的密度(比重大于1.00),从而片剂在与水接触时会下沉。
在某些实施例中,本披露内容的片剂可以进一步包含涂膜,例如非功能性涂膜。非功能性涂膜可以包含聚合物组分(例如HPMC)、任选地连同其他成分,例如一种或多种增塑剂、着色剂等。在某些实施例中,片剂在压型后进行附加的涂膜步骤。本文使用的术语“非功能性”是指基本上对片剂特性释放不具有影响的手段,并且不应当被解读为意味着涂膜没有有益的作用。例如,这样的涂膜可以赋予片剂独特的外观、在包装和运输过程中提供保护防止磨损、和/或其他的好处。
该片剂组合物可被制造为适合于其施加的任何尺寸。在某些实施例中,该片剂是约0.01g至约20g、约0.05g至约20g、约0.1g至约20g、约0.2g至约20g、约0.5g至约20g、约0.5g至约15g、约0.5g至约10g、约1g至约10g、约1g至约5g、约2g至约5g、约3g至约5g、约3g至约4.5g、约3g至约4g、约3.0g至约3.4g。
在某些实施例中,该片剂具有约5mm至约100mm、约5mm至约50mm、约5mm至约40mm、约5mm至约35mm、约5mm至约30mm、约10mm至约15mm、约10mm至约30mm、约15mm至约30mm、约20mm至约30mm、约20mm至约25mm、约20至约22mm、约20mm或约22mm的直径。
在某些实施例中,当本文提供的组合物按重量计1%在水中稀释时,其具有从5.0至8.0、任选地从6.0至7.0的pH值范围。在某些实施例中,本文提供的组合物具有约6.5、6.7或6.8的pH值(按重量计1%在水中稀释)。
硬度是对使用前贮存、运输、和操作情况下造成压块压碎所需的力的量度,并且典型地以单位诸如千磅(kp)、Strong-Cobb单位(SCU)或牛顿(N)表示。约1SCU的硬度表示大约0.7kp的力或约7N。包含本文提供的至少一种起水溶性杀有害生物剂基质作用的填料的未涂膜的片剂或涂膜前的片剂芯,可能需要具有特定的最小硬度,以便能抵抗由于高速压片操作的过程中(包括直到并包括将片剂填充至容器中的所有步骤)施加的机械应力造成的破碎和/或磨损。最小可接收的硬度将取决于若干因素(包括机械应力的严重性),但是其典型地至少是约70N(例如,大于80N、90N、100N、或105N)。在某些实施例中,本文提供的片剂组合物具有106、79、或75N的片剂硬度。
在共混、研磨和压实前,可以将制剂成分干燥。在真空烘箱中、45℃至60℃下干燥16小时足以将预混料的水含量减少至小于约3.0%。这样有助于在贮存过程中残留的水分不会引起泡腾反应。典型地,将成分在研磨机(例如,空气研磨机或锤磨机)中磨碎和混合。将磨碎的预混料刷过70至200目筛网。在某些实施例中,该组合物的水含量小于约3.0%、2.5%、2.0%、1.9%、1.8%、1.7%、1.6%、1.5%、1.0%、或0.5%。
本披露内容还提供一种防治作物中有害生物的方法,该方法包括将农业上有效量的组合物施加到有需要的作物或其环境。
本文使用的术语“农业上有效量”是指当向作物或牧草施加时,杀有害生物剂组合物杀死或实质伤害存在其中的有害生物或杂草或真菌群体的显著部分、和/或在生长周期任何阶段对作物或牧草实质减少损害的量或施加比率。
在某些实施例中,该作物是农学或非农学的。
术语“农学作物”是指大田作物诸如用于食物的那些和纤维并且包括玉米;大豆和其他豆类;谷类(例如,小麦、燕麦、大麦、黑麦、稻、和玉蜀黍);蔬菜,例如,叶类蔬菜(例如,莴苣、甘蓝、和其他甘蓝类作物)、果实类蔬菜(例如,番茄、辣椒、茄子、十字花科类和瓜类)、马铃薯、蕃薯;棉;水果、葡萄、乔木果实(例如,梨果、核果和柑橘)、小浆果(例如,浆果和樱桃);以及其他特种作物(例如,油菜籽、向日葵和橄榄)。
术语“非农学作物”是指其他园艺作物(例如,温室、苗圃或不在大田中生长的观赏植物,城镇中住宅和商业结构以及工业场所中的植物)、草皮(例如,草场(sod farm)、牧场、高尔夫球场、草坪、住宅区域、娱乐场所和运动场)、木材产品、储存产品、用于公共健康(即人类)和动物健康(例如,宠物、家畜和家禽以及非家养动物诸如自然动物)应用的农林业和植被。
在农学和非农学应用中,通过将有效量的本披露内容中提供的组合物施加到有害生物环境(包括侵害的农学和/或非农学所在地)、施加到待保护的区域、或直接施加到待防治的有害生物,来防治无脊椎有害生物。
本文使用的术语“无脊椎有害生物”涵括作为有害生物的经济重要的节肢动物、腹足动物和线虫类动物。术语“节肢动物”涵括昆虫、螨虫、蜘蛛、蝎子、蜈蚣、千足虫、鼠妇(pill bug)和综合虫(symphylan)。术语“腹足动物”涵括蜗牛、蛞蝓和其他柄眼目(Stylommatophora)。术语“线虫类动物”涵括所有蠕虫,诸如:蛔虫、犬心丝虫(heartworm)、和植食性线虫(线虫动物门(Nematoda))、吸虫(吸虫纲(Tematoda))、棘头动物门(Acanthocephala)、和绦虫(多节绦虫亚纲(Cestoda))。
农学施加包括典型地通过种植前向作物种子、播种期间向犁沟、向作物植株的叶子、茎、花和/或果实、或者作物种植前或后或当种植作物时向土壤或者其他生长介质(例如,稻田)施加本披露内容的组合物或组合物的混合物保护大田作物不受无脊椎有害生物之害。非农学施加是指在作物植株以外的区域中的无脊椎有害生物防治。非农学施加包括在储存的谷物、豆类和其他食品以及纺织品诸如衣服和地毯中的无脊椎有害生物防治。非农学施加还包括在观赏植物、森林、庭院、路边和铁路用地以及草皮诸如草坪、高尔夫球场和牧场中的无脊椎有害生物防治。非农学施加还包括在房屋和可能被人类和/或伴侣动物、农场动物、牧场动物、动物园动物或其他动物占据的其他建筑物中的无脊椎有害生物防治。非农学施加还包括可能损害建筑物中使用的木材或其他结构材料的有害生物诸如白蚁的防治。非农学施加还包括通过防治寄生的或传播感染性疾病的无脊椎有害生物来保护人类和动物健康。此类有害生物包括,例如,恙螨(chigger)、蜱虫(tick)、虱、蚊子、蝇和跳蚤。
组合物施加的一个实施例是通过喷雾。可替代地,包含本披露内容的组合物的片剂组合物可以施加到植物叶子或土壤。也通过使植株与作为片剂制剂到土壤中的土壤浸液、育苗箱处理物或移植浸渍液施加的本披露内容的组合物接触来通过植物吸收有效地递送本披露的化合物。在某些实施例中,该作物是稻并且将该组合物施加到稻田中。在某些实施例中,将该组合物手动或机械地分散到稻田上,即,在不进入稻田中的情况下从稻田之间的路径通过手动投掷,或者可从稻田投掷。
该方法适用于作物任何需要防治有害生物或有害生物生命阶段的情形。该方法当与播种或移植过程结合时能有用,而且还可用于成熟作物,特别是已建立的稻田。
可以通过该组合物防治的有害生物包括但不限于鳞翅目(Lepidoptera)的幼虫,如夜蛾科(Noctuidae)中的粘虫(armyworm)、毛虫(cutworm)、尺蠖(looper)和棉铃虫(heliothine)(例如,秋粘虫(秋叶蛾(Spodoptera fugiperda J.E.Smith))、甜菜夜蛾(beet armyworm,Spodoptera exigua Hübner)、小地虎(小地老虎(Agrotis ipsilonHufnagel))、粉纹夜蛾(cabbage looper,Trichoplusia ni Hübner)、和烟夜蛾(夜蛾(Heliothis virescens Fabricius)));来自螟蛾科(Pyralidae)的螟虫(borer)、鞘蛾(casebearer)、结网虫(webworm)、球果虫(coneworm)、甘蓝虫(cabbageworm)和雕叶虫(skeletonizer)(例如,欧洲玉米螟(Ostrinia nubilalis Hübner)、脐橙螟(Amyeloistransitella Walker)、玉米根结网虫(Crambus caliginosellus Clemens)、和草地螟(水稻切叶野螟(Herpetogramma licarsisalis Walker)));卷蛾科(Tortricidae)中的卷叶虫(leafroller)、卷叶蛾(budworm)、种实虫(seed worm)和果实虫(fruit worm)(例如苹果蠹蛾(codling moth,Cydia pomonella L.(L.意指Linnaeus))、葡萄小食心虫(Endopizaviteana Clemens)、和梨小食心虫(Grapholita molesta Busck));以及许多其他经济上重要的鳞翅目(如小菜蛾(菜蛾科的小菜蛾(Plutella xylostella L.))、棉红铃虫(麦蛾科的棉红铃虫(Pectinophora gossypiella Saunders))、和舞毒蛾(毒蛾科的舞毒蛾(Lymantria dispar L.)));来自鞘翅目(Coleoptera)的食叶幼虫和成虫,包括来自长角象虫科(Anthribidae)、豆象科(Bruchidae)、和象甲科(Curculionidae)的象鼻虫(weevil)(例如,棉铃象鼻虫(墨西哥棉铃象(Anthonomus grandis Boheman))、稻水象虫(水象甲(Lissorhoptrus oryzophilus Kuschel))、和稻米象鼻虫(米象(Sitophilus oryzaeL.)));叶甲科(Chrysomelidae)中的跳甲(flea beetle)、黄守瓜(cucumber beetle)、根虫(rootworm)、叶甲(leaf beetle)、马铃薯甲虫(potato beetle)和潜叶虫(leafminer)(例如,科罗拉多马铃薯甲虫(Leptinotarsa decemlineata Say)、和西方玉米根虫(Diabrotica virgifera LeConte));来自金龟子科(Scaribaeidae)的金龟子和其他甲虫(例如,日本丽金龟(Japanese beetle,Popillia japonica Newman)和欧洲金龟(Europeanchafer,Rhizotrogus majalis Razoumowsky));来自叩头甲科(Elateridae)的金针虫和来自小蠹科(Scolytidae)的小蠹虫;革翅目(Dermaptera)的成虫和幼虫,包括来自蠼螋科(Forficulidae)的蠼螋(earwig)(例如,欧洲蠼螋(Forficula auricularia L.)和黑蠼螋(Chelisoches morio Fabricius));半翅目(Hemiptera)和同翅目(Homoptera)的成虫和若虫,诸如来自盲蝽科(Miridee)的盲蝽(plant bug)、来自蝉科(Cicadidae)的蝉(cicada)、来自大叶蝉科(Cicadellidae)的叶蝉(leafhopper)(例如,小绿叶蝉属(Empoasca)spp.)、来自蜡蝉科(Fulgoroidae)和飞虱科(Delphacidae)的飞虱(planthopper)、来自角蝉科(Membracidae)的角蝉(treehopper)、来自木虱科(Psyllidae)的木虱(psyllid)、来自粉虱科(Aleyrodidae)的粉虱(whiteflies)、来自蚜科(Aphididae)的蚜虫、来自根瘤蚜科(Phylloxeridae)的根瘤蚜(phylloxera)、来自粉蚧科(Pseudococcidae)的粉蚧(mealybug)、来自蚧科(Coccidae)、盾蚧科(Diaspididae)和绵蚧科(Margarodidae)的介壳虫(scale)、来自网蝽科(Tingidae)的网蝽(lace bug)、来自蝽科(Pentatomidae)的蝽象(stink bug)、来自长蝽科(Lygaeidae)的长蝽(cinch bugs)(例如,土长蝽属(Blissus)spp.)和其他来自长蝽科的籽长蝽(seed bug)、来自沫蝉科(Cercopidae)的沫蝉(spittlebug)、来自缘蝽科(Coreidae)的缘蝽(squash bug)以及来自红蝽科(Pyrrhocoridae)的红蝽(red bug)和棉红蝽(cotton stainer);直翅目(Orthoptera)的成虫和未成年虫,包括蚱蜢、蝗虫和蟋蟀(例如,迁徙蚱蜢(例如,迁徙蚱蜢(Melanoplussanguinipes Fabricius)和长额负蝗(M.differentialis Thomas))、美洲蚱蜢(例如,美洲沙漠蝗(Schistocerca americana Drury))、沙漠蝗(沙漠蝗(Schistocerca gregariaForskal))、飞蝗(飞蝗(Locusta migratoria L.))、和蝼蛄(蛄蝼属(Gtyllotalpaspp.)));双翅目(Diptera)的成虫和未成年虫,包括潜叶虫(leafminer)、蠓(midge)、果蝇(实蝇科(Tephritidae))、黄潜蝇(例如,黑麦秆蝇(Oscinella frit L.))、土壤蛆和其他长角亚目;缨翅目(Thysanoptera)成虫和未成年虫,包括洋葱蓟马(Thrips tabaciLindeman)和其他食叶的蓟马。
在某些实施例中,可以通过该组合物防治的有害生物包括但不限于,稻水象虫(lissorhoptrus oryzophilus)、秋粘虫(fall armyworm)、秋叶蛾(spodopterafrugiperda)、甘蔗螟(sugarcane borer)、甘蔗蛀虫(diatrea saccharalis)、三化螟(scirpophaga incertulas)、稻秆螟(chilo polychrysa)、大螟(sesamia inferens)、二点黑尾叶蝉(nephotettix virescens)、黑尾叶蝉(nephotettix nigropictus)、褐飞虱(nilaparvata lugens)、禾蛛缘椿象(leptocarisa acuta)、白背飞虱(sogatellafurcifera)、电光叶蝉(recilla dorsalis)、稻蓟马(thrips oryzae)、黏虫(mythimnaseparata)、贪叶夜蛾(spodoptera mauritia)、水稻铁甲(dicladispa armigera)、稻纵卷叶螟(cnaphalocrisis medinalis)、稻三点水螟(nymphyla depunctalis)、稻苞虫(parnara guttata)和稻瘿蚊(orseolia oryzae)。
用于有效防治所需的施加比率(即“农业上有效量”)将取决于诸如以下的因素:活性成分、操作者、待防治的无脊椎动物物种、有害生物的生命周期、生命阶段、其大小、位置、一年中的时间、宿主作物或动物取食行为、交配行为、作物播种或种植的密度和模式、环境湿度、温度、以及施加该组合物是作为预防性操作还是挽救性操作。在正常情况下,可以在农业生态系统中以从约每公顷10克活性成分(gai/ha)至约10,000gai/ha(例如,约10至约5000gai/ha、约10至约1000gai/ha、约10至约500gai/ha、约10至约200gai/ha、约10至约100gai/ha、约10至约90gai/ha、约10至约80gai/ha、约10至约70gai/ha、约10至约60gai/ha、约10至约50gai/ha、约20至约50gai/ha、约30至约50gai/ha、或约40gai/ha)的比率范围施加该组合物,但低至0.1gai/ha可能足够、或者可能需要多达80,000gai/ha。在某些实施例中,以约40gai/ha的比率施加该组合物。对于非农学应用,有效使用率范围将从约1.0至50毫克/平方米(m2)(例如,约1-40mg/m2、约1-35mg/m2、约1-30mg/m2、约1-25mg/m2、约1-20mg/m2、约1-15mg/m2、约1-10mg/m2、或约1-5mg/m2),但低至0.1mg/m2可能足够、或者可能需要多达150mg/m2。本领域技术人员可以容易地确定用于无脊椎有害生物防治期望水平所必需的农业有效量。
实例
将通过具体实例的方法对本发明进行更详细的描述。以下实例出于说明性目的而提供,且不旨在以任何方式限制本发明。本领域技术人员将容易认识到各种非关键参数,可以改变或修改这些非关键参数以产生大致相同的结果。
实例1。邻氨基苯甲酰胺片剂的筛选
制备
实例中测试的片剂根据以下步骤制备:将所有成分称重并且完全混合,然后进行筛分,以得到70至200目范围的颗粒,再通过60千克牛顿(kN)压片机压平。然后形成由此得到的重量3.0-3.5g且具有约20-22mm直径的片剂。
初步筛选
筛选含有氯虫苯甲酰胺的制剂中使用的增强剂和分散剂前,进行以下初步筛选程序。
酸和碱。在以下方面筛选酸和碱的不同组合:(a)与水接触时生成持续合适时间段的合适量的泡腾的能力以及促进活性成分在当植物生长的水中完全分散的能力,(b)成本,以及(c)工业可加工性(诸如从安全性的角度)。基于筛选,确认优选的酸和碱的组合并将其使用在以下实例中。
润滑剂、粘结剂和填料。筛选不同类的润滑剂、粘结剂和填料。基于筛选,确认优选的润滑剂、粘结剂和填料并将其使用在以下实例中。
增强剂和分散剂筛选
制备不同配方的片剂(包含,例如,增强剂和分散剂二者、仅增强剂、仅分散剂、或不同类型的增强剂和分散剂)并在与水接触时片剂的气泡度和扩散速度方面进行比较。通过视觉检查气泡度,并且使用色素追踪片剂的扩散。将这些配方和结果总结于以下表1中。可以发现,在气泡度和扩散速度方面,配方1-4、配方1-5和配方1-7较其他配方示出更好的性能,其以符号+表示,更多+表示更好的性能。
表1
通过以下方法进一步检查配方1-4、配方1-5、配方1-7和配方1-8的分布概况:(a)提供半径1.2m的一个圆形水池,并且如图1中示出的,在每个采样位置下放置观察镜,其中每两个相邻外围之间的距离是15cm,选择均匀分布在一外围上的4个点(诸如A1、A2、A3和A4)作为采样位置;(b)以约5cm深的自来水填充水池;(c)投掷一枚片剂(3g)至水池中;(d)30分钟后,覆盖观察镜并从水池中取出;(e)通过HPLC分析收集的观察镜中的活性成分(包括溶解和悬浮在水中和沉积在观察镜上的活性成分)的含量;(e)计算收集自4个点的活性成分的平均值。结果在图2中示出。可以发现同时有包含二烷基磺基琥珀酸钠的增强剂和包含聚羧酸盐的分散剂的片剂(即配方1-4、1-5和1-7)与其他配方相比实现了更好的效果。
实例2。新型邻氨基苯甲酰胺片剂
表2
分布概况分析
使用如实例1中描述的相同方法检查表2中的片剂的分布概况。发现表2中的片剂实现了改进的效果。
稳定性测试
贮存14天后,测试表2中的片剂的稳定性。数据在表3中示出。
表3
功效分析(片剂施加后21天)
在4.5叶期将稻幼苗移植到稻田并且生长7天,以使幼苗有可能在杀昆虫剂施加前变绿。将表2中的氯虫苯甲酰胺片剂和可商购的氯虫苯甲酰胺产品和(参考用)分别施加到所选择的大田条件一致的大田。该片剂和均通过撒施法施加,而通过叶面施加法施加。稻移植后第7天通常以40gai/ha的施加率均匀地施加氯虫苯甲酰胺片剂和 通常与水混合,并在二化螟卵孵化初期以30gai/ha的比率通过叶面施加法施加。选择一块对照检查(未做任何处理,“CK”)稻田用作功效参考。该片剂施加后21天,进一步研究该片剂的功效。整个样地调查采取对每块施加样地中因二化螟造成显示枯心的稻幼苗计数,并且通过以下公式计算功效:
功效%=((CK组中的枯心数)-(处理组中的枯心数))/(CK组中的枯心数)*100。
结果在表4中示出。
表4
表4中示出的结果表明以40gai/ha施加的氯虫苯甲酰胺片剂可以有效地防治稻螟虫。1%氯虫苯甲酰胺片剂、2.5%氯虫苯甲酰胺片剂以及5%氯虫苯甲酰胺片剂实现了相似的防治或者甚至实现了与含有相同剂量氯虫苯甲酰胺的颗粒剂和悬浮剂(“SC”,)相比略好的防治,而片剂制剂的施加更为节省劳力。
大田中测试主体中的活性成分氯虫苯甲酰胺的残留
将1%氯虫苯甲酰胺片剂(4g)、2.5%氯虫苯甲酰胺片剂(1.6g)、5%氯虫苯甲酰胺片剂(0.8g)、(计算为0.04gai/25m2,0.4%颗粒剂)、以及(计算为0.04gai/25m2,200g/L SC)施加到5*5m的样地中。在该制剂施加后第3天(3DAA)和第20天(20DAA)对稻幼苗采样。由于二化螟主要攻击稻茎,因此测试稻茎中氯虫苯甲酰胺的残留以证实活性成分的吸收,其可能被二化螟摄取并造成中毒。为了提取活性成分氯虫苯甲酰胺,将稻幼苗砍下并且挑出茎,并将其浸入酸性乙腈中24小时。进一步摇振所得溶液2小时,并且然后过滤以及通过GC-MS分析,以测量被稻幼苗吸收的活性成分氯虫苯甲酰胺的量。
根据GC-MS的测试结果,将稻中氯虫苯甲酰胺的残留量(μg/kg)总结在表5中,并且将其展示在图3中。在制剂施加后第3天和第20天时,施加1%氯虫苯甲酰胺片剂(4g)、2.5%氯虫苯甲酰胺片剂(1.6g)、或5%氯虫苯甲酰胺片剂(0.8g)的幼苗比施加或的那些吸收的活性成分氯虫苯甲酰胺的量更多,表明包含要求保护的增强剂和分散剂的片剂制剂在稻田水中更有效地分散。
表5
如以上描述的对与施加点不同距离处收集的幼苗中的氯虫苯甲酰胺的浓度进行测量,并且将结果总结在表6和表7中,并且在图4中示出。
表6
表7
实例3。更多片剂
制备含有与表2中的片剂相似的成分、但是不同杀有害生物活性成分的数种片剂。那些包含要求保护的增强剂和分散剂的片剂预期能在扩散性和渗透性方面实现与表2中的那些片剂相似的改进的效果。
本发明还可以被广义地表述为包括在本说明书中单独地或共同地提及或指示的部分、要素和特征,以及任何两个或更多个部分、要素、构件或特征的任何或所有组合,并且在本文中提及的具体整数具有已知等效物的情况下,此类等效物被视为如同单独地阐述一样并入本文。
已具体参考本发明某些实施例对本发明进行了描述。将理解,在不脱离本发明的范围的情况下可以对上述实施例进行各种修改。本领域技术人员亦将理解由有目的的构建表示的概念。
Claims (22)
1.一种包含组合物的制剂,该组合物包含:
(a)杀有害生物活性成分;
(b)增强剂,其中该增强剂包括二烷基磺基琥珀酸盐、十二烷基硫酸盐、十二烷基苯磺酸盐、脂肪醇衍生物、烷基萘磺酸盐、或烷基萘硫酸盐、或其混合物;
(c)分散剂,其中该分散剂包括聚羧酸盐、酚磺酸缩合物、聚氧丙烯-聚氧乙烯嵌段共聚物、或萘磺酸缩合物、或其混合物;
(d)粘结剂;以及
(e)任选地填料。
2.一种包含组合物的制剂,该组合物包含基于该组合物的总重量按重量计的以下项:
(a)约0.1%至约20%的杀有害生物活性成分;
(b)约0.1%至约5%的至少一种增强剂,其中该增强剂包括二烷基磺基琥珀酸盐、十二烷基硫酸盐、十二烷基苯磺酸盐、脂肪醇衍生物、烷基萘磺酸盐、或烷基萘硫酸盐、或其混合物;
(c)约0.1%至约10%的至少一种分散剂,其中该分散剂包括聚羧酸盐、酚磺酸缩合物、聚氧丙烯-聚氧乙烯嵌段共聚物、或萘磺酸缩合物、或其混合物;
(d)约0.1%至约20%的至少一种粘结剂;以及
(e)约0.1%至约50%的至少一种填料。
3.一种片剂组合物,其包含根据权利要求1或2所述的制剂。
4.一种片剂组合物,其包含基于该组合物的总重量按重量计的以下项:
(a)约0.1%至约20%的杀有害生物活性成分;
(b)约0.1%至约5%的至少一种增强剂,其中该增强剂包括二烷基磺基琥珀酸盐、十二烷基硫酸盐、十二烷基苯磺酸盐、脂肪醇衍生物、烷基萘磺酸盐、或烷基萘硫酸盐、或其混合物;
(c)约0.1%至约10%的至少一种分散剂,其中该分散剂包括聚羧酸盐、酚磺酸缩合物、聚氧丙烯-聚氧乙烯嵌段共聚物、或萘磺酸缩合物、或其混合物;
(d)约0.1%至约20%的至少一种粘结剂;以及
(e)约0.1%至约50%的至少一种填料。
5.根据权利要求1或2所述的制剂或根据权利要求3-4中任一项所述的片剂组合物,其中,该杀有害生物活性成分是除草剂或杀昆虫剂,或其混合物。
6.根据权利要求1或2所述的制剂或根据权利要求3-4中任一项所述的片剂组合物,其中,该杀有害生物活性成分是二酰胺、新烟碱、或沙蚕毒素类似物杀昆虫剂,或其混合物。
7.根据权利要求1、2、5和6中任一项所述的制剂或根据权利要求3-6中任一项所述的片剂组合物,其中,该组分(a)包含氯虫苯甲酰胺、溴氰虫酰胺、四唑虫酰胺、环溴虫酰胺、氯氟氰虫酰胺、四氯虫酰胺、溴虫苯甲酰胺、双氯虫酰胺、噻虫嗪、噻虫胺、噻虫啉、杀虫单、或杀虫双、或其混合物,任选地,其中该组分(a)包含氯虫苯甲酰胺。
10.根据权利要求1、2和5-9中任一项所述的制剂或根据权利要求3-9中任一项所述的片剂组合物,其中,该组分(d)包含至少一种选自由以下项组成的组的物质:聚乙二醇(PEG)、麦芽糖、海藻糖、山梨醇、麦芽糖醇、聚乙烯基吡咯烷酮、磷酸氢钙、蔗糖、葡萄糖、玉米(玉蜀黍)淀粉、改性纤维素、海藻酸、羧甲基纤维素钠、和共聚维酮,任选地,该组分(d)包含PEG,任选地,该组分(d)包含至少一种选自由PEG2000、PEG4000、PEG6000、PEG8000和PEG10000组成的组的PEG,任选地,该组分(d)包含PEG 6000。
11.根据权利要求1、2和5-10中任一项所述的制剂或根据权利要求3-10中任一项所述的片剂组合物,其中,该组分(e)包含至少一种选自由以下项组成的组的物质:乳糖、乳糖一水合物、甘露醇、蔗糖、滑石、麦芽糊精、糊精、麦芽糖醇、山梨醇、木糖醇、粉末状纤维素、纤维素胶、微晶纤维素、淀粉、和磷酸钙;任选地,该组分(e)包含滑石或麦芽糊精,或其混合物;任选地,该组分(e)包含滑石和麦芽糊精的混合物,任选地,其中该滑石当使用时是按重量计该组合物的约1%至约15%、约1%至约10%、约1%至约8%、约2%至约8%、约3%至约8%、约4%至约8%、约5%至约8%、约6%至约8%、或约6%,并且该麦芽糊精当使用时是按重量计该组合物的约1%至约40%、约1%至约30%、约5%至约30%、约8%至约30%、约10%至约30%、约15%至约30%、约18%至约30%、约18%至约27%、或约20%至约27%。
12.根据权利要求1、2和5-11中任一项所述的制剂或根据权利要求3-11中任一项所述的片剂组合物,该制剂或该组合物进一步包含基于该组合物的总重量按重量计的以下项:组分(f)约0.1%至约40%的至少一种酸和组分(g)约0.1%至约40%的至少一种碱。
13.根据权利要求1、2和5-12中任一项所述的制剂或根据权利要求3-12中任一项所述的片剂组合物,其中,该组合物进一步包含基于该组合物的总重量按重量计的以下项:组分(h)约0.1%至约5%的至少一种润滑剂。
14.根据权利要求1、2和5-13中任一项所述的制剂或根据权利要求3-13中任一项所述的片剂组合物,其中,该组合物进一步包含基于该组合物的总重量按重量计的以下项:组分(i)约0.01%至约5%的至少一种苦味剂。
20.一种用于防治作物中有害生物的方法,该方法包括将农业上有效量的根据权利要求1、2和5-14中任一项所述的制剂或根据权利要求3-19中任一项所述的片剂组合物施加到有需要的作物或其环境。
21.根据权利要求20所述的方法,其中,该作物是稻并且将该制剂或该组合物施加到稻田。
22.根据权利要求20所述的方法,其中,该作物选自由稻、蔬菜和玉米组成的组,任选地,该作物是稻。
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