CN101415326A - 含有拟除虫菊酯的含水微乳液 - Google Patents
含有拟除虫菊酯的含水微乳液 Download PDFInfo
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- CN101415326A CN101415326A CNA200780012396XA CN200780012396A CN101415326A CN 101415326 A CN101415326 A CN 101415326A CN A200780012396X A CNA200780012396X A CN A200780012396XA CN 200780012396 A CN200780012396 A CN 200780012396A CN 101415326 A CN101415326 A CN 101415326A
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- alkylidene
- polyoxy
- alkyl
- surfactant
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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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pretreatment Of Seeds And Plants (AREA)
Abstract
本发明涉及含有有限水溶性的有机农药化合物的新的含水微乳液及其在植物保护,包括种子和作物保护以及非活体材料保护中的用途。该含水微乳液包含:a)至少一种拟除虫菊酯化合物P;b)至少一种选自式I化合物的有机溶剂:R1-(O-Alk)m-O-C(O)R2 (I),其中m为1、2或3,R1为H、C1-C6烷基或C(O)R3,R2为氢或C1-C4烷基,其可为未取代的或由OH取代,Alk为C2-C6亚烷基,和R3为氢或C1-C4烷基,其可为未取代的或由OH取代;c)至少一种表面活性剂;和d)水。
Description
本发明涉及含有一种或多种拟除虫菊酯(pyrethroid)化合物的新的含水微乳液及其在植物保护,包括种子和作物保护以及非活体材料保护中的用途。
背景技术
农药化合物经常以稀释的含水组合物的形式施用,以达到与目标生物体如植物、真菌和昆虫的良好相互作用。然而,用作农药的绝大部分活性成分,尤其是拟除虫菊酯化合物仅微溶或甚至不溶于水,即它们在25℃/1013毫巴下通常具有不超过5g/l,经常不超过1g/l,尤其是不超过0.1g/l的水溶性。为此,配方设计师经常面临难以将农药化合物配制为可容易地用水稀释的稳定配制剂。
通常将在水中溶解度有限的农药配制为可用水稀释的用于本领域的含水悬浮液浓缩物(SC)。悬浮液浓缩物为如下配制剂,其中活性成分以细碎的固体颗粒形式存在,所述活性成分使用表面活性化合物(表面活性剂)如润湿剂、分散剂和用于使活性成分颗粒在分散介质中稳定的流变助剂或悬浮助剂而悬浮在含水分散介质中。然而,经常遇到SC由于在延长储存或在升高的温度下储存过程中沉降,沉降的颗粒抵抗重新悬浮和在储存时形成晶体材料的问题。因此,配制剂难以处理且生物效力可能是不一致的。此外,SC受限于具有较高熔点的活性物质。SC通常不适合于配制拟除虫菊酯化合物。
配制微溶于水的活性成分的替代方案为所谓的可乳化的浓缩物(EC)。在EC中,活性成分与表面活性剂一起溶于水溶混性溶剂(溶解度通常<0.1g/l)如烃类溶剂,尤其是芳烃。EC通常是可用水稀释以形成乳白色水包油(o/w)乳液的稳定溶液,其所含的活性成分呈分散相的液滴。EC配制剂具有很大缺陷,因为它们通常含有很大量在生态和毒物学性能上完全不令人满意的烃类有机溶剂。因为用水稀释时形成的水包油乳液的液滴,活性成分的生物效力有时是不令人满意的。此外,在用水稀释时可能出现活性成分的分离,这可能导致剂量不准确和生物效力不均匀。
EC-配制剂的部分不足可通过微乳液(ME)配制技术克服。类似于也称作粗滴乳液的常规乳液,微乳液为包含分散相和连续相的多相体系。与粗滴乳液相反,微乳液中分散相的平均粒(液滴)度(Z均直径,通过光散射测定)至少比粗滴乳液中分散相的平均粒度小5倍且通常不超过200nm,而粗滴乳液中液滴的平均直径为μm范围。由于分散相的粒度(液滴尺寸)小,微乳液具有半透明外观。
农药化合物的ME配制剂通常基于水且额外含有至少一种表面活性剂和至少一种助溶剂或助表面活性剂,其通常为有机溶剂或低分子量的聚亚烷基醚。因为水为主要组分,与EC技术相比,通过使用ME配制剂,可降低诸如易燃性和毒性、环境影响和成本的风险。由于含有活性成分的分散相的粒度小,通常可实现生物利用率的增加。然而,难以维持水溶性低的活性成分的ME配制剂在液滴尺寸和均匀性方面的稳定性且可能发生活性成分的结晶。此外,当ME配制剂用水稀释时,还难以维持液滴尺寸的稳定性。这源于活性成分在水中的低溶解度。然而,为实现优选的生物活性,稀释后稳定的液滴尺寸,即维持小的液滴尺寸是重要的。为此,进行了很多努力以开发稳定的基于水的微乳液配制剂。
WO 88/07326和WO 90/03112描述了含有杀虫剂化合物的微乳液。配制剂含有很大量的烃类溶剂、表面活性剂和作为助表面活性剂的低HLB的低分子(氧化乙烯/氧化丙烯)嵌段共聚物。
JP 3299812描述了含有芳族溶剂和任选酮如环己酮和脂肪酸酯如油酸甲酯作为助溶剂的除草ME配制剂。
WO 98/00010公开了含有烃类溶剂和选自C3-C12链烷醇和醚链烷醇如二甘醇单己基醚、二甘醇单丁基醚和丙二醇单丁基醚的助溶剂的杀虫剂化合物微乳液。
U.S.5317042描述了拟除虫菊酯杀虫剂的含水ME,其含有C1-C4烷基吡咯烷酮作为助溶剂。
通过使用亲油性烃类溶剂如甲苯、二甲苯或烃类混合物如Solvesso、Exxsol、Shellsol等,可获得稳定配制剂,所述配制剂显示活性成分的结晶倾向降低。然而,这些溶剂导致皮肤敏化增加。用较小毒性的极性溶剂如N-烷基吡咯烷酮、C1-C3链烷醇、酮、乙二醇、丙二醇、二C2-C3亚烷基二醇等替换这些溶剂,导致稀释稳定性降低,这源于在稀释条件下活性成分在溶剂中的溶解度降低。上述问题在拟除虫菊酯化合物的情况下尤其明显。
为此,现在需要均匀稳定的拟除虫菊酯化合物的ME配制剂。配制剂在用水稀释时尤其应该是稳定的,即用水稀释后它们应提供小液滴的稳定尺寸分布。此外,尤其是在用水稀释配制剂后,它们应使活性成分的结晶倾向降低。此外,在低温下,即在低于0℃的温度下,ME配制剂应维持其液态。非常希望不使用烃类溶剂而实现这些目的,以增加生态相容性,降低皮肤刺激性的风险。尤其需要提供拟除虫菊酯类酯(pyrethroid ester),尤其是具有双苯基醚结构部分的拟除虫菊酯类酯,特别是氟氰菊酯(flucythrinate)或α-氯氰菊酯(alpha-cypermethrin)或其混合物的稳定配制剂的ME配制剂。
发明概述
令人惊讶的是,该目的可通过提供含有本文所定义的式I有机溶剂和包含至少一种阴离子表面活性剂和至少一种非离子表面活性剂的表面活性剂混合物的微乳液配制剂而实现。
为此,本发明涉及呈含水微乳液形式的拟除虫菊酯化合物P的配制剂,其中配制剂包含:
a)至少拟除虫菊酯化合物P;
b)至少一种选自式I化合物的有机溶剂:
R1-(O-Alk)m-O-C(O)R2 (I)
其中m为1、2或3,
R1为H、C1-C6烷基或C(O)R3,
R2为氢或C1-C4烷基,其可为未取代的或由OH取代,
Alk为直链或支化C2-C6亚烷基,和
R3为氢或C1-C4烷基,其可为未取代的或由OH取代;
c)包含如下物质的表面活性剂混合物:
c.1:至少一种阴离子表面活性剂,和
c.2:至少一种非离子表面活性剂,
和
d)水。
本发明微乳液为清澈稳定的稳定液体配制剂,在储存时不形成固体。此外,它们在低于0℃的温度下仍为液体,而不失去其有益性能。其凝固点通常低于-5℃。
本发明的ME配制剂可容易地用水稀释而不形成粗料且含水稀释液具有增强的物理稳定性,即甚至在延长的储存时间之后也没有观察到稀释后固体形成,例如在室温下24小时之后也没有观察到结晶。在用水稀释时,本发明组合物形成浅蓝色或甚至清澈的乳液,说明分散其中的液滴/颗粒具有非常小的尺寸。液滴/颗粒的平均粒径通常不超过200nm,尤其是100nm,更尤其是50nm且可为10nm或甚至小于10nm。小的颗粒/尺寸甚至在延长的储存时间之后也维持,例如在室温下储存24小时之后粒度的增加通常小于10%。此处所指的平均粒度为可通过动态光散射测定的Z均粒径。熟练技术人员熟悉例如描述在如下文献的这些方法:H.Wiese(D.Distler,编辑),Aqueous Polymer Dispersions(聚合物水分散体),Wiley-VCH 1999,第4.2.1章,第40页及随后各页,以及其中引用的文献;H.Auweter,D.Horn,J.Colloid Interf.Sci.105(1985),第399页;D.Lilge,D.Horn,Colloid Polym.Sci.269(1991),第704页;和H.Wiese,D.Horn,J.Chem.Phys.94(1991),第6429页。与常规配制剂相比,由于用水稀释后的小的粒度,活性成分的生物利用率和因此的生物活性常常增加。此外,实现本发明微乳液的有益性能不需要烃类溶剂。因此,配制剂的生态相容性优良且可降低皮肤刺激性的风险。
本发明的微乳液通常为水包油乳液,即水形成连续相,而溶剂和拟除虫菊酯化合物P存在于分散相。它们例如可通过使成分简单混合,通过将水加入溶液或将溶液加入水而混合预形成的拟除虫菊酯化合物P在式II溶剂中的溶液而获得。
本发明的ME配制剂尤其提供拟除虫菊酯化合物,尤其是拟除虫菊酯类酯,更优选具有双苯基醚结构部分的拟除虫菊酯类酯,特别是氟氰菊酯或α-氯氰菊酯或其混合物的稳定的配制剂。
发明详述
本文使用的术语烷基指具有前缀中给出的碳原子数的饱和的直链或支化烃基。因此,C1-C6烷基指具有1-4、5或6个碳原子,特别是1-4个碳原子(C1-C4烷基)的饱和直链或支化烃基如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基和1-乙基-2-甲基丙基。
本文使用的术语C2-C6亚烷基指具有2、3、4、5或6个碳基的饱和二价直链或支化烃链,其中实例包括乙烷-1,2-二基、丙烷-1,3-二基、丙烷-1,2-二基、2-甲基丙烷-1,2-二基、2,2-二甲基丙烷-1,3-二基、丁烷-1,4-二基、丁烷-1,3-二基(=1-甲基丙烷-1,3-二基)、丁烷-1,2-二基、丁烷-2,3-二基、2-甲基-丁烷-1,3-二基、3-甲基-丁烷-1,3-二基(=1,1-二甲基丙烷-1,3-二基)、戊烷-1,4-二基、戊烷-1,5-二基、戊烷-2,5-二基、2-甲基戊烷-2,5-二基(=1,1-二甲基丁烷-1,3-二基)和己烷-1,6-二基。
本文使用的术语芳基指苯基或萘基。
本发明微乳液含有至少一种上述式I的溶剂。在式I的溶剂中优选其中相互独立,优选组合的变量具有下述意义的那些:
m 为1或2,尤其是1,
R1 为C1-C6烷基或C(O)R3,尤其是甲基或乙基,
R2 为C1-C4烷基,尤其是甲基,
Alk 为C3-C6亚烷基,尤其是丙烷-1,3-二基、丁烷-1,3-二基、丁烷-1,4-二基,以及3-甲基-丁烷-1,3-二基,或如果R1为C3-C6烷基或C(O)R3,则Alk还可为乙烷-1,2-二基。
R3 为C1-C4烷基,尤其是甲基。
优选溶剂的实例包括乙酸3-甲氧基-3-甲基丁基酯、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、二丙二醇甲醚乙酸酯、丙二醇二乙酸酯、乙二醇单丁醚乙酸酯、二甘醇单丁醚乙酸酯及其混合物。特别优选乙酸3-甲氧基-3-甲基丁基酯、丙二醇单甲醚乙酸酯和丙二醇单乙醚乙酸酯。
本发明微乳液配制剂中溶剂的量通常取决于拟除虫菊酯化合物P的量。通常而言,式I有机溶剂与拟除虫菊酯化合物P的重量比例为0.5:1-100:1,优选1:1-50:1,尤其是1.5:1-30:1。溶剂的总量基于配制剂的总重量通常为0.1-30重量%,尤其是1-25重量%,更优选5-20重量%。
本发明的微乳液配制剂还含有包含至少一种阴离子表面活性剂和至少一种非离子表面活性剂的表面活性剂混合物。术语“表面活性剂”指表面活性化合物,其在下文中也称作洗涤剂或乳化剂。表面活性剂混合物用于减小连续相和分散相之间的表面张力,从而稳定分散相的液滴。表面活性剂还有助于增溶拟除虫菊酯化合物P。用于微乳液配制剂的合适表面活性剂在本领域内是众所周知的,例如从McCutcheon’s Detergents andEmulsifiers,Int.Ed.,Ridgewood,New York已知。表面活性剂可为聚合物表面活性剂或非聚合物表面活性剂。优选主要用量,优选至少90%,尤其是全部用量的存在于微乳液中的表面活性剂选自非聚合物表面活性剂,也称作乳化剂。相对于聚合物表面活性剂,非聚合物表面活性剂(乳化剂)的分子量通常低于2000道尔顿(数均),尤其是150-2000道尔顿,优选200-1500道尔顿。
阴离子表面活性剂尤其包括如下物质的钠盐、钾盐、钙盐或铵盐:
- C6-C22烷基磺酸盐如月桂基磺酸盐、异十三烷基磺酸盐;
- C6-C22烷基硫酸盐如月桂基硫酸盐、异十三烷基硫酸盐、鲸蜡基硫酸盐和硬脂酰基硫酸盐;
- 芳基-和磺酸盐,尤其是C1-C16烷基苯磺酸盐,例如枯基磺酸盐、辛基苯磺酸盐、壬基苯磺酸盐,以及十二烷基苯磺酸盐、萘基磺酸盐、单-和二C1-C16烷基萘磺酸盐如二丁基萘磺酸盐;
- 单-和二C1-C16烷基二苯基醚(二)磺酸盐如十二烷基二苯基醚二磺酸盐;
- 脂肪酸和脂肪酸酯的硫酸盐和磺酸盐;
- 聚氧-C2-C3亚烷基C8-C22烷基醚硫酸盐,尤其是乙氧基化C8-C22链烷醇的硫酸盐如乙氧基化月桂醇的硫酸盐;
- 聚氧-C2-C3亚烷基C1-C16烷基苯醚硫酸盐,尤其是乙氧基化C1-C16烷基苯酚的硫酸盐;
- 磺基琥珀酸的二C4-C18烷基酯(=磺基琥珀酸C4-C18-二烷基酯)如二辛基磺基琥珀酸酯;
- 萘磺酸、C1-C16烷基萘磺酸或苯酚磺酸与甲醛的缩合物(=(C1-C16烷基)萘磺酸盐-甲醛缩合物和苯酚磺酸盐甲醛缩合物);
- 聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯基醚硫酸盐,尤其是单-、二-或三苯乙烯基苯酚的聚乙氧基化物;
- 单-和二C8-C22-烷基硫酸盐;
- 聚氧-C2-C3亚烷基C8-C22烷基醚磷酸盐;
- 聚氧-C2-C3亚烷基C1-C16烷基苯醚磷酸盐;
- 聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯基醚磷酸盐;
- 聚氧亚乙基聚羧酸盐,尤其是具有3-8个碳原子的单烯属不饱和一元或二元羧酸的均聚物和共聚物,其中共聚物还具有聚氧化乙烯侧链;
脂肪酸盐如硬脂酸盐;和
多磷酸盐如六偏磷酸盐和三磷酸盐(=三聚磷酸盐)。
非离子表面活性剂尤其包括:
- 聚氧-C2-C3亚烷基C8-C22烷基醚,尤其是线性或支化C8-C22链烷醇的聚乙氧基化物和聚-乙氧基化物-丙氧基化物,更优选聚乙氧基化脂肪醇和聚乙氧基化羰基合成醇,如聚乙氧基化月桂醇、聚乙氧基化异十三烷醇、聚乙氧基化鲸蜡醇、聚乙氧基化硬脂醇及其酯,如乙酸酯;
- 聚氧-C2-C3亚烷基芳基醚和聚氧-C2-C3亚烷基C1-C16烷基芳基醚,如聚氧-C2-C3亚烷基C8-C22烷基苯醚,尤其是C1-C16烷基苯酚的聚乙氧基化物,如壬基酚、癸基酚、异癸基酚、十二烷基酚或异十三烷基酚的聚乙氧基化物,
- 聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯醚,尤其是单-、二-和三苯乙烯基苯酚的聚乙氧基化物;及其甲醛缩合物及其酯,例如乙酸酯;
- C6-C22烷基葡糖苷和C6-C22烷基聚葡糖苷;
- C6-C22烷基葡糖苷的聚乙氧基化物和C6-C22烷基聚葡糖苷的聚乙氧基化物;
- 脂肪胺的聚乙氧基化物;
- 脂肪酸的聚乙氧基化物和羟基脂肪酸的聚乙氧基化物;
- 多元醇与C6-C22-链烷酸的偏酯,尤其是甘油的单-和二酯和失水山梨糖醇的单-、二-和三酯,如甘油单硬脂酸酯、失水山梨糖醇单油酸酯、失水山梨糖醇三硬脂酸酯;
- 多元醇与C6-C22链烷酸的偏酯的聚乙氧基化物,尤其是甘油的单-和二酯的聚乙氧基化物和失水山梨糖醇的单-、二-和三酯的聚乙氧基化物,如甘油单硬脂酸酯的聚乙氧基化物,失水山梨糖醇单油酸酯的聚乙氧基化物,失水山梨糖醇单硬脂酸酯的聚乙氧基化物和失水山梨糖醇三硬脂酸酯的聚乙氧基化物;
- 植物油或动物脂肪的聚乙氧基化物,如玉米油乙氧基化物,蓖麻油乙氧基化物,牛油乙氧基化物;
- 炔二醇如2,4,7,9-四甲基-4,7-双(羟基)-5-癸炔;
- 聚氧乙烯-聚氧丙烯嵌段共聚物;和
- 脂肪胺、脂肪酰胺或脂肪酸二乙醇酰胺的聚乙氧基化物。
术语聚氧-C2-C3亚烷基醚指源自氧化乙烯或氧化丙烯的聚醚基团。术语聚乙氧基化物指源自氧化乙烯的聚醚基团。同样,术语聚氧化乙烯-聚氧化丙烯指源自氧化乙烯和氧化丙烯的混合物的聚醚基团。聚醚基团中重复单元的数目通常在2-100,常常在4-100,尤其是在5-50中变化。
如果表面活性剂存在的话,优选其基于存在的表面活性剂的总量包含至少50重量%如下表面活性剂混合物,其中所述混合物包含至少一种非离子表面活性剂和至少一种阴离子表面活性剂。表面活性剂混合物基于存在于配制剂中的表面活性剂的总量尤其占至少80重量%,尤其是至少90重量%。更优选表面活性剂仅选自所述至少一种阴离子表面活性剂和所述至少一种非离子表面活性剂的混合物。
优选的阴离子表面活性剂选自上述物质中的下列物质:
- C1-C16烷基苯磺酸盐;
- C1-C16烷基萘磺酸盐;
- 萘磺酸盐-甲醛缩合物和C1-C16烷基萘磺酸盐-甲醛缩合物;
- 聚氧-C2-C3亚烷基C8-C22烷基醚硫酸盐;
- 聚氧-C2-C3亚烷基C8-C22烷基醚磷酸盐;
- 聚氧-C2-C3亚烷基C1-C16烷基苯醚硫酸盐;
- 聚氧-C2-C3亚烷基C1-C16烷基苯醚磷酸盐,
- C8-C22烷基硫酸盐,
- 磺基琥珀酸C4-C18二烷基酯,
- 聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯醚硫酸盐,
- 聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯醚磷酸盐,
- 聚氧化乙烯聚羧酸盐,和
- 聚磷酸盐及其混合物。
特别优选的阴离子表面活性剂包括C8-C22烷基硫酸盐、C1-C16烷基萘磺酸盐、C1-C16烷基苯磺酸盐,尤其是C1-C16烷基苯磺酸盐,尤其是钠盐、钾盐和钙盐。
优选的非离子表面活性剂选自上述物质中的如下物质:
- 聚氧-C2-C3亚烷基C8-C22烷基醚,
- 聚氧-C2-C3亚烷基C8-C22烷基苯醚,
- 聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯醚,
- 聚氧-C2-C3亚烷基单-或二苯乙烯基苯醚-甲醛缩合物,
- 炔二醇及其混合物。
特别优选的非离子表面活性剂包括聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯醚和聚氧-C2-C3亚烷基单-或二苯乙烯基苯醚-甲醛缩合物及其混合物。
在本发明的优选实施方案中,存在于微乳液中的表面活性剂选自包含如下物质的混合物:
(i)至少一种阴离子表面活性剂,尤其是至少一种如一种或两种优选的阴离子表面活性剂,和
(ii)至少一种非离子表面活性剂,尤其是至少一种如一种、两种或三种优选的非离子表面活性剂。
在本发明非常优选的实施方案中,存在于微乳液中的表面活性剂选自包含如下物质的混合物:
(i)至少一种选自C1-C16烷基苯磺酸盐的阴离子表面活性剂,和
(ii)至少一种选自聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯醚和聚氧-C2-C3亚烷基单-或二苯乙烯基苯醚-甲醛缩合物的非离子表面活性剂。
表面活性剂混合物中阴离子和非离子表面活性剂的重量比例优选为0.1:1-10:1,尤其是2:1-1:5。
本发明微乳液配制剂中表面活性剂的量通常取决于拟除虫菊酯化合物P和溶剂的量。表面活性剂与溶剂I和拟除虫菊酯化合物P的总量的重量比例通常为0.1:1-10:1,优选5:1-1:5,尤其是2:1-1:2。通常而言,表面活性剂以基于结晶前溶液的总重量为1-30重量%,尤其是基于微乳液的总重量为5-20重量%的量存在。
本发明微乳液配制剂中溶剂和表面活性剂的总量通常取决于拟除虫菊酯化合物P的量。通常而言,式I有机溶剂和表面活性剂与拟除虫菊酯化合物P的重量比例为200:1-1:1,优选100:1-1.5:1,尤其是50:1-2:1。溶剂+表面活性剂的总量基于配制剂的总重量通常为1.1-60重量%,尤其是6-50重量%,更优选10-40重量%。
本发明微乳液还包含至少一种拟除虫菊酯化合物P。通常而言,拟除虫菊酯化合物微溶或不溶于水。通常而言,在25℃和1013毫巴下溶解度低于5g/l,绝大部分低于1g/l,常常低于0.5g/l,尤其是低于0.1g/l。通常而言,拟除虫菊酯化合物P可溶于有机溶剂I,即在25℃下化合物P在式I中的溶解度为至少10g/l,更优选至少50g/l,特别优选至少100g/l。
拟除虫菊酯化合物P的量基于微乳液的总重量通常为0.0001-20重量%,常常为0.01-10重量%,尤其是0.1-8重量%,更优选0.5-5重量%。
术语“拟除虫菊酯化合物P”包括天然和合成的拟除虫菊酯,包括拟除虫菊酯醚和拟除虫菊酯类酯,以及合成的拟除虫菊酯类似物如1,4-二芳基-1-(环丙基或异丙基)-2-氟-2-丁烯。拟除虫菊酯化合物的实例包括拟除虫菊酯类酯如氟酯菊酯(acrinathrin)、丙烯除虫菊(allethrin)、熏虫菊(barthrin)、氟氯菊酯(bifenthrin)、反丙烯除虫菊(bioallethrin)、bioethanomethrin、生物氯菊酯(biopermethrin)、右旋反灭虫菊酯(bioresmethrin)、右旋反灭虫菊酯(cismethrin)、环虫菊(cyclethrin)、乙氰菊酯(cycloprothrin)、氟氯氰菊酯(cyfluthrin)、β-氟氯氰菊酯(beta-cyfluthrin)、(RS)氯氟氰菊酯(cyhalothrin)、γ-氯氟氰菊酯、λ-氯氟氰菊酯、氯氰菊酯(cypermethrin)、α-氯氰菊酯(alpha-cypermethrin)、β-氯氰菊酯(beta-cypermethrin)、θ-氯氰菊酯(theta-cypermethrin)、ζ-氯氰菊酯(zeta-cypermethrin)、苯醚氰菊酯(cyphenothrin)、溴氰菊酯(deltamethrin)、四氟甲醚菊酯(dimefluthrin)、苄菊酯(dimethrin)、烯炔菊酯(empenthrin)、高氰戊菊酯(esfenvalerate)、五氟苯菊酯(fenfluthrin)、吡氯氰菊酯(fenpirithrin)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、氟氰菊酯(flucythrinate)、氟胺氰菊酯(fluvalinate)、flurethrin、咪炔菊酯(imiprothrin)、metofluthrin、氯菊酯(permethrin)、苯醚菊酯(phenothrin)、炔酮菊酯(prallethrin)、profluthrin、反灭虫菊(pyresmethrin)、除虫菊酯I和II(pyrethrin I和II)、灭虫菊(resmethrin)、氟胺氰菊酯(Tau-Fluvalinate)、七氟菊酯(Tefluthrin)、环戊烯丙菊酯(terallethrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)和四氟菊酯(transfluthrin),拟除虫菊酯醚如醚菊酯(etofenprox)、氟丙苄醚(flufenprox)、卤醚菊酯(halfenprox)、protrifenbute和灭虫硅醚(silafluofen),以及结构相当的化合物如1-[1-(对氯苯基)-2-氟-4-(4-氟-3-苯氧基苯基)-2-丁烯基]-环丙烷(R,S)-(Z)及其混合物。
优选的拟除虫菊酯化合物包含双苯基醚结构部分,其中苯环可带有一个或多个,例如1、2或3个选自氟或甲基的取代基。优选的本发明拟除虫菊酯化合物为拟除虫菊酯类酯。这些化合物可通过通式P’描述:
其中
A为可带有1、2或3个选自甲基和氯的取代基的2-甲基丙烷-1,1-二基、环丙烷-1,1-二基、环丙烷-1,2-二基;
B为甲基、1,2,2,2-四溴乙基、可带有1或2个基团Rb的苯基,可带有1或2个基团Rb的苯基氨基,
其中Rb选自氯、氟、三氟甲基、二氟甲氧基、甲氧基和乙氧基,
或B为基团CRx=CRyRz,其中Rx为氢或卤素,尤其是氯或溴,Ry、Rz各自独立地选自氟、氯、溴、甲基,C1-C3烷氧羰基,如甲氧羰基、乙氧羰基或丙氧羰基和C1-C3-卤代烷氧羰基,如二氟甲氧羰基、三氟甲氧羰基、2,2,2-三氟乙氧羰基、1,1,1,3,3,3-六氟丙烷-2-基,或Ry、Rz一起为C3-C5亚烷基,如1,3-丙烷二基、1,4-丁烷二基或1,5-戊烷二基;
R氢或氰基,和
Cy为选自苯基和呋喃基的环状基团,其未被取代或带有选自甲基、氟、甲氧基甲基、苯基、苄基和苯氧基的基团,和/或1、2、3或4个选自甲基和氟的基团和/或2个与苯基的相邻碳原子相连接以形成结构部分OCH2O的基团;
或Cy为咪唑烷-2,5-二酮-1-基,其可在3位带有选自丙烯-3-基和丙炔-3-基、六氢异吲哚-1,3-二酮-2-基或C2-C6链烯基的基团;或
R和Cy与连接它们的碳原子一起形成2,3-环戊烯-1-酮-4-基基团,其可在4位带有选自丙烯-3-基、丙炔-3-基、2-呋喃基甲基的基团。
优选Cy为4-苯氧基苯基,其中苯环可带有选自甲基、氟或氯的基团。R优选为氰基。
拟除虫菊酯化合物P尤其为微乳液中仅有的农药化合物P或占微乳液中农药化合物总量的至少90重量%。在特别优选的实施方案中,拟除虫菊酯化合物P选自α-氯氰菊酯和氟氰菊酯。
本发明微乳液还含有水。水的量为至少40重量%,尤其是至少50重量%,更优选至少60重量%。不言而喻的是,水与所给出的其它成分的量一共为100重量%。
本发明微乳液可进一步含有常规助剂,如消泡剂、增稠剂、防腐剂、着色剂、稳定剂、防冻剂和常用于农药含水配制剂中的类似物。这些助剂的总量通常将不超过微乳液的15重量%,尤其是10重量%。除了防冻剂之外,这些助剂的总量通常将不超过微乳液的5重量%,尤其是3重量%。
合适的增稠剂包括无机增稠剂如粘土、水合硅酸镁和有机增稠剂如多糖胶如黄原胶、瓜尔豆胶、阿拉伯胶和纤维素衍生物。有机增稠剂以0.5-30g/l,优选1-10g/l的量使用,而无机增稠剂以0.5-30g/l,优选1-10g/l微乳液组合物的量使用。
防止本发明组合物中微生物破坏的合适防腐剂包括甲醛,对羟基苯甲酸的烷基酯,苯甲酸钠,2-溴-2-硝基丙烷-1,3-二醇,邻苯基苯酚,噻唑啉酮如苯并异噻唑啉酮、5-氯-2-甲基-4-异噻唑啉酮、五氯苯酚、2,4-二氯苯甲醇及其混合物。通常而言,防腐剂的量为0.1-10g/l微乳液组合物。
合适的消泡剂包括聚硅氧烷,如聚二甲基硅氧烷。消泡剂通常以0.1-5g/l微乳液组合物的量使用。
合适的稳定剂例如包括UV-吸收剂如肉桂酯、3,3-二苯基-2-氰基丙烯酸酯、羟基和/或烷氧基取代的二苯甲酮、N-(羟基苯基)-苯并三唑、羟基苯基-均三嗪、草酰胺和水杨酸酯,例如 3000、3008、3040、3048、3049、3050、3030、3035、3039、3088、 MC80和自由基捕捉剂如抗坏血酸,空间位阻胺(HALS-化合物)如4049H、4050H和5050H等和抗氧化剂如维生素E。稳定剂的量通常为0.01-10g/l微乳液组合物。
合适的防冻剂包括C1-C4-链烷醇和C2-C4烷基多元醇如乙醇、丙醇、乙二醇、丙二醇等。若存在的话,防冻剂的量为1-100g/l,尤其是1-50g/l微乳液。
这些常规助剂可含在本发明组合物中。然而,还可将用水稀释后的这些助剂加入即用含水组合物中。
本发明微乳液可通过将成分混合至形成外观均匀的液体而简单制备。加入成分的顺序不太重要。例如可将成分加入容器并例如通过搅拌使如此获得的混合物均化,直至形成外观均匀的液体。然而,还可将拟除虫菊酯化合物P溶解在式I的有机溶剂中或所述溶剂和表面活性剂的混合物中,并例如通过将溶液加入水中或通过将水加入溶液而使如此获得的溶液与水和剩余成分混合。混合温度和混合条件并不重要。成分通常在10-90℃,尤其是10-60℃的温度下混合。较高温度如35℃或40℃或更高可用于加快形成微乳液。然而,混合还可在较低温度如10℃至35℃或40℃下实现。
取决于拟除虫菊酯化合物P的类型,本发明微乳液用于对抗植物栽培和种子及非活体材料和家中的大量害虫。
此处所用的术语“害虫”涉及拟除虫菊酯可对抗或防治的所有类型害虫,包括昆虫害虫和蜘蛛害虫。
因此,本发明还涉及:
- 本文所述的微乳液在对抗害虫中的用途;和
- 对抗有害生物体的方法,其包括使所述有害生物体,其栖息地,繁殖地,食物供应源,有害生物体正在生长或将要生长的植物、种子、土壤、区域、材料或环境,或需要防止有害生物体侵袭或侵染的材料、植物、种子、土壤、表面或空间与有效量的本文所述的微乳液接触。
在本发明的第一方面,本文所述微乳液用于植物保护,包括种子处理,尤其是用于保护作物防止害虫侵袭或侵染,即用于对抗损害植物的动物生物体或用于保护作物防止这类有害生物体侵袭或侵染。本发明尤其涉及微乳液在植物保护中的用途,尤其是涉及一种对抗损害植物的害虫如昆虫、蜘蛛或线虫,尤其是昆虫和蜘蛛的方法,该方法包括使有效量的本文所述含水微乳液接触所述有害生物体,其栖息地,繁殖地,食物供应源,有害生物体正在生长或将要生长的植物、种子、土壤、区域、材料或环境,或需防止有害生物体侵袭或侵染的材料、植物、种子、土壤、表面或空间。本发明还涉及一种保护作物防止有害生物体如杂草、真菌、昆虫、蜘蛛或线虫侵袭或侵染的方法,其包括使有效量的本文所述含水微乳液接触作物。
在绝大多数情况下,微乳液在施加至待处理场所之前用水稀释。本发明微乳液通常每一份微乳液用至少1份水,优选至少10份水,尤其是至少100份水,例如用1-10,000,尤其是100-5,000,更优选500-2,000份水稀释(所有份数以重量份列出)。
稀释通常通过将本发明微乳液注入水中而实现。通常而言,稀释用搅动如搅拌实现,以确保浓缩物在水中快速混合。然而,搅动不是必需的。尽管混合温度并不关键,混合通常在0-50℃,尤其是10-30℃的温度下或在环境温度下进行。
用于混合的水通常为自来水。然而,水还可含有用于植物保护的水溶性化合物如营养品,肥料或水溶性农药。
稀释后的本发明微乳液通过本领域熟练技术人员熟悉的常用工具而施加。
本发明微乳液例如针对如下害虫而施用:
如下目的昆虫害虫:
千足虫(倍足亚纲(Diplopoda))如Blaniulus属,
蚁类(膜翅目(Hymenoptera)),如Atta capiguara、切叶蚁(Attacephalotes)、Atta laevigata、Atta robusta、Atta sexdens、Atta texana、小黄家蚁(Monomorium pharaonis)、热带火蚁(Solenopsis geminata)、红火蚁(Solenopsis invicta)、红蚁属(Pogonomyrmex)和大头蚁(Pheidolemegacephala),
甲虫(鞘翅目(Coleoptera)),例如梨窄吉丁(Agrilus sinuatus)、直条叩头虫(Agriotes lineatus)、暗色叩头虫(Agriotes obscurus)和其他叩甲属(Agriotes)、Amphimallus solstitialis、Anisandrus dispar、墨西哥棉铃象(Anthonomus grandis)、苹花象(Anthonomus pomorum)、Aracanthusmorei、甜菜隐食甲(Atomaria linearis)、拟步甲属(Blapstinus)、纵坑切梢小蠹(Blastophagus piniperda)、Blitophaga undata、Bothynoderespunciventris、蚕豆象(Bruchus rufimanus)、豌豆象(Bruchus pisorum)、欧洲兵豆象(Bruchus lentis)、苹卷象(Byctiscus betulae)、甜菜大龟甲(Cassidanebulosa)、Cerotoma trifurcata、白菜籽龟象(Ceuthorrhynchus assimilis)、芫菁龟象(Ceuthorrhynchus napi)、甜菜胫跳甲(Chaetocnema tibialis)、Conoderus vespertinus和其他金针虫属(Conoderus)、Conorhynchusmendicus、石刁柏负泥虫(Crioceris asparagi)、Cylindrocopturusadspersus、Diabrotica(longicornis)barberi、Diabrotica semi-punctata、南美叶甲(Diabrotica speciosa)、黄瓜十一星叶甲(Diabroticaundecimpunctata)、玉米根叶甲(Diabrotica virgifera)和其他叶甲属(Diabrotica)、Eleodes属、墨西哥豆瓢虫(Epilachna varivestis)、烟草跳甲(Epitrix hirtipennis)、棉灰蒙象变种(Eutinobothrus brasiliensis)、欧洲松树皮象(Hylobius abietis)、埃及苜蓿叶象(Hypera brunneipennis)、紫苜蓿叶象(Hypera postica)、云杉八齿小蠹(Ips typographus)、烟草负泥虫(Lemabilineata)、黑角负泥虫(Lema melanopus)、马铃薯叶甲(Leptinotarsadecemlineata)、Limonius californicus和其他金针虫属(Limonius)、稻水象甲(Lissorhoptrus oryzophilus)、阿根廷茎象甲(Listronotus bonariensis)、玉米叩甲(Melanotus communis)和其他叩甲属(Melanotus)、油菜露尾甲(Meligethes aeneus)、大栗鳃金龟(Melolontha hippocastani)、五月鳃金龟(Melolontha melolontha)、水稻负泥虫(Oulema oryzae)、葡萄黑耳喙象(Ortiorrhynchus sulcatus)、Oryazophagus oryzae、草莓根象甲(Otiorrhynchus ovatus)、稻叶甲(Oulema oryzae)、辣根猿叶甲(Phaedoncochleariae)、Phyllotreta chrysocephala、Phyllophaga cuyabana和其他食叶鳃金龟属(Phyllophaga)、庭园发丽金龟(Phyllopertha horticola)、大豆淡足跳甲(Phyllotreta nemorum)、黄曲条菜跳甲(Phyllotreta striolata)和其他跳甲属(Phyllotreta)、日本金龟子(Popillia japonica)、Promecopscarinicollis、Premnotrypes voraz、兰跳甲属(Psylliodes)、豌豆叶象(Sitonalineatus)、谷象(Sitophilus granaria)、Sternechus pinguis、Sternechussubsignatus以及Tanymechus palliatus和其他Tanymechus属,
蝇类(双翅目(Diptera)),如Agromyza oryzea、蛆症金蝇(Chrysomyabezziana)、Chrysomya hominivorax、Chrysomya macellaria、高粱瘿蚊(Contarinia sorghicola)、Cordylobia anthropophaga、瓜实蝇(Dacuscucurbitae)、油橄榄实蝇(Dacus oleae)、油菜叶瘿蚊(Dasineura brassicae)、葱蝇(Delia antique)、麦地种蝇(Delia coarctata)、灰地种蝇(Delia platura)、甘蓝地种蝇(Delia radicum)、小毛厕蝇(Fannia canicularis)、马蝇(Gasterophilus intestinalis)、Geomyza Tripunctata、刺舌蝇(Glossinamorsitans)、Haematobia irritans、Haplodiplosis equestris、纹皮蝇(Hypoderma lineata)、蔬菜斑潜蝇(Liriomyza sativae)、美国潜叶蝇(Liriomyza trifolii)、Lucilia caprina、铜绿蝇(Lucilia cuprina)、丝光绿蝇(Lucilia sericata)、Lycoria pectoralis、麦瘿蚊(Mayetiola destructor)、厩腐蝇(Muscina stabulans)、羊狂蝇(Oestrus ovis)、Opomyza florum、瑞典麦秆蝇(Oscinella frit)、天仙子泉蝇(Pegomya hysocyami)、葱蝇(Phorbiaantiqua)、萝卜蝇(Phorbia brassicae)、麦地种蝇(Phorbia coarctata)、Progonya leyoscianii、胡萝卜茎蝇(Psila rosae)、樱桃实蝇(Rhagoletiscerasi)、苹果实蝇(Rhagoletis pomonella)、Tabanus bovinus、Tetanopsmyopaeformis、Tipula oleracea和欧洲大蚊(Tipula paludosa),
异翅目昆虫(异翅目(Heteroptera)),例如拟绿蝽(Acrosternum hilare)、玉米长蝽(Blissus leucopterus)、大叶蝉科(Cicadellidae)如蚕豆微叶蝉(Empoasca fabae)、叶甲科(Chrysomelidae)、黑斑烟盲蝽(Cyrtopeltisnotatus)、飞虱科(Delpahcidae)、棉红蝽(Dysdercus cingulatus)、Dysdercusintermedius、麦扁盾蝽(Eurygaster integriceps)、Euschistus impictiventris、棉红铃喙缘蝽(Leptoglossus phyllopus)、美洲牧草盲蝽(Lygus lineolaris)、牧草盲蝽(Lygus pratensis)、黑尾叶蝉属(Nephotettix)、稻绿蝽(Nezaraviridula)、蝽科(Pentatomidae)、甜菜拟网蝽(Piesma quadrata)、Solubeainsularis和Thyanta perditor,
蚜虫和其他同翅目昆虫(同翅目(Homoptera)),例如Acyrthosiphononobrychis、落叶松球蚜(Adelges laricis)、Aphidula nasturtii、甜菜蚜(Aphisfabae)、草莓根蚜(Aphis forbesi)、大豆蚜(Aphis glycines)、棉蚜(Aphisgossypii)、北美茶簏子蚜(Aphis grossulariae)、苹果蚜(Aphis pomi)、Aphisschneideri、卷叶蚜(Aphis spiraecola)、Aphis sambuci、豌豆蚜(Acyrthosiphon pisum)、马铃薯蚜(Aulacorthum solani)、Brachycauduscardui、杏圆尾蚜(Brachycaudus helichrysi)、Brachycaudus persicae、Brachycaudus prunicola、甘蓝蚜(Brevicoryne brassicae)、Capitophorushorni、Cerosipha gossypii、Chaetosiphon fragaefolii、Cryptomyzus ribis、高加索冷杉椎球蚜(Dreyfusia nordmannianae)、云杉椎球蚜(Dreyfusiapiceae)、居根西圆尾蚜(Dysaphis radicola)、Dysaulacorthum pseudosolani、Dysaphis plantaginea、Dysaphis pyri、蚕豆微叶蝉(Empoasca fabae)、桃大尾蚜(Hyalopterus pruni)、Hyperomyzus lactucae、麦长管蚜(Macrosiphum avenae)、大戟长管蚜(Macrosiphum euphorbiae)、蔷薇管蚜(Macrosiphon rosae)、Megoura viciae、巢莱修尾蚜(Melanaphis pyrarius)、麦无网蚜(Metopolophium dirhodum)、Myzodes(Myzus)persicae、冬葱瘤额蚜(Myzus ascalonicus)、Myzus cerasi、李瘤蚜(Myzus varians)、Nasonoviaribis-nigri、稻飞虱(Nilaparvata lugens)、囊柄瘿绵蚜(Pemphigusbursarius)、杨脉瘿绵蚜(Pemphigus populivenae)和其他瘿绵蚜属(Pemphigus)、蔗飞虱(Perkinsiella saccharicida)、忽布疣蚜(Phorodonhumuli)、木虱科(Psyllidae)如苹木虱(Psylla mali)、梨木虱(Psylla piri)和其他木虱属(Psylla)、冬葱瘤蛾蚜(Rhopalomyzus ascalonicus)、玉米蚜(Rhopalosiphum maidis)、禾谷溢管蚜(Rhopalosiphum padi)、Rhopalosiphum insertum、Sappaphis mala、Sappaphis mali、麦二叉蚜(Schizaphis graminum)、Schizoneura lanuginosa、麦长管蚜(Sitobionavenae)、白粉虱(Trialeurodes vaporariorum)、Toxoptera aurantiiand和葡萄根瘤蚜(Viteus vitifolii);
鳞翅目(Lepidoptera),例如小地老虎(Agrotis ypsilon)、黄地老虎(Agrotis segetum)和其他地虎属(Agrotis),木棉虫(Alabama argillacea)、黎豆夜蛾(Anticarsia gemmatalis)、Argyresthia conj ugella、叉纹夜蛾(Autographa gamma)、树尺蠖(Bupalus piniarius)、Cacoecia murinana、Capua reticulana、Cheimatobia brumata、二化螟(Chilo suppresalis)和其他禾草螟属(Chilo),云杉色卷蛾(Choristoneura fumiferana)、Choristoneura occidentalis、二化螟(Cirphis unipuncta)、稻纵卷叶虫(Cnaphlocrocis medinalis)、苹果小卷蛾(Cydia pomonella)、松毛虫(Dendrolimus pini)、Diaphania nitidalis、西南玉米杆草螟(Diatraeagrandiosella)、埃及钻夜蛾(Earias insulana)、南美玉米苗斑螟(Elasmopalpus lignosellus)、女贞细卷蛾(Eupoecilia ambiguella)、切夜蛾属(Euxoa)、Evetria bouliana、Feltia subterranea、蜡螟(Galleria mellonella)、李小食心虫(Grapholitha funebrana)、梨小食心虫(Grapholitha molesta)、棉铃虫(Heliothis armigera)、烟芽夜蛾(Heliothis virescens)、玉米穗虫(Heliothis zea)、菜螟(Hellula undalis)、Hibernia defoliaria、美国白蛾(Hyphantria cunea)、苹果巢蛾(Hyponomeuta malinellus)、番茄虫蛾(Keiferia lycopersicella)、Lambdina fiscellaria、甜菜夜蛾(Laphygmaexigua)、Lerodea eufala、咖啡潜叶蛾(Leucoptera coffeella)、旋纹潜蛾(Leucoptera scitella)、Lithocolletis blancardella、葡萄浆果小卷蛾(Lobesiabotrana)、甜菜网螟(Loxostege sticticalis)、舞毒蛾(Lymantria dispar)、模毒蛾(Lymantria monacha)、桃潜蛾(Lyonetia clerkella)、黄褐天幕毛虫(Malacosoma neustria)、甘蓝夜蛾(Mamestra brassicae)、织蛾科(Momphidae)、黄杉毒蛾(Orgyia pseudotsugata)、玉米螟(Ostrinianubilalis)、小眼夜蛾(Panolis flammea)、棉花红铃虫(Pectinophoragossypiella)、疆夜蛾(Peridroma saucia)、圆掌舟蛾(Phalera bucephala)、马铃薯麦蛾(Phthorimaea operculella)、柑桔潜叶蛾(Phyllocnistis citrella)、欧洲粉蝶(Pieris brassicae)、苜蓿绿夜蛾(Plathypena scabra)、菜蛾(Plutellaxylostella)、大豆夜蛾(Pseudoplusia includens)、Rhyacionia frustrana、Scrobipalpula absoluta、Sesamia nonagrioides和其他蛀茎夜蛾属(Sesamia),麦蛾(Sitotroga cerealella)、葡萄卷叶蛾(Sparganothispilleriana)、草地夜蛾(Spodoptera frugiperda)、海灰翅夜蛾(Spodopteralittoralis)、斜纹夜蛾(Spodoptera litura)、Thaumatopoea pityocampa、绿色橡木飞蛾(Tortrix viridana)、粉纹夜蛾(Trichoplusia ni)和Zeirapheracanadensis;
直翅目(Orthoptera),例如珍蝶科(Acrididae)、居屋艾蟋(Achetadomestica)、东方蜚蠊(Blatta orientalis)、德国小蠊(Blattella germanica)、欧洲球螋(Forficula au ricularia)、蝼蛄(Gryllotalpa gryllotalpa)、飞蝗(Locusta migratoria)、双纹黑蝗(Melanoplus bivittatus)、红足黑蝗(Melanoplus femur-rubrum)、墨西哥黑蝗(Melanoplus mexicanus)、迁飞黑蝗(Melanoplus sanguinipes)、石栖黑蝗(Melanoplus spretus)、条纹红蝗(Nomadacris septemfasciata)、美洲蟑螂(Periplaneta americana)、美洲沙漠蝗(Schistocerca americana)、Schistocerca peregrina、Stauronotusmaroccanus和庭疾灶螽(Tachycines asynamorus);
白蚁(等翅目(Isoptera)),例如Calotermes flavicollis、乳白蚁属(Coptotermes)、玉米叶蝉(Dalbulus maidis)、Leucotermes flavipes、暗黄大白蚁(Macrotermes gilvus)、欧洲散白蚁(Reticulitermes lucifugus)和Termes natalensis;
蓟马(缨翅目(Thysanoptera)),例如烟褐蓟马(Frankliniella fusca)、苜蓿花蓟马(Frankliniella occidentalis)、东方花蓟马(Frankliniella tritici)和其他花蓟马属(Frankliniella),桔硬蓟马(Scirtothrips citri)、稻蓟马(Thripsoryzae)、棕榈蓟马(Thrips palmi)、菖蒲蓟马(Thrips simplex)和烟蓟马(Thrips tabaci),
和
蜘蛛,例如蜱螨目(Acarina),例如软蜱科(Argasidae)、硬蜱科(Ixodidae)和疥螨科(Sarcoptidae),如长星形壁虱(Amblyomma americanum)、热带花蜱(Amblyomma variegatum)、波斯锐缘蜱(Argas persicus)、牛壁虱(Boophilus annulatus)、Boophilus decoloratus、微小牛蜱(Boophilusmicroplus)、Dermacentor silvarum、Hyalomma truncatum、蓖子硬蜱(Ixodes ricinus)、Ixodes rubicundus、Ornithodorus moubata、Otobiusmegnini、鸡皮刺螨(Dermanyssus gallinae)、绵羊疥病(Psoroptes ovis)、Rhipicephalus appendiculatus、Rhipicephalus evertsi、人疥螨(Sarcoptesscabiei)和瘿螨属(Eriophyidae),如苹果刺锈螨(Aculus schlechtendali)、Phyllocoptrata oleivora和Eriophyes sheldoni;细螨属(Tarsonemidae),如Phytonemus pallidus和侧多食跗线螨(polyphagotarsonemus latus);细须螨属(Tenuipalpidae),如紫红短须螨(Brevipalpus phoenicis);叶螨属(tetranychidae),如朱砂叶螨(tetranychus cinnabarinus)、神泽叶螨(tetranychus kanzawai)、太平洋叶螨(tetranychus pacificus)、棉叶螨(tetranychus telarius)和二点叶螨(tetranychus urticae),苹果叶螨(Panonychus ulmi)、柑椐叶螨(Panonychus citri)和Oligonychus pratensis;
如果本发明微乳液含有对稻病原体呈活性的拟除虫菊酯化合物,则组合物也可用于防治稻病原体如例如稻象甲(Lissorhoptrus oryzaphilus),二化螟(Chilo suppresalis),稻纵卷叶螟(rice leaf roller),稻负泥虫,稻潜蝇(Agromyca oryzae),叶蝉(浮尘子属(Nephotettix spp.),尤其是小褐叶蝉(smaller brown leafhopper),黑尾叶蝉(green rice leafhopper)),飞虱(Delphacidae;尤其是白背飞虱,褐飞虱),臭蝽。
本发明微乳液可以常规方式施用,通常作为通过用水稀释微乳液而得到的含水稀释液施用。不含配制助剂的纯活性化合物的所需施用率取决于所需植物生长的密度、植物的发育阶段、使用组合物的场所的气候条件和施用方法。通常而言,活性物质施用率为0.001-3kg/ha,优选0.005-2kg/ha,尤其是0.01-1kg/ha,0.1g/ha-1kg/ha,1g/ha-500g/ha或5g/ha-500g/ha。
稀释的微乳液主要通过喷雾,尤其是叶面喷雾施加至植物。施用可通过常规喷雾技术,如使用水作为载体进行且喷雾液施用率为约100-1000l/ha(例如300-400l/ha)。
此外,可能有用的是将本发明微乳液作为与其它作物保护产品如农药或防治植物病原性真菌或细菌的试剂的混合物而联合施用。与用于治疗营养和痕量元素缺乏的无机盐溶液的溶混性也是有意义的。还可加入非植物毒性油和油浓缩物。
在本发明的另一实施方案中,微乳液含有对非作物害虫呈活性的拟除虫菊酯化合物。因此,本发明还涉及一种防治非作物害虫的方法,其包括使害虫或其食物供应源、栖息地、繁殖地或其所在地与至少包含杀虫剂的本发明配制剂接触。
本发明进一步涉及本发明微乳液在保护非活体有机材料对抗非作物害虫中的用途。
非作物害虫例如为唇足纲(Chilopoda)和倍足纲(Diplopoda)和等翅目(Isoptera)、Diptera(双翅目)、蜚蠊目(Blattaria)(Blattodea)、革翅目(Dermaptera)、半翅目(Hemiptera)、膜翅目(Hymenoptera)、直翅目(Orthoptera)、蚤目(Siphonaptera)、缨尾目(Thysanura)、毛虱目(Phthiraptera)、蜘蛛目(Araneida)、寄螨目(Parasitiformes)和粉螨亚目(Acaridida)的害虫,例如:
百足虫(唇足纲(Chilopoda)),例如Scutigera coleoptrata,
千足虫(倍足纲(Diplopoda)),例如Narceus属,
蜘蛛目(Araneida),例如毒蜘蛛(Latrodectus mactans)和褐丝蛛(Loxosceles reclusa),
scabies(Acaridida):例如sarcoptes属,
蜱科和小鼠寄生螨虫(parasitic mites)(Parasitiformes):硬蜱科(Ixodidae),例如黑脚硬蜱(Ixodes scapularis)、全环硬蜱(Ixodes holocyclus)、太平洋硬蜱(Ixodes pacificus)、Rhiphicephalus sanguineus、安氏革蜱(Dermacentor andersoni)、美洲大革蜱(Dermacentor variabilis)、长星形壁虱(Amblyomma americanum)、Ambryomma maculatum、Ornithodorushermsi、Ornithodorus turicata和小鼠寄生螨虫(Mesostigmata),例如柏氏禽刺螨(Ornithonyssus bacoti)和鸡皮刺螨(Dermanyssus gallinae),
白蚁(等翅目(Isoptera)),例如Calotermes flavicollis、Leucotermesflavipes、金黄异白蚁(Heterotermes aureus)、黄肢散白蚁(Reticulitermesflavipes)、美小黑散白蚁(Reticulitermes virginicus)、欧洲散白蚁(Reticulitermes lucifugus)、Termes natalensis和台湾乳白蚁(Coptotermesformosanus),
蟑螂(蜚蠊目(Blattaria-Blattodea),例如德国小蠊(Blattellagermanica)、Blattella asahinae、美洲大蠊(Periplaneta americana)、日本大蠊(Periplaneta japonica)、棕色蜚蠊(Periplaneta brunnea)、Periplanetafuligginosa、澳洲蜚蠊(Periplaneta australasiae)和东方蜚蠊(Blattaorientalis),
蝇、蚊(双翅目(Diptera)),例如埃及伊蚊(Aedes aegypti)、白纹伊蚊(Aedes albopictus)、剌扰伊蚊(Aedes vexans)、墨西哥果蝇(Anastrephaludens)、五斑按蚊(Anopheles maculipennis)、Anopheles crucians、白足按蚊(Anopheles albimanus)、冈比亚按蚊(Anopheles gambiae)、Anophelesfreeborni、海南岛白踝按蚊(Anopheles leucosphyrus)、云南微小按蚊(Anopheles minimus)、四斑按蚊(Anopheles quadrimaculatus)、红头丽蝇(Calliphora vicina)、蛆症金蝇(Chrysomya bezziana)、Chrysomyahominivorax、Chrysomya macellaria、鹿蝇(Chrysops discalis)、Chrysopssilacea、Chrysops atlanticus、螺旋蝇(Cochliomyia hominivorax)、嗜人瘤蝇蛆(Cordylobia anthropophaga)、狂怒库蠓(Culicoides furens)、尖音库蚊(Culex pipiens)、致倦库蚊(Culex quinquefasciatus)、媒斑蚊(Culextarsalis)、Culiseta inornata、Culiseta melanura、Dermatobia hominis、小毛厕蝇(Fannia canicularis)、马蝇(Gasterophilus intestinalis)、刺舌蝇(Glossina morsitans)、须舌蝇(Glossina palpalis)、Glossina fuscipes、胶舌蝇(Glossina tachinoides)、Haematobia irritans、Haplodiplosis equestris、潜蝇属(Hippelates spp.)、纹皮蝇(Hypoderma lineata)、Leptoconopstorrens、铜绿蝇(Lucilia cuprina)、丝光绿蝇(Lucilia sericata)、Lycoriapectoralis、Mansonia属、家蝇(Musca domestica)、厩腐蝇(Muscinastabulans)、羊狂蝇(Oestrus ovis)、银足白蛉(Phlebotomus argentipes)、Psorophora columbiae、Psorophora discolor、Prosimulium mixtum、赤尾麻蝇(Sarcophaga haemorrhoidalis)、肉蝇属(Sarcophaga)、Simuliumvittatum、厩螫蝇(Stomoxys calcitrans)、牛虻(Tabanus bovinus)、Tabanus atratus、红色原虻(Tabanus lineola)和Tabanus similis
蠼蛸(革翅目(Dermaptera)),例如欧洲球螋(forficula auricularia),
真正臭虫(半翅目(Hemiptera))如温带臭虫(Cimex lectularius)、热带臭虫(Cimex hemipterus)、Reduvius senilis、Triatoma属、Rhodniusprolixus和Arilus critatus,
蚂蚁、蜜蜂、黄蜂、锯蝇(膜翅目(Hymenoptera))如举腹蚁属(Crematogaster)、Hoplocampa minuta、Hoplocampa testudinea、小黄家蚁(Monomorium pharaonis)、热带火蚁(Solenopsis geminate)、红火蚁(Solenopsis invicta)、黑火蚁(Solenopsis richteri)、南方火蚁(Solenopsisxyloni)、红蚂蚁(Pogonomyrmex barbatus)、Pogonomyrmex californicus、天鹅绒蚂蚁(Dasymutilla occidentalis)、熊蜂属(Bombus)、大黄蜂(Vespulasquamosa)、Paravespula vulgaris、Paravespula pennsylvanica、Paravespulagermanica、姬胡蜂(Dolichovespula maculata)、黄边胡蜂(Vespa crabro)、胡蜂(Polistes rubiginosa)、Campodontus floridanus和阿根廷蚁(Linepithema humile),
蟋蟀、蚱蜢、蝗虫(直翅目(Orthoptera)),例如居屋艾蟋(Achetadomestica)、蝼蛄(Gryllotalpa gryllotalpa)、飞蝗(Locusta migratoria)、双纹黑蝗(Melanoplus bivittatus)、红足黑蝗(Melanoplus femurrubrum)、墨西哥黑蝗(Melanoplus mexicanus)、迁飞黑蝗(Melanoplus sanguinipes)、石栖黑蝗(Melanoplus spretus)、条纹红蝗(Nomadacris septemfasciata)、美洲沙漠蝗(Schistocerca americana)、沙漠蝗(Schistocerca gregaria)、摩洛哥戟纹蝗(Dociostaurus maroccanus)、庭疾灶螽(Tachycines asynamorus)、塞纳加尔小车蝗(Oedaleus senegalensis)、Zonozerus variegatus、非洲蔗蝗(Hieroglyphus daganensis)、Kraussaria angulifera、意大利蝗(Calliptamusitalicus)、澳洲草栖蝗(Chortoicetes terminifera)和褐色拟飞蝗(Locustanapardalina),跳蚤(蚤目(Siphonaptera)),例如猫跳蚤(Ctenocephalides felis)、狗跳蚤(Ctenocephalides canis)、印鼠客蚤(Xenopsylla cheopis)、致痒蚤(Pulexirritans)、穿皮潜蚤(Tunga penetrans)和具带病蚤(Nosopsyllusfasciatus),
衣鱼、家衣鱼(缨尾目(Thysanura)),例如西洋衣鱼(Lepisma saccharina)和斑衣鱼(Thermobia domestica),
虱(毛虱目(Phthiraptera)),例如人头虱(Pediculus humanus capitis)、人体虱(Pediculus humanus corporis)、阴虱(Pthirus pubis)、牛血虱(Haematopinus eurysternus)、猪血虱(Haematopinus suis)、牛颚虱(Linognathus vituli)、Bovicola bovis、鸡虱(Menopon gallinae)、Menacanthus stramineus和Solenopotes capillatus。
本发明还涉及一种保护非活体有机材料防止上述非作物害虫的方法,包括使害虫或其食物供应源、栖息地、繁殖地、它们的所在地或非活体有机材料本身与杀虫有效量的本发明配制剂接触。
此外,本发明配制剂可用于保护含纤维素的非活体有机材料如保护含纤维素的非活体有机材料防止选自等翅目、双翅目、蜚蠊目、膜翅目,以及直翅目的非作物害虫,最优选防止等翅目。
本发明还提供了一种保护含纤维素的非活体有机材料防止非作物害虫,优选选自等翅目、双翅目、蜚蠊目、膜翅目,以及直翅目,最优选选自等翅目的非作物害虫的方法,包括使害虫或其食物供应源、栖息地、繁殖地、它们的所在地或含纤维素的非活体有机材料本身与至少包含杀虫剂的本发明配制剂接触。
此外,包含至少一种拟除虫菊酯的本发明组合物可用于保护动物防止唇足纲类和蜘蛛目、半翅目、双翅目、毛虱目、蚤目、寄螨目和粉螨亚目的非作物害虫,其包括用本发明配制剂处理水体中和/或在包括但不限于墙壁、地面、粪堆、草地、牧场、下水道和用于建筑物构造中的材料的建筑物中和周围以及蚊帐、床垫和被褥中的害虫。
动物包括温血动物,其包括人类和鱼。因此,至少包含杀虫剂的本发明配制剂可用于保护温血动物如牛、绵羊、猪、骆驼、鹿、马、家禽、兔、山羊、狗和猫。
此外,本发明配制剂可用于保护木质材料如树、木栅栏、枕木等和建筑物如房子、附属建筑物、工厂,以及建筑材料、家具、皮革、纤维、乙烯系制品、电线和电缆等防止蚂蚁和/或白蚁,以及用于防治蚂蚁和白蚁损害作物和人类(例如当害虫侵入房子和公共设施时)。至少包含杀虫剂的本发明配制剂不仅可施加在周围的土壤表面或地板下土壤中以保护木质材料,而且还可施加至木制品如地板下混凝土、壁橱柱、横梁、胶合板、家具等,木制品如颗粒板、half board等和乙烯系制品如涂覆的电线、乙烯系板、绝热材料如苯乙烯泡沫等的表面。在施用以防止蚂蚁损害作物或人类的情况下,将本发明的防治蚂蚁组合物直接施加至蚂蚁穴或其周围或经由饵料接触。
此外,可预防性地将本发明微乳液施加至预期害虫出现的地方。
另一方面,本发明涉及种子的处理。术语种子处理包括本领域已知的所有合适的种子处理技术,例如但不限于拌种、种子包衣、种子浸泡、种子涂膜、种子多层包衣、种子包壳(seed encrusting)、种子滴淋(seed dripping)和种子造粒。术语种子包括所有类型的种子和植物繁殖体,包括但不限于真正种子(true seed)、种子切片(seed piece)、根出条、球茎、鳞茎(bulbs)、果实、块茎、谷粒、插条(cutting)、插枝等,且在优选实施方案中指真正种子。
如果本发明微乳液意欲用于种子处理,则配制剂可任选还包含染料或颜料。种子处理配制剂的合适颜料或染料为颜料蓝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。
本发明进一步包括用本发明微乳液处理过的种子。
合适的种子为禾谷类、根系作物、油料作物、蔬菜、香料作物、观赏植物的种子,例如如下作物的种子:硬粒小麦和其它小麦,大麦,燕麦,黑麦,玉米(甜玉米和饲料玉米),大豆,油料作物,十字花科作物,棉花,向日葵,香蕉,稻,油菜,芜菁,糖用甜菜,饲料甜菜,茄子,土豆,牧草,草坪,草料,西红柿,韭菜,南瓜,卷心菜,莴苣,胡椒,黄瓜,甜瓜,芸苔属,菜豆,豌豆,大蒜,洋葱,胡萝卜,块茎植物,如土豆、甘蔗,烟草,葡萄,矮牵牛,老鹳草/天竺葵,三色堇,凤仙花。
此外,微乳液还可用于处理植物种子,所述种子由于育种、突变和/或基因工程方法而耐受除草剂或杀真菌剂或杀虫剂或杀线虫剂的作用。
例如,微乳液可用于耐受如下除草剂的转基因作物:磺酰脲类(EP-A-0257993、美国专利No.5,013,659)、咪唑啉酮类(例如参见US6222100、WO 0182685、WO 0026390、WO 9741218、WO 9802526、WO 9802527、WO 04/106529、WO 05/20673、WO 03/14357、WO 03/13225、WO 03/14356、WO 04/16073)、草铵膦类(例如参见EP-A-0242236、EP-A-242246)或草甘膦类(例如参见WO 92/00377),或用于耐受选自环己二烯酮/芳氧基苯氧基丙酸除草剂(US 5,162,602、US 5,290,696、US5,498,544、US 5,428,001、US 6,069,298、US 6,268,550、US 6,146,867、US6,222,099、US 6,414,222)的除草剂的植物或用于转基因作物植物如棉花,它们能产生芽孢杆菌(Bacillus thuringiensis)毒素(Bt毒素)并且因此使植物耐受某些害虫(EP-A-0 142 924、EP-A-0 193 259)。
此外,微乳液还可用于处理与现有植物相比具有改进性能特征的植物的种子,所述种子例如可通过常规育种方法和/或产生突变体,或通过重组程序而产生。例如,对改性植物中合成的淀粉(例如WO 92/11376、WO92/14827、WO 91/19806)或脂肪酸组成改变的转基因作物植物(WO91/13972)而言,已经描述了许多重组改性作物植物的实例。
种子处理的应用通过在植物播种和植物出苗之前用有效量微乳液喷雾或对种子撒粉而进行。
在处理种子中,通过用有效量微乳液处理种子而施加对应微乳液。这里,拟除虫菊酯化合物P的施用率通常为每100kg种子0.1g-10kg,优选每100kg种子1g-5kg,尤其是每100kg种子1g-2.5kg。对特定作物如莴苣和洋葱而言,施用率可以更高。
如下实施例进一步阐述本发明。本发明范围不应认为限制于实施例,而是包括权利要求中所定义的全部主题。在实施例中,所有百分含量为整个组合物重量的百分数。
I 分析:
粒度通过在25℃下,用Zetasizer Nano ZS,Malvern Instruments的动态光散射测定。
II.制备本发明组合物:
实施例1-4,对比例1和2
将表1列出的全部成分加入配有搅拌器的容器中并在55℃下将混合物搅拌1小时。然后在环境温度下冷却混合物。如此得到的液体混合物清澈均匀。
表1:
成分 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例1 | 对比例2 |
氟氰菊酯1) | 4.4% | 4.4% | 4.4% | - | 4.4% | 4.4% |
α-氯氰菊酯 | -- | - | - | 1.0% | - | - |
表面活性剂12) | 12.0% | 12.0% | 12.0% | 12.0% | 8.0% | 12.0% |
表面活性剂23) | 4.0% | 4.0% | 4.0% | 4.0% | 2.0% | 4.0% |
乙酸3-甲氧基-3-甲基丁基酯 | 7.5% | - | - | - | - | - |
丙二醇单甲基醚乙酸酯 | - | 7.5% | - | 20.0% | - | - |
丙二醇单乙基醚乙酸酯 | - | - | 7.5% | - | - | - |
乙二醇 | - | - | - | - | 5.0% | |
二甘醇单甲基醚 | - | - | - | - | - | 7.5% |
去离子水 | 72.1% | 72.1% | 72.1% | 63.0% | 80.6% | 72.1% |
1)(R,S)-α-氰基-3-苯氧基苄基(S)-2二氟甲氧基苯基)-3-甲基丁酸酯)
2)含有37重量%聚氧乙烯三苯乙烯基苯基醚(19摩尔氧化乙烯)、12重量%聚氧乙烯二苯乙烯基苯基醚-甲醛缩合物(26摩尔氧化乙烯)、31重量%烷基苯磺酸钠和20%水。
3)聚氧乙烯苯乙烯基苯基醚(14摩尔氧化乙烯)
III.稳定性测试
1.活性成分的结晶
在研钵中研磨氟氰菊酯的SS-异构体。将10mg如此得到的粉末加入100ml实施例1-3的微乳液和对比例的样品中。在5℃下储存样品3周后,通过显微镜观察评价每个样品中晶种的生长。
*氟氰菊酯的SS-异构体(固体;在小于约52℃下)
不包括酯溶剂的对比例1和2的对比样品显示氟氰菊酯晶体的晶体生长,而在实施例1-3的微乳液中未观察到晶体生长。
2.稀释稳定性
为确定用水稀释后的稳定性,通过光散射测量微乳液稀释后的液滴尺寸分布。检测在紧邻稀释后和稀释后24小时进行,稀释率为1:30(重量/重量)结果列在表2中。
表2
对比例的微乳液显示用水稀释后液滴尺寸分布的急剧增加,而在实施例1-4的微乳液中未观察到液滴尺寸分布的改变。这意味着实施例1-4的微乳液的稀释稳定性比对比例的稀释稳定性要好的多。
3.凝固点
测量微乳液的凝固点。结果显示在表3中。
表3
这些结果说明实施例1-3中的溶剂I如对比例中的乙二醇起到防冻剂的作用。
Claims (17)
1.一种农药含水微乳液配制剂,其包含:
a)至少一种有机拟除虫菊酯化合物P;
b)至少一种选自式I化合物的有机溶剂:
R1-(O-Alk)m-O-C(O)R2(I)
其中m为1、2或3,
R1为H、C1-C6烷基或C(O)R3,
R2为氢或C1-C4烷基,其可为未取代的或由OH取代,
Alk为直链或支化C2-C6亚烷基,和
R3为氢或C1-C4烷基,其可为未取代的或由OH取代;
c)包含如下物质的表面活性剂混合物:
c.1:至少一种阴离子表面活性剂,和
c.2:至少一种非离子表面活性剂;
和
d)水。
2.根据权利要求1的配制剂,其中所述溶剂选自乙酸3-甲氧基-3-甲基丁基酯、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、二丙二醇甲醚乙酸酯、丙二醇二乙酸酯、乙二醇单丁醚乙酸酯、二甘醇单丁醚乙酸酯及其混合物。
3.根据前述权利要求中任一项的配制剂,其中式I中的Alk为直链或支化的C3-C6亚烷基。
4.根据前述权利要求中任一项的配制剂,其中所述至少一种阴离子表面活性剂选自C1-C16烷基苯磺酸盐,C1-C16烷基萘磺酸盐,木素磺酸盐,萘磺酸盐-甲醛缩合物,C1-C16烷基萘磺酸盐-甲醛缩合物,聚氧-C2-C3亚烷基C8-C22烷基醚硫酸盐,聚氧-C2-C3亚烷基C8-C22烷基醚磷酸盐,聚氧-C2-C3亚烷基C1-C16烷基苯醚硫酸盐,聚氧-C2-C3亚烷基C1-C16烷基苯醚磷酸盐,C8-C22烷基硫酸盐,磺基琥珀酸C4-C18二烷基酯,聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯醚硫酸盐,聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯醚磷酸盐,聚氧化乙烯聚羧酸盐,聚磷酸盐及其混合物。
5.根据前述权利要求中任一项的配制剂,其中所述至少一种非离子表面活性剂选自聚氧-C2-C3亚烷基C8-C22烷基醚,聚氧-C2-C3亚烷基C1-C16烷基苯醚,聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯醚,聚氧-C2-C3亚烷基单-或二苯乙烯基苯醚-甲醛缩合物以及炔二醇。
6.根据前述权利要求中任一项的配制剂,其中表面活性剂为包含如下物质的混合物:
c.1至少一种选自C1-C16烷基苯磺酸盐的阴离子表面活性剂,
c.2至少一种选自聚氧-C2-C3亚烷基单-、二-或三苯乙烯基苯醚和聚氧-C2-C3亚烷基单-或二苯乙烯基苯醚-甲醛缩合物的非离子表面活性剂。
7.根据前述权利要求中任一项的配制剂,其包含:
a)0.0001-10重量%所述至少一种有机农药化合物P;
b)0.1-30重量%至少一种式I的有机溶剂;
c)1-30重量%表面活性剂;和
d)水,加至100重量%。
8.根据前述权利要求中任一项的配制剂,其中式I的有机溶剂与农药化合物P的重量比例为0.5:1-100:1。
9.根据前述权利要求中任一项的配制剂,其中表面活性剂与溶剂I和农药化合物P的总量的重量比例为0.1:1-10:1。
10.根据前述权利要求中任一项的配制剂,其中所述至少一种化合物PI选自α-氯氰菊酯和氟氰菊酯。
11.权利要求1-10中任一项所要求的配制剂在对抗害虫中的用途。
12.权利要求1-10中任一项所要求的配制剂在植物保护中的用途。
13.权利要求1-10中任一项所要求的配制剂在保护非活体材料防止害虫侵袭或侵染中的用途。
14.权利要求1-10中任一项所要求的配制剂在对抗家中的害虫中的用途。
15.一种对抗害虫的方法,其包括使所述有害生物体,其栖息地,繁殖地,食物供应源,有害生物体正在生长或将要生长的植物、种子、土壤、区域、材料或环境,或需要防止有害生物体侵袭或侵染的材料、植物、种子、土壤、表面或空间与有效量的权利要求1-10中任一项所要求的配制剂接触。
16.一种保护作物防止害虫侵袭或侵染的方法,其包括使作物与有效量的权利要求1-10中任一项所要求的配制剂接触。
17.一种保护种子防止害虫侵袭或侵染的方法,其包括使种子与有效量的权利要求1-10中任一项所要求的配制剂接触。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP06006601.6 | 2006-03-29 | ||
EP06006601 | 2006-03-29 |
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CN101415326A true CN101415326A (zh) | 2009-04-22 |
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CNA200780012396XA Pending CN101415326A (zh) | 2006-03-29 | 2007-03-28 | 含有拟除虫菊酯的含水微乳液 |
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US (1) | US9295261B2 (zh) |
EP (1) | EP2001289B1 (zh) |
JP (1) | JP4904391B2 (zh) |
CN (1) | CN101415326A (zh) |
BR (1) | BRPI0708928B1 (zh) |
CA (1) | CA2643653A1 (zh) |
EA (1) | EA014880B1 (zh) |
WO (1) | WO2007110435A2 (zh) |
ZA (1) | ZA200809186B (zh) |
Cited By (4)
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CN101822269A (zh) * | 2010-05-21 | 2010-09-08 | 扬州大学 | 氯氰菊酯的水基型农药微乳剂 |
CN103442571A (zh) * | 2011-03-15 | 2013-12-11 | 日本化药株式会社 | 农业园艺用杀菌剂组合物 |
CN107333777A (zh) * | 2017-06-28 | 2017-11-10 | 河北八源生物制品有限公司 | 一种增稠性敌草快水剂配方、制备方法及使用方法 |
CN109414011A (zh) * | 2016-07-15 | 2019-03-01 | 陶氏环球技术有限责任公司 | 可乳化的浓缩物 |
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JP5262352B2 (ja) * | 2008-06-30 | 2013-08-14 | 住友化学株式会社 | ピレスロイド化合物含有の水性製剤 |
ES2350224B1 (es) * | 2008-06-30 | 2011-10-27 | Sumitomo Chemical Company, Limited | Composicion pesticida acuosa. |
WO2010076183A2 (de) * | 2008-12-29 | 2010-07-08 | Basf Se | Agrochemische zusammensetzungen umfassend verzweigte alkoxyalkanoate |
US8691858B2 (en) | 2009-05-20 | 2014-04-08 | Nippon Soda Co., Ltd. | Composition for preparing emulsion or microemulsion formulations |
CN201712857U (zh) | 2010-05-10 | 2011-01-19 | S.C.约翰逊父子公司 | 用于挥发性材料的散发装置及其壳体和散发片 |
UY33443A (es) * | 2010-06-19 | 2012-01-31 | Bayer Animal Health Gmbh | Preparacion que contiene ectoparasiticida para la formacion de emulsion espontanea |
US9205163B2 (en) | 2012-11-27 | 2015-12-08 | S.C. Johnson & Son, Inc. | Volatile material dispenser |
US9278151B2 (en) | 2012-11-27 | 2016-03-08 | S.C. Johnson & Son, Inc. | Volatile material dispenser |
EP3315567B1 (en) * | 2016-10-31 | 2023-04-19 | Nissin Chemical Industry Co., Ltd. | Dispersant, dispersion, ink composition, and methods of preparation thereof |
WO2019011825A1 (en) * | 2017-07-10 | 2019-01-17 | Basf Se | COMPOSITION COMPRISING AN AGROCHEMICALALLY ACTIVE COMPOUND AND ALCOXYLATE |
FR3080518B1 (fr) * | 2018-04-27 | 2021-09-24 | Apisolis | Formulation liquide pour enfumoir pour ruches |
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JPS5576176A (en) * | 1978-12-04 | 1980-06-09 | Toho Chem Ind Co Ltd | High temperature dyeing of polyester synthetic fiber |
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JP2861076B2 (ja) * | 1988-08-05 | 1999-02-24 | 住友化学工業株式会社 | 殺虫性水性液剤 |
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FR2655276B1 (fr) * | 1989-12-04 | 1992-11-27 | Rhone Poulenc Chimie | Microemulsions concentrees de matieres organiques diluables sous forme d'emulsions stables et leur procede de preparation. |
US5317042A (en) | 1989-12-11 | 1994-05-31 | Isp Investments Inc. | Water-based microemulsion formulations |
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-
2007
- 2007-03-28 CA CA002643653A patent/CA2643653A1/en not_active Abandoned
- 2007-03-28 WO PCT/EP2007/052972 patent/WO2007110435A2/en active Application Filing
- 2007-03-28 EP EP07727444A patent/EP2001289B1/en not_active Not-in-force
- 2007-03-28 US US12/282,529 patent/US9295261B2/en not_active Expired - Fee Related
- 2007-03-28 CN CNA200780012396XA patent/CN101415326A/zh active Pending
- 2007-03-28 JP JP2009502077A patent/JP4904391B2/ja active Active
- 2007-03-28 BR BRPI0708928-7A patent/BRPI0708928B1/pt not_active IP Right Cessation
- 2007-03-28 EA EA200801920A patent/EA014880B1/ru not_active IP Right Cessation
-
2008
- 2008-10-27 ZA ZA200809186A patent/ZA200809186B/xx unknown
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101822269A (zh) * | 2010-05-21 | 2010-09-08 | 扬州大学 | 氯氰菊酯的水基型农药微乳剂 |
CN101822269B (zh) * | 2010-05-21 | 2013-01-23 | 扬州大学 | 氯氰菊酯的水基型农药微乳剂 |
CN103442571A (zh) * | 2011-03-15 | 2013-12-11 | 日本化药株式会社 | 农业园艺用杀菌剂组合物 |
CN109414011A (zh) * | 2016-07-15 | 2019-03-01 | 陶氏环球技术有限责任公司 | 可乳化的浓缩物 |
CN107333777A (zh) * | 2017-06-28 | 2017-11-10 | 河北八源生物制品有限公司 | 一种增稠性敌草快水剂配方、制备方法及使用方法 |
Also Published As
Publication number | Publication date |
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CA2643653A1 (en) | 2007-10-04 |
EP2001289B1 (en) | 2012-06-13 |
WO2007110435A2 (en) | 2007-10-04 |
EA014880B1 (ru) | 2011-02-28 |
ZA200809186B (en) | 2010-01-27 |
JP2009531382A (ja) | 2009-09-03 |
EA200801920A1 (ru) | 2009-04-28 |
BRPI0708928B1 (pt) | 2018-02-06 |
US20100292323A1 (en) | 2010-11-18 |
JP4904391B2 (ja) | 2012-03-28 |
WO2007110435A3 (en) | 2008-07-10 |
US9295261B2 (en) | 2016-03-29 |
BRPI0708928A2 (pt) | 2011-06-14 |
EP2001289A2 (en) | 2008-12-17 |
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