CN101534650A - 杀虫剂组合物 - Google Patents
杀虫剂组合物 Download PDFInfo
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- CN101534650A CN101534650A CNA2007800422726A CN200780042272A CN101534650A CN 101534650 A CN101534650 A CN 101534650A CN A2007800422726 A CNA2007800422726 A CN A2007800422726A CN 200780042272 A CN200780042272 A CN 200780042272A CN 101534650 A CN101534650 A CN 101534650A
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/002—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 a foodstuff as carrier or diluent, i.e. baits
- A01N25/006—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 a foodstuff as carrier or diluent, i.e. baits insecticidal
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—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
- A01N25/06—Aerosols
-
- 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
- A01N25/08—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 solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
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Abstract
本发明涉及适于防治节肢动物害虫,尤其是昆虫的凝胶材料或固体材料形式的新型杀虫剂组合物。该凝胶或固体形式的杀虫剂组合物含有i)0.001-50重量%至少一种对节肢动物有效的杀虫剂化合物,ii)0.5-20重量%至少一种对去离子水的吸收容量为至少100g/1g聚合物P的超吸收聚合物P和iii)5-94.5重量%至少一种不同于水的填料,以及iv)5-94.5重量%水,其中重量%基于该组合物的总重量。本发明还涉及本文所述杀虫剂组合物在防治节肢动物中的用途以及一种防治节肢动物的方法,包括将本文所定义的凝胶组合物直接或作为含水稀释液施用于其中节肢动物与所述组合物接触的场所。
Description
本发明涉凝胶材料或固体材料形式的新型杀虫剂组合物,它们适于防治节肢动物害虫,尤其是昆虫。
节肢动物害虫以及尤其是选自昆虫和蜘蛛的害虫损坏生长和收获的作物并攻击木质居住和商业结构体,从而对食物供应和财产造成大的经济损失。它们还可以用作人、动物和植物病害的媒介并引起卫生问题。因此,已经倾注很多努力以提供有效防治害虫的方法。这些方法中的大多数依赖于施用干扰待防治害虫的代谢的有机化合物。为了有效防止,要求害虫与活性化合物或其代谢产物接触或甚至摄取它们。因此,要求将活性有机化合物以确保害虫与活性化合物接触或活性化合物被待防治害虫吸收的方式配制并施用。
在植物保护中,杀虫剂化合物大多数情况下以含水喷雾液或粉剂施用,以实现杀虫剂化合物的均匀分布。含水喷雾液通常通过稀释合适的杀虫剂浓缩物配制剂而得到。因为大多数杀虫剂化合物是水不溶性的,因此浓缩物配制剂含有相当量的表面活性剂。由于存在表面活性剂,雨水可能浸出杀虫剂化合物,从而导致活性和/或有效性损失。
杀虫剂化合物的其他施用形式包括固体或凝胶状配制剂,其直接施用于预计出现害虫的场所以实现杀虫剂化合物被要防治的害虫摄取或与其接触。施用的配制剂自然经受通常导致配制剂老化和有效性丧失的气候条件。
WO 91/07972描述了用于防治昆虫的凝胶型诱饵配制剂,包含水、杀虫活性成分和有效量的角叉胶以使水和杀虫活性成分形成凝胶。
WO 97/11602公开了用于防治昆虫的凝胶诱饵,包含可水合胶凝的物质和选自1-芳基吡唑的活性成分。该可胶凝物质选自结冷胶(gellan gum)、角叉胶、琼脂、明胶、节路顿胶、黄原胶、刺槐胶、多糖胶。
WO 2006/055275公开了一种用于防治苍蝇的凝胶配制剂,包含一种或多种新烟碱(neonicotinoid)、一种或多种胶凝剂和一种或多种引诱剂,该凝胶的Brookfield屈服值为50-1000且Brookfield粘度为20000-200000mPa.s。建议将淀粉、结冷胶、节路顿胶、角叉胶、琼脂、酪蛋白、明胶、角豆树胶(刺槐胶)、黄原胶、多糖胶、藻胶、聚丙烯酸酯聚合物、半合成纤维素衍生物如羧甲基纤维素、聚乙烯醇、羧基乙烯基化物、膨润土、硅酸盐和胶态二氧化硅用作胶凝剂,特别优选黄原胶以及Rhodopol G和Carbopol EZ-2型水溶性聚丙烯酸酯聚合物。
上述凝胶配制剂的活性并不令人满意,尤其是长期活性并不令人满意,因为在配制剂老化时有效性显著丧失。
WO89/12450公开了用于防治陆生昆虫或害虫种群的杀虫输送组合物,包含至少一种能够吸收超过其重量100倍的水的超吸收聚合物和至少一种杀昆虫或杀害虫化合物。超吸收聚合物用于引入或包封杀虫化合物。该文献没有解决可直接施用配制剂的老化问题,也没有解决当杀虫剂化合物以可喷雾液施用时的浸出问题。此外,WO89/12450所公开的组合物在这些问题上并不令人满意。
DE 10124297公开了用于植物保护的活性化合物配制剂,包含超吸收聚合物,提供了降低的活性化合物植物毒性并因此适用于植物的营养介质。这些配制剂通过将超吸收聚合物和活性成分在水存在下捏合而得到。这些配制剂的有效性并不完全令人满意。该文献没有解决与浸出和老化相关的问题。
DE 10157350公开了包含超吸收聚合物的活性化合物配制剂,通过在水存在下捏合超吸收聚合物和活性成分而得到。所测试的配制剂含有杀真菌剂。这些组合物的有效性并不完全令人满意。该文献没有解决与浸出和老化有关的问题。
本发明的目的是提供一种杀虫组合物,其可以直接施用或作为含水喷雾液施用且克服了现有技术的问题。具体而言,这些组合物应提供增加的杀虫剂化合物活性和/或降低老化或浸出。
惊人地发现这些和其他目的可以通过凝胶或固体形式的杀虫剂组合物实现,该组合物除了至少一种杀虫剂化合物外还含有0.5-20重量%至少一种超吸收聚合物P(对去离子水的吸收容量至少为100g/1g聚合物P),5-94.5重量%至少一种不同于水的填料和5-94.5重量%水,其中载体与超吸收聚合物P和水一起提供具有凝胶状或固体结构的杀虫剂组合物。
因此,本发明涉及一种凝胶或固体形式的杀虫剂组合物,其含有:
i)0.001-50重量%至少一种对节肢动物有效的杀虫剂化合物,
ii)0.5-20重量%至少一种对去离子水的吸收容量至少为100g/1g聚合物P的超吸收聚合物P,和
iii)5-94.5重量%至少一种不同于水的填料,和
iv)5-94.5重量%水,
其中重量%基于该组合物的总重量。
本发明还涉及本文所述杀虫剂组合物在防治节肢动物害虫中的用途以及一种防治节肢动物害虫的方法,包括将本文所定义的凝胶组合物直接或作为含水稀释液施用于其中节肢动物害虫与所述组合物接触的场所。
本发明组合物具有固体或凝胶状结构。该组合物的结构主要由填料与超吸收剂聚合物P和该组合物中存在的水的共同作用提供。本发明组合物提供优异的长效杀虫活性,尤其是与常规凝胶类型或固体配制剂相比。此外,它们与杀虫剂化合物的常规配制剂相比具有更高活性且因此允许降低杀虫剂化合物的施用率。此外,它们与常规液体配制剂相比显示出更好的储存稳定性。尤其是它们在储存时不显示出活性物质的分离。
根据本发明,该杀虫剂组合物包含至少一种对节肢动物有效的杀虫剂化合物。杀虫剂化合物通常是分子量为150-1000道尔顿的非聚合有机化合物。合适的杀虫剂化合物可以在室温下是固体或液体。
本发明的杀虫剂组合物优选基于该组合物的总重量含有0.01-20重量%,尤其是0.01-10重量%,尤其是0.02-5重量%的至少一种活性化合物,例如1、2、3或4种不同活性化合物,这些化合物对至少一种节肢动物,尤其是对至少一种昆虫品种具有活性。当然,该化合物可以以对不止一种昆虫品种具有活性的方式选择。
适合本发明组合物的杀虫剂化合物包括但不限于:
A.1.有机(硫代)磷酸酯类:例如高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、毒虫畏(chlorfenvinphos)、二嗪农(diazinon)、敌敌畏(dichlorvos)、百治磷(dicrotophos)、乐果(dimethoate)、乙拌磷(disulfoton)、乙硫磷(ethion)、杀螟松(fenitrothion)、倍硫磷(fenthion)、异噁唑磷(isoxathion)、马拉硫磷(malathion)、甲胺磷(methamidophos)、杀扑磷(methidathion)、甲基一六零五(methyl-parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸磷(oxydemeton-methyl)、对氧磷(paraoxon)、一六零五(parathion)、稻丰散(phenthoate)、伏杀磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、甲拌磷(phorate)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、丙硫磷(prothiofos)、乙丙硫磷(sulprophos)、杀虫威(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(triazophos)、敌百虫(trichlorfon);
A.2.氨基甲酸酯类:例如棉铃威(alanycarb)、涕灭威(aldicarb)、噁虫威(bendiocarb)、丙硫克百威(benfuracarb)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、双氧威(fenoxycarb)、呋线威(furathiocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、唑蚜威(triazamate);
A.3.合成除虫菊酯类:例如丙烯除虫菊(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、(RS)氯氟氰菊酯(cyhalothrin)、苯醚氰菊酯(cyphenothrin)、氯氰菊酯(cypermethrin)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、己体氯氰菊酯(zcta-cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、氯氟氰菊酯(lambda-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊酯(pyrethrin)I和II、灭虫菊(resmethrin)、灭虫硅醚(silafluofen)、氟胺氰菊酯(tau-fluvalinate)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin)、丙氟菊酯(profluthrin)、四氟甲醚菊酯(dimefluthrin);
A.4.生长调节剂:a)几丁质合成抑制剂:例如苯甲酰脲类,如定虫隆(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)、伏虫隆(teflubenzuron)、杀虫隆(tritlumuron);噻嗪酮(buprofezin)、噁茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯噁唑(etoxazole)、四螨嗪(clofentazine);b)蜕皮激素拮抗剂:例如特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide)、艾扎丁(azadirachtin);c)保幼激素类似物:例如蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)、双氧威(fenoxycarb);d)类脂生物合成抑制剂:例如螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)或螺虫乙酯(spirotetramat);
A.5.烟碱受体激动剂/拮抗剂化合物(烟碱杀虫剂或新烟碱):例如噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、吡虫清(acetamiprid)、噻虫啉(thiacloprid)或式P1的噻唑化合物:
A.6.GABA拮抗剂化合物:例如乙酰虫腈(acetoprole)、硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、式P2的苯基吡唑化合物(5-氨基-3-(氨基硫羰基)-1-(2,6-二氯-4-三氟甲基苯基)-4-(三氟甲基亚磺酰基)吡唑):
以及下述式P5的化合物,尤其是式P5a和P5b的化合物;
A.7.大环内酯杀虫剂:齐墩螨素(abamectin)、甲氨基阿维菌素(emamectin)、米尔螨素(milbemectin)、lepimectin、艾克敌105(spinosad)、式P3化合物(CAS No.187166-40-1):
A.8.线粒复合体I电子输送抑制剂(METI I化合物):例如喹螨醚(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、flufenerim;
A.9.线粒复合体II和/或复合体III电子输送抑制剂(METI II和III化合物):例如灭螨醌(acequinocyl)、fluacyprim、灭蚁腙(hydramethylnon);
A.10.分离剂化合物:例如氟唑虫清(chlorfenapyr);
A.11.氧化磷酸化抑制剂化合物:三环锡(cyhexatin)、杀螨硫隆(diafenthiuron)、杀螨锡(fenbutatin oxide)、克螨特(propargite);
A.12.蜕皮干扰剂(Moulting disruptor)化合物:例如cryomazine;
A.13.混合功能氧化酶抑制剂化合物:例如增效醚(piperonyl butoxide);
A.14.钠通道阻断剂化合物:例如噁二唑虫(indoxacarb)、氰氟虫胺(metaflumizone);
A.15.其他:benclothiaz、联苯肼酯(bifenazate)、杀螟丹(cartap)、氟啶虫酰胺(flonicamid)、啶虫丙醚(pyridalyl)、拒嗪酮(pymetrozine)、硫、硫环杀(thiocyclam)、氟虫酰胺(flubendiamide)、cyenopyrafen、吡氟硫磷(flupyrazofos)、丁氟螨酯(cyflumetofen)、amidoflumet、式P4的氨基喹唑啉化合物(1-乙酰基-2-氧代-3-(吡啶-3-基甲基)氨基-6-七氟丙基-1,2,3,4-四氢喹唑啉):
式P5化合物:
其中X和Y各自独立地为卤素,尤其氯;
W为卤素或C1-C2卤代烷基,尤其是三氟甲基;
R1为C1-C6烷基、C2-C6链烯基、C2-C6炔基、C1-C4烷氧基-C1-C4烷基或C3-C6环烷基,它们各自可以被1、2、3、4或5个卤原子取代,R1尤其为甲基或乙基;
R2和R3为C1-C6烷基,尤其是甲基,或者可以与相邻碳原子一起形成C3-C6环烷基结构部分,尤其是环丙基结构部分,其可以带有1、2或3个卤原子,实例包括2,2-二氯环丙基和2,2-二溴环丙基;和
R4为氢或C1-C6烷基,尤其是氢、甲基或乙基;
例如下式P5a和P5b的化合物:
和
式P6的邻氨基苯甲酰胺(anthranilamide)化合物:
其中A1为CH3、Cl、Br、I,X为C-H、C-Cl、C-F或N,Y’为F、Cl或Br,Y”为F、Cl、CF3,B1为氢、Cl、Br、I、CN,B2为Cl、Br、CF3、OCH2CF3、OCF2H以及RB为氢、CH3或CH(CH3)2;
以及如JP 2002 284608、WO 02/89579、WO 02/90320、WO 02/90321、WO 04/06677、WO 04/20399或JP 200499597所述的丙二腈化合物。
合适的杀虫剂化合物还包括微生物如苏云金芽孢杆菌(Bacillusthuringiensis)、Bacillus tenebrionis和枯草芽孢杆菌(Bacillus subtilis)。
合适的杀虫剂化合物尤其描述于“The Pesticide Manual”,第13版,British Crop Protection Council(2003)。式P2的硫羰胺及其制备已经描述于WO98/28279中。Lepimection由Agro Project,PJB Publications Ltd,2004年11月已知。Benclothiaz及其制备已经描述于EP-A 454621中。杀扑磷和对氧磷及其制备已经描述于Farm Chemicals Handbook,第88卷,Meister Publishing Company,2001中。乙酰虫腈及其制备已经描述于WO 98/28277中。氰氟虫胺及其制备已经描述于EP-A 462 456中。吡氟硫磷已经描述于Pesticide Science 54,1988,第237-243页和US 4822779中。Pyrafluprole及其制备已经描述于JP 2002193709和WO 01/00614中。Pyriprole及其制备已经描述于WO 98/45274和US 6335357中。Amidoflumet及其制备已经描述于US 6221890和JP 21010907中。Flufenerim及其制备已经描述于WO 03/007717和WO 03/007718中。丁氟螨酯及其制备已经描述于WO 04/080180中。式P5化合物例如已经描述于EP-A 604798中。式P6的邻氨基苯甲酰胺及其制备已经描述于WO 01/70671、WO 02/48137、WO 03/24222、WO 03/15518、WO 04/67528、WO 04/33468和WO 05/118552中。
优选的组合物含有至少一种选自合成除虫菊酯类、GABA拮抗剂化合物、钠通道阻断剂化合物、烟碱受体激动剂/拮抗剂化合物、式P5化合物、式P6化合物和分离剂化合物的杀虫剂化合物。特别优选的组合物含有至少一种选自氟氯菊酯、七氟菊酯、甲体氯氰菊酯或氯氟氰菊酯、乙虫清、pyriprole、锐劲特、氰氟虫胺、吡虫清、噻虫胺、吡虫啉、硝胺烯啶、噻虫啉、噻虫嗪、呋虫胺(dinetofuran)、式P5化合物(尤其是式P5a或P5b化合物)、式P6化合物和氟唑虫清的杀虫剂化合物。
在优选实施方案中,该杀虫剂组合物含有至少一种选自合成除虫菊酯类,尤其是选自氟氯菊酯、七氟菊酯、甲体氯氰菊酯或氯氟氰菊酯的杀虫剂化合物。
在另一优选实施方案中,该杀虫剂组合物含有至少一种选自GABA拮抗剂化合物,尤其是选自乙虫清、pyriprole和锐劲特的杀虫剂化合物。在该实施方案中,该杀虫剂组合物可以含有至少一种选自式P5化合物,尤其是式P5a或P5b化合物的杀虫剂化合物。
在另一优选实施方案中,该杀虫剂组合物含有至少一种选自钠通道阻断剂化合物,尤其是氰氟虫胺的杀虫剂化合物。
在另一优选实施方案中,该杀虫剂组合物含有至少一种选自烟碱受体激动剂/拮抗剂化合物化合物,尤其是选自吡虫清、噻虫胺、吡虫啉、硝胺烯啶、噻虫啉、噻虫嗪和呋虫胺的杀虫剂化合物。
在本发明的另一优选实施方案中,该杀虫剂组合物含有至少一种本文所定义的式P5化合物,尤其是式P5a或P5b化合物。
在本发明的另一优选实施方案中,该杀虫剂组合物含有至少一种本文所定义的式P6化合物。
在本发明的另一优选实施方案中,该杀虫剂组合物含有至少一种分离剂化合物,尤其是氟唑虫清。
本发明的杀虫剂组合物优选基于该组合物的总重量含有0.5-20重量%,尤其是0.8-10重量%,尤其是1-5重量%的至少一种超吸收聚合物。
取决于活性成分的类型,该组合物可以用于防治大量节肢动物害虫,包括昆虫和蜘蛛。
它们特别可以用于防治例如下列目的昆虫害虫:
鳞翅目昆虫(鳞翅目(Lepidoptera)),例如小地老虎(Agrotis ypsilon)、黄地老虎(Agrotis segetum)、木棉虫(Alabama argillacea)、黎豆夜蛾(Anticarsiagemmatalis)、Argyresthia conjugella、叉纹夜蛾(Autographa gamma)、树尺蠖(Bupalus piniarius)、Cacoecia murinana、Capua reticulana、Cheimatobia brumata、云杉色卷蛾(Choristoneura fumiferana)、Choristoneura occidentalis、二化螟(Cirphis unipuncta)、苹果小卷蛾(Cydiapomonella)、松毛虫(Dendrolimus pini)、Diaphania nitidalis、西南玉米杆草螟(Diatraea grandiosella)、埃及钻夜蛾(Earias insulana)、南美玉米苗斑螟(Elasmopalpus lignosellus)、女贞细卷蛾(Eupoecilia ambiguella)、Evetriabouliana、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(Heliothiszea)、菜螟(Hellula undalis)、Hibernia defoliaria、美国白蛾(Hyphantriacunea)、苹果巢蛾(Hyponomeuta malinellus)、番茄虫蛾(Keiferialycopersicella)、Lambdina fiscellaria、甜菜夜蛾(Laphygma exigua)、咖啡潜叶蛾(Leucoptera coffeella)、旋纹潜蛾(Leucoptera scitella)、Lithocolletisblancardella、葡萄浆果小卷蛾(Lobesia botrana)、甜菜网螟(Loxostegesticticalis)、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)、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、麦蛾(Sitotroga cerealella)、葡萄卷叶蛾(Sparganothis pilleriana)、草地夜蛾(Spodoptera frugiperda)、海灰翅夜蛾(Spodoptera littoralis)、斜纹夜蛾(Spodoptera litura)、Thaumatopoeapityocampa、绿色橡木飞蛾(Tortrix viridana)、粉纹夜蛾(Trichoplusia ni)和Zeiraphera canadensis;
甲虫(鞘翅目(Coleoptera)),例如梨窄吉丁(Agrilus sinuatus)、直条叩头虫(Agriotes Iineatus)、暗色叩头虫(Agriotes obscurus)、Amphimallussolstitialis、Anisandrus dispar、墨西哥棉铃象(Anthonomus grandis)、苹花象(Anthonomus pomorum)、Aphthona euphoridae、Athoushaemorrhoidalis、甜菜隐食甲(Atomaria linearis)、纵坑切梢小蠹(Blastophagus piniperda)、Blitophaga undata、蚕豆象(Bruchusrufimanus)、豌豆象(Bruchus pisorum)、欧洲兵豆象(Bruchus lentis)、苹卷象(Byctiscus betulae)、甜菜大龟甲(Cassida nebulosa)、Cerotomatrifurcata、金花金龟(Cetonia aurata)、白菜籽龟象(Ceuthorrhynchusassimilis)、芫菁龟象(Ceuthorrhynchus napi)、甜菜胫跳甲(Chaetocnematibialis)、Conoderus vespertinus、石刁柏负泥虫(Crioceris asparagi)、Ctenicera ssp.、长角叶甲(Diabrotica longicornis)、Diabroticasemipunctata、Diabrotica 12-punctata、南美叶甲(Diabrotica speciosa)、玉米根叶甲(Diabrotica virgifera)、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(Lema bilineata)、黑角负泥虫(Lema melanopus)、马铃薯叶甲(Leptinotarsadecemlineata)、Limonius californicus、稻水象甲(Lissorhoptrusoryzophilus)、Melanotus communis、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)、草莓根象甲(Otiorrhynchus ovatus)、辣根猿叶甲(Phaedon cochleariae)、梨树叶象(Phyllobius pyri)、Phyllotreta chrysocephala、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)、日本金龟子(Popillia japonica)、豌豆叶象(Sitona lineatus)和谷象(Sitophilus granaria);蝇、蚊(双翅目(Diptera)),例如埃及伊蚊(Aedes aegypti)、白纹伊蚊(Aedesalbopictus)、剌扰伊蚊(Aedes vexans)、墨西哥果蝇(Anastrepha ludens)、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)、橄榄蝇(bactrocera olea)、红头丽蝇(Calliphora vicina)、地中海实蝇(Ceratitiscapitata)、蛆症金蝇(Chrysomya bezziana)、Chrysomya hominivorax、Chrysomya macellaria、鹿蝇(Chrysops discalis)、Chrysops silacea、Chrysops atlanticus、螺旋蝇(Cochliomyia hominivorax)、高粱瘿蚊(Contarinia sorghicola)、嗜人瘤蝇蛆(Cordylobia anthropophaga)、狂怒库蠓(Culicoides furens)、尖音库蚊(Culex pipiens)、斑蚊(Culex nigripalpus)、致倦库蚊(Culex quinquefasciatus)、媒斑蚊(Culex tarsalis)、Culisetainornata、Culiseta melanura、瓜蝇(Dacus cucurbitae)、油橄榄实蝇(Dacusoleae)、油菜叶瘿蚊(Dasineura brassicae)、Delia antique、麦地种蝇(Deliacoarctata)、灰地种蝇(Delia platura)、甘蓝地种蝇(Delia radicum)、Dermatobia hominis、小毛厕蝇(Fannia canicularis)、GeomyzaTripunctata、马蝇(Gasterophilus intestinalis)、刺舌蝇(Glossina morsitans)、须舌蝇(Glossina palpalis)、Glossina fuscipes、胶舌蝇(Glossinatachinoides)、Haematobia irritans、Haplodiplosis equestris、潜蝇属(Hippelates)、花生田灰地种蝇(Hylemyia platura)、纹皮蝇(Hypodermalineata)、Leptoconops torrens、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、Mansonia titillanus、麦瘿蚊(Mayetiola destructor)、家蝇(Musca domestica)、厩腐蝇(Muscinastabulans)、羊狂蝇(Oestrus ovis)、Opomyza florum、欧洲麦秆蝇(Oscinellafrit)、天仙子泉蝇(Pegomya hysocyami)、葱蝇(Phorbia antiqua)、萝卜蝇(Phorbia brassicae)、麦地种蝇(Phorbia coarctata)、银足白蛉(Phlebotomusargentipes)、Psorophora columbiae、胡萝卜茎蝇(Psila rosae)、Psorophoradiscolor、Prosimulium mixtum、樱桃实蝇(Rhagoletis cerasi)、苹果实蝇(Rhagoletis pomonella)、赤尾麻蝇(Sarcophaga haemorrhoidalis)、肉蝇属(Sarcophaga)、Simulium vittatum、厩螫蝇(Stomoxys calcitrans)、牛虻(Tabanus bovinus)、Tabanus atratus、红色原虻(Tabanus lineola)、Tabanussimilis、Tipula oleracea和欧洲大蚊(Tipula paludosa);
蓟马(缨翅目(Thysanoptera)),例如兰花蓟马(Dichromothrips corbetti)、Dichromothrips ssp.、烟褐蓟马(Frankliniella fusca)、苜蓿花蓟马(Frankliniella occidentalis)、东方花蓟马(Frankliniella tritici)、桔硬蓟马(Scirtothrips citri)、稻蓟马(Thrips oryzae)、棕榈蓟马(Thrips palmi)和烟蓟马(Thrips tabaci);
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(Blattodea)),例如德国小蠊(Blattella germanica)、Blattellaasahinae、美洲蟑螂(Periplaneta americana)、日本大蠊(Periplanetajaponica)、棕色蜚蠊(Periplaneta brunnea)、Periplaneta fuligginosa、澳洲蜚蠊(Periplaneta australasiae)和东方蜚蠊(Blatta orientalis),
臭虫(半翅目(Hemiptera)),例如拟绿蝽(Acrosternum hilare)、玉米长蝽(Blissus leucopterus)、黑斑烟盲蝽(Cyrtopeltis notatus)、棉红蝽(Dysdercus cingulatus)、Dysdercus intermedius、麦扁盾蝽(Eurygasterintegriceps)、烟草蝽(Euschistus impictiventris)、棉红铃喙缘蝽(Leptoglossus phyllopus)、美洲牧草盲蝽(Lygus lineolaris)、牧草盲蝽(Lygus pratensis)、稻绿蝽(Nezara viridula)、甜菜拟网蝽(Piesmaquadrata)、Solubea insularis、Thyanta perditor、Acyrthosiphononobrychis、落叶松球蚜(Adelges Iaricis)、Aphidula nasturtii、甜菜蚜(Aphis fabae)、草莓根蚜(Aphis forbesi)、苹果蚜(Aphis pomi)、棉蚜(Aphis gossypii)、北美茶簏子蚜(Aphis grossulariae)、希奈德蚜(Aphisschneideri)、卷叶蚜(Aphis spiraecola)、接骨木蚜(Aphis sambuci)、豌豆蚜(Acyrthosiphon pisum)、茄无网蚜(Aulacorthum solani)、银叶粉虱(Bemisia argentifolii)、飞廉短尾蚜(Brachycaudus cardui)、李短尾蚜(Brachycaudus helichrysi)、桃短尾蚜(Brachycaudus persicae)、Brachycaudus prunicola、甘蓝蚜(Brevicoryne brassicae)、Capitophorushorni、Cerosipha gossypii、草莓中瘤钉毛蚜(Chaetosiphon fragaefolii)、茶镳隐瘤蚜(Cryptomyzus ribis)、高加索冷杉椎球蚜(Dreyfusianordmannianae)、云杉椎球蚜(Dreyfusia piceae)、居根西圆尾蚜(Dysaphisradicola)、Dysaulacorthum pseudosolani、车前圆尾蚜(Dysaphisplantaginea)、梨西圆尾蚜(Dysaphis pyri)、蚕豆微叶蝉(Empoascafabae)、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)、巢莱修尾蚜(Megoura viciae)、Melanaphispyrarius、麦无网蚜(Metopolophium dirhodum)、Myzodes persicae、冬葱瘤额蚜(Myzus ascalonicus)、Myzus cerasi、李瘤蚜(Myzus varians)、黑茶镳子衲长管蚜(Nasonovia ribis-nigri)、稻飞虱(Nilaparvata lugens)、囊柄瘿绵蚜(Pemphigus bursarius)、蔗飞虱(Perkinsiella saccharicida)、忽布疣蚜(Phorodon humuli)、苹木虱(Psylla mali)、梨木虱(Psylla piri)、冬葱瘤蛾蚜(Rhopalomyzus ascalonicus)、玉米蚜(Rhopalosiphum maidis)、禾谷溢管蚜(Rhopalosiphum padi)、苹草缢管蚜(Rhopalosiphum insertum)、Sappaphis mala、Sappaphis mali、麦二叉蚜(Schizaphis graminum)、Schizon euralanuginosa、麦长管蚜(Sitobion avenae)、白粉虱(Trialeurodes vaporariorum)、桔二叉蚜(Toxoptera aurantiiand)、葡萄根瘤蚜(Viteus vitifolii)、温带臭虫(Cimex lectularius)、热带臭虫(Cimexhemipterus)、Reduvius senilis、Triatoma属和Arilus critatus;
蚂蚁、蜜蜂、黄蜂、锯蝇(膜翅目(Hymenoptera)),例如新疆菜叶蜂(Athalia rosae)、切叶蚁(Atta cephalotes)、Atta capiguara、Attalaevigata、Atta robusta、Atta sexdens、Atta texana、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)、Pogonomyrmexcalifornicus、Pheidole megacephala、天鹅绒蚂蚁(Dasymutillaoccidcntalis)、熊蜂属(Bombus)、大黄蜂(Vespula squamosa)、Paravespula vulgaris、Paravespula pennsylvanica、Paravespulagermanica、姬胡蜂(Dolichovespula maculata)、黄边胡蜂(Vespacrabro)、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)、Oedaleus senegalensis、臭腹腺蝗(Zonozerus variegatus)、Hieroglyphusdaganensis、Kraussaria angulifera、意大利蝗(Calliptamus italicus)、澳大利亚灾蝗(Chortoicetes terminifera)和褐飞蝗(Locustana pardalina);
蠼螋(革翅目(Dermaptera)),例如地蜈蚣(forficula auricularia);
衣鱼、家衣鱼(缨尾目(Thysanura)),例如西洋衣鱼(Lepisma saccharina)和小灶衣鱼(Thermobia domestica);
虱(虱目(Phthiraptera)),例如人头虱(Pediculus humanus capitis)、人体虱(Pcdiculus humanus corporis)、耻阴虱(Pthirus pubis)、阔胸血虱(Haematopinus eurysternus)、猪血虱(Haematopinus suis)、狐颚虱(Linognathus vituli)、牛毛虱(Bovicola bovis)、鸡羽虱(Menopongallinac)、火鸡短角鸟虱(Menacanthus stramineus)和牛管虱(Solenopotescapillatus);以及
蚤(蚤目(Siphonaptera)),例如猫蚤(Ctenocephalides felis)、狗蚤(Ctcnocephalides canis)、鼠蚤(Xenopsylla cheopis)、致痒蚤(Pulexirritans)、穿皮潜蚤(Tunga penetrans)和具带病蚤(Nosopsyllus fasciatus)。
它们同样可以用于防治蜘蛛害虫(蛛形纲(Arachnida)),例如下列科: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)、Ambryomma maculatum、波斯锐缘蜱(Argas persicus)、牛壁虱(Boophilusannulatus)、Boophilus decoloratus、微小牛蜱(Boophilus microplus)、Dermacentor silvarum、Dermacentor andersoni、美国狗壁虱(Dermacentor variabilis)、Hyalomma truncatum、蓖子硬蜱(Ixodesricinus)、Ixodes rubicundus、黑脚硬蜱(Ixodes scapularis)、Ixodesholocyclus、太平洋硬蜱(Ixodes pacificus)、Ornithodorus moubata、Ornithodorus hermsi、Ornithodorus turicata、柏氏禽刺螨(Ornithonyssusbacoti)、Otobius megnini、鸡皮刺螨(Dermanyssus gallinae)、绵羊疥病(Psoroptes ovis)、血红扇头蜱(Rhipicephalus sanguineus)、Rhipicephalusappendiculatus、Rhipicephalus evertsi、人疥螨(Sarcoptes scabiei)和瘿螨属(Eriophyidae),如苹果刺锈螨(Aculus schlechtendali)、Phyllocoptrataoleivora和Eriophyes sheldoni;细螨属(Tarsonemidae),如Phytonemuspallidus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(Panonychusulmi)、柑椐叶螨(Panonychus citri)和oligonychuspratensisand;蜘蛛目(Araneida),例如黑寡妇(Latrodectus mactans)和棕色隐遁蜘蛛(Loxosceles reclusa)。
它们同样可以用于防治例如如下目的多足害虫(多足纲(myriapoda)):百足虫(唇足纲(Chilopoda)),如蚰蜒(Scutigera coleoptrata)和千足虫(倍足纲(Diplopoda)),例如Narceus spp.。
在本发明的优选实施方案中,杀虫剂化合物选自对至少一种选自下列目的昆虫品种具有活性的化合物:膜翅目,蜚蠊目,尤其是蜚蠊科(blattidae)和姬蜚蠊科(blattellidae),等翅目,双翅目和鳞翅目。在本发明的另一优选实施方案中,杀虫剂化合物选自对至少一种选自下列目的植物损害性昆虫品种具有活性的化合物:膜翅目、等翅目、双翅目、鞘翅目和鳞翅目。
在特别优选的实施方案中,杀虫剂化合物选自对鞘翅目昆虫品种,尤其是叶甲属(diabrotica)昆虫品种具有活性的化合物。
在另一特别优选的实施方案中,杀虫剂化合物选自对蜚蠊目昆虫品种具有活性的化合物。
在另一特别优选的实施方案中,杀虫剂化合物选自对双翅目昆虫品种,尤其是实蝇属(ceratitis)如地中海实蝇和小实蝇属(bactrocera)如橄榄蝇。
熟练技术人员熟知该类化合物且知道何种化合物对特定的目标生物体具有活性。
超吸收聚合物是众所周知的合成有机聚合物,它们为固体且亲水,不溶于水并且能够吸收多倍于其重量的水或水溶液,从而形成含水聚合物凝胶。本发明的超吸收聚合物通常能够吸收至少100重量份水/1重量份超吸收聚合物(去离子水,25℃,pH 7.5,1巴)。超吸收聚合物能够吸收的水或水溶液的量也称为吸收容量或最大吸收。对本发明而言,优选对去离子水的吸收容量(pH 7.5,25℃,1巴)至少为150g/g,例如150-500g/g,尤其是200-500g/g,更优选300-500g/g超吸收聚合物的超吸收聚合物。对本发明而言,优选对0.1重量%氯化钠水溶液的吸收容量至少为100g/g,尤其是100-300g/g超吸收聚合物(pH 7.5,25℃,1巴)的超吸收聚合物。最大吸收或吸收容量可以由例如从F.L.Buchholz等“现代超吸收聚合物技术”,Wiley-VCH 1998,第153页(吸收容量方法)或EP 993 337实施例6已知的常规方法测定。
优选的超吸收聚合物是具有中等溶胀速率的那些,即超吸收剂,其中达到最大吸收的60%所需时间至多为20分钟,尤其是1-10分钟。这些值可以根据F.L.Buchholz等,同上,第154页(溶胀动力学方法)中所述的标准方法测定。
该超吸收聚合物可以是非离子或离子性交联聚合物。对本发明而言,该超吸收聚合物优选选自交联的阴离子超吸收聚合物,尤其是共价交联的阴离子超吸收聚合物。合适超吸收聚合物的综述例如给于F.L.Buchholz等,同上,第11-14页中。
交联的阴离子超吸收聚合物是包含阴离子官能基团或可以在水中中和的酸性基团的交联聚合物,酸性基团例如为磺酸基团(SO3H或SO3 -)、膦酸基团(PO3H2或PO3 2-)或羧酸基团(CO2H或CO2 -)。这些聚合物原则上可以通过单烯属不饱和酸性单体和交联性单体任选在接枝基质存在下以及任选在其他中性单烯属不饱和单体存在下共聚而得到。在优选的超吸收聚合物中,羧酸基团占酸性基团的至少80mol%,尤其是至少95mol%。
合适的酸性单体包括具有3-8个碳原子的单烯属不饱和单羧酸和二羧酸,如丙烯酸、甲基丙烯酸、乙基丙烯酸、α-氯丙烯酸、巴豆酸、马来酸、马来酸酐、衣康酸、柠康酸、中康酸、戊烯二酸、乌头酸和富马酸;具有4-10个,优选4-6个碳原子的单烯属不饱和二羧酸的单酯,例如马来酸的单酯如马来酸单甲酯;单烯属不饱和磺酸和膦酸,例如乙烯基磺酸、烯丙基磺酸、丙烯酸磺基乙酯、甲基丙烯酸磺基乙酯、丙烯酸磺基丙酯、甲基丙烯酸磺基丙酯、2-羟基-3-丙烯酰氧基丙基磺酸、2-羟基-3-甲基丙烯酰氧基丙基磺酸、苯乙烯磺酸、2-丙烯酰胺基-2-甲基丙烷磺酸、乙烯基膦酸和烯丙基膦酸以及这些酸的盐,尤其是钠、钾和铵盐。酸性单体通常占超吸收聚合物的至少15重量%,优选至少20重量%,例如基于阴离子超吸收聚合物的酸性形式为15-99.9重量%,尤其是20-99.8重量%。
优选交联的阴离子超吸收聚合物,其中聚合的酸性单体包含至少一种单烯属不饱和羧酸CA或其盐。优选该单烯属不饱和羧酸CA或其盐占聚合的酸性单体总量的至少80mol%,尤其是至少95mol%。
有用的交联单体包括分子中具有至少2个,例如2、3、4或5个烯属不饱和双键的化合物。这些化合物也称为交联剂单体。交联剂单体的实例是N,N′-亚甲基双丙烯酰胺,聚乙二醇二丙烯酸酯和聚乙二醇二甲基丙烯酸酯(各自衍生于分子量为106-8500,优选400-2000的聚乙二醇),三羟甲基丙烷三丙烯酸酯,三羟甲基丙烷三甲基丙烯酸酯,乙二醇二丙烯酸酯,乙二醇二甲基丙烯酸酯,丙二醇二丙烯酸酯,丙二醇二甲基丙烯酸酯,丁二醇二丙烯酸酯,丁二醇二甲基丙烯酸酯,己二醇二丙烯酸酯,己二醇二甲基丙烯酸酯,二甘醇二丙烯酸酯,二甘醇二甲基丙烯酸酯,三甘醇二丙烯酸酯,三甘醇二甲基丙烯酸酯,二丙二醇二丙烯酸酯,二丙二醇二甲基丙烯酸酯,三丙二醇二丙烯酸酯,三丙二醇二甲基丙烯酸酯,甲基丙烯酸烯丙基酯,氧化乙烯和氧化丙烯的嵌段共聚物的二丙烯酸酯和二甲基丙烯酸酯,二-、三-、四-或五丙烯酸酯化或-甲基丙烯酸酯化多元醇,如甘油、三羟甲基丙烷、季戊四醇或二季戊四醇,单烯属不饱和羧酸与烯属不饱和醇如烯丙醇、环己烯醇和双环戊烯基醇的酯,例如丙烯酸烯丙基酯和甲基丙烯酸烯丙基酯,还有三烯丙基胺,二烷基二烯丙基卤化铵如二甲基二烯丙基氯化铵和二乙基二烯丙基氯化铵,四烯丙基乙二胺,二乙烯基苯,邻苯二甲酸二烯丙基酯,分子量为106-4000的聚乙二醇的聚乙二醇二乙烯基醚,三羟甲基丙烷二烯丙基醚,丁二醇二乙烯基醚,季戊四醇三烯丙基醚,1mol乙二醇二缩水甘油醚或聚乙二醇二缩水甘油醚与2mol季戊四醇三烯丙基醚或烯丙醇的反应产物,以及二乙烯基亚乙基脲。交联剂单体的量基于酸性形式的超吸收聚合物重量优选为0.1-10重量%,尤其是0.2-5重量%。
合适的接枝基质可以是天然或合成来源的。它们包括寡糖和多糖,如淀粉,即天然淀粉,选自玉米淀粉、土豆淀粉、小麦淀粉、稻淀粉、木薯淀粉、高粱淀粉、木薯淀粉、豌豆淀粉或其混合物,改性淀粉,淀粉降解产物,例如氧化、酶催或水解降解淀粉,糊精,例如焙炒糊精,还有低级寡糖和多糖,例如具有4-8个环成员的环糊精。有用的寡糖和多糖进一步包括纤维素以及淀粉和纤维素衍生物。还可以使用聚乙烯醇、N-乙烯基吡咯烷酮的均聚物和共聚物、聚胺、聚酰胺、亲水性聚酯或聚氧化烯,尤其是聚氧乙烯和聚氧丙烯作为接枝基质。接枝基质的量可以至多为酸性形式的超吸收聚合物重量的50重量%,例如1-50重量%。在优选实施方案中,接枝基质的量小于酸性形式的超吸收聚合物重量的10重量%,或者基本不存在接枝基质(<1重量%)。
形成超吸收聚合物的单体还可以含有不具有酸性基团的中性单烯属不饱和单体。实例是单烯属亲水性单体,即在25℃和1巴下水溶性至少为80g/l的单体,包括单烯属单羧酸的羟基烷基酯,例如丙烯酸和甲基丙烯酸的羟基烷基酯,如丙烯酸羟乙酯和甲基丙烯酸羟乙酯,单烯属单羧酸的酰胺如丙烯酰胺和甲基丙烯酰胺,具有聚醚基团的单体,如聚乙二醇的乙烯基、烯丙基和甲代烯丙基醚,以及单烯属单羧酸的和聚醚的酯,如聚乙二醇丙烯酸酯和聚乙二醇甲基丙烯酸酯。在本发明的优选实施方案中,中性单体占酸性形式的超吸收聚合物的10-84.9重量%,尤其是20-79.9重量%。
优选的阴离子超吸收聚合物具有中等电荷密度,即酸性基团在超吸收聚合物中的量优选为0.1-1.1mol/100g超吸收聚合物,尤其是0.2-1mol/100g超吸收聚合物,基于酸性形式的超吸收聚合物重量。
在本发明的非常优选实施方案中,超吸收聚合物为烯属不饱和单体M的交联共聚物或接枝共聚物,该单体M包含至少一种单烯属不饱和羧酸CA或其盐和至少一种单烯属不饱和酸的酰胺(单体AM)。
合适的单烯属不饱和羧酸CA包含具有3-8个碳原子的单烯属不饱和单羧酸,如丙烯酸和甲基丙烯酸,以及具有4-8个碳原子的单烯属不饱和二羧酸,如马来酸、富马酸、衣康酸和柠康酸。单烯属不饱和羧酸CA的合适盐包括碱金属盐和铵盐,尤其是钾或钠盐。优选的单烯属不饱和羧酸CA包括具有3-8个碳原子的单羧酸,尤其是丙烯酸和甲基丙烯酸及其盐,尤其是其碱金属盐,更优选丙烯酸的碱金属盐,尤其是丙烯酸的钠盐和钾盐。
单烯属不饱和羧酸的合适酰胺是具有3-8个碳原子的单烯属不饱和单羧酸的酰胺,尤其是丙烯酰胺和甲基丙烯酰胺。
在该实施方案中,超吸收聚合物优选为共价交联的共聚物,即该超吸收聚合物除了聚合的单体CA和AM外还含有聚合的交联单体,优选其量基于酸性形式的超吸收聚合物为0.1-10重量%,尤其是0.2-5重量%,单体AM和CA的总量基于酸性形式的超吸收聚合物占至少80重量%,更优选至少90重量%,尤其是90-99.9%。
优选羧酸CA和酰胺AM在形成超吸收聚合物的烯属不饱和单体M中占至少80重量%,更优选至少90重量%。
在特别优选的实施方案中,单体M基于单体M的总重量包含至少90重量%的丙烯酸或其盐(尤其是其碱金属盐,更优选丙烯酸的钾盐)与丙烯酰胺的混合物。
具体而言,超吸收聚合物以聚合形式包含:
-15-89.9重量%,尤其是20-79.8重量%至少一种羧酸CA或其盐,优选丙烯酸或其盐,尤其是其碱金属盐,更优选丙烯酸的钾盐(以酸性形式计算),
-10-84.9重量%,尤其是20-79.8重量%至少一种酰胺AM,优选具有3-8个碳原子的单烯属不饱和单羧酸的酰胺,尤其是丙烯酰胺;和
-0.1-10重量%,尤其是0.2-5重量%至少一种交联剂单体,
其中重量%基于酸性形式的超吸收聚合物,单体AM和CA的量在形成超吸收聚合物的单体中占至少90%,例如90-99.9%,或单体AM和CA的总量基于酸性形式的超吸收聚合物占至少80重量%,更优选至少90重量%,尤其是90-99.9%。
合适的这类超吸收聚合物在本领域是已知的,例如由US 4,417,992、US 3,669,103和WO 01/25493已知。它们还可以市购,例如由法国SNF SA.以商标,如3500S市购。
在本发明的另一非常优选实施方案中,超吸收聚合物为烯属不饱和单体M的交联共聚物或接枝共聚物,其基于单体M的总量包含至少80重量%,优选至少90重量%的至少一种单烯属不饱和羧酸CA,优选丙烯酸和至少一种单烯属不饱和羧酸CA的碱金属盐,优选其钾盐或钠盐,更优选丙烯酸的钾盐或钠盐的混合物。在该实施方案中,超吸收聚合物优选为共价交联的共聚物,即该超吸收聚合物除了聚合的羧酸CA和CA的盐外还含有聚合的交联单体,优选其量基于酸性形式的超吸收聚合物为0.1-10%,尤其是0.2-5重量%,羧酸CA和CA的盐的总量基于酸性形式的超吸收聚合物占至少80重量%,更优选至少90重量%,尤其是90-99.9%。
该实施方案的超吸收聚合物尤其以聚合形式包含:
-15-89.9重量%,尤其是20-79.8重量%至少一种羧酸CA,优选丙烯酸;
-10-84.9重量%,尤其是20-79.8重量%至少一种或其盐,尤其是其碱金属盐,更优选丙烯酸的钾盐(以酸性形式计算);和
-0.1-10重量%,尤其是0.2-5重量%至少一种交联剂单体,
其中重量%基于酸性形式的超吸收聚合物,其中羧酸CA和CA的盐的量在形成超吸收聚合物的单体中占至少90%,例如90-99.9%,或羧酸CA和CA的盐的总量基于酸性形式的超吸收聚合物占至少80重量%,更优选至少90重量%,尤其是90-99.9%。
超吸收聚合物通常用于制备粉末形式的组合物。优选超吸收剂颗粒的平均粒度不超过0.5mm,优选不超过0.3mm。平均粒度为可以通过显微镜或筛分分析测定的直径的重量平均。
在本发明的一个实施方案中,用于制备杀虫剂组合物的超吸收聚合物呈表面交联聚合物颗粒形式(见F.L.Buchholz,同上,第97-103页及其中所引用的文献)。在表面交联的聚合物颗粒中,超吸收聚合物颗粒的表面区域中的某些官能基团已经通过与多官能化合物反应而交联。表面交联可以是共价或离子交联。在另一实施方案中,超吸收聚合物颗粒没有表面交联。
根据本发明,该杀虫剂组合物进一步包含至少一种不同于水且当然也不同于杀虫剂化合物和超吸收聚合物P的填料。填料通常选自液体、固体或半固体(例如糊状)材料,其与水和超吸收聚合物P一起提供具有凝胶状或固体结构的杀虫剂组合物。填料的量基于该组合物的总重量优选为10-89.5重量%,尤其是15-84.5重量%,更优选20-79.5重量%。
填料通常为有机或无机材料或有机和无机材料的混合物,其中填料是固体、液体或半固体且本身没有杀虫活性或没有显著杀虫活性。当然,填料不同于水、杀虫剂化合物和超吸收聚合物。
填料优选为呈固体、液体或半固体且本身没有杀虫活性或没有显著杀虫活性的有机材料。合适的填料尤其包括存在于杀虫剂化合物的凝胶配制剂中的有机材料。典型填料的实例是引诱剂、辅助配制剂(即通常存在于常规杀虫配制剂中的有机材料)、调节该组合物的pH的物质和惰性载体材料。典型的填料包括引诱剂和辅助配制剂(即通常存在于常规杀虫配制剂中的有机材料),以及任选用于调节该组合物的pH的物质。然而,填料还可以包括可以为有机或无机的惰性载体材料。
优选填料包括至少一种使该组合物引诱待防治害虫的材料。该类组分也称为引诱剂。引诱剂是可以以下列方式中的一种或多种起作用的非杀虫物质:a)诱使昆虫接近该组合物或用该组合物处理的材料;b)诱使昆虫接触该组合物或用该组合物处理的材料;c)诱使昆虫采食该组合物或用该组合物处理的材料;和d)诱使昆虫返回该组合物或用该组合物处理的材料。合适的引诱剂包括非食物引诱剂和食物引诱剂,也称为进食刺激剂。
合适的非食物引诱剂是通常呈挥发性的材料。挥发性引诱剂起诱饵的作用且它们的类型以已知方式取决于要防治的害虫。非食物引诱剂包括:
-化学信息素如信息素,尤其是性信息素和聚集信息素,利它信息素,和
-天然或合成来源的调味剂。
合适的化学信息素例如可以由http://pherobase.com和T.D.Wyatt,Pheromones and Animal Behaviour:Communication by Smell and Taste,Cambridge 2003:Cambridge University Press得知。实例包括具有5-10个碳原子的挥发性链烷醇和链烯醇,具有5-10个碳原子的挥发性链烷醛和链烯醛,具有6-10个碳原子的链烷酮,1,7-二氧杂螺壬烷和3-或4-羟基-1,7-二氧杂螺十一烷,苄醇,Z-(9)-二十三碳烯(诱虫烯),二十一碳烯,丁二酮,具有5-10个碳原子的链烷酸如辛酸、月桂酸、α-蒎烯、甲基丁子香酚、十二烷酸乙酯、4-(或5-)氯-2-甲基环己烷甲酸叔丁酯、mycrenone和葫芦素。合适的调味剂包括肉调味剂、酵母调味剂、海鲜调味剂、牛奶调味剂、黄油调味剂、奶酪调味剂、洋葱调味剂以及水果调味剂如苹果、杏、香蕉、黑霉、樱桃、红醋栗、圆醋栗、葡萄、葡萄柚、悬钩子和草莓的调味剂。
合适的进食刺激剂包括:
-蛋白质,包括动物蛋白质和植物蛋白质,例如肉粉、鱼粉、鱼提取物、海鲜、海鲜提取物或血粉、昆虫部分、蟋蟀粉、酵母提取物、蛋黄、蛋白水解物、酵母自溶产物、谷蛋白水解物形式等;
-碳水化合物和氢化碳水化合物,尤其是单糖和二糖,如葡萄糖、阿拉伯糖、果糖、甘露糖、蔗糖、乳糖、半乳糖、麦芽糖、麦芽三糖、麦芽四糖或其混合物如糖蜜、玉米糖浆、槭树糖浆、转化糖和蜂蜜;多糖,包括淀粉如土豆淀粉、玉米淀粉和淀粉基材料如禾谷粉(例如小麦粉、玉米粉、麦芽粉、稻粉、稻糠),果胶和甘油,氢化单糖和寡糖(糖醇)如木糖醇、山梨醇、甘露糖醇、异麦芽糖、海藻糖和麦芽糖醇以及含麦芽糖醇的糖浆;
-脂肪和油,如植物油,例如玉米油、橄榄油、黄蒿油、亚麻子油、芥花籽油、花生油、油菜籽油、芝麻油、大豆油、向日葵油、动物来源的脂肪和油如鱼基油,还有衍生于上述脂肪和油的脂肪酸。
上述引诱剂还可以以包含挥发性材料和进食刺激剂如果汁、果浆和水果提取物,有机材料的腐败部分如水果、作物、植物、动物、昆虫或其特定部分的腐败部分的的复合混合物形式存在。
引诱剂的总量通常为该组合物的1-80重量%,尤其是5-70重量%,更优选10-60重量%。本发明的组合物尤其包含至少一种非食物引诱剂和至少一种进食刺激剂。非食物引诱剂(化学信息素和调味剂)的量通常为该组合物的0.0001-10重量%,尤其是0.001-1重量%。进食刺激剂的量通常为该组合物的1-80重量%,尤其是5-70重量%,更优选10-60重量%。
在优选实施方案中,该组合物包含至少一种选自碳水化合物和氢化碳水化合物的进食刺激剂,尤其是至少一种选自单糖或寡糖、禾谷粉和糖醇的材料,以及任选淀粉或果胶。若存在的话,碳水化合物材料和/或氢化碳水化合物材料的量为该组合物的1-50重量%,尤其是3-30重量%。在本发明的优选实施方案中,该组合物包含至少一种碳水化合物,尤其是至少一种单糖或寡糖和/或至少一种禾谷粉和至少一种氢化碳水化合物,尤其是至少一种糖醇如山梨醇或麦芽糖醇的混合物。
在本发明的优选实施方案中,该组合物包含至少一种选自脂肪酸、脂肪酸的甘油二酯和甘油三酯、脂肪醇及其混合物的疏水性材料。优选天然来源的疏水性材料,如植物或动物来源的脂肪和油以及脂肪酸,尤其是作为进食刺激剂提到的那些。本文所用术语“脂肪酸”指具有10-22个碳原子的脂族羧酸,其可以是饱和的或可以带有1、2或3个烯属双键。术语“脂肪醇”指具有10-22个碳原子的链烷醇。优选该疏水性材料选自天然来源的脂肪酸的甘油三酯如植物或动物来源的脂肪和油,实例是玉米油、亚麻子油、向日葵油、花生油、油菜籽油、橄榄油、花生黄油、芝麻油。若存在的话,疏水性材料的量通常为1-50重量%,尤其是3-30重量%。该疏水性材料可以部分或完全被具有3-10个碳原子的二醇或多元醇代替。
在本发明的优选实施方案中,该组合物包含至少一种蛋白质材料,其可以是动物或植物来源的。若存在的话,蛋白质材料的量将为该组合物的1-50重量%,尤其是2-20重量%。
本发明组合物还可以含有调节该组合物或由其得到的含水稀释液的pH的物质。调节pH的合适物质包括缓冲剂、碱和尤其是酸。
合适的酸包括有机和无机酸,尤其是有机羧酸如柠檬酸、马来酸、苹果酸、丙酮酸、乙醇酸等。其量基于该组合物的总重量通常不超过2重量%。酸尤其可以0.01-2重量%,更优选0.1-1重量%的量存在。
另外,该杀虫剂组合物可以包含辅助配制剂(添加剂),即存在于常规杀虫剂配制剂中或在杀虫剂配制剂中引入以改性其性能的化合物。辅助配制剂的量基于该组合物的总重量通常不超过20重量%或10重量%。辅助配制剂通常基于该组合物的总重量以0.01-20重量%,尤其是0.1-10重量%的量存在。
合适的辅助配制剂(添加剂)包括:
a)表面活性剂,如分散剂、润湿剂和乳化剂;
b)有机溶剂;
c)消泡剂(防沫剂);
d)增稠剂;
e)防腐剂;
f)染料或颜料;和
g)驱除剂。
表面活性剂可以是非离子、阴离子、阳离子或两性的。可以在本发明液体配制剂中包含的合适表面活性剂例如公开于“McCutcheon′sDetergents and Emulsifiers Annual”,MC Publishing Corp.,Ridgewood,NJ,USA 1981;H.Stache,“Tensid-Taschenbuch”,第2版,C.Hanser,Munich,Vienna,1981;M.和J.Ash,“Encyclopedia of表面活性剂”,第I-III卷,Chemical Publishing Co.,New York,NY,USA 1980-1981中。表面活性剂的量取决于组合物是否直接施用,即以即用凝胶形式施用。在即用凝胶中,表面活性剂的量通常基于该组合物除包含在进食刺激剂中的表面活性化合物和脂肪酸以外的总重量不超过1重量%。在水可稀释组合物中,表面活性剂的量通常基于该组合物总重量为0.1-10重量%,尤其是0.2-5重量%。
合适的表面活性剂包括:
a1)阴离子表面活性剂,包括:
-烷基磺酸盐,如月桂基磺酸盐或异十三烷基磺酸盐,
-烷基硫酸盐,尤其是脂肪醇硫酸盐,如月桂基硫酸盐、异十三烷基硫酸盐、鲸蜡基硫酸盐、硬脂基硫酸盐,
-芳基-和烷基芳基磺酸盐,如萘磺酸盐、二丁基萘磺酸盐、十二烷基二苯基醚磺酸盐、枯基磺酸盐、壬基苯磺酸盐、十二烷基苯磺酸盐;
-脂肪酸和脂肪酸酯的磺酸盐;
-脂肪酸和脂肪酸酯的硫酸盐;
-烷氧基化链烷醇的硫酸盐,如乙氧基化月桂醇的硫酸盐;
-烷氧基化烷基酚的硫酸盐;
-烷基磷酸盐,C8-C16烷基磷酸盐;
-二烷基磷酸盐,C8-C16二烷基磷酸盐;
-磺基琥珀酸的二烷基酯,如磺基琥珀酸二辛酯,
-酰基肌氨酸盐,
-脂肪酸,如硬脂酸盐,
-酰基谷氨酸盐,和
-木素磺酸盐,
通常呈碱金属盐、碱土金属盐或铵盐形式,尤其是呈钠、钾、钙或铵盐形式;
a2)非离子表面活性剂,包括:
-烷氧基化链烷醇,尤其是乙氧基化脂肪醇和乙氧基化羰基合成醇,如乙氧基化月桂醇、乙氧基化异十三烷醇、乙氧基化鲸蜡醇、乙氧基化硬脂醇,及其酯如乙酸酯
-烷氧基化烷基酚,如乙氧基化壬基酚、乙氧基化十二烷基酚、乙氧基化十三烷基酚及其酯,例如乙酸酯
-烷基葡糖苷和烷基聚葡糖苷,
-共聚物,尤其是氧化乙烯和氧化丙烯的嵌段共聚物,
-乙氧基化烷基葡糖苷和烷基聚葡糖苷,
-乙氧基化脂肪胺,
-乙氧基化脂肪酸,
-部分酯,如脂肪酸与甘油或脱水山梨糖醇的单酯、二酯和三酯,如甘油单硬脂酸酯、脱水山梨糖醇单油酸酯、脱水山梨糖醇三硬脂酸酯
-脂肪酸与甘油或脱水山梨糖醇的乙氧基化部分酯,如乙氧基化甘油单硬脂酸酯
-植物油或动物脂肪的乙氧基化物,如玉米油乙氧基化物、蓖麻油乙氧基化物、牛油乙氧基化物,
-脂肪胺、脂肪酰胺或脂肪酸二乙醇酰胺的乙氧基化物
a3)阳离子表面活性剂,例如
-季铵化合物,尤其是烷基三甲基铵盐和二烷基二甲基铵盐,例如卤化物、硫酸盐和烷基硫酸盐
-吡啶鎓盐,尤其是烷基吡啶鎓盐,例如卤化物、硫酸盐和C1-C4烷基硫酸盐,以及
-咪唑鎓盐,尤其是N,N′-二烷基咪唑鎓盐,例如卤化物、硫酸盐或甲基硫酸盐。
对于表面活性剂,本文所用术语“烷基”没有相反定义的情况下是具有4-30个,优选6-22个碳原子的线性或支化烷基,例如正己基、1-甲基戊基、正庚基、正辛基、2-乙基己基、正壬基、正癸基、1-甲基壬基、2-丙基庚基、正十二烷基、1-甲基十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基、正二十烷基等。术语“烷氧基化”和“烷氧基化物”指OH官能团已经与氧化烯,尤其是C2-C4氧化烯,优选氧化乙烯或氧化乙烯或氧化丙烯的混合物反应形成低聚氧化烯基团。同样,术语“乙氧基化”指OH官能团已经与氧化乙烯反应形成低聚氧化乙烯基团。烷氧基化(或乙氧基化)程度指氧化烯(氧化乙烯)重复单元的数均且通常为1-50,常常为1-30,特别是2-20。表面活性剂的量基于杀虫剂组合物的总重量优选不超过5重量%且基于该组合物总重量可以为0.001-5重量%,尤其是0.01-3重量%或基于该组合物中存在的杀虫剂化合物总重量为1-100重量%,尤其是5-50重量%。
有机溶剂包括在1巴下的沸点至多为250℃的有机液体。有机溶剂包括烃溶剂如芳族溶剂(例如Solvesso产品、二甲苯)、链烷烃(例如矿物油馏分)和脂族溶剂;醇,包括C1-C6链烷醇(例如甲醇、丁醇、戊醇、苄醇)和C2-C6多元醇,尤其是二醇如乙二醇和丙二醇;C3-C6酮(例如丙酮、环己酮);C4-C6内酯(例如γ-丁内酯),C4-C6内酰胺和C1-C8烷基-C4-C6内酰胺,尤其是吡咯烷酮和N-(C1-C8烷基)吡咯烷酮(例如N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-辛基吡咯烷酮),C1-C4脂族酸与C1-C8链烷醇或C2-C6多元醇的酯,尤其是其乙酸酯(例如二醇乙酸酯和二醇二乙酸酯);亚砜如二甲亚砜;C1-C4羧酸的二甲基酰胺。溶剂的量基于该组合物的总重量通常不超过10重量%。例如该组合物可以含有醇作为防冻添加剂。醇的量可以为该组合物的0.5-10重量%。
合适的消泡剂包括聚硅氧烷,如聚二甲基硅氧烷和蜡。消泡剂的量基于该组合物的总重量通常不超过1重量%。例如在水可稀释组合物中,消泡剂可以0.001-1重量%,尤其是0.001-0.8重量%的量存在。
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树胶,象结冷胶、节路顿胶、黄原胶、瓜耳胶、阿拉伯胶、刺槐胶、琼脂,水溶性聚丙烯酸酯聚合物,聚乙烯醇,水溶性肽如酪蛋白或明胶,以及纤维素衍生物如羧甲基纤维素。增稠剂的量基于该组合物的总重量通常不超过1重量%。例如在水可稀释组合物中,增稠剂可以0.001-1重量%,尤其是0.001-0.8重量%的量存在。
防止本发明配制剂被微生物污损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-1,3-丙二醇,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,2,4-二氯苄醇及其混合物。防腐剂的量基于该组合物的总重量通常不超过0.1重量%。
合适的颜料或染料包括颜料蓝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、颜料紫36、颜料紫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。染料和/或颜料的量基于该组合物除水的总重量通常不超过1重量%,并且染料或颜料可以0.001-1重量%,尤其是0.01-0.5重量%的量存在。
可以存在合适的驱除剂以避免被脊椎动物如鸟类、两栖动物、爬行动物或温血动物,尤其是人类吸收。驱除剂通常存在于即用凝胶中。合适的驱除剂是苦味剂如地那铵苯甲酸盐(N-苄基-2-(2,6-二甲基苯基氨基)-N,N-二乙基-2-氧代乙铵苯甲酸盐)和辛辣物质如几内亚胡椒。
合适的载体尤其是常用于制备固体杀虫剂配制剂的固体有机或无机材料,例如矿土如硅胶、硅酸盐、滑石、高岭土、活性粘土(attaclay)、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;磨碎的合成材料;肥料如硫酸铵、磷酸铵、硝酸铵、尿素;植物来源的产品如纤维素粉、树皮粉、木粉和坚果壳粉。惰性载体的量基于通常不超过该组合物的50重量%并且尤其不超过该杀虫剂组合物的30重量%或10重量%。在一个实施方案中,不存在该类惰性填料。
本发明组合物还含有水。水的量优选为10-84.5重量%,尤其是15-74.5重量%,更优选20-69.5重量%。水的量以提供凝胶状或固体结构的方式选择。
在本发明的一个优选实施方案中,将组合物配制成即用凝胶。即用凝胶直接施用并且因此以允许容易地分配于节肢动物与该凝胶组合物接触的场所的方式配制。
通常借助含有该即用凝胶的合适装置施用该即用凝胶。合适的装置是盒式分配器、可折叠管等。凝胶还可以包含在诱饵盒中,该盒可以由待防治的害虫进入。因此,本发明还涉及包含本发明即用凝胶的装置,如盒式分配器、盒、注射器、诱饵盒或可折叠管。
在本发明的即用凝胶中,填料通常含有疏水性组分,尤其是脂肪或油或其与上述链烷醇或多元醇的混合物。该疏水性组分的量如上所给且尤其为该即用凝胶的1-50重量%,更优选3-30重量%。
即用凝胶特别适合防治易于在人类或农场动物的栖息地繁殖的昆虫。即用凝胶尤其可用于防治选自膜翅目、蜚蠊目、等翅目、双翅目和鳞翅目的昆虫,尤其用于防治姬蜚蠊科和蜚蠊科昆虫。
在本发明的另一实施方案中,该组合物呈水可稀释凝胶或固体形式,尤其是水可稀释凝胶形式。凝胶可以容易地用水稀释,从而得到基本均匀的含水喷雾液,其中活性成分均匀分布。
该水可稀释的凝胶或固体通常以上面所给量包含至少一种表面活性剂,以使杀虫剂化合物在稀释液中的均匀分布稳定化。
优选该水可稀释凝胶还含有至少一种酸,更优选至少一种上述有机羧酸,例如选自柠檬酸、苹果酸、丙酮酸和乙醇酸的羧酸。羧酸的量优选为该水可稀释凝胶或固体的0.1-5重量%。
优选该水可稀释凝胶仅含有少量或甚至不含本文所定义的脂肪组分。具体而言,脂肪组分的量不超过该水可稀释凝胶的3重量%。在该水可稀释凝胶中,引诱剂优选包含至少一种选自水果、果汁、水果提取物或果汁提取物,单糖或二糖,氢化单糖或二糖和水溶性蛋白源如蛋白水解物或酵母自溶产物的进食刺激剂。该水可稀释凝胶当然还可以含有一种或多种化学信息素。
水可稀释凝胶尤其用于防治损害植物的害虫,尤其是刺吸式或植食性昆虫,例如膜翅目、等翅目、双翅目、鞘翅目和鳞翅目昆虫,尤其用于防治双翅目和鞘翅目昆虫。
本发明组合物可以容易地通过配制技术的常规方法制备。
通常而言,填料和任选水在混合设备中预加料并加入杀虫剂化合物的常规配制剂,然后混合各组分。然后可以加入组合物的其他成分。超吸收聚合物可以在该程序的任何阶段加入。优选预加料填料、至少一部分水和超吸收聚合物并在混合下向其中加入杀虫剂化合物的配制剂。随后任选加入进一步的水和进一步的组分如酸、染料或颜料。
然后均化各组分,得到凝胶配制剂。然后包装凝胶配制剂或在即用凝胶的情况下可以调制,例如在用于直接施用的合适装置中或在直接施用装置的盒中。
如上所述,本发明的组合物可以用于防治节肢动物害虫,尤其是昆虫。因此,本发明还涉及一种防治节肢动物害虫的方法,该方法包括将本发明组合物施用于其中节肢动物害虫与该组合物接触的场所。
当该组合物呈即用凝胶形式时,直接将该组合物施用于其中害虫可能出现并因此与该凝胶组合物接触的场所。例如,该即用凝胶可以借助合适的装置如注射器或盒式注射器注射到待防治害虫的孵化厂或窝巢中,或者施用于待防治害虫可能穿过的地方,如建筑物部分,例如害虫可能出现的房间(厨房、食物储存室)的地板、通风管和供应管,还有待防止所述害虫损害的植物部分。尤其可以将组合物施用于其中害虫聚集或繁殖的区域,如垃圾箱、大垃圾箱、废品区、填埋场等。还可以向诱饵盒或诱饵盘或套管中装入即用凝胶并在待防治的害虫可能出现或聚集时将诱饵盒或诱饵盘或套管放于例如其中待防治的害虫穿过或靠近要防止被待防治害虫侵染和损害的植物或食物的地上。
在水可稀释凝胶或固体的情况下,该组合物以水溶液施用,即该组合物用水稀释而得到含有活性成分可喷雾含水液体(通过稀释得到的含水液体也称为含水喷雾液或含水稀释液)。用于稀释该组合物的水量(基于体积)通常为该组合物体积的至少1倍,常常为至少5倍,优选至少10倍,更优选至少50倍,尤其是至少100倍。水的量当然取决于活性成分在含水喷雾液中的所需浓度,而后者本身以已知方式取决于活性成分和待防治害虫。然而,应考虑在大多数情况下本发明组合物提供增加的活性并因此允许降低施用率。本发明组合物通常允许将使用常规配制剂时必需的施用率降低至少20%,尤其是至少50%。含水稀释液中的杀虫剂浓度通常为1-3000mg/L,尤其是10-2000mg/L.
通过稀释水可分散凝胶或固体而得到的含水喷雾液通常用于保护生长的植物以免被植物损害性害虫,尤其是植物损害性昆虫侵袭或侵染。为了实现防治,将含水喷雾液施用于其中节肢动物与所述组合物接触的场所。通常将含水喷雾液施用于待防治害虫的栖息地,它们可以是植物或植物本身的部分,如茎、根和叶,或者待防治植物周围的土壤。优选将含水稀释液施用于待防治植物部分上。然而,还可以将含水喷雾液施用于待防治害虫的繁殖地。
本发明组合物还可以用于保护非活体物品,尤其是木质材料如木板、围栏、枕木等以及建筑物如房子、附属建筑物、工厂、建筑材料、家具、皮革、天然或合成纤维、塑料制品,用于将电线和电缆与可能损害这些材料的害虫如蚂蚁和白蚁隔离。这些组合物还可以用于防治蚂蚁和白蚁以使其不损害作物或人类(例如当害虫侵入房子和公共设施时)。为了实现有效防治,该组合物可以直接施用或以含水喷雾液施用。该组合物可以直接施用,但还可以施用于周围土壤表面或施用到地板下的土壤中以实现材料的有效保护。
本发明现由下列工作实施例进一步详细说明:
I.原料
超吸收聚合物SAP1:丙烯酸钾和丙烯酰胺的交联共聚物粉末,对去离子水的吸水容量为400g/g且粒度小于0.3mm(Aquasorb 3005 S,SNFFLOERGER,Andrézieux,法国)。
杀虫剂配制剂P1:甲体氯氰菊酯的悬浮浓缩物,含有100g/L甲体氯氰菊酯、5.2g/L表面活性剂、5.72g/L黄原胶、1.04g/L消泡剂、0.2g/L四丁基溴化铵、0.2g/L磷酸、1.54g/L生物杀伤剂、154.4g/L丙二醇和加至100重量%的水。
杀虫剂配制剂P2:含水悬浮浓缩物,含有240g/L氰氟虫胺、10.8g/L氧化乙烯/氧化丙烯共聚物(EO/PO聚合物)、97.4g表面活性剂混合物、54.1g/L丙二醇、5.4g/L消泡剂、1.1g/l生物杀伤剂、1.7g/L黄原胶和加至L的水。
杀虫剂配制剂P3:含水悬浮浓缩物,含有化合物P5a、表面活性剂混合物、增稠剂、生物杀伤剂、消泡剂和加至1L的水。
杀虫剂配制剂P4:粉末,含有约75重量%化合物P5a、11重量%表面活性剂混合物和24重量%高岭土粘土。
杀虫剂配制剂P5:可稀释浓缩物,含有约25重量%化合物P5a、45重量%碳酸亚丙酯和30重量%EO/PO嵌段共聚物。
杀虫剂配制剂P6:微乳液浓缩物,含有化合物P5、表面活性剂混合物、烃混合物和水。
市售含葫芦素组合物:含水甜瓜汁提取物,还含有单糖和二糖(Invite,购自Florida Food Products USA)。
市售红葡萄汁,含有162g/L单糖和二糖。
引诱剂组合物AtC 1:玉米谷蛋白水解物,含有44重量%水解玉米谷蛋白和56重量%惰性成分:Nu-Lure(购自Miller Chemicals and FertilizerCorp.PA USA.)
引诱剂组合物AtC2:衍生于酿酒酵母的食品级酵母自溶产物:酵母自溶产物SPA 400(购自Halcyons Proteins Pty Ltd.Australia)。
引诱剂组合物AtC 3:蛋白水解物:Buminal(购自Bayer AG)。
引诱剂组合物AtC 4:4-(或5-)氯-2-甲基环己烷甲酸叔丁酯:Capilure(购自Oecos Herfordshire UK Company)。
引诱剂组合物AtC 5:甲基丁子香酚,纯度>95%(购自Bronson &Jacobs Pty Ltd.Australia)。
脂肪化学品:5-25重量%甘油、5-25重量%丙二醇、5-25重量%己二醇、5-25重量%油酸、5-20重量%玉米油、5-20重量%油菜籽油、5-20重量%亚麻子油和5-20重量%大豆油的混合物。
胶凝剂:聚丙烯酸酯增稠剂(Carbopol EZ-2,Novenon Ohio USA)。
II.制备实施例
1.1 制备即用凝胶(配制剂1.a-1.e的通用配方)
a)将约22-32g去离子水加入混合容器中。然后依次缓慢加入0.75g胶凝剂1、17.0g浅棕色糖和8.0g葡甘露糖醇和葡山梨醇(异麦芽)的市售混合物并搅拌该混合物直到各组分完全溶解。然后加入17.8g玉米淀粉、0.5g花生黄油调味剂、2.5g冻干鸡肝粉和2.5g冻干蟋蟀粉并将该混合物搅拌直到固体材料均匀分散在液体赋形剂中。然后加入0.2g市售防腐剂(ProxelGXL)和超吸收聚合物粉末(SAP)并搅拌该混合物直到材料均匀分布在液体赋形剂中。然后加入丙二醇或油(用量给于表1中)并搅拌该混合物直到得到基本均相凝胶。
b)将50g二甘醇正丁基醚在第二混合容器中预加料。在搅拌下加入5g锐劲特原药(100%)并搅拌该混合物直到锐劲特完全溶解。然后在搅拌下加入1167g山梨醇的70重量%水溶液。然后在搅拌下加入0.5g地那铵苯甲酸盐。
c)将在步骤b)中得到的12.2g锐劲特配制剂加入在步骤a)中得到的凝胶中并搅拌该混合物直到得到基本均相凝胶。
1.2 制备即用凝胶(对比配制剂C1和C2的通用配方)
对比配制剂如对配制剂1.a-1.e所述制备。然而,不加入超吸收聚合物。相反在加入生物杀伤剂之后加入NaOH水溶液。此外在加入异麦芽之后加入角叉胶。凝胶配制剂的组成给于表1中(所有量以重量%给出)。
表1:
C1* | C2* | 1.a | 1.b | 1.c | 1.d | 1.e | |
锐劲特 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
胶凝剂 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 |
浅棕色糖 | 17.00 | 17.00 | 17.00 | 17.00 | 17.00 | 17.00 | 17.00 |
异麦芽 | 8.00 | 8.00 | 8.00 | 8.00 | 8.00 | 8.00 | 8.00 |
角叉胶 | 1.00 | 1.00 | --- | --- | --- | --- | --- |
玉米淀粉 | 17.80 | 17.80 | 17.80 | 17.80 | 17.80 | 17.80 | 17.80 |
花生黄油调味剂 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 |
鸡肝粉 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 |
蟋蟀粉 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 |
生物杀伤剂 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
SAP 1 | --- | --- | 1.00 | 1.00 | 1.00 | 1.00 | --- |
SAP 2 | --- | --- | --- | --- | --- | --- | 1.00 |
NaOH | 0.27 | 0.27 | --- | --- | --- | --- | --- |
山梨醇(70重量%) | 11.67 | 11.67 | 11.67 | 11.67 | 11.67 | 11.67 | 11.67 |
二甘醇正丁基醚 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 |
地那铵苯甲酸盐 | 0.005 | 0.005 | 0.005 | 0.005 | 0.005 | 0.005 | 0.005 |
C1* | C2* | 1.a | 1.b | 1.c | 1.d | 1.e | |
丙二醇 | 5.00 | --- | --- | 15.00 | 10.00 | --- | 10.00 |
油酸 | --- | 5.00 | --- | --- | --- | --- | --- |
亚麻子油 | --- | --- | 15.00 | --- | --- | --- | --- |
大豆油 | --- | --- | --- | --- | --- | 15.00 | --- |
水 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
*对比例
1.3 制备即用凝胶(配制剂1.f-1.m的通用配方)
如对配制剂1.a-1.e所述使用杀虫剂配制剂P3-P6和超吸收聚合物SAP1制备配制剂1.f-1.m。凝胶配制剂的组成在下表1.a-1.d中给出(所有量以重量%给出):
表1a:
1.f | 1.g | |
化合物P5a | 0.125 | 0.125 |
表面活性剂 | 0.018 | 0.018 |
高岭土 | 0.023 | 0.023 |
SAP1 | 1.53 | 1.53 |
丙二醇 | 7.5 | 7.5 |
大豆油 | 5.0 | -- |
玉米油 | -- | 5.0 |
蔗糖 | 10.0 | 10.0 |
山梨醇 | 10.0 | 10.0 |
乳糖 | 10.0 | 10.0 |
小麦粉 | 10.0 | -- |
玉米粉 | -- | 10.0 |
花生黄油调味剂 | 1.0 | 1.0 |
鸡肝粉 | 2.5 | 2.5 |
蟋蟀粉 | 2.5 | 2.5 |
鱼粉 | 5.0 | 5.0 |
生物杀伤剂 | 0.2 | 0.2 |
地那铵苯甲酸盐 | 0.005 | 0.005 |
水 | 加至100 | 加至100 |
表1b:
1.h | 1.i |
1.h | 1.i | |
化合物P5a | 0.125 | 0.125 |
表面活性剂混合物 | 0.3 | 0.3 |
烃混合物 | 0.1 | 0.1 |
SAP1 | 1.53 | 1.53 |
丙二醇 | 7.5 | 7.5 |
大豆油 | 5.0 | -- |
玉米油 | -- | 5.0 |
蔗糖 | 10.0 | 10.0 |
山梨醇 | 10.0 | 10.0 |
乳糖 | 10.0 | 10.0 |
小麦粉 | 10.0 | -- |
玉米粉 | -- | 10.0 |
花生黄油调味剂 | 1.0 | 1.0 |
鸡肝粉 | 2.5 | 2.5 |
蟋蟀粉 | 2.5 | 2.5 |
鱼粉 | 5.0 | 5.0 |
生物杀伤剂 | 0.2 | 0.2 |
地那铵苯甲酸盐 | 0.005 | 0.005 |
水 | 加至100 | 加至100 |
表1c:
1.j | 1.k | |
化合物P5a | 0.125 | 0.125 |
表面活性剂混合物 | 0.03 | 0.03 |
消泡剂 | 0.001 | 0.001 |
SAP1 | 1.53 | 1.53 |
丙二醇 | 7.5 | 7.5 |
大豆油 | 5.0 | -- |
玉米油 | -- | 5.0 |
蔗糖 | 10.0 | 10.0 |
山梨醇 | 10.0 | 10.0 |
乳糖 | 10.0 | 10.0 |
小麦粉 | 10.0 | -- |
玉米粉 | -- | 10.0 |
花生黄油调味剂 | 1.0 | 1.0 |
鸡肝粉 | 2.5 | 2.5 |
蟋蟀粉 | 2.5 | 2.5 |
鱼粉 | 5.0 | 5.0 |
1.j | 1.k | |
生物杀伤剂 | 0.2 | 0.2 |
地那铵苯甲酸盐 | 0.005 | 0.005 |
水 | 加至100 | 加至100 |
表1d:
1.I | 1.m | |
化合物P5a | 0.125 | 0.125 |
EO/PO嵌段共聚物 | 0.23 | 0.23 |
碳酸亚丙酯 | 0.17 | 0.17 |
SAP1 | 1.53 | 1.53 |
丙二醇 | 8.1 | 8.1 |
大豆油 | 5.0 | -- |
玉米油 | -- | 5.0 |
蔗糖 | 10.0 | 10.0 |
山梨醇 | 10.0 | 10.0 |
乳糖 | 10.0 | 10.0 |
小麦粉 | 10.0 | -- |
玉米粉 | -- | 10.0 |
花生黄油调味剂 | 1.0 | 1.0 |
鸡肝粉 | 2.5 | 2.5 |
蟋蟀粉 | 2.5 | 2.5 |
鱼粉 | 5.0 | 5.0 |
生物杀伤剂 | 0.2 | 0.2 |
地那铵苯甲酸盐 | 0.005 | 0.005 |
水 | 加至100 | 加至100 |
2.制备水可分散凝胶
通用配方A
将50-60g去离子水加入混合容器中。然后加入0.2g市售防腐剂(ProxelGXL)、5g蔗糖、5g红葡萄汁和10g甘油并搅拌该混合物直到各组分完全溶解。然后加入杀虫剂配制剂P1并再次搅拌该混合物直到得到基本均相分散体。然后依次加入2种不同的引诱剂组合物并再次搅拌该混合物直到得到基本均相分散体。缓慢加入超吸收聚合物并搅拌该混合物直到得到基本均相凝胶。
所得凝胶的组成在表2中给出(所有量以重量%给出)。
表2
2.a | 2.b | 2.c | 2.d | 2.e | 2.f | |
甲体氯氰菊酯 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 |
丙二醇 | 0.78 | 0.78 | 0.78 | 0.78 | 0.78 | 0.78 |
H3PO4 | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
黄原胶 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
消泡剂 | 0.005 | 0.005 | 0.005 | 0.005 | 0.005 | 0.005 |
TBA | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
表面活性剂 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
蔗糖 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
葡萄汁 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
甘油 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 |
生物杀伤剂 | 0.20 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
AtC 1 | 10.0 | 10.0 | -- | -- | -- | -- |
AtC 2 | 10.0 | -- | 10.0 | -- | 10.0 | -- |
AtC 3 | -- | 10.0 | -- | 10.0 | -- | 10.0 |
AtC 4 | -- | -- | 10.0 | 10.0 | -- | -- |
AtC 5 | -- | -- | -- | -- | 10.0 | 10.0 |
SAP 1 | 2.50 | 3.33 | 2.00 | 2.50 | 2.00 | 2.50 |
水 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
通用配方B
将30-40g去离子水加入混合容器中。然后加入0.2g市售防腐剂(ProxelGXL)、5g蔗糖、5g红葡萄汁和10g甘油并搅拌该混合物直到各组分完全溶解。然后加入杀虫剂配制剂P2并再次搅拌该混合物直到得到基本均相分散体。然后依次加入2种不同的引诱剂组合物并再次搅拌该混合物直到得到基本均相分散体。缓慢加入超吸收聚合物并搅拌该混合物直到得到基本均相凝胶。
所得凝胶的组成在表3中给出(所有量以重量%给出)。
表3
3.a | 3.b | 3.c | 3.d | 3.e | 3.f | |
氰氟虫胺 | 5.00 | 5.00 | 5.00 | 5.00 | 5.00 | 5.00 |
EO/PO聚合物 | 0.23 | 0.23 | 0.23 | 0.23 | 0.23 | 0.23 |
表面活性剂混合物 | 2.02 | 2.02 | 2.02 | 2.02 | 2.02 | 2.02 |
丙二醇 | 1.13 | 1.13 | 1.13 | 1.13 | 1.13 | 1.13 |
消泡剂 | 0.11 | 0.11 | 0.11 | 0.11 | 0.11 | 0.11 |
黄原胶 | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 | 0.04 |
3.a | 3.b | 3.c | 3.d | 3.e | 3.f | |
蔗糖 | 5.00 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
葡萄汁 | 5.00 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
甘油 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 |
生物杀伤剂 | 0.20 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
AtC 1 | 10.0 | 10.0 | -- | -- | -- | -- |
AtC 2 | 10.0 | -- | 10.0 | -- | 10.0 | -- |
AtC 3 | -- | 10.0 | -- | 10.0 | -- | 10.0 |
AtC 4 | -- | -- | 10.0 | 10.0 | -- | -- |
AtC 5 | -- | -- | -- | -- | 10.0 | 10.0 |
SAP 1 | 2.50 | 2.50 | 1.27 | 1.00 | 1.50 | 2.50 |
水 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 | 加至100 |
通用配方C
在搅拌下向混合容器中加入68g含葫芦素组合物(甜瓜汁提取物,Invite,见上)。然后依次加入超吸收聚合物和柠檬酸,并将混合物搅拌直到得到基本均匀的凝胶。向该凝胶中加入9.7或4.9g杀虫剂配制剂P1(或13.6或6.8g杀虫剂配制剂P2)和5g丙二醇并将混合物搅拌直到得到基本均匀的凝胶。
所得凝胶的组成在表4a和4b中给出。
表4a
4.a | 4.b | |
氰氟虫胺 | 3.00 | 1.50 |
EO/PO聚合物 | 0.14 | 0.07 |
表面活性剂混合物 | 0.90 | 0.46 |
丙二醇 | 5.68 | 5.34 |
消泡剂 | 0.07 | 0.035 |
黄原胶 | 0.02 | 0.01 |
生物杀伤剂 | 0.014 | 0.007 |
甜瓜汁提取物 | 68.0 | 68.0 |
柠檬酸 | 0.50 | 0.50 |
SAP 1 | 2.00 | 2.00 |
水 | 加至100 | 加至100 |
表4b
5.a | 5.b | |
甲体氯氰菊酯 | 1.00 | 0.50 |
5.a | 5.b | |
表面活性剂混合物 | 0.56 | 0.28 |
改性粘土 | 0.04 | 0.02 |
黄原胶 | 0.02 | 0.01 |
II3PO4 | 0.01 | 0.005 |
消泡剂 | 0.03 | 0.015 |
烃溶剂 | 1.42 | 0.71 |
生物杀伤剂 | 0.016 | 0.008 |
丙二醇 | 5.91 | 5.46 |
SAP 1 | 2.00 | 2.00 |
甜瓜汁提取物 | 68.0 | 68.0 |
柠檬酸 | 0.50 | 0.50 |
水 | 加至100 | 加至100 |
III.生物试验
1.对蟑螂的活性(组合物1.a-1.e)
进行实验室试验以在交替食物源存在下(选择测试)比较II.1中所述即用凝胶在防治德国小蠊(Blattella germanica)雄性成虫中的效力。
通过下列程序分别将诱饵在实验室中陈化1、2或3个月:借助多剂量施用器将约0.03g或相应凝胶施用于VWR聚苯乙烯称量盘(微尺寸)中。将如此制备的诱饵盘置于托盘上并放置在实验室中的底部箱内。将诱饵在约22℃下维持在持续黑暗中。
为了进行生物分析,将蟑螂挨饿24小时(提供庇护和水,但不提供食物),然后开始试验。各处理重复3次,每次重复使用20只蟑螂。将带有通风盖的塑料蟑螂盒用作试验设备。该设备的顶部3-4cm用凡士林和矿物油处理以防止蟑螂逃逸。按需要提供水。将蟑螂置于盒中并挨饿24小时,然后引入诱饵。将含有约0.03g凝胶的称量盘置于盒中。将该盒维持在22℃并每日观察蟑螂死亡率。每日记录蟑螂死亡率并取出死亡个体。结果显示在表5a、5b和5c中。
表5a:陈化1个月后对德国小蠊的凝胶活性
12004年8月30日开始试验
2对比配制剂
3凝胶中锐劲特的重量%
表5b:陈化2月后对德国小蠊的凝胶活性
12004年10月5日开始试验
2对比配制剂
3凝胶中锐劲特的重量%
表5c:陈化3个月后对德国小蠊的凝胶活性
12004年10月5日开始试验
2对比配制剂
3凝胶中锐劲特的重量%
2.橄榄蝇的嗅觉响应
橄榄蝇成虫对喷有含水稀释液的切割橄榄枝的嗅觉响应借助风道式嗅觉计测定。将喷雾的枝条转移到风道式嗅觉计中并记录橄榄蝇成虫对它们的响应。
配制剂以含水稀释液使用。配制剂2.a-2.f和3.a-3.f用水以1:10 v/v的比例稀释。配制剂P1用水以8.3:1000 v/v的比例稀释。配制剂P2用水以34.7:1000 v/v的比例稀释。将稀释液喷雾于两年的盆栽橄榄树上。喷雾施用使用高体积支撑喷雾器进行且将枝条喷雾至滴流。在喷雾之后将树转移并维持在未加热的温室中。温室的侧窗保持打开以确保场地的适当通风。在喷雾后以一定时间间隔(0、3和7天)将已处理橄榄树的枝条切割并转移到实验室中进行生物分析。
在有机玻璃风道式嗅觉计中进行生物分析。嗅觉计为矩形笼(2m长×0.6m宽×0.6m高),由有机玻璃制成且在两条相对的小边上各自具有圆柱形开口以允许气流。圆柱形开口用网筛封闭以防止蝇从嗅觉计中逃逸。通过排风扇(连接于该笼的上风口)将新鲜空气送入该笼中并通过柔性铝管(连接于下风口)送出。该笼的顶部具有两个带有有机玻璃盖的圆柱形开口,距该室的各端15cm,以利于蝇和橄榄枝在室内转移。在该室内和距离上风口25cm处放置圆柱形网筛笼(直径15cm,高40cm)。该笼的侧面用TungelFoot胶覆盖。在网筛笼的内部放置喷有测试产物的橄榄枝。将4或5根10-20cm长的橄榄枝垂直固定在网筛笼的中间。
用于生物分析的蝇成虫在橄榄果实内部由卵发育成成虫并使用液体膳食(水:糖:酵母水解物的混合物,5:3:1)在实验室中的木质筛笼中维持在25±2℃和16:8LD的光周期下。在试验前24小时从笼中取出成虫的食物并使蝇仅接近结晶糖和水。对于每个生物分析使用20只10-20天龄的橄榄蝇成虫(10只雄性和10只雌性)。首先将蝇吸入玻璃小瓶中。用尼龙网筛将小瓶顶部封闭。然后将带有蝇的小瓶转移到风道下风端的昆虫释放点。使蝇适应风道条件10分钟,然后由该瓶中释放。在适应期间操作风道上风端的风扇。
对于生物分析,将20只10-15天龄雌性和雄性蝇成虫转移到下风端的嗅觉计室中。半小时后开启排风扇以将空气泵入室内并使其通过带有已喷雾橄榄枝的网筛而达到蝇上并通过端部开口送出实验室外部。在室内的空气速度在0.5-0.9m/sec间变化。通过时间控制器调节风扇的操作以每隔10分钟开启和关闭。在生物分析期间室温在26℃-28℃间变化并且相对湿度为39-60%。
在笼中转移蝇12小时后,记录对喷雾的橄榄枝响应且在笼的胶侧捕获的蝇数目。将在笼侧面捕获的蝇百分数用作蝇对不同测试产物的相对响应的指数。在生物分析结束时从风道中取出带有橄榄枝的筛笼并记录捕获在胶上的蝇数目(即被引诱到诱饵枝上的蝇)。用乙醇彻底清洁风道、网筛和风扇叶片的侧面并在下一次生物分析之前适当对房间换气。
蝇对喷有水的橄榄枝的响应用作对照处理。
试验在喷雾3-5小时后、喷雾3天后和喷雾7天后进行。结果给于表6a、6b和6c中。
表6a.喷雾3-5小时后橄榄蝇成虫对处理橄榄的嗅觉响应(响应%:引诱到喷有测试产物的橄榄枝上的蝇成虫百分数)
处理 | %响应平均值±标准偏差 | 最小 | 最大 |
P1* | 15.0±2.0 | 10.0 | 20.0 |
2.a | 56.3±6.9 | 40.0 | 70.0 |
2.b | 43.8±3.1 | 35.0 | 50.0 |
2.c | 55.0±4.6 | 45.0 | 65.0 |
2.d | 67.5±4.3 | 55.0 | 75.0 |
2.e | 41.3±5.2 | 30.0 | 50.0 |
2.f | 60.0±4.6 | 50.0 | 70.0 |
P2* | 15.0±2.0 | 10.0 | 20.0 |
3.a | 55.0±3.5 | 45.0 | 60.0 |
3.b | 51.3±7.5 | 35.0 | 70.0 |
3.c | 52.5±3.2 | 45.0 | 60.0 |
3.d | 63.8±6.3 | 50.0 | 80.0 |
3.e | 61.3±4.3 | 50.0 | 70.0 |
3.f | 43.8±6.8 | 30.0 | 60.0 |
对照 | 16.3±1.3 | 15.0 | 20.0 |
*对比配制剂
表6b.喷雾3天后橄榄蝇成虫对处理橄榄的嗅觉响应(响应%:引诱到喷有测试产物的橄榄枝上的蝇成虫百分数)
处理 | %响应平均值±标准偏差 | 最小 | 最大 |
P1* | 13.8±2.4 | 10.0 | 20.0 |
2.a | 33.8±2.4 | 30.0 | 40.0 |
2.b | 41.3±3.1 | 35.0 | 50.0 |
2.c | 52.5±4.8 | 45.0 | 65.0 |
2.d | 63.8±5.5 | 50.0 | 75.0 |
2.e | 25.0±2.0 | 20.0 | 30.0 |
2.f | 22.5±4.8 | 10.0 | 30.0 |
P2* | 16.3±1.3 | 15.0 | 20.0 |
3.a | 27.5±7.2 | 10.0 | 45.0 |
3.b | 40.0±2.0 | 35.0 | 45.0 |
3.c | 31.3±3.1 | 25.0 | 40.0 |
3.d | 47.5±3.2 | 40.0 | 55.0 |
3.e | 33.8±2.4 | 30.0 | 40.0 |
3.f | 37.5±4.8 | 30.0 | 50.0 |
对照 | 17.5±2.5 | 15.0 | 25.0 |
*对比配制剂
表6c.喷雾7天后橄榄蝇成虫对处理橄榄的嗅觉响应(响应%:引诱到喷有测试产物的橄榄枝上的蝇成虫百分数)
处理 | %响应平均值±标准偏差 | 最小 | 最大 |
P1* | 13.8±2.4 | 10.0 | 20.0 |
2.a | 30.0±2.0 | 25.0 | 35.0 |
2.b | 31.3±3.1 | 25.0 | 40.0 |
2.c | 38.8±3.1 | 30.0 | 45.0 |
2.d | 42.5±6.6 | 30.0 | 60.0 |
2.e | 23.8±2.4 | 20.0 | 30.0 |
2.f | 27.5±3.2 | 20.0 | 35.0 |
P2* | 13.8±2.4 | 10.0 | 20.0 |
3.a | 35.0±3.5 | 25.0 | 40.0 |
3.b | 28.8±2.4 | 25.0 | 35.0 |
3.c | 28.8±2.4 | 25.0 | 35.0 |
3.d | 25.0±2.0 | 20.0 | 30.0 |
3.e | 27.5±1.4 | 25.0 | 30.0 |
3.f | 22.5±4.3 | 10.0 | 30.0 |
对照 | 17.5±3.2 | 10.0 | 25.0 |
*对比配制剂
3.对地中海实蝇的活性
将待测试组合物用10倍水(基于体积)稀释。将1ml所得稀释液以25%的浓度施用(在C和D试验中施用0.5mL)在滤纸圈上(直径9cm)。将该处理的圈放置在陪替氏皿上。在每一皿中放置5只地中海实蝇。密封陪替氏皿并在T+1、T+6、T+24和T+48小时记录死亡率,重复4次。该试验进行4次。蝇为2天龄,但试验A中为4天龄。结果在表7a-7d中给出。
表7a:试验A
组合物 | T+1 | T+2 | T+3 | T+4 | T+24 |
3.e | 25 | 26 | 25 | 35 | 55 |
3.f | 10 | 20 | 55 | 60 | 80 |
2.a | 10 | 10 | 40 | 75 | 80 |
2.c | 10 | 40 | 55 | 65 | 75 |
2.d | 25 | 40 | 60 | 60 | 75 |
2.e | 15 | 56 | 50 | 50 | 95 |
2.f | 10 | 30 | 50 | 60 | 80 |
表7b:试验B
组合物 | T+1 | T+2 | T+3 | T+4 | T+24 |
3.e | 6 | 10 | 20 | 30 | 35 |
3.f | 6 | 16 | 30 | 36 | 65 |
2.a | 6 | 10 | 40 | 46 | 65 |
2.b | 6 | 6 | 0 | 6 | 15 |
2.c | 10 | 16 | 20 | 20 | 35 |
2.d | 16 | 16 | 36 | 36 | 50 |
2.e | 16 | 20 | 30 | 36 | 65 |
2.f | 16 | 26 | 40 | 40 | 85 |
表7c:试验C
组合物 | T+1 | T+2 | T+3 | T+4 | T+6 |
3.c | 0 | 0 | 0 | 26 | 90 |
3.d | 0 | 0 | 0 | 26 | 100 |
3.e | 0 | 10 | 10 | 96 | 100 |
3.f | 0 | 6 | 16 | 80 | 96 |
2.a | 10 | 26 | 36 | 60 | 90 |
2.b | 6 | 46 | 50 | 70 | 96 |
2.c | 10 | 20 | 30 | 40 | 90 |
2.d | 30 | 36 | 40 | 66 | 76 |
2.e | 36 | 50 | 56 | 46 | 96 |
2.f | 66 | 96 | 86 | 90 | 100 |
表7d:试验D
组合物 | T+1 | T+2 | T+3 | T+4 | T+24 |
组合物 | T+1 | T+2 | T+3 | T+4 | T+24 |
3.a | 6 | 10 | 20 | 26 | 75 |
3.b | 6 | 16 | 16 | 16 | 45 |
3.c | 20 | 20 | 20 | 16 | 66 |
3.d | 6 | 6 | 10 | 16 | 70 |
3.e | 10 | 26 | 36 | 30 | 76 |
3.f | 16 | 16 | 36 | 26 | 75 |
2.a | 36 | 46 | 80 | 96 | 65 |
2.b | 46 | 60 | 76 | 76 | 100 |
2.c | 50 | 46 | 66 | 70 | 100 |
2.d | 20 | 40 | 56 | 70 | 100 |
2.e | 6 | 46 | 56 | 76 | 95 |
2.f | 30 | 56 | 76 | 90 | 100 |
4.对玉米根叶甲成虫的活性
试验以大田试验在12m×200m的单独地块中进行,各地块含有适当数目的玉米植株(种植紧密度为约80,000-90,000棵植株/公顷)。植株显示出玉米根叶甲成虫的平均侵染。含水喷雾液通过用34L水稀释1L各配制剂而制备。在35L/ha的施用率下用含水喷雾液喷雾植株。施用在玉米植株的VT阶段(抽穗阶段)进行。在处理2天(DAT)和7DAT后计数存活的玉米根叶甲个体数并与此时未处理对照地块中的玉米根叶甲个体数比较。由这些数字通过Abbot公式计算效力:
E=100×(1-x/y)
x=处理地块中的昆虫个体数
y=未处理对照地块中昆虫个体数
活性成分的施用率和结果给于小表8中。
表8:
组合物 | 活性成分 | 施用率g/ha1) | 效力2DAT[%] | 效力7DAT[%] |
P2 | 氰氟虫胺 | 240 | 90-95 | 90-95 |
4.a | 氰氟虫胺 | 15 | 75-80 | 90-95 |
4.b | 氰氟虫胺 | 30 | 85-90 | 90-95 |
5.a | 甲体氯氰菊酯 | 5 | 90-95 | 90-95 |
5.b | 甲体氯氰菊酯 | 10 | 85-90 | 85-90 |
1)每公顷的活性成分量
5.对蟑螂的活性(组合物1.f-1.m)
进行实验室试验以在交替食物源存在下(选择测试)比较II.1.2中所述即用凝胶在防治德国小蠊雄性成虫中的效力。
通过下列程序分别将诱饵在实验室中陈化1、2、3或4周:借助多剂量施用器将约0.5g或相应凝胶施用于VWR聚苯乙烯称量盘(微尺寸)中。将如此制备的诱饵盘置于托盘上并放置在实验室中的底部箱内。将诱饵在约22℃下维持在持续黑暗中。
为了进行生物分析,将蟑螂挨饿24小时(提供庇护和水,但不提供食物),然后开始试验。各处理重复3次,每次重复使用5只蟑螂。将一次性塑料容器用作试验设备。该设备的顶部3-4cm用凡士林和矿物油处理以防止蟑螂逃逸。对容器提供水浸泡的棉牙签。将蟑螂置于盒中并挨饿24小时,然后引入诱饵。将含有约0.5g凝胶的称量盘置于盒中。将该盒维持在22℃并每日观察蟑螂死亡率。4小时和1天后记录蟑螂死亡率并取出死亡个体。结果显示在表9a、9b、9c和9d中。
表9a:没有陈化
12006年9月20日开始测试
2对比配制剂
3凝胶中化合物P5a的重量%
表9b:陈化1周后
12006年9月20日开始测试
2对比配制剂
3凝胶中化合物P5a的重量%
表9c:陈化3周后
12006年9月20日开始测试
2对比配制剂
3凝胶中化合物P5a的重量%
表9d:陈化4周后
12006年9月20日开始测试
2对比配制剂
3凝胶中化合物P5a的重量%
Claims (26)
1.一种凝胶或固体形式的杀虫剂组合物,包含
i)0.001-50重量%至少一种对节肢动物有效的杀虫剂化合物,
ii)0.5-20重量%至少一种对去离子水的吸收容量至少为100g/1g聚合物P的超吸收聚合物P,和
iii)5-94.5重量%至少一种不同于水的填料,和
iv)5-94.5重量%水,
其中重量%基于该组合物的总重量。
2.如权利要求1所要求的组合物,其中所述填料包括引诱剂。
3.如权利要求2所要求的组合物,其中所述填料包括进食刺激剂。
4.如权利要求3所要求的组合物,其中所述进食刺激剂包括至少一种可食用碳水化合物和/或至少一种可食用氢化碳水化合物。
5.如前述权利要求中任一项所要求的组合物,其中所述填料包括疏水性组分,所述疏水性组分选自天然油和脂肪、脂肪酸、脂肪醇及其混合物。
6.如前述权利要求中任一项所要求的组合物,其中所述超吸收聚合物P为烯属不饱和单体M的交联共聚物,所述单体M基于单体M的总重量包含至少90重量%的至少一种单烯属不饱和羧酸CA。
7.如权利要求6所要求的组合物,其中所述单体M基于单体M的总重量包含至少90重量%的至少一种单烯属不饱和羧酸CA或至少一种单烯属不饱和羧酸CA或其盐与至少一种单烯属不饱和酸AM的酰胺的混合物。
8.如权利要求7所要求的组合物,其中所述单体M基于单体M的总重量包含至少90重量%的丙烯酸或其碱金属盐与丙烯酰胺的混合物。
9.如权利要求6所要求的组合物,其中所述单体M基于单体M的总重量包含至少90重量%的丙烯酸和丙烯酸碱金属盐的混合物。
10.如前述权利要求中任一项所要求的组合物,其中所述至少一种杀虫剂化合物选自如下:
-生长调节剂,
-烟碱类杀虫剂,
-有机(硫代)磷酸酯,
-氨基甲酸酯,
-合成除虫菊酯,
-GABA拮抗剂化合物,
-大环内酯杀虫剂,
-线粒复合体I电子输送抑制剂,
-线粒复合体III电子输送抑制剂,
-分离剂化合物,
-氧化磷酸化抑制剂化合物,
-蜕皮干扰剂化合物,
-混合功能氧化酶抑制剂化合物,
-钠通道阻断剂化合物,
-式P5化合物:
其中X和Y各自独立地为卤素,
W为卤素或C1-C2卤代烷基,
R1为C1-C6烷基、C2-C6链烯基、C2-C6炔基、C1-C4烷氧基-C1-C4烷基或C3-C6环烷基,它们各自可以被1、2、3、4或5个卤原子取代,
R2和R3为C1-C6烷基或者可以与相邻碳原子一起形成可以带有1、2或3个卤原子的C3-C6环烷基结构部分,和
R4为氢或C1-C6烷基;
或其可农用盐,
-式P6的邻氨基苯甲酰胺化合物:
其中A1为CH3、Cl、Br、I,X为C-H、C-Cl、C-F或N,Y’为F、Cl或Br,Y”为F、Cl、CF3,B1为氢、Cl、Br、I、CN,B2为Cl、Br、CF3、OCH2CF3、OCF2H以及RB为氢、CH3或CH(CH3)2;
benclothiaz、联苯肼酯、杀螟丹、氟啶虫酰胺、啶虫丙醚、拒嗪酮、硫、硫环杀、氟虫酰胺、cyenopyrafen、吡氟硫磷、丁氟螨酯、amidoflumet、1-乙酰基-2-氧代-3-(吡啶-3-基甲基)氨基-6-七氟丙基-1,2,3,4-四氢喹唑啉)和丙二腈化合物。
11.如前述权利要求中任一项所要求的组合物,呈水可稀释凝胶或固体形式。
12.如权利要求11所要求的组合物,包含不同于所述杀虫剂化合物的酸。
13.如权利要求11所要求的组合物,包含至少一种表面活性剂。
14.如前述权利要求中任一项所要求的组合物,呈即用凝胶形式。
15.如前述权利要求中任一项所要求的组合物在防治节肢动物害虫中的用途。
16.一种防治节肢动物害虫的方法,包括将如权利要求1-14中任一项所定义的组合物直接或以含水稀释液形式施用于节肢动物与所述组合物接触的场所。
17.如权利要求16所要求的方法,其中所述组合物直接以即用凝胶形式施用。
18.如权利要求17所要求的方法,其中所述节肢动物害虫为选自膜翅目、蜚蠊目、等翅目、双翅目和鳞翅目的昆虫。
19.如权利要求17或18所要求的方法,其中施用所述组合物的场所为建筑物部分。
20.一种含有如权利要求14所定义的即用凝胶组合物的装置。
21.如权利要求11所定义的杀虫剂组合物在制备稀释的含水可喷雾杀虫剂组合物中的用途。
22.如权利要求16所要求的方法,包括将通过用水稀释如权利要求11-13中任一项所定义的组合物而得到的稀释的含水可喷雾杀虫剂组合物施用于其中节肢动物害虫与所述组合物接触的场所。
23.如权利要求22所要求的方法,其中使用所述组合物的场所是植物或植物部分或植物周围的土壤。
24.如权利要求22或23所要求的方法,其中所述节肢动物害虫为破坏植物的昆虫。
25.如权利要求24所要求的方法,其中昆虫选自膜翅目、等翅目、双翅目、鞘翅目和鳞翅目。
26.如权利要求24所要求的方法,其中昆虫选自刺吸式和植食性昆虫。
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CN105309448A (zh) * | 2015-12-14 | 2016-02-10 | 济南舜昊生物科技有限公司 | 一种含有benclothiaz和多杀菌素的杀虫组合物 |
JP2019520378A (ja) * | 2016-07-06 | 2019-07-18 | クロップ エンハンスメント、インコーポレイテッド | 農業用用途のための非毒性コーティング濃縮物 |
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