CN103298338B - 包含包封农药的农业化学配制剂 - Google Patents
包含包封农药的农业化学配制剂 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/02—Polyureas
-
- 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
- A01N25/26—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 in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2310/00—Agricultural use or equipment
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dispersion Chemistry (AREA)
Abstract
本发明涉及包含聚脲壳和核的微胶囊,所述核含有农药、水不溶混性溶剂A和基于所述核中溶剂的总重量为至少5重量%的非质子性极性溶剂B,所述溶剂B在20℃下在水中的溶解度为0.5-20g/l。进一步涉及包含壳和核的微胶囊,所述核含有农药和2-庚酮;涉及一种制备所述微胶囊的方法;涉及一种包含所述微胶囊的含水组合物;以及涉及一种用所述微胶囊防治植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法。
Description
本发明涉及包含聚脲壳和核的微胶囊,所述核含有农药、水不溶混性溶剂A和基于所述核中溶剂的总重量为至少5重量%的非质子性极性溶剂B,所述溶剂B在20°C下在水中的溶解度为0.5-20g/l。进一步涉及包含壳和核的微胶囊,所述核含有农药和2-庚酮;涉及一种制备所述微胶囊的方法;涉及一种包含所述微胶囊的含水组合物;以及涉及一种用所述微胶囊防治植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法。优选实施方案与其他优选实施方案的组合在本发明范围内。
包含聚脲壳以及含有农药和溶剂的核的微胶囊是已知的:
WO96/33611公开了一种含有有机液体的微胶囊,该有机液体包含UV光敏性生物活性物质和颗粒状UV光保护剂。合适的溶剂例如是烃类、环己酮或苯乙酮。
EP0619073公开了包封水不溶混性农药的聚脲微胶囊。该农药溶于其中的合适溶剂例如为矿物油或环己酮。
EP0611253公开了包封水不溶混性农药的聚脲胶囊。该农药溶于其中的合适溶剂例如为芳族烃或环己酮。
EP0747116公开了包含农药和溶剂如芳族烃或酮类的聚脲胶囊。
US4,056,610公开了包含液体装填物的聚脲微胶囊,该液体装填物含有合成除虫菊酯类和水不溶混性有机溶剂如芳族烃或高级酮类。
WO2004/017734公开了一种微囊包封的组合物,其中包封的材料包含农业化学品、助剂和水不溶混性溶剂,如芳族溶剂、甲基乙基酮、异佛尔酮或二氢异佛尔酮。
现有技术具有各种缺点:活性成分存在高结晶倾向;配制剂的稳定性在宽温度范围内相当低;或者仅具有击倒效力或仅具有残留效力。本发明的目的是克服该类问题。
该目的由包含聚脲壳和核的微胶囊解决,所述核含有农药、水不溶混性溶剂A和基于所述核中溶剂的总重量为至少5重量%的非质子性极性溶剂B,所述溶剂B在20°C下在水中的溶解度为0.5-20g/l。
水不溶混性溶剂A的合适实例是:
-烃类溶剂,如脂族、环状和芳族烃类(例如甲苯、二甲苯、石蜡、四氢萘、烷基化萘或其衍生物、中到高沸点的矿物油馏分(如煤油、柴油、煤焦油));
-植物油如玉米油、菜籽油;
-脂肪酸酯如C10-C22脂肪酸的C1-C10烷基酯;或
-植物油的甲基或乙基酯如菜籽油甲基酯或玉米油甲基酯。
上述溶剂的混合物也是可能的。该水不溶混性溶剂A通常可市购,如商标名为200、200或28的烃类。可以以贫萘质量等级使用芳族烃类。
优选的溶剂A是烃类,尤其是芳族烃。
优选溶剂A在20°C下在水中的溶解度为至多20g/l,更优选至多5g/l,尤其是至多0.5g/l。
溶剂A通常具有超过100°C,优选超过150°C,尤其是超过180°C的沸点。
非质子性极性溶剂B在20°C下在水中的溶解度为0.5-20g/l。优选溶剂B在水中的溶解度为0.5-10.0g/l,尤其是0.5-5.0g/l。不同种类溶剂B的混合物也是可能的。优选溶剂B为在20°C下在水中的溶解度为0.5-20g/l的酮类。更优选溶剂B为包含6-18(优选7-16)个碳原子且在20°C下在水中的溶解度为0.5-20g/l的酮类。作为溶剂B尤其优选2-庚酮和/或苯乙酮。溶剂B尤其为2-庚酮。溶剂B优选不含碳-碳双键和/或叁键以避免副反应。上述溶剂的混合物也是可能的。
例如,列出一些溶解度值(所有数据为在20°C下的值):苯乙酮5.5g/l,2-庚酮4.3g/l,3-庚酮(2.6g/l),2-己酮(14g/l),5-甲基-2-己酮(5.4g/l),5-甲基-3-庚酮(3.0g/l),3-甲基-2-己酮(4.1g/l),4-甲基-2-己酮(4.3g/l),2-甲基-3-己酮(6.3g/l),4-甲基-3-己酮(5.2g/l),5-甲基-3-己酮(5.2g/l),3-乙基-2-戊酮(4.6g/l),3,3-二甲基-2-戊酮(7.3g/l),3,4-二甲基-2-戊酮(6.7g/l),4,4-二甲基-2-戊酮(10.4g/l),2,2-二甲基-3-戊酮(10.4g/l),2,4-二甲基-3-戊酮(5.7g/l),2-辛酮(0.9g/l),2,5-二甲基-3-己酮(2.6g/l),2,2-二甲基-3-己酮(2.8g/l),3,3-二甲基-2-己酮(2.7g/l),3,4-二甲基-2-己酮(1.4g/l),4,4-二甲基-3-己酮(2.5g/l),3-乙基-4-甲基-2-戊酮(1.7g/l),2-甲基-3-庚酮(1.4g/l),2-甲基-4-庚酮(1.7g/l),3-甲基-2-庚酮(0.9g/l),3-甲基-4-庚酮(1.9g/l),5-甲基-3-庚酮(1.1g/l),6-甲基-2-庚酮(0.8g/l),6-甲基-3-庚酮(0.9g/l),3-辛酮(0.8g/l),4-辛酮(1.0g/l),2,2,4-三甲基-3-戊酮(5.5g/l),3-乙基-3-甲基-2-戊酮(1.8g/l),5-甲基-2-庚酮(1.0g/l),异佛尔酮(15g/l)。
不适合用作溶剂B的例如是丙酮(与水完全溶混)、环己酮(24g/l)、甲基乙基酮(353g/l)或二苯甲酮(<0.005g/l)。
除了溶剂A和溶剂B外,该核可以含有其他溶剂。基于该核中所有溶剂的总重量,该核通常包含小于40重量%,优选小于20重量%,尤其小于5重量%的其他溶剂。
具有包含聚脲的包封材料的胶囊是众所周知的且可以通过类似于现有技术制备。它们优选通过合适聚合物壁形成材料如多异氰酸酯和多胺的界面聚合方法制备。界面聚合通常在核材料的含水的水包油乳液或悬浮液中进行,该核材料含有溶于其中的至少一部分聚合物壁形成材料。在聚合过程中,该聚合物与核材料分离而到达该核材料与水的边界表面,由此形成微胶囊的壁。由此得到微胶囊材料的含水悬浮液。用于制备含有农药化合物的微胶囊的界面聚合方法的合适方法已经公开在现有技术中。
聚脲通常通过具有至少两个异氰酸酯基团的多异氰酸酯与具有至少两个伯氨基的多胺反应形成聚脲壁材料而形成。在另一实施方案中,聚脲可以通过使多异氰酸酯与水接触而形成。优选该聚脲壳以缩聚形式含有多异氰酸酯和多胺。合适的多异氰酸酯例如由US2010/0248963A1段落[0135]-[0158]已知,全面参考这些段落。合适的多胺例如由US2010/0248963A1段落[0159]-[0169]已知,全面参考这些段落。
多异氰酸酯可以单独使用或者作为两种或更多种多异氰酸酯的混合物使用。合适的多异氰酸酯例如为脂族异氰酸酯或芳族异氰酸酯。这些异氰酸酯可以作为单体或低聚异氰酸酯存在。NCO含量可以根据ASTMD5155-96A测定。
合适的脂族二异氰酸酯实例包括四亚甲基二异氰酸酯、五亚甲基二异氰酸酯和六亚甲基二异氰酸酯,以及脂环族异氰酸酯如异佛尔酮二异氰酸酯,1,4-二异氰酸酯基环己烷和二(4-异氰酸酯基环己基)甲烷。
合适的芳族异氰酸酯包括甲苯二异氰酸酯(TDI:2,4-和2,6-异构体的混合物),二苯基甲烷-4,4’-二异氰酸酯(MDI),多亚甲基多苯基异氰酸酯,2,4,4’-二苯基醚三异氰酸酯,3,3’-二甲基-4,4’-二苯基二异氰酸酯,3,3’-二甲氧基-4,4’-二苯基二异氰酸酯,1,5-萘二异氰酸酯和4,4’,4’’-三苯基甲烷三异氰酸酯。还合适的是上述二异氰酸酯的更高级低聚物如上述二异氰酸酯的异氰脲酸酯和缩二脲及其与上述二异氰酸酯的混合物。
在另一优选实施方案中,多异氰酸酯为低聚异氰酸酯,优选芳族低聚异氰酸酯。该类低聚异氰酸酯可以以低聚形式包含上述脂族二异氰酸酯和/或芳族异氰酸酯。该低聚异氰酸酯具有的平均官能度为2.0-4.0,优选2.1-3.2,更优选2.3-3.0。这些低聚异氰酸酯通常具有20-1000mPas,更优选80-500mPas,尤其是150-320mPas的粘度(根据DIN53018测定)。该类低聚异氰酸酯可市购,例如由BASFSE以商标名M10,M20,M50,M70,M200,MM103市购或由BayerAG以A270市购。
还合适的是二异氰酸酯与多元醇如乙二醇、甘油和三羟甲基丙烷的加合物,这通过每摩尔多元醇加成对应于相应醇的羟基数的摩尔数的二异氰酸酯而得到,以及所述加合物与上述二异氰酸酯的混合物。以此方式将数分子的二异氰酸酯通过氨基甲酸酯基团连接于多元醇而形成高分子量多异氰酸酯。特别合适的这类产品L(BayerCorp.,Pittsburgh)可以通过使3摩尔甲苯二异氰酸酯与1摩尔2-乙基甘油(1,1-二羟甲基丙烷)反应而制备。其他合适的产品通过六亚甲基二异氰酸酯或异佛尔酮二异氰酸酯与乙二醇或甘油加成而得到。
优选的多异氰酸酯是异佛尔酮二异氰酸酯,二苯基甲烷-4,4’-二异氰酸酯,甲苯二异氰酸酯以及低聚异氰酸酯,尤其优选低聚异氰酸酯。
在本发明范围内合适的多胺应理解为通常是指在分子中含有两个和更多个氨基的那些化合物,这些氨基可以连接于脂族或芳族结构部分。
合适脂族多胺的实例是式H2N-(CH2)n-NH2的α,ω-二胺,其中n为2-6的整数。该类二胺的实例是乙二胺,1,3-丙二胺,四亚甲基二胺,五亚甲基二胺和六亚甲基二胺。优选的二胺为六亚甲基二胺。其他合适的脂族多胺为式H2N-(CH2-CH2-NH)n-H的聚乙烯亚胺,其中n为2-20,优选3-5的整数。该类聚乙烯亚胺的代表性实例是二亚乙基三胺、三亚乙基四胺、四亚乙基五胺和五亚乙基六胺。其他合适的脂族多胺是二氧杂链烷烃-α,ω-二胺,如式H2N-(CH2)3O-(CH2)4O-(CH2)3-NH2的4,9-二氧杂十二烷-1,12-二胺。
合适的芳族多胺的实例是1,3-苯二胺,2,4-和2,6-甲苯二胺,4,4’-二氨基二苯基甲烷,1,5-二氨基萘,1,3,5-三氨基苯,2,4,6-三氨基甲苯,1,3,6-三氨基萘,2,4,4’-三氨基二苯基醚,3,4,5-三氨基-1,2,4-三唑和1,4,5,8-四氨基蒽醌。在水中不可溶或不充分可溶的那些多胺可以作为其盐酸盐使用。
多胺如上述那些可以单独使用或者以两种或更多种多胺的混合物使用。优选的多胺是聚乙烯亚胺,如四亚乙基五胺。
各互补的壁形成组分的相对量随其当量而变化。通常优选大致化学计算量,但也可以使用过量的一种组分,尤其是过量的多异氰酸酯。壁形成分的总量大致对应于聚合物壁形成材料的总量。
胶囊的平均粒度(借助光散射的z均;优选平均D4,3)为0.5-50μm,优选0.5-20μm,更优选1-10μm,尤其是1-8μm。
术语农药涉及至少一种选自杀真菌剂、杀虫剂、杀线虫剂、除草剂、安全剂和/或生长调节剂的活性物质。优选的农药是杀真菌剂、杀虫剂、除草剂和生长调节剂。尤其优选的农药是杀虫剂。还可以使用上述类别中两种或更多种农药的混合物。本领域技术人员熟知该类农药,它们例如可以在thePesticideManual,第15版(2009),TheBritishCropProtectionCouncil,London中找到。合适的杀虫剂是选自如下类别的杀虫剂:氨基甲酸酯类、有机磷酸酯类、有机氯杀虫剂、苯基吡唑类、合成除虫菊酯类、新类烟碱类、斯皮诺素类(spinosins)、阿维菌素类(avermectins)、米尔霉素类(milbemycins)、保幼激素类似物、烷基卤、有机锡化合物、沙蚕毒素类似物、苯甲酰脲类、二酰基肼类、METI杀螨剂以及杀虫剂如氯化苦(chloropicrin)、拒嗪酮(pymetrozin)、氟啶虫酰胺(flonicamid)、四螨嗪(clofentezin)、噻螨酮(hexythiazox)、特苯唑(etoxazole)、杀螨硫隆(diafenthiuron)、克螨特(propargite)、三氯杀螨砜(tetradifon)、氟唑虫清(chlorfenapyr)、二硝酚(DNOC)、噻嗪酮(buprofezine)、灭蝇胺(cyromazine)、双甲脒(amitraz)、灭蚁腙(hydramethylnon)、灭螨醌(acequinocyl)、fluacrypyrim、鱼藤酮(rotenone)或其衍生物。合适的杀真菌剂是选自如下类别的杀真菌剂:二硝基苯胺类、烯丙基胺类、苯胺基嘧啶类、抗生素类、芳族烃类、苯磺酰胺类、苯并咪唑类、苯并异噻唑类、二苯甲酮类、苯并噻二唑类、苯并三嗪类、苄基氨基甲酸酯类、氨基甲酸酯类、羧酰胺类、羧酸二酰胺类、氯代腈类、氰基乙酰胺肟类、氰基咪唑类、环丙烷羧酰胺类、二羧酰亚胺类、二氢二嗪类、二硝基苯基巴豆酸酯类、二硫代氨基甲酸酯类、二硫戊环类、乙基膦酸酯类、乙基氨基噻唑羧酰胺类、胍类、羟基-(2-氨基)嘧啶类、羟基酰替苯胺类、咪唑类、咪唑啉酮类、无机物质、异苯并呋喃酮类、甲氧基丙烯酸酯类、甲氧基氨基甲酸酯类、吗啉类、N-苯基氨基甲酸酯类、唑烷二酮类、肟基乙酸酯类、肟基乙酰胺类、肽基嘧啶核苷、苯基乙酰胺类、苯基酰胺类、苯基吡咯类、苯基脲类、膦酸酯类、硫代磷酸酯类、邻氨甲酰苯甲酸类、苯邻二甲酰亚胺类、哌嗪类、哌啶类、丙酰胺类、哒嗪酮类、吡啶类、吡啶基甲基苯甲酰胺类、嘧啶胺类、嘧啶类、嘧啶酮腙类、吡咯并喹啉酮类、喹唑啉酮类、喹啉类、醌类、磺酰胺类、氨磺酰三唑类、噻唑羧酰胺类、硫代氨基甲酸酯类、托布津类(thiophanates)、噻吩羧酰胺类、甲苯甲酰胺类、三苯基锡化合物、三嗪类、三唑类。合适的除草剂是选自如下类别的除草剂:乙酰胺类、酰胺类、芳氧基苯氧基丙酸酯类、苯甲酰胺类、苯并呋喃、苯甲酸类、苯并噻二嗪酮类、联吡啶、氨基甲酸酯类、氯代乙酰胺类、氯代羧酸类、环己烷二酮类、二硝基苯胺类、二硝基苯酚类、二苯基醚类、甘氨酸类、咪唑啉酮类、异唑类、异唑烷酮类、腈类、N-苯基苯邻二甲酰亚胺类、二唑类、唑烷二酮类、羟乙酰胺类、苯氧基羧酸类、苯基氨基甲酸酯类、苯基吡唑类、苯基吡唑啉类、苯基哒嗪类、次膦酸类、氨基磷酸酯类、二硫代磷酸酯类、邻氨甲酰苯甲酸酯类、吡唑类、哒嗪酮类、吡啶类、吡啶羧酸类、吡啶羧酰胺类、嘧啶二酮类、嘧啶基(硫代)苯甲酸酯类、喹啉羧酸类、缩氨基脲类、磺酰氨基羰基三唑啉酮类、磺酰脲类、四唑啉酮类、噻二唑类、硫代氨基甲酸酯类、三嗪类、三嗪酮类、三唑类、三唑啉酮类、三唑并羧酰胺类、三唑并嘧啶类、三酮类、尿嘧啶类、脲类。
该农药优选包括杀虫剂,尤其是甲体氯氰菊酯(alphacypermethrin)。
该农药优选在20°C下在水中的溶解度小于10g/l。更优选它的溶解度小于1.0g/l,尤其小于0.2g/l。例如,在水中的溶解度为:唑菌胺酯(pyraclostrobin)1.9mg/l,丙氯灵(prochloraz)34mg/L,苯菌酮(metrafenon)0.5mg/l,甲体氯氰菊酯0.01mg/l。
在20°C下,该农药通常在沸程为235-290°C的芳烃(例如200ND)与2-庚酮的混合物(1:1重量%)中的溶解度为至少10重量%,优选至少20重量%,尤其是至少30重量%。
该农药通常具有的熔点为至少30°C,优选至少40°C,尤其是至少45°C。例如熔点为:唑菌胺酯64°C,丙氯灵47°C,苯菌酮100°C,甲体氯氰菊酯79°C。
该农药可以以溶解形式、作为悬浮液、乳液或悬浮乳液存在于该核中。优选该农药以溶解形式存在。
在该核中该农药(或者在不止一种农药存在于该核中的情况下所有农药的总和)与该核中所有溶剂(即溶剂A和溶剂B)的总和的重量比通常为5:1-1:20,优选1:1-1:10,更优选1:1.2-1:5,尤其是1:1.5-1:3。
基于核材料的总量,该核含有至少5重量%,优选至少15重量%,尤其是至少25重量%农药。该核可以含有至多70重量%,优选至多50重量%农药。核材料的量通常由该核中所有农药和溶剂的量总计。
该核基于核材料的总量含有至少10重量%,优选至少20重量%,尤其是至少35重量%的溶剂A。在另一优选形式中,该核基于核材料的总量含有至少25重量%溶剂A。该核可以含有至多90重量%,优选至多70重量%溶剂A。在另一优选形式中,该核可以含有至多55重量%,优选至多45重量%溶剂A。
基于核材料的总量,该核可以含有至少5重量%,优选至少10重量%,尤其是至少18重量%溶剂B。在另一优选形式中,该核基于核材料的总量含有至少25重量%,优选至少30重量%溶剂B。该核可以含有至多80重量%,优选至多65重量%溶剂B。在另一优选形式中,该核可以含有至多55重量%,优选至多45重量%溶剂B。
溶剂A与溶剂B的重量比通常为5:95-95:5,优选10:1-1:5,更优选5:1-1:2,尤其是3:1-1:1。在另一优选形式中,溶剂A与溶剂B的重量比通常为5:1-1:5,优选3:1-1:2,更优选2:1-1:2。
该核任选可以含有助剂,如下面所提到的那些。优选该核含有至少一种助剂(例如有机改性的聚硅氧烷,如BreakThruS醇烷氧基化物,如AtplusAtplusMBAPlurafacLF和LutensolONEO/PO嵌段聚合物,例如PluronicRPE和Genapol醇乙氧基化物,如LutensolXP以及磺基琥珀酸二辛酯钠,如Leophen
该微胶囊含有至多15重量%,优选至多10重量%,尤其是至多6重量%的壳(例如基于农药、核中所有溶剂(优选溶剂A和溶剂B)、多异氰酸酯和多胺的总量)。该微胶囊通常含有至少0.5重量%,优选至少1.5重量%壳。
本发明进一步涉及一种制备本发明微胶囊的方法,包括混合油相和水相的步骤,其中油相包含所述农药、溶剂A、溶剂B和所述多异氰酸酯。水相通常含有所述多胺。通常将该混合物加热到至少50°C,优选至少60°C。
本发明进一步涉及一种包含本发明微胶囊的含水组合物。优选该组合物包含未包封农药。该未包封农药可以以溶解形式存在,或者作为悬浮液、乳液或悬浮乳液存在。它可以与该核中的农药相同或不同。
该含水组合物通常含有5-80重量%,优选10-60重量%该微胶囊。该含水组合物通常包含至少2重量%,优选至少5重量%,尤其是至少8重量%包封农药。该组合物通常包含0.5-25重量%,优选1.0-20重量%,尤其是2.0-15重量%表面活性物质。合适的表面活性物质列于下面。具体实例是G5000,20,796P,FLK,4D384,S25,BSU,PE6400,PE6800,PE10500,VA64,K30,TO10,ON70,35010。
本发明的含水组合物还可以包含常用于农业化学品配制剂的辅助剂。所用辅助剂分别取决于特定施用形式和活性物质。合适辅助剂的实例是分散剂或乳化剂(如其他加溶剂、保护性胶体、表面活性剂和粘附剂),有机和无机增稠剂,杀菌剂,防冻剂,消泡剂,合适的话还有着色剂和增粘剂或粘合剂(例如用于种子处理配制剂)。
合适的表面活性物质(辅助剂、润湿剂、增粘剂、分散剂或乳化剂)是芳族磺酸如木素磺酸(类型,挪威Borregaard)、苯酚磺酸、萘磺酸(类型,AkzoNobel,USA)和二丁基萘磺酸(类型,德国BASF)及脂肪酸的碱金属、碱土金属和铵盐,烷基-和烷基芳基磺酸盐,烷基硫酸盐,月桂基醚硫酸盐和脂肪醇硫酸盐,以及硫酸化十六-、十七-和十八烷醇及脂肪醇乙二醇醚的盐,磺化萘及其衍生物与甲醛的缩合物,萘或萘磺酸与苯酚和甲醛的缩合物,聚氧乙烯辛基酚醚,乙氧基化异辛基酚、辛基酚或壬基酚,烷基苯基聚乙二醇醚,三丁基苯基聚乙二醇醚,烷基芳基聚醚醇,异十三烷醇,脂肪醇/氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚或聚氧丙烯烷基醚,月桂醇聚乙二醇醚乙酸酯,山梨醇酯,木素亚硫酸盐废液,以及蛋白质,变性蛋白,多糖(例如甲基纤维素),疏水改性淀粉,聚乙烯醇(类型,瑞士Clariant),聚羧酸盐(类型,德国BASF),聚烷氧基化物,聚乙烯胺(类型,德国BASF),聚乙烯亚胺(类型,德国BASF),聚乙烯基吡咯烷酮及其共聚物。
特别合适的表面活性剂是阴离子性、阳离子性、非离子性和两性表面活性剂,嵌段聚合物和聚电解质。合适的阴离子性表面活性剂是磺酸、硫酸、磷酸或羧酸的碱金属、碱土金属或铵盐。磺酸盐的实例是烷基芳基磺酸盐、二苯基磺酸盐、α-烯烃磺酸盐、脂肪酸和油的磺酸盐、乙氧基化烷基酚的磺酸盐、缩合萘的磺酸盐、十二烷基-和十三烷基苯的磺酸盐、萘和烷基萘的磺酸盐、磺基琥珀酸盐或磺基琥珀酰胺酸盐。硫酸盐的实例是脂肪酸和油的硫酸盐、乙氧基化烷基酚的硫酸盐、醇的硫酸盐、乙氧基化醇的硫酸盐或脂肪酸酯的硫酸盐。磷酸盐的实例是磷酸盐酯。羧酸盐的实例是烷基羧酸盐和羧化醇或烷基酚乙氧基化物。
合适的非离子表面活性剂是烷氧基化物,N-烷基化脂肪酸酰胺,胺氧化物,酯或糖基表面活性剂。烷氧基化物的实例是诸如已经烷氧基化的醇、烷基酚、胺(例如牛油脂肪胺)、酰胺、芳基酚、脂肪酸或脂肪酸酯的化合物。氧化乙烯和/或氧化丙烯可以用于烷氧基化,优选氧化乙烯。N-烷基化脂肪酸酰胺的实例是脂肪酸葡糖酰胺或脂肪酸链烷醇酰胺。酯的实例是脂肪酸酯、甘油酯或甘油单酯。糖基表面活性剂的实例是脱水山梨醇、乙氧基化脱水山梨醇、蔗糖和葡萄糖酯或烷基聚葡糖苷。合适阳离子性表面活性剂的实例是季表面活性剂,例如具有一个或两个疏水性基团的季铵化合物,或长链伯胺的盐。合适的两性表面活性剂是烷基甜菜碱和咪唑啉类。合适的嵌段聚合物是包含聚氧乙烯和聚氧丙烯的嵌段的A-B或A-B-A型嵌段聚合物或包含链烷醇、聚氧乙烯和聚氧丙烯的A-B-C型嵌段聚合物。合适的聚电解质是聚酸或聚碱。聚酸的实例是聚丙烯酸的碱金属盐。聚碱的实例是聚乙烯基胺或聚乙烯胺。
增稠剂(即赋予组合物以改性的流动性,即静止条件下的高粘度和搅动过程中的低粘度的化合物)的实例是多糖以及有机和无机粘土,如XanthanGum(CPKelco,USA),23(法国Rhodia),(R.T.Vanderbilt,USA)或(EngelhardCorp.,NJ,USA)。可以加入杀菌剂来保存和稳定该组合物。合适杀菌剂的实例是基于双氯酚和苄醇半缩甲醛的那些(ICI的或ThorChemie的RS以及Rohm&Haas的MK)以及异噻唑啉酮衍生物如烷基异噻唑啉酮类和苯并异噻唑啉酮类(ThorChemie的MBS)。合适防冻剂的实例是乙二醇、丙二醇、尿素和甘油。消泡剂的实例是聚硅氧烷乳液(例如SRE,德国Wacker或法国Rhodia),长链醇,脂肪酸,脂肪酸盐,有机氟化合物及其混合物。增粘剂或粘合剂的实例是聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇和纤维素醚(日本Shin-Etsu)。
本发明进一步涉及一种防治植物病原性真菌和/或不希望的植物生长和/或不希望的昆虫或螨虫侵袭和/或调节植物生长的方法,其中使本发明的微胶囊或含水组合物作用于特定有害物、其栖息地或待防止特定有害物的植物、土壤和/或不希望的植物和/或有用植物和/或其生长地。
可以处理各种栽培植物,如禾谷类,例如小麦、黑麦、大麦、小黑麦、燕麦或稻;甜菜,例如糖用甜菜或饲料甜菜;水果,如仁果、核果或浆果,例如苹果、梨、李、桃、杏仁、樱桃、草莓、悬钩子、黑莓或鹅莓;豆科植物,例如扁豆、豌豆、苜蓿或大豆;油料植物,例如油菜、芥菜、橄榄、向日葵、椰子、可可豆、蓖麻油植物、油棕、花生或大豆;葫芦科植物,例如南瓜、黄瓜或甜瓜;纤维植物,例如棉花、亚麻、大麻或黄麻;柑桔类水果,例如橙子、柠檬、葡萄柚或橘;蔬菜,例如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、西红柿、土豆、葫芦或柿子椒;月桂类植物,例如鳄梨、肉桂或樟脑;能量和原料植物,例如玉米、大豆、油菜、甘蔗或油棕;玉米;烟草;坚果;咖啡;茶;香蕉;葡萄藤(食用葡萄和酿酒用葡萄);啤酒花;草坪;甜叶菊(也称Stevia);天然橡胶植物或观赏和森林植物,例如花卉、灌木、阔叶树或常绿树,例如针叶树,以及植物繁殖材料如种子和这些植物的作物材料。
就本发明而言,“昆虫或螨虫”优选选自节肢动物和线虫,更优选有害昆虫、蜘蛛和线虫,甚至更优选昆虫、螨和线虫,其中最优选昆虫。实例是:
鳞翅目昆虫(鳞翅目(Lepidoptera)),例如小地老虎(Agrotisypsilon)、黄地老虎(Agrotissegetum)、木棉虫(Alabamaargillacea)、黎豆夜蛾(Anticarsiagemmatalis)、Argyresthiaconjugella、叉纹夜蛾(Autographagamma)、树尺蠖(Bupaluspiniarius)、Cacoeciamurinana、Capuareticulana、Cheimatobiabrumata、云杉色卷蛾(Choristoneurafumiferana)、Choristoneuraoccidentalis、二化螟(Cirphisunipuncta)、苹果小卷蛾(Cydiapomonella)、松毛虫(Dendrolimuspini)、Diaphanianitidalis、西南玉米杆草螟(Diatraeagrandiosella)、埃及钻夜蛾(Eariasinsulana)、南美玉米苗斑螟(Elasmopalpuslignosellus)、女贞细卷蛾(Eupoeciliaambiguella)、Evetriabouliana、Feltiasubterranea、蜡螟(Galleriamellonella)、李小食心虫(Grapholithafunebrana)、梨小食心虫(Grapholithamolesta)、棉铃虫(Heliothisarmigera)、烟芽夜蛾(Heliothisvirescens)、玉米穗虫(Heliothiszea)、菜螟(Hellulaundalis)、Hiberniadefoliaria、美国白蛾(Hyphantriacunea)、苹果巢蛾(Hyponomeutamalinellus)、番茄虫蛾(Keiferialycopersicella)、Lambdinafiscellaria、甜菜夜蛾(Laphygmaexigua)、咖啡潜叶蛾(Leucopteracoffeella)、旋纹潜蛾(Leucopterascitella)、Lithocolletisblancardella、葡萄浆果小卷蛾(Lobesiabotrana)、甜菜网螟(Loxostegesticticalis)、舞毒蛾(Lymantriadispar)、模毒蛾(Lymantriamonacha)、桃潜蛾(Lyonetiaclerkella)、黄褐天幕毛虫(Malacosomaneustria)、甘蓝夜蛾(Mamestrabrassicae)、黄杉毒蛾(Orgyiapseudotsugata)、玉米螟(Ostrinianubilalis)、小眼夜蛾(Panolisflammea)、棉花红铃虫(Pectinophoragossypiella)、疆夜蛾(Peridromasaucia)、圆掌舟蛾(Phalerabucephala)、马铃薯麦蛾(Phthorimaeaoperculella)、柑桔潜叶蛾(Phyllocnistiscitrella)、欧洲粉蝶(Pierisbrassicae)、苜蓿绿夜蛾(Plathypenascabra)、菜蛾(Plutellaxylostella)、大豆夜蛾(Pseudoplusiaincludens)、Rhyacioniafrustrana、Scrobipalpulaabsoluta、麦蛾(Sitotrogacerealella)、葡萄卷叶蛾(Sparganothispilleriana)、草地夜蛾(Spodopterafrugiperda)、海灰翅夜蛾(Spodopteralittoralis)、斜纹夜蛾(Spodopteralitura)、Thaumatopoeapityocampa、绿色橡木飞蛾(Tortrixviridana)、粉纹夜蛾(Trichoplusiani)和Zeirapheracanadensis;
甲虫(鞘翅目(Coleoptera)),例如梨窄吉丁(Agrilussinuatus)、直条叩头虫(Agrioteslineatus)、暗色叩头虫(Agriotesobscurus)、Amphimallussolstitialis、Anisandrusdispar、墨西哥棉铃象(Anthonomusgrandis)、苹花象(Anthonomuspomorum)、甜菜隐食甲(Atomarialinearis)、纵坑切梢小蠹(Blastophaguspiniperda)、Blitophagaundata、蚕豆象(Bruchusrufimanus)、豌豆象(Bruchuspisorum)、欧洲兵豆象(Bruchuslentis)、苹卷象(Byctiscusbetulae)、甜菜大龟甲(Cassidanebulosa)、Cerotomatrifurcata、白菜籽龟象(Ceuthorrhynchusassimilis)、芫菁龟象(Ceuthorrhynchusnapi)、甜菜胫跳甲(Chaetocnematibialis)、Conoderusvespertinus、石刁柏负泥虫(Criocerisasparagi)、长角叶甲(Diabroticalongicornis)、Diabrotica12-punctata、玉米根叶甲(Diabroticavirgifera)、墨西哥豆瓢虫(Epilachnavarivestis)、烟草跳甲(Epitrixhirtipennis)、棉灰蒙象变种(Eutinobothrusbrasiliensis)、欧洲松树皮象(Hylobiusabietis)、埃及苜蓿叶象(Hyperabrunneipennis)、紫苜蓿叶象(Hyperapostica)、云杉八齿小蠹(Ipstypographus)、烟草负泥虫(Lemabilineata)、黑角负泥虫(Lemamelanopus)、马铃薯叶甲(Leptinotarsadecemlineata)、Limoniuscalifornicus、稻水象甲(Lissorhoptrusoryzophilus)、Melanotuscommunis、油菜露尾甲(Meligethesaeneus)、大栗鳃金龟(Melolonthahippocastani)、五月鳃金龟(Melolonthamelolontha)、水稻负泥虫(Oulemaoryzae)、葡萄黑耳喙象(Ortiorrhynchussulcatus)、草莓根象甲(Otiorrhynchusovatus)、辣根猿叶甲(Phaedoncochleariae)、Phyllotretachrysocephala、食叶鳃金龟属(Phyllophagasp.)、庭园发丽金龟(Phylloperthahorticola)、大豆淡足跳甲(Phyllotretanemorum)、黄曲条菜跳甲(Phyllotretastriolata)、日本金龟子(Popilliajaponica)、豌豆叶象(Sitonalineatus)和谷象(Sitophilusgranaria);
双翅目昆虫(双翅目(Diptera)),例如埃及伊蚊(Aedesaegypti)、剌扰伊蚊(Aedesvexans)、墨西哥果蝇(Anastrephaludens)、五斑按蚊(Anophelesmaculipennis)、地中海实蝇(Ceratitiscapitata)、蛆症金蝇(Chrysomyabezziana)、Chrysomyahominivorax、Chrysomyamacellaria、高粱瘿蚊(Contariniasorghicola)、Cordylobiaanthropophaga、尖音库蚊(Culexpipiens)、瓜蝇(Dacuscucurbitae)、油橄榄实蝇(Dacusoleae)、油菜叶瘿蚊(Dasineurabrassicae)、小毛厕蝇(Fanniacanicularis)、马蝇(Gasterophilusintestinalis)、刺舌蝇(Glossinamorsitans)、Haematobiairritans、Haplodiplosisequestris、花生田灰地种蝇(Hylemyiaplatura)、纹皮蝇(Hypodermalineata)、蔬菜斑潜蝇(Liriomyzasativae)、美国潜叶蝇(Liriomyzatrifolii)、Luciliacaprina、铜绿蝇(Luciliacuprina)、丝光绿蝇(Luciliasericata)、Lycoriapectoralis、麦瘿蚊(Mayetioladestructor)、家蝇(Muscadomestica)、厩腐蝇(Muscinastabulans)、羊狂蝇(Oestrusovis)、欧洲麦秆蝇(Oscinellafrit)、天仙子泉蝇(Pegomyahysocyami)、Phorbiaantiqua、萝卜蝇(Phorbiabrassicae)、Phorbiacoarctata、樱桃实蝇(Rhagoletiscerasi)、苹果实蝇(Rhagoletispomonella)、牛虻(Tabanusbovinus)、Tipulaoleracea和欧洲大蚊(Tipulapaludosa);
蓟马(缨翅目(Thysanoptera)),例如兰花蓟马(Dichromothripscorbetti)、烟褐蓟马(Frankliniellafusca)、苜蓿花蓟马(Frankliniellaoccidentalis)、东方花蓟马(Frankliniellatritici)、桔梗蓟马(Scirtothripscitri)、稻蓟马(Thripsoryzae)、棕榈蓟马(Thripspalmi)和烟蓟马(Thripstabaci);
膜翅目昆虫(膜翅目(Hymenoptera)),例如新疆菜叶蜂(Athaliarosae)、切叶蚁(Attacephalotes)、Attasexdens、Attatexana、Hoplocampaminuta、Hoplocampatestudinea、小黄家蚁(Monomoriumpharaonis)、热带火蚁(Solenopsisgeminate)和红火蚁(Solenopsisinvicta);
异翅目昆虫(异翅目(Heteroptera)),例如拟绿蝽(Acrosternumhilare)、玉米长蝽(Blissusleucopterus)、黑斑烟盲蝽(Cyrtopeltisnotatus)、棉红蝽(Dysdercuscingulatus)、Dysdercusintermedius、麦扁盾蝽(Eurygasterintegriceps)、烟草蝽(Euschistusimpictiventris)、棉红铃喙缘蝽(Leptoglossusphyllopus)、美洲牧草盲蝽(Lyguslineolaris)、牧草盲蝽(Lyguspratensis)、稻绿蝽(Nezaraviridula)、甜菜拟网蝽(Piesmaquadrata)、Solubeainsularis和Thyantaperditor;
同翅目昆虫(同翅目(Homoptera)),例如Acyrthosiphononobrychis、落叶松球蚜(Adelgeslaricis)、Aphidulanasturtii、甜菜蚜(Aphisfabae)、草莓根蚜(Aphisforbesi)、苹果蚜(Aphispomi)、棉蚜(Aphisgossypii)、北美茶簏子蚜(Aphisgrossulariae)、Aphisschneideri、卷叶蚜(Aphisspiraecola)、Aphissambuci、豌豆蚜(Acyrthosiphonpisum)、马铃薯蚜(Aulacorthumsolani)、银叶粉虱(Bemisiaargentifolii)、烟粉虱(Bemisiatabaci)、Brachycauduscardui、杏圆尾蚜(Brachycaudushelichrysi)、Brachycauduspersicae、Brachycaudusprunicola、甘蓝蚜(Brevicorynebrassicae)、Capitophorushorni、Cerosiphagossypii、Chaetosiphonfragaefolii、Cryptomyzusribis、高加索冷杉椎球蚜(Dreyfusianordmannianae)、云杉椎球蚜(Dreyfusiapiceae)、居根西圆尾蚜(Dysaphisradicola)、Dysaulacorthumpseudosolani、Dysaphisplantaginea、Dysaphispyri、蚕豆微叶蝉(Empoascafabae)、桃大尾蚜(Hyalopteruspruni)、Hyperomyzuslactucae、麦长管蚜(Macrosiphumavenae)、大戟长管蚜(Macrosiphumeuphorbiae)、蔷薇管蚜(Macrosiphonrosae)、Megouraviciae、巢莱修尾蚜(Melanaphispyrarius)、麦无网蚜(Metopolophiumdirhodum)、Myzodespersicae、冬葱瘤额蚜(Myzusascalonicus)、Myzuscerasi、桃蚜(Myzuspersicae)、李瘤蚜(Myzusvarians)、Nasonoviaribis-nigri、稻飞虱(Nilaparvatalugens)、囊柄瘿绵蚜(Pemphigusbursarius)、蔗飞虱(Perkinsiellasaccharicida)、忽布疣蚜(Phorodonhumuli)、苹木虱(Psyllamali)、梨木虱(Psyllapiri)、冬葱瘤蛾蚜(Rhopalomyzusascalonicus)、玉米蚜(Rhopalosiphummaidis)、禾谷溢管蚜(Rhopalosiphumpadi)、Rhopalosiphuminsertum、Sappaphismala、Sappaphismali、麦二叉蚜(Schizaphisgraminum)、Schizoneuralanuginosa、麦长管蚜(Sitobionavenae)、白背飞虱(Sogatellafurcifera)、白粉虱(Trialeurodesvaporariorum)、Toxopteraaurantiiand和葡萄根瘤蚜(Viteusvitifolii);
白蚁(等翅目(Isoptera)),例如Calotermesflavicollis、Leucotermesflavipes、黄肢散白蚁(Reticulitermesflavipes)、欧洲散白蚁(Reticulitermeslucifugus)和Termesnatalensis;
直翅目昆虫(直翅目(Orthoptera)),例如居屋艾蟋(Achetadomestica)、东方蜚蠊(Blattaorientalis)、德国小蠊(Blattellagermanica)、欧洲球螋(Forficulaauricularia)、蝼蛄(Gryllotalpagryllotalpa)、飞蝗(Locustamigratoria)、双纹黑蝗(Melanoplusbivittatus)、红足黑蝗(Melanoplusfemur-rubrum)、墨西哥黑蝗(Melanoplusmexicanus)、迁飞黑蝗(Melanoplussanguinipes)、石栖黑蝗(Melanoplusspretus)、条纹红蝗(Nomadacrisseptemfasciata)、美洲蟑螂(Periplanetaamericana)、美洲沙漠蝗(Schistocercaamericana)、Schistocercaperegrina、Stauronotusmaroccanus和庭疾灶螽(Tachycinesasynamorus),
蜘蛛纲(Arachnoidea),如蜘蛛(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(Amblyommaamericanum)、热带花蜱(Amblyommavariegatum)、波斯锐缘蜱(Argaspersicus)、牛壁虱(Boophilusannulatus)、Boophilusdecoloratus、微小牛蜱(Boophilusmicroplus)、Dermacentorsilvarum、Hyalommatruncatum、蓖子硬蜱(Ixodesricinus)、Ixodesrubicundus、Ornithodorusmoubata、Otobiusmegnini、鸡皮刺螨(Dermanyssusgallinae)、绵羊疥病(Psoroptesovis)、Rhipicephalusappendiculatus、Rhipicephalusevertsi、人疥螨(Sarcoptesscabiei),和瘿螨属(Eriophyidae),如苹果刺锈螨(Aculusschlechtendali)、Phyllocoptrataoleivora和Eriophyessheldoni;细螨属(Tarsonemidae),如Phytonemuspallidus和侧多食跗线螨(Polyphagotarsonemuslatus);细须螨属(Tenuipalpidae),如紫红短须螨(Brevipalpusphoenicis);叶螨属(Tetranychidae),如朱砂叶螨(Tetranychuscinnabarinus)、神泽叶螨(Tetranychuskanzawai)、太平洋叶螨(Tetranychuspacificus)、棉叶螨(Tetranychustelarius)和二点叶螨(Tetranychusurticae),苹果叶螨(Panonychusulmi)、柑椐叶螨(Panonychuscitri)和oligonychuspratensis;蚤目(Siphonatera),例如印鼠客蚤(Xenopsyllacheopsis)、角叶属(Ceratophyllus)。
施用可以在播种之前或之中进行。分别将农业化学化合物及其组合物施用或处理于植物繁殖材料,尤其是种子上的方法在本领域是已知的并且包括拌种、包衣、造粒、撒粉、浸泡和繁殖材料的犁沟内施用方法。在优选实施方案中,通过不诱发萌发的方法,例如通过拌种、造粒、包衣和撒粉分别将微胶囊或其组合物施用于植物繁殖材料上。在优选实施方案中,将悬浮类型(FS)组合物用于种子处理。FS组合物通常可以包含1-800g/l活性物质,1-200g/l表面活性剂,0-200g/l防冻剂,0-400g/l粘合剂,0-200g/l颜料和至多1升溶剂,优选水。
微胶囊或含水组合物可以直接使用或者以其农业化学配制剂形式,例如以可直接喷雾溶液、悬浮液、分散体、乳液、油分散体形式借助喷雾、雾化、撒粉、铺展、刷涂、浸渍或浇灌来使用。施用形式完全取决于意欲的目的;在任何情况下意欲确保农药的最佳可能分布。即用制剂中的活性物质浓度可在较宽范围内变化。它们通常为0.0001-10重量%,优选0.001-1重量%活性物质。活性物质还可以成功地以超低容量法(ULV)使用,其中可以施用包含超过95重量%活性物质的组合物或者甚至可以施用不含添加剂的活性物质。
当用于植物保护中时,活性物质(也称为农药)的施用量取决于所需效果的类型为0.001-2kg/ha,优选0.005-2kg/ha,更优选0.05-0.9kg/ha,尤其为0.1-0.75kg/ha。在例如通过撒粉、包衣或浸透种子而处理植物繁殖材料如种子中,每100kg植物繁殖材料(优选种子)通常要求的活性物质量为0.1-1000g,优选1-1000g,更优选1-100g,最优选5-100g。当用于材料或储存产品的保护中时,活性物质的施用量取决于施用区域的种类和所需效果。在材料保护中的常规施用量例如为0.001g-2kg活性物质/米3被处理材料,优选0.005g-1kg活性物质/米3被处理材料。
各种类型的油、润湿剂、辅助剂、除草剂、杀菌剂、其他杀真菌剂和/或农药可加入含水组合物中,合适的话恰在紧临使用前加入(桶混合)。这些试剂通常可以与本发明组合物以1:100-100:1,优选1:10-10:1的重量比混合。可以使用的辅助剂尤其是有机改性的聚硅氧烷如BreakThruS醇烷氧基化物如AtplusAtplusMBAPlurafacLF和LutensolONEO/PO嵌段聚合物,例如PluronicRPE和Genapol醇乙氧基化物如LutensolXP以及磺基琥珀酸二辛酯钠如
本发明进一步涉及包含壳和核的微胶囊,所述核含有农药和2-庚酮。优选该壳为聚脲壳。聚脲壳和农药的合适实例如上所述。
本发明具有多种优点:本发明降低了活性成分的结晶;它提高了该配制剂在宽温度范围内的稳定性;存在击倒和残留效力;它改善了与其他农药的相容性;它降低了随风漂移;包封的活性成分被有效保护而防止UV光;胶囊可以负载油溶性和水溶性活性成分和助剂;胶囊具有增加的耐雨水冲刷性;对工人和用户具有降低的毒理学效果;该配制剂对UV光或阳光非常稳定;胶囊具有高物理稳定性;该配制剂具有优异的生物输送性;该配制剂具有非常低的毒理性(例如不刺激眼睛);该配制剂具有的喷雾液滴在叶子上的接触角低;该配制剂在叶子上具有高铺展性。
下列实施例进一步阐述本发明,但本发明并不限于这些实施例。
实施例
MDI基多异氰酸酯:不含溶剂的基于4,4’-二苯基甲烷二异氰酸酯(MDI)的多异氰酸酯,平均官能度为2.7,NCO含量为32g/100g。
芳族烃A:芳族烃溶剂,沸程240-295°C,凝固点-10°C至-20°C,萘含量小于1重量%。
芳族烃B:芳族烃溶剂,沸程175-215°C,凝固点-20°C至-25°C,萘含量小于1重量%。
PVA:部分水解的聚乙烯醇,粘度为17-19mPas(DIN53015)。
UV吸收剂:2-羟基-4-辛氧基二苯甲酮
实施例1—胶囊的制备
水相:
583g水
395g10重量%聚乙烯醇PVA水溶液
油相:
313g甲体氯氰菊酯
418g芳族烃A
209g2-庚酮
28gMDI基多异氰酸酯
进料1:
13g四亚乙基五胺
49g水
将油相加入水相中并用溶解式搅拌器在6000rpm下分散20分钟。然后在15分钟内加入进料1并将该乳液在80°C下加热2小时。在冷却至室温之后得到固体含量为49%的胶囊悬浮液。平均粒度D[4,3]为2.5μm。蒸发百分数(2h105°C,1h130°C)为2%。
实施例2—胶囊的制备
水相:
183g水
116g10重量%聚乙烯醇PVA水溶液
油相:
91g甲体氯氰菊酯
122g芳族烃A
61g2-庚酮
11gMDI基多异氰酸酯
10gUV吸收剂
进料:
5g四亚乙基五胺
14g水
将油相加入水相中并用溶解式搅拌器在6000rpm下分散20分钟。然后在15分钟内加入进料1并将该乳液在80°C下加热2小时。在冷却至室温之后得到固体含量为49%的胶囊悬浮液。平均粒度D[4,3]为2.2μm。
实施例3—胶囊的制备
水相:
139g水
88g10重量%聚乙烯醇PVA水溶液
油相:
69g甲体氯氰菊酯
92g芳族烃B
46g苯乙酮
8gMDI基多异氰酸酯
17gUV吸收剂
进料1:
4g四亚乙基五胺
11g水
将油相加入水相中并用溶解式搅拌器在6000rpm下分散20分钟。然后在15分钟内加入进料1并将该乳液在80°C下加热2小时。在冷却至室温之后得到固体含量为49%的胶囊悬浮液。平均粒度D[4,3]为2.6μm。
实施例4—胶囊的制备
水相:
149g水
92g10重量%聚乙烯醇PVA水溶液
油相:
74g甲体氯氰菊酯
98g芳族烃A
49g2-庚酮
9gMDI基多异氰酸酯
进料1:
4g二亚乙基三胺
12g水
将油相加入水相中并用溶解式搅拌器在6000rpm下分散20分钟。然后在15分钟内加入进料1并将该乳液在80°C下加热2小时。在冷却至室温之后得到固体含量为49%的胶囊悬浮液。平均粒度D[4,3]为3.0μm。
实施例5—胶囊的制备
水相:
192g水
120g10重量%聚乙烯醇PVA水溶液
油相:
96g甲体氯氰菊酯
128g芳族烃A
64g2-庚酮
12gMDI基多异氰酸酯
进料1:
3g四亚乙基五胺
15g水
将油相加入水相中并用溶解式搅拌器在2000rpm下分散20分钟。然后在15分钟内加入进料1并将该乳液在20°C下保持2小时。然后将其在60°C下加热2小时。在冷却至室温之后得到固体含量为49%的胶囊悬浮液。平均粒度D[4,3]为7.2μm。
实施例6—胶囊的制备
水相:
223g水
58g10重量%聚乙烯醇PVA水溶液
油相:
94g甲体氯氰菊酯
125g芳族烃A
63g2-庚酮
8gMDI基多异氰酸酯
进料1:
4g四亚乙基五胺
15g水
将油相加入水相中并用溶解式搅拌器在6000rpm下分散20分钟。然后在15分钟内加入进料1并将该乳液在80°C下加热2小时。在冷却至室温之后得到固体含量为49%的胶囊悬浮液。平均粒度D[4,3]为2.9μm。
实施例7—胶囊的制备
水相:
335g水
104g10重量%聚乙烯醇PVA水溶液
油相:
154g甲体氯氰菊酯
175g芳族烃A
175g2-庚酮
15gMDI基多异氰酸酯
进料1:
7g四亚乙基五胺
25g水
将油相加入水相中并用溶解式搅拌器在3500rpm下分散20分钟。然后在15分钟内加入进料1,将该乳液在加热1小时至80°C并在该温度下保持2小时。在冷却至室温之后得到固体含量为54%的胶囊悬浮液。平均粒度D[4,3]为2.9μm。
实施例8-14
详情在表1中指出并与实施例1-7相当。
表1
实施例15—农业化学品CS配制剂的制备
A)在室温下搅拌的同时将实施例1的胶囊粗悬浮液与水和添加剂混合。由此得到含有31.5重量%胶囊粗悬浮液、0.1重量%消泡剂、0.2重量%防腐剂、10.0重量%丙二醇防冻剂、8重量%非离子性烷基烷氧基化物表面活性剂、0.1重量%黄原胶和达到100%的水的含水CS农业化学品配制剂。
B)在室温下搅拌的同时将实施例2的胶囊粗悬浮液与水和添加剂混合。由此得到含有10重量%包封甲体氯氰菊酯、0.1重量%消泡剂、0.2重量%防腐剂、10.0重量%丙二醇防冻剂、3重量%非离子性烷基烷氧基化物表面活性剂和达到100%的水的含水CS农业化学品配制剂。
实施例16—储存稳定性
将实施例15B的胶囊配制剂样品用于储存测试。
为了对比,如实施例15B制备胶囊悬浮液,其中2-庚酮被环己酮替代。所有其他组分保持相同。
两种配制剂的样品在-10°C或+54°C下储存两周。
视觉检测结果:在实施例15B的样品中在2周后没有可见沉降。然而,在具有环己酮的对比样品中清楚可见沉降和清液。
Claims (12)
1.包含聚脲壳和核的微胶囊,所述核含有农药、水不溶混性溶剂A和基于所述核中溶剂的总重量为至少5重量%的非质子性极性溶剂B,
所述溶剂B在20℃下在水中的溶解度为0.5-20g/l,其中溶剂B为2-庚酮或苯乙酮;
其中溶剂A具有超过100℃的沸点,溶剂A在20℃在水中具有至多20g/l的溶解度,其中溶剂A为烃或其混合物;
溶剂A与溶剂B的重量比为10:1-1:5;
其中所述农药在20℃下在水中的溶解度小于10g/l,所述农药以溶解形式存在。
2.根据权利要求1的微胶囊,其中溶剂A与溶剂B的重量比为3:1-1:1。
3.根据权利要求1的微胶囊,含有1.5-10重量%所述壳。
4.根据权利要求2的微胶囊,含有1.5-10重量%所述壳。
5.根据权利要求1-4中任一项的微胶囊,其中所述聚脲壳以缩聚形式含有多异氰酸酯和多胺。
6.根据权利要求5的微胶囊,其中所述多胺包括聚乙烯胺。
7.根据权利要求1-4中任一项的微胶囊,其中溶剂A为芳族烃。
8.根据权利要求1-4中任一项的微胶囊,其中在所述核中所述农药与所有溶剂总和的重量比为1:1-1:10。
9.一种制备如权利要求1-8中任一项所定义的微胶囊的方法,包括混合油相和水相的步骤,其中所述油相包含所述农药、所述溶剂A、所述溶剂B和多异氰酸酯。
10.一种包含如权利要求1-8中任一项所定义的微胶囊的含水组合物。
11.根据权利要求10的组合物,包含未包封的农药。
12.一种防治植物病原性真菌和/或控制不希望的植物生长和/或控制不希望的昆虫或螨虫侵袭和/或调节植物生长的方法,其中使如权利要求1-8中任一项所定义的微胶囊或如权利要求10或11所定义的含水组合物作用于特定有害物、其栖息地或待保护以免于特定有害物的植物,和/或不希望的植物和/或有用植物和/或其生长地。
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EP2667708B1 (en) * | 2011-01-24 | 2018-09-05 | Basf Se | Agrochemical formulation comprising encapsulated pesticide |
BR112016025065B8 (pt) * | 2014-05-02 | 2023-05-16 | Dow Agrosciences Llc | Formulação de suspensão de microcápsulas, composição fertilizante, e processo para supressão de nitrificação de nitrogênio de amônio em meio de crescimento |
BR112018006127B1 (pt) * | 2015-10-22 | 2021-06-22 | Basf Se | Processo para preparação de uma dispersão aquosa de microcápsulas |
EP3170552A1 (en) | 2015-11-23 | 2017-05-24 | Basf Se | Microcapsule comprising a polymeric shell and a hydrophilic or hydrophobic core material |
WO2017157678A1 (en) * | 2016-03-17 | 2017-09-21 | Basf Se | Reduced photodegradation by co-dissolving pyraclostrobin and uv absorber |
GB2551814B (en) * | 2016-06-30 | 2021-02-24 | Syngenta Participations Ag | Microcapsules encapsulating lambda-cyhalothin |
EP3278666A1 (de) * | 2016-08-04 | 2018-02-07 | Bayer CropScience Aktiengesellschaft | Wässrige kapselsuspensionskonzentrate auf basis von 2-(2,4-dichlorbenzyl)-4,4-dimethyl-1,2-oxazolidin-3-on |
WO2019027632A1 (en) * | 2017-07-31 | 2019-02-07 | Dow Global Technologies Llc | ENCAPSULATION METHOD |
CN111117124B (zh) * | 2018-10-30 | 2021-02-12 | 华南理工大学 | 一种热水可溶的聚乙烯醇膜及其制备方法和应用 |
CN117378605B (zh) * | 2023-12-12 | 2024-03-15 | 中国农业科学院农业环境与可持续发展研究所 | 一种菊酯类农药微胶囊悬浮剂及其制备方法 |
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US20130287844A1 (en) | 2013-10-31 |
AU2012206618A1 (en) | 2013-07-25 |
CN103298338A (zh) | 2013-09-11 |
KR20140043326A (ko) | 2014-04-09 |
BR112013017684B1 (pt) | 2018-12-11 |
KR101948340B1 (ko) | 2019-02-14 |
EA201300811A1 (ru) | 2013-12-30 |
CA2823105A1 (en) | 2012-07-19 |
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