CN118368978A - 农药组合物及其制造方法 - Google Patents
农药组合物及其制造方法 Download PDFInfo
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- CN118368978A CN118368978A CN202280081093.8A CN202280081093A CN118368978A CN 118368978 A CN118368978 A CN 118368978A CN 202280081093 A CN202280081093 A CN 202280081093A CN 118368978 A CN118368978 A CN 118368978A
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- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 1
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- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 1
- XAIPTRIXGHTTNT-UHFFFAOYSA-N triflumuron Chemical compound C1=CC(OC(F)(F)F)=CC=C1NC(=O)NC(=O)C1=CC=CC=C1Cl XAIPTRIXGHTTNT-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- DBHVHTPMRCXCIY-UHFFFAOYSA-N tyclopyrazoflor Chemical compound N1=C(Cl)C(N(C(=O)CCSCCC(F)(F)F)CC)=CN1C1=CC=CN=C1 DBHVHTPMRCXCIY-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
- A01N25/12—Powders or granules
-
- 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
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
一种农药组合物,其含有:选自树脂乳液、表面处理高岭土、和有机改性膨润土与油类的组合这3种中的2种以上;以及农药有效成分。
Description
技术领域
本发明涉及农药组合物及其制造方法。
背景技术
作为农药的剂型,已知粉剂、粒剂、可湿性粉剂、可溶性粉剂、乳剂、可溶液体制剂、油剂等。其中粒剂由于具有施用时的飞散少、计量比较容易这样的特征,因此在日本国内被广泛使用。此外近年来,通过机械制造商的技术进步,从而在例如水稻栽培中,开发了使用粒剂的育苗箱处理机、插秧同时施药机等。因此,特别是对粒剂要求对作物(例如稻)的低药害性、药效的长期残效性、制造时的制造容易性、高效率性、机械散布机中的散布适应性这样的多种观点下的综合性能。
关于上述对作物的低药害性、药效的长期残效性,以控制农药有效成分的初期的急剧的溶出,将这些性质赋予农药组合物作为目的,迄今为止进行了若干农药组合物、其制造方法的研究。例如,在日本特开2001-233706号公报(专利文献1)中,记载了将农药有效成分、拒水剂、和羧基甲基纤维素进行混合并造粒的、缓释性农药粒剂的制造方法,作为上述拒水剂,可举出蜡类、疏水性二氧化硅。此外,例如,在日本特开平8-143402号公报(专利文献2)中,作为缓释性农药粒剂,记载了将固体状的农药活性成分的粒子与非晶质二氧化硅的粒子与辅助剂成分的混合物造粒而成的农药粒剂。进一步,例如,在日本特开2010-18527号公报(专利文献3)中,记载了以控制农药有效成分的溶出作为目的的、含有农药活性成分、海泡石、粘合剂、和表面活性剂的缓释性农药粒剂。此外,例如,在日本特开2011-6396号公报(专利文献4)中,作为溶出控制型农药组合物,记载了含有农药活性成分、脂肪酸和/或脂肪酸衍生物、水难溶性多糖类、和无机物质的农药组合物。
现有技术文献
专利文献
专利文献1:日本特开2001-233706号公报
专利文献2:日本特开平8-143402号公报
专利文献3:日本特开2010-18527号公报
专利文献4:日本特开2011-6396号公报
发明内容
发明所要解决的课题
然而,在以往的农药组合物的构成、其制造方法中,具有需要使用特殊的机械、或工序复杂、或特别是在含有在水中的溶解度(水溶解度)高的农药有效成分的粒剂的情况下造粒困难这样的课题。进一步,本发明人等发现,在以往的农药组合物中,具有农药有效成分、特别是上述溶解度高的农药有效成分向水中的初期的急剧的溶出的抑制仍然不充分,通过过剩地溶出了的农药有效成分而产生对作物的药害(生长不良等)、或农药有效成分的长期的残效性降低这样的课题。
本发明是鉴于上述现有技术所具有的课题而提出的,其以提供农药有效成分对水的初期的急剧的溶出被充分抑制、缓释性优异的缓释性农药组合物、和农药有效成分对水的初期的急剧的溶出被充分地抑制、可以容易地以高效率获得缓释性优异的缓释性农药粒剂的制造方法作为目的。
用于解决课题的手段
本发明人等为了解决上述课题而反复进行了深入研究,结果发现了,通过为含有选自树脂乳液、表面处理高岭土、和有机改性膨润土与油类的组合这3种中的2种以上、以及农药有效成分的构成,从而上述农药有效成分对水的初期的急剧的溶出被充分地抑制,可以制成缓释性优异的农药组合物,充分地减轻上述农药有效成分对作物造成的药害、或能够使上述农药有效成分的效果的持续性(长期残效性)提高。此外,也发现根据这样的构成,从而仅通过将上述成分进行混合并造粒就能够容易地并且以高效率制造充分的粒度的农药粒剂,从而完成了本发明。
通过这样的认识而获得的本发明的方案如下所述。
[1]
一种农药组合物,其含有:选自树脂乳液、表面处理高岭土、和有机改性膨润土与油类的组合这3种中的2种以上;以及农药有效成分。
[2]
根据[1]所述的农药组合物,上述树脂乳液为丙烯酸系树脂乳液。
[3]
根据[1]或[2]所述的农药组合物,上述表面处理高岭土为硅烷表面处理高岭土。
[4]
根据[1]~[3]中任一项所述的农药组合物,上述有机改性膨润土为季铵化合物表面处理膨润土。
[5]
根据[1]~[4]中任一项所述的农药组合物,上述油类为选自烃系油和植物性油脂中的至少1种。
[6]
根据[1]~[5]中任一项所述的农药组合物,其含有20~25℃下的水溶解度为50g/L以下的农药有效成分作为上述农药有效成分。
[7]
根据[1]~[6]中任一项所述的农药组合物,其含有选自氟虫啶胺、烯丙苯噻唑、噻虫嗪、吡虫啉、异丁乙氧喹啉、丙草胺、和它们的农药上可容许的酸加成盐中的至少1种作为上述农药有效成分。
[8]
根据[1]~[7]中任一项所述的农药组合物,其进一步含有选自表面活性剂和增量剂中的至少1种。
[9]
根据[1]~[8]中任一项所述的农药组合物,其为粒剂。
[10]
一种制造方法,是[9]所述的农药组合物的制造方法,其包含下述工序:将选自上述树脂乳液、上述表面处理高岭土、和上述有机改性膨润土与上述油类的组合这3种中的2种以上、与上述农药有效成分进行混合并造粒的工序。
[11]
一种制造方法,是[9]所述的农药组合物的制造方法,其包含下述工序:将选自上述树脂乳液、上述表面处理高岭土、和上述有机改性膨润土与上述油类的组合这3种中的2种以上进行混合并造粒的造粒工序;以及
使上述造粒工序中获得的造粒物中含有上述农药有效成分的工序。
发明的效果
根据本发明,能够提供农药有效成分对水的初期的急剧的溶出被充分抑制、缓释性优异的缓释性农药组合物,和农药有效成分对水的初期的急剧的溶出被充分地抑制、可以容易地以高效率获得缓释性优异的缓释性农药粒剂的制造方法。
具体实施方式
以下,按照其适合的实施方式对本发明详细地说明。
<农药组合物>
本发明的农药组合物含有:选自树脂乳液、表面处理高岭土、和有机改性膨润土与油类的组合这3种中的2种以上;以及农药有效成分。
(农药有效成分)
作为本发明涉及的农药有效成分,没有特别限制,可举出作为杀虫剂、杀菌剂、除草剂、和植物生长调节剂等而以往公知的化合物。可举出例如,“The Pesticide Manual,17th Edition(出版商:The British Crop Protection Council)”、“SHIBUYA INDEX,2014,(出版商:SHIBUYA INDEX RESEARCH GROUP)”所记载的化合物,可以为它们之中的1种,也可以为2种以上的组合。它们之中,关于本发明的农药组合物,从缓释性优异、可以长期维持效果考虑,作为上述农药有效成分,优选包含选自杀虫剂、杀菌剂、除草剂、和植物生长调节剂中的至少1种,更优选为选自上述组中的至少1种。此外,例如,出于也同时减轻对植物的药害这样的目的,优选含有选自杀虫剂和杀菌剂中的至少1种作为上述农药有效成分。
作为本发明涉及的农药有效成分,更优选可举出例如,有机磷酸酯系化合物、氨基甲酸酯系化合物、沙蚕毒素衍生物、有机氯系化合物、拟除虫菊酯系化合物、苯甲酰脲系化合物、保幼激素样化合物、蜕皮激素样化合物、新烟碱系化合物、神经细胞的钠通道阻滞剂、杀虫性大环状内酯、γ-氨基丁酸(GABA)拮抗剂、兰尼碱受体作用性化合物、杀虫性脲类、BT剂、昆虫病原病毒剂、聚醚系抗生素、硫胺拮抗药、和磺胺剂/叶酸拮抗药混配剂,可以为它们之中的1种,也可以为2种以上的组合。
作为上述杀虫剂,更具体而言,可举出例如,乙酰甲胺磷(acephate)、敌敌畏(dichlorvos)、EPN、杀螟硫磷(fenitrothion)、苯线磷(fenamiphos)、丙硫磷(prothiofos)、丙溴磷(profenofos)、吡唑硫磷(pyraclofos)、甲基毒死蜱(chlorpyrifos-methyl)、二嗪磷(diazinon)、噻唑膦(fosthiazate)、氰咪唑硫磷(imicyafos)、甲拌磷(phorate)等有机磷酸酯系化合物;灭多威(methomyl)、硫双威(thiodicarb)、涕灭威(aldicarb)、杀线威(oxamyl)、残杀威(propoxur)、甲萘威(carbaryl)、仲丁威(fenobucarb)、乙硫苯威(ethiofencarb)、苯硫威(fenothiocarb)、抗蚜威(pirimicarb)、克百威(carbofuran)、丁硫克百威(carbosulfan)、丙硫克百威(benfuracarb)等氨基甲酸酯系化合物;杀螟丹(cartap)、杀虫环(thiocyclam)等沙蚕毒素衍生物;三氯杀螨醇(dicofol)、三氯杀螨砜(tetradifon)等有机氯系化合物;氯菊酯(permethrin)、七氟菊酯(tefluthrin)、氯氰菊酯(cypermethrin)、四溴菊酯(tralomethrin)、溴氰菊酯(deltamethrin)、氯氟氰菊酯(cyhalothrin)、氰戊菊酯(fenvalerate)、氟胺氰菊酯(fluvalinate)、醚菊酯(etofenprox)、氟硅菊酯(silafluofen)、氯氟氰菊酯(cyhalothrin)等拟除虫菊酯系化合物;除虫脲(diflubenzuron)、氟苯脲(teflubenzuron)、氟虫脲(flufenoxuron)、氟啶脲(chlorfluazuron)等苯甲酰脲系化合物;烯虫酯(methoprene)、烯虫乙酯(hydroprene)、烯虫炔酯(kinoprene)等保幼激素样化合物;环虫酰肼(chromafenozide)等蜕皮激素样化合物;吡虫啉(imidacloprid)、噻虫胺(c1othianidin)、噻虫嗪(thiamethoxam)、啶虫脒(acetamiprid)、烯啶虫胺(nitenpyram)、噻虫啉(thiacloprid)、呋虫胺(dinotefuran)、氟啶虫胺腈(sulfoxaflor)、氟吡呋喃酮(flupyradifurone)、氟虫啶胺(flupyrimin)、二氯噻吡嘧啶(dicloromezotiaz)、三氟苯嘧啶(triflumezopyrim)、(fenmezoditiaz)等尼古丁性乙酰胆碱受体作用药(新烟碱系化合物);氟虫酰胺(flubendiamide)、氯虫酰胺(chlorantraniliprole)、溴氰虫酰胺(cyantraniliprole)、环溴虫酰胺(cyclaniliprole)、四唑虫酰胺(tetraniliprole)等二酰胺化合物;乙虫腈(ethiprole)、氟虫腈(fipronil)、嗪吡唑虫胺(pyrafluprole)、吡唑虫啶(pyriprole)、溴虫氟苯双酰胺(broflanilide)、氟唑酰胺(fluxametamide)等GABA受体作用性化合物(γ-氨基丁酸(GABA)拮抗剂);哒螨灵(pyridaben)、唑螨酯(fenpyroximate)、嘧螨醚(pyrimidifen)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)等呼吸链电子传递系复合体I抑制化合物;丁氟螨酯(cyflumetofen)、腈吡螨酯(cyenopyrafen)、吡唑酰苯胺(pyflubumide)等呼吸链电子传递系复合体II抑制化合物;嘧螨酯(fluacrypyrim)、灭螨醌(acequinocyl)、氟虫碳酸酯(flometoquin)等呼吸链电子传递系复合体III抑制化合物;螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramat)等ACCase抑制化合物;多杀霉素(spinosad)、阿维菌素(abamectin)、米尔贝霉素(milbemycin)、乙基多杀菌素(spinetoram)、雷皮菌素(lepimectin)、甲氨基阿维菌素苯甲酸盐(emamectin benzoate)等大环内酯化合物、和它们的农药上可容许的酸加成盐。
进一步,作为上述杀虫剂,作为其它化合物,也可举出噻嗪酮(buprofezin)、噻螨酮(hexythiazox)、双甲脒(amitraz)、杀虫脒(chlordimeform)、乙螨唑(etoxazole)、吡蚜酮(pymetrozine)、联苯肼酯(bifenazate)、氟啶虫酰胺(flonicamid)、虫螨腈(chlorfenapyr)、吡丙醚(pyriproxyfen)、茚虫威(indoxacarb)、啶虫醚(pyridalyl)、吡氟喹虫唑(pyrifluquinazon)、氰氟虫腙(metaflumizone)、氟蚁腙(hydramethylnon)、唑蚜威(triazamate)、双丙环虫酯(afidopyropen)、(1R,3S),(1S,3R)-氯氟醚菊酯(renofluthrin)、右旋反式氯丙炔菊酯(chloroprallethrin)、氯氟氰虫酰胺(cyhalodiamide)、三氟咪啶酰胺(fluazaindolizine)、ε-甲氧苄氟菊酯(epsilon-metofluthrin)、ε-甲氧氟菊酯(epsilon-momfluorothrin)、κ-联苯菊酯(kappa-bifenthrin)、κ-七氟菊酯(kappa-tefluthrin)、氟己虫腈(fluhexafon)、线噻吩(tioxazafen)、甲氧氟菊酯(momfluorothrin)、七氟甲醚菊酯(heptafluthrin)、嘧螨胺(pyriminostrobin)、环氧虫啶(cycloxaprid)、异唑虫酰胺(isocycloseram)、唑磺酰虫啶(oxazosulfyl)、氯吡唑虫胺(tyclopyrazoflor)、甲氧哌啶乙酯(spiropidion)、氟螨啶(acynonapyr)、嗪虫唑酰胺(dimpropyridaz)、吲唑虫酰胺(indazapyroxamet)、氟戊螨硫醚(flupentiofenox)、唑虫烟酰胺(nicofluprole)、三氟吡啶胺(cyclobutrifluram)、有机金属系化合物、二硝基系化合物、有机硫化合物、脲系化合物、三嗪系化合物、肼系化合物、和它们的农药上可容许的酸加成盐,此外,也可举出BT剂、昆虫病原病毒剂等那样的微生物农药。
它们之中,作为上述杀虫剂,优选为选自杀螟丹(cartap)、杀虫环(thiocyclam)、氟虫啶胺(flupyrimin)、三氟苯嘧啶(triflumezopyrim)、氯虫酰胺(chlorantraniliprole)、溴氰虫酰胺(cyantraniliprole)、四唑虫酰胺(tetraniliprole)、氟虫腈(fipronil)、吡蚜酮(pymetrozine)、氟啶虫酰胺(flonicamid)、唑磺酰虫啶(oxazosulfyl)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、和它们的农药上可容许的酸加成盐中的至少1种。
作为上述杀菌剂,更具体而言,可举出例如,嘧菌酯(azoxystrobin)、醚菌酯(kresoxim-methyl)、肟菌酯(trifloxystrobin)、苯氧菌胺(metominostrobin)、肟醚菌胺(orysastrobin)等嗜球果伞素系化合物;嘧菌胺(mepanipyrim)、嘧霉胺(pyrimethanil)、嘧菌环胺(cyprodinil)等苯胺基嘧啶系化合物;三唑酮(triadimefon)、联苯三唑醇(bitertanol)、氟菌唑(triflumizole)、叶菌唑(metconazole)、丙环唑(propiconazole)、戊菌唑(penconazole)、氟硅唑(flusilazole)、腈菌唑(myclobutanil)、环丙唑醇(cyproconazole)、戊唑醇(tebuconazole)、己唑醇(hexaconazole)、咪鲜胺(prochloraz)、硅氟唑(simeconazole)等唑系化合物;灭螨猛(chinomethionate)等喹喔啉系化合物;代森锰(maneb)、代森锌(zineb)、代森锰锌(mancozeb)、代森福美锌(polycarbamate)、丙森锌(propineb)等二硫代氨基甲酸酯系化合物;乙霉威(diethofencarb)等苯基氨基甲酸酯系化合物;百菌清(chlorothalonil)、五氯硝基苯(quintozene)等有机氯系化合物;苯菌灵(benomyl)、甲基硫菌灵(thiophanate-methyl)、多菌灵(carbendazim)等苯并咪唑系化合物;甲霜灵(metalaxyl)、霜灵(oxadixyl)、呋酰胺(ofurace)、苯霜灵(benalaxyl)、呋霜灵(furalaxyl)、酯菌胺(cyprofuram)等苯基酰胺系化合物;苯氟磺胺(dichlofluanid)等次磺酸系化合物;氢氧化铜(copper hydroxide)、喹啉铜(oxine-copper)等铜系化合物;霉灵(hydroxyisoxazole)等异唑系化合物;三乙膦酸铝(fosetyl-aluminium)、甲基立枯磷(tolclofos-methyl)等有机磷系化合物;克菌丹(captan)、敌菌丹(captafol)、灭菌丹(folpet)等N-卤代硫代烷基系化合物;腐霉利(procymidone)、异菌脲(iprodione)、乙烯菌核利(vinclozolin)等二甲酰亚胺系化合物;氟酰胺(flutolanil)、灭锈胺(mepronil)、呋吡菌胺(furametpyr)、噻氟菌胺(thifluzamide)、啶酰菌胺(boscalid)、吡噻菌胺(penthiopyrad)等羧基酰苯胺系化合物;丁苯吗啉(fenpropimorph)、烯酰吗啉(dimethomorph)等吗啉系化合物;三苯基氢氧化锡(fentin hydroxide)、三苯基乙酸锡(fentin acetate)等有机锡系化合物;咯菌腈(fludioxonil)、拌种咯(fenpiclonil)等氰基吡咯系化合物;和它们的农药上可容许的酸加成盐。
进一步,作为上述杀菌剂,作为其它化合物,也可举出三环唑(tricyclazole)、咯喹酮(pyroquilon)、环丙酰菌胺(carpropamid)、双氯氰菌胺(diclocymet)、稻瘟酰胺(fenoxanil)、四氯苯酞(fthalide)、氟啶胺(fluazinam)、霜脲氰(cymoxanil)、嗪氨灵(triforine)、啶斑肟(pyrifenox)、氯苯嘧啶醇(fenarimol)、苯锈啶(fenpropidin)、戊菌隆(pencycuron)、嘧菌腙(ferimzone)、氰霜唑(cyazofamid)、缬霉威(iprovalicarb)、苯噻菌胺异丙酯(benthiavalicarb-isopropyl)、双胍辛烷基苯磺酸盐(iminoctadinalbesilate)、环氟苄酰胺(cyflufenamid)、春雷霉素(kasugamycin)、井冈霉素(validamycin)、链霉素(streptomycin)、喹菌酮(oxolinic acid)、异丁乙氧喹啉(tebufloquin)、烯丙苯噻唑(probenazole)、活化酯(acibenzolar-S-methyl)、噻酰菌胺(tiadinil)、异噻菌胺(isotianil)、稻瘟灵(isoprothiolane)、三氟甲氧威(tolprocarb)、氟唑菌酰羟胺(pydiflumetofen)、四唑吡氨酯(picarbutrazox)、甲苯醚菌酯(mandestrobin)、噻英菌酮(dipymetitrone)、联苯吡嗪菌胺(pyraziflumid)、氟噻唑吡乙酮(oxathiapiprolin)、氟唑菌苯胺(penflufen)、氟菌磺酯(fluoxapiprolin)、二氟吡啶菌胺(florylpicoxamid)、氟醚菌酰胺(fluopimomide)、异丙菌喹啉(ipflufenoquin)、氟茚唑菌胺(fluindapyr)、异丙氟吡菌胺(isoflucypram)、氟菌喹啉(quinofumelin)、四唑菌酮(metyltetraprole)、氟苯菌哒嗪(pyridachlometyl)、吡炔菌酰胺(pyrapropoyne)、氨吡菌酯(aminopyrifen)、茚吡菌胺(inpyrfluxam)、二氯菌噻(dichlobentiazox)、和它们的农药上可容许的酸加成盐。
它们之中,作为上述杀菌剂,优选为选自嘧菌酯(azoxystrobin)、肟醚菌胺(orysastrobin)、噻氟菌胺(thifluzamide)、呋吡菌胺(furametpyr)、四氯苯酞(fthalide)、烯丙苯噻唑(probenazole)、活化酯(acibenzolar-S-methyl)、噻酰菌胺(tiadinil)、异噻菌胺(isotianil)、稻瘟灵(isoprothiolane)、三氟甲氧威(tolprocarb)、环丙酰菌胺(carpropamid)、双氯氰菌胺(diclocymet)、稻瘟酰胺(fenoxanil)、三环唑(tricyclazole)、咯喹酮(pyroquilon)、嘧菌腙(ferimzone)、异丁乙氧喹啉(tebufloquin)、硅氟唑(simeconazole)、井冈霉素(validamycin)、春雷霉素(kasugamycin)、戊菌隆(pencycuron)、氟唑菌苯胺(penflufen)、二氯菌噻(dichlobentiazox)、茚吡菌胺(inpyrfluxam)、和它们的农药上可容许的酸加成盐中的至少1种。
作为上述除草剂,更具体而言,可举出例如,氰氟草酯(cyhalofop-butyl)、唑禾草灵(fenoxaprop-ethyl)、吡氟禾草灵(fluazifop-butyl)、氟吡甲禾灵(haloxyfop-methyl)、唑酰草胺(metamifop)、喹禾灵(quizalofop-ethyl)等芳基氧基苯氧基丙酸酯系化合物;禾草灭(alloxydim)、丁苯草酮(butroxydim)、环苯草酮(profoxydim)、烯禾啶(sethoxydim)、吡喃草酮(tepralozydim)等环己烷二酮系化合物;唑啉草酯(pinoxaden)等苯基吡唑啉系化合物;咪草酸甲酯(imazamethabenz-methyl)、甲氧咪草烟(imazamox)、甲咪唑烟酸(imazapic)、咪唑烟酸(imazapyr)、咪唑喹啉酸(imazaquin)、咪唑乙烟酸(imazethapyr)等咪唑啉酮系化合物;双草醚(bispyribac-sodium)、嘧啶肟草醚(pyribenzoxim)、环酯草醚(pyriftalid)、嘧草醚(pyriminobac-methyl)、嘧草硫醚(pyrithiobac-sodium)等嘧啶基苯甲酸酯系化合物;嘧氟磺草胺(pyrimisulfan)、氟酮磺草胺(triafamone)、酰嘧磺隆(amidosulfuron)、四唑嘧磺隆(azimsulfuron)、苄嘧磺隆(bensulfuron-methyl)、氯嘧磺隆(chlorimuron-ethyl)、氯磺隆(chlorsulfuron)、醚磺隆(cinosulfuron)、环丙嘧磺隆(cyclosulfamuron)、胺苯磺隆(ethametsulfuron-methyl)、乙氧磺隆(ethoxysulfuron)、啶嘧磺隆(flazasulfuron)、氟吡磺隆(flucetosulfuron)、氟啶嘧磺隆钠盐(flupyrsulfuron-methyl-Na)、甲酰氨基嘧磺隆(foramsulfuron)、氯吡嘧磺隆(halosulfuron-methyl)、唑吡嘧磺隆(imazosulfuron)、甲基碘磺隆钠盐(iodosulfuron-methyl-Na)、甲基二磺隆(mesosulfuron-methyl)、双醚氯吡嘧磺隆(metazosulfuron)、甲磺隆(metsulfuron-methyl)、烟嘧磺隆(nicosulfuron)、嘧苯胺磺隆(orthosulfamuron)、环氧嘧磺隆(oxasulfuron)、氟嘧磺隆(primisulfuron-methyl)、丙嗪嘧磺隆(propyrisulfuron)、氟磺隆(prosulfuron)、吡嘧磺隆(pyrazosulfuron-ethyl)、砜嘧磺隆(rimsulfuron)、甲嘧磺隆(sulfometuron-methyl)、磺酰磺隆(sulfosulfuron)、噻吩磺隆(thifensulfuron-methyl)、醚苯磺隆(triasulfuron)等磺酰脲系化合物;炔苯酰草胺(propyzamide)、异酰草胺(isoxaben)、牧草胺(tebutam)等苯甲酰胺系化合物;氯酞酸甲酯(chlorthal-dimethyl)等苯甲酸系化合物;乙丁氟灵(benfluralin)、仲丁灵(butralin)、氨氟灵(dinitramine)、乙丁烯氟灵(ethalfluralin)、氯乙氟灵(fluchloralin)、异丙乐灵(isopropalin)、甲磺乐灵(nitralin)、氨磺乐灵(oryzalin)、二甲戊灵(pendimethalin)、氨氟乐灵(prodiamine)、环丙氟灵(profluralin)、氟乐灵(trifluralin)等二硝基苯胺系化合物;抑草磷(butamifos)、DMPA等有机磷系化合物;氟硫草定(dithiopyr)、噻唑烟酸(thiazopyr)等吡啶系化合物;草灭畏(chloramben)、麦草畏(dicamba)、TBA等苯甲酸酯系化合物;2,4,5,-T、2,4,-D、2,4-DB、氯甲酰草胺(clomeprop)、2,4-滴丙酸(dichlorprop)、2,4,5-涕丙酸(fenoprop)、MCPA、2甲4氯丙酸(mecoprop)、燕麦酸(chlorfenprop)、氯氨吡啶酸(aminopyralid)、二氯吡啶酸(clopyralid)、氯氟吡啶酸(florpyrauxifen)、氟氯吡啶酸(halauxifen)、氨氯吡啶酸(picloram)、氯氟吡氧乙酸(fluroxypyr)、三氯吡氧乙酸(triclopyr)、氯丙嘧啶酸(aminocyclopyrachlor)等嘧啶羧酸系化合物;氯甲喹啉酸(quinmerac)等喹啉羧酸系的化合物;敌稗(propanil)等酸酰胺系化合物;氯丙威(chlorprocarb)、甜菜安(desmedipham)、甜菜宁(phenmedipham)等苯基氨基甲酸酯系化合物;氯草敏(chloridazon)等哒嗪酮系化合物;莠灭净(ametryn)、莠去津(atrazine)、叠氮净(aziprotryne)、氰草津(cyanazine)、敌草净(desmetryne)、异丙净(dipropetryn)、甲氧丙净(methoprotryne)、扑草净(prometryne)、扑灭津(propazine)、另丁津(sebuthylazine)、仲丁通(secbumeton)、西玛津(simazine)、西草净(simetryn)、特丁通(terbumeton)、特丁津(terbuthylazine)、特丁净(terbutryne)、草达津(trietazine)、环丙腈津(procyazine)等三嗪系化合物;环嗪酮(hexazinone)、苯嗪草酮(metamitron)、嗪草酮(metribuzin)等三嗪酮系化合物;氨唑草酮(amicarbazone)等三唑啉酮系化合物;除草啶(bromacil)、环草定(lenacil)、特草定(terbacil)等尿嘧啶系化合物;溴苯隆(bromuron)、氯溴隆(chlorbromuron)、绿麦隆(chlorotoluron)、唑隆(dimefuron)、敌草隆(diuron)、磺噻隆(ethidimuron)、非草隆(fenuron)、异隆(isouron)、甲基苯噻隆(methabenzthiazuron)、溴谷隆(metobromuron)、甲氧隆(metoxuron)、绿谷隆(monolinuron)、草不隆(neburon)等脲系化合物;灭草松(bentazon)等苯并噻嗪酮系化合物;哒草特(pyridate)等苯基哒嗪系化合物;草甘膦(glyphosate)等甘氨酸系化合物;双丙氨膦酸(bialaphos)、草铵膦(glufosinate-ammonium)等次膦酸系化合物;氟啶草酮(fluridone)等二苯基杂环系化合物;氟咯草酮(flurochloridone)、氟草敏(norflurazon)等N-苯基杂环系化合物;氟丁酰草胺(beflubutamid)、吡氟酰草胺(diflufenican)、氟吡酰草胺(picolinafen)等苯基醚系化合物;二氯异草酮(bixlozone)、异草酮(clomazone)等异唑烷酮系化合物;三氟羧草醚(acifluorfen)、甲羧除草醚(bifenox)、甲氧除草醚(chlomethoxyfen)、草枯醚(chlornitrofen)、乙羧氟草醚(fluoroglycofen-ethyl)、氟磺胺草醚(fomesafen)、乳氟禾草灵(lactofen)、除草醚(nitrofen)、乙氧氟草醚(oxyfluorfen)等二苯基醚系化合物;氯酰亚胺(chlorphthalim)、吲哚酮草酯(cinidon-ethyl)、氟嘧草啶(epyrifenacil)、丙炔氟草胺(flumioxazin)、环戊草酮(pentoxazone)、苯嘧磺草胺(saflufenacil)、氟嘧硫草酯(tiafenacil)、嗪草酸甲酯(fluthiacet-methyl)等N-苯基酰亚胺系化合物;丙炔草酮(oxadiargyl)、草酮(oxadiazon)等N-苯基二唑系化合物;唑啶草酮(azafenidin)、唑草酯(carfentrazone-ethyl)、甲磺草胺(sulfentrazone)等N-苯基三唑啉酮系化合物;吡草醚(pyraflufen-ethyl)等苯基吡唑系化合物;唑草胺(cafenstrole)、四唑酰草胺(fentrazamide)、三唑酰草胺(ipfencarbazone)等唑基羧酰胺系化合物;呋草黄(benfuresate)、乙氧呋草黄(ethofumesate)等苯并呋喃系化合物;苯磺唑草(fenoxasulfone)、砜吡草唑(pyroxasulfone)等异唑啉系化合物;茚草酮(indanofan)、灭草环(tridiphane)等环氧乙烷系化合物;丁草敌(butylate)、环草敌(cycloate)、哌草丹(dimepiperate)、EPTC、戊草丹(esprocarb)、禾草敌(molinate)、坪草丹(orbencarb)、克草敌(pebulate)、苄草丹(prosulfocarb)、禾草丹(benthiocarb)、仲草丹(tiocarbazil)、野麦畏(tri-allate)、灭草敌(vernolate)等硫代氨基甲酸酯系化合物;乙草胺(acetochlor)、甲草胺(alachlor)、二丙烯草胺(allidochlor)、丁草胺(butachlor)、丁烯草胺(butenachlor)、异丁草胺(delachlor)、二甲草胺(dimethachlor)、二甲吩草胺(dimethenamid)、吡唑草胺(metazachlor)、异丙甲草胺(metolachlor)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、毒草胺(propachlor)、异丙草胺(propisochlor)、丙炔草胺(prynachlor)、噻吩草胺(thenylchlor)等α-氯乙酰胺系化合物;噻吩草胺(thenylchlor)、氟噻草胺(flufenacet)、苯噻酰草胺(mefenacet)等α-氧基乙酰胺系化合物;莎稗磷(anilofos)、哌草磷(piperophos)等α-硫代乙酰胺系化合物;二氟吡隆钠盐(diflufenzopyr-sodium)、萘草胺(naptalam)等芳基羧酸酯系化合物;牧草快(cyperquat)、敌草快(diquat)、百草枯(paraquat)等吡啶系化合物;燕麦灵(barban)、双酰草胺(carbetamide)、氯炔灵(chlorbufam)、氯苯胺灵(chlorpropham)、苯胺灵(propham)、灭草灵(swep)等氨基甲酸酯系化合物;DNOC、戊硝酚(dinosam)、地乐酚(dinoseb)、特乐酚(dinoterb)、硝草酚(etinofen)、丁硝酚(medinoterb)等二硝基酚系化合物;异唑草酮(isoxaflutole)等异唑系化合物;磺酰草吡唑(pyrasulfotole)、吡唑草酯(tolpyralate)、苯吡唑草酮(topramezone)、吡草酮(benzofenap)、吡唑特(pyrazolynate)、苄草唑(pyrazoxyfen)等吡唑系化合物;氟吡草酮(bicyclopyrone)、芬喹酮(fenquinotrione)、硝磺草酮(mesotrione)、磺草酮(sulcotrione)、呋喃磺草酮(tefuryltrione)、环磺酮(tembotorione)、双环磺草酮(benzobicyclon)等三酮系化合物;四氟络草胺(tetflupyrolimet)等芳基吡咯烷酮酰苯胺系化合物;茚嗪氟草胺(indaziflam)、三嗪氟草胺(triaziflam)等烷基嗪系化合物;氯硫酰草胺(chlorthiamid)、敌草腈(dichlobenil)、溴酚肟(bromofenoxim)、溴苯腈(bromoxynil)、碘苯腈(ioxynil)等腈系化合物;氟胺草唑(flupoxam)等三唑并羧基酰胺系化合物;环庚草醚(cinmethylin)、甲硫唑草啉(methiozolin)等苄基醚系化合物;苯草醚(aclonifen)等二苯基醚系化合物;环哒嗪草酯(cyclopyrimorate)等苯氧基哒嗪系化合物;杀草强(amitrole)等三唑系化合物;二氯喹啉酸(quinclorac)等喹啉羧酸酯系化合物;双苯酰草胺(diphenamid)、萘丙胺(naproanilide)敌草胺(napropamide)等乙酰胺系化合物;麦草氟甲酯(flamprop-m)等芳基氨基丙酸系化合物;茅草枯(dalapon)、四氟丙酸(flupropanate)、TCA等氯羧酸系化合物;地散磷(bensulide)等二硫代磷酸系化合物;氟磺酰草胺(mefluidide)、黄草伏(perfluidone)等三氟甲烷砜酰苯胺系化合物;和它们的农药上可容许的酸加成盐。
进一步,作为上述除草剂,作为其它化合物,也可举出双唑草腈(pyraclonil)、茵多酸(endothal)、溴丁酰草胺(bromobutide)、CAMA、二甲胂酸(cacodylic acid)、苄草隆(cumyluron)、DSMA、野燕枯(difenzoquat)、杀草隆(daimuron)、乙氧苯草胺(etobenzanid)、MSMA、甲基杀草隆(methyldymron)、油酸(oleic acid)、嗪草酮(oxaziclomefone)、壬酸(pelargonic acid)、稗草丹(pyributicarb)、灭藻醌(quinoclamine)、和它们的农药上可容许的酸加成盐。
它们之中,作为上述除草剂,优选为选自丙草胺(pretilachlor)及其农药上可容许的盐中的至少1种。
本发明的农药组合物无论所含有的农药有效成分的水溶解度如何,都可以发挥优异的缓释性。因此,作为该农药有效成分,根据上述农药组合物的形态、应用目的、应用对象、和应用方法、以及该农药有效成分的特性等来适当选择,没有特别限制,但作为本发明的农药组合物所含有的农药有效成分,例如,优选20~25℃下的水溶解度为50g/L以下。另外,上述20℃~25℃的范围容许20-0.5℃~25+0.5℃的范围。此外,作为上述水溶解度,更优选为45g/L以下,进一步优选为10g/L。另外,作为上述水溶解度的下限,可举出例如,0.1mg/L。
本发明中的“水溶解度”表示农药有效成分溶解于水的饱和溶液的浓度,通过OECD指导原则No.105(OECD GUIDELINE FOR THE TESTING OF CHEMICALS105,Adopted27.07.95,https://doi.org/10.1787/9789264069589-en)的方法而测定。在OECD指导原则No.105中记载了被应用于水溶解度超过10mg/L的农药有效成分的烧瓶法、和被应用于水溶解度低于10mg/L的农药有效成分的柱溶出法这2个方法,测定方法按照该指导原则来选择。此外,作为本发明中的“水溶解度”,可以采用在独立行政法人农林水产消费安全技术中心(FAMIC)的主页(http://www.acis.famic.go.jp/syouroku/index.htm)中公开的农药摘录中,作为各农药有效成分的水溶解度而被公开的水溶解度。
作为这样的水溶解度的农药有效成分,可举出例如,氟虫啶胺、烯丙苯噻唑、噻虫嗪、吡虫啉、异丁乙氧喹啉、丙草胺、和它们的农药上可容许的酸加成盐等,但不限定于它们。
在本发明中,作为上述农药上可容许的酸加成盐,可举出盐酸盐、硝酸盐、硫酸盐、磷酸盐、和乙酸盐等,可以为它们之中的1种,也可以为2种以上的组合。
作为本发明的农药组合物中的上述农药有效成分的含量(在农药有效成分为2种以上的情况下为它们的合计含量,以下相同),由于根据其种类、使用目的、和应用对象、应用方法等来适当调整,因此不可以一概而论,但相对于农药组合物的总质量,例如,可以为0.1~60质量%、0.2~50质量%、0.5~40质量%。
(树脂乳液)
在本发明中,所谓“树脂乳液”,表示由树脂形成的粒子的平均粒径在0.001~100μm的树脂粒子,作为上述平均粒径,优选为0.005~10μm,更优选为0.01~5μm。这样的树脂乳液的平均粒径例如通过激光衍射散射式粒度分布测定法、动态光散射式粒度分布测定法而测定。更具体而言,关于通过将树脂乳液适当用水悬浮或稀释直到适于测定的浓度,一边搅拌一边超声波处理而使粒子分散,从而调制出的测定用样品,可以将使用激光衍射式粒度分布测定装置(例如,LA-960(堀场))或动态光散射式粒度分布测定装置(例如,DLS-6500(大塚电子))进行测定而获得的粒度分布中的、体积基准的累积频率50%的中值粒径设为上述平均粒径。推测上述树脂乳液具有填埋农药组合物(特别是粒剂)的空隙,减慢水的侵入的作用。
作为上述树脂乳液涉及的树脂,可举出例如,丙烯酸系树脂、乙酸乙烯酯系树脂、氨基甲酸酯系树脂等,可以为它们之中的1种,也可以为2种以上的组合,其中,优选为丙烯酸系树脂。
在本发明中,所谓“丙烯酸系树脂”,表示至少以丙烯酸烷基酯和/或甲基丙烯酸烷基酯作为单体的高分子化合物(聚合物:上述单体的均聚物和共聚物、上述单体之中的1种以上与其它单体的共聚物)。作为上述丙烯酸烷基酯,可举出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、和丙烯酸2-乙基己酯等,可以为它们之中的1种,也可以为2种以上的组合。此外,作为上述甲基丙烯酸烷基酯,可举出甲基丙烯酸甲酯、甲基丙烯酸乙酯等,可以为它们之中的1种,也可以为2种以上的组合。
在上述丙烯酸系树脂中,以丙烯酸烷基酯和/或甲基丙烯酸烷基酯为主,在其中也包含其它单体例如选自芳香族乙烯基单体、烯烃单体、有机硅大分子单体、和支链烷烃羧酸乙烯酯中的至少1种单体聚合而成的高分子化合物(共聚物)。作为上述芳香族乙烯基单体,可举出苯乙烯等。此外,作为上述烯烃单体,可举出乙烯、丙烯、和丁二烯等,可以为它们之中的1种,也可以为2种以上的组合。
作为本发明的农药组合物所含有的上述丙烯酸系树脂,可以为上述之中的1种,也可以为2种以上的组合。
作为上述丙烯酸系树脂,更具体而言,可举出例如,丙烯酸烷基酯与甲基丙烯酸烷基酯的共聚物(例如,ジャパンコーティングレジン株式会社制Mowinyl-Powder LDM7000P等)、丙烯酸烷基酯与苯乙烯的共聚物(例如,ジャパンコーティングレジン株式会社制モビニール6485,Mowinyl-Powder LDM7400P等)、丙烯酸烷基酯与有机硅大分子单体的共聚物(例如,ジャパンコーティングレジン株式会社制モビニール7110等)、和甲基丙烯酸烷基酯与乙烯的共聚物(例如,三井·ダウポリケミカル株式会社制ニュクレルN1108C等)等。
在本发明中,所谓“乙酸乙烯酯系树脂”,表示至少以乙酸乙烯酯为单体的高分子化合物(聚合物:上述单体的均聚物或上述单体与其它单体的共聚物)。
在上述乙酸乙烯酯系树脂中,以乙酸乙烯酯为主,在其中也包含选自其它单体例如丙烯酸烷基酯、甲基丙烯酸烷基酯、支链烷烃羧酸乙烯酯、烯烃单体、卤代烯烃单体、和不饱和二羧酸中的至少1种单体聚合而成的高分子化合物(共聚物)。作为上述丙烯酸烷基酯,可举出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、和丙烯酸2-乙基己酯等,可以为它们之中的1种,也可以为2种以上的组合。作为上述甲基丙烯酸烷基酯,可举出甲基丙烯酸甲酯等,可以为它们之中的1种,也可以为2种以上的组合。此外,作为上述烯烃单体,可举出乙烯、丙烯、和丁二烯等,可以为它们之中的1种,也可以为2种以上的组合。作为上述卤代烯烃单体,可举出氯乙烯和1,1-二氯乙烯等,可以为它们之中的1种,也可以为2种以上的组合。
作为本发明的农药组合物所含有的上述乙酸乙烯酯系树脂,可以为上述之中的1种,也可以为2种以上的组合。
作为上述乙酸乙烯酯系树脂,更具体而言,可举出例如,乙酸乙烯酯与支链烷烃羧酸乙烯酯与丙烯酸烷基酯的共聚物(例如,ジャパンコーティングレジン株式会社制Mowinyl-Powder LDM2072P等)、乙酸乙烯酯与乙烯的共聚物(例如,ジャパンコーティングレジン株式会社制モビニール180E等)、和乙烯与乙酸乙烯酯与氯乙烯的共聚物(例如,住化ケムテックス株式会社制スミカフレックス808HQ等)等。
在本发明中,所谓“氨基甲酸酯系树脂”,表示具有氨基甲酸酯键的高分子化合物(聚合物),通过使多异氰酸酯与多元醇反应而获得。作为上述多异氰酸酯,可举出1,6-己二异氰酸酯和异佛尔酮二异氰酸酯等脂肪族异氰酸酯。此外,作为上述多元醇,可举出聚乙二醇和聚丙二醇等聚醚多元醇;聚己二酸乙二醇酯二醇和聚己二酸丁二醇酯二醇等聚酯多元醇;以及聚碳酸丁二醇酯二醇和聚碳酸己二醇酯二醇等聚碳酸酯多元醇。作为上述氨基甲酸酯系树脂,可以为这些多异氰酸酯与多元醇的反应物之中的1种,也可以为2种以上的组合。
作为本发明的农药组合物的制造所使用的树脂乳液,可以适当使用作为液状的树脂乳液液或粉状的树脂乳液粉末而一般流通的物质。
上述所谓树脂乳液液,表示由上述树脂形成的粒子乳化分散于水等分散介质而得的物质。作为上述树脂乳液液中的树脂乳液的含量,通常为15~70质量%左右。
作为这样的树脂乳液液,可举出例如,ジャパンコーティングレジン株式会社制モビニール6485(丙烯酸烷基酯与苯乙烯的共聚物)、日本エイアンドエル株式会社制ナルスターSR-140(被羧基化了的丁二烯-苯乙烯-甲基丙烯酸甲酯共聚物)、住化ケムテックス株式会社制スミカフレックス808HQ(乙烯与乙酸乙烯酯与氯乙烯的共聚物)、第一工业制药株式会社制スーパーフレックス500M(脂肪族异氰酸酯与聚酯多元醇聚合而得的氨基甲酸酯树脂)、和昭和电工株式会社制ポリゾールAP-3140、AP-3820(苯乙烯/丙烯酸系共聚树脂)等。
上述树脂乳液粉末也被称为再乳化型粉末树脂等,一般而言,为在上述树脂乳液液中根据需要加入稳定剂等,通过喷雾干燥等方法进行干燥而获得的能够再分散于水的微粉末状物质。
作为这样的树脂乳液粉末,可举出例如,ジャパンコーティングレジン株式会社制Mowinyl-Powder DM201P(乙酸乙烯酯与支链烷烃羧酸乙烯酯的共聚物)、ジャパンコーティングレジン株式会社制Mowinyl-Powder DM2072P(乙酸乙烯酯与支链烷烃羧酸乙烯酯与丙烯酸烷基酯的共聚物)、ジャパンコーティングレジン株式会社制Mowinyl-PowderLDM7000P(丙烯酸烷基酯与甲基丙烯酸烷基酯的共聚物)、ジャパンコーティングレジン株式会社制Mowinyl-Powder LDM7400P(丙烯酸烷基酯与苯乙烯的共聚物)、WACKERCHEMICALS公司制VINNAPAS2012E(丙烯酸烷基酯与苯乙烯的共聚物)、VINNAPAS2310E(丙烯酸烷基酯与苯乙烯和支链烷烃羧酸乙烯酯的共聚物)、Cleanese公司制ELOTEX TITAN7000(苯乙烯-丙烯酸酯的共聚物)、和Cleanese公司制ELOTEX FX7000(苯乙烯-丙烯酸酯的共聚物)等。
在本发明的农药组合物含有上述树脂乳液的情况下,作为其含量(由上述树脂形成的粒子的量;在树脂乳液为2种以上的情况下为它们的合计含量,以下相同),相对于农药组合物的总质量,优选为0.5~40质量%,更优选为1~30质量%,进一步优选为2~15质量%。如果上述树脂乳液的含量超过上述上限,则具有在制造农药组合物时附着于装置的原料的量变多、或在制造农药粒剂的情况下调整为所希望的大小变得困难(造粒不良)的倾向,另一方面,如果小于上述下限,则具有不能充分获得农药有效成分对水的溶出抑制效果(缓释效果)的倾向。
(表面处理高岭土)
在本发明中,所谓“表面处理高岭土”,表示通过表面处理剂而表面被改性处理了的高岭土。在本发明中,所谓“高岭土”,表示以高岭石(高岭土石,Al2Si2O5(OH)4)作为主成分的粘土。推测在本发明的农药组合物中,上述表面处理高岭土通过利用上述表面处理剂而被加成的化学修饰基,从而具有增强与粘合剂、上述树脂乳液等其它成分的相互作用,使农药有效成分的溶出抑制效果(缓释效果)提高的作用。
作为上述表面处理剂,可举出具有能够与高岭土表面的官能团反应的反应基、和上述化学修饰基(或能够产生上述化学修饰基的基团)的有机化合物。作为上述反应基,可举出例如,氨基、乙烯基、环氧基、甲基丙烯酰基、巯基。作为代表性的表面处理剂,可举出硅烷偶联剂、钛酸酯偶联剂、脂肪酸、表面活性剂等。
作为上述硅烷偶联剂,更具体而言,可举出例如,具有烷氧基甲硅烷基(-SiORn:在上述式中,R表示烷基,n表示1~3的整数,在n=1或2时,与硅原子(Si)结合的其它基团没有特别限定。)的有机化合物,例如,巯基硅烷、氨基硅烷、乙烯基硅烷、环氧硅烷。该硅烷偶联剂在高岭土表面加成硅烷醇基(-SiOH)作为上述化学修饰基。
作为上述巯基硅烷,可举出3-巯基丙基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷等。作为上述氨基硅烷,可举出N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基三甲氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-三乙氧基甲硅烷基-N-(1,3-二甲基-亚丁基)丙基胺、N-苯基-3-氨基丙基三甲氧基硅烷、N-(乙烯基苄基)-2-氨基乙基-3-氨基丙基三甲氧基硅烷、和它们的盐酸盐等。作为上述乙烯基硅烷,可举出乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷等。作为上述环氧硅烷,可举出2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二甲氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二乙氧基硅烷、3-环氧丙氧基丙基三乙氧基硅烷等。
作为上述钛酸酯偶联剂,更具体而言,可举出例如,异丙基三异硬脂酰基钛酸酯。此外,作为上述脂肪酸,更具体而言,可举出例如,硬脂酸、油酸等。
作为上述表面处理高岭土,可举出例如,乙烯基硅烷表面处理烧成高岭土(例如,BASF公司制Translink37、Translink77;KaMin LLC公司制Polyfil WC;イメリスミネラルズ·ジャパン公司制Polarite 103A、Polarite 503S等)、氨基硅烷表面处理烧成高岭土(例如,BASF公司制Translink 445、Translink 555;KaMin LLC公司制Nulok390;KentuckyTennessee Clay公司制Amlok321;イメリスミネラルズ·ジャパン公司制Polarite 102A、Polarite 402A、Polarite 502A等)、硬脂酸表面处理高岭土(BASF公司制ASP 101;KaMinLLC公司制Nucap 390、Nucote 7009等)、巯基硅烷表面处理烧成高岭土(KaMin LLC公司制Nucap 100G、Nucap 190W、Nucap 290W;Kentucky Tennessee Clay公司制Mercap 100、Mercap 200等)等,可以为它们之中的1种,也可以为2种以上的组合。
它们之中,作为本发明涉及的表面处理高岭土,优选为通过上述硅烷偶联剂而表面被硅烷处理了的硅烷表面处理高岭土。在本发明中,所谓“硅烷表面处理高岭土”,表示在高岭土表面加成了上述硅烷醇基的物质。作为这样的硅烷表面处理高岭土,上述硅烷偶联剂的含量相对于硅烷表面处理高岭土的总质量,优选为0.01~40质量%,更优选为0.05~20质量%。上述硅烷偶联剂的含量例如能够通过测定将硅烷表面处理高岭土加热而获得的变化的热重量分析法、元素分析法、非分散型红外线分析法等来测定。
此外,作为本发明涉及的表面处理高岭土,优选为粒子状的表面处理高岭土粒子。作为上述表面处理高岭土粒子,其平均粒径优选为0.01~50μm,更优选为0.05~10μm。上述表面处理高岭土粒子的平均粒径例如通过激光衍射散射式粒度分布测定法、动态光散射式粒度分布测定法而测定。更具体而言,关于通过将表面处理高岭土粒子用1%左右的表面活性剂(例如,六偏磷酸钠)水溶液适当混悬直到适于测定的浓度,一边搅拌一边超声波处理而使粒子分散,从而调制出的测定用样品,可以将使用激光衍射式粒度分布测定装置(例如,LA-960(堀场))或动态光散射式粒度分布测定装置(例如,DLS-6500(大塚电子))进行测定而获得的粒度分布中的、体积基准的累积频率50%的中值粒径设为上述平均粒径。
在本发明的农药组合物含有上述表面处理高岭土的情况下,作为其含量(在表面处理高岭土为2种以上的情况下为它们的合计含量,以下相同),相对于农药组合物的总质量,优选为0.1~60质量%,更优选为1~50质量%,进一步优选为5~30质量%。如果上述表面处理高岭土的含量超过上述上限,则具有在制造农药组合物时易于发生捏合不良、造粒不良的倾向,另一方面,如果小于上述下限,则具有不能充分获得农药有效成分对水的溶出抑制效果(缓释效果)的倾向。
(有机改性膨润土与油类的组合)
〔有机改性膨润土〕
在本发明中,所谓“有机改性膨润土”,表示使有机阳离子、主要是来源于脂肪腈的季铵离子与作为以蒙脱石为主成分的绿土(smectite)型粘土的膨润土反应而得的有机改性粘土,也被称为“有机膨润土”等。作为上述有机改性膨润土,优选为使膨润土的表面与季铵离子反应而得的季铵化合物表面处理膨润土。在本发明中,推测上述有机改性膨润土不仅与下述油类一起向本发明的农药组合物赋予优异的缓释性,而且作为改良剂(优选为造粒性改良剂)起作用而使制造性进一步提高。
在本发明中,在上述膨润土中,不仅包含以蒙脱石为主成分的弱碱性粘土矿物,而且包含贝得石、绿脱石、皂石、锂蒙脱石等绿土。此外,作为上述季铵离子,可举出氯化烷基三甲基铵、氯化二烷基二甲基铵、氯化苄基三烷基铵、苯扎氯铵等。
作为上述有机改性膨润土,可举出例如,二硬脂二甲铵锂蒙脱石、二甲基二硬脂基铵锂蒙脱石、二甲基二硬脂基铵膨润土、苄基二甲基硬脂基铵锂蒙脱石、三甲基硬脂基铵膨润土、苄基二甲基硬脂基铵膨润土等,可以为它们之中的1种,也可以为2种以上的组合。
作为上述有机改性膨润土,更具体而言,可举出例如,クニビス110、クニビス127(以上,クニミネ工業株式会社制);エスベン、エスベンNTO、エスベンNZ、エスベンNZ70、エスベンW(以上,株式会社ホージュン制);クレイトン34、クレイトン40、クレイトンEM、クレイトンER、クレイトンHT(以上,ビックケミー·ジャパン公司制)等。
此外,作为本发明涉及的有机改性膨润土,优选为粒子状的有机改性膨润土粒子。作为上述有机改性膨润土粒子,其平均粒径优选为0.001~100μm,更优选为0.005~60μm,进一步优选为0.01~30μm。上述有机改性膨润土粒子的平均粒径例如通过激光衍射散射式粒度分布测定法、动态光散射式粒度分布测定法而测定。更具体而言,关于通过将有机改性膨润土粒子用0.5%左右的表面活性剂(例如,六偏磷酸钠和十二烷基苯磺酸钠)水溶液适当混悬直到适于测定的浓度,一边搅拌一边超声波处理而使粒子分散从而调制出的测定用样品,可以将使用激光衍射式粒度分布测定装置(例如,LA-960(堀场))或动态光散射式粒度分布测定装置(例如,DLS-6500(大塚电子))进行测定而获得的粒度分布中的、体积基准的累积频率50%的中值粒径设为上述平均粒径。
在本发明的农药组合物含有上述有机改性膨润土的情况下,作为其含量(在有机改性膨润土为2种以上的情况下为它们的合计含量,以下相同),相对于农药组合物的总质量,优选为0.05~40质量%,更优选为0.1~30质量%,进一步优选为0.2~20质量%。如果上述有机改性膨润土的含量超过上述上限,则具有在制造农药组合物时易于发生捏合不良、造粒不良的倾向,另一方面,如果小于上述下限,则具有不能充分获得农药有效成分对水的溶出抑制效果(缓释效果)的倾向。
〔油类〕
在本发明中,在“油类”中不仅包含脂肪酸与甘油的酯化合物(油脂),而且也包含烃系油。在本发明中,推测上述油类不仅与上述有机改性膨润土一起向本发明的农药组合物赋予优异的缓释性,而且作为改良剂(优选为造粒性改良剂)起作用而使制造性更提高。
作为上述油脂,可举出例如,色拉油、精制菜籽油、玉米油、豆油、芝麻油、菜籽油(芥花油)、米油(米糠油)、棕榈仁油、棉籽油、蓖麻油等在常温下为液体的植物性油脂;鱼油、肝油等在常温下为液体的动物性油脂;可可脂、花生油、棕榈油、椰子油等在常温下为固体的植物性油脂;猪油(猪脂)、牛油(牛脂)、乳脂(黄油、酥油)等在常温下为固体的动物性油脂。
作为上述烃系油,可举出例如,以萜类等作为主成分的精油;正链烷烃、异链烷烃、液体石蜡等脂肪族烃;烷基苯、烷基萘等芳香族烃。此外,在上述烃系油中也包含例如,脂肪酸甲酯、二元酸甲酯等合成油(烃系酯)。
作为本发明涉及的油类,可以为它们之中的1种,也可以为2种以上的组合,但从作业容易性和安全性的观点考虑,优选在常温下为液体(高沸点油类),更优选为选自菜籽油、精制菜籽油、棉籽油等植物性油脂(优选在常温下为液体)、和烃系油中的至少1种,进一步优选为选自脂肪族烃(例如液体石蜡)等烃系油中的至少1种。这里,上述所谓常温,更具体而言,是指作为在第十八改正日本药典通则中规定的常温的“15℃~25℃”。此外,作为上述液体的性状,从作业时的操作的观点考虑,例如,使用B型粘度计(TOKIMEC制,VISCOMETERMODEL BM),在使用转子:3或4、转速:60r/分钟、测定时间:60秒的条件下测定的25℃的粘度优选为1000mPa·s以下,更优选为800mPa·s以下,进一步优选为500mPa·s以下。
在本发明的农药组合物含有上述油类的情况下,作为其含量(在油类为2种以上的情况下为它们的合计含量,以下相同),相对于农药组合物的总质量,优选为0.05~40质量%,更优选为0.1~30质量%,进一步优选为0.5~20质量%。如果上述油类的含量超过上述上限,则具有在制造农药组合物时附着于装置的原料的量变多、或在制造农药粒剂的情况下调整为所希望的大小变得困难(造粒不良)的倾向,另一方面,如果小于上述下限,则具有不能充分获得农药有效成分对水的溶出抑制效果(缓释效果)的倾向。
此外,对于本发明的农药组合物,在含有上述油类的情况下也含有上述有机改性膨润土,在含有上述有机改性膨润土的情况下也含有上述油类。然而,不排除除了上述树脂乳液和上述表面处理高岭土以外,还含有上述有机改性膨润土和上述油类之中的仅任一者的农药组合物。推测上述有机改性膨润土和上述油类通过组合而被包含于农药组合物,从而不仅向本发明的农药组合物赋予优异的缓释性,而且作为改良剂(优选为造粒性改良剂)起作用而使制造性更提高。
在本发明的农药组合物含有有机改性膨润土与油类的组合的情况下,作为它们的含量(上述有机改性膨润土的含量与上述油类的含量的合计含量,以下相同),相对于农药组合物的总质量,优选为0.1~50质量%,更优选为0.2~40质量%,进一步优选为0.7~30质量%。如果上述合计含量超过上述上限,则具有在制造农药组合物时附着于装置的原料的量变多、或在制造农药粒剂的情况下调整为所希望的大小变得困难(造粒不良)的倾向,另一方面,如果小于上述下限,则具有不能充分获得农药有效成分对水的溶出抑制效果的倾向。
此外,作为此时的本发明的农药组合物中的上述有机改性膨润土的含量与上述油类的含量的质量比(有机改性膨润土的含量:油类的含量),从与上述同样的观点考虑,优选为1:30~30:1,更优选为1:20~20:1,进一步优选为1:10~10:1,进一步更优选为1:5~5:1。
作为本发明的农药组合物,只要含有选自上述树脂乳液、上述表面处理高岭土、和上述有机改性膨润土与上述油类的组合这3种中的2种以上即可,可举出例如,下述组合。
(树脂乳液与表面处理高岭土的组合)
在该情况下,作为上述树脂乳液的含量与上述表面处理高岭土的含量的合计含量,相对于农药组合物的总质量,优选为0.6~70质量%,更优选为2~60质量%,进一步优选为7~50质量%。如果上述合计含量超过上述上限,则具有在制造农药组合物时附着于装置的原料的量变多、或在制造农药粒剂的情况下调整为所希望的大小变得困难(造粒不良)的倾向,另一方面,如果小于上述下限,则具有不能充分获得农药有效成分对水的溶出抑制效果(缓释效果)的倾向。
(树脂乳液与有机改性膨润土与油类的组合)
在该情况下,作为上述树脂乳液的含量与上述有机改性膨润土和油类的含量的合计含量,相对于农药组合物的总质量,优选为0.6~50质量%,更优选为1.2~40质量%,进一步优选为2.7~30质量%。如果上述合计含量超过上述上限,则具有在制造农药组合物时附着于装置的原料的量变多、或在制造农药粒剂的情况下调整为所希望的大小变得困难(造粒不良)的倾向,另一方面,如果小于上述下限,则具有不能充分获得农药有效成分对水的溶出抑制效果(缓释效果)的倾向。
(表面处理高岭土与有机改性膨润土与油类的组合)
在该情况下,作为上述表面处理高岭土的含量与上述有机改性膨润土和油类的含量的合计含量,相对于农药组合物的总质量,优选为0.2~60质量%,更优选为1.2~50质量%,进一步优选为5.7~40质量%。如果上述合计含量超过上述上限,则具有在制造农药组合物时附着于装置的原料的量变多、或在制造农药粒剂的情况下调整为所希望的大小变得困难(造粒不良)的倾向,另一方面,如果小于上述下限,则具有不能充分获得农药有效成分对水的溶出抑制效果(缓释效果)的倾向。
(树脂乳液与表面处理高岭土与有机改性膨润土与油类的组合)
在该情况下,作为上述树脂乳液的含量与上述表面处理高岭土的含量与上述有机改性膨润土和油类的含量的合计含量,相对于农药组合物的总质量,优选为0.7~70质量%,更优选为2.2~60质量%,进一步优选为7.7~50质量%。如果上述合计含量超过上述上限,则具有在制造农药组合物时附着于装置的原料的量变多、或在制造农药粒剂的情况下调整为所希望的大小变得困难(造粒不良)的倾向,另一方面,如果小于上述下限,则具有不能充分获得农药有效成分对水的溶出抑制效果(缓释效果)的倾向。
(辅助剂)
作为本发明的农药组合物,除了上述农药有效成分、和上述3种成分(树脂乳液、表面处理高岭土、有机改性膨润土与油类的组合)以外,还可以在不损害本发明的效果的范围内进一步含有表面活性剂、粘合剂、增量剂、防霉剂、着色剂、稳定剂等辅助剂。
在本发明的农药组合物含有上述辅助剂的情况下,该辅助剂可以为1种,也可以为2种以上的组合,作为其含量(在辅助剂为2种以上的情况下为它们的合计含量),可以根据其种类、组合来适当调整,例如,相对于农药组合物的总质量,可以为0.01~80质量%,优选为1~80质量%,更优选为5~70质量%。
〔表面活性剂〕
作为上述表面活性剂,可举出例如,阴离子性表面活性剂、非离子性表面活性剂、阳离子性表面活性剂、和两性表面活性剂等,可以为它们之中的1种,也可以为2种以上的组合。
作为上述阴离子性表面活性剂,可举出例如,聚氧化烯烷基醚硫酸盐、聚氧化烯烷基苯基醚硫酸盐、聚氧化烯苯乙烯基苯基醚硫酸盐、聚氧乙烯聚氧丙烯嵌段聚合物硫酸盐、烷基硫酸盐、烷烃磺酸盐、α-烯烃磺酸盐、二烷基磺基琥珀酸盐、烷基苯磺酸盐、烷基磺酸盐、烷基二苯基醚二磺酸盐、木质素磺酸盐、烷基萘磺酸盐、(烷基)萘磺酸的甲醛缩合物盐、聚氧化烯烷基苯基醚磺酸盐、脂肪酸盐、N-甲基-脂肪酸肌氨酸盐、树脂酸盐、聚氧化烯烷基醚磷酸盐、聚氧化烯烷基苯基醚磷酸盐、多元羧酸型表面活性剂等。另外,上述聚氧化烯只要不损害本发明的效果,就没有特别限定,但优选为选自聚氧乙烯和聚氧丙烯中的1种或它们的混合。
作为上述非离子性表面活性剂,可举出例如,失水山梨糖醇脂肪酸酯、聚氧化烯失水山梨糖醇脂肪酸酯、蔗糖脂肪酸酯、聚氧化烯脂肪酸酯、聚氧化烯树脂酸酯、聚氧化烯蓖麻油、聚氧化烯氢化蓖麻油、聚氧化烯烷基醚、聚氧化烯烷基苯基醚、聚氧乙烯聚氧丙烯嵌段聚合物、聚氧乙烯聚氧丙烯烷基醚、聚氧化烯烷基胺、聚氧化烯脂肪酸酰胺、聚氧化烯苯乙烯基苯基醚、有机硅系表面活性剂、炔属二醇系表面活性剂等。另外,上述聚氧化烯只要不损害本发明的效果,就没有特别限定,但优选为选自聚氧乙烯和聚氧丙烯中的1种或它们的混合。
作为上述阳离子性表面活性剂,可举出烷基三甲基氯化铵、烷基二甲基苯扎氯铵、烷基胺等。此外,作为上述两性表面活性剂,可举出二烷基氨基乙基甜菜碱、烷基二甲基苄基甜菜碱等。
在本发明的农药组合物含有上述表面活性剂的情况下,作为其含量(在表面活性剂为2种以上的情况下为它们的合计含量),相对于农药组合物的总质量,优选为0.01~20质量%,更优选为0.1~10质量%。
〔粘合剂〕
作为上述粘合剂,可举出例如,木质素磺酸盐;羧基甲基纤维素钠、甲基纤维素、羟基丙基甲基纤维素等纤维素衍生物;淀粉、糊精等加工淀粉;葡萄糖、蔗糖等糖类;聚丙烯酸钠等聚丙烯酸酯类(上述丙烯酸系树脂乳液除外);聚乙烯醇、聚乙烯吡咯烷酮等聚乙烯基衍生物(上述乙酸乙烯酯系树脂乳液除外);藻酸钠、阿拉伯胶、明胶、刺槐豆胶、黄原酸胶、和酪蛋白等来源于天然物的胶类,但不限定于这些,可以为它们之中的1种,也可以为2种以上的组合。
在本发明的农药组合物含有上述粘合剂的情况下,作为其含量(在粘合剂为2种以上的情况下为它们的合计含量),相对于农药组合物的总质量,优选为0.05~20质量%,更优选为0.1~10质量%。
〔增量剂〕
作为上述增量剂,可举出粘土、滑石、膨润土(上述有机改性膨润土除外)、高岭土(烧成高岭土、含水高岭土等;上述表面处理高岭土除外)、沸石、酸性白土、硅藻土、蛭石、珍珠岩、浮石等天然矿物质、其烧成品;碳酸钙、氯化钾、硫酸铵、硫酸钠等无机盐类;木粉、玉米壳轴等来源于植物的物质;尿素、白炭墨、二氧化钛等,但不限定于这些,可以为它们之中的1种,也可以为2种以上的组合。
在本发明的农药组合物含有上述增量剂的情况下,作为其含量(在增量剂为2种以上的情况下为它们的合计含量),相对于农药组合物的总质量,优选为2~80质量%,更优选为5~70质量%。
〔防霉剂、着色剂、稳定剂〕
作为上述防霉剂,可举出例如,苯甲酸钠、山梨酸钾、对羟基苯甲酸酯、1,2-苯并异噻唑啉-3-酮等,但不限定于这些,可以为它们之中的1种,也可以为2种以上的组合。
作为上述着色剂,可举出例如,蓝色1号、红色2号等焦油色素;焦油色素等,但不限定于这些,可以为它们之中的1种,也可以为2种以上的组合。
作为上述稳定剂,可举出例如,抗氧化剂、紫外线防止剂、干燥剂等,但不限定于这些,可以为它们之中的1种,也可以为2种以上的组合。
(农药粒剂)
作为本发明的农药组合物的形态,可举出粉剂(包含DL粉剂、FD剂)、粉粒剂、粒剂、可湿性粉剂(包含流动剂、水分散性粒剂)、可溶性粉剂(包含可溶性粒剂)、乳剂(包含浓乳剂、悬浮乳剂)、可溶液体制剂、油剂、气雾剂、发烟剂、微胶囊剂等,但从发挥优异的缓释性的观点考虑,优选为粒剂(本说明书中,根据情况也称为“农药粒剂”)。
上述所谓粒剂,一般表示最大粒径为0.03~100mm的物质(在本发明中优选为0.06~10mm、0.1~2.0mm、或0.3~1.7mm),在本发明中,片剂、粒也包含于粒剂。作为上述粒剂的形状,没有特别限制,可举出圆柱状、小球状、片状等。作为上述粒剂,可以为将其包装在水溶性膜等内的包装状的形态。另外,上述所谓最大粒径,为将上述粒剂向平面投影的情况下的圆的直径,在投影不是圆形的情况下(粒子为平板状、板状等、棒状、多边状等形状的情况下),是指其外接圆的直径。
(缓释性)
根据本发明,提供可以充分地抑制农药有效成分对水的初期的急剧的溶出的农药组合物,即,缓释性农药组合物。在本发明中,所谓“缓释性”,是指在将农药组合物(优选为上述粒剂)投入到水中时,农药有效成分向该水中的每小时的溶出量少,例如,可以通过在加入了40℃的去离子水100mL的试验容器中,投入农药组合物500mg而经过3小时后,对上述试验容器内的溶液通过高效液相色谱进行测定的农药有效成分的量(溶出量)或浓度(溶出浓度)来评价。
(应用方法)
本发明的农药组合物没有特别限制,可以根据所含有的农药有效成分的种类,以该农药有效成分成为有效量(通过农药有效成分的种类、应用目的、应用方法等来调整)的方式,应用于适当对象。例如,可以将本发明的农药组合物(优选为粒剂)直接均匀散布于栽培作物的田面水中、旱田、培养载体(水耕栽培、砂耕、NFT(Nutrient Film Technique)、岩棉耕等的营养液;人工培土、育苗用人工垫等固体培养基等)中。此外,本发明的农药组合物(优选为粒剂)也可以作为植穴处理剂、箱处理剂而使用。
本发明的农药组合物由于缓释性优异,可以充分地抑制对作物的药害,因此作为能够应用的作物,也没有特别限定,可举出例如,谷类、豆类、砂糖制造用绿草类、蔬菜类、果树类等有用植物。例如,从特别要求农药有效成分向水的急剧的溶出的抑制的观点考虑,可举出包含水稻的禾本科的作物。
<农药组合物的制造方法>
作为本发明的农药组合物的制造方法,没有特别限制,例如,可以将选自上述树脂乳液、上述表面处理高岭土、上述有机改性膨润土与上述油类的组合这3种中的2种以上、上述农药有效成分、以及根据需要的上述辅助剂和/或溶剂(例如水)进行混合,通过作为农药的制剂制造方法而以往公知的方法或按照其的方法来获得。
它们之中,在本发明的农药组合物为粒剂(农药粒剂)的情况下,作为这样的农药粒剂的制造方法,优选包含下述工序:将选自上述树脂乳液、上述表面处理高岭土、上述有机改性膨润土与上述油类的组合这3种中的2种以上、上述农药有效成分、以及根据需要的上述辅助剂和/或溶剂(例如水)进行混合并造粒的工序。
作为上述混合方法和造粒方法,没有特别限制,可以适当采用作为农药的制剂制造方法而以往公知的方法或按照其的方法,可以举出例如,挤出造粒法、转动造粒法、转动流动造粒法、流化床造粒法、搅拌混合造粒法、压缩造粒法、和压片法。例如,在制造圆柱状的粒剂的情况下,优选为挤出造粒法,此外,在制造球状的粒剂的情况下,优选为转动造粒法和搅拌混合造粒法。
在挤出造粒法的情况下,例如,首先,将选自上述树脂乳液、上述表面处理高岭土、上述有机改性膨润土与上述油类的组合这3种中的2种以上、与上述农药有效成分、与根据需要的上述辅助剂使用高速搅拌混合机、带型混合机等均匀地混合而获得混合物。作为上述各成分,可以使用根据需要预先实施了粉碎处理的物质。此外,在使用上述树脂乳液的情况下,可以使用上述树脂乳液液和树脂乳液粉末中的任一者,但从制造性更优异的观点考虑,优选使用上述树脂乳液粉末。
接着,在所得的混合物中添加水等溶剂,使用双臂捏合机、带型混合机等进一步混合(捏合)而获得捏合物。接着,将所得的捏合物使用篮型造粒机、螺旋式造粒机等挤出造粒机进行造粒。作为造粒时的挤出孔径(筛网径),没有特别限制,通常,例如为0.03~100mm(优选为0.3~10mm,更优选为0.5~5mm)的范围。根据本发明的制造方法,可以在不受上述溶剂量大幅限制的情况下实现高成品率,因此可以容易地以高效率获得本发明的农药粒剂。
接着,可以通过将所得的造粒物根据需要用球形整粒机等进行了整粒后,使用流化床干燥机、床式干燥机等进行干燥而将上述溶剂除去,根据需要进行筛分等,从而获得本发明的农药粒剂。
此外,作为本发明的农药粒剂的制造方法,可以为将选自上述树脂乳液、上述表面处理高岭土、上述有机改性膨润土与上述油类的组合这3种中的2种以上、与根据需要的上述辅助剂和/或溶剂(例如水)进行混合而进行了造粒后,使所得的造粒物含有上述农药有效成分的方法。
作为获得上述造粒物的方法(造粒工序),不使用上述农药有效成分,除此以外如上所述。此外,作为使上述造粒物含有上述农药有效成分的方法,可举出例如,使上述农药有效成分(例如,上述农药有效成分的溶剂(例如有机溶剂)液)含浸于上述造粒物的方法、用喷雾器等喷射后,根据需要将上述农药有效成分的溶剂干燥除去的方法等。
实施例
以下,举出实施例和比较例具体地说明本发明,但本发明不限定于下述实施例。另外,在各实施例和比较例中,氟虫啶胺的水溶解度是在20℃下,按照OECD指导原则No.105(OECD GUIDELINE FOR THE TESTING OF CHEMICALS105(OECD化学品测试准则105),27.07.95通过,https://doi.org/10.1787/9789264069589-en)所记载的方法而测定的,其以外的各农药有效成分的水溶解度是在独立行政法人农林水产消费安全技术中心(FAMIC)的主页(http://www.acis.famic.go.jp/syouroku/index.htm)中被公开的农药摘录中,作为该农药有效成分的水溶解度而被公开的。
(实施例1)
首先,将烯丙苯噻唑(水溶解度(20℃):36.6mg/L,纯度97.6%,Meiji Seikaファルマ株式会社制)10.25质量份(烯丙苯噻唑:10.004质量份)、氟虫啶胺(水溶解度(20℃):167mg/L,纯度100.0%,Meiji Seikaファルマ株式会社制)2.00质量份、表面处理高岭土(巯基硅烷表面处理烧成高岭土,Nucap 290W,KaMin LLC公司制)20.00质量份、有机改性膨润土(季铵化合物表面处理膨润土,クニビス127,クニミネ工業株式会社制)3.00质量份、油类(烃系油,流動パラフィンNo.260S,三光化学工业株式会社制)5.00质量份、表面活性剂(月桂基硫酸钠(烷基硫酸盐):エマール10PT,花王株式会社制)0.30质量份、粘合剂(聚乙烯醇:クラレポバール44-88S,株式会社クラレ制)2.00质量份、和增量剂(粘土,昭和クレー70N,昭和KDE株式会社制)57.45质量份用混合机(纤维混合机,パナソニック株式会社制)进行混合而获得了混合物。在所得的混合物中加入适当量的水,用立式捏合机(ACM08LVT-B型,株式会社爱工舍制作所制)进行了捏合。将所得的捏合物使用安装了直径1.0mm的筛网的マルチグラン(湿式挤出造粒机)(MG-55型,株式会社ダルトン制)而造粒,在60℃下干燥2小时将水除去,获得了农药组合物(粒剂)。在下述表1中显示所得的农药组合物的组成。
(实施例2~5、比较例1~6)
使农药组合物的组成为下述表1或表2所示的组成,除此以外,与实施例1同样地操作,获得了各农药组合物(粒剂)。在表1中,作为树脂乳液,使用了ジャパンコーティングレジン株式会社制的モビニールLDM7400P(丙烯酸系树脂乳液(粉末),Mowinyl-PowderLDM7400P)。在表2中,作为烧成高岭土,使用KaMin LLC公司制的カオリン70C,作为有机改性膨润土,使用クニミネ工業株式会社制的クニビス110(季铵化合物表面处理膨润土),作为膨润土,使用了クニミネ工業株式会社制的クニゲルV1。
表1
表2
(溶出试验)
首先,在试验容器(100mL容量)中加入去离子水100mL,在恒温槽内静置,使水温为40℃。接着,将在实施例和比较例中获得的各农药组合物500mg投入到上述试验容器中。从投入起经过3小时后,将试验容器内的溶液以变得均匀的方式温和地进行振荡后,取约1mL,用孔径0.45μm的膜滤器进行了过滤。分别通过高效液相色谱而测定滤液中的农药有效成分(烯丙苯噻唑和氟虫啶胺)的浓度,算出了上述3小时后的上述试验容器内的各农药有效成分的浓度(溶出浓度(ppm))。将结果示于下述表3和表4中。
(药害试验)
首先,在育苗箱中播种相当于150g/箱的催芽稻谷(稻),将在实施例和比较例中获得的各农药组合物以成为50g/箱的方式均匀地处理后,进行了覆土。在30℃下,在2天黑暗下进行发芽后,在昼30℃、夜12℃的条件下进行了栽培。在从播种起13天后从各育苗箱筛选任意的20根而计测草高,算出了其平均值(cm)。将所得的平均值(草高(cm))一并示于下述表3和表4中。
表3
表4
如表3~4所示那样,溶出试验的结果确认了,在本发明的农药组合物(例如实施例1~5)中,与不包含本发明涉及的树脂乳液、表面处理高岭土、有机改性膨润土、和油类中的任一者的农药组合物(例如比较例1,2)相比,农药有效成分的溶出浓度都充分低,具有优异的缓释性。进一步,药害试验的结果确认了,用本发明的农药组合物(例如实施例1~5)进行了处理的稻的草高都充分大,药害被充分减轻。另一方面确认了,对于不包含本发明涉及的树脂乳液、表面处理高岭土、有机改性膨润土、和油类中的任一者的农药组合物(例如比较例1~4)、至少不包含本发明涉及的树脂乳液、表面处理高岭土、和有机改性膨润土与油类的组合之中的2种以上的农药组合物(例如比较例5~6),在溶出浓度和草高之中的至少任一者中,比本发明的农药组合物差。
(实施例6)
首先,将烯丙苯噻唑(水溶解度(20℃):36.6mg/L,纯度97.6%,Meiji Seikaファルマ株式会社制)10.25质量份(烯丙苯噻唑:10.004质量份)、氟虫啶胺(水溶解度(20℃):167mg/L,纯度100.0%,Meiji Seikaファルマ株式会社制)2.00质量份、树脂乳液(丙烯酸系树脂乳液(粉末)、モビニールLDM7400P(Mowinyl-Powder LDM7400P)、ジャパンコーティングレジン株式会社制)10.00质量份、有机改性膨润土(季铵化合物表面处理膨润土,クニビス127,クニミネ工業株式会社制)3.00质量份、油类(烃系油,流動パラフィンNo.260S,三光化学工业株式会社制)5.00质量份、表面活性剂(月桂基硫酸钠(烷基硫酸盐):エマール10PT,花王株式会社制)0.30质量份、粘合剂(聚乙烯醇:クラレポバール44-88S,株式会社クラレ制)0.50质量份、和增量剂(粘土,昭和クレー70N,昭和KDE株式会社制)68.95质量份用混合机(纤维混合机,パナソニック公司制)进行混合而获得了混合物。在所得的混合物中以成为9%(水分量:水的质量/(混合物的质量+水的质量)×100(%))的方式加入水,用立式捏合机(ACM08LVT-B型,株式会社爱工舍制作所制)进行了捏合。将所得的捏合物使用安装了直径1.0mm的筛网的マルチグラン(MG-55型,株式会社ダルトン制)进行造粒,在60℃下干燥2小时将水除去,获得了农药组合物(粒剂)。在下述表5中显示所得的农药组合物的组成。此外,使上述水分量为11%、15%、或16%,除此以外,同样地操作,获得了以各水分量制造出的农药组合物(粒剂)(所得的农药组合物的组成与使水分量为9%而制造出的农药组合物的组成相同)。
(比较例7~10)
使农药组合物的组成为下述表5所示的组成,此外,使上述水分量为下述表6所示的量,除此以外,与实施例6同样地操作,获得了各农药组合物(粒剂)。另外,在表5中,作为膨润土,使用了クニミネ工業株式会社制的クニゲルV1。
表5
(制造性试验)
首先,将在实施例和比较例中获得的各农药组合物使用筛孔1.7mm、0.3mm的筛进行筛分,求出了粒径为1.7mm以下并且大于0.3mm的粒的合计重量相对于全部农药组合物重量的比例(重量分率(%))。将结果示于下述表6中。另外,在表6中,“-”表示未调制对应的农药组合物。在本试验中,在上述水分量少于最适合量的情况下,粒径小于0.3mm的粒的重量分率增加。另一方面,在上述水分量多于最适合量的情况下,粒径超过1.7mm的粒的重量分率增加。
表6
如表6所示那样,对于本发明的农药组合物(例如实施例6),至少以9~16%的宽范围的水分量获得了97%以上的重量分率(成品率)。即,确认了由于水分量的最适合量的范围宽,因此可以容易地以高效率获得粒剂,制造性优异。另一方面,确认了对于除本发明涉及的构成以外的农药组合物(例如比较例7~10),水分量的最适合量的范围(例如,上述重量分率成为95%以上的范围)窄、或难以确认该最适合量,在制造时要求严格的控制、或发生由以最适合量外的水分量进行造粒引起的造粒物的粉化、造粒物彼此的结合等,制造变得困难。
(实施例7)
首先,将噻虫嗪(水溶解度(25℃):4.1g/L,纯度100.0%,东京化成工业株式会社制)2.00质量份、树脂乳液(丙烯酸系树脂乳液(粉末),ELOTEX TITAN7000,Celanese公司制)10.00质量份、表面处理高岭土(巯基硅烷表面处理烧成高岭土,Nucap 290W,KaMin LLC公司制)20.00质量份、有机改性膨润土(季铵化合物表面处理膨润土,クニビス127,クニミネ工業株式会社制)3.00质量份、油类(植物性油脂,菜籽油,富士フィルム和光純薬工業株式会社制)5.00质量份、表面活性剂(月桂基硫酸钠(烷基硫酸盐):エマール10PT,花王株式会社制)0.30质量份、粘合剂(聚乙烯醇:クラレポバール44-88S,株式会社クラレ制)0.50质量份、和增量剂(粘土,昭和クレー70N,昭和KDE株式会社制)59.20质量份用混合机(纤维混合机,パナソニック株式会社制)进行混合而获得了混合物。在所得的混合物中加入适当量的水,用立式捏合机(ACM08LVT-B型,株式会社爱工舍制作所制)进行了捏合。将所得的捏合物使用安装了直径1.0mm的筛网的マルチグラン(MG-55型,株式会社ダルトン制)进行造粒,在60℃下干燥2小时将水除去,获得了农药组合物(粒剂)。在下述表7中显示所得的农药组合物的组成。
(比较例11~12)
使农药组合物的组成为下述表7所示的组成,除此以外,与实施例7同样地操作,获得了各农药组合物(粒剂)。
表7
(实施例8)
代替噻虫嗪,使用了吡虫啉(水溶解度(20℃):480mg/L,纯度96.5%,东京化成工业株式会社制),作为树脂乳液,使用了ジャパンコーティングレジン株式会社制的モビニールLDM7400P(丙烯酸系树脂乳液(粉末),Mowinyl-Powder LDM7400P),作为表面处理高岭土,使用了BASF公司制的Translink445(氨基硅烷表面处理烧成高岭土),作为有机改性膨润土,使用了クニミネ工業株式会社制的クニビス110(季铵化合物表面处理膨润土),作为油类,使用了富士フィルム和光純薬工業株式会社制的油酸甲酯(烃系油),除此以外,与实施例7同样地操作,获得了农药组合物(粒剂)。在下述表8中显示所得的农药组合物的组成。
(实施例9、比较例13~14)
使农药组合物的组成为下述表8所示的组成,除此以外,与实施例8同样地操作,获得了各农药组合物(粒剂)。
表8
(实施例10)
代替噻虫嗪,使用了异丁乙氧喹啉(水溶解度(20℃):20.2mg/L,纯度98.8%,株式会社MMAG制),作为油类,使用了三光化学工业株式会社制的流動パラフィンNo.260S(烃系油),设为下述表9所示的组成,除此以外,与实施例7同样地操作,获得了农药组合物(粒剂)。
(实施例11、比较例15)
使农药组合物的组成为下述的表9所示的组成,除此以外,与实施例10同样地操作,获得了各农药组合物(粒剂)。
表9
(实施例12)
代替噻虫嗪,使用了丙草胺(水溶解度(25℃):74mg/L,纯度97.9%,东京化成工业株式会社制),作为树脂乳液,使用了ジャパンコーティングレジン株式会社制的モビニールLDM7400P(丙烯酸系树脂乳液(粉末),Mowinyl-Powder LDM7400P),作为表面处理高岭土,使用了BASF公司制的Translink37(乙烯基硅烷表面处理烧成高岭土),作为有机改性膨润土,使用了株式会社ホージュン制的エスベンW(季铵化合物表面处理膨润土),作为油类,使用了三光化学工业株式会社制的流動パラフィンNo.260S(烃系油),除此以外,与实施例7同样地操作,获得了农药组合物(粒剂)。在下述表10中显示所得的农药组合物的组成。
(实施例13~14、比较例16)
使农药组合物的组成为下述表10所示的组成,除此以外,与实施例12同样地操作,获得了各农药组合物(粒剂)。
表10
(溶出试验)
〔噻虫嗪、吡虫啉〕
首先,在试验容器(100mL容量)中加入去离子水100mL,在恒温槽内静置,使水温为40℃。接着,将在各实施例和比较例中获得的农药组合物500mg投入到上述试验容器中。从投入起经过3小时后,将试验容器内的溶液以变得均匀的方式温和地进行振荡后,取约1mL,用孔径0.45μm的膜滤器进行了过滤。分别通过高效液相色谱而测定滤液中的农药有效成分(噻虫嗪、吡虫啉)的浓度,算出上述3小时后的上述试验容器内的各农药有效成分的浓度(溶出浓度(ppm))。将结果分别示于下述表11~12中。
[表11]
[表12]
〔异丁乙氧喹啉、丙草胺〕
首先,在试验容器(200mL容)中加入去离子水200mL,在恒温槽内静置,使水温为40℃。接着,将在各实施例和比较例中获得的含有异丁乙氧喹啉的农药组合物250mg或含有丙草胺的农药组合物500mg投入到上述试验容器中。从投入起经过3小时后,将试验容器内的溶液以变得均匀的方式温和地进行振荡后,取约1mL,用孔径0.45μm的膜滤器进行了过滤。分别通过高效液相色谱而测定滤液中的农药有效成分(异丁乙氧喹啉、丙草胺)的浓度,算出上述3小时后的上述试验容器内的各农药有效成分的浓度(溶出浓度(ppm))。将结果分别示于下述表13~14中。
[表13]
[表14]
如表11~14所示那样确认了,对于本发明的农药组合物(例如实施例7~14),在使用了噻虫嗪、吡虫啉、异丁乙氧喹啉、和丙草胺作为农药有效成分的情况下,也与使用了烯丙苯噻唑、氟虫啶胺的情况同样地,与不包含本发明涉及的树脂乳液、表面处理高岭土、有机改性膨润土、和油类中的任一者的农药组合物(例如比较例12、14、15、16)相比,农药有效成分的溶出浓度都充分低,无论农药有效成分的种类如何,都发挥优异的缓释性。另一方面确认了,对于不包含本发明涉及的树脂乳液、表面处理高岭土、和有机改性膨润土与油类的组合之中的2种以上的农药组合物(例如比较例11~16),无论农药有效成分的种类如何,溶出浓度都变高,在缓释性方面比本发明的农药组合物差。
产业可利用性
根据本发明,能够提供可以容易地以高效率获得农药有效成分对水的初期的急剧的溶出被充分地抑制、缓释性优异的缓释性农药组合物,和农药有效成分对水的初期的急剧的溶出被充分地抑制、缓释性优异的缓释性农药粒剂的制造方法。
Claims (10)
1.一种农药组合物,其含有:
选自树脂乳液、表面处理高岭土、和有机改性膨润土与油类的组合这3种中的2种以上;以及
农药有效成分。
2.根据权利要求1所述的农药组合物,所述树脂乳液为丙烯酸系树脂乳液。
3.根据权利要求1所述的农药组合物,所述表面处理高岭土为硅烷表面处理高岭土。
4.根据权利要求1所述的农药组合物,所述有机改性膨润土为季铵化合物表面处理膨润土。
5.根据权利要求1所述的农药组合物,所述油类为选自烃系油和植物性油脂中的至少1种。
6.根据权利要求1所述的农药组合物,其含有20~25℃下的水溶解度为50g/L以下的农药有效成分作为所述农药有效成分。
7.根据权利要求1所述的农药组合物,其进一步含有选自表面活性剂和增量剂中的至少1种。
8.根据权利要求1~7中任一项所述的农药组合物,其为粒剂。
9.一种制造方法,是权利要求8所述的农药组合物的制造方法,其包含下述工序:将选自所述树脂乳液、所述表面处理高岭土、和所述有机改性膨润土与所述油类的组合这3种中的2种以上与所述农药有效成分进行混合并造粒的工序。
10.一种制造方法,是权利要求8所述的农药组合物的制造方法,其包含下述工序:
将选自所述树脂乳液、所述表面处理高岭土、和所述有机改性膨润土与所述油类的组合这3种中的2种以上进行混合并造粒的造粒工序;以及
使在所述造粒工序中获得的造粒物含有所述农药有效成分的工序。
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