CN114051378A - 含有四氟醚唑的液体农用化学混合物及其在农作物中作为杀菌剂的相关用途 - Google Patents
含有四氟醚唑的液体农用化学混合物及其在农作物中作为杀菌剂的相关用途 Download PDFInfo
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- CN114051378A CN114051378A CN202080048887.5A CN202080048887A CN114051378A CN 114051378 A CN114051378 A CN 114051378A CN 202080048887 A CN202080048887 A CN 202080048887A CN 114051378 A CN114051378 A CN 114051378A
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
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Abstract
本发明涉及一种液体农用化学混合物,包含:‑油相,其至少包含四氟醚唑和任选的至少一种共溶剂;‑分散或溶解在所述油相中的至少一种除四氟醚唑之外的农用化学活性成分;其中相对于混合物的重量,所述四氟醚唑和所述至少一种除四氟醚唑以外的农用化学活性成分的总量等于或大于40重量%,优选等于或大于45重量%。本发明还涉及上述液体农用化学混合物在作物中作为杀菌剂的用途。
Description
技术领域
本发明涉及一种含有四氟醚唑的液体农用化学混合物及其在农作物中作为杀菌剂的相关用途。
现有技术
四氟醚唑,即具有以下化学结构的2-(2,4-二氯苯基)-3-(1H-1,2,4-***-1-基)丙基-1,1,2,2-四氟***,
是一种广谱***类杀菌剂,其作用是通过抑制麦角甾醇的生物合成来实现的,麦角甾醇是一种在真菌细胞膜的形成、稳定性和功能中起重要作用的成分。
四氟醚唑传统上以其外消旋形式使用,但它也可以作为旋光异构体使用,即作为(R)或(S)异构体使用。
本领域已知用于农用化学领域的许多含有麦角甾醇生物合成抑制剂的制剂。此类制剂可以是固体或液体制剂的形式,或者是液体中的固体悬浮剂的形式。
四氟醚唑在室温下表现为粘性液体,因此不适合配制成液体介质中固体颗粒的悬浮剂。因此,通常通过将活性成分溶解在合适的溶剂中来制备仅基于四氟醚唑的制剂,以获得随时间稳定的液体制剂。
此外,为了拓宽作用谱并减少耐药现象,四氟醚唑可与其他活性成分混合使用。如果其他活性成分为固体形式,则此类混合物通常配制为悬浮剂(SE)。悬浮剂是一种液体制剂,其特征在于存在两种或两种以上活性成分,其中至少一种为水乳液形式,以及至少一种为分散在水中的固体颗粒形式。
如本领域技术人员所知,悬浮剂是复杂的非均相制剂,随着时间的推移会发生物理降解现象,例如均质絮凝、异质絮凝或聚结。
悬浮剂所能包含的活性成分的最大浓度也有限制,这是由于***(包含作为分散介质的水和有机溶剂)粘度过大,并且需要使用高浓度的表面活性剂以保持制剂稳定。
一些农用药物可以以油分散剂(OD)的形式有效使用,这是一种液体农艺制剂,其中一种或多种活性成分与辅助制剂化合物一起分散在油相中;任选地随后对由此获得的悬浮液进行研磨,直到获得所需微粒形式的活性成分颗粒。
油分散剂通常表现出比悬乳剂更高的稳定性,因此允许配制在水性环境中不稳定的活性成分,即通过在水中降解而发生化学反应的物质,或引起物理不稳定现象的物质,例如絮凝或结晶。
然而,本领域技术人员已知,即使在油分散剂中,活性物质的总浓度也相当有限,因为具有相对高浓度活性成分的制剂不稳定、过于粘稠,因此不能有效地用于农艺目的。
因此,在农艺领域,强烈需要具有相对高浓度农用化学活性成分的液体制剂,以减少在每次处理中达到使用剂量所必须使用的最终制剂的体积,从而降低生产、运输和处置成本。
发明内容
申请人发现,上述现有技术的缺点(这些缺点将在以下描述中更为明显)可以通过使用四氟醚唑除作为农用化学活性成分外,还作为制备含有一种或多种其他农用化学活性成分的液体农用化学混合物的分散介质来克服。事实上,已观察到四氟醚唑可有效地用于完全或部分溶解或分散其他农用化学活性成分,从而避免使用常规稀释油相或在任何情况下使用相对较低的量,显著低于已知技术的农用化学液体混合物中使用的量。
出人意料地,其中四氟醚唑同时发挥农用化学活性成分功能和油分散相功能的液体农用化学混合物是浓缩的、随时间稳定并且具有在水中产生均匀和稳定分散体的优异特性。
因此,本发明的第一个目的是一种液体农用化学混合物,其包含:
-油相,其至少包含四氟醚唑和任选的至少一种共溶剂(co-solvent);
-分散或溶解在所述油相中的至少一种除四氟醚唑之外的农用化学活性成分;
其中相对于混合物的重量,所述四氟醚唑和所述至少一种除四氟醚唑以外的农用化学活性成分的总量等于或大于40重量%,优选等于或大于45重量%。
出于本说明书和权利要求的目的,动词“包含”及其派生的所有术语也包括动词“由……组成”及其派生的术语的含义。
在本说明书和所附权利要求中表达的数值范围和区间还包括所提及的一个或多个数值。此外,所有范围包括所示最大值和最小值的任何组合以及任何中间子范围,即使未明确提及。
术语“活性农用化学成分”或“农用化学化合物”旨在作为一种保护作物免受有害生物侵害、保护和/或控制作物的活性物质。例如,活性农用化学成分选自:杀菌剂、杀虫剂、杀线虫剂、除草剂、植物保护剂和/或生长调节剂。杀菌剂是特别优选的农用化学化合物。
根据本发明的液体农用化学混合物,除了四氟醚唑之外,还包括至少一种除四氟醚唑以外的其他农用化学活性成分,或除四氟醚唑之外的两种或两种以上其他农用化学活性成分的混合物。
除四氟醚唑以外的其他农用化学活性成分可以作为在油相中具有低溶解度(25℃时溶解度低于10g/l)的分散固体存在于液体农用化学混合物中,或者它们可以在油相中完全溶解或部分溶解(25℃时溶解度大于10g/l)。
例如,其他活性成分可以是FRAC(杀菌剂抗性行动委员会(Fungicide ResistanceAction Committee))中描述的杀菌剂,并且具有选择以下的作用方式:
A.核酸合成抑制剂;
B.有丝***和细胞***抑制剂;
C.呼吸链抑制剂;
D.氨基酸和蛋白质的合成抑制剂;
E.信号转导抑制剂;
F.脂质和膜合成抑制剂;
G.麦角甾醇合成抑制剂;
I.黑色素生物合成抑制剂;
M.具有多位点活性的化合物;
P.寄主植物防御诱导剂;
Z.作用方式未知的化合物。
农用化学混合物中可能存在的具有作为核酸合成抑制剂(A组)的作用方式的杀菌剂的实例有:苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M(Kiralaxyl))、磺嘧菌灵(bupirimate)、甲菌定(dimethirimol)、乙菌定(ethirimol)、呋氨丙灵(furalaxyl)、甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M)、甲呋酰胺(ofurace)、噁霜灵(oxadixyl)。
农用化学混合物中可能存在的具有诸如有丝***和细胞***抑制剂(B组)作用方式的杀菌剂的实例有:苯菌灵(benomyl)、多菌灵(carbendazim)、乙霉威(diethofencarb)、噻唑菌胺(ethaboxam)、氟吡菌胺(fluopicolide)、麦穗宁(fuberidazole)、苯菌酮(metrafenone)、戊菌隆(pencycuron)、甲氧苯唳菌(pyriofenone)、噻菌灵(thiabendazole)、甲基硫菌灵(thiophanate-methyl)、苯酰菌胺(zoxamide)。
优选地,所述属于B组的杀菌剂是:多菌灵(carbendazim)、乙霉威(diethofencarb)、苯菌酮(metrafenone)、甲氧苯唳菌(pyriofenone)、甲基硫菌灵(thiophanate-Methyl)。
农用化学混合物中可能存在的具有作为可作用在配合物I(C1亚组)、配合物II(C2亚组)、在Qo和Qi位点的配合物III(分别为C3和C4亚组)上,例如氧化磷酸化解偶联剂(C5亚组)或作为氧化磷酸化抑制剂(C6亚组)的呼吸链抑制剂(C组)的作用方式的杀菌剂的实例有:
C1:氟嘧菌胺(diflumetorim)、喹螨醚(fenazaquin)、唑虫酰胺(tolfenpyrad);
C2:麦锈灵(benodanil)、苯并烯氟菌唑(benzovindiflupyr)、联苯吡菌胺(bixafen)、啶酰菌胺(boscalid)、萎锈灵(carboxin)、甲呋酰胺(fenfuram)、氟茚唑菌胺(fluindapyr)、氟吡菌酰胺(fluopyram)、氟酰胺(flutolanil)、氟唑菌酰胺(fluxapyroxad)、呋吡菌胺(furametpyr)、inpyrfluxam、异丙噻菌胺(isofetamid)、isoflucypram、吡唑萘菌胺(isopyrazam)、丙氧灭绣胺(mepronil)、氧化萎锈灵(oxycarboxin)、戊苯吡菌胺(penflufen)、吡噻菌胺(penthiopyrad)、氟唑菌酰羟胺(pydiflumetofen)、联苯吡嗪菌胺(pyraziflumid)、氟唑环菌胺(sedaxane)、噻呋酰胺(thifluzamide);优选地,所述C2亚组的杀菌剂为苯并烯氟菌唑(benzovindiflupyr)、联苯吡菌胺(bixafen)、啶酰菌胺(boscalid)、氟茚唑菌胺(fluindapyr)、氟吡菌酰胺(fluopyram)、氟酰胺(flutolanil)、氟唑菌酰胺(fluxapyroxad)、呋吡菌胺(furametpyr)、异丙噻菌胺(isofetamid)、吡唑萘菌胺(isopyrazam)、戊苯吡菌胺(penflufen)、吡噻菌胺(penthiopyrad)、氟唑菌酰羟胺(pydiflumetofen)、氟唑环菌胺(sedaxane)、噻呋酰胺(thifluzamide);
C3:嘧菌酯(azoxystrobin)、甲香菌酯(coumethoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌酯(enoxastrobin)、噁唑菌酮(famoxadone)、咪唑菌酮(fenamidone)、fenaminostrobin,氟菌螨酯(flufenoxystrobin)、氟嘧菌酯(fluoxastrobin)、醚菌酯(kresoxim-methyl)、mandestrobin、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、吡唑醚菌酯(pyraclostrobin)、唑胺菌酯(pyrametostrobin)、唑菌酯(pyraoxystrobin)、吡菌苯威(pyribencarb)、氯啶菌酯(triclopyricarb)、肟菌酯(trifloxystrobin);优选地,所述C3亚组的杀菌剂为:嘧菌酯(azoxystrobin)、噁唑菌酮(famoxadone)、咪唑菌酮(fenamidone)、氟菌螨酯(flufenoxystrobin)、醚菌酯(kresoxim-methyl)、mandestrobin,叉氨苯酰胺(metominostrobin)、啶氧菌酯(picoxystrobin)、吡唑醚菌酯(pyraclostrobin)、吡菌苯威(pyribencarb)、肟菌酯(trifloxystrobin);
C4:吲唑磺菌胺(amisulbrom)、氰唑磺菌胺(cyazofamid)、fenpicoxamid、吡啶菌酰胺(florypicoxamid);
C5:乐杀螨(binapacryl)、氟啶胺(fluazinam)、消螨多(meptyldinocap);优选地,所述C5亚组的杀菌剂是:氟啶胺(fluazinam)、消螨多(meptyldinocap);
C6:薯瘟锡(fentin acetate)、三苯锡氯(fentin chloride)、毒菌锡(fentinhydroxide)。
农用化学混合物中可能存在的具有作为氨基酸和蛋白质(D组)的合成抑制剂的作用方式的杀菌剂的实例有:灭瘟素(blasticidin-S)、嘧菌环胺(cyprodinil)、春雷素(kasugamycin)、嘧菌胺(mepanipyrim)、土霉素(oxytetracycline)、二甲嘧菌胺(pyrimethanil)。
优选地,属于D组的所述杀菌剂是:嘧菌环胺(cyprodinil)。
农用化学混合物中可能存在的具有作为信号转导抑制剂(E组)的作用方式的杀菌剂的实例有:乙菌利(chlozolinate)、拌种咯(fenpiclonil)、咯菌腈(fludioxonil)、异菌脲(iprodione)、腐霉利(procymidone)、丙氧喹啉(proquinazid)、喹氧灵(quinoxyfen)、乙烯菌核利(vinclozolin)。
优选地,所述属于E组的杀菌剂是:咯菌腈(fludioxonil)、丙氧喹啉(proquinazid)、喹氧灵(quinoxyfen)。
农用化学混合物中可能存在的具有作为脂质和膜合成抑制剂(F组)的作用方式的杀菌剂的实例有:联苯(biphenyl)、地茂散(chloroneb)、克瘟散(edifenphos)、植物提取物、土菌灵(etridiazole)、异稻瘟净(iprobenfos)、稻瘟灵(isoprothiolane)、氟噻唑吡乙酮(oxathiapiprolin)、霜霉威(propamocarb)、胺丙威(prothiocarb)、定菌磷(pyrazophos)、五氯硝基苯(quintozene)、四氯硝基苯(tecnazene)、甲基立枯磷(tolclofos-methyl)。
优选地,属于F组的所述杀菌剂是植物提取物,例如丁子香酚(eugenol)、香叶醇(geraniol)、互叶白千层(Melaleuca alternifolia)、百里酚(thymol)。
农用化学混合物中可能存在的具有可以作为脱甲基酶抑制剂(DMI)(G1亚组)、还原酶抑制剂(SBI)(G2亚组)或作为酮还原酶抑制剂(KBI)(G3亚组)的麦角甾醇合成抑制剂(G组)的作用方式的杀菌剂的实例有:
G1:戊环菌(azaconazole)、联苯***醇(Bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、苯醚甲环唑(difenoconazole)、烯唑醇(diniconazole)、氟环唑(epoxiconazole)、乙环唑(etaconazole)、氯苯嘧啶醇(fenarimol)、腈苯唑(fenbuconazole)、氟喹唑(fluquinconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、抑霉唑(imazalil)、亚胺唑(Imibenconazole)、种菌唑(ipconazole)、ipfentrifluconazole、氯氟醚菌唑(mefentrifluconazole)、叶菌唑(metconazole)、腈菌唑(myclobutanil)、氟苯嘧啶醇(nuarimol)、噁咪唑(oxpoconazole)、多效唑(paclobutrazol)、稻瘟酯(pefurazoate)、戊菌唑(penconazole)、咪鲜胺(prochloraz)、丙环唑(propiconazole)、丙硫菌唑(prothioconazole)、啶斑肟(pyrifenox)、啶菌噁唑(pyrisoxazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、***酮(triadimefon)、***醇(triadimenol)、氟菌唑(triflumizole)、嗪氨灵(triforine)、灭菌唑(Triticonazole);优选地,所述G1组的杀菌剂是:苯醚甲环唑(difenoconazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、ipfentrifluconazole、氯氟醚菌唑(mefentrifluconazole)、叶菌唑(metconazole)、腈菌唑(myclobutanil)、丙硫菌唑(prothioconazole);
G2:苯锈啶(fenpropidin)、丁苯吗啉(fenpropimorph)、螺环菌胺(spiroxamine)、十三吗琳(tridemorph);优选,所述G2亚组的杀真菌剂是苯锈啶(fenpropidin)、螺环菌胺(spiroxamine);
G3:环酰菌胺(fenhexamid)、胺苯吡菌酮(fenpyrazamine)。
农用化学混合物中可能存在的具有作为黑色素合成抑制剂(I组)的作用方式的杀菌剂的实例有:环丙酰菌胺(carpropamid)、双氯氰菌胺(diclocymet)、氰菌胺(fenoxanil)、咯喹酮(pyroquilon)、tolprocarb、三环唑(tricyclazole)。
优选地,所述I组的杀菌剂为:三环唑(tricyclazole)。
农用化学混合物中可能存在的具有作为多位点活性的化合物(M组)的作用方式的杀菌剂的实例有:敌菌灵(anilazine)、波尔多液(Bordeaux混合剂)、敌菌丹(captafol)、克菌丹(captan)、灭螨猛(chinomethionat)、百菌清(chlorothalonil)、氢氧化铜、环烷酸铜、氧化铜、氧氯化铜、硫酸铜、抑菌灵(dichlofluanid)、二噻农(dithianon)、灭菌丹(folpet)、双胍盐(guazatine)、双胍辛醋酸盐(iminoctadine)、代森锰锌(mancozeb)、代森锰(maneb)、代森联(metiram)、代森联锌(metiram-zinc)、磺菌威(methasulfocarb)、喹啉铜(oxine-copper)、甲基代森锌(propineb)、硫、福美双(thiram)、对甲抑菌灵(tolylfluanid)、代森锌(zineb)和福美锌(ziram)。
优选地,所述M组的杀菌剂为:波尔多液(Bordeaux混合剂)、敌菌丹(captafol)、克菌丹(captan)、百菌清(chlorothalonil)、氢氧化铜、环烷酸铜、氧化铜、氧氯化铜、硫酸铜、灭菌丹(folpet)、代森锰锌(mancozeb)、代森联(metiram)、对甲抑菌灵(tolylfluanid)。
农用化学混合物中可能存在的具有作为寄主植物防御诱导剂(P组)的作用方式的杀菌剂的实例有:活化酯(Acibenzolar-S-methyl)、乙膦铝(Fosetyl-Al)、isothianil、海带多糖(laminarin)、亚磷酸、噻菌灵(probenazole)、噻酰菌胺(thiadinil)。
优选地,所述P组的杀菌剂为海带多糖(laminarin)、亚磷酸。
农用化学混合物中可能存在的具有未知作用方式(Z组)的杀菌剂的实例有:环氟菌胺(cyflufenamid)、霜脲氰(cymoxanil)、flutianil、多果定(dodine)、tebufloquin、叶枯酞(tecloftalam)。
优选地,所述Z组的杀菌剂为:环氟菌胺(cyflufenamid)、flutianil。
优选地,上述除四氟醚唑之外的至少一种农用化学活性成分为选自以下化合物的化合物:丙硫菌唑(prothioconazole)、嘧菌酯(azoxystrobin)、氢氧化铜、氧氯化铜、硫酸铜、百菌清(chlorothalonil)及其混合物。
当液体农用化学混合物含有一种或多种其他农用化学活性成分时,包括四氟醚唑在内的农用化学活性成分的总浓度优选为45%至85重量%,更优选48%至70重量%,相对于液体农用化学混合物的重量。
优选地,四氟醚唑与除四氟醚唑之外的其他一种或多种农用化学活性成分的重量比为10:1至1:10。
优选地,相对于混合物的重量,四氟醚唑在液体农用化学混合物中的量为1%至60重量%,更优选为10%至55重量%。
油相可包括至少一种共溶剂。特别地,当液体农用化学混合物中存在的四氟醚唑的量不足以溶解或分散存在的一种或多种其他活性成分时,使用共溶剂。
当存在共溶剂时,其浓度优选不大于40重量%,更优选浓度低于35重量%,相对于液体农用化学混合物的重量。
当四氟醚唑以足以溶解或分散其他活性农用化学成分的量存在时,共溶剂可以不存在或可能以相对低的量存在,优选不高于1重量%,更优选不高于0.5重量%,相对于液体农用化学混合物的重量。
在一个实施方案中,当在液体农用化学混合物中四氟醚唑与除四氟醚唑之外的其他农用化学活性成分的总重量的重量比大于1:1时,优选地当所述比例高于1:1且低于或等于3.5:1时,油相包括至少一种共溶剂,其总量不超过1重量%,相对于混合物的重量。
在另一个实施方案中,当在农用化学混合物中四氟醚唑与除四氟醚唑之外的其他农用化学活性成分的总重量的重量比等于或低于1:1时,优选地当所述比例为1:1.1至1:6时,油相包括至少一种共溶剂,其总量等于或高于1重量%,优选为1%至40重量%,例如2%-35重量%,相对于混合物的重量。
共溶剂为有机液相,基本上与水不混溶。共溶剂可以包括例如以下化合物之一:石油馏出物,例如苯衍生的芳烃,例如烷基苯和烷基萘(例如甲苯、二甲苯);脂肪烃(例如己烷、辛烷、环己烷等);聚亚烷基二醇醚;脂肪酸酰胺;碳酸二亚烷基酯(dialkylenecarbonates);脂肪族或石蜡族矿物油,芳香族和脂肪族烃的混合物;植物油(例如菜籽油、豆油、橄榄油、蓖麻油、亚麻籽油等)以及用C1-C6烷基酯化的衍生物,特别是C12-C22脂肪酸的C1-C4烷基酯;甘油;单丙二醇、直链二羧酸的二烷基酯,例如戊二酸二甲酯、琥珀酸二甲酯、己二酸二甲酯及其混合物(RDPE)。
植物油的酯化衍生物可通过植物油与甲醇、乙醇、丁醇和戊醇等短链醇进行酯交换反应得到,或通过将植物油皂化所得的脂肪酸馏分与相同的醇进行酯化得到。
优选地,油相为植物油或相对酯化的衍生物C1-C6。更优选地,油相为菜籽油,甚至更优选为菜籽油的甲酯。
油相还可包含两种或更多种共溶剂的混合物。
液体农用化学混合物还可以包含其他传统助剂,例如至少一种非离子表面活性剂和至少一种流变改性剂。
非离子表面活性剂主要起乳化剂的作用,即它存在于液体农用混合物中有利于油相与用于稀释油相的水的乳化,以制备即用型制剂。优选地,通过使用包含至少一种非离子表面活性剂与至少一种阴离子表面活性剂的组合的乳化体系获得乳化效果。
优选地,至少一种非离子乳化表面活性剂选自:乙氧基化嵌段共聚物、乙氧丙氧基化嵌段共聚物、乙氧基化三苯乙烯基苯酚、乙氧丙氧基化三苯乙烯基苯酚、乙氧基化三苯乙烯基苯酚磷酸盐(酸形式)、乙氧基化三苯乙烯基苯酚硫酸盐(酸形式)、脱水山梨糖醇单月桂酸酯、乙氧基化脱水山梨糖醇单月桂酸酯、脱水山梨糖醇单油酸酯、乙氧基化脱水山梨糖醇单油酸酯、乙氧基化植物油、乙氧基化脂肪醇、有机硅化合物及其混合物。更优选地,所述至少一种非离子表面活性剂为是乙氧丙氧基化三苯乙烯基苯酚。
优选地,所述至少一种乳化非离子表面活性剂在液体农用化学品混合物中的总量为1%至40重量%,更优选为3%至25重量%,相对于所述农用化学混合物的重量。
优选地,所述至少一种阴离子表面活性剂选自:乙氧基化三苯乙烯基苯酚磷酸盐(盐化形式)、乙氧基化三苯乙烯基苯酚硫酸盐(盐化形式)、十二烷基苯磺酸钙及其混合物。更优选地,所述至少一种阴离子表面活性剂选自:十二烷基苯磺酸钙和乙氧基化三苯乙烯基苯酚磷酸盐(盐化形式)。
如果存在,所述至少一种阴离子表面活性剂在液体农用化学混合物中的总量为1%至40重量%,更优选为5%至30重量%,相对于所述农用化学混合物的重量。
优选地,流变改性剂选自:粘土、改性粘土、高表面积二氧化硅、纤维素衍生物、氢化蓖麻油及其混合物。优选地,流变改性剂是粘土,例如凹凸棒石或膨润土,或者是高表面积二氧化硅。
优选地,流变改性剂在液体农用化学混合物中的总量为0.1%至10重量%,更优选为1%至7重量%,相对于所述农用化学混合物的重量。
任选地,根据本发明的液体农用化学混合物可包含除上述之外的其他助剂,例如,用于提高生物活性的化合物、抗漂移剂、渗透剂、润湿剂、消泡剂、稳定剂、螯合剂、防腐剂、增粘剂等。
根据本发明的液体农用化学混合物的制备可以根据已知的方法进行,以所需的比例混合组分,并且对组分混合的顺序没有特别限制。
根据本发明的液体农用化学混合物显示出高杀菌活性,并且对其所施用的作物没有显示出显著的植物毒性。
因此,本发明的另一个目的是根据本发明的液体农用化学混合物用于控制农作物中的植物病原真菌的用途。
本发明的另一个目的是控制农作物中植物病原真菌的方法,该方法包括将至少有效剂量的本发明的液体农用化学混合物施用于农作物。
感兴趣的作物的实例是:果树、蔬菜和广泛作物,如水稻、小麦和大豆。
根据本发明的液体农用化学混合物可在加水后施用于植物的任何部分,例如叶、茎、枝和根,或在播种前施用于种子,或施用于植物生长的土壤。
根据本发明的液体农用化学混合物也可用于在水中稀释后制备悬乳剂,该悬乳剂包含含有四氟醚唑的油相的乳液和除四氟醚唑之外的至少第二农用化学活性成分的固体颗粒悬浮液。悬乳剂可包含其他成分,例如润湿剂、乳化剂、稳定剂等。其他成分可存在于所述液体农用混合物中或用于制备悬乳剂的稀释水中。
因此,本发明的另一个目的是制备农艺制剂的方法,优选悬乳剂形式,包括:
-提供至少一种根据本发明的液体农用化学混合物,
-用水稀释所述液体农用化学混合物以获得所述农艺制剂。
向液体农用化学混合物中加入达到所需农艺制剂体积所需量的水。
施用于农作物以获得所需的农用化学效果的液体农用化学混合物或农艺制剂的量可以根据各种因素而变化,例如,作物类型、气候条件、土壤特性、施用方法。所述量可由本领域技术人员根据其技术知识和常规实验容易地确定。
为了更好地说明本发明,现在提供以下实施例,这些实施例被认为是说明性的和非限制性的。
实施例
含有四氟醚唑的液体农用化学混合物
制备具有表1中所示组成的根据本发明的液体农用化学混合物1-7。
用于制备上述混合物的商品如下:
-Amesolv CME,共溶剂,来自菜籽油的脂肪酸甲酯的混合物;
-Soprophor 796/P,非离子表面活性剂,乙氧丙氧基化三苯乙烯基苯酚;
-Rhodacal 60/BE,阴离子表面活性剂,苯磺酸钙盐;
-Soprophor FLK,阴离子表面活性剂,磷酸三苯乙烯基苯酚乙氧基化物,K盐;
-Emulson AG/PE,非离子表面活性剂,乙氧丙氧基化嵌段共聚物;
-Alkamuls T/20,非离子表面活性剂,乙氧基化脱水山梨糖醇单月桂酸酯;
-Imbirol OT/NA/70,阴离子表面活性剂,多库酯钠(sodium docusate);
-Geronol ODESSA 05,油中非离子和阴离子乳化剂的混合物,含有流变改性剂;
-Alkamuls T85V,非离子表面活性剂,乙氧基化三油酸脱水山梨醇酯;
-Rhodiasolv RP/DE,共溶剂,戊二酸二甲酯、琥珀酸二甲酯和己二酸二甲酯的混合物;
-Attagel 40,流变改性剂,凹凸棒石;
-PVP-K30,流变改性剂,聚乙烯吡咯烷酮;
-Alkamuls OR36,非离子表面活性剂,一种乙氧基化蓖麻油;
-BreakThru AF 5503,非离子表面活性剂,具有消泡功能的有机硅化合物;
-BreakThru OE 440,非离子表面活性剂,有机硅化合物。
表1
TNI=非离子表面活性剂;TA=阴离子表面活性剂;MR=流变改性剂。
对混合物1-7进行物理参数分析以验证制剂在室温下和加速储存后的稳定性(储存稳定性测试,缩写为SST-MT Cipac 46,其中包括将样品在54℃的恒温烘箱中保存14天)。
对以下参数进行了评估:
-外观:视觉分析;
-粘度:用Brookfield RV粘度计测量,叶轮4转速为2.5rpm,温度25℃;
-湿筛试验:Cipac MT185;
-冷稳定性测试:Cipac MT39。
上述参数的评估结果见表2。
表2
表2-续
根据本发明的液体农用化学混合物含有高浓度的活性成分(约50%至约70重量%,相对于混合物的重量)、低浓度的共溶剂(约12%至约30重量%,相对于混合物的重量),并且在储存期间稳定。
Claims (16)
1.一种液体农用化学混合物,包含:
-油相,其至少包含四氟醚唑和任选的至少一种共溶剂;
-分散或溶解在所述油相中的至少一种除四氟醚唑之外的农用化学活性成分;
其中相对于混合物的重量,所述四氟醚唑和所述至少一种除四氟醚唑之外的农用化学活性成分的总量等于或大于40重量%,优选等于或大于45重量%。
2.根据权利要求1所述的液体农用化学混合物,其中所述油相包含至少一种共溶剂,其总量不超过混合物重量的40重量%。
3.根据权利要求1所述的液体农用化学混合物,其中所述四氟醚唑与所述至少一种除四氟醚唑之外的农用化学活性成分的重量比为10:1至1:10。
4.根据前述权利要求中任一项所述的液体农用化学混合物,其中当所述四氟醚唑与所述至少一种除四氟醚唑之外的农用化学活性成分的重量比高于1:1,优选高于1:1且低于或等于3.5:1时,所述油相包含至少一种共溶剂,其总量不超过混合物重量的1重量%。
5.根据权利要求1所述的液体农用化学混合物,其中所述四氟醚唑与所述至少一种除四氟醚唑之外的农用化学活性成分的重量比等于或小于1:1,优选为1:1.1至1:6,并且所述油相包含至少一种共溶剂,其总量等于或高于混合物重量的1重量%,优选为1%至40重量%。
6.根据前述权利要求中任一项所述的液体农用化学混合物,其中所述至少一种除四氟醚唑之外的农用化学活性成分为优选具有选自以下的至少一种作用模式的化合物:
A.核酸合成抑制剂;
B.有丝***和细胞***抑制剂;
C.呼吸链抑制剂;
D.氨基酸和蛋白质的合成抑制剂;
E.信号转导抑制剂;
F.脂质和膜合成抑制剂;
G.麦角甾醇合成抑制剂;
I.黑色素生物合成抑制剂;
M.具有多位点活性的化合物;
P.寄主植物防御诱导剂;
Z.作用方式未知的化合物。
7.根据权利要求6所述的液体农用化学混合物,其中所述至少一种除四氟醚唑之外的农用化学活性成分为具有多位点活性的化合物,优选选自:敌菌灵(anilazine)、波尔多液(Bordeaux混合剂)、敌菌丹(captafol)、克菌丹(captan)、灭螨猛(chinomethionat)、百菌清(chlorothalonil)、氢氧化铜、环烷酸铜、氧化铜、氧氯化铜、硫酸铜、抑菌灵(dichlofluanid)、二噻农(dithianon)、灭菌丹(folpet)、双胍盐(guazatine)、双胍辛醋酸盐(iminoctadine)、代森锰锌(mancozeb)、代森锰(maneb)、代森联(metiram)、代森联锌(metiram-zinc)、磺菌威(methasulfocarb)、喹啉铜(oxine-copper)、甲基代森锌(propineb)、硫、福美双(thiram)、对甲抑菌灵(tolylfluanid)、代森锌(zineb)和福美锌(ziram)及其混合物。
8.根据权利要求6所述的液体农用化学混合物,其中所述至少一种除四氟醚唑之外的其他农药活性成分为抑制Qo位点呼吸链复合物III的化合物,优选选自:嘧菌酯(azoxystrobin)、噁唑菌酮(famoxadone)、咪唑菌酮(fenamidone)、氟嘧菌酯(fluoxastrobin)、醚菌酯(kresoxim-methyl)、mandestrobin、叉氨苯酰胺(metominostrobin)、啶氧菌酯(picoxystrobin)、吡唑醚菌酯(pyraclostrobin)、吡菌苯威(pyribencarb)、肟菌酯(trifloxystrobin)及其混合物。
9.根据权利要求6所述的液体农用化学混合物,其中所述至少一种除四氟醚唑之外的农用化学活性成分是选自以下化合物的化合物:丙硫菌唑(prothioconazole)、嘧菌酯(azoxystrobin)、氢氧化铜、氧氯化铜、硫酸铜、百菌清(chlorothalonil)及其混合物。
10.根据前述权利要求中任一项所述的液体农用化学混合物,其包含至少一种非离子表面活性剂,其含量为1%至40重量%,优选3%至25重量%,相对于混合物的重量。
11.根据前述权利要求中任一项的液体农用化学混合物,其包含至少一种阴离子表面活性剂,其含量为1%至40重量%,优选5%至30重量%,相对于混合物的重量。
12.根据前述权利要求中任一项所述的液体农用化学混合物,其包含至少一种流变改性剂,其含量为0.1%至10重量%,相对于混合物的重量。
13.根据前述权利要求中任一项所述的液体农用化学混合物,其中所述共溶剂选自:衍生自苯的芳烃;脂肪烃;聚亚烷基二醇醚;脂肪酸酰胺;碳酸二亚烷基酯、脂肪族或石蜡族矿物油、植物油和相关酯化衍生物、甘油和丙二醇。
14.一种用于制备农艺制剂的方法,包括:
-提供至少一种根据前述权利要求中任一项所述的液体农用化学混合物,
-用水稀释所述混合物以获得所述农艺制剂。
15.根据权利要求1-13中任一项所述的液体农用化学混合物在农作物中作为杀菌剂的用途。
16.一种控制农作物中植物病原真菌的方法,其包括将至少一个有效剂量的根据权利要求1-13中任一项的液体农用化学混合物施用于农作物。
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PCT/IB2020/057138 WO2021019452A1 (en) | 2019-07-31 | 2020-07-29 | Agrochemical liquid mixture containing tetraconazole and relative use as fungicide in agricultural crops |
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- 2020-07-29 US US17/625,162 patent/US20220272978A1/en active Pending
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