CN101778561B - 种子处理组合物和方法 - Google Patents
种子处理组合物和方法 Download PDFInfo
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- CN101778561B CN101778561B CN2008801031813A CN200880103181A CN101778561B CN 101778561 B CN101778561 B CN 101778561B CN 2008801031813 A CN2008801031813 A CN 2008801031813A CN 200880103181 A CN200880103181 A CN 200880103181A CN 101778561 B CN101778561 B CN 101778561B
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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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
- A01N25/30—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 characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
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Abstract
本发明涉及包含活性成分、多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐和具有聚烷氧基醚侧链的共聚物的种子处理组合物。将与具有聚烷氧基醚侧链的共聚物结合的多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐用作分散剂,尤其用于提供悬浮的活性成分的分散体。本发明还涉及用这种组合物处理种子的方法。
Description
本发明涉及种子处理组合物和处理种子的方法。本发明还涉及多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐以及具有聚烷氧基醚侧链的共聚物在种子处理组合物中的用途。
种子处理是将活性成分施用于种子,以支持各种作物萌发和/或生长的方法。典型实例包括施用农药如杀真菌剂、杀虫剂和植物生长调节剂以及其他活性成分如肥料。
作为传统的广泛喷雾农药的替换,种子处理组合物必须满足许多特殊要求,这些要求包括它们在工业装置中施用于种子的适用性,活性成分对处理的种子的粘合以及处理的种子的良好流动性。当然,处理的种子必须仍然能够萌发。
许多广泛用于种子处理的组合物为分散体。这类组合物需要一种或多种分散剂以降低粘度和稳定分散体防止团聚和晶体生长。
WO 2005/036963描述了包含如下物质的悬浮液浓缩物,唑类和/或嗜球果伞素,来自链烷醇烷氧基化物组的穿透促进剂,分散剂,水和任选其他助剂。分散剂为2-甲基-2-丙烯酸甲醚和α-(2-甲基-1-氧代-2-丙烯基)-ω-甲氧基-聚(氧基-1,2-乙烷二基)的聚合物,或三苯乙烯基酚乙氧基化物和/或分子量为8.000-10.000的氧化丙烯-氧化乙烯嵌段共聚物。据说组合物可用于处理植物、种子和土壤。
尽管在本领域中将分散剂用于种子处理组合物是众所周知的,常用分散剂倾向于提供不完全令人满意的种子处理组合物。结合了种子的特定和一般要求的种子处理组合物仍然特别难以实现。
本发明的目的是提供能够形成稳定的分散体并适用于种子处理的种子处理组合物。
令人惊讶的是,现在发现多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐与具有聚烷氧基醚侧链的共聚物的结合形成了用于种子处理组合物中的大量农业化学品的优异分散体系。
因此,本发明涉及包含活性成分、多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐和具有聚烷氧基醚侧链的共聚物的种子处理组合物。组合物的特定实施方案如权利要求所定义并公开在本文中。
本发明组合物显示分散的,尤其是悬浮的活性成分的稳定粒度。
如本文所用的“组合物”包含至少一种活性成分和至少一种助剂。
如本文所用的成分包括活性成分和助剂。
在本发明中,“活性成分”为直接表现出生物相关作用的化合物,优选为显示本文所述的农药作用的化合物。
术语“助剂”是指其本身不显示生物相关作用,但支持活性成分作用的化合物或化合物组合。当使用助剂时,它们的选择取决于活性成分以及取决于种子处理所选的程序。
因此,组合物通常包含活性成分组分(“A”)和助剂组分(“B”)。组合物的活性成分组分(“A”)包含一种或超过一种活性成分。助剂组分(“B”)包含一种或多种助剂。
如本文所用的术语“至少一种”是指1、2、3或更多种成员并包括2、3或更多种不同成员的混合物。
除非另有说明,所有以重量%表示的量是指整个组合物(或配制剂)的重量。
组合物通常包含0.005-95重量%,优选0.01-90重量%,尤其是0.1或0.5-50重量%活性成分组分“A”,平衡量由组分“B”形成。就此而言,活性成分以90-100%,优选95-100%的纯度(根据NMR谱)使用。
根据本发明,活性成分尤其选自植物保护活性试剂(农药)。如具有防止任何害虫侵染植物或驱除、阻止或破坏害虫或以其它方式降低由害虫造成的损害的目的或作用的试剂。植物害虫可属于不同组的生物体;较高级动物,尤其是昆虫和螨虫,包括许多种重要害虫,如线虫和蜗牛;脊椎动物,如哺乳动物和鸟类目前在工业化国家中是第二重要的。包括真菌、细菌,支原体、病毒和类病毒的微生物包括在害虫中,甚至与有用植物竞争有限的生长地或其它资源的杂草可在宽意义上归类于害虫中。农药尤其包括杀蚜虫剂、杀螨剂、干燥剂、杀菌剂、化学绝育剂、脱叶剂、拒食剂、杀真菌剂、除草剂、除草剂安全剂、昆虫引诱剂、杀虫剂、昆虫驱除剂、杀软体动物剂、杀线虫剂、交配干扰剂、植物活化剂、植物生长调节剂、杀鼠剂、哺乳动物驱除剂、协同增效剂、鸟类驱虫剂和杀病毒剂。
下列可根据本发明使用的农药意欲阐述可行的活性成分而不施加任何限制。
A.杀虫剂和杀螨剂
A.1.有机(硫代)磷酸酯类:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyriphos-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(oxydemetonmethyl)、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(pirimiphosmethyl)、丙溴磷(profenofos)、丙硫磷(prothiofos)、乙丙硫磷(sulprofos)、杀虫畏(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(triazophos)、敌百虫(trichlorfon);
A.2.氨基甲酸酯类:棉铃威(alanycarb)、涕灭威(aldicarb)、噁虫威(bendiocarb)、丙硫克百威(benfuracarb)、甲奈威(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: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(zeta-cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(ethofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、λ-(RS)氯氟氰菊酯(lambda-cyhalothrin)、γ-(RS)氯氟氰菊酯(gamma-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊(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)、profluthrin、四氟甲醚菊酯(dimefluthrin);
A.4.生长调节剂:a)几丁质合成抑制剂:苯甲酰脲类: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(triflumuron);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:特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxy fenozide)、双苯酰肼(tebufenozide)、艾扎丁(azadirachtin);c)拟保幼激素:蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)、双氧威(fenoxycarb);d)类脂生物合成抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、spirotetramat;
A.5.烟碱受体激动剂/拮抗剂化合物: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)、式(Γ1)的噻唑化合物:
A.6.GABA拮抗剂化合物:acetoprole、硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、式(Γ2)的苯基吡唑化合物:
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(Γ3)化合物(CAS号187166-40-1):
A.8.METI I化合物:芬杀螨(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、flufenerim;
A.9.METI II和III化合物:灭醌螨(acequinocyl)、fluacyprim、灭蚁腙(hydramethylnon);
A.10.去偶化合物: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.蜕皮干扰剂化合物:cryomazine;
A.13.混合功能氧化酶抑制剂化合物:增效醚(piperonyl butoxide);
A.14.钠通道阻断剂化合物:噁二唑虫(indoxacarb)、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(Γ4)的氨基喹唑啉酮化合物:
N-R’-2,2-二halo-1-R”-环丙烷甲酰胺2-(2,6-二氯-α,α,α-三氟对甲苯基)腙或N-R’-2,2-二(R”’)-丙酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)腙,其中R’为甲基或乙基,halo为氯或溴,R”为氢或甲基且R”’为甲基或乙基,式(Γ5)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H、F、Cl、CF3,B1为氢、Cl、Br、I、CN,B2为Cl、Br、CF3、OCH2CF3、OCF2H且RB为氢、CH3或CH(CH3)2,以及如JP 2002284608、WO 02/89579、WO 02/90320、WO 02/90321、WO 04/06677、WO 04/20399、JP 200499597、WO 05/68423、WO 05/68432或WO 05/63694所述的丙二腈化合物,特别是丙二睛化合物CF3(CH2)2C(CN)2CH2(CF2)3CF2H、CF3(CH2)2C(CN)2CH2(CF2)5CF2H、CF3(CH2)2C(CN)2(CH2)2C(CF3)2F、CF3(CH2)2C(CN)2(CH2)2(CF2)3CF3、CF2H(CF2)3CH2C(CN)2CH2(CF2)3CF2H、CF3(CH2)2C(CN)2CH2(CF2)3CF3、CF3(CF2)2CH2C(CN)2CH2(CF2)3CF2H和CF3CF2CH2C(CN)2CH2(CF2)3CF2H。
A组的市售化合物可以在其他出版物中的The Pesticide Manual(农药手册),第13版,British Crop Protection Council(2003)中找到。
式(Γ2)的硫酰胺及其制备描述于WO 98/28279中。Lepimectin由AgroProject,PJB Publications Ltd,2004年11月已知。Benclothiaz及其制备描述于EP-A1 454621中。杀扑磷和对氧磷及其制备描述于Farm ChemicalsHandbook,第88卷,Meister Publishing Company,2001中。Acetoprole及其制备描述于WO 98/28277中。氰氟虫胺及其制备描述于EP-A1 462 456中。吡氟硫磷描述于Pesticide Science 54,1988,第237-243页和US 4822779中。Pyrafluprole及其制备描述于JP 2002193709和WO 01/00614中。Pyriprole及其制备描述于WO 98/45274和US 6335357中。Amidoflumet及其制备描述于US 6221890和JP 21010907中。Flufenerim及其制备描述于WO 03/007717和WO 03/007718中。丁氟螨酯及其制备描述于WO04/080180中。
式(Γ5)的邻氨基苯甲酰胺及其制备描述于WO 01/70671、WO02/48137、WO 03/24222、WO 03/15518、WO 04/67528、WO 04/33468和WO 05/118552中。丙二睛化合物CF3(CH2)2C(CN)2CH2(CF2)3CF2H、CF3(CH2)2C(CN)2CH2(CF2)5CF2H、CF3(CH2)2C(CN)2(CH2)2C(CF3)2F、CF3(CH2)2C(CN)2(CH2)2(CF2)3CF3、CF2H(CF2)3CH2C(CN)2CH2(CF2)3CF2H、CF3(CH2)2C(CN)2CH2(CF2)3CF3、CF3(CF2)2CH2C(CN)2CH2(CF2)3CF2H和CF3CF2CH2C(CN)2CH2(CF2)3CF2H描述于WO 05/63694中。
B.杀真菌剂:
B.1.嗜球果伞素类(Strobilurins),如腈嘧菌酯(azoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌酯(enestroburin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、肟菌酯(trifloxystrobin)、肟醚菌胺(orysastrobin)、(2-氯-5-[1-(3-甲基苄氧亚氨基)乙基]苄基)氨基甲酸甲酯、(2-氯-5-[1-(6-甲基吡啶-2-基甲氧基亚氨基)乙基]苄基)氨基甲酸甲酯、2-(邻-((2,5-二甲基苯氧基亚甲基)苯基)-3-甲氧基丙烯酸甲酯;
B.2.羧酰胺类,如
羧酰苯胺类:苯霜灵(benalaxyl)、麦锈灵(benodanil)、啶酰菌胺(boscalid)、萎锈灵(carboxin)、丙氧灭绣胺(mepronil)、呋菌胺(fenfuram)、环酰菌胺(fenhexamide)、氟酰胺(flutolanil)、呋吡唑灵(furametpyr)、甲霜灵(metalaxyl)、甲呋酰胺(ofurace)、噁霜灵(oxadixyl)、氧化萎锈灵(oxycarboxin)、吡噻菌胺(penthiopyrad)、溴氟唑菌(thifluzamide)、噻酰菌胺(tiadinil)、N-(4’-溴联苯-2-基)-4-二氟甲基-2-甲基噻唑-5-甲酰胺、N-(4’-三氟甲基联苯-2-基)-4-二氟甲基-2-甲基噻唑-5-甲酰胺、N-(4’-氯-3’-氟联苯-2-基)-4-二氟甲基-2-甲基噻唑-5-甲酰胺、N-(3’,4’-二氯-4-氟联苯-2-基)-3-二氟甲基-1-甲基吡唑-4-甲酰胺、N-(2-氰基苯基)-3,4-二氯异噻唑-5-甲酰胺;
羧酸吗啉化物:烯酰吗啉(dimethomorph)、氟吗啉(flumorph);
苯甲酰胺类:氟联苯菌(flumetover)、fluopicolide(氟吡菌胺(picobenzamid))、苯酰菌胺(zoxamide);
其他羧酰胺:氯环丙酰胺(carpropamid)、双氯氰菌胺(diclocymet)、双炔酰菌胺(mandipropamid)、N-(2-(4-[3-(4-氯苯基)丙-2-炔氧基]-3-甲氧基苯基)乙基)-2-甲基磺酰基氨基-3-甲基丁酰胺、N-(2-(4-[3-(4-氯苯基)丙-2-炔氧基]-3-甲氧基苯基)乙基)-2-乙烷磺酰基氨基-3-甲基丁酰胺;
B.3.唑类,如
三唑类:双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、噁醚唑(difenoconazole)、烯唑醇(diniconazole)、烯菌灵(enilconazole)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、氟硅唑(flusilazole)、喹唑菌酮(fluquinconazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、酰胺唑(imibenconazole)、环戊唑醇(ipconazole)、环戊唑菌(metconazole)、腈菌唑(myclobutanil)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazole)、唑菌醇(triadimenol)、三唑酮(triadimefon)、戊叉唑菌(triticonazole);
咪唑类:氰霜唑(cyazofamid)、烯菌灵(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizole);
苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole);
其他:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole);
B.4.含氮杂环基化合物:如吡啶类:氟啶胺(fluazinam)、啶斑肟(pyrifenox)、3-[5-(4-氯苯基)-2,3-二甲基异噁唑烷-3-基]吡啶;
嘧啶类:磺嘧菌灵(bupirimate)、环丙嘧啶(cyprodinil)、嘧菌腙(ferimzone)、异嘧菌醇(fenarimol)、嘧菌胺(mepanipyrim)、氟苯嘧啶醇(nuarimol)、二甲嘧菌胺(pyrimethanil);
哌嗪类:嗪氨灵(triforine);
吡咯类:氟噁菌(fludioxonil)、拌种咯(fenpiclonil);
吗啉类:4-十二烷基-2,6-二甲基吗啉(aldimorph)、吗菌灵(dodemorph)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph);
二羧酰亚胺类:异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin);
其他:噻二唑素(acibenzolar-S-methyl)、敌菌灵(anilazine)、克菌丹(captan)、敌菌丹(captafol)、棉隆(dazomet)、哒菌清(diclomezine)、氰菌胺(fenoxanil)、灭菌丹(folpet)、苯锈啶(fenpropidin)、噁唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、异噻菌酮(octhilinone)、噻菌灵(probenazole)、丙氧喹啉(proquinazid)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、三环唑(tricyclazole)、5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、N,N-二甲基-3-(3-溴-6-氟-2-甲基吲哚-1-磺酰基)-[1,2,4]三唑-1-磺酰胺;
B.5.氨基甲酸盐和二硫代氨基甲酸盐,如
二硫代氨基甲酸盐:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、代森联(metiram)、威百亩(metam)、甲基代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram);
氨基甲酸盐类:乙霉威(diethofencarb)、flubenthiavalicarb、异丙菌胺(iprovalicarb)、百维灵(propamocarb)、3-(4-氯苯基)-3-(2-异丙氧羰基氨基-3-甲基丁酰氨基)丙酸甲酯、N-(1-(1-(4-氰基苯基)乙基磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
B.6.其他杀真菌剂,如
胍类:多果定(dodine)、双胍辛醋酸盐(iminoctadine)、双胍盐(guazatine);抗菌素类:春雷素(kasugamycin)、多氧霉素(polyoxins)、链霉素(streptomycin)、井冈霉素(validamycin A);
有机金属化合物类:三苯锡基盐;
含硫的杂环基化合物:稻瘟灵(isoprothiolane)、二噻农(dithianon);
有机磷化合物:克瘟散(edifenphos)、藻菌磷(fosetyl)、乙膦铝(fosetyl-aluminum)、异稻瘟净(iprobenfos)、定菌磷(pyrazophos)、甲基立枯磷(tolclofos-methyl)、亚磷酸及其盐;
有机氯化合物:甲基托布津(thiophanate-methyl)、百菌清(chlorothalonil)、抑菌灵(dichlofluanid)、对甲抑菌灵(tolylfluanid)、磺菌胺(flusulfamide)、四氯苯酞(phthalide)、六氯苯(hexachlorobenzene)、戊菌隆(pencycuron)、五氯硝基苯(quintozene);
硝基苯基衍生物:乐杀螨(binapacryl)、敌螨普(dinocap)、敌螨通(dinobuton);
无机活性化合物:波尔多液(Bordeaux混合物)、醋酸铜、氢氧化铜、王铜(copper oxychloride)、碱式硫酸铜、硫;
其他:螺噁茂胺(spiroxamine)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、苯菌酮(metrafenone)。
C.除草剂
C.1类脂生物合成抑制剂,如炔禾灵(chlorazifop)、炔草酯(clodinafop)、氯丁草(clofop)、氰氟草酯(cyhalofop)、氯甲草(diclofop)、噁唑禾草灵(fenoxaprop)、高噁唑禾草灵(fenoxaprop-p)、噻唑禾草灵(fenthiaprop)、吡氟禾草灵(fluazifop)、精吡氟禾草灵(fluazifop-P)、吡氟氯禾灵(haloxyfop)、精吡氟氯禾灵(haloxyfop-P)、恶草醚(isoxapyrifop)、噁唑酰草胺(metamifop),喔草酯(propaquizafop)、喹禾灵(quizalofop)、精喹禾灵(quizalofop-P)、三氟苯氧丙酸(trifop)、枯杀达(alloxydim)、丁氧环酮(butroxydim)、烯草酮(clethodim)、环己烯草酮(cloproxydim)、噻草酮(cycloxydim)、环苯草酮(profoxydim)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim)、苏达灭(butylate)、草灭特(cycloate)、燕麦敌(di-allate)、哌草丹(dimepiperate)、扑草灭(EPTC)、禾草畏(esprocarb)、抑草威(ethiolate)、氮草(isopolinate)、甲硫苯威(methiobencarb)、草达灭(molinate)、坪草丹(orbencarb)、克草猛(pebulate)、苄草丹(prosulfocarb)、草克死(sulfallate)、杀草丹(thiobencarb)、丁草威(tiocarbazil)、野麦畏(tri-allate)、灭草猛(vernolate)、呋草黄(benfuresate)、乙呋草黄(ethofumesate)和地散磷(bensulide);
C.2ALS抑制剂,如磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、氯嘧黄隆(chlorimuron)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、胺苯黄隆(ethametsulfuron)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟定黄隆(flupyrsulfuron)、甲酰氨磺隆(foramsulfuron)、吡氯黄隆(halosulfuron)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、甲基二磺隆(mesosulfuron)、甲黄隆(metsulfuron)、烟嘧黄隆(nicosulfuron)、环丙氧黄隆(oxasulfuron)、氟嘧黄隆(primisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、乙黄黄隆(sulfosulfuron)、噻黄隆(thifensulfuron)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、三氟啶磺隆(trifloxysulfuron)、氟胺磺隆(triflusulfuron)、三氟甲磺隆(tritosulfuron)、咪草酯(imazamethabenz)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr)、唑嘧磺胺盐(cloransulam)、唑嘧磺胺(diclosulam)、双氟磺草胺(florasulam)、氟唑啶草(flumetsulam)、唑草磺胺(metosulam)、五氟磺草胺(penoxsulam)、双嘧苯甲酸(bispyribac)、肟啶草(pyriminobac)、丙苯磺隆(propoxycarbazone)、氟酮磺隆(flucarbazone)、嘧苯草肟(pyribenzoxim)、环酯草醚(pyriftalid)和嘧硫苯甲酸(pyrithiobac);
C.3光合成抑制剂,如莠去通(atraton)、莠去津(atrazine)、莠灭净(ametryn)、叠氮津(aziprotryne)、草净津(cyanazine)、硫草净津(cyanatryn)、可乐津(chlorazine)、环草津(cyprazine)、敌草净(desmetryn)、戊草津(dimethametryn)、杀草净(dipropetryn)、草止津(eglinazine)、抑草津(ipazine)、麦苏百津(mesoprazine)、醚草通(methometon)、盖草津(methoprotryne)、环氰津(procyazine)、丙草止津(proglinazine)、扑灭通(prometon)、扑草净(prometryn)、扑灭津(propazine)、另丁津(sebuthylazine)、密草通(secbumeton)、西玛津(simazine)、西玛通(simeton)、西草净(simetryn)、甲氧去草净(terbumeton)、特丁津(terbuthylazine)、去草净(terbutryn)、草达津(trietazine)、特津酮(ametridione)、特草嗪酮(amibuzin)、六嗪同(hexazinone)、嗪丁草(isomethiozin)、苯嗪草(metamitron)、赛克津(metribuzin)、除草定(bromacil)、异草定(isocil)、环草定(lenacil)、特草定(terbacil)、溴杀草敏(brompyrazon)、杀草敏(chloridazon)、敌米达松(dimidazon)、异苯敌草(desmedipham)、敌克草(phenisopham)、苯敌草(phenmedipham)、乙苯敌草(phenmedipham-ethyl)、噻草隆(benzthiazuron)、丁噻隆(buthiuron)、噻二唑隆(ethidimuron)、异恶隆(isouron)、噻唑隆(methabenzthiazuron)、monoisouron、丁唑隆(tebuthiuron)、赛唑隆(thiazafluron)、疏草隆(anisuron)、播土隆(buturon)、氯溴隆(chlorbromuron)、乙氧苯隆(chloreturon)、绿麦隆(chlorotoluron)、枯草隆(chloroxuron)、枯莠隆(difenoxuron)、丁噁隆(dimefuron)、敌草隆(diuron)、非草隆(fenuron)、伏草隆(fluometuron)、氟苯隆(fluothiuron)、异丙隆(isoproturon)、利谷隆(linuron)、灭草恒(methiuron)、色满隆(metobenzuron)、秀谷隆(metobromuron)、甲氧隆(metoxuron)、绿谷隆(monolinuron)、灭草隆(monuron)、草不隆(neburon)、对伏隆(parafluron)、稀草隆(phenobenzuron)、环草隆(siduron)、氟氧隆(tetrafluron)、赛二唑素(thidiazuron)、莎草快(cyperquat)、二乙除草双(diethamquat)、苯敌快(difenzoquat)、敌草快阳离子(diquat)、伐草快(morfamquat)、对草快(paraquat)、糠草腈(bromobonil)、溴苯腈(bromoxynil)、羟敌草腈(chloroxynil)、碘草腈(iodobonil)、碘苯腈(ioxynil)、氨唑草酮(amicarbazone)、杀草全(bromofenoxim)、三氟噁嗪(flumezin)、灭草定(methazole)、噻草平(bentazone)、敌稗(propanil)、蔬草灭(pentanochlor)、达草止(pyridate)和pyridafol;
C.4原卟啉原-IX氧化酶抑制剂,如氟锁草醚(acifluorfen)、治草醚(bifenox)、氯硝醚(chlomethoxyfen)、草枯醚(chlornitrofen)、氯氟草醚(ethoxyfen)、消草醚(fluorodifen)、乙羧氟草醚(fluoroglycofen)、氯草醚(fluoronitrofen)、氟黄胺草醚(fomesafen)、氟呋草醚(furyloxyfen)、氟硝磺酰胺(halosafen)、乳氟禾草灵(lactofen)、除草醚(nitrofen)、硝氟草醚(nitrofluorfen)、氟硝草醚(oxyfluorfen)、异丙吡草酯(fluazolate)、氟唑草酯(pyraflufen)、吲哚酮草酯(cinidon-ethyl)、酰亚胺苯氧乙酸(flumiclorac)、氟噁嗪酮(flumioxazin)、炔草胺(flumipropyn)、达草氟(fluthiacet)、噻二唑胺(thidiazimin)、恶草灵(oxadiazon)、炔丙噁唑草(oxadiargyl)、唑啶炔草(azafenidin)、氟酮唑草(carfentrazone)、磺胺草唑(sulfentrazone)、戊噁唑草(pentoxazone)、双苯嘧草酮(benzfendizone)、氟丙嘧草酯(butafenacil)、双唑草腈(pyraclonil)、氟唑草胺(profluazol)、氟哒嗪草酯(flufenpyr)、flupropacil、吡氯草胺(nipyraclofen)和乙胺草醚(etnipromid);
C.5白化除草剂,如氟哒草(metflurazon)、达草灭(norflurazon)、氟苯啶草(flufenican)、吡氟草胺(diflufenican)、氟吡酰草胺(picolinafen)、氟丁酰草胺(beflubutamid)、氟草同(fluridone)、氟咯草酮(flurochloridone)、呋草酮(flurtamone)、甲基磺草酮(mesotrione)、磺草酮(sulcotrione)、异恶氯草酮(isoxachlortole)、异噁氟草(isoxaflutole)、吡草酮(benzofenap)、吡唑特(pyrazolynate)、苄草唑(pyrazoxyfen)、苯并双环酮(benzobicyclon)、杀草强(amitrole)、异恶草酮(clomazone)、苯草醚(aclonifen)、4-(3-三氟甲基苯氧基)-2-(4-三氟甲基苯基)嘧啶以及式II的3-杂环基取代的苯甲酰基衍生物(参见WO 96/26202、WO 97/41116、WO 97/41117和WO-A-97/41118):
其中变量R8-R13如下所定义:
R8、R10为氢、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6烷基亚磺酰基或C1-C6烷基磺酰基;
R9为选自如下的杂环基:如噻唑-2-基、噻唑-4-基、噻唑-5-基、异噁唑-3-基、异噁唑-4-基、异噁唑-5-基、4,5-二氢异噁唑-3-基、4,5-二氢异噁唑-4-基和4,5-二氢异噁唑-5-基,其中上述9个基团可被单取代或多取代,例如可以被卤素、C1-C4烷基、C1-C4烷氧基、C1-C4卤代烷基、C1-C4卤代烷氧基或C1-C4烷硫基单-、二-、三-或四取代;
R11为氢、卤素或C1-C6烷基;
R12为C1-C6烷基;
R13为氢或C1-C6烷基。
C.7EPSP合成酶抑制剂,如草甘膦(glyphosate);
C.8谷氨酰胺合成酶抑制剂,如草铵膦(glufosinate)和双丙氨酰磷(bilanaphos);
C.9DHP合成酶抑制剂,如黄草灵(asulam);
C.10有丝分裂抑制剂,如氟草胺(benfluralin)、地乐胺(butralin)、敌乐胺(dinitramine)、丁氟消草(ethalfluralin)、氟消草(fluchloralin)、异乐灵(isopropalin)、氟烯硝草(methalpropalin)、磺乐灵(nitralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、卡乐施(profluralin)、氟乐灵(trifluralin)、甲基胺草磷(amiprofos-methyl)、草胺磷(butamifos)、氟硫草定(dithiopyr)、噻氟啶草(thiazopyr)、拿草特(propyzamide)、丙戊草胺(tebutam)、敌草索(chlorthal)、长杀草(carbetamide)、氯草灵(chlorbufam)、氯苯胺灵(chlorpropham)和苯胺灵(propham);
C.11VLCFA抑制剂,如乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、丁烯草胺(butenachlor)、敌草乐(delachlor)、安塔(diethatyl)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、精噻吩草胺(dimethenamid-P)、吡草胺(metazachlor)、异丙甲草胺(metolachlor)、S-异丙甲草胺(S-metolachlor)、丙草胺(pretilachlor)、扑草胺(propachlor)、异丙草胺(propisochlor)、广草胺(prynachlor)、猛杀草(terbuchlor)、噻醚草胺(thenylchlor)、二甲苯草胺(xylachlor)、草毒死(allidochlor)、草立死(CDEA)、磺唑草(epronaz)、草乃敌(diphenamid)、草萘胺(napropamide)、萘丙胺(naproanilide)、烯草胺(pethoxamid)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、四唑酰草胺(fentrazamide)、莎稗磷(anilofos)、哌草磷(piperophos)、胺草唑(cafenstrole)、茚草酮(indanofan)和灭草环(tridiphane);
C.12纤维素生物合成抑制剂,如敌草腈(dichlobenil)、草克乐(chlorthiamid)、异恶草胺(isoxaben)和胺草唑(flupoxam);
C.13去偶除草剂,如消草酯(dinofenate)、硝丙酚(dinoprop)、戊硝酚(dinosam)、地乐酚(dinoseb)、地乐消酚(dinoterb)、二硝甲酚(DNOC)、硝草酚(etinofen)和丁硝酚(medinoterb);
C.14植物生长素除草剂,如稗草胺(clomeprop)、2,4-滴(2,4-D)、2,4,5-涕(2,4,5-T)、2甲4氯(MCPA)、酚硫杀(MCPA-thioethyl)、2,4-滴丙酸(dichlorprop)、高2,4-滴丙酸(dichlorprop-P)、2甲4氯丙酸(mecoprop)、高2甲4氯丙酸盐(mecoprop-P)、2,4-滴丁酸(2,4-DB)、2甲4氯丁酸(MCPB)、草灭平(chloramben)、麦草畏(dicamba)、草芽平(2,3,6-TBA)、杀草畏(tricamba)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、二氯皮考啉酸(clopyralid)、氟草烟(fluroxypyr)、毒莠定(picloram)、定草酯(triclopyr)和草除灵(benazolin);
C.15植物生长素输送抑制剂,如抑草生(naptalam)、二氟吡隆(diflufenzopyr);
C.16新燕灵(benzoylprop)、氟燕灵(flamprop)、麦草伏M(flamprop-M)、溴丁酰草胺(bromobutide)、氯甲丹(chlorflurenol)、环庚草醚(cinmethylin)、苯丙隆(methyldymuron)、乙苯酰草(etobenzanid)、膦铵素(fosamine)、威百亩(metam)、稗草畏(pyributicarb)、氯噁嗪草(oxaziclomefone)、棉隆(dazomet)、苯氧丙胺津(triaziflam)和溴甲烷(methyl bromide)。
D.安全剂
解草酮(benoxacor)、喹氧乙酸(cloquintocet)、抑害腈(cyometrinil)、抑害胺(dichlormid)、dicyclonon、dietholate、解草唑(fenchlorazole)、解草啶(fenclorim)、解草胺(flurazole)、肟草安(fluxofenim)、解草呋(furilazole)、双苯恶唑酸(isoxadifen)、吡咯二酸(mefenpyr)、mephenate、萘二甲酸酐(naphthalic anhydride)、2,2,5-三甲基-3-(二氯乙酰基)-1,3-噁唑烷(R-29148)、4-(二氯乙酰基)-1-氧杂-4-氮杂螺[4.5]癸烷(AD-67;MON 4660)和解草腈(oxabetrinil)。
优选杀虫剂选自:
吡虫清(acetamiprid)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、氟氯菊酯(bifenthrin)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、噻虫胺(clothianidin)、乙氰菊酯(cycloprothrin)、氟氯氰菊酯(cyfluthrin)、氯氰菊酯(cypermethrin)、溴氰菊酯(deltamethrin)、氟脲杀(diflubenzuron)、呋虫胺(dinotefuran)、醚菊酯(etofenprox)、杀螨锡(fenbutatin oxide)、甲氰菊酯(fenpropathrin)、锐劲特、氟氰戊菊酯(flucythrinate)、吡虫啉(imidacloprid)、λ-(RS)氯氟氰菊酯(Lambda-Cyhalothrin)、硝胺烯啶(nitenpyram)、信息素、艾克敌105(spinosad)、伏虫隆(teflubenzuron)、七氟菊酯(tefluthrin)、特丁磷(terbufos)、噻虫啉(thiacloprid)、噻虫嗪(thiamethoxam)、硫双灭多威(thiodicarb)、四溴菊酯(tralomethrin)、唑蚜威(triazamate)、己体氯氰菊酯(zeta-cypermethrin)、spirotetramat、flupyrazofos、NC 512、唑虫酰胺(tolfenpyrad)、氟虫酰胺(flubendiamide)、双三氟虫脲(bistrifluron)、benclothiaz、DPX-E2Y45、HGW86、pyrafluprole、pyriprole、F-7663、F-2704、amidoflumet、flufenerim、丁氟螨酯(cyflumetofen)。特别优选噻虫胺(clothianidin)、锐劲特、吡虫啉(imidacloprid)和噻虫嗪(thiamethoxam)。
优选杀真菌剂选自:
甲霜灵(metalaxyl)、噁霜灵(oxadixyl)、双胍盐(guazatine)、二甲嘧菌胺(pyrimethanil)、链霉素(streptomycin)、噁醚唑(difenoconazole)、氧唑菌(epoxiconazole)、喹唑菌酮(fluquinconazole)、粉唑醇(flutriafol)、土菌消(hymexazole)、烯菌灵(imazalil)、环戊唑菌(metconazole)、丙氯灵(prochloraz)、丙硫菌唑(prothioconazole)、戊唑醇(tebuconazole)、涕必灵(thiabendazole)、唑菌醇(triadimenol)、戊叉唑菌(triticonazole)、异丙定(iprodione)、代森锰(maneb)、代森锰锌(mancozeb)、代森联(metiram)、福美双(thiram)、苯菌灵(benomyl)、啶酰菌胺(boscalid)、多菌灵(carbendazim)、萎锈灵(carboxin)、棉隆(dazomet)、硅噻菌胺(silthiofam)、铜杀真菌剂、氟噁菌(fludioxonil)、硫、棉隆(dazomet)、腈嘧菌酯(azoxystrobin)、亚胺菌(kresoxim-methyl)、肟醚菌胺(orysastrobin)、唑菌胺酯(pyraclostrobin)、肟菌酯(trifloxystrobin)、克菌丹(captan)、烯酰吗啉(dimethomorph)。特别优选唑菌胺酯(pyraclostrobin)、戊叉唑菌(triticonazole)和喹唑菌酮(fluquinconazole)。
本发明的特定实施方案涉及包含唑菌胺酯(pyraclostrobin)和戊叉唑菌(triticonazole)的种子处理组合物。
在本发明特定的实施方案中,种子处理组合物可包含一种或多种用于温血动物如鸟类、狗和刺猬的驱除剂,例如壬酸香草基酰胺。驱除剂的量基于组合物的总重量优选为0.1-5重量%。
多芳基酚聚烷氧基醚磷酸盐和多芳基酚聚烷氧基醚硫酸盐本身已知。多芳基酚聚烷氧基醚硫酸盐例如以商品名4D384或TERSPERSE(CAS登记号:119432-41-6)销售;多芳基酚聚烷氧基醚磷酸盐例如以商品名FLK(CAS登记号:176776-21-9)销售。
优选多芳基酚聚烷氧基醚磷酸盐和硫酸盐为具有式(I)的三苯乙烯基酚聚烷氧基醚硫酸盐和磷酸盐或其可农用的碱加成盐:
其中各R独立地表示氢或C1-C4烷基;Alk表示C2-C6亚烷基;n具有5-60的值;和X为-SO3H2或-PO3H。
磷酸盐或硫酸盐可以质子化(游离酸)形式使用。优选其为包含可农用阳离子,如碱金属阳离子,优选锂、钠和钾阳离子;碱土金属阳离子,优选钙、镁和钡阳离子;过渡金属阳离子,优选锰、铜、锌和铁阳离子;铵阳离子;正离子化胺,优选带有1-4个C1-4烷基取代基或除0-3个C1-4烷基取代基外的1个苯基或苄基取代基的铵阳离子,更优选二异丙基铵、四甲基铵、三甲基苄基铵和四丁基铵阳离子;鏻阳离子;锍阳离子,优选三(C1-4烷基)锍阳离子;氧化锍阳离子,优选三(C1-4烷基)氧化锍阳离子的碱加成盐。此处术语“C1-4烷基”用于指具有1-4个碳原子的线性或支化饱和烃基,如甲基、乙基、丙基、甲基乙基、丁基、1-甲基丙基、2-甲基丙基或di甲基乙基。特别优选金属阳离子和铵阳离子。
烷氧基化得自与一种或超过一种的通常具有2-6个,优选2或3个碳原子的合适氧化烯反应。这些氧化烯尤其包括1,2-氧化乙烯(EO)、1,2-氧化丙烯(PO)、1,2-氧化丁烯(BO)、1,2-氧化戊烯(PeO)或1,2-氧化己烯(HO)。特别优选1,2-氧化乙烯(EO)。
在每种情况下,烷氧基化度是用于反应的氧化烯量和反应条件的结果。就此而言,其通常是统计平均值,因为反应产生的每分子多芳基酚的氧化烯单元的数目是变化的。
烷氧基化度,即聚醚链的平均链长度(即n的值)可通过多芳基酚与氧化烯的摩尔比和用于制备聚烷氧基化物的反应条件控制。聚烷氧基醚结构部分通常具有超过5个,优选超过10个,尤其是超过15个氧化烯单元。其通常具有不超过60个,优选不超过50个,尤其是不超过40个氧化烯单元。优选具有5-30个,优选10-20个,尤其是14-18个氧化烯单元的多芳基酚聚烷氧基醚磷酸盐和多芳基酚聚烷氧基醚硫酸盐。
根据特定实施方案,种子处理组合物包含至少0.1重量%,优选至少0.5重量%,尤其是至少1重量%多芳基酚聚烷氧基醚磷酸盐和/或硫酸盐。
根据另一特定实施方案,种子处理组合物包含至多50重量%,优选至多20重量%,尤其是至多5重量%多芳基酚聚烷氧基醚磷酸盐和/或硫酸盐。
根据一个方面,多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐与固体活性成分的重量比为至少1∶1,优选至少5∶1,尤其是至少10∶1。
根据另一方面,多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐与固体活性成分的重量比为至多500∶1,优选至多100∶1,尤其是至多50∶1。
具有聚烷氧基醚侧链的共聚物通常包含一个连接聚烷氧基醚侧链的单体单元和任选一个或多个可共聚的共聚单体的额外单体单元。
根据本发明的特定实施方案,共聚物包含:
(i)至少一种烯属不饱和羧酸的酯的单体单元,其中羧酸酯具有通式(II)的烷氧基化物残基:
(R1)n-X-(CHR2CH2O)w-(CHR3CH2O)x-(CHR4(CH2)yO)z- (II),
其中
R1为氢或具有1-40个碳原子的脂族烃残基,优选线性或支化的饱和或不饱和C1-C6烷基;
R2、R3、R4相互独立地为氢或C1-C4烷基;
w、x、z相互独立地对应于0-100的值,其中w、x和z的总和大于0;
y对应于1-20的值;和
X为N或O,
如果X为O,则n为1;或如果X为N,则n为2;和
(ii)至少一种额外的可共聚的共聚单体的单体单元。
就本发明的公开内容而言,术语“单体单元”是指已经掺入共聚物中的单体,其中与加载入聚合反应中的实际单体相比,已经掺入共聚物的单体,即单体单元不仅由于聚合反应而发生结构上的变化,而且还具有其他改性。因此,尤其可由加载入反应中的单体通过酯化衍生得到羧酸酯的单体单元。
作为醇部分,羧酸酯具有式(II)的线性或支化、饱和或不饱和的伯、仲或叔醇或胺的烷氧基化物。这些烷氧基化物对应于共聚物的聚烷氧基醚侧链。
根据优选实施方案,X为氧(醇烷氧基化物)。
式(II)的烷氧基化物的特定实施方案如下:如果z对应于1-100的值且w和x为0(烷氧基化物,如乙氧基化物(R4=H;y=1)或丙氧基化物(R4=CH3;y=1));如果w为0且x和z相互独立地对应于1-100的值(例如具有EO-PO嵌段排列的EO/PO嵌段烷氧基化物(y=1;R3=CH3;R4=H),或具有PO-EO嵌段排列的EO/PO嵌段烷氧基化物(y=1;R3=H;R4=CH3));如果w、x和z相互独立地对应于1-100的值(例如具有EO-PO-EO嵌段排列的EO/PO/EO嵌段烷氧基化物(y=1;R2=H;R3=CH3;R4=H),或具有PO-EO-PO嵌段排列的EO/PO/EO嵌段烷氧基化物(y=1;R2=CH3;R3=H;R4=CH3))。
根据本发明,已经证明尤其合适的是其中R1为优选具有1-6个碳原子的烷基残基(如果X=O),或其中一个R1为优选具有1-6个碳原子的烷基残基且另一个为氢(如果X=N)的式(II)的醇残基。
非常特别合适的是式(IIa)的乙氧基化物残基:
R1-O-(C2H4O)z- (IIa)
其中
R1具有上述含义且优选为线性或支化、饱和或不饱和C1-C6烷基;和
z对应于1-100的值,优选为1-30,
因此,R1尤其表示如下烷基残基之一:甲基、乙基、正丙基、异丙基。
烷氧基化得自与通常具有2-15个,优选2-6个碳原子的合适氧化烯的反应。此处尤其可提及1,2-氧化乙烯(EO)、1,2-氧化丙烯(PO)、1,2-氧化丁烯(BO)、1,2-氧化戊烯(PeO)和1,2-氧化己烯(HO)。
在每种情况下,所得烷氧基化度取决于用于反应的氧化烯量和反应条件。就此而言,其通常是统计平均值,因为反应产生的醇烷氧基化物残基的氧化烯单元的数目是变化的。
烷氧基化度,即合适的烷氧基化物残基的聚醚链的平均链长度可通过用于制备烷氧基化物的醇或胺与氧化烯的摩尔量比控制。优选具有约1-50,优选约1-20,尤其是1-10个氧化烯单元(w、x、z的总和),尤其是氧化乙烯单元的烷氧基化物。
优选烯属不饱和羧酸酯在羧酸部分中具有4-8,尤其是4-6个碳原子。
尤其可提及(甲基)丙烯酸酯。在这些羧酸酯中,特别优选甲基丙烯酸酯。
就此应提及表述“(甲基)丙烯酸”表示“丙烯酸”和“甲基丙烯酸”。
本发明共聚物可包含数种单体单元(i),如具有不同羧酸和/或不同烷氧基化物残基的羧酸酯。根据特定实施方案,存在于共聚物中的单体单元(i)源自一种羧酸,尤其是本文作为优选描述的羧酸之一。特别合适的是,具有基本包含(甲基)丙烯酸酯,尤其是甲基丙烯酸酯的单体单元的单体单元(i)的共聚物。
因此,共聚物尤其包括式(IIIa)和/或式(IIIb)单体单元(i):
其中
R为本文所述的烷氧基化物残基之一;和
b可相同或不同且为共聚物中的式(IIIa)或(IIIb)的单体单元的平均数并优选对应于1-100,有利的是5-50,尤其是11-25的数。
在(IIIa)或(IIIb)中,R有利地为式(II)的烷氧基化物残基,尤其是式(IIa)的烷氧基化物残基。
原则上,所有具有至少一个双键的可共聚的烯属不饱和共聚单体,尤其是单烯属不饱和共聚单体适合作为单体单元(ii)。
特别优选作为组分(ii)的是通式(IV)的共聚单体:
Y-C(O)CR5=CHR6 (IV)
其中
Y选自-OM、-OR7、NH2、-NHR7或N(R7)2,其中R7残基可相同或不同并且选自氢、线性或支化C1-C40烷基、N,N-二甲基氨基乙基、2-羟基乙基、2-甲氧基乙基、2-乙氧基乙基、羟基丙基、甲氧基丙基和乙氧基丙基;
M为选自碱金属、碱土金属和过渡金属阳离子,尤其是Na+、K+、Mg++、Ca++和Zn++,NH4 +和季铵阳离子,尤其是烷基铵、二烷基铵、三烷基铵和四烷基铵的阳离子;和
R5、R6相互独立地选自氢、线性或支化C1-C8烷基、甲氧基、乙氧基、2-羟基乙氧基、2-甲氧基乙氧基和2-乙氧基乙基。
优选丙烯酸或甲基丙烯酸的盐、酯和酰胺,其中R7选自氢和线性或支化C1-C6烷基,优选C1-C4烷基,尤其是甲基。
此外,线性C1-C40、支化C3-C40或碳环C3-C40羧酸的烯丙基酯,乙烯基卤化物或烯丙基卤化物,优选乙烯基氯和烯丙基氯,乙烯基甲酰胺,乙烯基甲基乙酰胺,乙烯基胺;乙烯基或烯丙基取代的杂环化合物,优选乙烯基吡啶,乙烯基噁唑啉和烯丙基吡啶也是合适的。
同样可用作单体单元(ii)的共聚单体为烯烃,即原则上所有具有至少一个烯属不饱和的可聚合双键的不饱和烃。有利的是具有末端双键的烯烃。优选单烯属不饱和烯烃。特别优选具有末端双键的单烯属不饱和烯烃。
优选烯烃具有4-40个,尤其是4且优选8至24个碳原子。根据特定实施方案,烯烃具有8或18或20至24个碳原子。
合适的烯烃例如包括丁-1-烯、丁-2-烯、丁二烯、2-甲基丙-1-烯(异丁烯)、戊-1-烯、异戊二烯、2-甲基丁-1-烯、3-甲基丁-1-烯、己-1-烯、环己-二烯、2-甲基戊-1-烯、3-甲基戊-1-烯、4-甲基戊-1-烯、2-乙基丁-1-烯、4,4-二甲基丁-1-烯、2,4-二甲基丁-1-烯、2,3-二甲基戊-1-烯、3,3-二甲基戊-1-烯、2,4-二甲基戊-1-烯、3,4-二甲基戊-1-烯、4,4-二甲基戊-1-烯、辛-1-烯、2,4,4-三甲基戊-1-烯、2,4,4-三甲基戊-2-烯、二异丁烯,尤其是工业上作为主要是2,4,4-三甲基戊-1-烯和2,4,4-三甲基戊-2-烯的异构体混合物存在的那些,例如比例为约80重量%至约20重量%,4,4-二甲基己-1-烯、2-乙基己-1-烯,分子量小于2000的低聚和聚合异丁烯,分子量小于1000的低聚丙烯,癸-1-烯、十二烷-1-烯、十四烷-1-烯、十六烷-1-烯、十七烷-1-烯、十八烷-1-烯、C18-1-烯烃、C20-1-烯烃、C22-1-烯烃、C24-1-烯烃、C20-C24-1-烯烃、C24-C28-1-烯烃、C30-1-烯烃、C35-1-烯烃、苯乙烯、烷基取代的苯乙烯,如α-甲基苯乙烯、叔丁基苯乙烯或乙烯基甲苯,环烯烃如环辛烯,以及这些单体的混合物。
乙烯、丙烯和偏二氯乙烯原则上也适合用作单体单元(ii)的共聚单体。
另外合适的单体单元(ii)为乙烯基醚,其醇部分具有1-30,优选1-20个碳原子。此处,尤其可提及C1-C30烷基乙烯基醚,其中烷基残基可以是线性、支化或环状的并且可被取代或未被取代。合适的烷基乙烯基醚的实例为甲基乙烯基醚、乙基乙烯基醚、丙基乙烯基醚、异丙基乙烯基醚、丁基乙烯基醚和十二烷基乙烯基醚。
其它合适的单体单元(ii)为N-乙烯基酰胺。这些尤其包括非环状代表物,如N-乙烯基甲酰胺和N-乙烯基乙酰胺,以及N-乙烯基内酰胺。根据本发明,N-乙烯基内酰胺为环状酰胺,其中具有4-6个碳原子的那些特别重要。这些N-乙烯基内酰胺可在环上具有1、2或3个优选具有1-4个碳原子的相同或不同烷基残基。N-乙烯基内酰胺尤其包括N-乙烯基吡咯烷酮、N-乙烯基己内酰胺或相应的被甲基或乙基取代的N-乙烯基内酰胺。
可用于单体单元(ii)的共聚单体尤其如下所述:
丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯、丙烯酸癸酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸癸酯、乙基丙烯酸甲酯、乙基丙烯酸乙酯、乙基丙烯酸正丁酯、乙基丙烯酸异丁酯、乙基丙烯酸叔丁酯、乙基丙烯酸2-乙基己酯、乙基丙烯酸癸酯、(甲基)丙烯酸硬脂醇酯、丙烯酸2,3-二羟基丙基酯、甲基丙烯酸2,3-二羟基丙基酯、丙烯酸2-羟基乙酯、丙烯酸羟基丙酯、甲基丙烯酸2-羟基乙酯、乙基丙烯酸2-羟基乙酯、丙烯酸2-甲氧基乙酯、甲基丙烯酸2-甲氧基乙酯、乙基丙烯酸2-甲氧基乙酯、甲基丙烯酸2-乙氧基乙酯、乙基丙烯酸2-乙氧基乙酯、甲基丙烯酸羟基丙酯、甘油单丙烯酸酯、甘油单甲基丙烯酸酯和不饱和磺酸如丙烯酰胺基丙烷磺酸;
丙烯酰胺、甲基丙烯酰胺、乙基丙烯酰胺、N-甲基丙烯酰胺、N,N-二甲基丙烯酰胺、N-乙基丙烯酰胺、N-异丙基丙烯酰胺、N-丁基丙烯酰胺、N-叔丁基丙烯酰胺、N-辛基丙烯酰胺、N-叔辛基丙烯酰胺、N-十八烷基丙烯酰胺、N-苯基丙烯酰胺、N-甲基甲基丙烯酰胺、N-乙基甲基丙烯酰胺、N-十二烷基甲基丙烯酰胺、1-乙烯基咪唑、1-乙烯基-2-甲基乙烯基咪唑、(甲基)丙烯酸N,N-二甲基氨基甲基酯、(甲基)丙烯酸N,N-二乙基氨基甲基酯、(甲基)丙烯酸N,N-二甲基氨基乙基酯、(甲基)丙烯酸N,N-二乙基氨基乙基酯、(甲基)丙烯酸N,N-二甲基氨基丁基酯、(甲基)丙烯酸N,N-二乙基氨基丁基酯、(甲基)丙烯酸N,N-二甲基氨基己基酯、(甲基)丙烯酸N,N-二甲基氨基辛基酯、(甲基)丙烯酸N,N-二甲基氨基十二烷基酯、N-[3-(二甲基氨基)丙基]甲基丙烯酰胺、N-[3-(二甲基氨基)丙基]丙烯酰胺、N-[3-(二甲基氨基)丁基]甲基丙烯酰胺、N-[8-(二甲基氨基)辛基]甲基丙烯酰胺、N-[12-(二甲基氨基)十二烷基]甲基丙烯酰胺、N-[3-(二乙基氨基)丙基]甲基丙烯酰胺、N-[3-(二乙基氨基)丙基]丙烯酰胺;
二烯丙基二甲基氯化铵、乙烯基甲酰胺、乙烯基甲基乙酰胺、乙烯基胺;甲基乙烯基酮、乙烯基吡啶、乙烯基咪唑、乙烯基呋喃、苯乙烯、苯乙烯磺酸盐、烯丙醇及其混合物。
其中特别优选丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸2-乙基己酯、丙烯酸硬脂醇酯、甲基丙烯酸硬脂醇酯、N-叔丁基丙烯酰胺、N-辛基丙烯酰胺、丙烯酸2-羟基乙酯、丙烯酸羟基丙酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸羟基丙酯、苯乙烯,不饱和磺酸如丙烯酰胺基丙烷磺酸,乙烯基甲酰胺,乙烯基甲基乙酰胺,乙烯基胺、1-乙烯基咪唑、1-乙烯基-2-甲基咪唑、甲基丙烯酸N,N-二甲基氨基甲酯和N-[3-(二甲基氨基)丙基]甲基丙烯酰胺;3-甲基-1-乙烯基咪唑鎓氯化物、3-甲基-1-乙烯基咪唑鎓甲基硫酸盐、甲基丙烯酸N,N-二甲基氨基乙酯、用甲基氯、硫酸甲酯或硫酸二乙酯季铵化的N-[3-(二甲基氨基)丙基]甲基丙烯酰胺。
可将具有碱性氮原子的共聚单体或相应的单体单元季铵化。
碱性共聚单体也可通过用无机酸,如硫酸、盐酸、氢溴酸、氢碘酸、磷酸或硝酸,或用有机酸,如甲酸、乙酸、乳酸或柠檬酸中和而阳离子化。
根据特定实施方案,共聚物包含至少一种丙烯酸和/或甲基丙烯酸的酯的单体单元,其中该羧酸酯具有如本文所定义的通式(II)或(IIa)的烷氧基化物残基,以及如本文所定义的丙烯酸酯和/或甲基丙烯酸酯,特别是丙烯酸甲酯和甲基丙烯酸甲酯的单体单元。
根据一个实施方案,本发明共聚物包含一种单体单元(ii),如选自丙烯酸或甲基丙烯酸的盐和酯的单体单元。根据另外的实施方案,本发明共聚物包含两种或更多种单体单元(ii),如两种或更多种选自丙烯酸或甲基丙烯酸的盐和酯的单体单元,或一种选自丙烯酸或甲基丙烯酸的盐和酯的单体单元和至少一种选自上述其他可共聚单体单元的其他类型单体单元。
根据特定实施方案,单体单元(i)的比例优选占10-99mol%,有利的是40-95mol%,尤其是60-90mol%以及单体单元(ii)的比例优选占90-1mol%,有利的是60-5mol%,尤其是40-10mol%。
就此而言,应想到的事实是,在较低分子量时,由于特定末端单体单元数量增加,也可发生偏离所给值。
本发明共聚物的重均分子量为5000-800000g/mol,优选7500-600000g/mol,特别优选10000-400000g/mol。
本发明共聚物优选未交联。
共聚物可通过将对应于单体单元(i)和(ii)的合适单体共聚而制备。为此,单体或共聚单体可使用自由基引发剂或者通过高能辐照活化而聚合,高能辐照应理解为也包括高能电子活化(例如参见EP 9 169 A1、EP 9 170A1和EP 276 464)。
聚合例如可作为溶液聚合、本体聚合、乳液聚合、反相乳液聚合、悬浮聚合、反相悬浮聚合或沉淀聚合进行,并且可使用的方法并不仅限于此。
在本体聚合中,可如此进行,将组(i)单体和组(ii)单体相互混合,并在加入聚合引发剂之后,使混合物完全聚合。聚合也可如下半分批进行,首先引入一部分,如10%的待聚合的组(i)和(ii)的单体或共聚单体的混合物和引发剂,将混合物加热至聚合温度,在聚合开始之后,根据聚合过程加入剩余的待聚合混合物。共聚物也可如下得到,将组(i)的单体引入反应器,加热至聚合温度,一次全部、逐步或优选连续加入至少一种组(ii)的单体和聚合引发剂并聚合。在该方法中聚合可借助保护胶体如现有技术所述进行。
需要的话,上述聚合也可在溶剂中进行。合适的溶剂例如为醇,如甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、正己醇和环己醇,二醇,如乙二醇、丙二醇和丁二醇,以及二元醇的甲基或乙基醚,二甘醇,三甘醇,甘油和二噁烷。优选使用对所用羧酸酯惰性的溶剂。
聚合也可在作为溶剂的水中进行。此时,取决于所加入组(i)和(ii)的单体量,或多或少的首先存在的混合物可溶于水。为了溶解在聚合中可能形成的水不溶性产物,例如可加入有机溶剂如具有1-3个碳原子的一元醇、丙酮或二甲基甲酰胺。然而,也可在水中如此进行聚合,从而通过加入常规乳化剂或保护胶体,如聚乙烯醇将水不溶性聚合物转化为细碎分散体。
所用的乳化剂的实例为具有3-13的HLB值的离子或非离子表面活性剂。对于HLB的定义,尤其参考W.C.Griffin,J.Soc.Cosmetic Chem.,第5卷,249(1954)的出版物。
表面活性剂的量基于聚合物通常为0.1-10重量%。当将水用作溶剂时,得到聚合物的溶液或分散体。如果制备聚合物在有机溶剂或在有机溶剂和水的混合物中的溶液,则通常每100重量份聚合物使用5-2000重量份,优选10-500重量份有机溶剂或溶剂混合物。
可根据本发明使用的共聚物尤其可通过共聚如下单体得到:
(1)至少一种烯属不饱和羧酸和/或至少一种烯属不饱和羧酸衍生物,尤其是羧酸酯,和
(2)至少一种额外的可共聚的共聚单体,
以及需要的话,部分或完全溶剂分解和/或衍生化,尤其是酯化或酯交换羧酸和/或羧酸衍生物。
需要的话,尤其可使得自共聚的共聚物CP′经受一个或多个如下额外的工艺步骤:
(4)至少部分溶剂分解衍生化的羧酸基团;
(5)酯化羧酸基团;
(6)至少部分中和羧酸基团。
所选用于共聚目的的单体和共聚单体的相对量可从上文对单体单元(i)和(ii)的比例的说明推出。
根据本发明优选直接产生所需共聚物CP的单体和共聚单体的聚合。
可是,待使用的单体或共聚单体的种类并不仅仅取决于待形成的单体单元。相反,在许多情况下有利的是,将在聚合反应之后转化为所需单体单元的单体或共聚单体聚合。该程序过程可通过反应和工艺技术调节。
可用于单体单元(i)的单体尤其可不同于涉及形成共聚物CP的单体单元。因此,可首先将羧酸或特定的羧酸衍生物聚合。随后,将如此形成的共聚物CP′的单体单元(i′)通常进行工艺步骤(4),(5)和/或(6)中的一个或多个,最后产生共聚物CP或其盐。在此意义上,也可聚合具有短链的可易于水解的酯基的羧酸酯,如在烷基部分中优选具有1-3个碳原子的烷基酯,其中随后将其醇部分离解并用另外的醇替换。
可通过共聚得到的共聚物CP′因此可包含羧基和/或衍生化的羧基,如酯基,需要的话,随后将其以类似聚合物的反应转化并通常形成羧酸酯。优选类似于聚合物的反应为(4)溶剂分解,如羧酸衍生物的水解和醇解,和(5)羧基的酯化。
根据一个实施方案,待根据本发明使用的共聚物CP可通过(i)选择至少一种烯属不饱和羧酸并将其与常用单体或共聚单体共聚,和通过使所得共聚产物CP′的至少一部分羧基与合适的醇反应形成酯而得到。
在聚合之后的类似于聚合物的反应可在溶剂,如丙酮或四氢呋喃存在下进行。然而,优选使待反应的共聚物CP′直接与衍生化试剂,如对应于上述式(II)的醇反应。反应物的用量取决于所需的衍生化程度。
如果衍生化为酯化反应,这以常规方式进行,即通常在升高温度如50-200℃,优选80-150℃下,合适的话在常规催化剂,如对甲苯磺酸存在下进行。通常的反应时间为0.5-20小时,尤其是1-10小时。优选使存在于聚合物中的酸酐基团反应。合适的话,这可在溶剂不存在下或在溶剂中进行。如果使用溶剂,特别合适的是,对酸酐基团惰性并且不仅溶解或溶胀原料而且溶解或溶胀反应产物,即至少部分酯化的共聚物的那些有机流体。就此而言,可提及甲苯、二甲苯、乙苯、脂族烃和酮,如丙酮或甲基乙基酮。在酯化之后,将溶剂(如果存在的话)例如通过蒸馏从反应混合物中除去。
为了形成盐,可在聚合之前或之后,用碱部分或完全中和聚合物,例如以调节水溶性或水分散性至所需程度。
作为用于酸基的中和剂,例如可使用无机碱,如碳酸钠,碱金属氢氧化物,如氢氧化钠或氢氧化钾,碱土金属氢氧化物和氨,或有机碱,如烷基胺,二烷基胺,三烷基胺,氨基醇,特别是异丙基胺,乙基胺,二异丙基胺,二乙基胺,三异丙基胺,三乙基胺,2-氨基-2-甲基-1-丙醇,单乙醇胺,二乙醇胺,三乙醇胺,三异丙醇胺,三(2-羟基-1-丙基)胺,2-氨基-2-甲基-1,3-丙二醇或2-氨基-2-羟基甲基-1,3-丙二醇,和二胺如赖氨酸。
根据特定实施方案,种子处理组合物包含至少0.1重量%,优选至少0.2重量%,尤其是至少1重量%共聚物。
根据另一特定实施方案,种子处理组合物包含至多20重量%,优选至多10重量%,尤其是至多3重量%共聚物。
根据一个方面,共聚物与固体活性成分的重量比为0.01∶1,优选至少0.05∶1,尤其是至少0.1∶1。
根据另一方面,共聚物与固体活性成分的重量比为至多4∶1,优选至多1∶1,尤其是至多0.5∶1。
此外,多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐与共聚物的重量比通常为至少0.1∶1,优选至少0.2∶1,尤其是至少0.5∶1。
另一方面,多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐与共聚物的重量比通常为至多10∶1,优选至多5∶1,尤其是至多2∶1。
在本发明组合物中,将多芳基酚聚烷氧基醚磷酸盐和/或硫酸盐和具有聚烷氧基醚侧链的共聚物用作分散剂,尤其用于提供悬浮的活性成分的分散体。
本发明因此还涉及与具有聚烷氧基醚侧链的共聚物结合的多芳基酚聚烷氧基醚磷酸盐和/或硫酸盐在种子处理组合物中作为分散剂的用途。多芳基酚聚烷氧基醚磷酸盐和/或硫酸盐如本文所定义。具有聚烷氧基醚侧链的共聚物也如本文所定义。
本发明组合物为种子处理组合物。本发明种子处理组合物包含至少一种特别适用于种子处理的助剂,即尤其促进活性成分与种子粘合和/或穿透入种子中和/或另外改善组合物或用该组合物处理的种子的稳定性和/或可操作性的助剂。因此,本发明种子处理组合物包含至少一种种子处理助剂和任选一种或多种其他助剂。
种子处理助剂尤其选自适用于种子包衣材料的试剂、适用于固体基质打底材料的试剂、适用于促进种子吸收的穿透提高剂、着色剂、防冻剂和胶凝剂。
根据优选实施方案,种子包衣材料包含粘合剂(或增粘剂)。包衣材料还任选包含一种或多种选自填料和增塑剂的额外的种子处理助剂。
粘合剂(或增粘剂)为可用于种子处理组合物的所有常规粘合剂(或增粘剂)。可用于本发明的粘合剂(或增粘剂)优选包含可以是天然或部分或全部合成的且对待包衣的种子没有植物毒性作用的粘合聚合物。优选粘合剂(或增粘剂)可生物降解。
粘合剂(或增粘剂)可选自聚酯、聚醚酯、聚酸酐、聚酯型聚氨酯、聚酯酰胺;聚乙酸乙烯酯;聚乙酸乙烯酯共聚物;聚乙烯醇和纤基乙酸钠;聚乙烯醇共聚物;聚乙烯基吡咯烷酮;多糖,包括淀粉、改性淀粉和淀粉衍生物,糊精,麦芽糊精,藻酸盐,壳聚糖和纤维素,纤维素酯,纤维素醚和纤维素醚酯,包括乙基纤维素、甲基纤维素、羟甲基纤维素、羟丙基纤维素和羧甲基纤维素;脂;油;蛋白质,包括酪蛋白、明胶和玉米蛋白;阿拉伯胶;紫胶;偏二氯乙烯和偏二氯乙烯共聚物;木素磺酸盐,尤其是木素磺酸钙;聚丙烯酸酯、聚甲基丙烯酸酯和丙烯酸类共聚物;聚乙烯基丙烯酸酯;聚氧乙烯;聚丁烯、聚异丁烯、聚苯乙烯、聚乙烯胺、聚乙烯酰胺;丙烯酰胺聚合物和共聚物;聚丙烯酸羟乙酯、甲基丙烯酰胺单体;和聚氯丁二烯。
在本发明的特定实施方案中,种子处理组合物含有至少一种聚酯,其尤其选自聚乳酸,部分芳族的聚酯(对苯二甲酸、己二酸和脂族二醇的共聚物),聚乙交酯、聚羟基链烷酸酯和聚酒石酸酯。
粘合剂(或增粘剂)在组合物中的量可变化,但是如果存在的话为总重量的约0.01%至约25%,更优选约1%至约15%,甚至更优选约5%至约10%。
如上所述,包衣材料也可任选包含填料。填料可为吸收剂或惰性填料,如本领域已知的那些且可包括木细粉,谷粉,树皮粉,木粉和坚果壳粉,糖类,尤其是多糖,活性炭,细颗粒无机固体,硅胶,硅酸盐,粘土,白垩,硅藻土,碳酸钙,碳酸镁,白云石,氧化镁,硫酸钙等。可使用的粘土和无机固体包括钙膨润土、高岭土、陶土、滑石、珍珠岩、云母、蛭石、硅酸盐、石英粉、蒙脱土、绿坡缕石、红玄武土、黄土、石灰石、石灰及其混合物。可使用的糖类包括糊精和麦芽糊精。谷粉包括小麦粉、燕麦粉和大麦粉。填料也可包含肥料物质如硫酸铵、磷酸铵、硝酸铵、尿类及其混合物。
选择填料以使其对种子提供合适的小气候,例如使用填料以增加活性成分的负载率和调节活性成分的控制-释放。填料可有助于种子的生产或包衣加工。填料量可变化,但如果存在的话填料组分的重量通常为总重量的约0.05-约75%,更优选约0.1-约50%,甚至更优选约0.5-15%。
优选选择粘合剂(或增粘剂)以使其可用作活性成分的基质。虽然如上所公开的粘合剂均可用作基质,优选形成一种或多种粘合剂化合物的固体连续相,其中分布活性成分的非连续相。任选填料和/或其它组分也可存在于基质中。术语“基质”应理解为包括视为基质体系、储存体系或微胶囊体系的那些。通常而言,基质体系由均匀分散在聚合物中的活性成分和填料组成,而储存体系由包含活性成分的分散相组成,活性成分物理分散在周围的限制速率的聚合物相。微胶囊化包括小颗粒或液滴包衣,以及固体基质中的分散体。
尤其是如果用于包衣的活性成分为油性类型的组合物并且存在少量或不存在惰性填料,则可能有用的是通过干燥组合物加速干燥过程。该任选步骤可伴随本领域众所周知的措施且可包括加入填料,如碳酸钙、高岭土或膨润土粘土、珍珠岩、硅藻土,或任何吸收材料,其优选与活性成分的包衣层一起加入以吸收油或过量水分。有效提供干燥包衣所需吸收剂量为种子重量的约0.5-约10%。
任选包衣材料包含增塑剂。增塑剂常用于使包衣层形成的膜更柔软,以改进粘合和伸展性,以及改进加工速率。改进的膜的柔软性对储存、处理和播种过程中的碎片、碎裂或剥落最小化具有重要性。可使用许多种增塑剂,然而,有用的增塑剂包括聚乙二醇、低聚亚烷基二醇、甘油、烷基苄基邻苯二甲酸酯,尤其是丁基苄基邻苯二甲酸酯,二醇苯甲酸酯和相关的化合物。如果存在的话,增塑剂在包衣层中的量为约0.1-约20重量%。
适用于可用于本发明的固体基质打底材料的试剂包括聚丙烯酰胺、淀粉、粘土、硅石、氧化铝、土壤、沙、聚脲、聚丙烯酸酯,或能够吸收或吸附活性成分并能够将活性成分释放入种子中或种子上的任何其它材料。其用于确保活性成分和固体基质材料相互相容。例如,应选择固体基质材料,以使其可以合理的速率,例如经数分钟、数小时或数天释放活性成分。
适合促进种子吸收的穿透提高剂包括可农用表面活性化合物。如果存在的话,穿透提高剂的量基于配制剂总重量通常不超过20重量%。优选穿透提高剂的量为2-20重量%。
本发明着色剂为常用于此的所有染料和颜料。就此而言,可以使用微溶于水的颜料和可溶于水的染料。例如作为实例可以提到如下已知的着色剂:若丹明B、C.I.颜料红112和C.I.溶剂红1、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48:2、颜料红48:1、颜料红57:1、颜料红53:1、颜料橙43、颜料橙34、颜料橙5、颜料绿36、颜料绿7、颜料白6、颜料棕25、碱性紫10、碱性紫49、酸性红51、酸性红52、酸性红14、酸性蓝9、酸性黄23、碱性红10、碱性红108。如果存在的话,着色剂量通常不超过组合物的20重量%,优选基于组合物总重量为1-15重量%。通常优选着色剂也用作温血动物的驱除剂,如氧化铁、二氧化钛、普鲁士蓝、蒽醌染料、偶氮染料和金属酞菁染料。
可特别用于含水组合物的防冻剂原则上为所有导致水的熔点降低的那些物质。合适的防冻剂包括醇类如甲醇、乙醇、异丙醇、丁醇、乙二醇、甘油、二乙基乙二醇等。防冻剂的量基于组合物总重量通常不超过20重量%,以及如果存在的话,经常为1-15重量%。
合适的胶凝剂为可为此用于农业化学组合物中的所有物质,例如纤维素衍生物、聚丙烯酸衍生物,黄原胶,改性粘土,尤其是有机改性的层状硅酸盐和高度分散的硅酸盐。特别合适的胶凝剂为角叉菜胶胶凝剂的量基于组合物的总重量不超过组合物的5重量%,以及如果存在的话,优选为0.5-5重量%。
可存在于种子处理组合物中的其它助剂包括溶剂、润湿剂、分散剂、乳化剂、表面活性剂、增稠剂、保护胶体、消泡剂和防腐剂。
水为优选溶剂。根据特定实施方案,本发明组合物包含至少5重量%,优选至少10重量%,尤其是至少30重量%水。另一方面,本发明组合物通常包含至多99重量%,优选至多90重量%,尤其是至多80重量%水。
合适的溶剂的其他实例为有机溶剂如芳族溶剂(如Solvesso产品、二甲苯)、石蜡(如矿物油馏分)、醇类(如甲醇、丁醇、戊醇、苄醇)、酮类(如环己酮、γ-丁内酯)、吡咯烷酮(NMP、NOP)、乙酸酯(乙二醇二乙酸酯)、二元醇、脂肪酸二甲基酰胺、脂肪酸及脂肪酸酯。原则上还可以使用溶剂混合物。然而,根据特定的实施方案,本发明组合物含有小于15重量%,优选小于6重量%的所述有机溶剂。
合适的表面活性化合物为所有适合配制农业活性成分,尤其是活性成分的那些表面活性剂,其可以是非离子、阳离子、阴离子或两性的。根据它们的作用,表面活性剂-有时称作“添加剂”-可分为润湿剂、分散剂、乳化剂或保护胶体;然而,这些特定的组可重叠并且不可严格划分。
由于本发明组合物包含多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐以及具有聚烷氧基醚侧链的共聚物,通常无需将其他分散剂加入组合物中。其他分散剂的量通常不超过10重量%。优选基于组合物的总重量不超过5重量%,尤其是1重量%。根据特定实施方案,本发明组合物不含有显著量的其他分散剂,即它们不含有其他分散剂或其他分散剂的量基于组合物总重量低于0.5重量%,优选低于0.1重量%。HLB值超过5的其他表面活性剂的量通常不超过10重量%。优选不超过5重量%,尤其是1重量%。根据特定实施方案,本发明组合物不含有显著量的这类其他表面活性剂,即它们不含有这类其他表面活性剂或其他表面活性剂的量基于组合物的总重量低于0.5重量%,优选低于0.1重量%。
合适的润湿剂为所有促进润湿且常用于配制农业活性成分的那些物质。可优选使用烷基萘磺酸盐如二异丙基-或二异丁基萘磺酸盐。
合适的分散剂和/或乳化剂为所有常用于配制农业活性成分的非离子、阴离子和阳离子分散剂或乳化剂。可优选使用以下那些:非离子或阴离子分散剂和/或乳化剂,或非离子或阴离子分散剂和/或乳化剂的混合物。
可使用的合适的非离子分散剂和/或乳化剂尤其为氧化乙烯/氧化丙烯嵌段共聚物、烷基酚聚乙二醇醚和三苯乙烯基酚聚乙二醇醚,例如聚氧乙烯辛基酚醚,乙氧基化异辛基酚、辛基酚、壬基酚,烷基酚聚乙二醇醚,三丁基苯基聚乙二醇醚,三硬脂基苯基聚乙二醇醚,烷基芳基聚醚醇,醇和脂肪醇氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚,乙氧基化聚氧丙烯,月桂醇聚乙二醇醚缩醛,山梨醇酯和甲基纤维素。
可使用的合适的分散剂和/或乳化剂尤其为木素磺酸、萘磺酸、苯酚磺酸、二丁基萘磺酸的碱金属盐、碱土金属盐和铵盐,烷基芳基磺酸盐,烷基硫酸盐,烷基磺酸盐,脂肪醇硫酸盐,脂肪酸和硫酸化脂肪醇乙二醇醚,还有芳基磺酸盐/甲醛缩合物,如磺化萘和萘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,木素磺酸盐,木素亚硫酸盐废液,磷酸化或硫酸化甲基纤维素衍生物和聚丙烯酸的盐。
增稠剂为典型的水溶性聚合物,其在含水介质中具有合适的塑性。实例包括阿拉伯胶、刺梧桐树胶、黄蓍树胶、瓜尔胶、蝗虫豆树脂、黄原胶、角叉菜胶、藻酸盐、酪蛋白、葡聚糖、果胶、琼脂、2-羟基乙基淀粉、2-氨基乙基淀粉、2-羟基乙基纤维素、甲基纤维素、羧甲基纤维素盐、纤维素硫酸盐。优选黄原胶。增稠剂的量通常不超过20重量%,并且如果存在的话,经常基于组合物的总重量为1-15重量%。
保护胶体通常为水溶性的两性聚合物。实例包括蛋白质和变性蛋白如酪蛋白,多糖如水溶性淀粉衍生物和纤维素衍生物,尤其是疏水改性淀粉和纤维素,还有聚羧酸化物如聚丙烯酸和丙烯酸共聚物,聚乙烯醇,聚乙烯基吡咯烷酮,乙烯基吡咯烷酮共聚物,聚乙烯胺,聚乙烯亚胺和聚亚烷基醚。保护胶体的量通常不超过组合物的3重量%,如果存在的话,优选基于组合物的总重量为0.1-2重量%。
可使用的消泡剂为所有抑制泡沫形成且常用于配制农业化学活性成分的那些物质。特别合适的是聚硅氧烷消泡剂,即聚硅氧烷含水乳液(例如Wacker的SRE,或Rhodia的),长链醇类,脂肪酸及其盐,如硬脂酸镁。消泡剂的量通常不超过组合物的3重量%,如果存在的话,基于组合物的总重量优选为0.1-2重量%。
可使用的防腐剂为所有为此用于农业化学组合物的防腐剂。可提及的实例为双氯芬、异噻唑啉酮(isothiazolene)和异噻唑酮(isothiazolone)类,如1,2-苯并异噻唑-3(2H)-酮、2-甲基-2H-异噻唑-3-酮-盐酸盐、5-氯-2-(4-氯苄基)-3(2H)-异噻唑酮、5-氯-2-甲基-2H-异噻唑-3-酮、5-氯-2-甲基-2H-异噻唑-3-酮、5-氯-2-甲基-2H-异噻唑-3-酮-盐酸盐、4,5-二氯-2-环己基-4-异噻唑啉-3-酮、4,5-二氯-2-辛基-2H-异噻唑-3-酮、2-甲基-2H-异噻唑-3-酮、2-甲基-2H-异噻唑-3-酮-氯化钙配合物、2-辛基-2H-异噻唑-3-酮和苄醇半缩醛。防腐剂的量通常不超过配制剂的2重量%,以及如果存在的话,基于配制剂的总重量优选为0.01-1重量%。
熟练技术人员熟知活性成分的农业组合物(例如参见Ullmann’sEncyclopedia of Industrial Chemistry,Fungicides(杀真菌剂),第4章,第5版,CD-ROM,Wiley-VCH,1997和Mollet,H.,Grubemann,A.,Formulation technology(配制技术),Wiley VCH Verlag GmbH,Weinheim(德意志联邦共和国),2001,此处将其完全引入作为参考)。
其实例包括水溶性浓缩物(SL、LS)、分散性浓缩物(DC)、乳油(EC)、乳液(EW、EO、ES)、悬浮液(SC、OD、FS)、水分散性颗粒(WG、SG)、水分散性或水溶性粉末(WP、SP、SS、WS)、粉剂或可撒粉粉末(DP、DS)、颗粒(GR、FG、GG、MG)、ULV溶液(UL)和凝胶配制剂(GF)。对种子处理而言,这类组合物可直接施用或在加入合适的液体,尤其是水以溶解、乳化、分散、悬浮或稀释组合物之后施用。因此,施用于种子的即用制剂的类型取决于所用组合物的类型和用于处理种子的方法。
这类组合物可以以已知方式制备(例如参见综述US 3,060,084,EP-A707 445(对于液体浓缩物),Browning,“Agglomeration”(团聚),ChemicalEngineering,1967年,12月4日,147-48,Perry’s Chemical Engineer’sHandbook,第4版,McGraw-Hill,New York,1963,第8-57页及随后各页。WO 91/13546,US 4,172,714,US 4,144,050,US 3,920,442,US5,180,587,US 5,232,701,US 5,208,030,GB 2,095,558,US 3,299,566,Klingman,Weed Control as a Science(杂草防治科学),John Wiley andSons,Inc.,New York,1961,Hance等,Weed Control Handbook(杂草防治手册),第8版,Blackwell Scientific Publications,Oxford,1989和Mollet,H.,Grubemann,A.,Formulation technology(配制技术),WileyVCH Verlag GmbH,Weinheim(德国),2001,2.D.A.Knowles,Chemistryand Technology of Agrochemical Formulations(农业配制剂化合物和技术),Kluwer Academic Publishers,Dordrecht,1998(ISBN 0-7514-0443-8)),例如通过将活性成分组分与一种或多种助剂粘附而制备,此处完全引入这些文献作为参考。
如下配制剂简单阐述所述组合物。
A分散性浓缩物(DC)
将20重量份活性成分溶于70重量份环己酮中并加入10重量份分散剂。由此得到活性成分含量为20重量%的配制剂。用水稀释得到分散体。
B悬浮液(SC、OD、FS)
在搅拌的球磨机中,将20重量份活性成分粉碎并加入10重量份分散剂和任选湿润剂以及70重量份水或有机溶剂,得到细碎活性化合物悬浮液,由此得到活性成分含量为20重量%的配制剂。用水稀释得到稳定的活性成分悬浮液。
C水分散性颗粒(WG、SG)
将50重量份活性成分细碎研磨并加入50重量份分散剂和任选湿润剂,借助工业装置(如挤出机、喷雾塔、流化床)将其制成水分散性或水溶性颗粒。由此得到活性成分含量为50重量%的配制剂。用水稀释得到稳定的活性化合物分散体或溶液。
D水分散性粉末(WP、WS)
将75重量份活性成分在转子-定子磨机中研磨并加入25重量份分散剂和任选湿润剂和硅胶。由此得到活性成分含量为75重量%的配制剂。用水稀释得到稳定的活性成分分散体或溶液。
E凝胶配制剂(GF)
在搅拌的球磨机中,将20重量份活性成分粉碎并加入10重量份分散剂、1重量份胶凝剂以及70重量份水或有机溶剂,得到细碎活性化合物悬浮液。由此得到具有20重量%活性成分的配制剂。用水稀释得到稳定的活性成分悬浮液。
配制剂A-E可在施用前用水稀释或直接施用。
根据本发明的特定实施方案,种子处理组合物为液体或以液体施用。优选悬浮液,特别是含水悬浮液。悬浮颗粒为熔点高于30℃的活性成分或助剂。
对于根据本发明的种子处理,优选粉末或颗粒,如水分散性粉末或颗粒,和悬浮液。此外,优选凝胶配制剂。
根据本发明特别优选如下配制剂:可流动浓缩物(特别是FS),还优选凝胶配制剂(特别是GF)。这些配制剂可经稀释或不经稀释而施用于种子。
根据特定的实施方案,本发明涉及FS配制剂。通常而言,FS配制剂可包含1-800g/l活性成分,1-200g/l多芳基酚聚烷氧基醚硫酸盐和/或磷酸盐,1-200g/l具有烷氧基醚侧链的共聚物,0-200g/l防冻剂,0-400g/l粘合剂,0-200g/l着色剂和至多1升溶剂,优选水。
根据另一特定实施方案,本发明种子处理组合物为种子包衣配制剂。
这类种子包衣配制剂包含活性成分、分散剂和至少一种粘合剂(或增粘剂)和任选至少一种选自填料和增塑剂的其它助剂。
包含粘合剂、填料和/或增塑剂的种子包衣配制剂在本领域是众所周知的。种子包衣配制剂例如公开于美国专利号5,939,356、5,882,713、5,876,739、5,849,320、5,834,447、5,791,084、5,661,103、5,622,003、5,580,544、5,328,942、5,300,127、4,735,015、4,634,587、4,383,391、4,372,080、4,339,456、4,272,417和4,245,432和其它文献中。
包括在包衣配制剂中的活性成分的量取决于种子类型而变化,但包衣配制剂应含有农药有效量的活性成分。活性成分在包衣配制剂中的量通常为总重量的约0.005-约75%。活性成分的更优选的范围是约0.01-约40%;更优选约0.05-约20%。
包括在包衣配制剂中的活性成分确切量由本领域熟练技术人员容易地确定且取决于待包衣的种子的尺寸和其它特征(表面结构等)而变化。包衣配制剂的活性成分不准抑制种植萌发且应在目标害虫对种子或植物造成损害的其生命周期中有效保护种子和/或植物。包衣通常应在播种后有效约0-120天,优选约0-60天。
由活性成分形成的包衣配制剂能够通过扩散或运动经由基质以缓慢速率释放活性成分至种子或周围介质中。
本发明还涉及本文所定义的组合物在处理种子中的用途。
本发明也涉及一种用本文所述的组合物处理种子的方法,其包括向一批种子施用有效量的如本文所公开的组合物。
术语“批次”或“批”是指经受种子处理的一组种子。种子的量和重量可取决于处理而变化。
术语“负载量”是指粘附于各种子的基于种子整体量的活性成分的实际量。
如本文所用的术语“种子”是指与植物的生长阶段物理分离和/或可储存延长时间和/或可用于再长出相同种类的另一植物个体的植物任何休眠阶段。此处,术语“休眠”是指其中在合理限度内,尽管没有生长(即非种子)阶段所必需的光、水和/或营养品,植物保持发育能力的阶段。该术语尤其指真正种子,而不包括植物繁殖体如吸根、球根、鳞茎、果实、块茎、谷物、插条(cutting)和伐枝(cut shoot)。
如本文所用的术语“植物”是指整个植物或植物部分。术语“整个植物”是指植物生长,即非种子阶段的整个植物个体,其特征在于存在根、枝和叶的排列,取决于植物发育阶段还有花和/或果实,所有这些物理连接形成个体,该个体在合理条件下可无需人工措施而生存。该术语也指直接收获的整个植物。
术语“植物部分”是指根、枝、叶、花或植物生长阶段的其他部分,这些部分当离开剩余部分和与剩余部分分离时,除非有人工措施支持否则不能存活,或者不能再长出失去的部分以形成整个植物。如本文所用的果实也认为是植物部分。
如本文所用的术语“根”是指为了履行其生理功能通常位于土壤表面以下的植物部分。优选,该术语是指在种子下面并且直接从种子长出,或从其他根长出,而不是从枝或叶长出的植物部分。
如本文所用的植物的“枝和叶”应理解为指在种子萌发后的植物的枝、茎、枝条、叶以及茎和枝条的其他附属物,但不包括植物的根。优选植物的枝和叶应理解为指从种子长出并且距离其长出的种子(种子的外部区域)至少一英寸的距离的非根的植物部分,更优选理解为指在土壤表面处或以上的非根的植物部分。
如本文所用的“果实”理解为指含有种子和/或用于传播种子和/或可从植物中取出而不损害其生存能力的植物部分。
根据本发明,种子处理包括将本发明组合物施用于种子。尽管本发明方法可使用于任何生理阶段的种子,优选种子处于在处理方法中不发生显著损害的足够耐久的阶段。该种子通常为从田间收获的种子;从植物中取出的种子;和/或从果实和任何穗轴、荚、秆、外壳和围绕的果肉或其他非种子的植物材料中分离的种子。还优选种子生物学上足够稳定,以使处理不会对种子造成生物损害。在一个实施方案中,例如处理可施用于已经收获、清洁并干燥至水分含量低于约15重量%的种子。在替代实施方案中,种子可以是已经干燥,然后用水或其他材料打底,然后在用本发明组合物处理之前或之中再干燥。
术语种子处理包括本领域已知的所有合适的种子处理,特别是拌种技术,如种子包衣(如种子造粒)、种子撒粉和种子吸收(如种子浸泡)。此处,“种子处理”是指使种子和本发明组合物相互接触的所有方法,“拌种”是指向种子提供一定量活性成分的种子处理方法,即该方法产生包含活性成分的种子。原则上,处理可施用于从种子收获至种子播种的任何时间的种子。种子例如可使用“播种箱”或“种植箱”方法紧邻种植种子之前或种植种子的过程中处理。然而,处理也可在种植种子之前数周或数月,例如至多12个月,例如以拌种处理的形式进行处理,而没有观察到效力的显著降低。
有利的是将处理施用于未播种的种子。如本文所用的术语“未播种种子”意味着包括从种子收获到将种子播种到地面以使植物萌发和生长的任何时间中的种子。
当提及“处理”未播种种子时,该处理并不意味着包括其中将农药施用于土壤,而不是直接施用于种子的那些措施。
通过在种子播种之前将处理施用于种子使操作简化。以此方式例如可在中心场所处理种子,然后将种子分配用于种植。这允许种植种子的人避免处理和使用活性成分,并且仅以常用于未处理种子的常规方式处理和种植处理的种子,这减少了对人的暴露。
具体而言,种子处理根据如下程序进行,其中将种子暴露于具体所需量的包含活性成分的制剂。制剂可以是直接施用或例如用水预先稀释的本发明组合物;例如,可能有利的是以2-10倍稀释种子处理组合物,从而产生0.01-60重量%,优选0.1-40重量%的活性化合物在即用制剂中的浓度。在某些情况下,可能有利的是,在不具有分散剂或分散剂量不足的组合物中加入本发明分散剂。当加入分散剂并任选用水稀释时,所得组合物形成分散体。
因此,活性成分在即用制剂中的浓度可在显著范围内变化。它们基于制剂总重量通常为0.01-80重量%,常常0.1-50重量%,优选0.5-20重量%。活性成分也可成功地以浓缩形式施用,其中可以向种子施用超过80重量%活性成分的制剂,或甚至不含添加剂的活性成分。添加剂的量具有在每种情况下基于制剂总重量通常不超过30重量%,优选20重量%,尤其为0.1-20重量%。
通常使用适合于种子处理的装置,例如用于固体或固体/液体组分的混合器,直至制剂均匀分布在种子上。因此,制剂可通过标准种子处理方法施用至种子,其包括但不限于在容器(如瓶、袋或转鼓)混合,机械施用,转鼓处理,喷雾和浸渍。合适的话,随后干燥。
本发明的特定实施方案包括种子包衣和吸收(如浸泡)。“包衣”是指赋予种子外表面部分或完整的非植物材料层的任何方法,“吸收”是指导致活性成分穿透入种子的可萌发部分和/或其天然外壳(sheath)、(内)壳(husk)、皮(hull)、壳、荚和/或珠被(integument)的任何方法。因此,本发明还涉及包括向种子提供包含活性成分的包衣的种子处理,以及包括使种子吸收活性成分的种子处理。
在容许高负载的活性成分中,包衣特别有效,所述高负载在处理典型的难以防治的害虫时需要,同时防止由于活性成分的负载增加而引起的不可接受的植物毒性。
包衣可使用常规包衣技术和机器如流化床技术、辊研磨机方法、滚动静态(rotostatic)种子处理器和转鼓涂敷机而施用于种子。其它方法如喷淋床技术也可能是有用的。种子可在包衣之前预施胶。在包衣之后,通常将种子干燥,然后转移至施胶机中施胶。
这类程序在本领域是已知的。种子包衣方法和应用它们的装置例如公开于美国专利号5,918,413、5,891,246、5,554,445、5,389,399、5,107,787、5,080,925、4,759,945和4,465,017中。
在另一特定实施方案中,固体的活性成分,例如作为固体细颗粒配制剂,如粉末或粉剂可直接与种子混合。可任选使用增粘剂以将固体,如粉末粘附至种子表面。例如,可将一定量的种子与增粘剂(其增加颗粒在种子表面上的粘附)混合并任选搅动以促进增粘剂对种子的均匀涂敷。例如,种子可与足够量的增粘剂混合,这导致增粘剂对种子的部分或完全涂敷。然后将如此预处理的种子与含有活性成分的固体配制剂混合,以实现固体配制剂在种子材料表面上的粘附。该混合物例如可通过转鼓搅动,以促进增粘剂与活性成分的接触,由此导致固体活性成分粘附在种子上。
用活性成分处理种子的另一特定方法为吸收。例如,可使种子与在溶剂如水中包含约1-约75重量%活性成分的水溶液结合一段时间。优选,溶液的浓度为约5-约50重量%,更优选约10-约25重量%。在种子与溶液结合的过程中,种子吸收(吸收)至少部分活性成分。任选地,可例如通过振摇、滚动、转鼓或其它手段搅动种子和溶液的混合物。在吸收方法之后,可将种子与溶液分离,并任选以合适的方式,如通过轻拍或风干而干燥。
在本发明的又一特定的实施方案中,活性成分可通过使用固体基质打底(priming)而引至种子上或种子内。例如,可将一定量的活性成分与固体基质材料混合,然后可放入种子,使其与固体基质材料接触一段时间,以允许将活性成分引至种子。然后可任选将种子的混合物与固体基质材料分离并储存或使用,或可优选将固体基质材料加上种子的混合物直接储存或种植/播种。
在本发明的各实施方案中,优选将本发明组合物以有效量施用于种子,即对种子和由种子长出的植物提供足以防止害虫的保护量。当然,本发明的种子处理不仅保护种子,而且保护由种子长出的植物。
与未处理种子或由未处理种子长出的植物相比,如果对种子和/或植物的进食损害百分数在害虫侵染10天后(侵染后天数(DAI))对于处理的种子和由处理的种子长出的植物显著降低,则实现了如本文所用的“保护”。为了有效保护,活性成分的用量通常为0.1-500g/100kg种子,优选0.5-200g/100kg种子,尤其是0.75-100g/100kg种子。
根据本发明,所述种子处理的一个目的是防治害虫。因此,该种子处理涉及对种子和/或由种子长出的植物提供防止害虫造成损害的保护的农药作用或农药活性。种子处理可尤其用于保护种子和秧苗防止较早季节的病害和昆虫害虫影响作物出苗和生长。
如本文所用的术语“农药作用”和“农药活性”是指对目标害虫任何直接或间接作用,分别与未处理种子或由未处理种子长出的植物相比,其导致对处理种子的进食损害的减少,以及还导致对由处理的种子长出的植物的果实、根、枝和/或叶的进食损害的减少。术语“对(第一或第二)害虫的活性”也具有相同含义。该直接或间接作用包括杀死害虫、从植物种子、果实、根、枝和/或叶中驱除害虫,以及抑制害虫,或延迟其在植物种子、果实、根、枝和/或叶上进食或产卵,以及抑制或防止害虫的繁殖。
害虫尤其包括土生(soil-borne)和土居(soil-dwelling),枝和叶面害虫。
待防治的真菌尤其包括如下:
观赏植物、蔬菜和向日葵上的白锈属(Albugo)(白锈病)(如蔬菜上的白锈菌(A.candida)和向日葵上的婆罗门参白锈(A.tragopogonis);蔬菜、油菜籽、糖用甜菜、水果、稻、大豆、土豆和小麦上的链格孢(Alternaria)属(链格孢叶斑病),油菜籽上的芸苔链格孢(A.brassicola或brassicae),糖用甜菜上的细极链格孢(A.tenuis),如土豆上的早疫链格孢(A.solani)或细交链孢(A.alternate),西红柿上的早疫链格孢(A.solani)或细交链孢(A.alternata);糖用甜菜和蔬菜上的丝囊霉(Aphanomyces)属;禾谷类和蔬菜上的壳二孢(Ascochyta)属,例如小麦上的小麦裾叶炫菌(Ascochytatritici)(炭疽病)和大麦上的大麦锈病菌(P.hordei);玉米、禾谷类、稻和草坪中的平脐蠕孢(Bipolaris)属和内脐蠕孢(Drechslera)属(有性型:旋孢腔菌(Cochliobolus)属),例如玉米上的玉米小斑病菌(D.maydis)),禾谷类上的小麦根腐平脐蠕孢(B.sorokiniana):叶斑病,稻上的稻平脐蠕孢菌(B.oryzae);禾谷类(例如小麦或大麦)中的禾白粉菌(Blumeria(以前为Erysiphe)graminis)(白粉病);水果和浆果(如草莓)、蔬菜(如莴苣、萝卜、芹菜和卷心菜)、油菜籽、花卉、葡萄藤、森林植物和小麦上的灰葡萄孢(Botrytiscinerea(有性型:灰霉病菌(Botryotinia fuckeliana):灰霉病));莴苣上的莴苣盘梗霉(Bremia lactucae)(霜霉病);阔叶树和常绿树上的长喙壳属(Ceratocystis)(同义词Ophiostoma)属(立枯病或枯萎),如榆树上的榆长喙壳(C.Ulmi)(榆枯萎病);玉米、稻、糖用甜菜、甘蔗、蔬菜、咖啡、大豆和稻上的尾孢属(Cercospora)(尾孢叶斑病),如糖用甜菜上的C.beticola,例如大豆上的大豆尾孢(Cercospora sojina)或菊池尾孢(Cercosporakikuchii);土豆和禾谷类上的枝孢属(Cladosporium)(如黄枝孢(C.Fulvum):叶霉病),如小麦上的扁豆枝孢(Cladosporium herbarum)(黑霉病);禾谷类上的麦角菌(Claviceps purpurea)(麦角病);玉米、禾谷类和稻上的旋孢腔菌(无性型:Cochliobolus)属(平脐蠕孢属的长蠕孢(Helminthosporium)属),如玉米上的C.carbonum,禾谷类上的禾旋孢腔菌(Cochliobolus sativus),无性型:B.Sorokiniana,和稻上的宫部旋孢腔菌(Cochliobolus miyabeanus,无性型:H.oryzae));棉花、玉米、无核小水果、土豆、豆类和大豆上的剌盘孢(Colletotricum)属(有性型:小丛壳属(Glomerella))(炭疽病),如棉花上的棉刺盘孢(C.gossypii)、玉米上的禾生刺盘孢(C.graminicola)、土豆上的C.coccodes:黑斑病、豆类上的豆刺盘孢(C.lindemuthianum)和大豆上的大豆上的平头刺盘孢(Colletotrichumtruncatum或C.gloeosporioides);伏革菌属(Corticium),如稻上的笹木伏革菌(Corticium sasakii)(枯纹病);大豆和观赏植物上的山扁豆生棒孢(Corynespora cassiicola)(叶斑病);Cycloconium属,如橄榄树上的油橄榄孔雀斑病菌(C.oleaginum);果树、葡萄藤和观赏植物上的柱孢(Cylindrocarpon)属(如果树蛀孔或幼葡萄藤下垂,有性型:丛赤壳(Nectria或Neonectria)属),如葡萄藤上的C.liriodendri,有性型:Neonectrialiriodendri:黑脚病(Black Foot);大豆上的白纹羽束丝菌(Dematophoranecatrix)(有性型:褐座坚壳(Rosellinia necatrix))(根/颈腐病);间座壳属(Diaporthe),如大豆上的菜豆间座壳(D.Phaseolorum)(立枯病);玉米、禾谷类、稻和草坪上的内脐蠕孢(Drechslera)属(同义词长蠕孢(Helminthosporium)属,有性型:核腔菌(Pyrenophora)属,例如大麦上的大麦网斑内脐蠕孢(D.Teres,网斑病)和小麦上的D.tritci-repentis:褐斑病);由Formitipora punctata(同义词斑孔木层孔菌(Phellinus punctatus))、F.mediterranea、Phaeoacremonium chlamydosporium(以前称为Phaeoacremonium chlamydosporum)、Phaeoacremonium Aleophilum和/或葡萄座腔菌属(Botryosphaeria obtusa)引起的葡萄藤上的埃斯卡(Esca)(顶枯病,干枯病);仁果、无核小水果和葡萄藤上的痂囊腔菌(Elsinoe)属,如仁果上的E.pyri、无核小水果上的E.veneta:炭疽病和葡萄藤上的痂囊腔菌(Elsinoe ampelina:炭疽病);稻上的Entyloma oryzae(叶黑粉病);小麦上的附球菌属(Epicoccum)(黑霉病);糖用甜菜、蔬菜、卷心菜、油菜籽上的白粉菌(Erysiphe)属(白粉病),如糖用甜菜上的E.betae,蔬菜上的豌豆白粉菌(E.Pisi),如葫芦上的二孢白粉菌(Erysiphe cichoracearum),油菜籽上的克鲁白粉菌(E.Cruciferarum);果树、葡萄藤和观赏木材上的Eutypalata(Eutypa蛀孔或顶枯病,无性型:Cytosporina lata,同义词Libertellablepharis);玉米上的突脐蠕孢(Exserohilum)属(同义词长蠕孢(Helminthosporium)属),如E.turcicum;各种植物上的镰孢霉(Fusarium)属(有性型:赤霉(Gibberella)属)(枯萎、根腐病或茎腐病),例如禾谷类(如小麦或大麦)上的禾谷镰刀菌(F.graminearum)或大刀镰孢(F.culmorum)(根腐病;疮痂病或赤霉病),西红柿上的尖镰孢(F.oxysporum),大豆上的真马特腐皮镰孢(Fusarium Solani)和玉米上的轮状镰刀霉(F.verticillioides);禾谷类,如大麦或小麦和玉米上的禾顶囊壳(Gaeumannomyces graminis)属(小麦全蚀病);禾谷类和稻上的赤霉(Gibberella)属,例如禾谷类上的玉蜀黍赤霉(G.zeae)和稻上的藤仓赤霉(Gibberella fujikuroi:稻恶苗病);葡萄藤、仁果和其它植物上的围小丛壳(Glomerella cingulata)以及棉花上的G.gossypii;稻上的革兰氏染色配合物(Grainstaining complex);葡萄藤上的葡萄球座菌(Guignardia bidwellii)(黑腐病);蔷薇植物和刺柏属上的Gymnosporangium属,如梨上的G.sabinae(锈病);玉米、禾谷类和稻上的长蠕孢(Helminthosporium)属(同义词Drechslera,有性型:旋孢腔菌(Cochliobolus)属);咖啡上的Hemileia属,如H.vastatrix(咖啡叶锈病);葡萄藤上的褐斑拟棒束孢(Isariopsisclavispora)(同义词Cladosporium vitis);大豆和棉花上的菜豆格孢(Macrophomina phaseolina)(同义词phaseoli)(根腐病和茎腐病);禾谷类(如小麦或大麦)上的Michrodochium(同义词Fusarium)nivale(紫雪霉病);大豆上的Microsphaera diffusa(白粉病);核果和其它蔷薇植物上的链核盘菌(Monilinia)属,如核果链核盘菌(M.laxa),M.fructicola和果生链核盘菌(M.fructigena)(花和嫩枝疫病,褐腐病);禾谷类、香蕉、无核小水果和花生上的球腔菌(Mycosphaerella)属,例如小麦上的禾生球腔菌(M.graminicola)(无性型:小麦壳针孢(Septoria tritici),壳针孢叶斑病)或香蕉上的M.fijiesis(香蕉叶斑病);甘蓝、油菜籽、洋葱、烟草和大豆上的霜霉(Peronospora)属(霜霉病),例如甘蓝上的芸苔霜霉(P.brassicae),洋葱上的P.destructor,烟草上的P.tabacina和大豆上的东北霜霉(Peronosporamanshurica);大豆上的豆薯层锈菌(Phakopsora pachyrhizi)和山马蟥层锈菌(Phakopsara meibomiae)(大豆锈病);葡萄藤和大豆上的瓶霉病(Phialophora)属,如葡萄藤上的P.tracheiphila和P.tetraspora,和大豆的Phialophora gregata:茎腐病;油菜籽和卷心菜以及糖用甜菜上的黑胫茎点霉(Phoma lingam)(根腐病和茎腐病)和甜菜茎点霉(P.betae)(根腐病、叶斑病和幼苗或插枝腐烂);向日葵、葡萄藤和大豆上的拟茎点霉(Phomopsis)属,如葡萄藤上的葡萄拟茎点霉(P.viticola:can和叶斑病),大豆上的茎腐病:P.phaseoli:有性型:菜豆间座壳(Diaporthe phaseolorum));玉米上的玉蜀黍节壶菌(Physoderma maydis)(褐斑病);各种植物上的疫霉属(Phytophthora)(枯萎,根、叶、果实和茎腐病),例如胡椒和葫芦上的辣椒疫霉(P.capsici),大豆上的大雄疫霉(P.megasperma,同义词P.sojae),土豆和西红柿上的致病疫霉(P.infestans:晚疫病),和阔叶树上的(P.ramorum:栎树突然死亡);卷心菜、油菜籽、萝卜和其它植物上的芸苔根肿菌(Plasmodiophora brassicae)(根肿病);Plasmopara属,如葡萄藤上的葡萄生单轴霉(Plasmopara viticola,葡萄霜霉病)和向日葵上的P.halstedii;蔷薇植物、啤酒花、梨果和无核小水果上的叉丝单囊壳(Podosphaera)属(白粉病),如苹果上的苹果白粉病菌(Podosphaera leucotricha);禾谷类如大麦和小麦以及糖用甜菜上的多粘霉(Polymyxa)属,如小麦上的多粘霉(P.graminis)和糖用甜菜上的P.betae,以及由此转变的病毒病害;禾谷类上如小麦或大麦的小麦基腐病菌(Pseudocercosporella herpotrichoides)(眼斑病,有性型:Tapesia yallundae);各种植物上的假霜霉(Pseudoperonospora)属(霜霉病),例如黄瓜上的古巴假霜霉(P.cubenis)或啤酒花上的葎草假霜霉(P.humili);葡萄藤上的Pseudopezicula tracheiphilai(红火病(red firedisease)或,rotbrenner’,无性型:瓶霉属(Phialophora));各种植物上的柄锈菌(Puccinia)属(锈病),例如禾谷类如小麦、大麦和燕麦上的小麦锈病菌(P.triticina)(褐锈病或叶锈病),条锈病菌(P.striformis)(条锈病),大麦锈病菌(P.hordei)(矮锈病)或禾柄锈菌(P.graminis)(茎锈病或黑锈病),隐匿柄锈菌(P.recondite)(褐锈病或叶锈病),以及芦笋上的芦笋锈病菌(P.asparagi);小麦上的Pyrenophora(无性型:内脐蠕孢属)tritici-repentis(褐斑病)或大麦上的Pyrenophora teres(网斑病);Pyricularia属,如稻上的稻瘟病菌(Pyricularia oryzae)(有性型:Magnaporthe grisea,稻瘟病)以及草坪和禾谷类上的稻梨孢菌(Pyricularia grisea);草坪、稻、玉米、小麦、棉花、油菜籽、向日葵、大豆、糖用甜菜、蔬菜和其他植物上的腐霉(Pythium)属(立枯病),例如终极腐霉(P.ultimum)或瓜果腐霉(P.aphanidermatum));大麦上的Ramularia collo-cygni(柱隔孢(Ramularia)叶斑病,生理叶斑病)和糖用甜菜上的R.beticola;棉花、稻、土豆、草坪、玉米、油菜籽、土豆、糖用甜菜、蔬菜和各种植物上的丝核菌(Rhizoctonia)属,例如大豆上的立枯丝核病菌(Rhizoctonia solani)(根和茎腐病),稻上的立枯丝核病菌(Rhizoctonia solani)(鞘枯病)或小麦或大麦上的禾谷丝核菌(Rhizoctoniacerealis)(Rhizoctonia spring blight);草莓、萝卜、卷心菜、葡萄藤和西红柿上的匍枝根霉(Rhizopus stolonifer)(黑霉病,软腐病);大麦、黑麦和黑小麦上的黑麦喙孢(Rhynchosporium secalis)(褐斑病);稻上的帚梗柱孢属(Sarocladium oryzae)和稻叶鞘腐败病菌(S.attenuatum)(鞘腐病);蔬菜、大田作物如油菜籽、向日葵和大豆上的核盘菌(Sclerotinia)属(根腐病或白霉病),例如向日葵上的核盘菌(S.sclerotiorum)和大豆上的Sclerotiniarolfsii或核盘菌(S.sclerotiorum);各种植物上的壳针孢(Septoria)属,如大豆上的大豆壳针孢(Septoria glycines)(褐斑病),小麦上的小麦壳针孢(Septoria tritici)(小麦壳针孢斑病)和禾谷类上的颖枯壳多孢(Stagonospora(同义词Stagonospora)nodorum)(颖枯壳多孢斑病);葡萄藤上的葡萄钩丝壳(Erysiphe(同义词Uncinula necator)(白粉病,无性型:葡萄粉孢(Oidium tuckeri));玉米和草坪上的Setospaeria属(叶枯病)(如S.turcicum,同义词大斑病长蠕孢(Helminthosporium turcicum));玉米、高粱和甘蔗上的Sphacelotheca属(黑穗病),如玉米上的丝轴黑粉菌(Sphacelotheca reilinia:丝黑穗病);葫芦上的单丝壳白粉菌(Sphaerothecafuliginea)(白粉病);土豆上的Spongospora subterranea(粉痂病)和由其转变的病毒病害;禾谷类上的壳多孢(Stagonospora)属,如小麦上的颖枯壳多孢(Stagonospora nodorum)(壳多孢斑病,有性型:小麦小球腔菌(Leptosphaeria[同义词Phaeosphaeria]nodorum));土豆上的内生集壶菌(Synchytrium endobioticum)(土豆癌肿病);外囊菌(Taphrina)属,如桃上的畸形外囊菌(T.deformans)(缩叶病)和李子上的李外囊菌(T.pruni)(李囊果病);烟草、仁果、蔬菜、大豆和棉花上的根串珠霉属(Thielaviopsis)(黑根腐病),如根串珠霉(T.basicola)(同义词Chalara elegans);禾谷类上的腥黑粉菌(Tilletia)属(普通腥黑穗病或麦类黑穗病),如小麦上的T.tritici(同义词小麦网腥黑粉菌(T.caries),小麦腥黑穗病)和小麦矮腥黑粉菌(T.controversa)(矮黑穗病);小麦或大麦上的肉孢核瑚菌(Typhulaincarnate)(灰雪霉病);黑麦上的条黑粉菌(Urocystis)属,如隐条黑粉菌(U.Occulta)(秆黑粉病);蔬菜、豆类和糖用甜菜上的单胞锈菌(Uromyces)属(锈病),如豆类上的疣顶单胞锈菌(U.appendiculatus),同义词U.Phaseoli,和糖用甜菜上的甜菜单胞锈菌(U.betae);禾谷类、玉米和甘蔗上的黑粉菌(Ustilago)属(黑穗病),例如禾谷类上的裸黑粉菌(U.nuda)和燕麦散黑粉菌(U.avaenae),玉米上的玉蜀黍黑粉菌(U.maydis:玉米黑粉病);苹果和梨上的黑星菌(Venturia)属(黑星病),例如苹果上的苹果黑星病(V.inaequalis),以及各种植物如水果和观赏植物、葡萄藤、无核小水果、蔬菜和大田作物上的轮枝孢(Verticillium)属(枯萎),例如草莓、油菜籽、土豆和西红柿上的大丽花轮枝孢(V.dahliae)。
待防治的昆虫特别包括下列:
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(Anticarsia gemmatalis)、Argyresthia conj ugella、叉纹夜蛾(Autographagamma)、树尺蠖(Bupalus piniarius)、Cacoecia murinana、Capuareticulana、Cheimatobia brumata、云杉色卷蛾(Choristoneurafumiferana)、Choristoneura occidentalis、二化螟(Cirphis unipuncta)、苹果小卷蛾(Cydia pomonella)、松毛虫(Dendrolimus pini)、Diaphanianitidalis、西南玉米杆草螟(Diatraea grandiosella)、埃及钻夜蛾(Eariasinsulana)、南美玉米苗斑螟(Elasmopalpus lignosellus)、女贞细卷蛾(Eupoecilia ambiguella)、Evetria bouliana、Feltia subterranea、蜡螟(Galleria mellonella)、李小食心虫(Grapholitha funebrana)、梨小食心虫(Grapholitha molesta)、棉铃虫(Heliothis armigera)、烟芽夜蛾(Heliothisvirescens)、玉米穗虫(Heliothis zea)、菜螟(Hellula undalis)、Hiberniadefoliaria、美国白蛾(Hyphantria cunea)、苹果巢蛾(Hyponomeutamalinellus)、番茄虫蛾(Keiferia lycopersicella)、Lambdina fiscellaria、甜菜夜蛾(Laphygma exigua)、咖啡潜叶蛾(Leucoptera coffeella)、旋纹潜蛾(Leucoptera scitella)、Lithocolletis blancardella、葡萄浆果小卷蛾(Lobesiabotrana)、甜菜网螟(Loxostege sticticalis)、舞毒蛾(Lymantria dispar)、模毒蛾(Lymantria monacha)、桃潜蛾(Lyonetia clerkella)、黄褐天幕毛虫(Malacosoma neustria)、甘蓝夜蛾(Mamestra brassicae)、黄杉毒蛾(Orgyiapseudotsugata)、玉米螟(Ostrinia nubilalis)、小眼夜蛾(Panolis flammea)、棉花红铃虫(Pectinophora gossypiella)、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(Plutella xylostella)、大豆夜蛾(Pseudoplusiaincludens)、Rhyacionia frustrana、Scrobipalpula absoluta、麦蛾(Sitotrogacerealella)、葡萄卷叶蛾(Sparganothis pilleriana)、草地夜蛾(Spodopterafrugiperda)、海灰翅夜蛾(Spodoptera littoralis)、斜纹夜蛾(Spodopteralitura)、Thaumatopoea pityocampa、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 lineatus)、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(Otiorrhynchus 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 sp.)、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(Aedes albopictus)、剌扰伊蚊(Aedes vexans)、墨西哥果蝇(Anastrephaludens)、五斑按蚊(Anopheles maculipennis)、Anopheles crucians、白足按蚊(Anopheles albimanus)、冈比亚按蚊(Anopheles gambiae)、Anophelesfreeborni、海南岛白踝按蚊(Anopheles leucosphyrus)、云南微小按蚊(Anopheles minimus)、四斑按蚊(Anopheles quadrimaculatus)、红头丽蝇(Calliphora vicina)、地中海实蝇(Ceratitis capitata)、蛆症金蝇(Chrysomyabezziana)、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(Culexquinquefasciatus)、媒斑蚊(Culex tarsalis)、Culiseta inornata、Culisetamelanura、瓜蝇(Dacus cucurbitae)、油橄榄实蝇(Dacus oleae)、油菜叶瘿蚊(Dasineura brassicae)、Delia antique、麦地种蝇(Delia coarctata)、灰地种蝇(Delia platura)、甘蓝地种蝇(Delia radicum)、Dermatobia hominis、小毛厕蝇(Fannia canicularis)、Geomyza Tripunctata、马蝇(Gasterophilus intestinalis)、刺舌蝇(Glossina morsitans)、须舌蝇(Glossina palpalis)、Glossina fuscipes、胶舌蝇(Glossina tachinoides)、Haematobia irritans、Haplodiplosis equestris、潜蝇属(Hippelates spp.)、花生田灰地种蝇(Hylemyia platura)、纹皮蝇(Hypoderma lineata)、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)、秋家蝇(Musca autumnalis)、家蝇(Muscadomestica)、厩腐蝇(Muscina stabulans)、羊狂蝇(Oestrus ovis)、Opomyzaflorum、欧洲麦秆蝇(Oscinella frit)、天仙子泉蝇(Pegomya hysocyami)、葱蝇(Phorbia antiqua)、萝卜蝇(Phorbia brassicae)、麦地种蝇(Phorbiacoarctata)、银足白蛉(Phlebotomus argentipes)、Psorophora columbiae、胡萝卜茎蝇(Psila rosae)、Psorophora discolor、Prosimulium mixtum、樱桃实蝇(Rhagoletis cerasi)、苹果实蝇(Rhagoletis pomonella)、赤尾麻蝇(Sarcophaga haemorrhoidalis)、肉蝇属(Sarcophaga)、Simuliumvittatum、厩螫蝇(Stomoxys calcitrans)、牛虻(Tabanus bovinus)、Tabanus atratus、红色原虻(Tabanus lineola)、Tabanus similis、Tipulaoleracea和欧洲大蚊(Tipula paludosa);
蓟马(缨翅目(Thysanoptera)),例如兰花蓟马(Dichromothripscorbetti)、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)、Reticulitermes santonensis、Reticulitermesgrassei、Termes natalensis和台湾乳白蚁(Coptotermes formosanus),蟑螂(蜚蠊目(Blattaria)-Blattodea),例如德国小蠊(Blattella germanica)、Blattella asahinae、美洲大蠊(Periplaneta americana)、日本大蠊(Periplaneta japonica)、棕色蜚蠊(Periplaneta brunnea)、Periplanetafuligginosa、澳洲蜚蠊(Periplaneta australasiae)和东方蜚蠊(Blattaorientalis),
臭虫、蚜虫、叶蝉、粉虱、介壳虫、蝉(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)、Dysdercusintermedius、麦扁盾蝽(Eurygaster integriceps)、烟草蝽(Euschistusimpictiventris)、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(Nezaraviridula)、甜菜拟网蝽(Piesma quadrata)、Solubea insularis、Thyantaperditor、Acyrthosiphon onobrychis、落叶松球蚜(Adelges laricis)、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(Aphisgrossulariae)、希奈德蚜(Aphis schneideri)、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(Brevicorynebrassicae)、Capitophorus horni、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(Dreyfusia nordmannianae)、云杉椎球蚜(Dreyfusia piceae)、居根西圆尾蚜(Dysaphis radicola)、Dysaulacorthum pseudosolani、车前圆尾蚜(Dysaphis plantaginea)、梨西圆尾蚜(Dysaphis pyri)、蚕豆微叶蝉(Empoasca fabae)、桃大尾蚜(Hyalopterus pruni)、Hyperomyzuslactucae、麦长管蚜(Macrosiphum avenae)、大戟长管蚜(Macrosiphumeuphorbiae)、蔷薇管蚜(Macrosiphon rosae)、巢莱修尾蚜(Megouraviciae)、Melanaphis pyrarius、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(Psyllamali)、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)、Schizoneura lanuginosa、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(Cimexlectularius)、热带臭虫(Cimex hemipterus)、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、Atta laevigata、Atta robusta、Atta sexdens、Atta texana、举腹蚁属(Crematogaster)、Hoplocampa minuta、Hoplocampa testudinea、黑毛蚁(Lasius niger)、小黄家蚁(Monomorium pharaonis)、热带火蚁(Solenopsis geminate)、红火蚁(Solenopsis invicta)、黑火蚁(Solenopsis richteri)、南方火蚁(Solenopsisxyloni)、红蚂蚁(Pogonomyrmex barbatus)、Pogonomyrmex californicus、Pheidole megacephala、天鹅绒蚂蚁(Dasymutilla occidentalis)、熊蜂属(Bombus)、大黄蜂(Vespula squamosa)、Paravespula vulgaris、Paravespulapennsylvanica、Paravespula germanica、姬胡蜂(Dolichovespula maculata)、黄边胡蜂(Vespa crabro)、胡蜂(Polistes rubiginosa)、Campodontusfloridanus和阿根廷蚁(Linepithema humile),
蟋蟀、蚱蜢、蝗虫(直翅目(Orthoptera)),例如居屋艾蟋(Achetadomestica)、蝼蛄(Gryllotalpa gryllotalpa)、飞蝗(Locusta migratoria)、双纹黑蝗(Melanoplus bivittatus)、红足黑蝗(Melanoplus femurrubrum)、墨西哥黑蝗(Melanoplus mexicanus)、迁飞黑蝗(Melanoplus sanguinipes)、石栖黑蝗(Melanoplus spretus)、条纹红蝗(Nomadacris septemfasciata)、美洲沙漠蝗(Schistocerca americana)、沙漠蝗(Schistocerca gregaria)、摩洛哥戟纹蝗(Dociostaurus maroccanus)、庭疾灶螽(Tachycines asynamorus)、塞纳加尔小车蝗(Oedaleus senegalensis)、Zonozerus variegatus、非洲蔗蝗(Hieroglyphus daganensis)、Kraussaria angulifera、意大利蝗(Calliptamusitalicus)、澳洲草栖蝗(Chortoicetes terminifera)和褐色拟飞蝗(Locustanapardalina),
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(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、安氏革蜱(Dermacentor andersoni)、美洲大革蜱(Dermacentor variabilis)、Hyalomma truncatum、蓖子硬蜱(Ixodesricinus)、Ixodes rubicundus、黑脚硬蜱(Ixodes scapularis)、全环硬蜱(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)、Rhipicephalus sanguineus、Rhipicephalusappendiculatus、Rhipicephalus evertsi、人疥螨(Sarcoptes scabiei),瘿螨(Eriophyidae)属,如苹果刺锈螨(Aculus schlechtendali)、Phyllocoptrataoleivora和Eriophyes sheldoni;细螨(Tarsonemidae)属,如Phytonemuspallidus和侧多食跗线螨(Polyphagotarsonemus latus);细须螨(Tenuipalpidae)属,如紫红短须螨(Brevipalpus phoenicis);叶螨(Tetranychidae)属,如朱砂叶螨(Tetranychus cinnabarinus)、神泽叶螨(Tetranychus kanzawai)、太平洋叶螨(Tetranychus pacificus)、棉叶螨(Tetranychus telarius)和二点叶螨(Tetranychus urticae),苹果叶螨(Panonychus ulmi)、柑椐叶螨(Panonychus citri)和草地小爪螨(Oligonychuspratensis);蜘蛛目(Araneida),例如毒蜘蛛(Latrodectus mactans)和褐丝蛛(Loxosceles reclusa),
跳蚤(蚤目(Siphonaptera)),例如猫跳蚤(Ctenocephalides felis)、狗跳蚤(Ctenocephalides canis)、印鼠客蚤(Xenopsylla cheopis)、致痒蚤(Pulexirritans)、穿皮潜蚤(Tunga penetrans)和具带病蚤(Nosopsyllus fasciatus),衣鱼、家衣鱼(缨尾目(Thysanura)),例如西洋衣鱼(Lepisma saccharina)和斑衣鱼(Thermobia domestica),
百足虫(唇足纲(Chilopoda)),例如Scutigera coleoptrata,
千足虫(倍足纲(Diplopoda)),例如Narceus属,
蠼蛸(革翅目(Dermaptera)),例如欧洲球螋(forficula auricularia),
虱(毛虱目(Phthiraptera)),例如人头虱(Pediculus humanus capitis)、人体虱(Pediculus humanus corporis)、阴虱(Pthirus pubis)、牛血虱(Haematopinus eurysternus)、猪血虱(Haematopinus suis)、牛颚虱(Linognathus vituli)、Bovicola bovis、鸡虱(Menopon gallinae)、Menacanthus stramineus和Solenopotes capillatus,
弹尾目(collembola)(跳虫),如棘跳属(Onychiurus),
本发明组合物还适用于防治线虫:植物寄生线虫如根结线虫,北方根结线虫(Meloidogyne hapla)、南方根结线虫(Meloidogyne incognita)、爪哇根结线虫(Meloidogyne javanica)和其他根结线虫属(Meloidogyne);形成胞囊的线虫,马铃薯金线虫(Globodera rostochiensis)和其他球胞囊属(Globodera);禾谷胞囊线虫(Heterodera avenae)、大豆胞囊线虫(Heterodera glycines)、甜菜胞囊线虫(Heterodera schachtii)、三叶草胞囊线虫(Heterodera trifolii)和其他胞囊线虫属(Heterodera);种子肿瘿线虫,粒线虫属(Anguina);茎叶线虫,滑刃线虫属(Aphelenchoides);刺线虫,杂草刺线虫(Belonolaimus longicaudatus)和其他针刺线虫属(Belonolaimus);松线虫,松材线虫(Bursaphelenchus xylophilus)和其他伞滑刃线虫属(Bursaphelenchus);环形线虫,环纹线虫属(Criconema)、小环线虫属(Criconemella)、轮线虫属(Criconemoides)、中环线虫属(Mesocriconema);球茎线虫,腐烂茎线虫(Ditylenchus destructor)、甘薯茎线虫(Ditylenchus dipsaci)和其他茎线虫属(Ditylenchus);锥线虫,锥线虫属(Dolichodorus);螺旋形线虫,Heliocotylenchus multicinctus和其他Helicotylenchus属;鞘线虫和鞘形(sheathoid)线虫,鞘线虫属(Hemicycliophora)和Hemicriconemoides属;Hirshmanniella属;冠线虫,Hoploaimus属;伪根结线虫,珍珠线虫属(Nacobbus);针线虫,Longidoruselongatus和其他长针线虫属(Longidorus);根腐线虫,疏忽短体线虫(Pratylenchus neglectus)、穿刺根腐线虫(Pratylenchus penetrans)、Pratylenchus curvitatus、古迪短体线虫(Pratylenchus goodeyi)和其他根腐线虫属(Pratylenchus);穿孔线虫,香蕉穿孔线虫(Radopholus similis)和其他穿孔线虫属(Radopholus);肾形线虫,Rotylenchus robustus和其他盘旋线虫属(Rotylenchus);Scutellonema属;残根线虫,Trichodorus primitivus和其他毛刺线虫属(Trichodorus)、拟毛刺属(Paratrichodorus);阻长线虫,克莱顿矮化线虫(Tylenchorhynchus claytoni)、不定矮化线虫(Tylenchorhynchus dubius)和其他矮化线虫属(Tylenchorhynchus);柑桔线虫,垫刃线虫属(Tylenchulus);剑线虫,剑线虫属(Xiphinema);以及其他植物寄生线虫属。
本发明组合物也用于防治蛛形纲(Arachnoidea),如蜘蛛(蜱螨目),例如软蜱科(Argasidae)、硬蜱科(Ixodidae)和疥螨科(Sarcoptidae),如长星形壁虱(Amblyomma americanum)、热带花蜱(Amblyomma variegatum)、波斯锐缘蜱(Argas persicus)、牛壁虱(Boophilus annulatus)、Boophilusdecoloratus、微小牛蜱(Boophilus microplus)、Dermacentor silvarum、Hyalomma truncatum、蓖子硬蜱(Ixodes ricinus)、Ixodes rubicundus、Ornithodorus moubata、Otobius megnini、鸡皮刺螨(Dermanyssusgallinae)、绵羊疥病(Psoroptes ovis)、Rhipicephalus appendiculatus、Rhipicephalus evertsi、人疥螨(Sarcoptes scabiei),以及瘿螨科(Eriophyidae),如斯氏刺瘿螨(Aculus schlechtendali)、桔皱叶刺瘿螨(Phyllocoptrata oleivora)和桔芽瘿螨(Eriophyes sheldoni);跗绒螨科(Tarsonemidae),如Phytonemus pallidus和侧多食跗线螨(Polyphagotarsonemus latus);细须螨科(Tenuipalpidae),如紫红短须螨(Brevipalpus phoenicis);叶螨科(Tetranychidae),如朱砂叶螨(Tetranychuscinnabarinus)、神泽叶螨(Tetranychus kanzawai)、太平洋叶螨(Tetranychuspacificus)、棉叶螨(Tetranychus telarius)和二点叶螨(Tetranychus urticae),苹果全爪螨(Panonychus ulmi)、柑桔全爪螨(Panonychus citri)和草地小爪螨(oligonychus pratensis)。
本发明还提供了通过本文所述方法处理的种子。还提供了可通过本文所述方法得到的种子。
此外,本发明还提供了用本文所述的种子处理组合物处理的种子,尤其是用组合物包衣的种子或含有组合物的种子。还提供了可通过使用本文所述的组合物得到的种子。
根据特定实施方案,用本发明组合物处理的种子的活性成分的负载量为0.1-500g/100kg种子,优选0.5-200g/100kg种子,尤其是0.75-100g/100kg种子。
此处,术语“涂有和/或含有”是指活性成分在施用时绝大部分在种子表面上,然而,取决于施用方法或多或少的部分活性成分可穿透入种子中。当(再)种植所述种子时,其可吸收活性成分。
根据一个实施方案,这种包含活性成分的种子具有包衣,其中包衣包含活性成分。根据另一实施方案,这种包含活性成分的种子为其可萌发部分和/或其天然外壳、壳、荚或珠被包含活性成分的种子。活性成分也可同时存在于包衣和种子的可萌发部分和/或其天然外壳、壳、荚和/或珠被中。
优选这类种子包含有效量的活性成分。因此,以此方式包衣、浸渍或包衣并浸渍种子降低了萌发和出苗过程中的害虫损害。
用本发明组合物处理的种子也可用膜外涂层包封以保护活性成分包衣。该外涂层在本领域是已知的且可使用常规流化床和转鼓膜涂覆技术施用。
本发明种子可用于繁殖植物。可将种子储存、处理、种植/播种和耕作。
实施例
本发明通过如下实施例说明,所述实施例不应理解为限制本发明。
实施例1-7:
悬浮液浓缩物通过将所有成分(除了黄原胶)混合并在两步中研磨这些悬浮液而制备,其中首先在机械磨机,然后在珠磨机中研磨至粒度的特征在于D90<6μm,这通过激光散射测定。最后,将黄原胶以2%的水溶液形式加入。
1 | 2 | 2a | 3 | 3a | 4 | 5 | 6 | 7 | |
氧唑菌 | 200 | - | - | - | - | - | - | - | |
甲体氯氰菊酯 | - | 500 | 500 | - | - | - | - | - | |
戊叉唑菌 | - | - | - | 200 | 200 | 25 | |||
颜料红48:2 | 45 | ||||||||
唑菌胺酯 | - | - | - | - | - | 200 | - | - | |
锐劲特 | - | - | - | - | - | - | 600 | - | |
喹唑菌酮 | - | - | - | - | - | - | - | 100 | |
PE10500 | - | - | - | - | 20 |
Soprophor4D384 | 10 | 20 | 40 | 10 | 20 | 10 | 5 | 10 | |
Atlox 4913 | 33 | 66.7 | 33 | 30 | 30 | 15 | 30 | ||
甘油 | 100 | 60 | 60 | 100 | 100 | 138 | 100 | 60 | 150 |
黄原胶,2%,在水中 | 130 | 60 | 60 | 100 | 100 | 130 | 150 | 40 | 40 |
水 | 610 | 400 | 447 | 630 | 650 | 670 | 550 | 470 | 640 |
D90新鲜[μm] | 3.6 | 3.5 | 3.2 | 2.5 | 2.2 | 3.2 | 4.0 | 2.2 | 3.3 |
D90,在2W50之后[μm] | 3.6 | 4.8 | 6.1 | 3.3 | 4.2 | - | - | - | - |
D90,在8W40之后[μm] | - | - | - | - | - | 3.3 | 4.8 | 2.4 | 3.4 |
浆料[%] | 6 | - | 9 | 21 | 49 | 2 | 13 | 6.5 | 10.4 |
根据实施例1-7的配制剂阐述了本发明组合物。实施例2a和3a的配制剂用于对比目的。
Claims (38)
1.一种包含如下组分的组合物在种子处理中的用途:
活性成分;
具有式(I)的多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐或其可农用的碱加成盐:
其中各R独立地表示氢或C1-C4烷基;Alk表示C2-C6亚烷基;n具有5-60的值;和X为-SO3H2或-PO3H,和
共聚物,该共聚物包含:
(i)至少一种烯属不饱和羧酸的酯的单体单元,其中羧酸酯具有通式(II)的烷氧基化物残基:
(R1)n-X-(CHR2CH2O)w-(CHR3CH2O)x-(CHR4(CH2)yO)z-(II),
其中
R1为氢或具有1-40个碳原子的脂族烃残基;
R2、R3、R4相互独立地为氢或C1-C4烷基;
w、x、z相互独立地对应于0-100的值,其中w、x和z的总和大于0;
y对应于1-20的值;和
X为N或O,
如果X为O,则n为1;或如果X为N,则n为2;和
(ii)至少一种额外的可共聚的共聚单体的单体单元。
2.根据权利要求1的用途,其中R1为线性或支化的饱和或不饱和C1-C6烷基。
3.根据权利要求1的用途,其中所述多芳基酚聚烷氧基醚硫酸盐为具有CAS号119432-41-6的化合物或所述多芳基酚聚烷氧基醚磷酸盐为具有CAS号176776-21-9的化合物。
4.根据权利要求2的用途,其中所述多芳基酚聚烷氧基醚硫酸盐为具有CAS号119432-41-6的化合物或所述多芳基酚聚烷氧基醚磷酸盐为具有CAS号176776-21-9的化合物。
5.根据权利要求1的用途,其中所述组合物包含至少0.5重量%多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐且至多20重量%多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐。
6.根据权利要求3的用途,其中所述组合物包含至少0.5重量%多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐且至多20重量%多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐。
7.根据权利要求1-6中任一项的用途,其中所述烯属不饱和羧酸为丙烯酸和/或甲基丙烯酸。
8.根据权利要求1-6中任一项的用途,其中通式(II)的烷氧基化物残基为式(IIa)的乙氧基化物残基:
R1-O-(C2H4O)z-(IIa)
其中
R1如权利要求1或2所定义;和
z对应于1-100的值。
9.根据权利要求1-6中任一项的用途,其中所述可共聚的共聚单体为丙烯酸甲酯和/或甲基丙烯酸甲酯。
10.根据权利要求1-6中任一项的用途,其中所述共聚物的重均分子量为至少5kDa。
11.根据权利要求1-6中任一项的用途,其中所述共聚物为具有CAS号111740-36-4的化合物。
12.根据权利要求1-6中任一项的用途,其中所述组合物包含至少0.2重量%共聚物且至多10重量%共聚物。
13.根据权利要求1-6中任一项的用途,其中所述组合物进一步包含防冻剂。
14.根据权利要求13的用途,其中所述防冻剂为甘油。
15.根据权利要求1-6中任一项的用途,其中除了所述多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐以及共聚物之外,所述组合物还任选包含HLB值超过5的其他表面活性剂。
16.根据权利要求15的用途,其中如果存在的话,HLB值超过5的其他表面活性剂的量为至多1重量%。
17.根据权利要求16的用途,其中如果存在的话,HLB值超过5的其他表面活性剂的量为至多0.5重量%。
18.根据权利要求1-6中任一项的用途,其中所述组合物为含水悬浮液浓缩物。
19.根据权利要求1-6中任一项的用途,其中所述组合物包含唑茵胺酯、戊叉唑茵,或者唑菌胺酯和戊叉唑菌作为活性成分。
20.一种包含如下组分的种子处理组合物:
唑菌胺酯;
具有式(I)的多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐或其可农用的碱加成盐:
其中各R独立地表示氢或C1-C4烷基;Alk表示C2-C6亚烷基;n具有5-60的值;和X为-SO3H2或-PO3H,和
共聚物,该共聚物包含:
(i)至少一种烯属不饱和羧酸的酯的单体单元,其中羧酸酯具有通式(II)的烷氧基化物残基:
(R1)n-X-(CHR2CH2O)w-(CHR3CH2O)x-(CHR4(CH2)yO)z-(II),
其中
R1为氢或具有1-40个碳原子的脂族烃残基;
R2、R3、R4相互独立地为氢或C1-C4烷基;
w、x、z相互独立地对应于0-100的值,其中w、x和z的总和大于0;
y对应于1-20的值;和
X为N或O,
如果X为O,则n为1;或如果X为N,则n为2;和
(ii)至少一种额外的可共聚的共聚单体的单体单元。
21.根据权利要求20的组合物,其中R1为线性或支化的饱和或不饱和C1-C6烷基。
22.根据权利要求20的组合物,其中所述组合物进一步包含戊叉唑茵。
23.根据权利要求21的组合物,其中所述组合物进一步包含戊叉唑茵。
24.根据权利要求20-23中任一项的组合物,其中所述多芳基酚聚烷氧基醚硫酸盐为具有CAS号119432-41-6的化合物或所述多芳基酚聚烷氧基醚磷酸盐为具有CAS号176776-21-9的化合物。
25.根据权利要求20-23中任一项的组合物,其中所述组合物包含至少0.5重量%且至多20重量%多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐。
26.根据权利要求20-23中任一项的组合物,其中所述烯属不饱和羧酸为丙烯酸和/或甲基丙烯酸。
27.根据权利要求20-23中任一项的组合物,其中通式(II)的烷氧基化物残基为式(IIa)的乙氧基化物残基:
R1-O-(C2H4O)z-(IIa)
其中
R1如权利要求20或21所定义;和
z对应于1-100的值。
28.根据权利要求20-23中任一项的组合物,其中所述可共聚的共聚单体为丙烯酸甲酯和/或甲基丙烯酸甲酯。
29.根据权利要求20-23中任一项的组合物,其中所述共聚物的重均分子量为至少5kDa。
30.根据权利要求20-23中任一项的组合物,其中所述共聚物为具有CAS号111 740-36-4的化合物。
31.根据权利要求20-23中任一项的组合物,其中所述组合物包含至少0.2重量%且至多10重量%共聚物。
32.根据权利要求20-23中任一项的组合物,其中所述组合物进一步包含防冻剂。
33.根据权利要求32的组合物,其中所述防冻剂为甘油。
34.根据权利要求20-23中任一项的组合物,其中除了所述多芳基酚聚烷氧基醚磷酸盐和/或多芳基酚聚烷氧基醚硫酸盐以及共聚物之外,所述组合物还任选包含HLB值超过5的其他表面活性剂。
35.根据权利要求34的组合物,其中如果存在的话,HLB值超过5的其他表面活性剂的量为至多1重量%。
36.根据权利要求34的组合物,其中如果存在的话,HLB值超过5的其他表面活性剂的量为至多0.5重量%。
37.根据权利要求20-23中任一项的组合物,其中所述组合物为含水悬浮液浓缩物。
38.一种处理种子的方法,其包括向一批种子施用有效量的根据权利要求20-37中任一项的组合物。
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KR20100074129A (ko) | 2010-07-01 |
EP2180783B1 (en) | 2017-02-22 |
EP3150068A1 (en) | 2017-04-05 |
PL2180783T3 (pl) | 2017-08-31 |
IL203431A (en) | 2017-04-30 |
MX2010001666A (es) | 2010-03-10 |
BRPI0814941A2 (pt) | 2014-09-30 |
NZ599997A (en) | 2013-08-30 |
EP3150068B1 (en) | 2019-10-09 |
WO2009021985A2 (en) | 2009-02-19 |
AU2008288385B2 (en) | 2013-11-07 |
ZA201001810B (en) | 2011-05-25 |
CN101778561A (zh) | 2010-07-14 |
AR068194A1 (es) | 2009-11-11 |
AU2008288385A1 (en) | 2009-02-19 |
CA2695417C (en) | 2015-10-06 |
US9137984B2 (en) | 2015-09-22 |
CA2695417A1 (en) | 2009-02-19 |
EA019834B1 (ru) | 2014-06-30 |
JP2010536729A (ja) | 2010-12-02 |
NZ583007A (en) | 2012-06-29 |
US20110166022A1 (en) | 2011-07-07 |
PL3150068T3 (pl) | 2020-04-30 |
EP2180783A2 (en) | 2010-05-05 |
CL2008002420A1 (es) | 2009-10-23 |
WO2009021985A3 (en) | 2009-12-30 |
UA98802C2 (ru) | 2012-06-25 |
EA201000322A1 (ru) | 2010-10-29 |
US20150342182A1 (en) | 2015-12-03 |
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