CN116669551A - 具有改善的漂移、吸收和耐雨性能的农业化学组合物 - Google Patents
具有改善的漂移、吸收和耐雨性能的农业化学组合物 Download PDFInfo
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Classifications
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Abstract
本发明涉及农业化学组合物:其用于叶面施用的用途;其在低喷雾量下的使用;其通过装备配备有常规喷嘴以及脉冲宽度调制喷嘴的悬臂式喷雾器或旋转盘式液滴涂抹器的无人机系统(UAS)、无人引导车辆(UGV)和拖拉机的使用;以及其用于防治农业害虫、杂草或病害,特别是在蜡质叶片上的应用,并且特别地本发明涉及具有减少的漂移(特别是在喷雾应用中)的农业化学组合物。
Description
本发明涉及农业化学组合物:其用于叶面施用的用途;其在低喷雾量下的使用;其通过装备着配备有常规喷嘴以及脉冲宽度调制喷嘴的悬臂式喷雾器或旋转盘式液滴涂抹器的无人机系统(UAS)、无人引导车辆(UGV)和拖拉机的使用;以及其用于防治农业害虫、杂草或病害,特别是在蜡质叶片上的应用,并且特别是本发明涉及具有减少的漂移(特别是在喷雾应用中)的农用化学组合物。
农药活性化合物(AI),例如,除草剂、杀真菌剂、杀虫剂、杀细菌剂、杀螨剂、植物生长调节剂等,以及它们的配制产品通常在含水喷雾液体中稀释后喷雾到植物和/或其栖息地上。
虽然现代农业在以安全和可持续的方式生产足够的粮食方面面临着诸多挑战,但是同样需要利用作物保护产品来提高安全性、质量和产量,同时最大程度地减小对环境和农业土地的影响。许多作物保护产品——无论化学的还是生物的——通常以相对较高的喷雾量施用,例如在特定情况下大于50L/ha,并且经常大于150-400L/ha。这导致的结果是,必须消耗大量能量来携带大量喷雾液体,然后通过喷雾施用施用到作物上。这可由大型拖拉机完成,由于大型拖拉机的重量以及喷雾液体的重量,其由于所涉及的机械作业产生CO2并且对土壤造成有害的压实,这影响植物的根系生长、健康和产量,并且随后在补救这些影响中也损耗能量。
此外,当施用所述喷雾制剂时,可以观察到含有活性物质的喷雾溶液或多或少明显的漂移,其取决于风力状况、喷嘴类型和其他施用参数,例如喷嘴压力、吊杆高度和拖拉机速度。
农药喷雾漂移是农业对自然生态系统和城市地区的环境影响方面的一个主要问题。另外,这种漂移是不合需要的,因为就处理区域的预期施用率而言,它导致施用的农用化学品的某一部分损失。
更重要的是,漂移物质可能对邻近作物造成损害,尤其是对当地环境(例如,地表水、非目标植物群)以及居民区的旁观者和居住者。
需要一种解决方案,其在喷雾时显著减少活性成分/制剂的漂移,同时优选地减少大量喷雾液体并减少施用产品所需的设备的重量。
使用各种方法来防止喷雾漂移到田地边界之外。天然或人工防风林的使用是众所周知的。然而,已经描述了即使当使用所述屏障时,漂移也会导致活性物质在所述边界后面的沉积(例如“Deposition of spray drift behind border stmctures”,M.DeSchampheleire等人.Crop Protection 28(2009)1061-1075)。另一种常用的漂移缓解措施是缓冲区,无论是非作物或作物。非作物缓冲区的缺点是部分田地不能播种作物,这是农民的经济成本。作物缓冲区的缺点是部分作物没有得到充分保护,导致产量较低,可能还会产生抗性。显然,这是农民想要避免的。
除了物理限制喷雾漂移之外,还可以改变喷雾云的结构,使更少的液滴倾向于漂移,即,通常那些易于漂移的液滴具有100μm以下的直径。这可以通过选择不同类型的喷嘴、改变产生喷雾云的压力或通过改变喷雾液体本身的性质来完成。特别是改变喷嘴和/或喷嘴压力是农民不愿做的事情,因为这是耗时的并且使他们的作物的生产更昂贵。并且,喷雾器上处理可变施用率所需的设备并不常见。出于这些原因,优化喷雾云使其导致更少或更有限的漂移的更可接受的方式是通过调节喷雾液体的性质。
虽然其他因素(如气象条件和喷杆高度)也可能导致漂移,喷雾液滴尺寸分布已经被发现是主要因素。Teske等人(Teske M.E.,Hewitt A.J.,Valcore,D.L.2004.The RoleofSmall Droplets in Classifying Drop Size Distributions ILASS Americas 17thAnnual Conference:Arlington VA)已经报道了<156微米(μm)的值的部分作为喷雾液滴分布导致漂移。其他研究人员认为直径<150μm的液滴最容易漂移(J.H.Combellack,N.M.Westen and R.G.Richardson,Crop Prot.,1996,15,147-152,O.Permin,L.N.Jorgensen and K.Persson,Crop Prot.,1992,11,541-546)。另一组(H.Zhu,R.W.Dexter,R.D.Fox,D.L.Reichard,R.D.Brazee and H.E.Ozkan,J.Agric.EngineeringRes.,1997,67,35-45.)引用<200μm的值作为可漂移部分。基于理论研究和计算机模拟,直径<100μm的喷雾液滴已经被确认是最容易漂移的(H.Holterman,Kinetics andevaporation of water drops in air,2003,IMAG Report 2003-12;P.A.Hobson,P.C.H.Miller,P.J.Walklate,C.R.Tuck and N.M.Western,J.Agr.Eng.Res.,1993,54,293-305;P.C.H.Miller,The measurement of spray drift,Pesticide Outlook,2003,14,205-209)。因此,可能导致漂移的液滴尺寸的良好估计是低于约100μm的部分(可漂移部分)。液滴越小,在空气中的停留时间越长,并且蒸发和/或漂移而非储存在田地边界内的趋势越高。使漂移效应最小化的一种方式是通过将合适的漂移控制剂添加到农药制剂中,所述漂移控制剂增加喷雾云中的液滴的尺寸——即,使液滴光谱向较大的液滴移动。当寻找克服漂移问题的解决方案时,必须考虑到所得制剂的生物性能没有降低。使用喷雾液滴尺寸增加的制剂(罐装物和桶混物)可能在一定程度上降低功效,主要是因为减少了覆盖(例如"Biological efficacy ofherbicides and fungicides applied with low-drift andtwin-fluid nozzles"P.K.Jensen et al.Crop Protection 20(2001)57-64)。较大的液滴在叶片表面上的保留可能减少,因为它们会流失或反弹或破碎并重新分布。更少的粘附到叶表面的较大的液滴会降低总体生物学功效。此外,对于喷雾云必须渗透到作物的冠层中的作物,非常大的液滴可以直接穿过冠层,或者从叶子上反弹,或者破碎并重新分布到土壤中。以大液滴施用活性化合物的所有所述效果可能加重功效的降低。
同样必须考虑的是,添加到制剂中以改善功效、储存、耐雨性和其他重要性质的多种化合物通常对喷雾汤的漂移性质具有负面影响,即,倾向于减小液滴尺寸或增强后续的蒸发。
此外,在农业领域中,低喷雾量应用技术,包括装备着配备有脉冲宽度调制喷嘴的悬臂式喷雾器或旋转盘式液滴涂抹器的无人机系统(UAS)、无人引导车辆(UGV)和拖拉机,这为农民提供了以低喷雾量施用产品的解决方案,喷雾量通常低至10至20L/ha或更少。这些方案的优点包括,例如它们需要显著少的水,这在供水量有限的地区非常重要;它们需要更少量的能量来运输和施用喷雾液体;喷雾液体装罐和施用均很快速;它们减少了喷雾液体运输量和使用更小更轻的车辆,这均减少了CO2的产生和土壤的压实损害,并且能使用更便宜的应用系统。
然而,Wang等人[Field evaluation of an unmanned aerial vehicle(UAV)sprayer:effect of spray volume on deposition and the control of pests anddisease in wheat.Pest Management Science 2019doi/epdf/10.1002/ps.5321]表明,随着喷雾量从450和225L/ha降低至28.1、16.8和9.0L/ha,在水敏纸上测量的覆盖范围(%面积)、单位面积的喷雾沉积物的数量以及喷雾沉积物的直径均降低(参见表3,Wang等人,2019)。与此同时,在低喷雾量下对于麦蚜虫防治和白粉病防治的生物防治效果均降低,其中在9.0L/ha下观察到最大的降低,其次为在16.8L/ha下(参见图6、7和8,Wang等人,2019)。
因此,需要设计这样的制剂体系,其克服了在低喷雾量下覆盖范围和喷物沉积物的直径的降低,即使单位面积喷物沉积物的数量在下降:随着喷雾量的减少,对于相同喷雾液滴谱尺寸,每单位面积上的喷雾液滴的数量呈比例地减小。这在低于25L/ha,更特别是低于17L/ha,甚至更特别是在10L/ha以下时是特别必要的。
此外,由于喷雾溶液中佐剂的浓度增加以增强植物的吸收,由于佐剂的局部浓度较高,因此喷雾溶液的洗去概率较高。
此外,在低喷雾量制剂和喷雾汤中较高浓度的表面活性剂通常导致较小的液滴尺寸,这进而增加漂移。
因此,需要提供这样的制剂,当根据本发明不仅以“正常”体积(50-500l/ha)而且以超低喷雾量喷雾时,其显示出对作物的良好覆盖以提供良好的生物功效,同时具有良好或可接受的吸收并且不显示出高洗去率。
所述溶液由根据权利要求1所述的制剂提供,并且具体地由含有特定漂移减少剂与特定浓度的所选吸收剂和耐雨剂组合的制剂提供。所述制剂提供最小化的或至少维持的漂移,同时在低喷雾量下提供增加的喷雾沉积物的覆盖范围和增加的直径,同时维持或改善吸收、生物功效和耐雨性。此外,喷雾沉积物的增加的覆盖范围和增加的直径与在正常较高喷雾量下获得的覆盖范围相当。
此外,例示本发明的制剂在难以湿润的叶表面上特别有效,其中更常规的喷雾量具有较差的保留和覆盖。
与常规高喷雾量下所需的水平相比,总量低的所有成分所带来的本发明用于小体积施用的一个特别的优点是,制剂的成本较低且易于生产。其他的优点包括改善的制剂稳定性、简化了生产过程、较低的商品成本和对环境的影响较小。
现有技术中已知的含有漂移减少剂的制剂,包括桶混物,主要是被设计用于更高的喷雾量,并且喷雾液体中通常含有较低浓度的吸收增强剂。然而,由于现有技术中使用高喷雾量,因此在环境中使用的试剂总量高于本发明。
漂移减少剂的浓度是本发明的重要要素,因为特别是对于也用作渗透增强剂的油基漂移阻滞剂,合适的效果在低浓度下已经发生,先于活性物质的渗透的任何效果。因此,可以显著降低较低量的所述油和对环境漂移的小影响。“较低量的所述漂移减少剂(也称为漂移阻滞剂)”是指小于25g/l。这意味着,已经用5至10g/ha的量代替常规的100-500g/ha就可以实现良好的漂移减少,常规的100-500g/ha对于吸收效果是必须存在的。
另一方面,高含油量增加了产品的体积、制造复杂性并可降低产品稳定性,因此如果不需要作为吸收增强剂或溶剂,则应避免使用它们。
实现漂移减少剂的最小浓度,通常为0.5g/l。
关于低体积施用中的吸收剂,在现有技术中使用的500l/ha的喷雾量中,将需要约250g/ha的吸收剂以实现合适的吸收。因此,面对减少喷雾量的任务,技术人员将在制剂中应用相同浓度的吸收剂。例如,对于10l/ha的喷雾量,将需要约5g/ha(在喷雾汤中约0.05%)的吸收剂。然而,在如此低量和如此低吸收剂浓度下,不能实现充分的吸收(参见实施例)。
此外,如上所述,根据本发明,必须存在吸收增强剂以使活性成分能够吸收到植物中以增强生物功效,同时,必须存在耐雨添加剂以防止不可接受量的洗去。
如先前申请中所示,我们已经发现,随着喷雾量减小而增加吸收剂的浓度可以弥补由于喷雾量减小而导致的覆盖范围损失(由于增强的吸收)。出乎意料地发现,喷雾量每减少50%,吸收剂的浓度应大致加倍。
因此,尽管吸收剂的绝对浓度相比于现有技术的制剂增加了,但可减少每公顷的相对总量,这在经济和生态上都是有利的,同时本发明的制剂覆盖范围和功效均得到改善、维持或至少保持在可接受的水平,同时低施用量也有其他优点,例如由于较低的商品成本使得制剂的成本较低、具有较小工作成本的较小车辆、土壤压实更少等等。
此外,我们出人意料地发现,当与不含本领域已知的漂移阻滞剂的制剂相比时,根据本发明的制剂显示出低漂移和相当的或增强的活性成分吸收。
我们同样发现,尽管吸收剂(吸收增强剂)的浓度高,但根据本发明的制剂的耐雨性和漂移减少也与基于现有技术的参考制剂的耐雨性和漂移减少相当或更佳。
此外,发现当使用植物油的甲酯作为b)时,还观察到对发泡的积极作用,即减少制剂的泡沫,特别是与有机硅氧烷扩散剂有关的泡沫。
如上所述,根据叶表面纹理,本发明的制剂特别适合于低量施用。Bico等人[Wetting of textured surface,Colloids and Surfaces A,206(2002)41-46]已经证实,与光滑的表面相比,有纹理的表面可以提高接触角度<90°的制剂喷雾稀释液的润湿,并降低触角度>90°的润湿。
当根据本发明的方法进行喷雾时,这也适用于叶表面的情况,尤其是有纹理的叶表面。
有纹理的叶表面包括表面含有微米级蜡晶体的叶片,例如大蒜、洋葱、韭菜、大豆(<GS 16(BBCH 16))、燕麦、小麦、大麦、水稻、甘蔗、菠萝、香蕉、亚麻籽、百合、兰花、玉米(<GS 15(BBCH 15))、卷心菜、甘蓝、西兰花、花椰菜、黑麦、油菜籽、郁金香和花生;以及具有表面纹理的叶片,例如荷叶。
对于有纹理的叶表面的杂草的施用显然也是如此,例如决明(Cassiaobtusifolia)、藜(Chenopodium album)、偃麦草(Agropyron repens)、大穗看麦娘(Alopecurus myosuroides)、丝状本茨草(Apera spica-venti)、野燕麦(Avena fatua)、巴拉草(Brachiaria plantaginea)、黑雀麦(Bromus secalinus)、狗牙根(Cynodondactylon)、马唐(Digitaria sanguinalis)、稗草(Echinochloa crus-galli)、洋野黍(Panicum dichotomiflorum)、早熟禾(Poa annua)、大狗尾草(Setaria faberi)和石茅(Sorghum halepense)等。
表面纹理可通过扫描电子显微镜(SEM)观察来确定。综上所述,本发明的目的是提供一种可以高(200-500l/ha或甚至更高)至低容量(即<20L/ha)施用的制剂,同时仍能提供良好的漂移减少、吸收以及对真菌病原体、杂草和害虫的生物功效,并提供良好的耐雨性,同时减少了每公顷施用的额外添加剂的量;以及一种以高至低容量(<20L/ha)使用所述制剂的方法;以及所述制剂以如上所述的低容量施用的用途。
虽然优选在有纹理的叶片上施用,但出乎意料地发现,与200L/ha的典型喷雾施用制剂相比,本发明的制剂在无纹理的叶片上也显示出良好的成果。
一些方面,本发明涉及本发明的组合物用于叶面施用的用途。
如果没有其他说明,本申请中的%表示重量百分比(%重量/重量)。
应理解,在各种成分组合的情况下,制剂中所有成分的百分比总和为100。
此外,如果没有其他说明,涉及水的“补足至容积(to volume)”表示将水加至1000mL(1L)的制剂总体积。为了清楚起见,应理解,如果不清楚,则制剂的密度应理解为1g/cm3。
在本发明的上下文中,水基农业化学组合物包括至少5%的水且包括悬浮剂、水悬液、悬乳剂或胶囊悬浮剂,优选悬浮剂和水悬液。
此外,应理解,本说明书中给出的施用量或施用率以及各成分的优选给定范围可以自由组合,并且本文公开了所有组合,然而,在一个更优选的实施方案中,所述成分优选存在于相同优选程度的范围内,甚至更优选所述成分存在于最优选的范围内。
还应理解,本发明的制剂并非是指桶混物制剂,而是指即用型(罐装物)制剂,其可以在不进一步添加佐剂(如表面活性剂、湿润剂、吸收增强剂、漂移或耐雨性桶混添加剂)的情况下使用。
图1示出了小麦叶片上的喷雾沉积物。(i)和(iii)的喷雾稀释浓度为10l/ha,(ii)和(iv)的喷雾稀释浓度为200l/ha。(i)和(ii)是对比配方,(iii)和(iv)是说明本发明的配方。图像取自实施例FN9。
图2显示了在15l/ha的喷雾稀释浓度下番茄植物上的喷雾沉积物,(i)是对比配方,(ii)是说明本发明的配方。图像取自实施例FN10。
一方面,本发明涉及一种制剂,其包括:
a)一种或多种活性成分,
b)一种或多种漂移减少剂,
d)一种或多种吸收增强剂,
e)一种或多种耐雨添加剂,
f)其他配方,
g)一种或多种补足至溶剂(1L或1kg)的载体,
其中在一个优选的实施方案中,b)是植物油或植物油的酯或二酯,在另一个实施方案中,组分b)是聚合物漂移减少剂。
在另一个优选的实施方案中,b)以0.01至50g/l存在。
如果没有其他说明,在本发明中,通常使用载体来使制剂定容。优选地,根据本发明的制剂中载体的浓度为至少5%重量/重量,更优选至少10%重量/重量,例如至少20%重量/重量、至少40%重量/重量、至少50%重量/重量、至少60%重量/重量、至少70%重量/重量和至少80%重量/重量或分别至少50g/l。更优选至少100g/l,例如至少200g/l、至少400g/l、至少500g/l、至少600g/l、至少700g/l和至少800g/l。
将该制剂优选用于作物上的喷雾施用。
在另一个优选的实施方案中,制剂是含有颗粒形式的活性成分的可流动制剂,特别是SC、SE和OD制剂。最优选的制剂是SC制剂。
在根据本发明的优选的实施方案中,同样对于说明书中的以下实施方案,载体是水。
在一个优选的实施方案中,本发明的制剂包括
a)一种或多种活性成分,
b)一种或多种漂移减少成分,
d)一种或多种吸收增强剂,
e)一种或多种耐雨添加剂,
f)任选地其他配方,
g)一种或多种补足至容积的载体,
包含以下量的组分a)至g)
a)5至500g/l,
b)0.01至50g/l,并且在b)为植物油或酯的情况下为1至50g/l,在b)为漂移减少聚合物的情况下为0.05至3g/l,
d)10至180g/l,
e)5至150g/l,
g)补足至容积的载体。
在一个优选的实施方案中,本发明的制剂包括
a)一种或多种活性成分,
b)一种或多种漂移减少成分,
d)一种或多种吸收增强剂,
e)一种或多种耐雨添加剂,
f1)至少一种合适的非离子表面活性剂和/或合适的离子表面活性剂,
f2)任选地,流变改性剂,
f3)任选地,合适的消泡物质,
f4)任选地,合适的防冻剂,
f5)任选地,合适的其他配方,
g)补足至容积的载体,
其中b)以0.01至50g/l存在,并且其中水甚至更优选作为载体,并且其中在一个优选的实施方案中,b)是植物油或植物油的酯或二酯,并且在另一个实施方案中,组分b)是聚合物漂移减少剂。
在另一个实施方案中,f2、f3、f4和f5中的至少一个是强制性的,优选地,f1、f2、f3、f4和f5中的至少两个是强制性的,并且在又一个实施方案中,f1、f2、f3、f4和f5是强制性的。
在一个优选的实施方案中,组分a)优选以5至500g/l,优选10至320g/l,最优选20至230g/l的量存在。
在一个替代的实施方案中,组分a)是杀真菌剂。
在一个替代的实施方案中,组分a)是杀虫剂。
在一个替代的实施方案中,组分a)是除草剂。
在一个优选的实施方案中,组分b)以0.01至50g/l,优选0.1至30g/l,最优选1至20g/l存在。
在b)选自植物油和酯的情况下,b)优选以1至50g/l,优选5至30g/l,最优选6至30g/l存在。
在b)选自聚合物漂移减少剂的情况下,b)优选以0.05至10g/l,优选0.1至8g/l,最优选0.2至6g/l存在。
在一个优选的实施方案中,组分d)以10至180g/l,优选20至150g/l,最优选30至140g/l存在。
在一个优选的实施方案中,组分e)以5至150g/l,优选10至100g/l,最优选20至80g/l存在。
在一个优选的实施方案中,一种或多种组分f1)以4至250g/l,优选8至120g/l,最优选10至80g/l存在。
在一个优选的实施方案中,一种或多种组分f2)以0至60g/l,优选1至20g/l,最优选2至10g/l存在。
在一个优选的实施方案中,一种或多种组分f3)以0至30g/l,优选0.5至20g/l,最优选1至12g/l存在。
在一个优选的实施方案中,一种或多种组分f4)以0至200g/l,优选5至150g/l,最优选10至120g/l存在。
在一个优选的实施方案中,一种或多种组分f5)以0至200g/l,优选0.1至120g/l,最优选0.5至80g/l存在。
在一个实施方案中,制剂包含以下量的组分a)至f)
a)5至500g/l,优选10至320g/l,最优选20至230g/l,
b)0.01至50g/l,优选0.1至30g/l,最优选1至20g/l,以及在b)为植物油或酯的情况下为1至50g/l,优选5至30g/l,最优选6至30g/l,在b)为漂移减少聚合物的情况下为0.05至10g/l,优选0.1至8g/l,最优选0.2至6g/l。
d)10至180g/l,优选20至150g/l,最优选30至140g/l,
e)5至150g/l,优选10至100g/l,最优选20至80g/l,
f)4至250g/l,优选8至120g/l,最优选10至80g/l,
g)补足至容积的载体。
在另一个实施方案中,制剂包含以下量的组分a)至f)
a)5至500g/l,优选10至320g/l,最优选20至230g/l,
b)0.01至50g/l,优选0.1至30g/l,最优选1至20g/l,以及在b)为植物油或酯的情况下为1至50g/l,优选5至30g/l,最优选6至30g/l,在b)为漂移减少聚合物的情况下为0.05至10g/l,优选0.1至8g/l,最优选0.2至6g/l。
d)10至180g/l,优选20至150g/l,最优选30至140g/l,
e)5至150g/l,优选10至100g/l,最优选20至80g/l,
f1)4至250g/l,优选8至120g/l,最优选10至80g/l,
f2)0至60g/l,优选1至20g/l,最优选2至10g/l,
f3)0至30g/l,优选0.5至20g/l,最优选1至12g/l,
f4)0至200g/l,优选5至150g/l,最优选10至120g/l,
f5)0至200g/l,优选0.1至120g/l,最优选0.5至80g/l,
g)补足至容积的载体。
应当理解,在使用固体载体的情况下,上述量是指1kg而非1l,即g/kg。
如上所述,始终将组分g)加入至容积,即至1l或1kg。
在本发明的另一个优选的实施方案中,制剂仅由指定量和范围的上述成分a)至g)组成。
在一个优选的实施方案中,除草剂与安全剂组合使用,所述安全剂优选地选自双苯恶唑酸(isoxadifen-ethyl)和吡唑解草酯(mefenpyr-diethyl)。
本发明还适用于上述制剂的施用方法,其中所述制剂以1至30l/ha,优选1至20l/ha,更优选2至15l/ha,最优选5至15l/ha的喷雾量施用。
更优选地,本发明适用于上述制剂的施用方法,其中制剂以1至30l/ha,优选1至20l/ha,更优选2至15l/ha,最优选5至15l/ha的喷雾量施用,以及a)以5至500g/l,优选10至320g/l,最优选20至230g/l的量存在,以及甚至进一步优选地b)以0.01至50g/l,优选0.1至30g/l,最优选1至20g/l的量存在,在b)为植物油或酯的情况下为1至50g/l,优选5至30g/l,最优选6至30g/l,在b)为漂移减少聚合物的情况下为0.05至10g/l,优选0.1至8g/l,最优选0.2至6g/l,以及更优选地d)以10至180g/l,优选20至150g/l,最优选30至140g/l的量存在,以及甚至进一步优选地e)以5至150g/l,优选10至100g/l,最优选20至80g/l的量存在。
在另一个方面,本发明适用于上述制剂的施用方法,
其中所述制剂以1至30l/ha,优选1至20l/ha,更优选2至15l/ha,最优选5至15l/ha的喷雾量施用,并且
其中a)对作物的施用量优选为2至150g/ha,优选5至120g/ha,更优选20至100g/ha。
此外,在b)为植物油或植物油的酯的情况下,漂移减少剂b)优选以0.1g/ha至50g/ha,更优选1g/ha至40g/ha,最优选5g/ha至30g/ha施用。
此外,在b)为聚合物的情况下,漂移减少剂b)优选以0.01g/ha至25g/ha,更优选0.05g/ha至10g/ha,最优选0.1g/ha至6g/ha施用。
与作为漂移减少剂的上述油相反,在本制剂中相应的聚合物必须以较高浓度存在,以防其将在稍后以较高喷雾量喷雾,因为稀释对其具有更强的影响。
此外,吸收剂d)优选以5g/ha至150g/ha,更优选7.5g/ha至100g/ha,最优选10g/ha至60g/ha施用。
在一个实施方案中,用上述方法施用于作物的a)的量为2至10g/ha。
在另一个实施方案中,用上述方法施用于作物的a)的量为40至110g/ha。
在上述应用的一个实施方案中,活性成分(ai)a)优选以2至150g/ha,优选5至120g/ha,更优选20至100g/ha施用,而相应地,吸收剂优选以10g/ha至100g/ha,更优选20g/ha至80g/ha,最优选40g/ha至60g/ha施用。
特别地,本发明的制剂可用于以1至20l/ha,优选2至15l/ha,更优选5至15l/ha的喷雾量施用于有纹理的叶表面的植物或作物,优选小麦、大麦、水稻、油菜籽、大豆(幼苗)和卷心菜。
此外,本发明涉及处理有纹理的叶表面的作物(优选小麦、大麦、水稻、油菜籽、大豆(幼苗)和卷心菜)的方法,喷雾量为1至20l/ha,优选2至15l/ha,更优选5至15l/ha。
在一个优选的实施方案中,将上述制剂施用于有纹理的叶表面的作物上,优选小麦、大麦、水稻、油菜籽、大豆(幼苗)和卷心菜。
在一个实施方案中,活性成分是一种杀真菌剂或两种杀真菌剂的混合物或三种杀真菌剂的混合物。
在另一个实施方案中,活性成分是一种杀虫剂或两种杀虫剂的混合物或三种杀虫剂的混合物。
在另一个实施方案中,活性成分是除草剂或两种除草剂的混合物或三种除草剂的混合物,其中优选在混合物中的混合伴侣是安全剂。
在一个实施方案中,添加剂b)至e)在如本文所述的农业化学组合物的喷雾液体中的浓度为
添加剂b)为0.005至1g/l,最优选0.04至0.6g/l,其中b)为聚合物,
添加剂b)为0.01至5g/l,最优选0.02至2.5g/l,其中b)为油,
添加剂d)为1至20g/l,最优选2至8g/l,
添加剂e)为0.5至10g/l,最优选2至6g/l。
在一个实施方案中,添加剂b)至e)在如本文所述的农业化学组合物的喷雾液体中每ha的剂量为
添加剂b)为0.05至10g/l,最优选0.4至6g/l,其中b)为聚合物,
添加剂b)为0.1至50g/l,最优选0.2至30g/l,其中b)为油,
添加剂d)为10至200g/l,最优选40至80g/l。
添加剂e)为5至100g/l,最优选20至60g/l,
在一个实施方案中,制剂中的浓度、喷雾液体中的浓度和每公顷添加剂b)至e)的剂量以以下方式组合
添加剂b)在制剂中为0.4至6g/l,在喷雾液体中为0.02至0.6g/l,b)为聚合物时为0.2至6g/ha,
添加剂b)在制剂中为0.1至50g/l,在喷雾液体中为0.01至5g/l,b)为聚合物时为0.2至30g/ha,
添加剂d)在制剂中为40至160g/l,在喷雾液体中为2至8g/l,以及40至80g/l,
添加剂e)在制剂中为20至80g/l,在喷雾液体中为1至6g/l,以及20至60g/ha。
根据本发明的制剂中的吸收剂(d)的相应剂量与施用剂量为:
2l/ha的液体制剂递送
-50g/ha吸收剂含有25g/l吸收增强剂(d)。
-30g/ha吸收剂含有15g/l吸收增强剂(d)。
-12g/ha吸收剂含有6g/l吸收增强剂(d)。
-10g/ha吸收剂含有5g/l吸收增强剂(d)。
1l/ha的液体制剂递送
50g/ha吸收剂含有50g/l吸收增强剂(d)。
30g/ha吸收剂含有30g/l吸收增强剂(d)。
12g/ha吸收剂含有12g/l吸收增强剂(d)。
10g/ha吸收剂含有10g/l吸收增强剂(d)。
0.5l/ha的液体制剂递送
50g/ha吸收剂含有100g/l吸收增强剂(d)。
30g/ha吸收剂含有60g/l吸收增强剂(d)。
12g/ha吸收剂含有24g/l吸收增强剂(d)。
10g/ha吸收剂含有20g/l吸收增强剂(d)。
0.2l/ha的液体制剂递送
50g/ha吸收剂含有250g/l吸收增强剂(d)。
30g/ha吸收剂含有150g/l吸收增强剂(d)。
12g/ha吸收剂含有60g/l吸收增强剂(d)。
10g/ha吸收剂含有50g/l吸收增强剂(d)。
2kg/ha的固体制剂递送
50g/ha吸收剂含有25g/kg吸收增强剂(d)。
30g/ha吸收剂含有15g/kg吸收增强剂(d)。
12g/ha吸收剂含有6g/kg吸收增强剂(d)。
10g/ha吸收剂含有5g/kg吸收增强剂(d)。
1kg/ha的固体制剂递送
50g/ha吸收剂含有50g/kg吸收增强剂(d)。
30g/ha吸收剂含有30g/kg吸收增强剂(d)。
12g/ha吸收剂含有12g/kg吸收增强剂(d)。
10g/ha吸收剂含有10g/kg吸收增强剂(d)。
0.5kg/ha的固体制剂递送
50g/ha吸收剂含有100g/kg吸收增强剂(d)。
30g/ha吸收剂含有60g/kg吸收增强剂(d)。
12g/ha吸收剂含有24g/kg吸收增强剂(d)。
10g/ha吸收剂含有20g/kg吸收增强剂(d)。
以其他剂量/公顷施用率施用的制剂中的吸收剂(d)的浓度可以以相同的方式计算。
在本发明的上下文中,合适的制剂类型根据定义为悬浮浓缩物、水性悬浮液、悬乳剂或胶囊悬浮液、乳剂浓缩物、水分散性颗粒、油分散体、可乳化浓缩物、可分散浓缩物、可湿性颗粒,优选悬浮浓缩物、水性悬浮液、悬乳剂和油分散体,其中在非水性制剂或固体制剂的情况下,可喷雾制剂通过加入水获得。
活性成分(a):
本文中以其“通用名称”提及的活性化合物是已知的,并且记载于例如农药手册(《农药手册(The Pesticide Manual)》,第16版,British Crop Protection Council2012)或者可以在互联网(例如http://www.alanwood.net/pesticides)上检索到。该分类以提交该专利申请时适用的IRAC作用方式分类方案为基础。
本发明的杀真菌剂(a)的实例为:
1)麦角固醇生物合成抑制剂,例如(1.001)环丙唑醇(cyproconazole)、(1.002)苄氯三唑醇(diclobutrazole)、(1.003)氟环唑(epoxiconazole)、(1.004)环酰菌胺(fenhexamid)、(1.005)苯锈啶(fenpropidin)、(1.006)丁苯吗啉(fenpropimorph)、(1.007)胺苯呲菌酮(fenpyrazamine)、(1.008)氟喹唑(fluquinconazole)、(1.009)粉唑醇(flutriafol)、(1.010)抑霉唑(imazalil)、(1.011)烯菌灵(imazalil sulphate)、(1.012)种菌唑(ipconazole)、(1.013)叶菌唑(metconazole)、(1.014)腈菌唑(myclobutanil)、(1.015)多效唑(paclobutrazole)、(1.016)咪鲜胺(prochloraz)、(1.017)丙环唑(propiconazole)、(1.018)丙硫菌唑(prothioconazole)、(1.019)啶菌唑(pyrisoxazole)、(1.020)螺环菌胺(spiroxamine)、(1.021)戊唑醇(tebuconazole)、(1.022)四氟醚唑(tetraconazole)、(1.023)三唑醇(triadimenol)、(1.024)十三吗啉(tridemorph)、(1.025)灭菌唑(triticonazole)、(1.026)(1R,2S,5S)-5-(4-氯苄基)-2-氯甲基-2-甲基-1-(1-H-1,2.4-三唑-1-亚甲基)环戊醇、(1.027)(1S,2R,5R)-5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1-H-1,2.4-三唑-1-亚甲基)环戊醇、(1.028)(2R)-2-(1-氯环丙基)-4-[(1R)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.029)(2R)-2-(1-氯代环丙基)-4-[(1S)-2,2-二氯代环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.030)(2R)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.031)(2S)-2-(1-氯环丙基)-4-[(1R)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.032)(2S)-2-(1-氯环丙基)-4-[(1S)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.033)(2S)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.034)(R)-[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.035)(S)-[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.036)[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.037)1-({(2R,4S)-2-[2-氯-4-(4-氯苯氧基)苯基]-4-甲基-1,3-二氧戊环-2-基}甲基)-1H-1,2,4-三唑、(1.038)1-({(2S,4S)-2-[2-氯-4-(4-氯苯氧基)苯基]-4-甲基-1,3-二氧戊环-2-基}甲基)-1H-1,2,4-三唑、(1.039)1-{[3-(2-氯苯基)-2-(2,4-二氟苯基)氧杂环丙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫氰酸酯、(1.040)1-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)氧杂环丙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫氰酸酯、(1.041)1-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)氧杂环丙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫氰酸酯、(1.042)2-[(2R,4R,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.043)2-[(2R,4R,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.044)2-[(2R,4S,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.045)2-[(2R,4S,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.046)2-[(2S,4R,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.047)2-[(2S,4R,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.048)2-[(2S,4S,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.049)2-[(2S,4S,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.050)2-[1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.051)2-[2-氯-4-(2,4-二氯苯氧基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.052)2-[2-氯-4-(4-二氯苯氧基)苯基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.053)2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.054)2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)戊-2-醇、(1.055)氯氟醚菌唑、(1.056)2-{[3-(2-氯苯基)-2-(2,4-二氟苯基)氧杂环丙烷-2-基]甲基}-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.057)2-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟-苯基)氧杂环丙烷-2-基]甲基}-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.058)2-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)氧杂环丙烷-2-基]甲基}-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.059)5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)环戊醇、(1.060)5-(烯丙基硫基)-1-{[3-(2-氯苯基)-2-(2,4-二氟苯基)氧杂环丙烷-2-基]甲基}-1H-1,2,4-三唑、(1.061)5-(烯丙基硫基)-1-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)氧杂环丙烷-2-基]甲基}-1H-1,2,4-三唑、(1.062)5-(烯丙基硫基)-1-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)氧杂环丙烷-2-基]甲基}-1H-1,2,4-三唑、(1.063)N'-(2,5-二甲基-4-{[3-(1,1,2,2-四氟乙氧基)苯基]硫基}苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.064)N'-(2,5-二甲基-4-{[3-(2,2,2-三氟乙氧基)苯基]硫基}苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.065)N'-(2,5-二甲基-4-{[3-(2,2,3,3-四氟丙氧基)苯基]硫基}苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.066)N'-(2,5-二甲基-4-{[3-(五氟乙氧基)苯基]硫基}苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.067)N'-(2,5-二甲基-4-{3-[(1,1,2,2-四氟乙基)硫基]苯氧基}苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.068)N'-(2,5-二甲基-4-{3-[(2,2,2-三氟乙基)硫基]苯氧基}苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.069)N'-(2,5-二甲基-4-{3-[(2,2,3,3-四氟丙基)硫基]苯氧基}苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.070)N'-(2,5-二甲基-4-{3-[(五氟乙基)硫基]苯氧基}苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.071)N'-(2,5-二甲基-4-苯氧基苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.072)N'-(4-{[3-(二氟甲氧基)苯基]硫基}-2,5-二甲基苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.073)N'-(4-{3-[(二氟甲基)硫基]苯氧基}-2,5-二甲基苯基)-N-乙基-N-甲基亚氨基甲酰胺、(1.074)N'-[5-溴-6-(2,3-二氢-1H-茚-2-基氧基)-2-甲基吡啶-3-基]-N-乙基-N-甲基亚氨基甲酰胺、(1.075)N'-{4-[(4,5-二氯-1,3-噻唑-2-基)氧基]-2,5-二甲基苯基}-N-乙基-N-甲基亚氨基甲酰胺、(1.076)N'-{5-溴-6-[(1R)-1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.077)N'-{5-溴-6-[(1S)-1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.078)N'-{5-溴-6-[(顺式-4-异丙基-环己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.079)N'-{5-溴-6-[(反式-4-异丙基环己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.080)N'-{5-溴-6-[1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.081)ipfentrifluconazole、(1.082)2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.083)2-[6-(4-溴苯氧基)-2-(三氟甲基)-3-吡啶基]-1-(1,2,4-三唑-1-基)丙-2-醇、(1.084)2-[6-(4-氯苯氧基)-2-(三氟甲基)-3-吡啶基]-1-(1,2,4-三唑-1-基)丙-2-醇、(1.085)3-[2-(1-氯环丙基)-3-(3-氯-2-氟-苯基)-2-羟基-丙基]咪唑-4-甲腈、(1.086)4-[[6-[rac-(2R)-2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(5-硫酮-4H-1,2,4-三唑-1-基)丙基]-3-吡啶]氧基]苯甲腈、(1.087)N-异丙基-N'-[5-甲氧基-2-甲基-4-(2,2,2-三氟-1-羟基-1-苯基乙基)苯基]-N-甲基亚氨基甲酰胺、(1.088)N'-{5-溴-2-甲基-6-[(1-丙氧基丙-2-基)氧基]吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.089)己唑醇(hexaconazole)、(1.090)戊菌唑(penconazole)、(1.091)腈苯唑(fenbuconazole)。
2)呼吸链复合物I或II的抑制剂,例如(2.001)苯并烯氟菌唑(benzovindiflupyr)、(2.002)联苯吡菌胺(bixafen)、(2.003)啶酰菌胺(boscalid)、(2.004)萎锈灵(carboxin)、(2.005)氟吡菌酰胺(fluopyram)、(2.006)氟酰胺(flutolanil)、(2.007)氟唑菌酰胺(fluxapyroxad)、(2.008)呋吡菌胺(furametpyr)、(2.009)异丙噻菌胺(Isofetamid)、(2.010)吡唑萘菌胺(isopyrazam)(反式差向异构对映体1R,4S,9S)、(2.011)吡唑萘菌胺(isopyrazam)(反式差向异构对映体1S,4R,9R)、(2.012)吡唑萘菌胺(isopyrazam)(反式差向异构外消旋体1RS,4SR,9SR)、(2.013)吡唑萘菌胺(isopyrazam)(顺式差向异构外消旋体1RS,4SR,9RS和反式差向异构外消旋体1RS,4SR,9SR的混合物)、(2.014)吡唑萘菌胺(isopyrazam)(顺式差向异构对映体1R,4S,9R)、(2.015)吡唑萘菌胺(isopyrazam)(顺式差向异构对映体1S,4R,9S)、(2.016)吡唑萘菌胺(isopyrazam)(顺式差向异构外消旋体1RS,4SR,9RS)、(2.017)戊苯吡菌胺(penflufen)、(2.018)吡噻菌胺(penthiopyrad)、(2.019)氟唑菌酰羟胺(pydiflumetofen)、(2.020)Pyraziflumid、(2.021)环丙吡菌胺(sedaxane)、(2.022)1,3-二甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺、(2.023)1,3-二甲基-N-[(3R)-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1H-吡唑-4-甲酰胺、(2.024)1,3-二甲基-N-[(3S)-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1H-吡唑-4-甲酰胺、(2.025)1-甲基-3-(三氟甲基)-N-[2'-(三氟甲基)联苯基-2-基]-1H-吡唑-4-甲酰胺、(2.026)2-氟-6-(三氟甲基)-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)苯甲酰胺、(2.027)3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺、(2.028)inpyrfluxam、(2.029)3-(二氟甲基)-1-甲基-N-[(3S)-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1H-吡唑-4-甲酰胺、(2.030)氟茚唑菌胺(fluindapyr)、(2.031)3-(二氟甲基)-N-[(3R)-7-氟-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1-甲基-1H-吡唑-4-甲酰胺、(2.032)3-(二氟甲基)-N-[(3S)-7-氟-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1-甲基-1H-吡唑-4-甲酰胺、(2.033)5,8-二氟-N-[2-(2-氟-4-{[4-(三氟甲基)-吡啶-2-基]氧基}苯基)乙基]喹啉-4-胺、(2.034)N-(2-环戊基-5-氟苄基)-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.035)N-(2-叔丁基-5-甲基苄基)-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.036)N-(2-叔丁基苄基)-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.037)N-(5-氯-2-乙基苄基)-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.038)isoflucypram、(2.039)N-[(1R,4S)-9-(二氯亚甲基)-1,2,3,4-四氢-1,4-亚甲基萘-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰胺、(2.040)N-[(1S,4R)-9-(二氯亚甲基)-1,2,3,4-四氢-1,4-亚甲基萘-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰胺、(2.041)N-[1-(2,4-二氯苯基)-1-甲氧基丙-2-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰胺、(2.042)N-[2-氯-6-(三氟甲基)苄基]-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.043)N-[3-氯-2-氟-6-(三氟甲基)苄基]-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.044)N-[5-氯-2-(三氟甲基)苄基]-N-环丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.045)N-环丙基-3-(二氟甲基)-5-氟-1-甲基-N-[5-甲基-2-(三氟甲基)苄基]-1H-吡唑-4-甲酰胺、(2.046)N-环丙基-3-(二氟甲基)-5-氟-N-(2-氟-6-异丙基苄基)-1-甲基-1H-吡唑-4-甲酰胺、(2.047)N-环丙基-3-(二氟甲基)-5-氟-N-(2-异丙基-5-甲基苄基)-1-甲基-1H-吡唑-4-甲酰胺、(2.048)N-环丙基-3-(二氟甲基)-5-氟-N-(2-异丙基苄基)-1-甲基-1H-吡唑-4-硫代甲酰胺、(2.049)N-环丙基-3-(二氟甲基)-5-氟-N-(2-异丙基苄基)-1-甲基-1H-吡唑-4-甲酰胺、(2.050)N-环丙基-3-(二氟甲基)-5-氟-N-(5-氟-2-异丙基苄基)-1-甲基-1H-吡唑-4-甲酰胺、(2.051)N-环丙基-3-(二氟甲基)-N-(2-乙基-4,5-二甲基苄基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.052)N-环丙基-3-(二氟甲基)-N-(2-乙基-5-氟苄基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.053)N-环丙基-3-(二氟甲基)-N-(2-乙基-5-甲基苄基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.054)N-环丙基-N-(2-环丙基-5-氟苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.055)N-环丙基-N-(2-环丙基-5-甲基苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.056)N-环丙基-N-(2-环丙基苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲酰胺、(2.057)pyrapropoyne、(2.058)N-[rac-(1S,2S)-2-(2,4-二氯苯基)环丁基]-2-(三氟甲基)-烟酰胺、(2.059)N-[(1S,2S)-2-(2,4-二氯苯基)环丁基]-2-(三氟甲基)烟酰胺。
3)呼吸链复合物III抑制剂,例如(3.001)辛唑嘧菌胺(ametoctradin)、(3.002)吲唑磺菌胺(amisulbrom)、(3.003)嘧菌酯(azoxystrobin)、(3.004)甲香菌酯(coumethoxystrobin)、(3.005)coumoxystrobin、(3.006)氰霜唑(cyazofamid)、(3.007)醚菌胺(dimoxystrobin)、(3.008)烯肟菌酯(enestroburin)、(3.009)噁唑菌酮(famoxadone)、(3.010)咪唑菌酮(fenamidone)、(3.011)氟菌螨酯(flufenoxystrobin),(3.012)氟嘧菌酯(fluoxastrobin)、(3.013)醚菌酯(kresoxim-methyl)、(3.014)苯氧菌胺(metominostrobin)、(3.015)肟醚菌胺(orysastrobin)、(3.016)啶氧菌酯(picoxystrobin)、(3.017)唑菌胺酯(pyraclostrobin)(3.018)唑胺菌酯(pyrametostrobin)、(3.019)唑菌酯(pyraoxystrobin)、(3.020)肟菌酯(trifloxystrobin)、(3.021)(2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-氟-2-苯基乙烯基]氧基}苯基)亚乙基]氨基}氧基)甲基]苯基}-2-(甲氧基亚氨基)-N-甲基乙酰胺、(3.022)(2E,3Z)-5-{[1-(4-氯苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亚氨基)-N,3-二甲基戊-3-酰胺、(3.023)(2R)-2-{2-[(2,5-二甲基苯氧基)甲基]苯基}-2-甲氧基-N-甲基乙酰胺、(3.024)(2S)-2-{2-[(2,5-二甲基苯氧基)甲基]苯基}-2-甲氧基-N-甲基乙酰胺、(3.025)fenpicoxamid、(3.026)mandestrobin、(3.027)N-(3-乙基-3,5,5-三甲基环乙基)-3-甲酰胺-2-羟基苯甲酰胺、(3.028)(2E,3Z)-5-{[1-(4-氯-2-氟苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亚氨基)-N,3-二甲基戊-3-酰胺、(3.029){5-[3-(2,4-二甲基苯基)-1H-吡唑-1-基]-2-甲基苄基}氨基甲酸甲酯、(3.030)metyltetraprole、(3.031)florylpicoxamid。
4)有丝分裂和细胞分裂的抑制剂,例如(4.001)多菌灵(carbendazim)、(4.002)乙霉威(diethofencarb)、(4.003)噻唑菌胺(ethaboxam)、(4.004)氟吡菌胺(fluopicolide)、(4.005)戊菌隆(pencycuron)、(4.006)噻菌灵(thiabendazole)、(4.007)甲基硫菌灵(thiophanate-methyl)、(4.008)苯酰菌胺(zoxamide)、(4.009)pyridachlometyl、(4.010)3-氯-5-(4-氯苯基)-4-(2,6-二氟苯基)-6-甲基哒嗪、(4.011)3-氯-5-(6-氯吡啶-3-基)-6-甲基-4-(2,4,6-三氟苯基)哒嗪、(4.012)4-(2-溴-4-氟苯基)-N-(2,6-二氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.013)4-(2-溴-4-氟苯基)-N-(2-溴-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.014)4-(2-溴-4-氟苯基)-N-(2-溴苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.015)4-(2-溴-4-氟苯基)-N-(2-氯-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.016)4-(2-溴-4-氟苯基)-N-(2-氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.017)4-(2-溴-4-氟苯基)-N-(2-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.018)4-(2-氯-4-氟苯基)-N-(2,6-二氟苯基)-1,3-二苯基-1H-吡唑-5-胺、(4.019)4-(2-氯-4-氟苯基)-N-(2-氯-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.020)4-(2-氯-4-氟苯基)-N-(2-氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.021)4-(2-氯-4-氟苯基)-N-(2-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.022)4-(4-氯苯基)-5-(2,6-二氟苯基)-3,6-二甲基哒嗪、(4.023)N-(2-溴-6-氟苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.024)N-(2-溴苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.025)N-(4-氯-2,6-二氟苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.026)氟醚菌酰胺(fluopimomide)。
5)具有多位点作用的化合物,例如(5.001)波尔多液(Bordeaux mixture)、(5.002)敌菌丹(captafol)、(5.003)克菌丹(captan)、(5.004)百菌清(chlorothalonil)、(5.005)氢氧化铜(copper hydroxide)、(5.006)环烷酸铜(copper naphthenate)、(5.007)氧化铜(copper oxide)、(5.008)氧氯化铜(copper oxychloride)、(5.009)硫酸铜(copper(2+)sulphate)、(5.010)二噻农(dithianon)、(5.011)多果定(dodine)、(5.012)灭菌丹(folpet)、(5.013)代森锰锌(mancozeb)、(5.014)锌代森锰(maneb)、(5.015)代森联(metiram)、(5.016)metiram zinc、(5.017)喹啉铜(oxine-copper)、(5.018)丙森锌(propineb)、(5.019)包括多硫化钙的硫和硫制剂、(5.020)福美双(thiram)、(5.021)代森锌(zineb)、(5.022)福美锌(ziram)、(5.023)6-乙基-5,7-二氧代-6,7-二氢-5H-吡咯并[3',4':5,6][1,4]二噻英并[2,3-c][1,2]噻唑-3-甲腈。
6)能诱导宿主防御的化合物,例如(6.001)苯并噻二唑(acibenzolar-S-methyl)、(6.002)异噻菌胺(isotianil)、(6.003)烯丙苯噻唑(probenazole)、(6.004)噻酰菌胺(tiadinil)。
7)氨基酸和/或蛋白质生物合成的抑制剂,例如(7.001)嘧菌环胺(cyprodinil)、(7.002)春雷霉素(kasugamycin)、(7.003)春雷霉素盐酸盐水合物(kasugamycinhydrochloride hydrate)、(7.004)氧四环素(oxytetracycline)、(7.005)嘧霉胺(pyrimethanil)、(7.006)3-(5-氟-3,3,4,4-四甲基-3,4-二氢异喹啉-1-基)喹啉。
8)ATP产生抑制剂,例如(8.001)硅噻菌胺(silthiofam)。
9)细胞壁合成的抑制剂,例如(9.001)苯噻菌胺(benthiavalicarb)、(9.002)烯酰吗啉(dimethomorph)、(9.003)氟吗啉(flumorph)、(9.004)异丙菌胺(iprovalicarb)、(9.005)双炔酰菌胺(mandipropamid)、(9.006)吡吗啉(pyrimorph)、(9.007)霜霉灭(valifenalate)、(9.008)(2E)-3-(4-叔丁基苯基)-3-(2-氯吡啶-4-基)-1-(吗啉-4-基)丙-2-烯-1-酮、(9.009)(2Z)-3-(4-叔丁基苯基)-3-(2-氯吡啶-4-基)-1-(吗啉-4-基)丙-2-烯-1-酮。
10)脂质和膜合成抑制剂,例如(10.001)霜霉威(propamocarb)、(10.002)霜霉威盐酸盐(propamocarb hydrochloride)、(10.003)甲基立枯磷(tolclofos-methyl)。
11)黑色素生物合成抑制剂,例如(11.001)三环唑(tricyclazole)、(11.002)tolprocarb。
12)核酸合成抑制剂,例如(12.001)苯霜灵(benalaxyl)、(12.002)精苯霜灵(benalaxyl-M、kiralaxyl)、(12.003)甲霜灵(metalaxyl)、(12.004)高效甲霜灵(metalaxyl-M)(精甲霜灵(mefenoxam))。
13)信号转导抑制剂,例如(13.001)咯菌腈(fludioxonil)、(13.002)异菌脲(iprodione)、(13.003)腐霉利(procymidone)、(13.004)丙氧喹啉(proquinazid)、(13.005)喹氧灵(quinoxyfen)、(13.006)乙烯菌核利(vinclozolin)。
14)能够作为解偶联剂的化合物,例如(14.001)氟啶胺(fluazinam)、(14.002)消螨多(meptyldinocap)。
15)其他杀真菌剂,其选自(15.001)脱落酸(abscisic acid)、(15.002)苯噻硫氰(benthiazole)、(15.003)bethoxazin、(15.004)卡巴西霉素(capsimycin)、(15.005)香芹酮(carvone)、(15.006)灭螨猛(chinomethionat)、(15.007)硫杂灵(cufraneb)、(15.008)环氟菌胺(cyflufenamid)、(15.009)霜脲氰(cymoxanil)、(15.010)环丙磺酰胺(cyprosulfamide)、(15.011)flutianil、(15.012)三乙膦酸铝(fosetyl-aluminium)、(15.013)三乙膦酸钙(fosetyl-calcium)、(15.014)三乙膦酸钠(fosetyl-sodium)、(15.015)异硫氰酸甲酯(methyl isothiocyanate)、(15.016)苯菌酮(metrafenon)、(15.017)米多霉素(mildiomycin)、(15.018)纳他霉素(natamycin)、(15.019)福美镍(nickel dimethyldithiocarbamate)、(15.020)酞菌酯(nitrothal-isopropyl)、(15.021)oxamocarb、(15.022)氟噻唑吡乙酮(oxathiapiprolin)、(15.023)oxyfenthiin、(15.024)五氯苯酚及盐、(15.025)亚磷酸及其盐、(15.026)霜霉威乙膦酸盐(propamocarb-fosetylate)、(15.027)pyriofenone(chlazafenone)、(15.028)异丁乙氧喹啉(tebufloquin)、(15.029)叶枯酞(tecloftalam)、(15.030)甲磺菌胺(tolnifanide)、(15.031)1-(4-{4-[(5R)-5-(2,6-二氟苯基)-4,5-二氢-1,2-噁唑-3-基]-1,3-噻唑-2-基}哌啶-1-基)-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、(15.032)1-(4-{4-[(5S)-5-(2,6-二氟苯基)-4,5-二氢-1,2-噁唑-3-基]-1,3-噻唑-2-基}哌啶-1-基)-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、(15.033)2-(6-苄基吡啶-2-基)喹唑啉、(15.034)dipymetitrone、(15.035)2-[3,5-双(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-丙-2-炔-1-基氧基)苯基]-4,5-二氢-1,2-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(15.036)2-[3,5-双(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-氯-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氢-1,2-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(15.037)2-[3,5-双(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-氟-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氢-1,2-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(15.038)2-[6-(3-氟-4-甲氧基苯基)-5-甲基吡啶-2-基]喹唑啉、(15.039)2-{(5R)-3-[2-(1-{[3,5-双(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氢-1,2-噁唑-5-基}-3-氯苯基甲磺酸酯、(15.040)2-{(5S)-3-[2-(1-{[3,5-双(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氢-1,2-噁唑-5-基}-3-氯苯基甲磺酸酯、(15.041)Ipflufenoquin、(15.042)2-{2-氟-6-[(8-氟-2-甲基喹啉-3-基)氧基]苯基}丙-2-醇、(15.043)fluoxapiprolin、(15.044)2-{3-[2-(1-{[3,5-双(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氢-1,2-噁唑-5-基}苯基甲磺酸酯、(15.045)2-苯基苯酚及其盐、(15.046)3-(4,4,5-三氟-3,3-二甲基-3,4-二氢异喹啉-1-基)喹啉、(15.047)quinofumelin、(15.048)4-氨基-5-氟嘧啶-2-醇(互变异构形式:4-氨基-5-氟嘧啶-2(1H)-酮)、(15.049)4-氧代-4-[(2-苯基乙基)氨基]丁酸、(15.050)5-氨基-1,3,4-噻二唑-2-硫醇、(15.051)5-氯-N'-苯基-N'-(丙-2-炔-1-基)噻吩-2-磺酰肼、(15.052)5-氟-2-[(4-氟苄基)氧基]嘧啶-4-胺、(15.053)5-氟-2-[(4-甲基苄基)氧基]嘧啶-4-胺、(15.054)9-氟-2,2-二甲基-5-(喹啉-3-基)-2,3-二氢-1,4-苯并氧杂吖庚因、(15.055){6-[({[(Z)-(1-甲基-1H-四唑-5-基)(苯基)亚甲基]氨基}氧基)甲基]吡啶-2-基}氨基甲酸丁-3-炔-1-基酯、(15.056)(2Z)-3-氨基-2-氰基-3-苯基丙烯酸乙酯、(15.057)吩嗪-1-甲酸、(15.058)3,4,5-三羟基苯甲酸丙酯、(15.059)喹啉-8-醇、(15.060)喹啉-8-醇硫酸酯(2:1)、(15.061){6-[({[(1-甲基-1H-四唑-5-基)(苯基)亚甲基]氨基}氧基)甲基]吡啶-2-基}氨基甲酸叔丁酯、(15.062)5-氟-4-亚氨基-3-甲基-1-[(4-甲基苯基)磺酰基]-3,4-二氢嘧啶-2(1H)-酮、(15.063)aminopyrifen、(15.064)(N'-[2-氯-4-(2-氟苯氧基)-5-甲基苯基]-N-乙基-N-甲基亚氨基甲酰胺)、(15.065)(N'-(2-氯-5-甲基-4苯氧基苯基)-N-乙基-N-甲基亚氨基甲酰胺)、(15.066)(2-{2-[(7,8-二氟-2-甲基喹啉-3-基)氧代]-6-氟苯基}丙-2-醇)、(15.067)(5-溴-1-(5,6-二甲基吡啶-3-基)-3,3-二甲基-3,4-二氢异喹啉)、(15.068)(3-(4,4-二氟-5,5-二甲基-4,5-二氢噻吩并[2,3-c]吡啶-7-基)喹啉)、(15.069)(1-(4,5-二甲基-1H-苯并咪唑-1-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉)、(15.070)8-氟-3-(5-氟-3,3-二甲基-3,4-二氢异喹啉-1-基)喹诺酮、(15.071)8-氟-3-(5-氟-3,3,4,4-四甲基-3,4-二氢异喹啉-1-基)喹诺酮、(15.072)3-(4,4-二氟-3,3-二甲基-3,4-二氢异喹啉-1-基)-8-氟喹啉、(15.073)(N-甲基-N-苯基-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺)、(15.074){4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基}氨基甲酸甲酯、(15.075)(N-{4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苄基}环丙烷甲酰胺)、(15.076)N-甲基-4-(5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.077)N-[(E)-甲氧基亚氨基-甲基]-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.078)N-[(Z)-甲氧基亚氨基甲基]-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.079)N-[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]环丙烷甲酰胺、(15.080)N-(2-氟苯基)-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.081)2,2-二氟-N-甲基-2-[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]乙酰胺、(15.082)N-烯丙基-N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基)苯基]甲基]乙酰胺、(15.083)N-[(E)-N-甲氧基-C-甲基-碳酰亚胺基]-4-(5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.084)N-[(Z)-N-甲氧基-C-甲基-碳酰亚胺基]-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.085)N-烯丙基-N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]丙酰胺、(15.086)4,4-二甲基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]吡咯烷-2-酮、(15.087)N-甲基-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯硫代甲酰胺、(15.088)5-甲基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]吡咯烷-2-酮、(15.089)N-((2,3-二氟-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]-3,3,3-三氟丙酰胺、(15.090)1-甲氧基-1-甲基-3-[[4-[5-(三氟甲基}-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.091)1,1-二乙基-3-[[4-[5-(三氟甲基}-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.092)N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]丙酰胺、(15.093)N-甲氧基-N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]环丙烷甲酰胺、(15.094)1-甲氧基-3-甲基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.095)N-甲氧基-N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]环丙烷甲酰胺、(15.096)N,2-二甲氧基-N-[[4-[5-(三氟甲基}-1,2,4-噁二唑-3-基]苯基]甲基]丙酰胺、(15.097)N-乙基-2-甲基-N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基)苯基]甲基]丙酰胺、(15.098)1-甲氧基-3-甲基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.099)1,3-二甲氧基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.100)3-乙基-1-甲氧基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.101)1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]哌啶-2-酮、(15.102)4,4-二甲基-2-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]-甲基]异噁唑烷-3-酮、(15.103)5,5-二甲基-2-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]异噁唑烷-3-酮、(15.104)3,3-二甲基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]哌啶-2-酮、(15.105)1-[[3-氟-4-(5-(三氟甲基)-1,2,4-噁二唑3-基]-苯基]甲基]氮杂环庚-2-酮、(15.106)4,4-二甲基-2-[[4-(5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]异噁唑-3-酮、(15.107)5,5-二甲基-2-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]异噁唑-3-酮、(15.108)1-{4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苄基}-1H-吡唑-4-甲酸乙酯、(15.109)N,N-二甲基-1-{4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苄基}-1H-1,2,4-三唑-3-胺、(15.110)N-{2,3-二氟-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苄基}丁酰胺、(15.111)N-(1-甲基环丙基)-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.112)N-(2,4-二氟苯基)-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.113)1-(5,6-二甲基吡啶-3-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.114)1-(6-(二氟甲基)-5-甲基-吡啶-3-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.115)1-(5-(氟甲基)-6-甲基-吡啶-3-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.116)1-(6-(二氟甲基)-5-甲氧基-吡啶-3-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.117)4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基二甲基-氨基酸甲酯、(15.118)N-{4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基}丙酰胺、(15.119)3-[2-(1-{[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-1,5-二氢-2,4-苯并二氧杂环庚烯-6-基甲磺酸酯、(15.120)9-氟-3-[2-(1-{[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-1,5-二氢-2,4-苯并二氧杂环庚烯-6-基甲磺酸酯、(15.121)3-[2-(1-{[3,5-双(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-1,5-二氢-2,4-苯并二氧杂环庚烯-6-基甲磺酸酯、(15.122)3-[2-(1-{[3,5-二(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-9-氟-1,5-二氢-2,4-苯并二氧杂环庚烯-6-基甲磺酸酯、(15.123)1-(6,7-二甲基吡唑并[1,5-a]吡啶-3-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.124)8-氟-N-(4,4,4-三氟-2-甲基-1-苯基丁-2-基)喹啉-3-甲酰胺、(15.125)8-氟-N-[(2S)-4,4,4-三氟-2-甲基-1-苯基丁-2-基]喹啉-3-甲酰胺、(15.126)N-(2,4-二甲基-1-苯基戊-2-基)-8-氟喹啉-3-甲酰胺和(15.127)N-[(2S)-2,4-二甲基-1-苯基戊-2-基)-8-氟喹啉-3-甲酰胺。
根据本发明的杀虫剂(a)的实例是:
(1)乙酰胆碱酯酶(Acetylcholinesterase)(AChE)抑制剂,例如氨基甲酸盐:棉铃威(alanycarb)、涕灭威(aldicarb)、噁虫威(bendiocarb)、丙硫克百威(benfuracarb)、丁酮威(butocarboxim)、丁酮砜威(butoxycarboxim)、甲萘威(carbaryl)、克百威(carbofuran)、丁硫克百威(carbosulfan)、乙硫苯威(ethiofencarb)、仲丁威(fenobucarb)、伐虫脒(formetanate)、呋线威(furathiocarb)、异丙威(isoprocarb)、甲硫威(methiocarb)、灭多威(methomyl)、速灭威(metolcarb)、杀线威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、久效威(thiofanox)、唑蚜威(triazamate)、混杀威(trimethacarb)、XMC和灭杀威(xylylcarb);或有机磷酸酯类:乙酰甲胺磷(acephate)、甲基吡恶磷(azamethiphos)、益棉磷(azinphos-ethyl)、保棉磷(azinphos-methyl)、硫线磷(cadusafos)、氯氧磷(chlorethoxyfos)、毒虫畏(chlorfenvinphos)、氯甲硫磷(chlormephos)、甲基毒死蜱(chlorpyrifos-methyl)、蝇毒磷(coumaphos)、杀螟腈(cyanophos)、甲基内吸磷(demeton-S-methyl)、二嗪农(diazinon)、敌敌畏(dichlorvos/DDVP)、百治磷(dicrotophos)、乐果(dimethoate)、甲基毒虫畏(dimethylvinphos)、乙拌磷(disulphoton)、苯硫磷(EPN)、乙硫磷(ethion)、灭线磷(ethoprophos)、伐灭磷(famphur)、苯线磷(fenamiphos)、杀螟硫磷(fenitrothion)、倍硫磷(fenthion)、噻唑酮磷(fosthiazate)、庚烯磷(heptenophos)、imicyafos、异柳磷(isofenphos)、O-(甲氧基氨基硫代磷酰基)水杨酸异丙酯(isopropyl O-(methoxyaminothiophosphoryl)salicylate)、恶唑磷(isoxathion)、马拉硫磷(malathion)、灭蚜磷(mecarbam)、甲胺磷(methamidophos)、杀扑磷(methidathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、二溴磷(naled)、氧乐果(omethoate)、亚砜磷(oxydemeton-methyl)、甲基对硫磷(parathion-methyl)、稻丰散(phenthoate)、甲拌磷(phorate)、伏杀硫磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、辛硫磷(phoxim)、嘧啶磷(pirimiphos-methyl)、丙溴磷(profenofos)、胺丙畏(propetamphos)、丙硫磷(prothiofos)、吡唑硫磷(pyraclofos)、哒嗪硫磷(pyridaphenthion)、喹噁磷(quinalphos)、治螟磷(sulfotep)、丁基嘧啶磷(tebupirimfos)、双硫磷(temephos)、特丁硫磷(terbufos)、杀虫畏(tetrachlorvinphos)、甲基乙拌磷(thiometon)、三唑磷(triazophos)、敌百虫(triclorfon)和蚜灭磷(vamidothion)。
(2)GABA门控氯化物通道阻断剂,优选的环戊二烯-有机氯类,其选自氯丹(chlordane)和硫丹(endosulfan);或苯基吡唑类(phenylpyrazoles(fiproles)),其选自乙虫腈(ethiprole)和氟虫腈(fipronil)。
(3)钠通道调节剂/电压依赖性钠通道阻滞剂,例如拟除虫菊酯类,例如氟丙菊酯(acrinathrin)、丙烯菊酯(allethrin)、d-顺-反丙烯菊酯
(d-cis-trans allethrin)、d-反丙烯菊酯(d-trans allethrin)、氟氯菊酯(bifenthrin)、生物烯丙菊酯(bioallethrin)、生物烯丙菊酯-S-环戊烯基异构体(bioallethrin s-cyclopentenyl isomer)、生物烯丙菊酯(bioresmethrin)、乙氰菊酯(cycloprothrin)、氟氯氰菊酯(cyfluthrin)、β-氟氯氰菊酯(beta-cyfluthrin)、氯氟氰菊酯(cyhalothrin)、λ-氯氟氰菊酯(lambda-cyhalothrin)、γ-氯氟氰菊酯(gamma-cyhalothrin)、氯氰菊酯(cypermethrin)、α-氯氰菊酯(alpha-cypermethrin)、β-氯氰菊酯(beta-cypermethrin)、θ-氯氰菊酯(theta-cypermethrin)、ζ-氯氰菊酯(zeta-cypermethrin)、苯醚氰菊酯(1R-反式异构体)(cyphenothrin[(1R)-trans-isomers])、溴氰菊酯(deltamethrin)、右旋烯炔菊酯((EZ)-1R异构体)(empenthrin[(EZ)-(1R)-isomers])、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、氰杀菊酯(fenvalerate)、氟氰戊菊酯(flucythrinate)、氟氯苯菊酯(flumethrin)、τ-氟胺氰菊酯(tau-fluvalinate)、溴氟醚菊酯(halfenprox)、咪炔菊酯(imiprothrin)、噻嗯菊酯(kadethrin)、momfluorothrin,氯菊酯(permethrin)、苯醚菊酯(1R-反式异构体)(phenothrin(1R-transisomer)、右旋炔丙菊酯(prallethrin)、除虫菊素(pyrethrins)(除虫菊(pyrethrum))、苄呋菊酯(resmethrin)、氟硅菊酯(silafluofen)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、胺菊酯[(1R)-异构体]、四溴菊酯(tralomethrin)和四氟苯菊酯(transfluthrin),或DDT或甲氧滴滴涕(methoxychlor)。
(4)烟碱乙酰胆碱受体(nAChR)竞争性调节剂,优选新烟碱类(neonicotinoids),其选自啶虫脒(acetamiprid)、噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、烯啶虫胺(nitenpyram)、噻虫啉(thiacloprid)和噻虫嗪(thiamethoxam);或烟碱(nicotine);或磺酰胺类(sulfoximines),其选自氟啶虫胺腈(sulfoxaflor);或丁烯羟酸内酯(butenolids),其选自氟吡呋喃酮(flupyradifurone);或中离子(mesoionics),其选自三氟苯嘧啶(triflumezopyrim)。
(5)烟碱乙酰胆碱受体(nAChR)变构调节剂(位点I),优选多杀霉素类(spinosyns),其选自乙基多杀菌素(spinetoram)和多杀菌素(spinosad)。
(6)谷氨酸盐门控氯化物通道(GluCl)变构调节剂,优选阿维菌素类(avermectins)/米尔贝霉素类(milbemycins),其选自阿维菌素(abamectin)、甲氨基阿维菌素苯甲酸盐(emamectin benzoate)、雷皮菌素(lepimectin)和米尔倍霉素(milbemycin)。
(7)保幼激素类似物类,优选保幼激素类似物,选自烯虫乙酯(hydroprene)、烯虫炔酯(kinoprene)和烯虫酯(methoprene)、或苯氧威(fenoxycarb)或吡丙醚(pyriproxifen)。
(8)各类非特异性(多位点)抑制剂,优选卤代烃,其选自甲基溴化物和其他卤代烃,或氯化苦(chloropicrine)或磺酰基氟化物(sulphuryl fluoride)或硼砂(borax)或吐酒石(tartar emetic)或异氰酸甲酯激发剂,其选自棉隆(diazomet)和威百亩(metam)。
(9)弦音器TRPV通道调节剂,选自吡蚜酮(pymetrozin)和氟虫吡喹(pyrifluquinazon)。
(10)螨生长抑制剂,其选自四螨嗪(clofentezine)、噻螨酮(hexythiazox)、氟螨嗪(diflovidazin)和乙螨唑(etoxazole)。
(11)昆虫肠膜的微生物干扰剂,其选自苏云金芽孢杆菌以色列亚种(Bacillusthuringiensis subspecies israelensis)、球星芽孢杆菌(Bacillus sphaericus)、苏云金芽胞杆菌鲇泽亚种(Bacillus thuringiensis subspecies aizawai)、苏云金芽孢杆菌库尔斯塔克亚种(Bacillus thuringiensis subspecies kurstaki)、苏云金芽孢杆菌粉虫亚种(Bacillus thuringiensis subspecies tenebrionis),以及B.t植物蛋白,其选自Cry1Ab、Cry1Ac、Cry1Fa、Cry1A.105、Cry2Ab、Vip3A、mCry3A、Cry3Ab、Cry3Bb和Cry34Ab1/35Ab1。
(12)线粒体ATP合酶抑制剂,优选ATP干扰剂类,其选自丁醚脲(diafenthiuron);或有机锡化合物,其选自三唑锡(azocyclotin)、三环锡(cyhexatin)、苯丁锡(fenbutatin-oxide);或炔螨特(propargite)或三氯杀螨砜(tetradifon)。
(13)通过破坏质子梯度起作用的氧化磷酸化解偶联剂,其选自虫螨腈(chlorfenapyr)、二硝甲酚(DNOC)和氟虫胺(sulfluramid)。
(14)烟碱乙酰胆碱受体通道阻断剂,其选自杀虫磺(bensultap)、杀螟丹盐酸盐(cartap-hydrochloride)、杀虫环(thiocylam)和杀虫双(thiosultap-sodium)。
(15)0型几丁质生物合成抑制剂,选自双三氟虫脲(bistrifluron)、氟啶脲(chlofluazuron)、除虫脲(diflubenzuron)、氟环脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、虱螨脲(lufenuron)、氟酰脲(novaluron)、多氟脲(noviflumuron)、氟苯脲(teflubenzuron)和杀铃脲(triflumuron)。
(16)1型几丁质生物合成抑制剂,选自噻嗪酮(buprofezin)。
(17)蜕皮干扰剂类(特别是双翅目,即双翅目昆虫),选自灭蝇胺(cyromazine)。
(18)蜕皮激素受体激动剂,选自环虫酰肼(chromafenozid)、氯虫酰肼(halofenozid)、甲氧虫酰肼(methoxyfenozid)和虫酰肼(tebufenozid)。
(19)章鱼胺受体激动剂,选自双甲脒(amitraz)。
(20)线粒体复合体III电子转移抑制剂,选自灭蚁腙(hydramethylnone)、灭螨醌(acequinocyl)和嘧螨酯(fluacrypyrim)。
(21)线粒体复合体I电子转移抑制剂,优选所谓的METI杀螨剂,其选自喹螨醚(fenazaquin)、唑螨酯(fenpyroximat)、嘧螨醚(pyrimidifen)、哒螨灵(pyridaben)、吡螨胺(tebufenpyrad)和唑虫酰胺(tolfenpyrad)、或鱼藤酮(rotenone(Derris))。
(22)电位依赖性钠通道阻断剂,选自茚虫威(indoxacarb)和氰氟虫胺(metaflumizone)。
(23)乙酰辅酶A羧化酶抑制剂,优选特窗酸和特胺酸(tetronic and tetramicacid)衍生物,其选自螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramat)和spidoxamate(IUPAC名:1l-(4-氯-2,6-甲苄基)-12-羟基-1,4-二氧杂-9-氮杂二螺[4.2.4.2]十四烷基-11-烯-10-酮)。
(24)线粒体复合体IV电子转移抑制剂,优选磷化物(phosphides),其选自磷化铝、磷化钙、磷化氢和磷化锌;或氰化物,其选自氰化钙、氰化钾和氰化钠。
(25)线粒体复合体II电子转移抑制剂,优选β-开托利(beta-ketonitrile)衍生物,其选自唑螨氰(cyenopyrafen)和丁氟螨酯(cyflumetofen);或羧酰替苯胺类(carboxanilides),其选自pyflubumide。
(28)兰尼碱(ryanodin)受体调节剂,优选二酰胺,其选自氯虫酰胺(chlorantraniliprol)、溴氰虫酰胺(cyantraniliprol)和氟虫酰胺(flubendiamid)。
(29)弦音器调节剂(具有不确定靶点),其选自氟啶虫酰胺(flonicamid)。
(30)其他活性化合物,选自Acynonapyr、双丙环虫酯(Afidopyropen)、阿福拉纳(Afoxolaner)、印楝素(Azadirachtin)、Benclothiaz、苯螨特(Benzoximat)、Benzpyrimoxan、Bifenazat、Broflanilid、溴螨酯(Bromopropylat)、灭螨猛(Chinomethionat)、右旋反式氯丙炔菊酯(Chloroprallethrin)、冰晶石(Cryolit)、Cyclaniliprol、环氧虫啶(Cycloxaprid)、氯氟氰虫酰胺(Cyhalodiamid)、二氯噻吡嘧啶(Dicloromezotiaz)、三氯杀螨醇(Dicofol)、嗪虫唑酰胺(Dimpropyridaz)、ε-甲氧苄氟菊酯(epsilon-Metofluthrin)、epsilon-Momfluthrin、Flometoquin、三氟咪啶酰胺(Fluazaindolizin)、联氟砜(Fluensulfon)、嘧虫胺(Flufenerim)、氟菌螨酯(Flufenoxystrobin)、丁虫腈(Flufiprol)、Fluhexafon、氟吡菌酰胺(Fluopyram)、Flupyrimin、氟雷拉纳(Fluralaner)、Fluxametamid、Fufenozid、戊吡虫胍(Guadipyr)、七氟甲醚菊酯(Heptafluthrin)、氯噻啉(Imidaclothiz)、异菌脲(Iprodione)、异噁唑虫酰胺(Isocycloseram)、kappa-联苯菊酯(kappa-Bifenthrin)、kappa-七氟菊酯(kappa-Tefluthrin)、洛替拉纳(Lotilaner)、美氟菊酯(Meperfluthrin)、Oxazosulfyl、哌虫啶(Paichongding)、三氟甲吡醚(Pyridalyl)、氟虫吡喹(Pyrifluquinazon)、嘧螨胺(Pyriminostrobin)、螺螨双酯(Spirobudiclofen)、甲氧哌啶乙酯(Spiropidion)、四氟醚菊酯(Tetramethylfluthrin)、Tetraniliprol、四氯虫酰胺(Tetrachlorantraniliprol)、Tigolaner、Tioxazafen、硫氟肟醚(Thiofluoximat)和碘甲烷(Iodomethan);坚强芽孢杆菌(Bacillus firmus)产品(I-1582,BioNeem,Votivo),以及下列化合物:1-{2-氟-4-甲基-5-[(2,2,2-三氟乙烷)亚磺酰基]苯基}-3-(三氟甲基)-1H-1,2,4-三唑-5-胺(由WO 2006/043635知)(CAS 885026-50-6)、{1'-[(2E)-3-(4-氯苯基)丙-2-炔-1-基]-5-氟螺环[吲哚-3,4'-哌啶]-1(2H)-基}(2-氯吡啶-4-基)甲酮(由WO
2003/106457知)(CAS 637360-23-7)、2-氯-N-[2-{1-[(2E)-3-(4-氯苯基)丙-2-炔-1-基]哌啶-4-基}-4-(三氟甲基)苯基]异烟酰胺(由WO 2006/003494知)(CAS 872999-66-1)、3-(4-氯2,6-二甲基苯基)-4-羟基-8-甲氧基-1,8-二氮杂螺环[4.5]葵-3-烯-2-酮(由WO 2010/052161知)(CAS 1225292-17-0)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-2-氧-1,8-二氮杂螺环[4.5]dec-3-en-4-yl乙烷基碳酸盐(由EP 2647626知)(CAS 1440516-42-6)、4-(丁-2-炔-1-氧基)-6-(3,5-二甲基哌啶-1-基)-5-氟嘧啶(由WO 2004/099160知)(CAS 792914-58-0)、PF1364(由JP 2010/018586知)(CAS Reg号1204776-60-2)、(3E)-3-[1-[(6-氯-3-吡啶基)甲基]-2-吡啶亚基]-1,1,1-三氟-丙-2-酮(由WO 2013/144213知)(CAS 1461743-15-6)、N-[3-(苄氧基羰基)-4-氯苯基]-1-甲基3-(五氟乙基)-4-(三氟甲基)-1H-吡唑-5-甲酰胺(由WO 2010/051926知)(CAS 1226889-14-0)、5-溴-4-氯-N-[4-氯-2-甲基-6-(甲基氨基甲酰基)苯基]-2-(3-氯-2-吡啶基)吡唑-3-甲酰胺(由CN 103232431知)(CAS 1449220-44-3)、4-[5-(3,5-二氯苯基)-4,5-二氢-5-(三氟甲基)-3-异噁唑基]-2-甲基-N-(顺式-1-氧负离子基-3-硫杂环丁基)-苯甲酰胺、4-[5-(3,5-二氯苯基)-4,5-二氢-5-(三氟甲基)-3-异噁唑基]-2-甲基-N-(反式-1-氧负离子基-3-硫杂环丁基)-苯甲酰胺和4-[(5S)-5-(3,5-二氯苯基)-4,5-二氢-5-(三氟甲基)-3-异噁唑基]-2-甲基-N-(顺式-1-氧负离子基-3-硫杂环丁基)-苯甲酰胺(由WO 2013/050317A1知)(CAS 1332628-83-7)、N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亚硫酰基]-丙酰胺、(+)-N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亚磺酰基]-丙酰胺和(-)-N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亚磺酰基]-丙酰胺(由WO 2013/162715 A2,WO 2013/162716 A2,美国2014/0213448A1知)(CAS 1477923-37-7)、5-[[(2E)-3-氯-2-丙烯-1-基]氨基]-1-[2,6-二氯-4-(三氟甲基)苯基]-4-[(三氟甲基)亚磺酰基]-1H-吡唑-3-甲腈(由CN 101337937 A知)(CAS 1105672-77-2)、3-溴-N-[4-氯-2-甲基-6-[(甲胺基)甲酸基]苯基]-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺、(Liudaibenjiaxuanan,由CN 103109816 A知)(CAS 1232543-85-9);N-[4-氯-2-[[(1,1-二甲基乙基)氨基]羰基]-6-甲基苯基]-1-(3-氯-2-吡啶基)-3-(氟甲氧基)-1H-吡唑-5-甲酰胺(由WO 2012/034403 A1知)(CAS 1268277-22-0)、N-[2-(5-氨基-1,3,4-噻二唑-2-基)-4-氯-6-甲基苯基]-3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(由WO 2011/085575 A1知)(CAS 1233882-22-8)、4-[3-[2,6-二氯-4-[(3,3-二氯-2-丙烯-1-基)氧基]苯氧基]丙氧基]-2-甲氧基-6-(三氟甲基)-嘧啶(由CN 101337940 A知)(CAS 1108184-52-6);(2E)-和2(Z)-2-[2-(4-苯腈)-1-[3-(三氟甲基)苯基]亚乙基]-N-[4-(二氟甲氧基)苯基]-肼甲酰胺(由CN 101715774 A知)(CAS 1232543-85-9);3-(2,2-二氯乙烯基)-2,2-二甲基-4-(1H-苯并咪唑-2-基)苯基-环丙甲酸酯(由CN 103524422A知)(CAS 1542271-46-4);(4aS)-7-氯-2,5-二氢-2-[[(甲酯基)[4-[(三氟甲基)硫基]苯基]氨基]羰基]-茚并[1,2-e][1,3,4]噁二嗪-4a(3H)-羧酸甲酯(由CN 102391261A知)(CAS 1370358-69-2);6-脱氧-3-O-乙基-2,4-二-O-甲基-,1-[N-[4-[1-[4-(1,1,2,2,2-五氟乙氧基)苯基]-1H-1,2,4-三唑-3-基]苯基]氨基甲酸酯]-α-L-吡喃甘露糖(由美国2014/0275503A1知)(CAS1181213-14-8);8-(2-环丙基甲氧基-4-三氟甲基-苯氧基)-3-(6-三氟甲基-哒嗪-3-基)-3-硫唑嘌呤-双环醇并[3.2.1]辛烷(CAS 1253850-56-4)、(8-反式)-8-(2-环丙基甲氧基-4-三氟甲基-苯氧基)-3-(6-三氟甲基-哒嗪-3-基)-3-硫唑嘌呤-双环醇并[3.2.1]辛烷(CAS 933798-27-7)、(8-顺式)-8-(2-环丙基甲氧基-4-三氟甲基-苯氧基)-3-(6-三氟甲基-哒嗪-3-基)-3-硫唑嘌呤-双环醇并[3.2.1]辛烷(由WO 2007/040280A1,WO 2007/040282 A1知)(CAS 934001-66-8)、N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)硫基]-丙酰胺(由WO 2015/058021A1,WO 2015/058028 A1知)(CAS1477919-27-9)和N-[4-(甲氧基氨基)-2-甲基-6-[(甲胺基)羰基]苯基]-3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(由CN 103265527 A知)(CAS 1452877-50-7)、5-(1,3-二噁烷-2-基)-4-[[4-(三氟甲基)苯基]甲氧基]-嘧啶(由WO 2013/115391 A1知)(CAS 1449021-97-9)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-1-甲基-1,8-二氮杂螺环[4.5]癸烷-2,4-二酮(由WO 2014/187846 A1知)(CAS 1638765-58-8)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-1-甲基-2-氧基-1,8-二氮杂螺环[4.5]癸-3-烯-4-基-碳酸乙酯(由O 2010/066780A1,WO2011151146 A1知)(CAS 1229023-00-0)、4-[(5S)-5-(3,5-二氯-4-氟苯基)-4,5-二氢-5-(三氟甲基)-3-异噁唑基]-N-[(4R)-2-乙基-3-氧基-4-异噁唑烷基]-2-甲基-苯甲酰胺(由WO 2011/067272,WO 2013/050302知)(CAS 1309959-62-3)。
除草剂a)根据本发明的实例有:
乙草胺(Acetochlor)、三氟羧草醚(acifluorfen)、三氟羧草醚钠盐(acifluorfen-sodium)、苯草醚(aclonifen)、甲草胺(alachlor)、二丙烯草胺(allidochlor)、禾草灭(alloxydim)、禾草灭钠盐(alloxydim-sodium)、莠灭净(ametryn)、氨唑草酮(amicarbazone)、先甲草胺(amidochlor)、酰嘧磺隆(amidosulfuron)、4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶-2-羧酸、环丙嘧啶酸(aminocyclopyrachlor)、环丙嘧啶酸钾盐(aminocyclopyrachlor-potassium)、环丙嘧啶酸甲酯(aminocyclopyrachlor-methyl)、氨基吡啶酸(aminopyralid)、杀草强(amitrole)、氨基磺酸铵(ammoniumsulfamate)、莎稗磷(anilofos)、黄草灵(asulam)、阿特拉津(atrazine)、草芬定(azafenidin)、四唑嘧磺隆(azimsulfuron)、氟丁酰草胺(beflubutamid)、草除灵(benazolin)、草除灵乙酯(benazolin-ethyl)、氟草胺(benfluralin)、呋草黄(benfuresate)、苄嘧磺隆(bensulfuron)、苄嘧磺隆甲酯(bensulfuron-methyl)、地散磷(bensulide)、噻草平(bentazone)、苯并双环酮(benzobicyclon)、吡草酮(benzofenap)、双环哌喃酮(bicyclopyron)、治草醚(bifenox)、双丙氨酰膦(bilanafos)、双丙氨酰膦钠盐(bilanafos-sodium)、双草醚(bispyribac)、双草醚钠盐(bispyribac-sodium)、bixlozone、除草定(bromacil)、溴丁酰草胺(bromobutide)、溴酚肟(bromofenoxim)、溴苯腈(bromoxynil)、溴苯腈丁酸盐、钾盐、庚酯和辛酸酯(bromoxynil-butyrate、-potassium、-heptanoate and-octanoate)、羟草酮(busoxinone)、丁草胺(butachlor)、氟丙嘧草酯(butafenacil)、抑草磷(butamifos)、丁烯草胺(butenachlor)、双丁乐灵(butralin)、丁氧环酮(butroxydim)、丁草敌(butylate)、唑草胺(cafenstrole)、卡草胺(carbetamide)、唑草酮(carfentrazone)、唑草酮乙酯(carfentrazone-ethyl)、草灭平(chloramben)、灭落宁(chlorbromuron)、1-{2-氯-3-[(3-环丙基-5-羟基-1-甲基-1H-吡唑-4-基)羰基]-6-(三氟甲基)苯基}哌啶-2-酮、4-{2-氯-3-[(3,5-二甲基-1H-吡唑-1-基)甲基]-4-(甲基磺酰基)苯甲酰}-1,3-二甲基-1H-吡唑-5-基-1,3-二甲基-1H-吡唑-4-羧酸盐、伐草克(chlorfenac)、伐草克钠盐(chlorfenac-sodium)、燕麦酯(chlorfenprop)、整形醇(chlorflurenol)、整形醇甲酯(chlorflurenol-methyl)、氯草敏(chloridazon)、氯嘧磺隆(chlorimuron)、氯嘧磺隆乙酯(chlorimuron-ethyl)、2-[2-氯-4-(甲基磺酰基)-3-(吗啉-4-基甲基)苯甲酰]-3-羟基环己-2-烯-1-酮、4-{2-氯-4-(甲基磺酰基)-3-[(2,2,2-三氟乙氧基)甲基]苯甲酰}-1-乙基-1H-吡唑-5-基-1,3-二甲基-1H-吡唑-4-羧酸盐、氯肽亚胺(chlorophthalim)、氯麦隆(chlorotoluron)、敌草索二甲基酯(chlorthal-dimethyl)、3-[5-氯-4-(三氟甲基)吡啶-2-基]-4-羟基-1-甲基咪唑烷-2-酮)、氯磺隆(chlorsulfuron)、吲哚酮(cinidon)、吲哚酮乙酯(cinidon-ethyl)、环庚草醚(cinmethylin)、醚磺隆(cinosulfuron)、氯酰草膦(clacyfos)、克草同(clethodim)、炔草酸(clodinafop)、炔草酯(clodinafop-propargyl)、可灭踪(clomazone)、稗草胺(clomeprop)、二氯吡啶酸(clopyralid)、氯酯磺草胺(cloransulam)、氯酯磺草胺甲酯(cloransulam-methyl)、苄草隆(cumyluron)、氨腈(cyanamide)、氰草津(cyanazine)、环草敌(cycloate)、cyclopyranil、环哒草特(cyclopyrimorate)、环磺隆(cyclosulfamuron)、环杀草(cycloxydim)、氰氟草酸(cyhalofop)、氰氟草酯(cyhalofop-butyl)、环草津(cyprazine)、2,4-D、2,4-D-丁氧基乙酯、丁基、二甲基胺、二乙醇胺、乙酯、-2-乙基己酯、异丁基、异辛基、异丙基铵盐、钾盐、三异丙醇铵盐和三乙醇胺(2,4-D、2,4-D-butotyl、-butyl、-dimethylammonium、-diolamin、-ethyl、-2-ethylhexyl、-isobutyl、-isooctyl、-isopropylammonium、-potassium、-triisopropanolammonium,and–trolamine)、2,4-DB、2,4-DB-丁基、二甲基铵盐、异辛基、钾盐和钠盐(2,4-DB、2,4-DB-butyl、-dimethylammonium、-isooctyl、-potassium,and-sodium)、杀草隆(daimuron(dymron))、茅草枯(dalapon)、棉隆(dazomet)、正癸醇(n-decanol)、甜菜安(desmedipham)、吡唑特(detosyl-pyrazolate(DTP))、百草敌(dicamba)、敌草腈(dichlobenil)、滴丙酸(dichlorprop)、精滴丙酸(dichlorprop-P)、禾草灵(diclofop)、禾草灵甲酯(diclofop-methyl)、精禾草灵甲酯(diclofop-P-methyl)、双氯磺草胺(diclosulam)、野燕枯(difenzoquat)、吡氟草胺(diflufenican)、二氟吡隆(diflufenzopyr)、二氟吡隆钠盐(diflufenzopyr-sodium)、噁唑隆(dimefuron)、哌草丹(dimepiperate)、二甲草胺(dimethachlor)、异戊乙净(dimethametryn)、二甲酚草胺(dimethenamid)、精二甲酚草胺(dimethenamid-P)、3-(2,6-二甲基苯基)-6-[(2-羟基-6-氧基环己-1-烯-1-基)羰基]-1-甲基二氮杂萘-2,4(1H,3H)-二酮、1,3-二甲基-4-[2-(甲基磺酰基)-4-(三氟甲基)苯甲酰]-1H-吡唑-5-基-1,3-二甲基-1H-吡唑-4-羧酸盐、醚黄隆(dimetrasulfuron)、敌乐胺(dinitramine)、特乐酚(dinoterb)、草乃敌(diphenamid)、敌草快(diquat)、敌草快二溴化物(diquat-dibromid)、氟氯草定(dithiopyr)、敌草隆(diuron)、DMPA、DNOC、草多索(endothal)、EPTC、戊草丹(esprocarb)、烯氟灵(ethalfluralin)、胺苯磺隆(ethametsulfuron)、胺苯磺隆甲酯(ethametsulfuron-methyl)、乙嗪草酮(ethiozin)、乙呋草黄(ethofumesate)、氯氟草醚(ethoxyfen)、氯氟草醚乙酯(ethoxyfen-ethyl)、乙氧嘧磺隆(ethoxysulfuron)、乙氧苯草胺(etobenzanid)、([(3-{2-氯-4-氟-5-[3-甲基-2,6-二氧基-4-(三氟甲基)-3,6-二氢嘧啶-1(2H)-基]苯氧基}吡啶-2-基)氧基]乙酸乙酯、F-9960、F-5231,即N-{2-氯-4-氟-5-[4-(3-氟丙基)-5-氧基-4,5-二氢-1H-四唑-1-基]苯基}乙基磺酰胺、F-7967,即3-[7-氯-5-氟-2-(三氟甲基)-1H-苯并咪唑-4-基]-1-甲基-6-(三氟甲基)嘧啶-2,4(1H,3H)-二酮、噁唑禾草灵(fenoxaprop)、精噁唑禾草灵(fenoxaprop-P)、噁唑禾草灵乙酯(fenoxaprop-ethyl)、精噁唑禾草灵乙酯(fenoxaprop-P-ethyl)、异噁苯砜(fenoxasulfone)、fenquinotrione、四唑酰草胺(fentrazamide)、氟燕灵(flamprop)、高效氟燕灵异丙酯(flamprop-M-isopropyl)、高效氟燕灵甲酯(flamprop-M-methyl)、嘧啶磺隆(flazasulfuron)、双氟磺草胺(florasulam)、氟禾草灵(fluazifop)、精氟禾草灵(fluazifop-P)、氟禾草灵丁酯(fluazifop-butyl)、精氟禾草灵丁酯(fluazifop-P-butyl)、氟酮磺隆(flucarbazone)、氟酮磺隆钠盐(flucarbazone-sodium)、氟吡磺隆(flucetosulfuron)、氟消草(fluchloralin)、氟噻草胺(flufenacet)、氟哒嗪(flufenpyr)、氟哒嗪草酯(flufenpyr-ethyl)、唑嘧磺草胺(flumetsulam)、氟亚胺(flumiclorac)、氟亚胺草酯(flumiclorac-pentyl)、丙炔氟草胺(flumioxazin)、伏草隆(fluometuron)、芴丁酸(flurenol)、芴丁酯、二甲基铵盐和甲酯(flurenol-butyl、-dimethylammonium and-methyl)、乙羧氟草醚(fluoroglycofen)、乙羧氟草醚乙酯(fluoroglycofen-ethyl)、氟丙酸(flupropanate)、氟啶嘧磺隆(flupyrsulfuron)、氟啶嘧磺隆甲酯钠盐(flupyrsulfuron-methyl-sodium)、氟啶草酮(fluridone)、氟咯草酮(fluro-chloridone)、氟草烟(fluroxypyr)、氟草烟异辛酯(fluroxypyr-meptyl)、呋草酮(flurtamone)、氟噻草酯(fluthiacet)、氟噻草酯甲酯(fluthiacet-methyl)、氟磺胺草醚(fomesafen)、氟磺胺草醚钠盐(fomesafen-sodium)、甲酰胺磺隆(foramsulfuron)、杀木膦(fosamine)、草铵膦(glufosinate)、草铵膦铵盐(glufosinate-ammonium)、精草铵膦钠盐(glufosinate-P-sodium)、精草铵膦铵盐(glufosinate-P-ammonium)、精草铵膦钠盐(glufosinate-P-sodium)、草甘膦(glyphosate)、草甘膦铵盐、异丙基铵盐、二铵盐、钾盐、钠盐和三甲基硫盐(glyphosate-ammonium,-isopropylammonium,-diammonium,-dimethylammonium,-potassium,-sodium,and–trimesium)、H-9201,即O-(2,4-二甲基-6-硝基苯基)O-乙基异丙基硫代磷酰胺酯、哈洛昔芬(halauxifen)、氟氯吡啶酯(halauxifen-methyl)、氟硝磺酰胺(halosafen)、氯吡嘧磺隆(halosulfuron)、氯吡嘧磺隆甲酯(halosulfuron-methyl)、合氯氟(haloxyfop)、精合氯氟(haloxyfop-P)、合氯氟乙氧基乙酯(haloxyfop-ethoxyethyl)、精合氯氟乙氧基乙酯(haloxyfop-P-ethoxyethyl)、合氯氟甲酯(haloxyfop-methyl)、精合氯氟甲酯(haloxyfop-P-methyl)、环嗪酮(hexazinone)、HW-02,即1-(二甲氧基磷酰基)(2,4-二氯苯氧基)乙酸乙酯、4-羟基-1-甲氧基-5-甲基-3-[4-(三氟甲基)吡啶-2-基]咪唑烷-2-酮、4-羟基-1-甲基-3-[4-(三氟甲基)吡啶-2-基]咪唑烷-2-酮、(5-羟基-1-甲基-1H-吡唑-4-基)(3,3,4-三甲基-1,1-二氧化-2,3-二氢-1-苯并噻吩-5-基)甲酮、6-[(2-羟基-6-氧基环己-1-烯-1-基)羰基]-1,5-二甲基-3-(2-甲基苯基)二氮杂萘-2,4(1H,3H)-二酮、咪草酸(imazamethabenz)、咪草酸甲酯(imazamethabenz-methyl)、甲氧咪草烟(imazamox)、甲氧咪草烟铵盐(imazamox-ammonium)、甲咪唑烟酸(imazapic)、甲咪唑烟酸铵盐(imazapic-ammonium)、灭草烟(imazapyr)、灭草烟异丙基铵盐(imazapyr-isopropylammonium)、咪唑喹啉酸(imazaquin)、咪唑喹啉酸铵盐(imazaquin-ammonium)、咪唑乙烟酸(imazethapyr)、咪唑乙烟酸亚铵盐(imazethapyr-immonium)、唑吡嘧磺隆(imazosulfuron)、茚草酮(indanofan)、三嗪茚草胺(indaziflam)、碘磺隆(iodosulfuron)、碘磺隆甲酯钠盐(iodosulfuron-methyl-sodium)、碘苯腈(ioxynil)、碘苯腈辛酸盐、钾盐和钠盐(ioxynil-octanoate、-potassium and-sodium)、卤苯胺唑(ipfencarbazone)、异丙隆(isoproturon)、异噁隆(isouron)、异噁酰草胺(isoxaben)、异噁唑草酮(isoxaflutole)、卡草灵(karbutilate)、KUH-043,即3-({[5-(二氟甲基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-基]甲基}磺酰基)-5,5-二甲基-4,5-二氢-1,2-噁唑、keto-spiradox、禾草灵(lactofen)、环草定(lenacil)、利谷隆(linuron)、MCPA、MCPA丁氧基乙酯、二甲基铵盐、-2-乙基己酯、异丙基铵盐、钾盐和钠盐(MCPA-butotyl、-dimethylammonium、-2-ethylhexyl、-isopropylammonium、-potassium、and-sodium)、MCPB、MCPB甲酯、乙酯和钠盐(MCPB-methyl、-ethyl and–sodium)、2-甲-4-氯丙酸(mecoprop)、2-甲-4-氯丙酸钠盐和丁氧基乙酯(mecoprop-sodium,and-butotyl)、精2-甲-4-氯丙酸(mecoprop-P)、精2-甲-4-氯丙酸丁氧基乙酯、二甲基铵盐、-2-乙基己酯和钾盐(mecoprop-P-butotyl、-dimethylammonium、-2-ethylhexyl、and-potassium)、苯噻草胺(mefenacet)、氟磺酰草胺(mefluidide)、磺胺磺隆(mesosulfuron)、磺胺磺隆甲酯(mesosulfuron-methyl)、硝磺草酮(mesotrione)、甲基苯噻隆(methabenzthiazuron)、斯美地(metam)、噁唑酰草胺(metamifop)、苯嗪草酮(metamitron)、灭草胺(metazachlor)、双醚氯吡嘧磺隆(metazosulfuron)、甲基苯噻隆(methabenzthiazuron)、甲硫嘧磺隆(methiopyrsulfuron)、美西除灵(methiozolin)、2-({2-[(2-甲氧基乙氧基)甲基]-6-(三氟甲基)吡啶-3-基}羰基)环已醇-1,3-二酮、异硫氰酸甲酯、1-甲基-4-[(3,3,4-三甲基-1,1-二氧化-2,3-二氢-1-苯并噻吩-5-基)羰基]-1H-吡唑-5-基丙烷-1-磺酸盐、秀谷隆(metobromuron)、异丙甲草胺(metolachlor)、精异丙甲草胺(S-metolachlor)、磺草唑胺(metosulam)、甲氧隆(metoxuron)、嗪草酮(metribuzin)、甲磺隆(metsulfuron)、甲磺隆甲酯(metsulfuron-methyl)、草达灭(molinat)、绿谷隆(monolinuron)、单嘧磺隆(monosulfuron)、单嘧磺隆酯(monosulfuron-ester)、MT-5950,即N-(3-氯-4-异丙基苯基)-2-甲基戊酰胺、NGGC-011、灭落脱(napropamide)、NC-310,即[5-(苄氧基)-1-甲基-1H-吡唑-4-基](2,4-二氯苯基)-甲酮、草不隆(neburon)、烟嘧磺隆(nicosulfuron)、壬酸(nonanoic acid(pelargonic acid))、氟草敏(norflurazon)、油酸(oleic acid(fattyacids))、坪草丹(orbencarb)、嘧苯胺磺隆(orthosulfamuron)、安磺灵(oryzalin)、丙炔噁草酮(oxadiargyl)、噁草酮(oxadiazon)、乙氧氟草醚(oxasulfuron)、噁嗪草酮(oxaziclomefon)、乙氧氟草醚(oxyfluorfen)、百草枯(paraquat)、百草枯二氯盐(paraquat dichloride)、克草猛(pebulate)、二甲戊灵(pendimethalin)、五氟磺草胺(penoxsulam)、五氯苯酚(pentachlorphenol)、环戊恶草酮(pentoxazone)、烯草胺(pethoxamid)、石油(petroleum oils)、甜菜宁(phenmedipham)、毒莠定(picloram)、氟吡草胺(picolinafen)、唑啉草酯(pinoxaden)、哌草磷(piperophos)、丙草胺(pretilachlor)、氟嘧磺隆(primisulfuron)、氟嘧磺隆甲酯(primisulfuron-methyl)、氨基丙氟灵(prodiamine)、环苯草酮(profoxydim)、扑灭通(prometon)、扑草净(prometryn)、扑草胺(propachlor)、敌稗(propanil)、喔草酯(propaquizafop)、扑灭津(propazine)、苯胺灵(propham)、异丙草胺(propisochlor)、丙苯磺隆(propoxy-carbazone)、丙苯磺隆钠盐(propoxycarbazone-sodium)、丙嘧磺隆(propyrisulfuron)、戊炔草胺(propyzamide)、苄草丹(prosulfocarb)、氟磺隆(prosulfuron)、双唑草腈(pyraclonil)、吡草醚(pyraflufen)、吡草醚乙酯(pyraflufen-ethyl)、磺酰草吡唑(pyrasulfotole)、吡唑特(pyrazolynate(pyrazolate))、吡嘧磺隆(pyrazosulfuron)、吡嘧磺隆乙酯(pyrazosulfuron-ethyl)、苄草唑(pyrazoxyfen)、酯草醚(pyribambenz)、异丙酯草醚(pyribambenz-isopropyl)、丙酯草醚(pyribambenz-propyl)、嘧啶肟草醚(pyribenzoxim)、稗草丹(pyributicarb)、吡啶达醇(pyridafol)、哒草特(pyridate)、环酯草醚(pyriftalid)、嘧草醚(pyriminobac)、嘧草醚甲酯(pyriminobac-methyl)、嘧啶硫蕃(pyrimi-sulfan)、嘧硫草醚(pyrithiobac)、嘧硫草醚钠盐(pyrithiobac-sodium)、嘧氧砜(pyroxasulfone)、甲氧磺草胺(pyroxsulam)、二氯喹啉酸(quinclorac)、氯甲喹啉酸(quinmerac)、灭藻醌(quino-clamine)、喹禾灵(quizalofop)、喹禾灵乙酯(quizalofop-ethyl)、精喹禾灵(quizalofop-P)、精喹禾灵乙酯(quizalofop-P-ethyl)、精喹禾灵糖酯(quizalofop-P-tefuryl)、QYM-201、QYR-301、砜嘧磺隆(rimsulfuron)、苯嘧磺草胺(saflufenacil)、稀禾定(sethoxydim)、环草隆(siduron)、西玛津(simazine)、西草净(simetryn)、SL-261、磺草酮(sulcotrion)、氟磺唑草胺(sulfentrazone)、嘧磺隆(sulfometuron)、嘧磺隆甲酯(sulfometuron-methyl)、磺酰磺隆(sulfosulfuron)、SYN-523、SYP-249,即1-乙氧基-3-甲基-1-氧基丁-3-烯-2-基5-[2-氯-4-(三氟甲基)苯氧基]-2-硝基苯甲酸盐、SYP-300,即1-[7-氟-3-氧基-4-(丙-2-炔-1-基)-3,4-二氢-2H-1,4-苯并噁嗪-6-基]-3-丙基-2-硫代咪唑烷-4,5-二酮、2,3,6-TBA、TCA(三氯乙酸)、TCA钠盐、丁噻隆(tebuthiuron)、特呋三酮(tefuryltrione)、环磺酮(tembotrione)、吡喃草酮(tepraloxydim)、特草定(terbacil)、特草定(terbucarb)、特丁通(terbumeton)、特丁津(terbuthylazin)、特丁净(terbutryn)、四氟络草胺(tetflupyrolimet)、甲氧噻草胺(thenylchlor)、噻唑烟酸(thiazopyr)、噻酮磺隆(thiencarbazone)、噻酮磺隆甲酯(thiencarbazone-methyl)、噻吩磺隆(thifensulfuron)、噻吩磺隆甲酯(thifensulfuron-methyl)、禾草丹(thiobencarb)、氟嘧硫草酯(tiafenacil)、tolpyralate、吡草磺(topramezone)、三甲苯草酮(tralkoxydim)、氟酮磺草胺(triafamone)、野麦畏(tri-allate)、醚苯磺隆(triasulfuron)、三嗪氟草胺(triaziflam)、苯磺隆(tribenuron)、苯磺隆甲酯(tribenuron-methyl)、绿草定(triclopyr)、草达津(trietazine)、三氟啶磺隆(trifloxysulfuron)、三氟啶磺隆钠盐(trifloxysulfuron-sodium)、三氟草嗪(trifludimoxazin)、氟乐灵(trifluralin)、氟胺磺隆(triflusulfuron)、氟胺磺隆甲酯(triflusulfuron-methyl)、甲磺隆(tritosulfuron)、硝酸尿素(urea sulfate)、灭草猛(vernolate)、ZJ-0862,即3,4-二氯-N-{2-[(4,6-二甲氧基嘧啶-2-基)氧基]苄基}苯胺。
至少一种活性成分优选地选自杀真菌剂,所述杀真菌剂选自如上文所述的类别(1)呼吸链复合物的抑制剂,特别是唑类,(2)呼吸链复合物I或II的抑制剂,(3)呼吸链复合物的抑制剂,(4)有丝分裂和细胞分裂的抑制剂,(6)能够诱导宿主防御的化合物,(10)脂质和膜合成的抑制剂,和(15)。
进一步优选的,作为杀真菌剂的至少一种活性成分a)选自肟菌酯、联苯吡菌胺、丙硫菌唑、Inpyrfluxam、Isoflucypram、氟吡菌胺、氟吡菌酰胺、Fluoxapiprolin。
至少一种杀虫剂优选地选自如上文所述类别的杀虫剂:(2)GABA门控氯化物通道拮抗剂、(3)钠通道调节剂/电压依赖性钠通道阻滞剂、(4)烟碱乙酰胆碱受体(nAChR)竞争性调节剂、(23)乙酰辅酶A羧化酶抑制剂、(28)兰尼碱受体调节剂、(30)其他活性成分。
还进一步优选地,作为杀虫剂的至少一种活性成分a)选自螺虫乙酯、四唑虫酰胺(Tetraniliprole)、乙虫腈、吡虫啉、溴氰菊酯、氟吡呋喃酮。
最后进一步优选地,作为除草剂的至少一种活性成分a)选自氟酮磺草胺(triafamone)、环磺酮(tembotrione)、噻酮磺隆甲酯(thiencarbazone-methyl),优选与安全剂双苯恶唑酸(isoxadifen-ethyl)和cyprosulfamat结合。
甚至更优选地,至少一种活性成分选自肟菌酯、联苯吡菌胺、丙硫菌唑、inpyrfluxam、isoflucypram、氟吡菌胺、氟吡菌酰胺、fluoxapiprolin、螺虫乙酯、四唑虫酰胺、乙虫腈、吡虫啉、溴氰菊酯、氟吡呋喃酮、氟酮磺草胺、环磺酮、噻酮磺隆甲酯、双苯恶唑酸和cyprosulfamat。
如上所述的所有命名的活性成分可以以游离化合物的形式存在,或者如果其官能团允许的话,以其农业化学活性盐的形式存在。
此外,在适用的情况下,应包括内消旋形式以及立体异构体或对映异构体,因为这些修饰以及多晶型修饰是本领域技术人员所熟知的。
如果没有特别说明,本发明中的固体农业化学活性化合物a)应理解为常用于植物处理的所有物质,其熔点高于20℃。
漂移减少剂(b)
合适的漂移减少剂是聚(环氧乙烷),其中聚合物具有优选0.5至12百万g/mol,更优选0.75至10百万g/mol,最优选1至8百万g/mol的平均分子量,和羟丙基瓜尔胶,以及植物油和植物油酯和二酯(包括与甘油和丙二醇的酯)。
特别优选地为甲基、乙基、异丙基、异丁基、丁基、己基和乙基己基酯。
更优选地,植物油和酯选自油酸甲酯、棕榈酸甲酯、菜籽油甲酯、肉豆蔻酸异丙酯、棕榈酸异丙酯、棕榈酸乙基己酯、油酸乙基己酯、肉豆蔻酸乙基己酯/月桂酸乙基己酯的混合物、月桂酸乙基己酯、辛酸乙基己酯/癸酸乙基己酯的混合物、己二酸二异丙酯、椰子油丙二醇二酯、向日葵油、菜籽油、玉米油、大豆油、米糠油、棕榈油、花生油、混合的辛酸和癸酸甘油三酯、以及混合的癸酰和辛酰甘油酯。
矿物油也适合作为漂移减少剂。
吸收增强剂(d)
吸收增强剂还可以选自以下化合物的组:
其它合适的吸收增强剂为醇乙氧基化物,优选地选自乙氧基化醇、丙氧基-乙氧基化醇、乙氧基化羧酸、丙氧基-乙氧基化羧酸或包含具有8-18个碳原子和平均5-40个EO单元的脂肪酸的甘油的乙氧基化单酯、二酯或三酯。所述乙氧基化或丙氧基-乙氧基化醇或羧酸任选地通过向剩余的醇官能团添加甲基以进一步改性(参见“Me末端加帽”)。根据d)的术语“醇”是指可以是支链或直链的、饱和或不饱和的、具有6-22个碳原子并且任选地带有额外的取代基(如OH基团)的醇。根据d)的术语“羧酸”是指可以是支链或直链的、饱和或不饱和的、具有6-22个碳原子并且任选地带有额外的取代基(如OH基团)的羧酸。
根据d)的合适的组分例如为:
-具有2-20个EO单元的乙氧基化直链和/或支链脂肪醇(例如,Clariant的X型);
-包含2-20个EO单元的甲基末端加帽的乙氧基化直链和/或支链脂肪醇(例如,Clariant的XM型);
-包含2-20个EO单元的乙氧基化椰子醇(例如,Clariant的C型);
-包含2-20个EO单元的乙氧基化C12/15醇(例如,Croda的A型);
-支链或直链的丙氧基乙氧基化醇,例如Solvay的B/848、Croda的G5000、Levaco的/>HOT 5902;
-丙氧基乙氧基化脂肪酸,Me末端加帽,例如Lion的OC0503M;
-烷基醚柠檬酸盐表面活性剂(例如Adsee CE range、Akzo Nobel);
-烷基聚糖类(例如BASF的PG8107、PG8105;Croda的/>438、AL-2559、AL-2575);
-包含具有8-18个碳原子和平均10-40个EO单元的脂肪酸的乙氧基化甘油单酯或二酯(例如Croda的产品系列);
-包含平均5-40个EO单元的蓖麻油乙氧基化物(例如Nouryon的系列、Clariant的/>EL系列);
-包含2-20个EO单元的乙氧基化油酸(例如A和AP);
-包含具有8-18个碳原子和平均10-50个EO单元的脂肪酸的乙氧基化脱水山梨糖醇脂肪酸酯(例如T、Tween系列)。
耐雨添加剂(e)
合适的耐雨添加剂是丙烯酸基乳液聚合物或聚合物分散体和苯乙烯基乳液聚合物或聚合物分散体。d)是Tg在-100℃至30℃、优选-60℃至20℃、更优选-50℃至10℃、最优选-45℃至5℃范围内的水性聚合物分散体,例如Acronal V215、Acronal 3612、Acronal361、Licomer ADH 205和Atplus FA。特别优选的是Licomer ADH205和Atplus FA。
优选地,聚合物选自丙烯酸基聚合物、苯乙烯聚合物、乙烯基聚合物及其衍生物、聚烯烃、聚氨酯和天然聚合物及其衍生物。
更优选地,所述聚合物选自丙烯酸聚合物、苯乙烯丁二烯共聚物、苯乙烯-马来酸酐共聚物、聚乙烯醇、聚乙酸乙烯酯、部分水解的聚乙酸乙烯酯、甲基乙烯基醚-马来酸酐共聚物、羧基改性的聚乙烯醇、乙酰乙酰基改性的聚乙烯醇、二丙酮改性的聚乙烯醇和硅改性的聚乙烯醇、异丙基-马来酸酐共聚物、聚氨酯、聚乙烯醇、纤维素、明胶、酪蛋白、氧化淀粉、淀粉-乙酸乙烯酯接枝共聚物、羟乙基纤维素、甲基纤维素、乙基纤维素、羧甲基纤维素和乙酰纤维素。
最优选地,聚合物选自丙烯酸酯和苯乙烯的共聚物,其中,所述丙烯酸酯选自包括丙烯酸2-乙基己酯、丙烯酸丁酯、丙烯酸仲丁酯、丙烯酸乙酯、丙烯酸甲酯、丙烯酸、丙烯酰胺、丙烯酸异丁酯、甲基丙烯酸甲酯或其组合。所述苯乙烯选自苯乙烯、叔丁基苯乙烯、对甲基苯乙烯或其组合。
在一个优选的实施方案中,如上所述的聚合物具有不超过40000、优选不超过10000的分子量。
在一个优选的实施方案中,聚合物D是如WO2017/202684中所述的乳液聚合物。
玻璃化转变温度(Tg)对于许多聚合物是已知的并且在本发明中确定,并且如果没有另外定义,则根据ASTM E1356-08(2014)“Standard Test Method for Assignment ofthe Glass Transition Temperatures by Differential Scanning Calorimetry”,其中样品在DSC之前在110℃干燥1小时以消除水和/或溶剂的影响,DSC样品尺寸为10-15mg,在N2下以20℃/min从-100℃至100℃测量,其中Tg定义为过渡区的中点。
其他配方(f)
f1合适的非离子表面活性剂或分散助剂f1)是通常可用于农业化学试剂中的所有此类物质。优选地,聚环氧乙烷-聚环氧丙烷嵌段共聚物,优选地具有大于6,000g/mol的分子量或大于45%的聚环氧乙烷含量,更优选地具有大于6,000g/mol的分子量和大于45%的聚环氧乙烷含量、聚氧化烯胺衍生物、聚乙烯吡咯烷酮、聚乙烯醇和聚乙烯吡咯烷酮的共聚物、和(甲基)丙烯酸和(甲基)丙烯酸酯的共聚物。在上述实例中,选择的类别可以任选地被磷酸化、磺化或硫酸化并用碱中和。
可能的阴离子表面活性剂f1)是通常可用于农业化学试剂中的所有此类物质。优选烷基磺酸或烷基磷酸以及烷基芳基磺酸或烷基芳基磷酸的碱金属、碱土金属和铵盐。另一组优选的阴离子表面活性剂或分散助剂为聚苯乙烯磺酸的碱金属、碱土金属和铵盐、聚乙烯基磺酸的盐、烷基萘磺酸的盐、萘-磺酸-甲醛缩合产物的盐、萘磺酸、苯酚磺酸和甲醛的缩合产物的盐、以及木质素磺酸的盐。
f2流变改性剂是一种添加剂,当以可在储存期间减少分散的活性成分的重力分离的浓度添加到配方中时,导致在低剪切速率下粘度的显著增加。出于本发明的目的,低剪切速率定义为0.1s-1及以下,显著增加定义为大于×2。粘度可以通过旋转剪切流变仪测量。
合适的流变改性剂E2)例如为:
-多糖,包括黄原胶和羟乙基纤维素。实例为G和23、CX 911和/>250系列,
-粘土,包括蒙脱石、膨润土、海泡石、凹凸棒石、锂皂石、锂蒙脱石。实例为R、Van/>B、/>34、38、CT、HC、EW、/>M100、M200、M300、S、M、W、/>50、/>RD、/>
-气相和沉淀的二氧化硅,实例为200、/>22。
优选地为黄原胶、蒙脱石粘土、膨润土粘土和气相二氧化硅。
f3合适的消泡物质e3)是通常为此目的可用于农用化学试剂中的所有物质。优选地为硅油、硅油制剂。实例为Bluestar Silicones的426和432、Wacker的SRE和SC132、Silchem的/>Basildon Chemical Company Ltd的Foam-Clear/>Momentive的/>1572和/>30[二甲基硅氧烷和硅酮,CAS No.63148-62-9]。优选地为是/>1572。
f4合适的防冻剂是为此目的通常可用于农用化学试剂中的所有物质。合适的实例为丙二醇、乙二醇、脲和甘油。
f5合适的其它配方e5)选自杀生物剂、着色剂、pH调节剂、缓冲剂、稳定剂、抗氧化剂、惰性填充材料、湿润剂、晶体生长抑制剂、微量营养素,实例为:
可能的防腐剂是为此目的通常可用于农业化学试剂中的所有物质。防腐剂的合适实例是含有以下物质的制剂:5-氯-2-甲基-4-异噻唑啉-3-酮[CAS-No.26172-55-4]、2-甲基-4-异噻唑啉-3-酮[CAS-No.2682-20-4]或1,2-苯并异噻唑-3(2H)-酮[CAS-No.2634-33-5]。可提及的实例为D7(Lanxess)、/>CG/ICP(Dow)、/>SPX(Thor GmbH)和/>GXL(Arch Chemicals)。
可能的着色剂是为此目的通常可用于农业化学试剂中的所有物质。例如,可提及的实例为二氧化钛、炭黑、氧化锌、蓝色颜料、亮蓝FCF、红色颜料和永固红FGR。
可能的pH调节剂和缓冲剂是为此目的通常可用于农用化学试剂中的所有物质。例如,可提及的实例为柠檬酸、硫酸、盐酸、氢氧化钠、磷酸氢钠(Na2HPO4)、磷酸二氢钠(NaH2PO4)、磷酸二氢钾(KH2PO4)、磷酸氢钾(K2HPO4)。
合适的稳定剂和抗氧化剂是为此目的通常可用于农用化学试剂中的所有物质。优选地为丁基羟基甲苯[3,5-二叔丁基-4-羟基甲苯,CASNo.128-37-0]。
载体(g)是为此目的通常可用于农业化学制剂中的那些物质。
载体为固体或液体、天然或合成、有机或无机物质,其通常是惰性的,并且可以用作溶剂。载体通常改善化合物(例如向植物、植物部位或种子)的施用。合适的实例
固体载体包括但不限于铵盐,特别是硫酸铵、磷酸铵和硝酸铵;天然岩石粉,例如高岭土、粘土、滑石、白垩、石英、凹凸棒石、蒙脱石和硅藻土;硅胶;和合成岩石粉,例如细碎二氧化硅、氧化铝和硅酸盐。用于制备颗粒的典型有用的固体载体的实例包括但不限于压碎和分级的天然岩石,例如方解石、大理石、浮石、海泡石和白云石,无机和有机粉的合成颗粒和有机材料的颗粒,例如纸、锯末、椰子壳、玉米穗轴和烟草茎。
优选的固体载体选自粘土、滑石和二氧化硅。
合适的液体载体的实例包括但不限于水、有机溶剂及其组合。合适的溶剂的实例包括极性和非极性有机化学液体,例如来自以下类别:
-醇和多元醇(其也可以任选地被取代、醚化和/或酯化,例如乙醇、丙醇、丁醇、苄醇、环己醇或乙二醇、2-乙基己醇),
-醚类,例如二辛基醚、四氢呋喃、二甲基异山梨醇、丙酮缩甘油、环戊基甲基醚、由Dow的Dowanol产品系列提供的溶剂,例如Dowanol DPM、苯甲醚、苯乙醚、不同分子量等级的二甲基聚乙二醇、不同分子量等级的二甲基聚丙二醇、二苄基醚,
-酮(例如丙酮、甲基乙基酮、甲基异丁基酮、环戊酮、环己酮、环庚酮、苯乙酮、苯丙酮),
-乳酸酯,例如乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、乳酸2-乙基己酯,
-(聚)醚,例如不同分子量级的聚乙二醇、不同分子量级的聚丙二醇,
-未取代和取代的胺,
-酰胺(例如二甲基甲酰胺,或N,N-二甲基乳酰胺,或N-甲酰基吗啉,或脂肪酸酰胺,例如N,N-二甲基癸酰胺或N,N-二甲基癸-9-烯-酰胺)及其酯,
-内酰胺(例如2-吡咯烷酮,或N-烷基吡咯烷酮,例如N-甲基吡咯烷酮,或N-丁基吡咯烷酮,或N-辛基吡咯烷酮,或N-十二烷基吡咯烷酮或N-甲基己内酰胺,N-烷基己内酰胺),
-内酯类(例如γ-丁内酯、γ-戊内酯、δ-戊内酯或α-甲基γ-丁内酯,
-砜和亚砜(例如二甲基亚砜),
-腈,例如直链或环状烷基腈,特别是乙腈、环己烷腈、辛腈、十二腈),
-直链和环状碳酸酯,如碳酸二乙酯、碳酸二丙酯、碳酸二丁酯、碳酸二辛酯,或碳酸亚乙酯、碳酸亚丙酯、碳酸亚丁酯、碳酸甘油酯。
最优选的载体是水。
这些喷雾液体通过常规方法使用,例如通过喷雾、浇灌或注射,特别是通过喷雾,最特别是通过UAV喷雾。
本发明制剂的施用率可以在一个相对宽的范围内变化。这通过特定的活性农业化学品及其在制剂中的量决定。
借助于本发明的制剂,可以以一种特别有利的方式将活性农业化学品递送至植物和/或其生境。
本发明还涉及使用本发明的农业化学品组合物将所包含的农业化学活性化合物施用至植物和/或其生境。
可以使用本发明的制剂来处理所有植物和植物部位。这里的植物是指所有的植物和植物种群,例如所需的和不需的野生植物或作物(包括天然存在的作物植物)。作物植物可以是通过常规育种和优化方法或生物技术和基因技术以及通过这些方法组合获得的植物,包括转基因植物和受或不受品种权保护的植物品种。植物部位是指植物所有的地上和地下部位和器官,如芽、叶、花和根,示例性的列表包括叶、针、茎、树干、花、子实体、果实和种子以及根、块茎和根茎。植物部位同样包括采收物以及无性和有性繁殖材料。
在本文中需要强调的是,本发明制剂关于其在谷类植物中的使用具有特别有利的效果,所述谷类植物为例如小麦、燕麦、大麦、斯佩尔特小麦、黑小麦和黑麦,以及玉米、高粱和粟、水稻、甘蔗、大豆、向日葵、马铃薯、棉花、加拿大油菜、油菜、烟草、甜菜、饲料甜菜、芦笋、啤酒花,和水果植物(包括的仁果类如苹果、梨,核果类如桃、油桃、樱桃、李子和杏,柑橘类水果如橙、葡萄柚、酸橙、柠檬、金桔、柑橘和蜜橘,坚果类如开心果、杏仁、核桃和山核桃,热带水果如芒果、木瓜、菠萝、海枣、香蕉和葡萄)和蔬菜(包括叶类蔬菜如菊苣、野苣、茴香、莴苣、直立莴苣、唐莴苣、菠菜沙拉用菊苣,卷心菜类如花椰菜、西兰花、大白菜、甘蓝(Brassica oleracea)(L.)锥形叶变种(convar.acephala var.sabellica)(羽衣甘蓝、羽状卷心菜)、大头菜、抱子甘蓝、红卷心菜、白卷心菜和皱叶甘蓝,水果蔬菜包括茄子、黄瓜、辣椒、南瓜、番茄、西葫芦和甜玉米,根茎类蔬菜如块根芹、野萝卜、胡萝卜(包括黄色品种,黑萝卜(Raphanus sativus var.niger)和四季萝卜(Raphanus sativus var.radicula))、甜菜根、鸦葱属、芹菜,豆类如豌豆和菜豆,葱科蔬菜如韭菜和洋葱。
根据本发明,使用本发明的制剂对植物和植物部位进行的处理通过常规处理方法直接进行或作用于其环境、生境或储存空间来进行,如通过浸渍、喷雾、蒸发、雾化、撒播或涂抹以及在繁殖材料,特别是种子的情况下,还通过施用一层或多层包衣来进行。
所包含的活性农用化学品比以相应的常规制剂形式施用时表现出更好的生物活性。
如果在本申请中没有另外定义,分子量是指重均分子量Mw,其通过GPC在二氯甲烷中在25℃下以聚苯乙烯作为标准测定。
叶表面
在表M1a和表M1b中,示出了水在有纹理和无纹理的叶表面上的接触角。
表M1a具有有纹理叶片的植物
表M1b具有无纹理叶片的植物
植物 | 种属 | 水的接触角°(近轴的) |
苹果 | Malus Domestica | 104° |
番茄 | Solanum lycopersicum | 106° |
玉米,BBCH-15/16 | Zea mays | 108° |
玉米,BBCH-17 | Zea mays | 107° |
玉米,BBCH-18 | Zea mays | 96° |
玉米,BBCH-19 | Zea mays | 87° |
苘麻 | Abutilon theophrasti | 103° |
反枝苋 | Amaranthus retroflexus | 未测量 |
无纹理的作物和植物的实例包括西红柿、辣椒、土豆、胡萝卜、芹菜、甜菜、甜菜根、菠菜、莴苣、豆类、豌豆、三叶草、苹果、梨、桃子、杏、李子、芒果、鳄梨、橄榄、柑橘、橘子、柠檬、酸橙、葡萄、无花果、黄瓜、甜瓜、西瓜、草莓、树莓、蓝莓、向日葵、南瓜、大豆(≥GS 16(BBCH 16))、玉米(≥GS 15(BBCH 15))、棉花。
有纹理的作物和植物的实例包括大蒜、洋葱、韭菜、大豆(≤GS 16(BBCH 16))、燕麦、小麦、大麦、水稻、甘蔗、菠萝、香蕉、亚麻籽、百合、兰花、玉米(≤GS 15(BBCH 15))、卷心菜、球芽甘蓝、西兰花、花椰菜、黑麦、油菜、郁金香和花生。
无纹理的杂草的实例包括苘麻(Abutilon theophrasti)、荠菜(Capsella bursa-pastoris)、曼陀罗(Datura stramonium)、拉拉藤(Galium aparine)、圆叶牵牛(Ipomoeapurpurea)、酸模叶蓼(Polygonum lapathifolium)、马齿苋(Portulaca oleracea)、欧洲千里光(Senecio vulgaris)、刺黄花棯(Sida spinosa)、野芥(Sinapis arvensis)、龙葵(Solanum nigrum)、繁缕(Stellaria media)、东苍耳(Xanthium orientale)、香附子(Cyperus rotundus)和反枝苋(Amaranthus retroflexus)。
有纹理的杂草的实例包括决明、藜、偃麦草、大穗看麦娘、丝状本茨草、野燕麦、巴拉草、黑雀麦、狗牙根、马唐、稗草、洋野黍、早熟禾、大狗尾草和石茅等。
本发明通过以下实施例进行说明。
实施例
方法1:流动性SC和SE制剂(油)
流动性悬浮剂制剂和悬乳剂的制备方法在本领域是已知的,并且可以由本领域技术人员所熟知的方法来制备。在低剪切搅拌下制备在水中的黄原胶(f)与杀生物剂(f)的2%凝胶。如果存在于配方中,则通过在高剪切混合器下将油(50%)添加到水(49%)和Synperonic PE/F127(1%)的溶液(或等效表面活性剂)中来制备油(b)的50%水包油乳液。将活性成分(a)、非离子和阴离子分散剂(f)、消泡剂(f)和其他助剂(f)用水混合制成浆液,首先用高剪切转子-定子混合器/>进行混合,将粒径D(v,0.9)减小至约50微米,然后通过一个或多个珠磨机(/>250Mini Motormill),使粒径D(v,0.9)通常为1至15微米。然后加入作为上述制备的50%乳液的添加剂(b)、(d)、(e)和上述制备的黄原胶并通过低剪切搅拌混合至均匀。最后,如果需要,用酸或碱(f)调节pH。
含有少量乳化油的可流动制剂可以描述为悬浮浓缩物和悬浮乳液制剂类型(www.croplife.org,Technical Monograph No:2,Catalogue of pesticide formulationtypes and international coding system,Edition:March 2017)
方法2:流动性SC制剂(聚合物)
流动性悬浮剂制剂的制备方法在本领域是已知的,并且可以由本领域技术人员所熟知的方法来制备。在低剪切搅拌下制备在水中的黄原胶(f)与杀生物剂(f)的2%凝胶。如果存在于配方中,制备1-4%聚合物(b)。将活性成分(a)、非离子和阴离子分散剂(f)、消泡剂(f)和其他助剂(f)用水混合制成浆液,首先用高剪切转子-定子混合器进行混合,将粒径D(v,0.9)减小至约50微米,然后通过一个或多个珠磨机(/>250Mini Motormill),使粒径D(v,0.9)通常为1至15微米。然后加入作为上述制备的聚合物溶液的添加剂(b)、(d)、(e)和上述制备的黄原胶并通过低剪切搅拌混合至均匀。最后,如果需要,用酸或碱(f)调节pH。
根据配方中所需的粘度浓度极限和含量制备聚合物(b)溶液。典型值为:PolyoxWSR301(1-2%)、Polyox WSR N60K(1-3%)、Polyox WSR N12K(2-4%)、AgRho DS2000(1-2%)。
方法3:EC制剂
EC制剂的制备方法在本领域是已知的,并且可以由本领域技术人员所熟知的方法来制备。通常,EC制剂通过将活性成分在配备有搅拌装置的容器中混合来获得。在一些情况下,通过稍微升高温度(不超过60℃)来促进溶解或混合。继续搅拌直至获得均匀混合物。
方法4:OD制剂
将制剂组分称重,用高剪切装置(例如,Ultraturrax或胶体研磨机)均质化,随后将混合物在珠磨机(Dispermat SL 50,80%填充,1.0-1.25mm玻璃珠,4000rpm,循环研磨)中研磨。Dispermat SL 50,80%填充,1.0-1.25mm玻璃珠,4000rpm,循环研磨),直到实现<10μ的粒度。或者,将制剂组分在瓶中混合,然后加入约25vol.-%1.0-1.25mm玻璃珠。然后将瓶子封闭,夹在搅拌器装置(例如,Retsch MM 301),并在30Hz下处理几分钟,直到实现<10μ的粒度。
方法5:WG制剂
水分散性颗粒制剂的制备方法在本领域是已知的,并且可以由本领域技术人员所熟知的方法来制备。
例如,为制备流化床颗粒,首先需制备水基工艺浓缩液。在低剪切搅拌下,将所有成分(a,b和c),如表面活性剂、分散剂、粘合剂、消泡剂、抗漂移剂和填充剂在水中混合,最后在高剪切转子-定子混合器中预研磨,使粒径(v,0.9)减小至约50微米,然后通过一个或多个珠磨机(KDL,Bachofen,Dynomill,Bühler,Drais,Lehmann),使粒径D(v,0.9)通常为1至15微米。然后将这种水基工艺浓缩液在流化床造粒过程中进行喷雾干燥,形成可湿性颗粒(WG)。
根据CIPAC(CIPAC=国际农药分析合作委员会(Collaborative InternationalPesticides Analytical Council;www.cipac.org)方法MT187测定粒径。粒径分布根据激光衍射法确定。在环境温度下将代表性量的样品分散在脱气水中(样品自饱和),通过超声波处理(通常为60秒),然后用Malvern Mastersizer系列(Malvern Panalytical)设备测定。通过多元素探测器在不同角度测定散射光,并记录相关数值。通过弗朗霍夫(Fraunhofer)模型,根据散射数据计算出特定尺寸级别的比例,并据此计算出体积加权粒径分布。通常给出d50和d90值=活性成分粒径(所有体积颗粒的50或90%)。平均粒径表示d50值。
同样地,任何其他喷雾工艺,例如经典的喷雾干燥可用作造粒方法。
生产水分散性颗粒的另一种技术是例如低压挤出。将制剂的成分以干燥形式混合并随后研磨,例如,在干燥的环境中研磨。使用空气喷射研磨机以减小粒度。随后搅拌该干粉,同时向混合物中加入水(约10-30重量%,取决于制剂的组成)。在进一步的步骤中,将混合物推动通过具有通常在0.8和1.2mm之间的磨具尺寸的挤出机(如圆顶挤出机、双圆顶挤出机、篮式挤出机、筛磨机或类似装置)以形成挤出物。在最后的步骤中,将挤出物后干燥,例如在流化床干燥器中进行,以降低粉末的水含量,通常降低到1-3重量%的残余水的水平。
方法6:漂移风室
使用约2.8m宽、2.8m长和1m高的定制漂移室来测量制剂的漂移,所述漂移室包含喷嘴、水平风流和漂移收集器筛。喷嘴位于室底部上方0.5m的高度,并且与收集器筛相距1.4m的距离处,该收集器筛在喷雾室的端壁上的高度为约0.6m。
对由检测器屏幕收集的喷雾液体进行称重,并且从喷雾液体的流速和由检测器屏幕捕获的分数计算来自喷雾的漂移量。风速为3m/s。将制剂在水中稀释至所需浓度,在2巴的压力下通过TP8002EVS喷嘴喷雾,并且一旦达到稳态就记录漂移量。该技术提供了不同配方之间的漂移的比较测量。
方法7:漂移液滴尺寸P15
将制剂在水中稀释至所需浓度,在3巴的压力下通过TP8002EVS喷嘴喷雾,并且用Oxford Lasers VisiSize P15测量液滴尺寸谱,Oxford Lasers VisiSize P15可捕获喷雾液滴的图像并测量其尺寸。将喷嘴定位在图像捕获点上方20cm处,反复缓慢移动穿过VisiSize P15的图像捕获窗口,直到捕获5000至10000个液滴图像。液滴尺寸谱通过仪器软件计算为小于100微米的体积%和/或小于150微米的体积%,其通常被认为是喷雾液滴的可漂移部分。可漂移液滴的相对量计算为:本发明配方的体积%<100微米/对比配方的体积%<100微米×100(%),和/或本发明配方的体积%<150微米/对比配方的体积%×100(%)。因此,60%的值将表明,与对比配方相比,本发明配方仅具有60%的喷雾液滴的可漂移部分,对比配方在此将具有100%。
方法8:漂移液滴尺寸激光器
将制剂在水中稀释至所需浓度,通过TeeJet 11002VS喷嘴在3巴的压力下喷雾,并且用Malvern SprayTec激光衍射仪在喷嘴下方350mm的距离处跨喷雾扇进行单次长轴扫描来测量液滴尺寸谱。
方法9:漂移滤纸沉积物
将制剂在水中用少量荧光示踪剂(Tinopal SC)稀释至所需浓度,通过TeeJet11002E喷嘴在2巴的压力下喷雾到滤纸上,并使用ImageJ测量液滴尺寸谱。
使用数码相机以UV光[365nm]作为照明源对滤纸拍照。在滤纸的图片中,被荧光标记的液滴沉积物具有比滤纸和其他背景更高的强度。
图像在ImageJ软件(www.fiji.com)中处理。首先,根据原始图像的强度将RGB图像分成红色、绿色和蓝色通道,仅绿色或蓝色通道用于进一步分析。接下来,将“减去背景”算法应用于单通道图像以去除背景干扰,这反过来又提高了液滴沉积物与背景之间的对比度。之后,自动生成强度阈值并由软件应用,从而产生二进制图像,其中液滴沉积物保持具有最大强度,而背景(诸如滤纸本身)具有零强度。最后,将“分水岭”算法应用于二进制图像,以分割图像中连接的液滴。检测所有剩余和分割的对象,并标记它们的位置和尺寸。每个物体的尺寸代表每个沉积物的面积,单位为um2。
喷雾测试中使用的喷嘴具有210um的VMD。体积中值直径(VMD)由液滴体积V的累积分布函数(CDF)确定,具有小于VMD的尺寸的液滴占总喷雾体积的50%。由于从滤纸获得的沉积物面积与实际液滴尺寸/体积之间没有直接相关性,因此水的VMD已被用作重新调整制剂喷雾的CDF的参考。
根据ImageJ分析,记录滤纸上每个液滴沉积物的面积(A)。每个沉积物的直径dA=(4A/π)1/2,预估液滴体积V预估=π·dA 3/6。使用预估液滴体积V预估绘制基础制剂的CDF,其由滤纸上的沉积物面积计算,基础制剂的VMD也由CDF曲线获得。假设基础制剂具有与水相似的液滴尺寸分布,通过将基础制剂的VMD与水的VMD匹配,生成尺寸因子f=VMD基础/VMD水。给定滤纸的液滴沉积物面积A,实际液滴直径d=f·(4A/π)1/2,液滴体积V=π·d3/6。
不同制剂的液滴体积V的累积分布用对数标度箱绘制。从每个累积分布曲线,计数直径小于150um的液滴的百分比。细液滴的该体积百分比对应于漂移可能性的程度。使用基础制剂的百分比(p基础)作为参考,计算具有佐剂的制剂(p)与基础制剂之间的百分比的相对差异。相对差异r=p/p基础·100%。如果相对差异(r)低于100%,则与基础制剂相比,制剂具有较低的漂移可能性,反之亦然。
方法10:杀虫剂温室试验
选择的作物在温室条件下在含有“泥炭土T”的塑料盆中培养。在适当的作物阶段,准备植物用于处理,例如通过在处理前约2天用目标害虫侵染(参见下表)。
在需要时,喷雾溶液用不同剂量的活性成分直接通过用自来水稀释制剂并在桶混物中加入适量的添加剂来制备。
用履带式喷雾器(tracksprayer)以300l/ha或10l/ha的施用量在叶的上侧进行施用。所用喷嘴:TeeJet TP8003E(用于300l/ha)和Lechler的652.246连同脉冲宽度调节器(PWM)(用于10l/ha)。对于施用的每个单剂量,通常同时处理2至5个重复。
处理后,如果需要,将植物人工侵染,并在试验期间保持在温室或气候室中。在不同的时间点评价死亡率(通常,以%给出)和/或植物保护(例如从摄食损伤来计算,与相应的对照组相比)后,评定处理的功效。仅报告了平均值。
表M3:试验中使用的害虫和作物。
选择的作物在温室条件下在含有“泥炭土T”的塑料盆中培养。在适当的作物阶段,准备植物用于处理,例如通过在处理前约2天用目标害虫侵染(参见M3)。
在需要时,喷雾溶液用不同剂量的活性成分直接通过用自来水稀释制剂并在桶混物中加入适量的添加剂来制备。
用履带式喷雾器(tracksprayer)以300l/ha或10l/ha的施用量在叶的上侧进行施用。所用喷嘴:TeeJet TP8003E(用于300l/ha)和Lechler的652.246连同脉冲宽度调节器(PWM)(用于10l/ha)。对于施用的每个单剂量,通常同时处理2至5个重复。
处理后,如果需要,将植物人工侵染,并在试验期间保持在温室或气候室中。在不同的时间点评价死亡率(通常,以%给出)和/或植物保护(例如从摄食损伤来计算,与相应的对照组相比)后,评定处理的功效。仅报告了平均值。
方法11:除草剂温室试验说明
将作物和单子叶和双子叶有害植物的种子放置在塑料盆中的砂壤土中,用土壤覆盖并在温室中在最佳生长条件下栽培。播种2-3周后,在1-2叶期处理试验植物。制备不同浓度的试验除草剂制剂,并使用不同的水施用率喷雾到植物的绿色部分表面上:200l/ha作为标准常规施用率,10l/ha作为超低量(ULV)施用率。用于所有施用的喷嘴类型是TeeJet DG95015EVS。通过使用连接到喷嘴和履带式喷雾器装置的脉冲宽度调节器(PWM)系统来实现ULV施用率。施用后,将试验植物在温室中在最佳生长条件下静置3至4周。然后,目测评分除草剂制剂的活性(例如:100%活性=整个植物材料死亡,0%活性=植物与未处理的对照植物相似)。
表M4:试验中使用的植物物种。
方法12:杀真菌剂温室试验的说明
将种子放置在塑料盆中的砂壤土中,用土壤覆盖并在温室中在最佳生长条件下栽培。播种2-3周后,在1-2叶期处理试验植物。制备不同浓度的试验杀真菌剂制剂,并使用不同的水施用率喷雾到植物上:200l/ha作为标准常规施用率,10l/ha作为超低量(ULV)施用率。用于所有施用的喷嘴类型是TeeJet TP 8002E,使用2巴和500–600mm的高度以上的植物水平。谷物植物以45°角放置,因为这最好地反映了谷物田间的喷雾条件。通过使用连接到喷嘴和履带式喷雾器装置的脉冲宽度调节器(PWM)系统来实现ULV施用率,其为30Hz,开度8%-100%(10l/ha-200l/ha喷雾量)。
在保护性处理中,在喷雾施用1天后用相应的病害接种测试植物,并在温室中在最佳生长条件下静置1至2周。然后,目测评估杀真菌剂制剂的活性。
在治疗条件下,首先用病害接种植物,1-3天后用杀真菌剂制剂处理。在施用制剂3-6天后(dat)进行疾病的目测评估。
接种的实践是本领域技术人员所熟知的。
表M5:试验中使用的病害和作物。
方法13:角质层渗透试验
角质层渗透试验是最初由and Baur(/>J.,Baur,P.(1996),Effects of temperature,surfactants and other adjuvants on rates ofuptake of organic compounds.In:The plant cuticle-an integrated functionalapproach,134-155.Kerstiens,G.(ed.),BIOS Scientific publisher,Oxford)描述的测试方法SOFU(叶面吸收模拟)的进一步开发和改编的版本;其非常适合于关于制剂、助剂和溶剂对农用化学品渗透的影响的系统和机理研究。
如和Riederer(/>J.,Riederer,M.(1986),Plantcuticles sorb lipophilic compounds during enzymatic isolation.Plant CellEnviron.9,459-466)所描述的,从取自果园中生长的树的叶子分离苹果叶角质层。获得只有上部叶表面缺乏气孔的无气孔角质膜。从叶子上冲压出直径为18mm的圆片,并用果胶酶和纤维素酶的酶溶液渗透。从消化的叶细胞汤中分离角质膜,通过用水轻轻洗涤进行清洁并干燥。储存约4周后,角质层的渗透性达到恒定水平,角质膜准备用于渗透试验。
将角质膜应用于扩散容器。方向正确很重要:角质层的内表面应该面向扩散容器的内侧。在喷雾室中将喷雾施用到角质层的外表面。将扩散容器翻转并小心地用受体溶液填充。缓冲至pH 5.5的水性混合物用作受体介质以模拟质外体作为角质层内表面处的天然解吸介质。
将填充有受体和搅拌器的扩散容器转移到温度受控的不锈钢块中,该不锈钢块不仅确保了良好限定的温度,而且还确保了含有喷雾沉积物的角质层表面处的恒定湿度。实验开始时的温度为25℃、30℃或35℃,并在恒定60%相对湿度下保持恒定或在施用后24小时改变至35℃。
自动进样器以规则间隔取接收器的试样,并通过HPLC(DAD或MS)测定活性成分的含量。最终处理所有数据点以获得渗透动力学。由于角质层的渗透屏障的变化很大,因此对每个渗透动力学进行五到十次重复。
方法14:角质层洗去
将来自苹果角质层的圆片以外表面朝上的方式固定到具有中等粘度硅油薄层的玻璃显微镜载玻片上。用微量移液管向其中施加0.9μl滴在含有5%CIPAC C水的去离子水中喷雾稀释的不同制剂,并放置干燥1小时。在装有正交偏振滤光片的光学透射显微镜中检查每个沉积物并记录图像。将含有具有制剂的干燥液滴的角质层的载玻片保持在温和流动的去离子水(流速约300ml/分钟,在水龙头出口下方10cm的高度)下15秒。使载玻片干燥,并在显微镜中重新检查沉积物,并与原始图像进行比较。目测估计洗去的活性成分的量,并以10%的阶段记录。测量三个重复,并记录平均值。
方法15:叶片洗去
将苹果或玉米叶切片附着到玻璃显微镜载玻片上。用微量移液管向其中施加0.9至1.4μl滴在含有5%CIPAC水和少量荧光示踪剂(Tinopal OB,微米尺寸的水性悬浮液)的去离子水中喷雾稀释的不同制剂,并使其干燥1小时。在UV照射(365nm)下,通过数码相机对叶片沉积物成像。然后将叶切片保持在温和流动的去离子水(流速约300ml/分钟,在水龙头出口下方10cm的高度)下15秒。使叶切片干燥,并将沉积物重新成像并与原始图像进行比较。目测估计洗去的活性成分的量在5(大部分剩余)和1(大部分去除)之间。测量三个或更多个重复,并记录平均值。
方法16:覆盖范围(喷雾)
这些实验采用表M1a和M1b中所示的处于发育阶段的温室植物。在喷雾实验前剪下单片叶片,放置于培养皿中,两端用胶带以0°(水平方向)或60°(以使可喷雾50%的叶面积)粘接。小心移动叶片避免损坏蜡表面。这些水平朝向的叶片a)放置于通过液压喷嘴施用喷雾液体的喷雾室中。
在喷雾液体中加入少量UV染料用于观察紫外光照射下的喷雾沉积物。选择染料的浓度使得不影响喷雾液体表面性质且不会有助于其自身扩散。将Tinopal OB作为胶体悬浮液用于所有可流动和固体的制剂,如WG、SC、OD和SE。将Tinopal CBS-X或Blankophor SOL用于其中溶解了活性成分的制剂如EC、EW和SL。将Tinopal CBS-X溶于水相并将BlankophorSOL溶于油相。
在喷雾液体蒸发后,将叶片放置于Camag,Reprostar 3UV室中,其中在可见光和366nm的紫外光下拍摄喷雾沉积物的照片。将Canon EOS 700D数码相机连接到紫外线室,用于获取叶片的图像。在可见光下拍摄的照片用于从背景中减去叶片形状。将ImageJ软件用于计算a)所施用的喷雾对喷雾叶的覆盖百分比或b)移液滴的扩散面积,以mm2为单位。
方法17:覆盖范围(移液管)
这些实验采用表M1a和M1b中所示的处于发育阶段的温室植物。将1.4μl滴含有少量荧光示踪剂(Tinopal OB,微米尺寸的水性悬浮液)的喷雾液体移液到顶部而不接触叶片表面并使其干燥。在UV照射(365nm)下,通过数码相机对叶片沉积物成像,并使用ImageJ软件(www.fiji.com)测量沉积物的面积。
方法18:持久性泡沫
根据CIPAC方法MT 47.1测定持久性泡沫,条件是使用每个实施例中所示的配方剂量率和喷雾量,并在1分钟和3分钟后记录泡沫(www.cipac.org)。
材料
表MAT1:优选的漂移减少材料——聚合物(b)的示例性商品名和CAS编号
表MAT2:优选的漂移减少材料——油(b)的示例性商品名和CAS-编号
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表MAT4:优选的吸收增强化合物(d)的示例性商品名和CAS-编号
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表MAT5:优选的洗去减少材料(e)的示例性商品名
表MAT6:优选的化合物(f)的示例性商品名和CAS-编号
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杀真菌剂实施例
实施例FN1:肟菌酯20SC
表FN1.1:配方FN1.1、FN1.2和FN1.3。
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所用制备方法参考方法1。
温室
表FN1.2:对PHAKPA/大豆的生物学功效
方法12:大豆,1天保护,7dat后评估。
结果表明,与对比配方FN1.1相比,本发明的示例性配方FN1.2在10l/ha和200l/ha喷雾量下显示出更高的功效。
叶片洗去
根据方法15测定洗去。
表FN1.3:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与含有吸收增强添加剂(d)但不含耐雨添加剂(e)的对比配方FN1.1和FN1.3相比,本发明的示例性配方FN1.2显示出在10L/ha喷雾量下更高的施用制剂剩余量。
实施例FN2:Inpyrfluxam SC
表FN2.1:配方FN2.1、FN2.2、FN2.3、FN2.4和FN2.5
所用制备方法参考方法1。
温室
表FN2.2:对PHAKPA/大豆的生物学功效
方法12:大豆,1天保护,7dat后评估。
结果表明,与对比配方FN2.4相比,本发明的示例性配方FN2.5在10和200l/ha喷雾量下显示出相当或更高的功效。此外,与200l/ha相比,配方FN2.5在10l/ha下显示出更高的功效。
角质层渗透
苹果叶角质层的渗透根据角质层渗透测试方法13测定。
表FN2.3:inpyrfluxam SC配方的角质层渗透。
配方以0.5l/ha试验。
结果表明,本发明的示例性配方FN2.2在10l/ha和200l/ha具有比对比配方FN2.1更高的角质层渗透。此外,配方FN2.2在10l/ha下具有比200l/ha更高的渗透。
叶片洗去
根据方法15测定洗去。
表FN2.4:叶片洗去数据
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配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方FN2.1相比,本发明的示例性配方FN2.2显示出在10L/ha喷雾量下更高的施用制剂剩余量,并且与含有漂移减少添加剂(b)和吸收增强添加剂(d)但不含耐雨添加剂(e)的配方FN2.2相比,在10和200l/ha下更高的施用制剂剩余量。
实施例FN3:氟吡菌酰胺200SC
表FN3.1:配方FN3.1、FN3.2和FN3.3
所用制备方法参考方法1。
漂移
根据方法7测定漂移。
表FN3.2:氟吡菌酰胺SC配方的漂移数据。
配方以0.5l/ha试验。
结果表明,与不含漂移减少油(b)的对比配方FN3.3相比,本发明的示例性配方FN3.2在20l/ha喷雾量下显示出更低量的小于100微米的喷雾液滴可漂移部分。
叶片洗去
根据方法13测定洗去。
表FN3.3:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与不含耐雨剂(e)的对比配方FN3.3相比,本发明的示例性配方FN3.2显示出在20L/ha喷雾量下更高的施用制剂剩余量。
实施例FN4:丙硫菌唑20SC
表FN4.1:配方FN4.1和FN4.2
所用制备方法参考方法1。
温室
表FN4.3:对PHAKPA/大豆的生物学功效
方法12:大豆,1天保护,7dat后评估。
结果表明,与对比配方FN4.1相比,本发明的示例性配方FN4.2在200l/ha喷雾量下显示出更高的功效,并且在10l/ha下显示出相当的功效。
实施例FN5:Fluoxapiprolin 40SC
表FN5.1:配方FN5.1、FN5.2、FN5.3、FN5.4、FN5.5、FN5.6和FN5.7。
所用制备方法参考方法1。
漂移
根据方法7测定漂移。
表FN5.2:fluoxapiprolin SC配方的漂移数据。
配方以0.5l/ha试验。
结果表明,与不含漂移减少油(b)的对比配方FN5.1相比,具有本发明的漂移减少油(b)剂量的示例性配方FN5.3、FN5.4和FN5.5显示在20l/ha的喷雾量下喷雾液滴小于100微米和小于150微米的可漂移部分的量较低。此外,与含有显著更高量的漂移减少油(b)的配方FN5.6和FN5.7相比,配方FN5.4和FN5.5中低量的漂移减少油实现了喷雾液滴小于100微米和小于150微米的可漂移部分的量的相同水平的减少。
实施例FN6:联苯吡菌胺50SC
表FN6.1:配方FN6.1、FN6.2和FN6.3
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所用制备方法参考方法1。
漂移
根据方法7测定漂移。
表FN8.2:漂移数据。
配方以0.5l/ha试验。
结果表明,与不含漂移减少油(b)的对比配方FN8.3相比,本发明的示例性配方FN8.2在20l/ha喷雾量下显示出更低量的小于100微米的喷雾液滴可漂移部分。
温室
表FN6.3:对PHAKPA/大豆的生物学功效
方法12:大豆,1天保护,7dat后评估。
结果表明,与对比配方FN6.1相比,本发明的示例性配方FN6.2在10和200l/ha喷雾量下均显示出更高的功效。
叶片洗去
根据方法15测定洗去。
表FN6.4:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方FN6.1相比,本发明的示例性配方FN6.2显示出在10L/ha喷雾量下更高的施用制剂剩余量。
实施例FN7:氟吡菌胺150SC
表FN7.1:配方FN7.1、FN7.2、FN7.3和FN7.4
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角质层渗透
苹果叶角质层的渗透根据角质层渗透测试方法13测定。
表FN7.3:氟吡菌胺SC配方的角质层渗透。
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配方以0.5l/ha试验。
结果表明,与对比配方FN7.1相比,本发明的示例性配方FN7.2具有更高的角质层渗透。此外,与200l/ha相比,配方FN7.2在10l/ha下具有更高的渗透率。此外,含有少量油基漂移减少剂(OP)的配方FN7.3具有与不含任何油基漂移减少剂的对比配方FN7.1相当的角质层渗透,表明少量油不增强角质层渗透并且不以影响活性成分生物递送的水平存在。
叶片洗去
根据方法15测定洗去。
表FN7.4:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与含有吸收增强剂(d)但不含耐雨剂(e)的对比配方FN7.4相比,本发明的示例性配方FN7.2显示出在10L/ha喷雾量下更高的施用制剂剩余量。
实施例FN8:Isoflucypram 10SC
表FN8.1:配方FN8.1和FN8.2
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所用制备方法参考方法1。
温室
表FN8.3:对PUCCRT/小麦的生物学功效
方法12:小麦,2天保护,7dat后评估。
结果表明,本发明的示例性配方FN8.2在10和200l/ha喷雾量下均显示出比对比配方FN8.1更高的功效。此外,配方FN8.2在10l/ha下与200l/ha相比显示出更高的功效。
喷雾的小麦植物上的叶片沉积物的图像显示在图1中,并且显示出本发明的示例性配方FN8.2和对比配方FN8.1在10l/ha下均显示出差的覆盖范围。出人意料的是,本发明的示例性配方FN8.2在此显示出显著更高的功效,说明在低喷雾量下通过吸收增强剂吸收活性成分具有出人意料的良好生物学效应。
叶片洗去
根据方法13测定洗去。
表FN8.4:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方FN8.1相比,本发明的示例性配方FN8.2显示出在10和200L/ha喷雾量下更高的施用制剂剩余量。
实施例FN9:Fluoxapiprolin 10SC
表FN9.1:配方FN9.1和FN9.2
所用制备方法参考方法1。
漂移
根据方法9测定漂移。
表FN9.2:fluoxapiprolin SC配方的漂移数据。
配方以0.35l/ha试验。
结果表明,与不含漂移减少油(b)的对比配方FN9.1和对比配方FN9.3相比,本发明的示例性配方FN9.2在10L/ha喷雾量下显示出较低的漂移。
温室
表FN9.3:对PHYTIN/番茄的生物学功效
方法12:番茄,1天保护,4dat后评估。
结果表明,对比配方FN9.1显示出将喷雾量从200l/ha降低至15l/ha时的功效的大幅降低。说明本发明的配方FN9.2在喷雾量从200l/ha降低至15l/ha时保持了明显更好的功效。此外,与对比配方FN9.1相比,配方FN9.2在15l/ha的喷雾量下均显示出更高的功效。
喷雾的番茄植物上的叶沉积物的图像显示在图2中,并且显示本发明的示例性配方FN9.2和对比配方FN9.1在15l/ha下均显示出如对于以低喷雾量施用的喷雾所预期的差的覆盖范围。出人意料的是,本发明的示例性配方FN9.2在此显示出显著更高的功效,说明在低喷雾量下通过吸收增强剂吸收活性成分具有出人意料的良好生物学效应。
实施例FN10:氟吡菌胺SC
表FN10.1:配方FN10.1、FN10.2、FN10.3和FN10.4。
所用制备方法参考方法2。
在番茄植物上的扩散
用TP8002E喷嘴在2巴的压力下喷雾处于4叶生长期的番茄植物(BBCH14)。使用PWM装置实现15l/ha的喷雾量。将少量的荧光标记物添加到喷雾液体中,并在UV照射(365nm)下目测测定%覆盖范围。
表FN10.2:在番茄植物上的喷雾%覆盖范围。
配方以1.0l/ha施用。
结果表明,与对比配方FN10.1相比,本发明的示例性配方FN10.2在15l/ha和200l/ha喷雾量下均显示出相当的叶片覆盖范围。
温室
表FN10.3:对PHYTIN/番茄的生物学功效
方法12:番茄,1天保护,4dat后评估。
结果表明,与对比配方FN10.1相比,本发明的示例性配方FN10.2在200l/ha和15l/ha下均显示出更好的功效。此外,与200l/ha相比,因为观察到的覆盖范围较低(表FN10.3),配方FN10.2的功效在15l/ha下出人意料地高,表明了吸收增强剂(d)在15l/ha喷雾量下的有益效果。
物理方面
目测评估关于粘度的物理方面。
表FN10.4:配方的物理方面。
结果表明,配方FN10.4对于客户使用来说太粘稠,并且说明对于多少聚合物可以掺入SC配方中存在浓度上限。对于漂移减少聚合物AgRho DR2000,其为大约10g/l。
实施例FN11:Inpyrfluxam 10SC
表FN11.1:配方FN11.1、FN11.2和FN11.3
所用制备方法参考方法1。
漂移
根据方法7测定漂移。
表FN11.2:漂移数据。
配方以0.5l/ha试验。
结果表明,与不含漂移减少油(b)的对比配方FN11.3相比,本发明的示例性配方FN11.2在20l/ha喷雾量下显示出较低的可漂移液滴部分。
实施例FN12:Fluoxapiprolin SC
表FN12.1:配方FN12.1、FN12.2和FN12.3
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所用制备方法参考方法2。
漂移
根据方法7测定漂移。
表FN12.2:漂移数据。
配方以0.5l/ha试验。
结果表明,与不含漂移减少聚合物(b)的对比配方FN12.3相比,本发明的示例性配方FN12.2在20l/ha喷雾量下显示出较低的可漂移液滴部分。
实施例FN16:联苯吡菌胺SC
表FN16.1:配方FN16.1、FN16.2、FN16.3、FN16.4和FN16.5。
所用制备方法参考方法2。
物理方面
目测评估关于粘度的物理方面。
表FN16.4:配方的物理方面。
结果表明,聚合物WSR301可以在0.3至1.2g/L的浓度范围内并入SC配方中。
喷雾液滴尺寸
根据方法9测定喷雾液滴尺寸。
表FN16.4:喷雾液滴的可漂移部分。
配方在15l/ha的喷雾量中以0.5l/ha施用。
结果表明,聚合物WSR301可以在0.6至1.2g/L的浓度范围内降低<100微米和<150微米的喷雾液滴可漂移部分(对于在15l/ha的喷雾量中以0.5l/ha使用的配方)。
实施例FN17:戊唑醇SC
表FN17.1:配方FN17.1、FN17.2、FN17.3、FN17.4和FN17.5。
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所用制备方法参考方法2。
表FN17.2:配方FN17.6、FN17.7、FN17.8和FN17.9。
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所用制备方法参考方法2。
物理方面
目测评估关于粘度的物理方面。
表FN17.3:配方的物理方面。
结果表明,聚合物WSRN12K可以在0.6至2.4g/L的浓度范围内并入SC配方中。
喷雾液滴尺寸
根据方法9测定喷雾液滴尺寸。
表FN17.5:喷雾液滴的可漂移部分。
配方在15l/ha的喷雾量中以0.5l/ha施用。
结果表明,聚合物WSR N12K可以在0.6至2.4g/L的浓度范围内降低<100微米和<150微米的喷雾液滴可漂移部分(对于在15l/ha的喷雾量中以0.5l/ha使用的配方)。此外,这些结果表明,使用吸收增强剂(d)也观察到可漂移部分减少。
杀虫剂实施例
实施例IN1:螺虫乙酯150SC
表IN1.1:配方IN11和IN15。
所用制备方法参考方法1。
叶片上的移液扩散试验
根据方法17测定叶片沉积物尺寸。
表IN1.2:在无纹理的苹果叶片和有纹理的水稻叶片上的喷雾稀释的液滴尺寸和剂量
配方以8/15/100l/ha施用。
结果表明,本发明的示例性配方IN15显示在15L/ha的喷雾量下的沉积物尺寸大于100L/ha喷雾量下的沉积物尺寸,并且与对比配方IN11相比也是如此。
角质层渗透
苹果叶角质层的渗透根据角质层渗透测试方法13测定。
表IN1.3:螺虫乙酯SC配方的角质层渗透。
配方以0.5l/ha试验。
结果显示,本发明的示例性配方IN15在10l/ha和200l/ha下具有比对比配方IN11更高的角质层渗透。此外,配方IN15在48小时在10l/ha下具有比200l/ha更高的渗透。
叶片洗去
根据方法15测定洗去,但洗去率为600mL/min。
表IN1.4:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
实施例IN2:四唑虫酰胺80SC
表IN2.1:配方IN21、IN25和IN85
所用制备方法参考方法1(IN21、IN25)和方法2(IN85)。
叶片洗去
根据方法15测定洗去,但洗去率为600mL/min。
表IN2.2:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方IN21相比,本发明的示例性配方IN25和IN85显示出在10L/ha喷雾量下更高的施用制剂剩余量。
实施例IN3:吡虫啉+噻虫啉300SC
表IN3.1:配方IN31和IN35。
所用制备方法参考方法1。
叶片上的移液扩散试验
根据方法17测定叶片沉积物尺寸。
表IN3.2:在无纹理的苹果叶片和有纹理的水稻叶片上的喷雾稀释的液滴尺寸和剂量。
配方以8/15/100l/ha施用。
结果表明,本发明的示例性配方IN32显示在8和15L/ha的喷雾量下的沉积物尺寸大于100L/ha喷雾量下的沉积物尺寸,并且与对比配方IN31相比也是如此。
角质层渗透
苹果叶角质层的渗透根据角质层渗透测试方法13测定。
表IN3.3:吡虫啉+噻虫啉SC配方中吡虫啉的角质层渗透。
配方以0.5l/ha试验。
结果表明,本发明的示例性配方IN35在10l/ha和200l/ha下具有比对比配方IN31更高的角质层渗透。此外,配方IN35在10l/ha下具有比200l/ha更高的渗透。
表IN3.4:吡虫啉+噻虫啉SC配方中噻虫啉的角质层渗透。
配方以0.5l/ha试验。
结果表明,本发明的示例性配方IN35在10l/ha和200l/ha下具有比对比配方IN31更高的角质层渗透。此外,配方IN35在10l/ha下具有比200l/ha更高的渗透。
叶片洗去
根据方法15测定洗去,但洗去率为600mL/min。
表IN3.5:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方IN35相比,本发明的示例性配方IN35显示出在10L/ha和200L/ha喷雾量下更高的施用制剂剩余量。
实施例IN4:溴氰菊酯25SC
表IN4.1:配方IN41和IN45。
所用制备方法参考方法1。
叶片上的移液扩散试验
根据方法17测定叶片沉积物尺寸。
表IN4.2:在无纹理的苹果叶片和有纹理的水稻叶片上的喷雾稀释的液滴尺寸和剂量
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配方以8/15/100l/ha施用。
结果表明,本发明的示例性配方IN45显示在8和15L/ha的喷雾量下的沉积物尺寸大于100L/ha喷雾量下的沉积物尺寸,并且与对比配方IN41相比也是如此。
实施例IN5:乙虫腈200SC
表IN5.1:配方IN51和IN55。
所用制备方法参考方法1。
叶片上的移液扩散试验
根据方法17测定叶片沉积物尺寸。
表IN5.2:在无纹理的苹果叶片和有纹理的水稻叶片上的喷雾稀释的液滴尺寸和剂量
配方以8/15/100l/ha施用。
结果表明,本发明的示例性配方IN52显示在8和15L/ha的喷雾量下的沉积物尺寸大于100L/ha喷雾量下的沉积物尺寸,并且与对比配方IN51相比也是如此。
叶片洗去
根据方法15测定洗去,但洗去率为600mL/min。
表IN5.3:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方IN51相比,本发明的示例性配方IN55显示出在10L/ha和200L/ha喷雾量下更高的施用制剂剩余量。
实施例IN6:氟吡呋喃酮150SC
表IN6.1:配方IN61和IN65。
制备方法参考方法1。
叶片洗去
根据方法15测定洗去,但洗去率为600mL/min。
表IN6.2:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方IN61相比,本发明的示例性配方IN65显示出在200L/ha喷雾量下更高的施用制剂剩余量。
实施例IN7:Spidoxamat 48SC
表IN7.1:配方IN71和IN75。
制备方法参考方法1。
叶片洗去
根据方法15测定洗去,但洗去率为600mL/min。
表IN7.2:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方IN71相比,本发明的示例性配方IN75显示出在10和200L/ha喷雾量下更高的施用制剂剩余量。
除草剂实施例
实施例HB1.1:Triamanone 100SC
表HB1.1:配方HB1.1、HB1.2和HB1.3
制备方法参考方法2。
漂移
根据方法7测定漂移。
表HB1.2:漂移数据。
配方以0.5l/ha试验。
结果表明,与不含漂移减少添加剂(b)的对比配方HB1.3相比,本发明的示例性配方HB1.2在10l/ha喷雾量下显示出较低的小于150微米的可漂移液滴部分。
表HB1.3:漂移数据。
配方以0.5l/ha试验。
结果表明,与不含漂移减少添加剂(b)的对比配方HB1.3相比,本发明的示例性配方HB1.2在20l/ha喷雾量下显示出较低的小于150微米的可漂移液滴部分。
角质层渗透
苹果叶角质层的渗透根据角质层渗透测试方法13测定。
表HB1.4:Triamanone SC制剂的角质层渗透。
配方以0.5l/ha试验。
结果表明,本发明的示例性配方HB1.2在10l/ha和200l/ha下具有比对比配方HB1.1更高的角质层渗透。此外,配方HB1.2在10l/ha下具有比200l/ha更高的渗透。
叶片洗去
表HB.1.5:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方HB1.1相比,本发明的示例性配方HB1.2显示出在10L/ha和200L/ha喷雾量下更高的施用制剂剩余量。
实施例HB2:环磺酮+双苯恶唑酸315SC
表HB2.1:配方HB2.1和HB2.2
制备方法参考方法1。
角质层渗透
苹果叶角质层的渗透根据角质层渗透测试方法13测定。
表HB2.2:Triamanone SC制剂的角质层渗透。
配方以0.5l/ha试验。
结果表明,本发明的示例性配方HB2.2在10l/ha和200l/ha下具有比对比配方HB2.1更高的角质层渗透。此外,配方HB2.2在10l/ha下具有比200l/ha更高的渗透。
叶片洗去
表HB.2.3:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方HB2.1相比,本发明的示例性配方HB2.2显示出在10L/ha和200L/ha喷雾量下更高的施用制剂剩余量。
实施例HB3:噻酮磺隆+环丙磺酰胺200SC
表HB3.1:配方HB3.1、HB3.2和HB3.3
制备方法参考方法1。
漂移
根据方法7测定漂移。
表HB3.2:漂移数据。
配方以0.5l/ha试验。
结果显示,与不含漂移减少添加剂(b)的对比配方HB3.3相比,本发明的示例性配方HB3.2在20l/ha喷雾量下显示出更低量的小于100微米和小于150微米的喷雾液滴可漂移部分。
叶片洗去
表HB.3.3:叶片洗去数据
配方以0.5l/ha试验。(+=全部洗去,+++++=全部剩余)
结果表明,与对比配方HB3.1相比,本发明的示例性配方HB3.2显示出在10L/ha喷雾量下更高的施用制剂剩余量。
Claims (22)
1.农业化学制剂,其包括
a)一种或多种活性成分,
b)一种或多种漂移减少成分,
d)一种或多种吸收增强剂,
e)一种或多种耐雨添加剂,
f)任选地其他配方,
g)一种或多种补足至容积的载体,
包含以下量的组分a)至g)
a)5至500g/l,
b)0.01至50g/l,并且在b)为植物油或酯的情况下为1至50g/l,在b)为漂移减少聚合物的情况下为0.05至3g/l,
d)10至180g/l,
e)5至150g/l,
g)补足至容积的载体。
2.根据权利要求1所述的农业化学制剂,其中组分f)为强制性的并且以以下剂量存在:
f1)8至120g/l,
f2)1至20g/l,
f3)0.5至20g/l,
f4)5至150g/l,
f5)0.1至120g/l。
3.根据权利要求1或2所述的农业化学制剂,其中b)选自聚(乙烯)氧化物,其具有优选0.5至12百万g/mol,更优选0.75至10百万g/mol,最优选1至8百万g/mol的平均分子量,以及植物油和植物油酯和二酯,包括植物油与甘油和丙二醇的酯。
4.根据权利要求1或2所述的农业化学制剂,其中b)选自聚合物,所述聚合物选自羟丙基瓜尔胶和聚(乙烯)氧化物,其具有优选0.5至12百万g/mol,更优选0.75至10百万g/mol,最优选1至8百万g/mol的平均分子量,并且以0.05至10g/l,优选0.1至8g/l,最优选0.2至6g/l的量存在,其更优选地为聚(乙烯)氧化物。
5.根据权利要求1或2所述的农业化学制剂,其中b)选自植物油和植物油酯和二酯,包括植物油与甘油和丙二醇的酯,并且其以1至50g/l,优选5至30g/l,最优选6至30g/l的量存在。
6.根据权利要求1至5中任一项所述的农业化学制剂,其中d)选自乙氧基化醇、丙氧基-乙氧基化醇、乙氧基化羧酸、丙氧基-乙氧基化羧酸,或包含具有8-18个碳原子和平均5-40个EO单元的脂肪酸的甘油的乙氧基化单酯、二酯或三酯。
7.根据权利要求1至6中任一项所述的农业化学制剂,其中e)为Tg在-100℃至30℃的乳液聚合物或聚合物分散体,其中所述聚合物为丙烯酸酯和苯乙烯的共聚物,其中所述丙烯酸酯选自丙烯酸2-乙基己酯、丙烯酸丁酯、丙烯酸仲丁酯、丙烯酸乙酯、丙烯酸甲酯、丙烯酸、丙烯酰胺、丙烯酸异丁酯、甲基丙烯酸甲酯或其组合,以及其中所述苯乙烯选自苯乙烯、叔丁基苯乙烯、对甲基苯乙烯或其组合。
8.根据权利要求1至7中任一项所述的农业化学制剂,其中a)以10至320g/l,最优选20至230g/l的量存在。
9.根据权利要求1至8中任一项所述的农业化学制剂,其中d)以20至150g/l,最优选30至140g/l的量存在。
10.根据权利要求1至9中任一项所述的农业化学制剂,其中e)以10至100g/l,最优选20至80g/l的量存在。
11.根据权利要求1至10中任一项所述的农业化学制剂,其中根据权利要求5所述的b)以0.1至50g/ha,更优选1至40g/ha,最优选5至30g/ha施用。
12.根据权利要求1至10中任一项所述的农业化学制剂,其中根据权利要求4所述的b)以0.01至25g/ha,更优选0.05至10g/ha,最优选0.1至6g/ha施用。
13.根据权利要求1至12中任一项所述的农业化学制剂,其中所述活性成分选自肟菌酯、联苯吡菌胺、丙硫菌唑、inpyrfluxam、isoflucypram、氟吡菌胺、氟吡菌酰胺、fluoxapiprolin、异噻菌胺、螺虫乙酯、四唑虫酰胺、乙虫腈、吡虫啉、溴氰菊酯、氟吡呋喃酮、spidoxamat、triafamone、环磺酮、噻酮磺隆甲酯、双苯恶唑酸和cyprosulfamat。
14.根据权利要求1至13中任一项所述的农业化学制剂,其中组分f)包含至少一种非离子表面活性剂和/或离子表面活性剂(f1)、流变改性剂(f2)、消泡物质(f3)和至少一种防冻剂(f4)。
15.根据权利要求1至14中任一项所述的农业化学制剂,其包含以下量的组分a)至g)
a)10至320g/l,最优选20至230g/l,
b)0.1至30g/l,最优选1至20g/l,以及在b)为植物油或酯的情况下为5至30g/l,最优选6至30g/l,在b)为漂移减少聚合物的情况下为0.1至2g/l,最优选0.2至1.5g/l,
d)20至150g/l,最优选30至140g/l,
e)10至100g/l,最优选20至80g/l,
f1)8至120g/l,最优选10至80g/l,
f2)1至20g/l,最优选2至10g/l,
f3)0.5至20g/l,最优选1至12g/l,
f4)5至150g/l,最优选10至120g/l,
f5)0.1至120g/l,最优选0.5至80g/l,
g)补足至容积的载体。
16.根据权利要求1至15中任一项所述的农业化学制剂,其中所述制剂以1至30l/ha,优选1至20l/ha,更优选2至15l/ha,最优选5至15l/ha的喷雾量施用。
17.根据权利要求1至16中任一项所述的农业化学制剂,其中所述制剂为罐装物制剂。
18.根据权利要求1至16中任一项所述的农业化学制剂,其中添加剂b)至e)在喷雾液体中的浓度为
添加剂b)为0.005至1g/l,最优选0.04至0.6g/l,其中b)为聚合物,
添加剂b)为0.01至5g/l,最优选0.02至2.5g/l,其中b)为油,
添加剂d)为1至20g/l,最优选2至8g/l,
添加剂e)为0.5至10g/l,最优选2至6g/l。
19.根据权利要求1至16中任一项所述的农业化学制剂,其中添加剂b)至e)每ha的剂量为
添加剂b)为0.05至10g/ha,最优选0.4至6g/ha,其中b)为聚合物,
添加剂b)为0.1至50g/ha,最优选0.2至30g/ha,其中b)为油,
添加剂d)为10至200g/ha,最优选40至80g/ha,
添加剂e)为5至100g/ha,最优选20至60g/ha。
20.根据权利要求1至18中任一项所述的农业化学制剂,其中制剂中的浓度、喷雾液体中的浓度和每ha的添加剂b)至e)的剂量以以下方式组合
添加剂b)在制剂中为0.4至6g/l,在喷雾液体中为0.02至0.6g/l,并且为0.2至6g/ha,其中b)为聚合物,
添加剂b)在制剂中为0.1至50g/l,在喷雾液体中为0.01至5g/l,并且为0.2至30g/ha,其中b)为油,
添加剂d)在制剂中为40至160g/l,在喷雾液体中为2至8g/l,并且为40至80g/ha,
添加剂e)在制剂中为20至80g/l,在喷雾液体中为1至6g/l,并且为20至60g/ha。
21.将根据权利要求1至15中的一项或多项所述的农业化学制剂施用到作物的方法,其中所述制剂以1至30l/ha,优选1至20l/ha,更优选2至15l/ha,最优选5至15l/ha的喷雾量施用。
22.根据权利要求1至15中的一项或多项所述的农业化学组合物在施用农业化学化合物以防治有害生物中的用途,其中所述组合物通过UAV、UGV、PWM施用。
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