CN1173110A - 农药辅助剂组合物以及增强农药功效的方法 - Google Patents
农药辅助剂组合物以及增强农药功效的方法 Download PDFInfo
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- CN1173110A CN1173110A CN95197339A CN95197339A CN1173110A CN 1173110 A CN1173110 A CN 1173110A CN 95197339 A CN95197339 A CN 95197339A CN 95197339 A CN95197339 A CN 95197339A CN 1173110 A CN1173110 A CN 1173110A
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Abstract
一种农药辅助剂组合物,它包含至少一种脱水山梨醇/脂肪酸酯表面活性剂(A)和至少一种选自树脂酸表面活性剂和阴离子低聚物或聚合物型季铵盐表面活性剂的表面活性剂(B);这种辅助剂组合物可安全地用于各种农作物,不会引起对农作物的伤害,并能增强各种农药的功效。
Description
本发明的背景
发明领域
本发明涉及新的农药辅助剂组合物,增强农药功效的方法,该方法包括把所说的组合物和一种农药在一起使用,所说的组合物增强农药功效的用途以及新的农药组合物。
有关技术的描述
包括杀虫剂、杀真菌剂(或杀菌剂)、除草剂、杀螨剂(或灭螨剂)和植物生长调节剂的农药可以一些形式被使用,例如乳剂、可湿性粉剂、粒剂、粉剂和流动剂。在这些农药制剂的性质中,已经进行了各种尝试来使农药达到最佳功效。然而,很难通过制剂的调节来增强农药的功效。开发新的农药则更加困难。因此,进一步增进现有农药的功效将是对工业界的巨大贡献。
已经知道包括各种含氮化合物诸如季铵盐类、甜菜碱类和氧化胺类的表面活性剂可作为能增强农药功效的物质。知道在上述化合物中季铵化或进一步聚氧乙烯化的长链胺类对这一目的也是有效的但是。上述,包括含氮化合物的能增强农药功效的表面活性剂的效果并不总是令人满意。
另一方面,日本专利公开-B No.62-43968(1987年9月17日公开)和日本专利公开-A No.6-145003(1994年5月24日公开)公开了分别使用脱水山梨醇/脂肪酸酯作为农艺害虫防治组合物的成分,以及使用聚氧亚烷基/树脂酸酯作为农艺生物杀伤剂辅助剂的成分。但是,脱水山梨醇/脂肪酸酯和聚氧亚烷基/树脂酸酯当中的一种对于增强农药的功效却表现出不足够好的效果。
本发明的公开内容
发明概述
为了寻找一种能增强农药功效的化合物,本发明人已进行了广泛的研究。作为研究结果,本发明人已发现包含脱水山梨醇/脂肪酸酯表面活性剂和一种树脂酸表面活性剂或一种低聚物或聚合物类型的季铵盐表面活性剂的混合物能增强各种农药的功效。基于这一发现完成了本发明。
这样,本发明涉及一种农药辅助剂组合物,它包含至少一种脱水山梨醇/脂肪酸酯表面活性剂(A)和至少一种选自树脂酸表面活性剂和下式表示的季铵盐表面活性剂的表面活性剂(B):其中R1、R2、和R3中至少有一个表示具有8至30个碳原子的直链或支链烷基或链烯基,其余代表一个或两个选自-CH3、-CH2CH3、和
(n值为1至5)的基团,R4代表-CH3或-CH2CH3,抗衡离子X-代表一个阴离子基团,它是由重均分子量为300至20,000的低聚物或聚合物所衍生的,并选自(1):通过使含有至少一种选自不饱和羧酸及其衍生物作为必需组分的单体进行聚合得到的聚合物或共聚物,(2):通过使含有苯乙烯磺酸作为必需组分的单体进行聚合所得的聚合物或共聚物,和(3):可带有烃基团作为取代基的磺化芳族化合物与甲醛的缩合物。
进一步,本发明涉及一种增强农药功效的方法,该方法包括向将会从这种处理中受益的地点,与一种农药一起施用一种脱水山梨醇/脂肪酸酯表面活性剂(A)和至少一种选自上述树脂酸表面活性剂和季铵盐表面活性剂的表面活性剂(B)。
还有,本发明涉及使用脱水山梨醇/脂肪酸酯表面活性剂(A)和至少一种选自上述树脂酸表面活性剂和季铵盐表面活性剂的表面活性剂(B)的混合物来增强农药的功效。
此外,本发明涉及一种农药组合物,它包含至少一种脱水山梨醇/脂肪酸酯表面活性剂(A),至少一种选自上述树脂酸表面活性剂和季铵盐表面活性剂的表面活性剂(B),以及一种农药,其中表面活性剂(A)和表面活性剂(B)的总和对农药的重量比率为0.03至50。
由下面给出的详尽描述,本发明的进一步范围和适用性将变得很明显。但是,应该知道,详尽的描述和具体的实施例虽然指出了本发明优选的实施方案,但仅仅是为了说明的目的而给出的,因为对本领域技术人员来说,由此详尽说明,在本发明的精神和范围之内很显然可做出各种改变和修饰。
本发明的详尽描述
[农药辅助剂组合物]
用于本发明的脱水山梨醇/脂肪酸酯表面活性剂(A)的实例包括脱水山梨醇/脂肪酸酯和聚氧亚烷基脱水山梨醇/脂肪酸酯类,即脱水山梨醇脂肪酸酯的烯化氧加合物。在本发明中特别优选使用脱水山梨醇/脂肪酸酯类。
虽然脱水山梨醇/脂肪酸酯可以是任何一种单酯、二酯或三酯,但通常使用这些酯类的混合物。在本发明中使用按重量计单酯含量为40至70%的脱水山梨醇/脂肪酸酯混合物是合乎需要的。脱水山梨醇/脂肪酸酯的脂肪酸部分优选一种由含有8至22个碳原子的脂肪酸所衍生的脂肪酸基。这种含有8至22个碳原子的脂肪酸类的具体实例包括正癸酸、月桂酸、软脂酸、油酸和硬脂酸。
聚氧亚烷基脱水山梨醇/脂肪酸酯类是通过,例如,这样一种方法来生产的,即把一种烯化氧加到脱水山梨醇中以引入一个氧亚烷基(或烷基醚)基团,然后把得到的化合物通过与脂肪酸反应进行酯化。用于加成反应的烯化氧类的实例包括环氧乙烷、环氧丙烷和环氧丁烷,其中环氧乙烷是特别优选的。加入的烯化氧的平均摩尔数通常为每摩尔脱水山梨醇/脂肪酸酯2至30摩尔,优选5至25摩尔。
在本发明中树脂酸表面活性剂和/或季铵盐表面活性剂(B)是和上述脱水山梨醇/脂肪酸酯表面活性剂(A)一起使用的。
用于本发明中的树脂酸表面活性剂是指由树脂酸或松香产生的表面活性剂。
这里松香是指一种主要包含树脂酸的天然树脂,树脂酸包含在通过蒸馏松科植物的树脂油以除去挥发性物质诸如精油而得到的残留物中。构成这种天然树脂的主要树脂酸类的实例包括松香酸及其类似物以及海松酸。市售的松香可用作本发明中树脂酸表面活性剂的原料,虽然松香的成分和性质在某种程度上不同,因为它们是由天然产物衍生而来的。在这些松香中,特别优选以名称“浮油松香”出售的那些。市售浮油松香的实例包括Hartall Rosin R-X Hartall Rosin R-WW和Hartall RosinR-N(Harima Chemicals,Inc.的产品)。
用于本发明的树脂酸表面活性剂优选是一种聚氧亚烷基松香醚,即松香的烯化氧加合物,或一种聚氧亚烷基树脂酸醚,即一种树脂酸的烯化氧加合物。聚氧亚烷基松香醚是通过把烯化氧加到松香中合成的。聚氧亚烷基树脂酸醚是通过把烯化氧加到树脂酸中合成的。在本发明中使用的产物是那些往松香或树脂酸中按平均每摩尔松香或树脂酸优选加入2至50摩尔、更优选5至40摩尔、最优选8至30摩尔烯化氧所得到的产物。在加成反应中优选将环氧乙烷或环氧乙烷与其它烯化氧的组合用作烯化氧。
市售树脂酸表面活性剂的实例包括Hartall REO-15和REO-30(Harima Chemicals,Inc.的松香乙氧化物),以及BLAUNON REO-8〔聚氧亚乙基(8)松香醚〕,REO-15〔聚氧亚乙基(15)松香醚〕和REO-30〔聚氧亚乙基(30)松香醚〕(Aoki yushi Kogyo K.K.公司的产品)。
用于本发明的季铵盐表面活性剂是下式代表的那些化合物:其中R1、R2、或R3中至少有一个代表含有8至30个碳原子的直链或支链烷基或链烯基,其余代表一个或两个选自-CH3、-CH2CH3、和
(n值为1至5)的基团,R4代表-CH3或-CH2CH3,抗衡离子X-代表一个由重均分子量为300至20,000的低聚物或聚合物所衍生的阴离子基团,选自(1):通过使含有至少一种选自不饱和羧酸及其衍生物作为必需组分的单体进行聚合所得的聚合物或共聚物,(2):通过使含有苯乙烯磺酸作为必需组分的单体进行聚合所得的聚合物或共聚物,(3):可带有烃基团作为取代基的磺化的芳族化合物与甲醛的缩合物。
依赖于上式中官能团R1和R4的类型和抗衡离子X-,该季铵盐表面活性剂是各式各样的。这些季铵盐表面活性剂中的任选一种都可用于本发明中。也可使用两种或多种上述季铵盐表面活性剂的混合物。
现在将对提供季铵盐表面活性剂的抗衡离子的阴离子低聚物或聚合物(1)至(3)进行具体的描述。
(1):通过使含有至少一种选自不饱和羧酸及其衍生物作为必需组分的单体进行聚合所得的聚合物或共聚物:
生产这种聚合物或共聚物(1)所必需的单体(即至少一种选自不饱和羧酸及其衍生物的单体)包括不饱和一元羧酸诸如丙烯酸和甲基丙烯酸,不饱和二元羧酸诸如马来酸,及它们的衍生物,诸如烷基酯类(例如甲基酯类)以及上述羧酸的环氧乙烷加合物和上述羧酸的烷基酯类的环氧乙烷加合物。可以和上述必需单体一起使用的单体(共聚用单体)的实例包括醋酸乙烯酯、异丁烯、二异丁烯和苯乙烯。
这些单体类可用迄今已知的任何方法进行聚合。单体类的相对用量(比率)和聚合物或共聚物的聚合度没有特别的限制。
聚合物或共聚物(1)的实例包括一种丙烯酸聚合物、一种甲基丙烯酸聚合物、一种丙烯酸/甲基丙烯酸共聚物、一种丙烯酸/甲基丙烯酸聚氧乙烯醚共聚物、一种丙烯酸/丙烯酸甲酯共聚物、一种丙烯酸/醋酸乙烯酯共聚物、一种丙烯酸/马来酸共聚物、一种马来酸/异丁烯共聚物和一种马来酸/苯乙烯共聚物。
两种或多种这些聚合物或共聚物的混合物也可用作为提供本发明中上述季铵盐表面活性剂的抗衡离子的阴离子低聚物或聚合物。只要不会损害所需要的性能,这些低聚物或聚合物的羧基的一部分可以形成它们的碱金属盐、铵盐或有机胺盐。
用于本发明中的聚合物或共聚物(1)的重均分子量为300至20,000。
(2)通过使含有苯乙烯磺酸作为必需组分的单体进行聚合所得到的聚合物或共聚物。
苯乙烯磺酸均聚物可以容易地通过将苯乙烯磺酸聚合或将聚苯乙烯磺化而制得。苯乙烯磺酸聚合物包含下式的结构单元:
在本发明中被用作提供上述季铵盐表面活性剂的抗衡离子的阴离子低聚物或聚合物的苯乙烯磺酸均聚物的重均分子量优选是300至20,000,更优选300至10,000。
含有苯乙烯磺酸单元和其它单体单元的共聚物可以容易地通过把苯乙烯磺酸与其它单体进行共聚,或者把由苯乙烯单元和其它单体单元构成的共聚物进行磺化而制得。提供其它单体单元的共聚用单体类的实例包括疏水性单体类诸如丙烯酸烷基酯类、甲基丙烯酸烷基酯类、乙烯基烷基醚类、醋酸乙烯酯、乙烯、丙烯、丁烯、丁二烯、二异丁烯、氯乙烯、1,1-二氯乙烯、丙烯腈和苯乙烯;以及亲水性单体类诸如丙烯酸、甲基丙烯酸、马来酸、富马酸、马来酸酐、乙烯醇、丙烯酰胺、甲基丙烯酰胺、双丙酮丙烯酰胺、N-乙烯基吡咯烷酮、2-丙烯酰氨基-2-甲基丙烷磺酸、甲基丙烯磺酸、二甲苯磺酸和萘磺酸。
在本发明中用作提供上述季铵盐表面活性剂的抗衡离子的阴离子低聚物或聚合物的含有苯乙烯磺酸单元的共聚物的重均分子量优选是300至20,000,更优选1,000至10,000。这样的共聚物优选是(甲基)丙烯酸/苯乙烯磺酸共聚物。在共聚物中(甲基)丙烯酸单元对苯乙烯磺酸单元的摩尔比例优选是0.1至10,更优选1/3至4。
只要它们的效果不会受到损害,在聚合物或共聚物(2)中酸基(诸如磺酸基和羧基)不仅可以是游离酸的形式,也可以是它的一种盐的形式(诸如钠盐、钾盐、铵盐、二乙醇胺盐、三乙醇胺盐、一异丙醇胺盐、二异丙醇胺盐、三异丙醇胺盐和2-氨基-2-甲基-丙烷-1,3-二醇盐)。
(3)可带有烃基团作为取代基的磺化的芳族化合物与甲醛的缩合物:
磺化的芳族化合物与甲醛的缩合物的具体实例包括石油磺酸衍生物、木质素磺酸衍生物、萘磺酸衍生物、二甲苯磺酸衍生物和烷基苯磺酸衍生物的甲醛缩合物。
本发明的上述缩合物(3)可通过把例如萘、一种烷基取代的苯、一种烷基取代的萘、蒽、一种烷基取代的蒽、木质素或一种包含在石油残余物中的芳族化合物用普通方法进行磺化,接着把得到的磺化化合物与甲醛进行缩合而得到。
本发明的上述缩合物(3)的缩合度优选是至少2,更优选3至30。缩合物(3)的重均分子量为300至20,000。
各种芳族化合物均可用作上述缩合物(3)的原料,其中优选的是木质素、二甲苯、甲苯、萘和烷基部分含1至6个碳原子的烷基萘类。当然,它们的混合物也可被用作原料。多环芳族化合物优选用作缩合物(3)的原料。
上述缩合物(3)的磺酸基团的一部分可以是它的盐的形式,诸如一种碱金属盐,例如钠或钾盐;一种碱土金属盐,例如钙盐;一种胺盐或铵盐,只要不损害本发明季铵盐表面活性剂所需的性能。
在为本发明季铵盐表面活性剂提供抗衡离子的阴离子低聚物和聚合物(1)至(3)中,特别优选的是磺化的芳族化合物与甲醛的缩合物(3)。也可结合使用两种或多种阴离子低聚物(或聚合物)。
本发明中的季铵盐表面活性剂可以容易地通过使含有例如卤原子作为抗衡离子的季铵盐与一种离子交换树脂接触以形成季铵氢氧化物,然后再把得到的季铵氢氧化物与具有上述阴离子残基的低聚物或聚合物(1)、(2)或(3)反应以中和它而制得。在该方法中,不必用季铵盐氢氧化物中和含阴离子残基的低聚物或聚合物(1)、(2)或(3)中的所有阴离子残基。一部分阴离子残基可以是碱金属、胺盐、有机胺盐等的盐的形式,只要本发明所需的性能不会受到损害。
至少一种选自树脂酸表面活性剂和用上式代表的季铵盐表面活性剂的表面活性剂被用作本发明的表面活性剂(B)。优选使用树脂酸表面活性剂和季铵表面活性剂中的一种。
在本发明中表面活性剂(B)与脱水山梨醇/脂肪酸酯表面活性剂(A)的重量比率优选是0.01至5,更优选0.02至1。
当表面活性剂(A)和(B)与农药结合使用时,优选将表面活性剂稀释,使它们的总浓度为100至10,000ppm,尤其是200至1,000ppm。
在本发明中,一种除表面活性剂(A)和(B)以外的表面活性剂也可以和表面活性剂(A)和(B)结合使用。这类表面活性剂的实例包括除表面活性剂(A)和(B)以外的非离子表面活性剂、阴离子型表面活性剂、阳离子型表面活性剂和两性离子表面活性剂。它们可以单独使用,或者以含有至少两种这些表面活性剂的混合物的形式使用。
非离子型表面活性剂的实例包括聚氧乙烯烷基醚类、聚氧乙烯烷芳基醚类、聚氧乙烯烷芳基醚/甲醛缩合物类、聚氧亚烷基芳基醚类、聚氧亚烷基烷基酯类、聚氧亚烷基链烯基酯类、聚氧亚烷基烷基山梨醇酯类、聚氧亚烷基烷基甘油酯类、聚氧亚烷基嵌段共聚物类、聚氧亚烷基嵌段共聚物/烷基甘油酯类、聚氧亚烷基烷基氨磺酰类、聚氧亚烷基油醚类、聚氧亚烷基烷基酚类、烷基苷类、烷基多苷类、聚氧亚烷基烷基多苷类和聚亚烷基甘油/脂肪酸酯类。它们可以单独使用,或者以含有至少两种这些表面活性剂的混合物的形式使用。
在上述非离子型表面活性剂中,优选聚亚乙基甘油/脂肪酸单酯和二酯;特别优选聚亚乙基甘油单月桂酸酯和聚亚乙基甘油单油酸酯。
阳离子型表面活性剂的实例包括烷基胺/环氧乙烷加合物和烷基胺/环氧丙烷加合物,诸如一种由牛脂、大豆油脂肪酸或椰子油脂肪酸/环氧乙烷加合物衍生的胺,一种油胺/环氧乙烷加合物,合成的烷基胺/环氧乙烷加合物以及辛胺/环氧乙烷加合物。它们可以单独使用,或者以含有至少两种这些表面活性剂的混合物的形式使用。
在阴离子表面活性剂中,典型地是可以它们的水溶液或固体形式得到的那些。它们的实例包括一和二烷基萘磺酸钠、α-烯磺酸钠、烷磺酸钠、烷基磺基丁二酸盐类,烷基硫酸盐类、聚氧亚烷基烷基醚硫酸盐类、聚氧亚烷基烷基芳基醚硫酸盐类、聚氧亚烷基苯乙烯基苯基醚硫酸盐类、一和二烷基苯磺酸盐类、烷基萘磺酸盐类、烷基萘磺酸盐/甲醛缩合物、烷基二苯基醚磺酸盐、烯磺酸盐、一和二烷基磷酸盐、聚氧亚烷基一和二烷基醚磷酸盐、聚氧亚烷基一和二苯基醚磷酸盐、聚氧亚烷基一和二烷基苯基醚磷酸盐、聚羧酸盐类、直链和支链烷基聚氧亚烷基醚乙酸及其盐类、直链和支链链烯基聚氧亚烷基醚乙酸及其盐类、直链和支链烷基酰氨基聚氧亚烷基醚乙酸及其盐类、脂肪酸类诸如辛酸、月桂酸、硬脂酸、油酸及其盐类,以及N-甲基脂肪酸氨基乙磺酸酰胺。上述实例中的盐是指钠盐、钾盐、铵盐、胺盐等。它们可以单独使用,或者以含有至少两种这些表面活性剂的混合物的形式使用。
在上述阴离子型表面活性剂中,优选脂肪酸盐类;特别优选高级脂肪酸如油酸和蓖麻油脂肪酸的钠盐和钾盐。
两性离子表面活性剂的实例包括月桂基二甲基胺氧化物、AromoxC/12、Monaterics、Miranols、Lonzaines、以及其它氧化胺和甜菜碱化合物。它们可以单独使用,或者以含有至少两种这些表面活性剂的混合物的形式使用。
本发明的农药辅助剂组合物在使用中被用来增强农药的功效。
本发明的农药辅助剂组合物可安全地被用于各种农作物,而不会引起对农作物的损害。
[增强农药功效的方法]
在本发明的方法中,本发明的上述农药辅助剂组合物是和一种农药一起施用到可能从这种处理中受益的地点的,即上述表面活性剂(A)和(B)和农药在一起施用。具体地说,表面活性剂(A)和(B)以及一种农药被施用到例如植物、谷类植物、蔬菜类、水果类、树木、果树、草坪、杂草或种籽上,并且同时施用到真菌、细菌、昆虫、壁虱或螨身上。换言之,本发明的农药辅助剂组合物和一种农药的混合物被使用于农场、植物园、果园、菜园、草坪、树木和森林。
表面活性剂(A)和(B)优选以包含表面活性剂(A)和(B)、一种农药以及一种水溶液介质的混合物的形式被施用于例如植物上。具体地说,本发明的农药辅助剂组合物是当这种农药被稀释时加入到不含本发明辅助剂的农药组合物中的,或者另一种选择是,将各种形式之一的含有表面活性剂(A)和(B)以及农药的农药组合物稀释,以制备一种供例如喷雾用的农药的稀释液,并施用这种稀释液。在稀释液中表面活性剂(A)和(B)的总浓度优选是100至10,000ppm,更优选200至1,000ppm。表面活性剂(A)和(B)优选是以这样的量来施用,即表面活性剂(A)和(B)的总和与农药的重量比率为0.03至50。但是,当表面活性剂(A)和(B)与市售的农药制剂诸如Cyhalon、Scout、Nomolt和Milveknock等一起施用时,表面活性剂(A)和(B)的总和与农药的重量比率可以高一些,具体地说,可大于50至大约250。
[农药组合物]
本发明的农药组合物包含表面活性剂(A)、表面活性剂(B)和一种农药,并且表面活性剂(A)和(B)的总和与农药的重量比率,即[(A)+(B)/农药]为0.03至50,优选是0.1至50,更优选0.3至35。
本发明的农药组合物可制备成任何形式,例如选自液体制剂、乳剂、可湿性粉剂、粒剂、粉剂和流动剂的形式,该形式不受限制。这样,本发明的农药组合物可能包含其它的添加剂诸如乳化剂、溶剂、分散剂和/或载体,这依赖于剂型或它们的形式。
如果必要的话,这样一种农药组合物可能还包含螯合剂、pH调节剂、无机盐或增稠剂。
用于本发明农药组合物中的螯合剂的实例包括基于氨基聚羧酸类、芳族和脂族羧酸类、氨基酸类、醚聚羧酸类、膦酸类诸如亚氨基二甲基膦酸类(IDP)和烷基二膦酸类(ADPA)、羟基羧酸类和聚电解质类(包括低聚电解质类)的那些螯合剂以及二甲基乙二醛二肟(DG)。这些螯合剂各自可以是游离酸的形式,或者是盐诸如钠盐、钾盐和铵盐的形式。
螯合剂的用量为农药组合物中表面活性剂的总和的按摩尔计的0.01至30倍。
其次,用于本发明农药组合物中的农药的实例将被引证,虽然用于本发明中的农药并不限于这些。
关于杀真菌剂(或杀菌剂),包括代森锌〔亚乙基双(二硫代氨基甲酸)锌〕、代森锰〔亚乙基双(二硫代氨基甲酸)锰〕、福美双〔双(二甲基硫代氨基甲酰基)二硫化物〕、代森锰锌〔亚乙基双(二硫代氨基甲酸)锌和锰的复合物〕、福代锌〔双(二甲基二硫代氨基甲酸)亚乙基双(二硫代氨基甲酸)二锌〕、甲基代森锌〔聚合的亚丙基双(二硫代氨基甲酸)锌〕、苯并咪唑类杀真菌剂诸如苯菌灵〔1-(丁基氨基甲酰基)-2-苯并咪唑氨基甲酸甲酯〕和甲基托布津〔1,2-双(3-甲氧基羰基-2-硫脲基)苯〕;羰基酰亚胺类杀真菌剂诸如烯菌酮〔3-(3,5-二氯苯基)-5-甲基-5-乙烯基-1,3-噁唑烷-2,4-二酮〕、异丙定〔3-(3,5-二氯苯基)-N-异丙基-2,4-二氧代咪唑烷-1-甲酰胺〕、杀菌利〔N-(3,5-二氯苯基)-1,2-二甲基环丙烷-1,2-二甲酰胺〕;以及,此外,敌菌灵(Triazime)〔2,4-二氯-6-(2-氯苯胺基)-1,3,5-三嗪〕、氟菌唑〔(E)-4-氯-α,α,α,-三氟-N-(1-咪唑-1-基-2-丙氧亚乙基)-甲苯胺〕、氨丙灵〔N-(2-甲氧基乙酰基)-N-(2,6-二甲苯基)-DL-丙氨酸甲酯〕、双苯三唑醇〔全部外消旋的-1-(联苯-4-基氧基)-3,3-二甲基-1-(1H-1,2,4-三唑-1-基)-2-丁烷-2-醇〕、啶斑肟〔2′,4′-二氯-2-(3-吡啶基)苯乙酮(EZ)-O-甲基肟〕、异嘧菌醇〔2,4′-二氯-α-(吡啶-5-基)二苯甲基醇〕、嗪氨灵〔1,4-双(2,2,2-三氯-1-甲酰氨基乙基)哌嗪〕、双胍辛醋酸盐〔1,1′-亚氨基二(1,8-亚辛基)二胍三醋酸盐〕、有机铜化合物(喹啉酮〔8-羟基喹啉铜〕)、氢氧化铜,抗生素杀菌剂类(链霉素型、四环素型、多氧菌素型、杀稻瘟菌素S、春日霉素型、有效霉素型)、唑菌酮〔1-(4-氯苯氧基)-3,3-二甲基-1-(1,2,4-三唑-1-基)-2-丁酮〕、富士一号有机硫杀菌剂〔1,3-二硫戊环-2-亚基丙二酸二异丙酯〕、百菌清(Daconil,TPN)〔四氯异邻苯二甲腈〕、氯唑灵(Pansoil)〔5-乙氧基-3-三氯甲基-1,2,4-噻二唑〕、四氯苯酞〔4,5,6,7-四氯-2-苯并[c]呋喃酮〕、Iprobenfos(Kitazin P)〔O,O-二异丙基-S-硫代磷酸苄酯〕、克瘟散(Hinosan)〔O-乙基-S,S-二硫代磷酸二苯酯〕、Probenazole〔3-烯丙氧基-1,2-苯并异噻唑-1,1-二氧化物〕、Captan〔N-三氯甲基硫代四氢邻苯二甲酰亚胺〕和Fosetyl〔三(乙基磷酸铝)〕。
关于杀虫剂,包括拟除虫菊类杀虫剂诸如氯菊酯〔(1RS,3RS)-(1RS,3RS)-3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸3-苯氧苄基酯〕、氯氰菊酯〔(1RS,3RS)-(1RS,3RS)-3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸(RS)-α-氰基-3-苯氧苄基酯〕、杀灭菊酯〔2-(4-氯苯基)-3-甲基丁酸α-氰基-3-苯氧苄基酯〕以及氟氯氰菊酯(Bay throid)〔3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸α-氰基-4-氟-3-苯氧基苯甲基酯〕;有机磷杀虫剂诸如杀螟腈(Cyanophos,Cyanox)〔硫代磷酸对-氰基苯基二甲酯〕、DMTP(Methidathion)〔二硫代磷酸S-〔(2-甲氧基-5-氧代-1,3,4-噻二唑啉-4-基)甲基〕二甲酯〕、BRP(naled)〔磷酸1,2-二溴-2,2-二氯乙基二甲酯〕、杀抗松(Dioxabenzofes)〔2-甲氧基4H-1,3,2-苯并二噁磷-2-硫化物〕、敌敌畏(DDVP)〔磷酸二甲基2,2-二氯乙烯基酯〕、杀螟松(MEP)〔硫代磷酸O,O-二甲基-O-(3-甲基-4-硝基苯基)酯〕马拉硫磷(Malathon)〔硫羟硫代磷酸S-〔1,2-双(乙氧羰基)乙基〕二甲基酯〕、乐果〔二硫代磷酸二甲基S-(N-甲基-氨基甲酰基甲基)酯〕、稻丰散(Elsan)〔硫羟硫代磷酸S-〔α-(乙氧羰基)苄基〕二甲酯〕和倍硫磷(Baycid)〔硫代磷酸O,O-二甲基-O-〔3-甲基-4-(甲硫基苯基〕酯〕;氨基甲酸酯类杀虫剂诸如Fenobucarb(Bassa)〔甲基氨基甲酸O-仲丁基苯基酯〕、Metolcarb(MTMC)〔甲基氨基甲酸间甲苯基酯〕、Xylylcarb(Meobal)〔N-甲基氨基甲酸3,4-二甲基苯基酯〕、西维因(NAC)〔N-甲基氨基甲酸1-萘基酯〕;灭多虫〔N-(甲基氨基甲酰氧基)硫代亚氨逐乙酸S-甲基酯〕和巴丹〔1,3-双(氨基甲酰基硫基)-2-(N,N-二甲氨基)丙烷盐酸盐〕。
进一步,关于天然杀虫剂,包括源于除虫菊的除虫菊酯制剂和胡椒基丁醚制剂、来源于鱼藤的鱼藤酮制剂、是属于豆类植物的一种灌木,以及尼古丁制剂〔含有3-(1-甲基2-吡咯烷基)吡啶硫酸盐〕。关于昆虫生长调节剂(IGR),包括氟脲杀〔1-(4-氯苯基)-3-(2,6-二氟苯甲酰基)脲〕、伏虫隆〔1-(3,5-二氯-2,4-二氟苯基)-3-(2,6-二氟苯甲酰基)脲〕、定虫隆〔1-[3,5-二氯-4-(3-氯-5-三氟甲基-2-吡啶基氧基)苯基]-3-(2,6-二氟苯甲酰基)脲、Buprofezin〔2-叔丁基亚氨基-3-异丙基-5-苯基-3,4,5,6-四氢-2H-1,3,5-噻二嗪-4-酮〕和Fenoxycarb〔2-(4-苯氧基苯氧基)乙基氨基甲酸乙酯〕。
关于杀螨剂(或灭螨剂),包括杀螨酯(Chlorfenson)〔对-氯苯磺酸对-氯苯基酯〕、溴螨酯(Bromo propylate)〔P,P′-二溴二苯基乙醇酸异丙酯〕、三氯杀螨砜〔对-氯苯基2,4,5-三氯苯基砜〕、苯硫威〔二甲基硫代氨基甲酸S-4-苯氧丁基酯〕、唑螨酯〔(E)-α-(1,3-二甲基-5-苯氧基吡唑-4-基-亚甲基氨基氧基)-对甲苯甲酸叔丁基酯〕、氟啶胺〔3-氯-N-(3-氯-5-三氟甲基-2-吡啶基)-6-α,α,α-三氟-2,6-二硝基对甲苯胺〕、四螨嗪〔3,6-双(2-氯苯基)-1,2,4,5-四嗪〕、敌螨普(Dinocap)〔巴豆酸2,6(或2,4)-二硝基-4-辛基苯基酯的异构反应混合物〕、哒螨酮〔2-叔丁基-5-(4-叔丁基苄硫基)-4-氯哒嗪-3(2H)-酮〕、乐杀螨〔二甲基丙烯酸2,4-二硝基-6-叔丁基苯基酯〕、丙酯杀螨醇〔α,α-双(对-氯苯基)乙醇酸异丙酯〕、乙酯杀螨醇(A kar)〔4,4′-二氯苯基乙醇酸乙酯〕、开乐散(Kelthane)〔1,1-双(对氯苯基)-2,2,2-三氯乙醇〕、苯螨特(Citrazon)〔O-苯甲酰基-3-氯-2,6-二甲氧基苯基异羟肟酸乙酯〕、克螨特(Omite)〔亚硫酸2-(对-叔丁基苯氧基)环己基2-丙炔基酯〕、杀螨锡(Osadan)〔六(β,β-二甲基苯乙基)二锡噁烷〕、噻螨酮〔反式-5-(4-氯苯基)-N-环己基-4-甲基-2-氧代-噻唑烷-3-甲酰胺〕以及虫螨脒〔3-甲基-1,5-双(2,4-二甲苯基)-1,3,5-三氮杂戊-1,4-二烯〕。
关于除草剂,包括酸酰胺类除草剂诸如敌稗(DCPA)〔3′,4′-二氯-N-丙酰苯胺〕和草不绿〔2-氯-2′,6′-二乙基-N-(甲氧乙基)乙酰苯胺〕;脲类除草剂诸如敌草隆(DCMU)〔3-(3,4-二氯苯基)-1,1-二甲基脲〕和利谷隆〔3-(3,4-二氯苯基)-1-甲氧基-1-甲基脲〕;联吡啶类除草剂诸如Paraquat Dichloride(对草快)〔1,1′-二甲基-4,4-联吡啶鎓二氯化物〕和Diquat Dibromide(敌草快)〔6,7-二氯联吡啶基[1,2-a:2′,1′-c]吡嗪鎓二溴化物〕;二嗪类除草剂诸如除草定〔5-溴-3-仲丁基-6-甲基-尿嘧啶〕;S-三嗪类除草剂诸如西玛津〔2-氯-4,6-双(乙氨基)-1,3,5-三嗪〕和西草净〔2,4-双(乙氨基)-6-甲硫基-1,3,5-三嗪〕;腈类除草剂诸如敌草腈(DBN)〔2,6-二氯苯腈〕;二硝基苯胺类除草剂诸如氟乐灵〔α,α,α-三氟-2,6-二硝基-N,N-二丙基对甲苯胺〕;氨基甲酸酯类除草剂诸如杀草丹〔二乙基硫代氨基甲酸S-对氯苄基酯〕和灭草灵〔3,4-二氯苯氨基甲酸甲酯〕;二苯醚类除草剂诸如除草醚(NIP)〔2,4-二氯苯基-对硝基苯基醚〕;酚类除草剂诸如五氯酚〔五氯苯酚〕;苯甲酸类除草剂诸如麦草畏(MDBA)〔3,6-二氯-2-甲氧基苯甲酸二甲胺盐〕;苯氧基除草剂诸如2,4-滴〔2,4-二氯苯氧醋酸〕及其盐类(诸如钠盐和钾盐)以及除草佳(MCPCA)〔2′-氯-2-(4-氯-邻甲基苯氧基)乙酰苯胺〕;有机磷类除草剂诸如草甘膦〔N-(膦酰基甲基)甘氨酸〕及其盐类,双丙氨酰膦〔L-2-氨基-4-[(羟基)-(甲基)-氧膦基〕丁酰-L-丙氨酰-L-丙氨酸的钠盐]和草铵膦〔DL-高丙氨酸-4-基(甲基)-次膦酸铵〕,和脂族除草剂诸如TCA钠盐〔三氯醋酸钠〕和茅草枯(DPA)〔2,2-二氯丙酸钠〕。
关于植物生长调节剂,包括MH〔马来酰肼〕、乙烯利〔2-氯乙基膦酸〕、UASTA和双丙氨酰膦。
本发明的农药组合物还可能包含一种或多种成分诸如除上述的那些以外的植物生长调节剂、化肥和保存剂等。
本发明的农药组合物是为了用来防治真菌(或细菌)、昆虫、壁虱(或螨)以及杂草,或者用来调节植物的生长。
本发明的农药组合物可以下列的任何一种形式获得:
(a)所有成分包含在同一个容器中,
(b)本发明的农药辅助剂组合物包含在一个容器中,不含表面活性剂(A)和(B)的农药组合物包含在另一个容器中,和
(c)表面活性剂(A)和(B)包含在一个容器中,一种除表面活性剂(A)和(B)以外的表面活性剂包含在另一个容器中,和不含表面活性剂(A)和(B)的农药组合物包含在又一个容器中。
每个容器中内容物的形式没有特别的限制,它可依据它们的用途和目的来适当地选择。容器的材料没有特别的限制,只要它不与内容物反应或者不会对内容物有不利的影响。这类材料的实例包括塑料、玻璃和金属箔。
实施例
现在通过以下实施例对本发明作更详尽的描述,这些实施例不应被认为是对本发明范围的限制。实施例1
在三片菜豆叶片上按每片30只幼虫放上雌性神泽叶螨(Tetranychus Kanzawai Kishida)的幼虫,然后在25℃培育24小时。然后把整个叶片每片浸入试验溶液中5秒钟。从试验溶液中取出后再在25℃放置48小时。观测叶片并且基于未经处理的叶片上所得结果测定杀螨率(参照下面的等式)。
用作杀螨剂的Nissorun可湿性粉剂(含有10%(重量)的Hexy thiazox作为活性成分)和Osadan可湿性粉剂25(含有25%(重量)的PhenbutatinOxide作为活性成分)分别用每种稀释剂按1∶3,000进行稀释(每种稀释剂所含辅助剂组分的浓度列于表1或表2中),稀释剂是把列于表1和表2中的农药辅助剂组合物用城市水按1∶1,000的比率稀释而得到的,并且这样得到的每种稀释剂即被使用。还有,上述试验程序要在没有用任何辅助剂组合物的条件下重复。
结果列于表1和表2中。
表1
组合物(按重计的%) | (A)/(B)按重量计 | 活性成分浓度*(ppm) | 杀螨率(%) | |
神泽叶螨 | ||||
Osadan可湿性粉剂25 | Nissorun可湿性粉剂 | |||
没有辅助剂组合物(只有农药) | 45.6 | 47.8 | ||
脱水山梨醇单月桂酸酯/IPA=30/70=40/60=50/50=60/40=70/30=80/20脱水山梨醇单软脂酸酯/IPA=50/50=60/40=70/30脱水山梨醇单硬脂酸酯/IPA=60/40脱水山梨醇单油酸酯/IPA=60/40 | ----------- | 300400500600700800500600700600600 | 52.254.561.668.974.478.965.671.173.373.362.2 | 54.458.962.271.173.377.866.774.476.777.956.7 |
脱水山梨醇单月桂酸酯/POE(18)树脂酸/阴离子/IPA=70/3/4/23=70/6/4/20=70/10/4/16=70/20/4/6=75/6/4/15=80/6/4/10=60/6/4/30 | 1/0.0431/0.0861/0.1431/0.2861/0.0801/0.0751/0.100 | 730760800900810860660 | 91.187.897.8100.0100.0100.090.0 | 92.296.797.898.997.8100.088.9 |
表1(续)
组合物(按重计的%) | (A)/(B)按重量计 | 活性成分浓度*(ppm) | 杀螨率(%) | |
神泽叶螨 | ||||
Osadan可湿性粉剂25 | Nissorun可湿性粉剂 | |||
没有辅助剂组合物(只有农药) | 45.6 | 47.8 | ||
脱水山梨醇单月桂酸酯/POE(9)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(15)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(20)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(30)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(18)树脂酸/阴离子/IPA =30/20/4/46=30/30/4/36=25/25/4/46=35/3/4/58 | 1/0.0861/0.0861/0.0861/0.0861/0.6671/1.0001/1.0001/0.086 | 810810810810500600500380 | 93.397.894.494.492.293.390.091.1 | 95.697.8100.091.190.096.790.088.9 |
脱水山梨醇单月桂酸酯/季铵盐-1/非离子/IPA =30/5/30/35=40/5/30/25=50/5/30/15=60/5/30/5=70/5/20/5=50/10/30/10=50/15/30/5 | 1/0.1671/0.1251/0.1001/0.0831/0.0801/0.7141/0.300 | 350450550650750600650 | 75.688.991.194.497.898.896.7 | 78.984.488.996.798.994.497.8 |
表2
注)*:术语“活性成分”是指表面活性剂(A)和(B)。上面给出的浓度是活性成分在1∶1,000的农药辅助剂组合物的稀释剂中的浓度(此后也这样使用)。
组合物(按重计的%) | (A)/(B)按重量计 | 活性成分浓度*(ppm) | 杀螨率(%) | |
神泽叶螨 | ||||
Osadan可湿性粉剂25 | Nissorun可湿性粉剂 | |||
没有辅助剂组合物(只有农药) | 45.6 | 47.8 | ||
脱水山梨醇单月桂酸酯/阴离子/IPA =70/4/26POE(18)树脂酸/阴离子/IPA=6/4/90=10/4/86=20/4/76季铵盐-1/非离子/IPA =5/30/65非离子/IPA =30/70POE(20)脱水山梨醇单月桂酸酯/IPA =50/50=60/40=70/30POE(20)脱水山梨醇单月桂酸酯/IPA =60/40POE(20)脱水山梨醇单软脂酸酯/IPA =60/40POE(20)脱水山梨醇单硬脂酸酯/IPA =60/40POE(20)脱水山梨醇单油酸酯/IPA =60/40 | ------------- | 7006010020050-500600700600600600600 | 75.651.153.354.453.348.960.065.671.160.058.958.953.3 | 73.348.952.255.651.147.858.964.467.861.155.654.448.9 |
脱水山梨醇单月桂酸酯/POE(5)脱水山梨醇单月桂酸酯/POE(18)树脂酸/IPA =50/10/10/30POE(5)脱水山梨醇单月桂酸酯/POE(1 8)树脂酸/IPA =70/6/24=75/6/19POE(5)脱水山梨醇单月桂酸酯/季铵盐-1/非离子/IPA =50/10/30/10脱水山梨醇单月桂酸酯/POE(5)脱水山梨醇单月桂酸酯/季铵盐-1/非离子 =50/10/10/30 | 1/0.200/0.200(1/0.167)1/0.0861/0.0861/0.2001/0.200/0.200(1/0.167) | 700760810600700 | 87.881.185.675.694.4 | 86.782.290.071.193.3 |
在表中,“POE(n)树脂酸”是指这样一种化合物,其中平均n摩尔环氧乙烷被加到1摩尔树脂酸中。这种化合物含有式-CO(OE)nOH表示的官能团,其中OE表示氧代乙烯,也可称之为“POE(n)松香”,“POE(n)松香酸”,“POE(n)松香醚”,“POE(n)树脂酸醚或“POE(n)松香酸酯”。
还有,在表中,“IPA”是指异丙醇,“阴离子”是指蓖麻油脂肪酸皂(钾盐),“非离子”是指聚氧乙烯(加入的环氧乙烷平均摩尔数为8)单油酸酯,和“季铵盐-1”是指具有以下化学结构的化合物:
〔R=C12H25〕
这些术语在以下实施例中也这样使用。实施例2
重复实施例1中的同样试验,只是把雌性神泽叶螨幼虫换成绿桃蚜(Myzus Persicae Sulzer)的幼虫,并且用Elsan乳剂(含50%(重量)的二甲基二硫膦酰基苯乙酸乙酯作为活性成分)作为杀虫剂。
结果列于表3和表4中。
表3
组合物(按重计的%) | (A)/(B)按重量计 | 活性成分浓度*(ppm) | 杀虫率(%) |
绿桃蚜 | |||
Elsan 乳剂 | |||
没有辅助剂组合物(只有农药) | 55.6 | ||
脱水山梨醇单月桂酸酯/IPA=30/70=40/60=50/50=60/40=70/30=80/20脱水山梨醇单软脂酸酯/IPA=50/50=60/40=70/30脱水山梨醇单硬脂酸酯/IPA=60/40脱水山梨醇单油酸酯/IPA=60/40 | ----------- | 300400500600700800500600700600600 | 61.168.970.074.477.880.072.275.680.077.868.9 |
脱水山梨醇单月桂酸酯/POE(18)树脂酸/阴离子/IPA =70/3/4/23=70/6/4/20=70/10/4/16=70/20/4/6=75/6/4/15=80/6/4/10=60/6/4/30 | 1/0.0431/0.0861/0.1431/0.2861/0.0801/0.0751/0.100 | 730760800900810860660 | 94.495.6100.0100.096.8100.093.3 |
表3(续)
组合物(按重计的%) | (A)/(B)按重量计 | 活性成分浓度*(ppm) | 杀虫率(%) |
绿桃蚜 | |||
Elsan 乳剂 | |||
没有辅助剂组合物(只有农药) | 55.6 | ||
脱水山梨醇单月桂酸酯/POE(9)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(15)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(20)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(30)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(18)树脂酸/阴离子/IPA =30/20/4/46=30/30/4/36=25/25/4/46=35/3/4/58 | 1/0.0861/0.0861/0.0861/0.0861/0.6671/1.0001/1.0001/0.086 | 810810810810500600500380 | 92.295.698.998.985.688.988.988.9 |
脱水山梨醇单月桂酸酯/季铵盐-1/非离子/IPA =30/5/30/35=40/5/30/25=50/5/30/15=60/5/30/5=70/5/20/5=50/10/30/10=50/15/30/5 | 1/0.1671/0.1251/0.1001/0.0831/0.0801/0.7141/0.300 | 350450550650750600650 | 74.476.785.693.396.791.198.9 |
表4
买施例3
组合物(按重计的%) | (A)/(B)按重量计 | 活性成分浓度*(ppm) | 杀虫率(%) |
绿桃蚜 | |||
Elsan 乳剂 | |||
没有辅助剂组合物(只有农药) | 55.6 | ||
脱水山梨醇单月桂酸酯/阴离子/IPA =70/4/26POE(18)树脂酸/阴离子/IPA=6/4/90=10/4/86=20/4/76季铵盐-1/非离子/IPA =5/30/65非离子/IPA =30/70POE(20)脱水山梨醇单月桂酸酯/IPA =50/50=60/40=70/30POE(20)脱水山梨醇单月桂酸酯/IPA=60/40POE(20)脱水山梨醇单软脂酸酯/IPA=60/40POE(20)脱水山梨醇单硬脂酸酯/IPA=60/40POE(20)脱水山梨醇单油酸酯 /IPA=60/40 | ------------- | 7006010020050-500600700600600600600 | 80.056.760.063.360.056.764.472.272.268.966.767.860.0 |
脱水山梨醇单月桂酸酯/POE(5)脱水山梨醇单月桂酸酯/POE(18)树脂酸/IPA =50/10/10/30POE(5)脱水山梨醇单月桂酸酯/POE(18)脱水山梨醇单月桂酸酯/IPA=70/6/24=75/6/19POE(5)脱水山梨醇单月桂酸酯/季铵盐-1/非离子/IPA =50/10/30/10脱水山梨醇单月桂酸酯/POE(5)脱水山梨醇单月桂酸酯/季铵盐-1/非离子 =50/10/10/30 | 1/0.200/0.200(1/0.167)1/0.0861/0.0861/0.2001/0.200/0.200(1/0.167) | 700760810600700 | 86.678.986.772.291.1 |
把对杀真菌剂已有耐药性的黄瓜葡萄孢菌(Botrytis cinerea)的孢子悬浮液(107/毫升)施用到幼小的三叶期黄瓜秧苗上,剂量为每株10毫升,并把得到的秧苗在25℃、相对温度为90%的条件下放置一天。
然后,把市售的杀真菌剂,即Rovral可湿性粉剂(含有50%(重量)的3-(3,5-二氯苯基)-N-异丙基-2,4-二氧代咪唑啉-1-甲酰胺作为活性成分)按1∶2,000的比率用每种稀释剂稀释(每种稀释剂含有浓度为示于表5或表6中的浓度的辅助剂组分),这些稀释剂是把示于表5和表6中的农药辅助剂组合物按1∶1,000的比率用城市水稀释而制得的。这样制得的稀释剂每种按每株5毫升的剂量施用到秧苗上。把秧苗在25℃、相对湿度为85%的条件下放置后,计数受损情况并按下列等式计算预防值。还有,上述实验程序要在没有任何辅助剂组合物存在的条件下重复。
结果示于表5和表6中。
表5
组合物(按重计的%) | (A)/(B)按重量计 | 活性成分浓度*(ppm) | 预防值 |
黄瓜葡萄孢菌 | |||
Rovral可湿性粉剂 | |||
没有辅助剂组合物(只有农药) | 41.1 | ||
脱水山梨醇单月桂酸酯/IPA=30/70=40/60=50/50=60/40=70/30=80/20脱水山梨醇单软脂酸酯/IPA=50/50=60/40=70/30脱水山梨醇单硬脂酸酯/IPA=60/40脱水山梨醇单油酸酯/IPA=60/40 | ----------- | 300400500600700800500600700600600 | 48.250.260.563.267.470.359.464.266.660.465.6 |
脱水山梨醇单月桂酸酯/POE(18)树脂酸/阴离子/IPA =70/3/4/23=70/6/4/20=70/10/4/16=70/20/4/6=75/6/4/15=80/6/4/10=60/6/4/30 | 1/0.0431/0.0861/0.1431/0.2861/0.0801/0.0751/0.100 | 730760800900810860660 | 85.490.693.395.195.297.990.2 |
表5(续)
组合物(按重计的%) | (A)/(B)按重量计 | 活性成分浓度*(ppm) | 预防值 |
黄瓜葡萄包菌 | |||
Rovral可湿性粉剂 | |||
没有辅助剂组合物(只有农药) | 41.1 | ||
脱水山梨醇单月桂酸酯/POE(9)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(15)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(20)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(30)树脂酸/阴离子/IPA =75/6/4/15脱水山梨醇单月桂酸酯/POE(18)树脂酸/阴离子/IPA =30/20/4/46=30/30/4/36=25/25/4/46=35/3/4/58 | 1/0.0861/0.0861/0.0861/0.0861/0.6671/1.0001/1.0001/0.086 | 810810810810500600500380 | 94.895.698.897.757.966.960 965.2 |
脱水山梨醇单月桂酸酯/季铵盐-1/非离子/IPA =30/5/30/35=40/5/30/25=50/5/30/15=60/5/30/5=70/5/20/5=50/10/30/10=50/15/30/5 | 1/0.1671/0.1251/0.1001/0.0831/0.0801/0.7141/0.300 | 350450550650750600650 | 72.576.680.084.488.491.494.4 |
表6
组合物(按重计的%) | (A)/(B)按重量计 | 活性成分浓度*(ppm) | 预防值 |
黄瓜葡萄孢菌 | |||
Rovral可湿性粉剂 | |||
没有辅助剂组合物(只有农药) | 41.1 | ||
脱水山梨醇单月桂酸酯/阴离子/IPA =70/4/26POE(18)树脂酸/阴离子/IPA=6/4/90=10/4/86=20/4/76季铵盐-1/非离子/IPA =5/30/65非离子/IPA =30/70POE(20)脱水山梨醇单月桂酸酯/IPA =50/50=60/40=70/30POE(20)脱水山梨醇单月桂酸酯/IPA=60/40POE(20)脱水山梨醇单软脂酸酯/IPA=60/40POE(20)脱水山梨醇单硬脂酸酯/IPA=60/40POE(20)脱水山梨醇单油酸酯/IPA=60/40 | ------------- | 7006010020050-500600700600600600600 | 65.343.245.245.565.044.958.859.861.255.550.250.967.2 |
脱水山梨醇单月桂酸酯/POE(5)脱水山梨醇单月桂酸酯/POE(18)树脂酸/IPA =50/10/10/30POE(5)脱水山梨醇单月桂酸酯/POE(18)脱水山梨醇单月桂酸酯/IPA=70/6/24=75/6/19POE(5)脱水山梨醇单月桂酸酯/季铵盐-1/非离子/IPA =50/10/30/10脱水山梨醇单月桂酸酯/POE(5)脱水山梨醇单月桂酸酯/季铵盐-1/非离子 =50/10/10/30 | 1/0.200/0.200(1/0.167)1/0.0861/0.0861/0.2001/0.200/0.200(1/0.167) | 700760810600700 | 72.270.080.979.994.6 |
Claims (23)
1.一种农药辅助剂组合物,它包含至少一种脱水山梨醇/脂肪酸酯表面活性剂(A)和至少一种选自树脂酸表面活性剂和下式代表的季铵盐表面活性剂的表面活性剂(B):其中R1、R2、和R3中至少有一个代表含有8至30个碳原子的直链或支链的烷基或链烯基,其余代表一个或两个选自-CH3、-CH2CH3、和
(n值为1至5)的基团,R4代表-CH3或-CH2CH3,抗衡离子X-代表一个由重均分子量为300至20,000的低聚物或聚合物衍生的阴离子基团,并且选自(1):把含有至少一种选自不饱和羧酸及其衍生物作为必需组分的单体进行聚合得到的聚合物或共聚物,(2):把含有苯乙烯磺酸作为必需组分的单体进行聚合得到的聚合物或共聚物,(3):可带有烃基团作为取代基的磺化芳族化合物与甲醛的缩合物。
2.权利要求1的农药辅助剂组合物,其中表面活性剂(B)与表面活性剂(A)的重量比率为0.01至5。
3.权利要求1的农药辅助剂组合物,其中还包含除表面活性剂(A)和(B)以外的至少一种表面活性剂。
4.权利要求1的农药辅助剂组合物,其中脱水山梨醇/脂肪酸酯表面活性剂(A)是至少一种选自脱水山梨醇/脂肪酸酯类和聚氧亚烷基脱水山梨醇/脂肪酸酯类中的单体。
5.权利要求1的农药辅助剂组合物,其中脱水山梨醇/脂肪酸酯表面活性剂(A)是一种脱水山梨醇/脂肪酸酯。
6.权利要求1的农药辅助剂组合物,其中树脂酸表面活性剂(B)是一种聚氧亚烷基浮油松香。
7.权利要求6的农药辅助剂组合物,其中聚氧亚烷基浮油松香是通过往浮油松香中按每摩尔浮油松香加入平均5至40摩尔烯化氧而得到的。
8.权利要求6的农药辅助剂组合物,其中聚氧亚烷基浮油松香是通过往浮油松香中按每摩尔浮油松香加入平均5至40摩尔包括环氧乙烷作为必需组分的烯化氧而得到的。
9.权利要求1的农药辅助剂组合物,其中树脂酸表面活性剂(B)是一种聚氧亚烷基树脂酸。
10.权利要求9的农药辅助剂组合物,其中聚氧亚烷基树脂酸是通过往树脂酸中按每摩尔树脂酸加入平均5至40摩尔烯化氧而得到的。
11.权利要求9的农药辅助剂组合物,其中聚氧亚烷基树脂酸是通过往树脂酸中按每摩尔树脂酸加入平均5至40摩尔包括环氧乙烷作为必需组分的烯化氧而得到的。
12.一种增强农药功效的方法,它包括往将从这类处理受益的地点施用一种脱水山梨醇/脂肪酸酯表面活性剂(A)和至少一种选自树脂酸表面活性剂和下式代表的季铵盐表面活性剂的表面活性剂(B):其中R1、R2、和R3中至少有一个代表含有8至30个碳原子的直链或支链的烷基或链烯基,其余代表一个或两个选自-CH3、-CH2CH3、和
(n值为1至5)的基团,R4代表-CH3或-CH2CH3,抗衡离子X-代表一个由重均分子量为300至20,000的低聚物或聚合物衍生的阴离子基团,并且选自(1):把含有至少一种选自不饱和羧酸及其衍生物作为必需组分的单体进行聚合得到的聚合物或共聚物,(2):把含有苯乙烯磺酸作为必需组分的单体进行聚合得到的聚合物或共聚物,(3):可带有烃基团作为取代基的磺化芳族化合物与甲醛的缩合物。
13.权利要求12的增强农药功效的方法,其中表面活性剂(B)与表面活性剂(A)的重量比率为0.01至5。
14.权利要求12的增强农药功效的方法,其中与农药一起使用的还有除表面活性剂(A)和(B)以外的一种表面活性剂。
15.权利要求12的增强农药功效的方法,其中表面活性剂(A)和(B)的总和与农药的重量比率为0.03至50。
16.权利要求12的增强农药功效的方法,其中农药是一种杀真菌剂,一种杀虫剂,一种杀螨剂,一种除草剂或一种植物生长调节剂。
17.一种脱水山梨醇/脂肪酸酯表面活性剂(A)和至少一种选自树脂酸表面活性剂和下式代表的季铵盐表面活性剂的表面活性剂(B)的混合物的用途,该混合物用来增强农药的功效:其中R1、R2、和R3中至少有一个代表含有8至30个碳原子的直链或支链的烷基或链烯基,其余代表一个或两个选自-CH3、-CH2CH3、和
(n值为1至5)的基团,R4代表-CH3或-CH2CH3,抗衡离子X-代表一个由重均分子量为300至20,000的低聚物或聚合物衍生的阴离子基团,并且选自(1):把含有至少一种选自不饱和羧酸及其衍生物作为必需组分的单体进行聚合得到的聚合物或共聚物,(2):把含有苯乙烯磺酸作为必需组分的单体进行聚合得到的聚合物或共聚物,(3):可带有烃基团作为取代基的磺化芳族化合物与甲醛的缩合物。
18.权利要求17的用法,其中表面活性剂(B)与表面活性剂(A)的重量比率为0.01至5。
19.权利要求17的用法,其中农药是一种杀真菌剂,一种杀虫剂,一种杀螨剂,一种除草剂或一种植物生长调节剂。
20.一种农药组合物,它含有至少一种脱水山梨醇/脂肪酸酯表面活性剂(A),至少一种选自树脂酸表面活性剂类和下式代表的季铵盐表面活性剂类的表面活性剂(B),以及一种农药,其中表面活性剂(A)和(B)的总和与农药的重量比率为0.03至50:其中R1、R2、和R3中至少有一个代表含有8至30个碳原子的直链或支链的烷基或链烯基,其余代表一个或两个选自-CH3、-CH2CH3、和
(n值为1至5)的基团,R4代表-CH3或-CH2CH3,抗衡离子X-代表一个由重均分子量为300至20,000的低聚物或聚合物衍生的阴离子基团,并且选自(1):把含有至少一种选自不饱和羧酸及其衍生物作为必需组分的单体进行聚合得到的聚合物或共聚物,(2):把含有苯乙烯磺酸作为必需组分的单体进行聚合得到的聚合物或共聚物,(3):可带有烃基团作为取代基的磺化芳族化合物与甲醛的缩合物。
21.权利要求20的农药组合物,其中表面活性剂(B)与表面活性剂(A)的重量比率为0.01至5。
22.权利要求20的农药组合物,其中还包含至少一种除表面活性剂(A)和(B)以外的表面活性剂。
23.权利要求20的农药组合物,其中农药是一种杀真菌剂,一种杀虫剂,一种杀螨剂,一种除草剂或一种植物生长调节剂。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP291767/94 | 1994-11-25 | ||
JP291767/1994 | 1994-11-25 | ||
JP06291767A JP3113161B2 (ja) | 1994-11-25 | 1994-11-25 | 農薬用効力増強剤組成物及び農薬組成物 |
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CN1173110A true CN1173110A (zh) | 1998-02-11 |
CN1104195C CN1104195C (zh) | 2003-04-02 |
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CN95197339A Expired - Fee Related CN1104195C (zh) | 1994-11-25 | 1995-11-22 | 农药辅助剂组合物以及增强农药功效的方法 |
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US (1) | US5863909A (zh) |
EP (1) | EP0793416B1 (zh) |
JP (1) | JP3113161B2 (zh) |
CN (1) | CN1104195C (zh) |
BR (1) | BR9509816A (zh) |
ES (1) | ES2139249T3 (zh) |
WO (1) | WO1996016539A1 (zh) |
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- 1995-11-22 CN CN95197339A patent/CN1104195C/zh not_active Expired - Fee Related
- 1995-11-22 EP EP95937167A patent/EP0793416B1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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WO1996016539A1 (en) | 1996-06-06 |
CN1104195C (zh) | 2003-04-02 |
BR9509816A (pt) | 1997-09-30 |
EP0793416A1 (en) | 1997-09-10 |
US5863909A (en) | 1999-01-26 |
ES2139249T3 (es) | 2000-02-01 |
JP3113161B2 (ja) | 2000-11-27 |
JPH08151302A (ja) | 1996-06-11 |
EP0793416B1 (en) | 1999-10-13 |
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