CN102307468A - 基于铜盐的杀真菌组合物 - Google Patents
基于铜盐的杀真菌组合物 Download PDFInfo
- Publication number
- CN102307468A CN102307468A CN2009801563415A CN200980156341A CN102307468A CN 102307468 A CN102307468 A CN 102307468A CN 2009801563415 A CN2009801563415 A CN 2009801563415A CN 200980156341 A CN200980156341 A CN 200980156341A CN 102307468 A CN102307468 A CN 102307468A
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- CN
- China
- Prior art keywords
- copper
- kocide
- equivalent thickness
- cuh
- cupric salicylate
- Prior art date
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- 230000000855 fungicidal effect Effects 0.000 title claims abstract description 27
- 150000001879 copper Chemical class 0.000 title abstract 2
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- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 claims abstract description 42
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- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims description 96
- 229910052802 copper Inorganic materials 0.000 claims description 74
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 73
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 46
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Abstract
本发明描述杀真菌组合物,其包含:A)水杨酸铜,具有下述分子式(I):C7H4O3Cu·(H2O)n(I),其中n代表0,1,2或3;B)氢氧化铜Cu(OH)2(II);C)具有下式(III)的铜盐:3Cu(OH)2·X(Y)m(III),其中:X代表二价铜离子Cu2+或钙离子Ca2+;Y意指氯离子Cl-或硫酸根离子SO4 2-;m是等于1或2的整数;任选地存在农业上可接受的分散剂,稀释剂,表面活性剂和/或共配制剂,和有关的农学配制剂。本发明还描述这些杀真菌组合物和农学配制剂用于防治农作物中的致植物病性真菌的用途。
Description
本发明涉及基于铜盐的组合物并且涉及它们用于防治致植物病性真菌的用途。
尤其是,涉及基于铜盐的组合物,其能够有效防治导致经济作物损害的致植物病性真菌。
氢氧化铜,碱式氯化铜,氯氧化铜钙,三碱式硫酸铜,波尔多液,是熟知的活性成分,其单独地或与其它杀真菌剂混合以叶面施用用于防治致植物病性真菌。这些铜活性成分描述于例如″THE PESTICIDEMANUAL,第11版,BRITISH CROP PROTECTION COUNCIL,第136、268-270页″。
尽管铜产品在防治许多影响重要农作物的真菌疾病中经证实的有效性,由于对持续使用它们会导致的不希望毒理学效果的日益关注,将金属铜用量减少至经良好定义的界限内的诉求在近年变得特别重要。
欧洲专利EP 1471787描述杀真菌组合物,通过将氢氧化铜与至少一种其它无机铜盐,比如碱式氯化铜,三碱式硫酸铜,波尔多液,氯氧化铜钙混合可能用其减少铜的用量。然而,用这些组合物所能获得的金属铜含量减少仍旧不能令人满意。这些组合物的杀真菌作用范围也局限于属于卵菌纲(Oomycetes)(尤其是葡萄生单轴霉(Plasmopara viticola))的某些真菌。
美国专利US 4,075,326描述杀真菌组合物,其中将无机铜盐与不饱和二碱式有机酸铜盐相组合。尽管要求保护的增强效果,使用这些组合物并不都会导致铜剂量的真实减少。例如,该文献的实施例4描述组合物q对葫芦科刺盘孢(Colletotrichum lagenarium)的改善的杀真菌活性,所述组合物q由40%重量的对苯二甲酸铜(Cu含量=27.8%),20%重量的碱式氯化铜可湿性粉剂(Cu含量=41%),40%重量的氢氧化铜可湿性粉剂(Cu含量=54%)组成。因此,该组合物q具有的总铜含量等于27.8x0.4+41x0,2+54x0.4=40.92%重量。其中将组合物q的杀真菌活性与单独的对苯二甲酸铜(组合物I-1)的杀真菌活性进行比较,而其铜含量(27.8%重量)实际上低于组合物q的混合物。另外,对该三元混合物观察到的活性增加相对单独使用的铜有机产品实际上是中等的(10-20%),因为需要考虑到组合物q的铜含量增加了46%重量。
水杨酸铜盐对于致植物病性真菌的″体外″抗微生物剂活性也是已知的,描述于例如″Pesticides″,1980,14(10),第29-30页和″IndianJournal of Microbiology″,1981,第331-334页。
然而,由于降低的持久性、偶然出现的植物毒性现象和减少的作用范围,这些化合物作为杀真菌剂的实际使用并不完全令人满意,甚至与能够增加它们作为植物中有关真菌疾病的系统性获得抗性诱导剂(SAR)作用的化合物联用也是如此,如国际专利申请WO 2005/094580的描述。
申请人现已发现三元组合物克服根据现有技术的组合物的上述缺点,其以适宜比率包含水杨酸铜(其中水杨酸和铜存在的摩尔比是约1∶1),氢氧化铜,另一铜盐选自碱式氯化铜,三碱式硫酸铜,波尔多液,氯氧化铜钙。尤其是,这些三元组合物显示令人惊讶地高的杀真菌活性,其在比水杨酸铜本身和描述于欧洲专利EP 1,471,787的无机铜盐混合物低得多的铜剂量起作用。这些组合物也具有更宽的作用范围和更持续的效力,还显示降低的植物毒性或没有植物毒性,这允许可以将其安全地用在重要作物上。
因此,本发明目的涉及杀真菌剂组合物,其包含:
A)水杨酸铜,具有下述分子式(I):
C7H4O3Cu·(H2O)n (I)
其中n代表0,1,2或3;
B)氢氧化铜Cu(OH)2(II);
C)具有下式(III)的铜盐:
3Cu(OH)2·X(Y)m (III)
其中:
-X代表二价铜离子Cu2+或钙离子Ca2+;
-Y意指氯离子Cl-或硫酸根离子SO4 2-;
-m是等于1或2的整数;
任选地存在农学上可接受的分散剂,稀释剂,表面活性剂和/或共配制剂。
因此,本发明的又一目的涉及农学配制剂,其包含上述组合物和农学上可接受的可能的分散剂,稀释剂,表面活性剂和/或共配制剂。
尤其是,具有式(III)的化合物能够选自碱式氯化铜[3Cu(OH)2·CuCl2],氯氧化铜钙[3Cu(OH)2·CaCl2],三碱式硫酸铜[3Cu(OH)2·CuSO4],波尔多液[3Cu(OH)2·CaSO4]。
根据本发明的优选组合物是那些,其中具有式(I)、(II)和(III)的化合物具有的铜当量比分别为0.2∶1∶0.3至2∶1∶3,优选0.4∶1∶0.8至1.2∶1∶1.2。
甚至更优选的组合物是那些,其中在具有式(I)的化合物中n代表1而具有式(I)、(II)和(III)的化合物分别以0.2∶1∶0.3至2∶1∶3,优选0.4∶1∶0.8至1.2∶1∶1.2的铜当量比存在。
更优选的组合物是那些,其中在具有式(I)的化合物中n代表1,具有式(III)的化合物是碱式氯化铜[3Cu(OH)2·CuCl2]或三碱式硫酸铜[3Cu(OH)2·CuSO4]而具有式(I)、(II)和(III)的化合物分别以0.2∶1∶0.3至2∶1∶3,优选0.4∶1∶0.8至1.2∶1∶1.2的铜当量比存在。
特别优选的组合物是:
C1:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为1∶1∶1;
C2:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.4∶1∶1;
C3:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.6∶1∶1;
C4:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.8∶1∶1;
C5:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.4∶1∶1.2;
C6:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.8∶1∶1.2;
C7:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为1.2∶1∶0.8;
C8:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为2∶1∶0.3;
C9:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.2∶1∶3;
C10:水杨酸铜C7H4O3Cu+氢氧化铜+碱式氯化铜,其铜当量比为0.4∶1∶1;
C11:水杨酸铜C7H4O3Cu·+氢氧化铜+碱式氯化铜,其铜当量比为1∶1∶1;
C12:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+三碱式硫酸铜,其铜当量比为0.4∶1∶1;
C13:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+三碱式硫酸铜,其铜当量比为1∶1∶1;
C14:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+三碱式硫酸铜,其铜当量比为0.7∶1∶1;
C15:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+波尔多液,其铜当量比为1∶1∶1;
C16:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+氯氧化铜钙,其铜当量比为1∶1∶1;
C17:水杨酸铜C7H4O3Cu·2H2O+氢氧化铜+碱式氯化铜,其铜当量比为1∶1∶1;
C18:水杨酸铜C7H4O3Cu·3H2O+氢氧化铜+碱式氯化铜,其铜当量比为1∶1∶1。
本发明目的组合物可以根据不同方法进行制备,还取决于这些组合物仅包含铜盐,或者呈适宜的农学配制剂形式。
在前一种情况下,根据本发明的组合物这样获得:机械地混合适宜的数量的已单独制备的具有式(I)的水杨酸铜,氢氧化铜(II)和具有式(III)的铜盐。
氢氧化铜(II)和具有式(III)的铜盐可作为工业产品商购。
具有式(I)的水杨酸铜能够以各种方式制备,例如将水杨酸在含水介质中与碱反应,随后加入可溶铜盐比如硫酸铜,或者将水杨酸直接与碱性铜盐比如碳酸铜或氢氧化铜反应。
另选地,如果用于制备具有式(I)的化合物的铜盐是氢氧化铜,则本发明组合物能够这样制备:以适宜摩尔比将水杨酸加入氢氧化铜(II),随后加入具有式(III)的铜盐。
此外,本发明组合物还能够这样制备:以适宜摩尔比将水杨酸原样加入氢氧化铜(II)和具有式(III)的铜盐的混合物。
如果组合物是适宜的农学配制剂形式,则它们可以是可湿性粉剂,颗粒剂,水可分散性颗粒剂,浓缩悬浮液,等。
它们能够这样制备:将已经以适宜比例混合的铜盐一起配制,或者以任意次序混合分开配制的各盐。
此外,在制备配制剂期间,可以以适宜的摩尔比将水杨酸原样加入氢氧化铜(II)和具有式(III)的铜盐的混合物。
能够用于配制剂中的固体稀释剂是例如:二氧化硅,高岭土,斑脱土,滑石,硅藻土,白云石,碳酸钙,氧化镁,石膏,粘土,合成的硅酸盐,凹凸棒石,海泡石。
能够使用的液体稀释剂是例如:水,芳族或烷烃有机溶剂,醇,酯,酮,酰胺。
能够使用的表面活性剂是,例如:烷基萘磺酸,聚萘磺酸,苯基磺酸,聚羧酸,磺基琥珀酸,烷基磺基琥珀酸,烷基硫酸,木质素磺酸,烷基芳基磺酸的钠、钾、三乙醇胺盐;并且还能够使用聚乙氧基化的脂肪醇,聚乙氧基化的烷基酚,山梨糖醇的聚乙氧基化的酯,聚丙氧基聚乙氧基化物(嵌段聚合物)。
组合物还能够含有用于特定用途的特别添加剂,例如防冻剂比如丙二醇,或粘合剂比如阿拉伯胶,聚乙烯醇,聚乙烯吡咯烷酮,等。
在根据本发明的植物卫生配制剂中,来自具有式(I)、(II)和(III)的铜盐三元混合物的当量金属铜的百分比含量可以是3%至50%,优选10%至35%。
正如已经指出的那样,本发明目的,也即本发明组合物与单独使用组分的活性相比发挥令人惊讶地高的杀真菌活性。
因此,本发明的又一目的涉及杀真菌组合物的用途,所述杀真菌组合物包含:
A)水杨酸铜,具有下述分子式(I):
C7H4O3Cu·(H2O)n (I)
其中n代表0,1,2或3;
B)氢氧化铜Cu(OH)2(II);
C)具有下式(III)的铜盐:
3Cu(OH)2·X(Y)m (III)
其中:
-X代表二价铜离子Cu2+或钙离子Ca2+;
-Y意指氯离子Cl-或硫酸根离子SO4 2-;
-m是等于1或2的整数;
任选地存在农学上可接受的分散剂,稀释剂,表面活性剂和/或共配制剂,其用于防治农作物中致植物病性真菌的用途。
本发明的目的还涉及通过施用如前文所定义的杀真菌组合物来在农作物中防治致植物病性真菌的方法。
能用根据本发明的杀真菌组合物或农学配制剂有效防治的致植物病性真菌的实例是:藤本植物上的葡萄生单轴霉(Plasmopara viticola),蔬菜上的疫霉属(Phytophthora spp.),葫芦科植物上的古巴假霜霉菌(Pseudoperonospora cubensis),烟草上的烟霜霉(Peronospora tabacina),莴苣和菠菜上的莴苣盘梗霉(Bremia lactucae),果树上的黑星菌属(Venturia spp.),菜豆上的疣顶单胞锈菌(Uromyces appendiculatus),蔬菜和果树上的链格孢属(Alternaria spp.),葫芦科植物上的单丝壳(Sphaeroteca fuliginea),蔬菜和禾谷类上的白粉菌属(Erysiphe spp.)。
本发明组合物还能够有效用于防治细菌和致植物病性病毒。
根据本发明的杀真菌组合物或植物卫生配制剂能够在农学实践中用来施用于植物或在其部分,尤其是在植物全部部分,叶子,茎干,枝条和根。
根据本发明的杀真菌组合物或植物卫生配制剂能够方便地在农学实践中单独使用,或者为了拓宽其作用范围,与其它杀真菌活性成分联合使用。
出于示例意图并且不加任何限制地,将某些活性成分列于下文,其能够方便地与本发明的组合物或配制剂混合使用:
吲唑磺菌胺(amisulbrom),苯霜灵,精苯霜灵,苯噻菌胺酯,克菌丹,氰霜唑,霜脲氰,二硝基巴豆酸酯,百菌清,烯酰吗啉,噻唑菌胺,土菌灵,噁唑菌酮,咪唑菌酮,氟啶胺,氟吗啉,氟吡菌胺,灭菌丹,三乙膦酸铝,呋霜灵,噁霉灵(hymenaxol),缬霉威,双炔酰菌胺,甲霜灵,精甲霜灵,呋酰胺,噁霜灵,戊菌隆,腐霉利,霜霉威,硫菌威,硫,tiram,甲基立枯磷,缬氨菌酯(valifenalate)(IR5885),苯酰菌胺。
出于示例和非限制性的发明意图提供下述实例。
实施例1
制备水杨酸铜C7H4O3Cu·H2O(I-1)。
将70.6g(0.724摩尔)的Cu(OH)2分批加入100g(0.724摩尔)水杨酸在1升水中的悬浮液,在室温下将混合物搅拌2小时。必须提供适当搅拌系统的原因是,随反应进行并且pH增加至最终值约6,粘度将增加。颜色自绿色变为最终产品的赭色。然后,将反应混合物在布氏漏斗上过滤,在空气中干燥,获得148g的所希望产品(MW=217.5)。
反应混合物还能够用作为后续配制剂(实施例7)准备的浆料。
元素分析%:C=38.85(理论38.71);H=2.65(理论2.70);Cu=29.10(理论29.2)。
实施例2
制备水杨酸铜C7H4O3Cu·H2O(I-1)。
将NaOH,58g(1.45摩尔)的300ml溶液加入100g(0.724摩尔)水杨酸在400ml水中的悬浮液,直至实现完全溶解。然后,加入CuSO4,180.8g(0.724摩尔)的300ml水溶液,在室温下将混合物搅拌8小时。必须提供适当搅拌系统的原因是,随反应进行pH增加至最终值约6,沉淀出细分的绿色固体,其颜色随后变为最终产品的赭色,并且粘度增加。
然后,将反应混合物在布氏漏斗上过滤,用水(500ml)洗涤,在空气中干燥,获得150g的所希望产品。
元素分析%:C=38.80(理论38.71);H=2.60(理论2.70);Cu=29.10(理论29.2)。
实施例3
制备水杨酸铜C7H4O3Cu·H2O(I-1)+氢氧化铜(II)的铜当量比1∶1混合物。
将141.3g(1.447摩尔)的Cu(OH)2分批加入100g(0.724摩尔)水杨酸在1升水中的悬浮液,在室温下将混合物搅拌4小时。然后,将反应混合物在布氏漏斗上过滤,在空气中干燥,获得215g的所希望产品(元素分析)。
反应混合物还能够用作为后续配制剂准备的浆料。
实施例4
制备组合物C1:水杨酸铜C7H4O3Cu·H2O(I-1)+氢氧化铜(II)+碱式氯化铜(III-1),其铜当量比为1∶1∶1。
将70.6g(0.724摩尔)Cu(OH)2分批加入100g(0.724摩尔)水杨酸在1.5升水中的悬浮液,在室温下将混合物搅拌2小时。必须提供适当搅拌系统的原因是,随反应进行并且pH增加至最终值约6,粘度增加。颜色自绿色变为最终产品的赭色。此时,加入额外的70.6g(0.724摩尔)Cu(OH)2和77.3g(0.181摩尔)的碱式氯化铜3Cu(OH)2·CuCl2(相应于0.724当量铜),搅拌混合物30分钟。然后,将反应混合物在布氏漏斗上过滤,在空气中干燥,获得290g的所希望混合物(元素分析)。
反应混合物还能够用作为后续配制剂准备的浆料。
实施例5
制备组合物C2:水杨酸铜C7H4O3Cu·H2O(I-1)+氢氧化铜(II)+碱式氯化铜(III-1),其铜当量比为0.4∶1∶1。
将40g(0.289摩尔)水杨酸加入98.8g(1.014摩尔)Cu(OH)2和77.3g(0.181摩尔)碱式氯化铜3Cu(OH)2·CuCl2(相应于0.724当量铜)在1.5升水中的悬浮液;在室温下将混合物搅拌4小时。然后,将反应混合物在布氏漏斗上过滤,在空气中干燥,获得192g的所希望混合物(元素分析)。
反应混合物还能够用作为后续配制剂准备的浆料。
实施例6
制备作为可湿性粉剂(WP)的水杨酸铜C7H4O3Cu·H2O:I-1/WP
可湿性粉剂类的配制剂这样制备:适宜地混合和研磨下述成分:
实施例7
制备作为可分散性粒剂(WG)的水杨酸铜C7H4O3Cu·H2O:I-1/WG
含20%铜(WG)的可分散性粒剂类配制剂这样制备:将下述成分加入如实施例1的描述获得的浆料:
通过蒸发所存在的水(流化床造粒)造粒如此制备的浆料,获得具有下述组成的最终可分散性粒剂(WG):
实施例8
制备作为可湿性粉剂(WP)的氢氧化铜+碱式氯化铜的铜当量比1∶1混合物:CHCO-1/WP
含50%铜(WP 50)的可湿性粉剂类配制剂这样制备:适宜地混合和研磨下述成分:
实施例9
制备作为可分散性粒剂(WG)的氢氧化铜+碱式氯化铜的铜当量比1∶1混合物:CHCO-1/WG
含50%铜(WG)的可分散性粒剂类配制剂这样制备:适宜地混合、研磨和造粒下述成分:
实施例10
制备作为可湿性粉剂(WP)的组合物C2:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.4∶1∶1:C2/WP
含30%铜(WP)的可湿性粉剂类配制剂这样制备:适宜地混合和研磨下述成分:
类似地,通过适宜地调整水杨酸铜、氢氧化铜和碱式氯化铜的比率,用含30%铜的铜当量比1∶1∶1的水杨酸铜C7H4O3Cu·H2O(I-1)+氢氧化铜(II)+氯氧化铜(III-1)制备可湿性粉剂配制剂;C1/WP。
实施例11
制备作为可分散性粒剂(WG)的组合物C1:水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为1∶1∶1:C1/WG
起始自下述成分按实施例8的描述制备又一WG配制剂:
实施例12
对藤本植物上的葡萄生单轴霉(Plasmopara viticola)的温室预防活性(7天)。
通过在两侧均用测试产品喷雾对生长在瓶中受控环境24℃和60%的R.H.(相对湿度)下的藤本植物叶片(栽培种Barbera)进行处理。
在处理之后7天,通过较低侧用压缩空气枪喷雾用葡萄生单轴霉(Plasmopara viticola)分生孢子的含水悬浮液(200.000分生孢子/cc)接种植物。
在21℃于湿度饱和环境保持24小时之后,将上述植物在温育时间段(7天)转移至70%的R.H.和21℃的受控环境。
在该时间段之后,出现病原体的外部症状,因此可以通过视觉评价受影响叶面积的百分比等级来进行感染强度的评价;所述等级包括值0(健康植物)和值100(完全感染的植物),作为端点。
该表指出对于下述产品/组合物所获得的结果:
I-1/WP:含50%(14.6%的铜)水杨酸铜C7H4O3Cu·H2O(I-1)的可湿性粉剂配制剂,描述于实施例5;
CHCO-1/WP:含铜50%的可湿性粉剂配制剂,氢氧化铜(II)+氯氧化铜(III-1)的铜当量比为1∶1,描述于实施例8;
C1/WP:含铜30%的可湿性粉剂配制剂,其中水杨酸铜C7H4O3Cu·H2O(I-1)+氢氧化铜(II)+碱式氯化铜(III-1)的铜当量比为1∶1∶1,描述于实施例10;
C2/WP:含铜30%的可湿性粉剂配制剂,其中水杨酸铜C7H4O3Cu·H2O(I-1)+氢氧化铜(II)+碱式氯化铜(III-1)的铜当量比为0.4∶1∶1,描述于实施例10;
通过将获得的活性与期望的那些进行比较来评价组合物的增效效果,都应用适用三元混合物的Limpel公式,并考虑组分的加合效果。
根据Limpel公式(″Pesticide Science″(1987),第19卷,第309-315页):
Eexp=EI+EII+III-(EIxEII+III/100)
其中:
-Eexp是对混合剂量DI的组分(I)和剂量DII+III的组分(II)+(III)获得的混合物所期望的杀真菌活性;
-EI是以剂量DI单独使用组分(I)所观察到的活性;
-EII+III是以剂量DII+III单独使用混合物(II)-(III)所观察到的活性。
考虑加合效果:
Eadd=EI+EII+III
在组合物的观察活性Eobs高于期望活性Eexp和Eadd的情况下出现增效效果。
从结果明显可见,组合物C1和C2所获得的杀真菌活性对比期望活性有显著增加。组合物C1和C2的强增效效果由比较C1/WP、C2/WP、I-1/WP,CHCO-1/WP在30ppm铜用量下观察到的活性所进一步确认。
表.对藤本植物上的葡萄生单轴霉(Plasmopara viticola)的温室预防活性(7天)。
Claims (13)
1.杀真菌组合物,包含:
A)水杨酸铜,具有下述分子式(I):
C7H4O3Cu·(H2O)n (I)
其中n代表0,1,2或3;
B)氢氧化铜Cu(OH)2(II);
C)具有下式(III)的铜盐:
3Cu(OH)2·X(Y)m (III)
其中:
-X代表二价铜离子Cu2+或钙离子Ca2+;
-Y意指氯离子Cl-或硫酸根离子SO4 2-;
-m是等于1或2的整数;
任选地存在农学上可接受的分散剂,稀释剂,表面活性剂和/或共配制剂。
2.根据权利要求1的杀真菌组合物,其特征在于,式(I)、(II)和(III)化合物分别以0.2∶1∶0.3至2∶1∶3,优选0.4∶1∶0.8至1.2∶1∶1.2的铜当量比存在。
3.根据权利要求1的杀真菌组合物,其特征在于,式(I)化合物具有等于1的n而式(I)、(II)和(III)化合物分别以0.2∶1∶0.3至2∶1∶3,优选0.4∶1∶0.8至1.2∶1∶1.2的铜当量比存在。
4.根据权利要求1的杀真菌组合物,其特征在于,式(I)化合物具有等于1的n,式(III)化合物是碱式氯化铜[3Cu(OH)2·CuCl2]或三碱式硫酸铜[3Cu(OH)2·CuSO4]而式(I)、(II)和(III)化合物分别以0.2∶1∶0.3至2∶1∶3,优选0.4∶1∶0.8至1.2∶1∶1.2的铜当量比存在。
5.根据权利要求1或2中任一项的杀真菌组合物,其特征在于,它们选自:
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为1∶1∶1;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.4∶1∶1;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.6∶1∶1;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.8∶1∶1;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.4∶1∶1.2;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.8∶1∶1.2;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为1.2∶1∶0.8;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为2∶1∶0.3;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+碱式氯化铜,其铜当量比为0.2∶1∶3;
-水杨酸铜C7H4O3Cu+氢氧化铜+碱式氯化铜,其铜当量比为0.4∶1∶1;
-水杨酸铜C7H4O3Cu+氢氧化铜+碱式氯化铜,其铜当量比为1∶1∶1;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+三碱式硫酸铜,其铜当量比为0.4∶1∶1;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+三碱式硫酸铜,其铜当量比为1∶1∶1;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+三碱式硫酸铜,其铜当量比为0.7∶1∶1;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+波尔多液,其铜当量比为1∶1∶1;
-水杨酸铜C7H4O3Cu·H2O+氢氧化铜+氯氧化铜钙,其铜当量比为1∶1∶1;
-水杨酸铜C7H4O3Cu·2H2O+氢氧化铜+碱式氯化铜,其铜当量比为1∶1∶1;
-水杨酸铜C7H4O3Cu·3H2O+氢氧化铜+碱式氯化铜,其铜当量比为1∶1∶1。
6.植物卫生配制剂,其包含根据权利要求1-5中任一项的杀真菌组合物和农学上可接受的分散剂,稀释剂,表面活性剂和/或共配制剂。
7.根据权利要求6的农学配制剂,其特征在于,它们是可湿性粉剂,颗粒剂,水可分散性粒剂或浓缩悬浮液。
8.根据权利要求6或7中任一项的农学配制剂,其特征在于,它们含有特别添加剂比如防冻剂或粘合剂。
9.根据权利要求6-8中任一项的农学配制剂,其特征在于,来自式(I)、(II)和(III)二价铜盐的三元混合物的铜金属当量百分含量可以是3%至50%,优选10%至35%。
10.杀真菌组合物的用途,所述杀真菌组合物包含:
A)水杨酸铜,具有下述分子式(I):
C7H4O3Cu·(H2O)n (I)
其中n代表0,1,2或3;
B)氢氧化铜Cu(OH)2(II);
C)具有下式(III)的铜盐:
3Cu(OH)2·X(Y)m (III)
其中:
-X代表二价铜离子Cu2+或钙离子Ca2+;
-Y意指氯离子Cl-或硫酸根离子SO4 2-;
-m是等于1或2的整数;
任选地存在农学上可接受的分散剂,稀释剂,表面活性剂和/或共配制剂,用于农作物中的致植物病性真菌防治。
11.根据权利要求2-5中任一项的杀真菌组合物用于农作物中的致植物病性真菌防治的用途。
12.根据权利要求6-9中任一项的农学配制剂用于农作物中的致植物病性真菌防治的用途。
13.通过施用如权利要求1-5中任一项中所定义的杀真菌组合物来防治农作物中的致植物病性真菌的方法。
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US4075326A (en) | 1973-12-22 | 1978-02-21 | Rohm And Haas Company | Fungicidal/algicidal composition for non-medical uses |
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ITMI20040402A1 (it) | 2004-03-03 | 2004-06-03 | Isagro Spa | Miscele e metodo per l'induzione di resistenza nella pianta |
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Publication number | Publication date |
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ES2545970T3 (es) | 2015-09-17 |
IT1393328B1 (it) | 2012-04-20 |
AU2009335226A1 (en) | 2011-07-28 |
JP5567593B2 (ja) | 2014-08-06 |
CA2748734C (en) | 2017-11-21 |
PT2384117E (pt) | 2015-09-03 |
CA2748734A1 (en) | 2010-07-08 |
WO2010076038A1 (en) | 2010-07-08 |
MX2011007170A (es) | 2011-12-14 |
CN102307468B (zh) | 2015-05-06 |
UA106736C2 (uk) | 2014-10-10 |
WO2010076038A8 (en) | 2010-09-23 |
KR101677307B1 (ko) | 2016-11-17 |
ITMI20090001A1 (it) | 2010-07-03 |
CO6400169A2 (es) | 2012-03-15 |
BRPI0924197B1 (pt) | 2017-12-19 |
EP2384117A1 (en) | 2011-11-09 |
AU2009335226B2 (en) | 2014-04-10 |
AR075680A1 (es) | 2011-04-20 |
KR20110108371A (ko) | 2011-10-05 |
PL2384117T3 (pl) | 2015-11-30 |
JP2012514580A (ja) | 2012-06-28 |
US20110318427A1 (en) | 2011-12-29 |
RU2527307C2 (ru) | 2014-08-27 |
RU2011129878A (ru) | 2013-02-10 |
BRPI0924197A2 (pt) | 2015-08-18 |
US9204656B2 (en) | 2015-12-08 |
EP2384117B1 (en) | 2015-05-27 |
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