CN107410322A - 含苯并烯氟菌唑的杀菌组合物 - Google Patents
含苯并烯氟菌唑的杀菌组合物 Download PDFInfo
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- CN107410322A CN107410322A CN201710247512.1A CN201710247512A CN107410322A CN 107410322 A CN107410322 A CN 107410322A CN 201710247512 A CN201710247512 A CN 201710247512A CN 107410322 A CN107410322 A CN 107410322A
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- bactericidal composition
- azoles
- bacterium azoles
- active components
- fluorine bacterium
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
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Abstract
本发明提供了一种含苯并烯氟菌唑的协同杀菌组合物，其特征在于包括活性成分A和B，其中，A为苯并烯氟菌唑，B为精呋霜灵、异丙噻菌胺、Tolprocarb、picarbutrazox、噻唑锌、Dichlobentiazox、氟茚唑菌胺(fluindapyr)、dipymetitrone中的一种或一种以上组合，还包括农药制剂加工中可以使用的助剂，制成常规的农药制剂，并应用于防治植物病害。
Description
技术领域
本发明属于农药应用技术领域，涉及一种农药组合物，具体的说是一种含苯并烯氟菌唑的杀菌组合物，应用于防治植物病害。
背景技术
在农业生产过程中，植物病害发生严重，危害植物茎、叶等营养器官，以及果实、种子、块茎等繁殖器官部位，影响植物光合作用，影响食用部位外观，使作物产量锐减，品质下降严重。病害发生严重时，导致作物绝收。因此，植物病害在生产实际上具有重要的防治意义，杀菌剂是防治植物病害的最为经济、快捷而有效的方法。
单一杀菌剂使用容易产生抗药性或防治谱有限，并不能很好地解决生产实际中的植物病害危害。混配杀菌剂具有可扩大防治谱、增强防效，延缓植物病原菌抗药性等优势，在生产实践中成为最受欢迎的应用形式。尤其是具有协同作用的杀菌剂，杀菌剂各有效组分间相互作用，使组合时效果优于单独使用效果的理论总和，因而在实际使用时可起到事半功倍的效果，更受使用者青睐。
苯并烯氟菌唑(benzovindiflupyr)是先正达近几年开发的琥珀酸脱氢酶抑制剂(SDHI)，通过干扰线粒体呼吸电子传递链中复合物Ⅱ中琥珀酸脱氢酶的活性，从而抑制线粒体功能。苯并烯氟菌唑广谱、高效，持效期长，可叶面喷雾或土壤处理，防治多种作物、草坪和花卉上的叶部病害和土传病害，如小麦锈病、小麦白粉病、大麦云纹病、玉米炭疽病、玉米褐斑病、棉花立枯病、大豆锈病、葫芦科蔬菜炭疽病、葡萄白粉病、花生菌核病、苹果树斑点落叶病等。由于其作用机理相对较为新颖，作用谱广泛，抑菌活性高，被视为最具潜力的SDHI类杀菌剂。CAS登录号为1072957-71-1。其结构式如下：
精呋霜灵(furalaxyl-M)、异丙噻菌胺(isofetamid)、Tolprocarb、picarbutrazox、Dichlobentiazox、氟茚唑菌胺(fluindapyr，CAS号为1383809-87-7)、dipymetitrone是近几年国外企业开发的杀菌剂，噻唑锌(zinc thiazole)是一种无机广谱性杀菌剂。上述几种杀菌剂对多种作物上的植物病害均表现出优良防效。
本发明经过大量的配方筛选试验研究发现，当苯并烯氟菌唑与精呋霜灵、异丙噻菌胺、Tolprocarb、picarbutrazox、Dichlobentiazox、氟茚唑菌胺(fluindapyr)、dipymetitrone、噻唑锌中的一种或一种以上药剂任意组合时，显示出令人惊讶的杀菌效果，即表现出良好的协同作用，实际杀菌效果明显优于单独使用的理论总和，在生产上具有非常广泛的应用前景。
发明内容
本发明涉及协同杀菌组合物，包括活性成分A和B，所述的活性成分A为苯并烯氟菌唑(benzovindiflupyr)，所述的活性成分B为精呋霜灵、异丙噻菌胺、Tolprocarb、picarbutrazox、Dichlobentiazox、氟茚唑菌胺(fluindapyr)、dipymetitrone、噻唑锌中的一种或一种以上组合。此外，还包括农药制剂加工中可以使用的助剂。
所述组合物可以特别良好的效果用于防治各种有用作物中的植物病害，所述有用作物包括但不限于常规育种作物、转基因作物、无性繁殖作物及无性繁殖材料、驯化栽培的野生植物等，特别适用于防治小麦、玉米、棉花、大豆、葫芦科蔬菜、葡萄、苹果等作物病害。
可提及的具体实例为一些可用本发明的组合物防治的代表性植物病害，所述实例并不限于特定属种。需要说明的是本发明并不局限于以下具体实例，还可以以相同方式延伸到其它植物病害，括号注明其病原拉丁文学名：
小麦叶锈病(Puccinia recondita)、条锈病(P.striiformis)、杆锈病(P.graminis)、壳针孢叶枯病(Septoria tritici)、网斑病(Pyrenophora teres)、白粉病(Blumeria graminis)，大麦云纹病(Rhynchosporium secalis)，玉米炭疽病(Colletotrichum graminicola)、锈病(Puccinia sorghi)、褐斑病(Physoderma maydis)、灰斑病(Cercospora sorghi)，棉花立枯病(Rhizoctonia solani)、锈病(Pucciniaschedonnardi)、茎枯病(Ascochyta gossypii)，大豆锈病(Phakopsora pachyrhizi)，葫芦科蔬菜炭疽病(Colletotrichum orbiculare)、白粉病(Sphaerotheca fuliginea)、链格孢叶斑病(Alternaria cucumerina)、壳针孢叶斑病(Septoria cucurbitacearum)，番茄炭疽病(Colletotrichum atramentarium)、灰斑病(Stemphyllium solani)、尾孢属叶斑病(Cercospora capsici)、白粉病(Oidiopsis sicula)，葡萄白粉病(Erysiphe necator)、链格孢叶斑病(Alternaria alternata)、褐斑病(Pseudocercospora vitis)，花生菌核病(Sclerotium rolfsii)、立枯病(Rhizoctonia solani)，苹果树黑星病(Venturiainaequalis)、白粉病(Podosphaera leucotricha)、斑点落叶病(Alternaria mali)等。
为了解决上述技术问题，本发明采用如下技术方案予以实现：
本发明组合物组分A和B可以任意比例混配，通常一种活性成分含量高于其余活性成分，优选混合比是100：1至1：100或50：1至1：50。
本发明组合物可通过将活性成分与农药制剂加工中可以使用的助剂混合，用已知方法制备为常规的制剂，如乳油、可湿性粉剂、水分散粒剂、悬浮剂、水乳剂、微乳剂、颗粒剂等。制剂中一般含有0.1～95％重量的活性成分，优选0.5～90％重量的活性成分。
农药制剂加工中可以使用的助剂包括但不限于：水、溶剂、填料、各种表面活性剂(乳化剂、分散剂、润湿剂等)、黏结剂、成膜剂、着色剂、防冻剂、增稠剂、助悬剂、崩解剂、消泡剂、渗透剂、增效剂、稳定剂、壁囊材料、pH调节剂、防腐剂等。并且，适当地，为了提高对特定作物耐受力，可适当添加安全剂；或者有时为了促进作物生长发育，可在混配组合物中添加常规农业肥料，制成药肥混剂。这些助剂都是农药制剂中常用或允许使用的成分，并无特别限定，可选择一种或一种以上助剂构成，具体成分和用量根据配方要求通过简单的试验确定。
所述组合物各种应用剂型的生产工艺均属现有已知技术，在此不再赘述。
本发明组合物可以多种方法使用，如兑水以常规方式喷雾使用，或直接撒施或沟施，或拌毒土撒施等，于植物播种时、出苗前、出苗后营养生长期和生殖生长期均可使用。用药量可在较宽范围内变化，并且取决于土壤的状况、使用方法、作物、待防治的植物病害种类及苗龄大小、当时的气候条件及其他因素。本发明组合物通常以0.001～0.5kg活性成分混合物/公顷的用量施用，更为优选地，以0.01～0.2kg活性成分混合物/公顷的用量施用。
本发明与现有技术相比，具有如下技术效果：
1、混配组合物具有良好的协同作用，应用效果明显优于单剂理论效果总和，即具有超叠加作用，可更好地控制植物病害发生危害；
2、混配组合物活性成分之间在植物病害防治谱上具有良好的互补性，可很好扩大防治谱，综合有效控制各种植物病害发生危害；
3、混配组合物具有良好的协同作用，可减少药剂使用量，降低使用成本和环境污染，提高对作物的安全性。
具体实施方式
以下给出本发明的具体实施例，需要说明的是本发明并不局限于以下具体实施例，凡在本申请技术方案基础上做的等同变换均落入本发明的保护范围。
实施例1：12％乳油
配方组成为：活性成分A为4％，活性成分B为8％，乳化剂十二烷基苯磺酸钙5％，乳化剂脂肪醇聚氧乙烯醚4％，溶剂二甲苯补足至100％。
制备方法为：将所有物料投入配料釜中，搅拌溶解至完全透明，化验合格后，转移至储罐灌装。
实施例2：25％悬浮剂
配方组成为：活性成分A为10％，活性成分B为15％，润湿剂脂肪醇聚氧乙烯醚5％，分散剂烷基酚聚氧乙烯醚磷酸酯4％，防冻剂乙二醇5％，增稠剂硅酸镁铝0.4％，水补足至100％。
制备方法为：将活性成分和润湿剂、分散剂、防冻剂和水投入搅拌釜中，充分搅拌后，将物料抽入砂磨机中进行充分研磨，研磨完成后，抽入高速剪切机中，加入增稠剂后，进行高速剪切，剪切完成后即制得悬浮剂。
实施例3：45％水分散粒剂
配方组成为：活性成分A为20％，活性成分B为25％，润湿剂十二烷基硫酸钠3％，分散剂木质素磺酸钠5％，崩解剂硫酸钠5％，黏结剂聚乙二醇0.5％，填料高岭土补足至100％。
制备方法为：将所有物料混合均匀后，经气流粉碎机粉碎，再次混合均匀，然后，加入一定量的水将此混合物捏合，挤压造粒，经干燥筛分，即得到水分散粒剂。
实施例4：18％水乳剂
配方组成为：活性成分A为6％，活性成分B为12％，溶剂二甲苯8％，乳化剂脂肪醇聚氧乙烯醚6％，乳化剂烷基酚甲醛树脂聚氧乙烯醚硫酸盐3％，防冻剂丙二醇3％，水补足至100％。
制备方法为：将活性成分A和B用溶剂充分溶解后，投入乳化剂充分搅拌后形成油相；将防冻剂加入水中溶解，形成水相；将水相缓慢加入油相中，使用高速剪切机剪切，即可得水乳剂。
实施例5：26％微乳剂
配方组成为：活性成分A为10％，活性成分B为16％，溶剂二甲苯10％，乳化剂十二烷基苯磺酸钙5％，乳化剂苯乙基酚聚氧乙烯醚6％，乳化剂烷基芳基聚氧丙烯聚氧乙烯醚3％，防冻剂丙三醇5％，水补足至100％。
制备方法为：将活性成分A和B用溶剂充分溶解后，投入乳化剂和防冻剂混合均匀，最后加入去离子水，进行高速剪切，即可得微乳剂。
实施例6：50％可湿性粉剂
配方组成为：活性成分A为20％，活性成分B为30％，润湿剂十二烷基硫酸钠2％，分散剂木质素磺酸钙4％，分散剂萘磺酸盐甲醛缩合物3％，填料硅藻土补足至100％。
制备方法为：将活性成分和各助剂混合均匀，投入机械粉粹机中进行初粉粹，之后经气流粉碎机粉碎，再混合均匀，即制得可湿性粉剂。
实施例7：6％颗粒剂
配方组成为：活性成分A为2％，活性成分B为4％，润湿剂十二烷基硫酸钠0.6％，分散剂木质素磺酸钙1％，着色剂炭黑0.2％，填料膨润土补足至100％。
制备方法为：将所有物料混合均匀后，加入一定量的水将此混合物捏合，挤压造粒，经干燥筛分，即得到颗粒剂。
应用效果实例：
1、试验方法
(1)对小麦叶锈病菌的生物活性
参照《NYT 1156.15-2008农药室内生物测定试验准则杀菌剂第15部分：防治麦类叶锈病试验盆裁法》进行。
以小麦叶锈病菌(Puccinia recondita)为供试病菌，实验室接种在新鲜小麦苗上扩繁备用。
以小麦感病品种“烟农19”为供试作物，每盆播20粒种子，出苗后选定其中10株，长至2叶1心期备用。
选取扩繁用发病叶片，将24h内产生的小麦叶锈病菌新鲜夏孢子用0.1％吐温-80水溶液洗下，并用双层纱布过滤，制成浓度为1×105个孢子/mL的孢子悬浮液，用于喷雾接种“烟农19”麦苗。麦苗接种后，黑暗保湿培养24h，将配制好的药液均匀喷施于叶面至全部润湿。然后在18～22℃的温室中培养，每天光照12h以上。每处理设置4次重复，每重复3盆，并设不含药剂的处理作空白对照。当空白对照发病率达到80％以上时，分级调查处理发病情况。计算各处理的病情指数和防治效果。
病情指数按式(1)计算，防治效果按式(2)计算，计算结果保留小数点后两位。
式中：
X—病情指数；
Ni—各级病叶数；
i—相对级数值；
N—调查总叶数；
9—最高级数值。
式中：
P—防治效果，单位为百分数(％)；
CK—空白对照病情指数；
PT—药剂处理病情指数。
(2)对苹果树斑点落叶病菌的生物活性
参照《NYT 1156.2-2006农药室内生物测定试验准则杀菌剂第2部分：抑制病原真菌菌丝生长试验平皿法》进行。
以苹果树斑点落叶病菌(Alternaria mali)为供试病原菌，田间采集，实验室分离纯化，接种在PDA培养基上培养，培养至菌落直径达6cm左右备用。
PDA培养基、去离子水、划线三角瓶、培养皿、枪头、打孔器、接种器等灭菌后备用。
在无菌操作条件下，将预先融化冷却至约50℃的灭菌PDA培养基定量加入灭菌划线三角瓶中，使培养基与划线处(60mL)平齐，然后从低浓度到高浓度依次吸取600μL药液，分别加入上述三角瓶中，充分摇匀，后等量倒入4个培养皿(Φ9cm)中，制成5个浓度梯度带药平板。并设不含药剂的处理作空白对照。将在PDA上培养好的病原菌，在无菌条件下用灭菌打孔器(Φ5mm)自菌落边缘同一圆周上切取菌饼，用接种器将菌饼接种于含药平板中央，菌丝面朝下，盖上皿盖，于28℃培养箱中黑暗培养。根据空白对照皿中菌丝生长情况，用卡尺测量菌落直径。每个菌落采用十字交叉法垂直测量，取其平均值，计算对菌丝生长的抑制率。
按公式(3)、(4)计算各处理浓度对苹果树斑点落叶病菌的菌丝生长抑制率，单位为百分率(％)，计算结果保留小数点后两位。
D＝D1-D2…………………………………………(3)
式中：
D—菌落增长直径，单位为毫米(mm)；
D1—菌落直径，单位为毫米(mm)；
D2—菌饼直径，单位为毫米(mm)。
式中：
I—菌丝生长抑制率，单位为百分数(％)；
D0—空白对照菌落增长直径，单位为毫米(mm)；
Dt—药剂处理菌落增长直径，单位为毫米(mm)。
(3)对黄瓜炭疽病菌的生物活性
参照《NYT 1156.14-2008农药室内生物测定试验准则杀菌剂第14部分：防治瓜类炭疽病试验盆裁法》进行。
以黄瓜炭疽病菌(Colletotrichum orbiculare)为供试病原菌，田间采集，实验室分离纯化，接种在PDA培养基上培养，待产生大量分生孢子后，用无菌水从菌落上洗取分生孢子，洗涤液用双层纱布过滤，用血球计数板计数，配制成1×105个孢子/mL的孢子悬浮液备用。
以黄瓜感病品种“山东密刺”为供试作物，可控日光温室内培养至3～5叶期备用。
用移液器移取10μL孢子悬浮液接种于黄瓜叶片正面(黄瓜炭疽病菌易侵染叶片正面)，每个叶片接种4个点。接种后移至保湿箱中(相对湿度95％～100％)黑暗培养24h，将配制好的药液均匀喷施于叶面至全部润湿。然后在(25±1)℃、光照强度20000Lux、相对湿度为80％～90％的人工气候箱内培养。每处理设置4次重复，每重复3盆，并设不含药剂的处理作空白对照。
待空白对照发病率达50％以上时，用游标卡尺以十字交叉法测量病斑直径，取平均值。
根据调查数据，按公式(5)计算防治效果，结果保留小数点后两位。
式中：
I—防治效果，单位为百分数(％)；
D0—空白对照病斑直径，单位为毫米(mm)；
D1—药剂处理病斑直径，单位为毫米(mm)。
(4)组合物预期活性判定
组合物预期活性借鉴拜耳、先正达、陶氏等跨国农药企业制剂专利中判定杀菌剂组合物预期活性的方法(COLBY法)：COLBY，S.R.：“Calculating Synergistic andAntagonistic Responses of Herbicide Combinations”，Weeds 15，p.20～22，1967进行。
组合物预期活性按(6)式计算：
式中：
X—杀菌剂1用量为P时的防效或抑制率；
Y—杀菌剂2用量为Q时的防效或抑制率；
E—杀菌剂1与杀菌剂2按上述比例混用后的实际防效或抑制率，即混配杀菌剂的实际活性；
E0—杀菌剂1用量为P+杀菌剂2用量为Q时的理论防效或抑制率，即混配杀菌剂的预期活性。
当E＞E0时，即如果混配药剂的实际活性超过所计算的预期活性，则该组合就具有超叠加作用，即协同作用。
2、试验结果
试验结果详见表1～5，可见，活性成分A(苯并烯氟菌唑)与选自活性成分B(fluindapyr、异丙噻菌胺、Tolprocarb、Dichlobentiazox等)的药剂混配后，实际活性均大于预期活性，说明苯并烯氟菌唑与活性成分B中的药剂混配具有协同作用。
表1苯并烯氟菌唑与氟茚唑菌胺(fluindapyr)混配对小麦叶锈病菌的联合作用效应
表2苯并烯氟菌唑与异丙噻菌胺混配对苹果树斑点落叶病菌的联合作用效应
表3苯并烯氟菌唑与Tolprocarb混配对黄瓜炭疽病菌的联合作用效应
表4苯并烯氟菌唑与Dichlobentiazox混配对黄瓜炭疽病菌的联合作用效应
表5苯并烯氟菌唑与picarbutrazox混配对黄瓜炭疽病菌的联合作用效应
Claims (5)
1.杀菌组合物，其特征在于，包括活性成分A和B。
2.如权利要求1所述的杀菌组合物，其特征在于，所述的活性成分A为苯并烯氟菌唑。
3.如权利要求1所述的杀菌组合物，其特征在于，所述的活性成分B为精呋霜灵、异丙噻菌胺、Tolprocarb、picarbutrazox、噻唑锌、Dichlobentiazox、氟茚唑菌胺(fluindapyr)、dipymetitrone中的一种或一种以上组合。
4.如权利要求1、2或3所述的杀菌组合物，其特征在于，除了活性成分A和B外，还包括农药制剂加工中可以使用的助剂。
5.如权利要求1、2、3或4所述的杀菌组合物，其特征在于，将其应用于防治植物病害。
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| CN108402043A (zh) * | 2018-03-23 | 2018-08-17 | 北京科发伟业农药技术中心 | 一种含异丙噻菌胺的杀菌组合物 |
| CN109452287A (zh) * | 2018-11-14 | 2019-03-12 | 东莞东阳光科研发有限公司 | 一种杀菌组合物及其用途和制备方法 |
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| CN104839165A (zh) * | 2014-09-09 | 2015-08-19 | 陕西美邦农药有限公司 | 一种苯并烯氟菌唑的杀菌组合物 |
| CN106922708A (zh) * | 2015-12-29 | 2017-07-07 | 浙江新农化工股份有限公司 | picarbutrazox与琥珀酸脱氢酶抑制剂类杀菌剂的组合物及其制剂和应用 |
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| CN106922708A (zh) * | 2015-12-29 | 2017-07-07 | 浙江新农化工股份有限公司 | picarbutrazox与琥珀酸脱氢酶抑制剂类杀菌剂的组合物及其制剂和应用 |
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| CN108402043A (zh) * | 2018-03-23 | 2018-08-17 | 北京科发伟业农药技术中心 | 一种含异丙噻菌胺的杀菌组合物 |
| CN109452287A (zh) * | 2018-11-14 | 2019-03-12 | 东莞东阳光科研发有限公司 | 一种杀菌组合物及其用途和制备方法 |
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