CN114304166B - 一种用于防控瓜类蔓枯病的杀菌组合物 - Google Patents
一种用于防控瓜类蔓枯病的杀菌组合物 Download PDFInfo
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- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
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Abstract
本发明公开了一种用于防控瓜类蔓枯病的杀菌组合物,其包括由氟唑菌酰羟胺和噻呋酰胺组成的有效成分，其中添加有适量的农用杀菌剂助剂，制成常用农用杀菌剂剂型。本发明的两种成份不存在交互抗性，两药剂按照一定比例组合后具有明显增效作用，对作物真菌性病害有更高的防治效果，组合使用可减少用药量，可延缓病菌对单一药剂的抗药性，有效降低生态破坏和环境污染，并能提高作物产量和质量；该组合物增加了抗病谱，可同时兼防瓜类白粉病、叶斑病、早疫病、褐斑病、灰霉病及镰刀菌引起枯萎病等常见病害。本发明中氟唑菌酰羟胺和噻呋酰胺均属低等毒性，并且对人畜、有益生物、环境安全。
Description
技术领域
本发明属于农用杀菌剂领域，具体涉及一种氟唑菌酰羟胺和噻呋酰胺的杀菌组合物，通过添加适量的助剂制成农用杀菌剂，有效防控瓜类蔓枯病，并同时兼防白粉病、叶斑病、褐斑病、灰霉病等常见的真菌病害。
背景技术
蔓枯病是一种在世界范围内广泛存在的植物真菌病害，主要危害葫芦科植物，包括西瓜、甜瓜、黄瓜、瓜蒌、丝瓜等作物。该病害可长期残留在土壤中的病残体中，在气候条件适宜的情况下快速侵染，并进行大面积传播、蔓延，发病率通常在50％以上，严重时可导致毁灭性的损失。近年来，伴随耕作模式和气候条件的变化，生产中盲目的最求产量和品质，通过设施大棚及水肥条件的改善植物生长环境，作物生长的同时，也被动的增加了蔓枯病流行趋势，使得蔓枯病成为瓜类作物生产的顽疾之一，严重影响了瓜类的产量和品质，制约了我国瓜类产业的健康发展。
近年来，通过分子进化水平的鉴定，明确了葫芦科蔓枯病的病原菌为包括为3个种，分别为Stagonosporopsis cucurbitacearum，Stagonosporopsis citrull和Stagonosporopsis caricae，这3种病原菌在亲缘关系上相近、形态学上基本一致，均可以危害葫芦科绝大部分植物，这其中，危害最普遍和发生最广泛的的病原菌为Stagonosporopsis cucurbitacearum。蔓枯病菌初侵染原为残留在病残体上子囊孢子，在温湿度适宜的条件下，子囊孢子快速成熟，释放后可快速侵染植物，在植物中形成大量的侵染菌丝，并形成分生孢子进行再侵染。病原菌在植株生长的整个生育期均可发生侵染，可危害植株的茎、蔓、叶、花、果等不同部位。茎蔓和叶片是最主要的发病部位，叶片发病初期可出现水渍状小斑点，后期逐渐发展为轮纹状的黄褐色斑点或呈“V”形病斑，严重时可在发病部位观察到黑色点状的分生孢子器。在植株生长的中后期发病最为严重，茎蔓部发病初期可出现水渍状褐色病斑，随着病情发展，病斑可沿茎蔓快速拓展几厘米到几十厘米。果实在蔓枯病发生严重时也可发病，引起果实腐烂，并在果实上着生大量菌丝。
目前，对栝楼蔓枯病的防控主要以化学药剂为主。然而，长期单一药剂的使用以及不合理的施药方式，使得病原菌很容易产生抗药性，导致药效下降、病害爆发，进而加大用药，形成恶性循环，加大用药成本，加剧环境污染，这也是化学防治的一大难题。如部分地区已经出现对嘧菌酯产生抗性蔓枯病菌菌株。因此，寻找新型防控药剂，并将其具有不同化学结构、不同作用机理的农药合理复配是克服抗药性发生与发展的有效措施，同时可以增强防效、减少单位面积的用药量，达到减药增效的目的，并为农业增效和解决农业面源污染这一矛盾问题提供解决思路。
氟唑菌酰羟胺(Pydiflumetofen)为苯基-乙基-吡唑-芳酰胺类琥珀酸脱氢酶抑制剂类杀菌剂，是先正达公司近年来开发的新型杀菌剂，结构式为(3-(二氟甲基)-N-甲氧基-1-甲基-N-[(RS)-1-甲基-2-(2，4，6-三氯苯基)乙基]吡唑-4-甲酰胺)，分子式为C16H16Cl3F2N3O2，沸点为557.9℃±50.0℃，密度为1.44±0.1g/cm3。氟唑菌酰羟胺属于琥珀酸脱氢酶抑制剂(SDHI)中的化合物之一，通过抑制复合酶II的活性来干扰植物病原的呼吸作用。与其它琥珀酸脱氢酶抑制剂类杀菌剂，如噻呋酰胺、氟吡菌酰胺和苯并烯氟菌唑等作用杀菌谱有所不同，且与这些杀菌剂之间不存在显著的交互抗性，推测是因为其作用在琥珀酸脱氢酶的不同亚基上。氟唑菌酰羟胺高效、广谱，适用于谷物、玉米、大豆、油菜、蔬菜、果树、特种作物、草坪、观赏植物等，防治包括镰刀菌(Fusarium spp.)、尾孢菌(Cercosporaspp.)、葡萄孢菌(Botrytis spp.)、链格孢菌(Alternaria spp.)等在内的许多病原菌引起的病害，如白粉病、叶斑病、褐斑病、灰霉病、赤霉病、菌核病等。但目前尚未有报道氟唑菌酰羟胺对蔓枯病防控效果。
噻呋酰胺是噻唑羧基N-苯酰胺类高效内吸性杀菌剂，具有强内吸传导性和长持效性。其作用机理是琥珀酸酯脱氢酶抑制剂。该药剂对丝核菌属、柄锈菌属、黑粉菌属、腥黑粉菌属、伏革菌属、核腔菌属等致病真菌均有活性，尤其对担子菌纲真菌引起的病害如纹枯病、立枯病等有特效。在推荐使用剂量下，对作物安全，无药害。可作为禾谷类作物的杀菌剂，但其使用成本高，且单独使用易产生抗药性。
发明内容
本发明提供了两个对瓜类蔓枯病防治效果显著的化合物，且两种化合物没有交互抗性，按一定比例组合后具有显著增效作用，该组合物在增加防效的同时，增加了抗病谱，可兼防瓜类白粉病、叶斑病、早疫病、褐斑病、灰霉病及镰刀菌引起枯萎病等常见病害。
本发明的技术方案为：
一种用于防控瓜类蔓枯病的杀菌组合物配方，所述杀菌剂由氟唑菌酰羟胺和噻呋酰胺组成。优选的，所述杀菌剂特征在于氟唑菌酰羟胺和噻呋酰胺的质量比为20∶1～1∶20。这其中用于大豆白绢病防治时，所述氟唑菌酰羟胺和噻呋酰胺的质量比为5∶1～1∶5。
所述的氟唑菌酰羟胺和噻呋酰胺的有效成分占杀菌组合物总质量的1％～80％，通过添加适量的农用杀菌剂助剂，制备成水悬浮剂、可湿性粉剂、微胶囊剂、水分散性粒剂或悬浮种衣剂，高效防治瓜类蔓枯病，并同时兼防瓜类白粉病、叶斑病、早疫病、褐斑病、灰霉病及镰刀菌引起枯萎病等常见病害。
本发明的显著效果和优点是：
本发明首次报道了氟唑菌酰羟胺对蔓枯病具有显著的防效，且两类化合物具备不同的结构类型和有差异作用位点，按一定比例组合后具有显著增效作用，该组合物在增加防效的同时，增加了抗病谱。通过添加高效助剂，加工成生产上容易使用的悬浮剂、可湿性粉剂、微胶囊剂、水分散性粒剂或悬浮种衣剂，生物活性高，增加了防病普，对生产中常发的瓜类蔓枯病及其它常见病害均具有较好的防控效果，且复配增效后单位面积上总的用药量下降，用药次数减少，降低了施药成本，延缓病原物抗药性产生和发展，延长了杀菌组合物中各组分的使用寿命，对作物安全性好，从而实现经济、高效、环保的发明目的。
具体实施方式
下面结合实施例对本发明作进一步说明，但本发明的内容并不限于下述实施例。
实施例1：氟唑菌酰羟胺和噻呋酰胺对蔓枯病菌的室内毒力测定。
对氟唑菌酰羟胺和噻呋酰胺的杀菌特性做细致分析。首先测定氟唑菌酰羟胺和噻呋酰胺两单一化合物(以下简称药剂)的EC50(药物安全性指标)，根据两单一药剂的EC50按Wadley法设定两药剂的组合比例，并根据Wadley增效系数SR值。
试验目标物为瓜类蔓枯病病菌(Stagonosporopsis cucurbitacearum)，但不限于此。取氟唑菌酰羟胺和噻呋酰胺，选用PDA固体培养基，配置成需药液平板，每皿约18ml。在预培养菌落边缘用灭菌的打孔器制取5mm直径的菌丝块，分别移到不同培养基平板上，25℃培养。试验采用菌丝生长测定法，按不同处理制作含药培养基，在预培养菌落边缘用灭菌的打孔器制取5mm直径的菌丝块，分别移到含药量不同的培养基平板上，采用十字交叉法测量菌落直径，量取菌落直径(mm)，由下列公式计算生长抑制率：
菌丝生长抑制率％＝(1-(药剂处理菌落直径5)/(对照菌落直径5))×100％
将菌丝生长抑制率换算成抑制机率值(y)，药剂浓度换算成浓度对数(x)，按浓度对数为横坐标、机率值为纵坐标作毒力回归直线，求得氟唑菌酰羟胺和噻呋酰胺单剂及其混剂对病菌的毒力回归方程，并计算EC50值及相关系数r值。
根据Wadley方法评价混剂的相互作用，计算公式如下：
EC50(理论值)＝(a+b)/(a/EC50a+b/EC50b)，
SR＝EC50(理论值)/EC50(实际值)。
其中a、b是各组分在混剂中含量比例，以SR值分析混配的效果。SR≤0.5，则两种药剂混配有拮抗作用；SR＝0.5～1.5，则两种药剂混配有加和作用；SR≥1.5，则两种药剂混配有增效作用。
表1氟唑菌酰羟胺和噻呋酰胺单剂及其混剂对蔓枯病菌的毒力测定结果
从上表可以看出，不同比例的氟唑菌酰羟胺和噻呋酰胺组合物对蔓枯病菌的抑菌效果各不相同，实验结果表明氟唑菌酰羟胺和噻呋酰胺质量比例在15∶1至1∶10范围内均有加和作用，其比例在5∶1至1∶5范围内有增效作用。
室内联合作用测定结果表明，氟唑菌酰羟胺和噻呋酰胺的组合物对蔓枯病菌有很好的生长抑制效果，两组分之间存在明显增效作用；两组分按照一定比例复配可减少用药量，有效降低生态破坏和环境污染，并能提高作物产量和质量；本发明中氟唑菌酰羟胺和噻呋酰胺均属低等毒性，并且对人畜、有益生物、环境安全；氟唑菌酰羟胺和噻呋酰胺之间不存在交互抗性，且杀菌普也有所差异，两组分混合使用可延缓病菌对单一药剂的抗药性，同时增加作物防病谱，达到兼防及减药的目的。
实施例2：制剂实施例。
制剂实施例1
18％氟唑菌酰羟胺·噻呋酰胺水分散粒剂的制备方法：按质量百分比。
氟唑菌酰羟胺：15％；噻呋酰胺：3％；木质素磺酸钠：6％；聚乙烯醇：4％；硫酸铵：8％；白炭黑：10％；高岭土：余量；
制备方法：将以上组分按配方比例加入混合机混合均匀后进行气流粉碎，粉碎完成后加入少量纯化水充分搅拌均匀，挤压造粒，烘干后即可得水分散粒剂产品。
制剂实施例2
20％氟唑菌酰羟胺·噻呋酰胺悬浮剂的制备方法：按质量百分比。
氟唑菌酰羟胺：10％；噻呋酰胺：10％；木质素磺酸钙：6％；烷基酚聚氧乙烯基磷酸酯：4％；黄原胶：0.1％；有机硅消泡剂：0.3％；水余量。
制备方法：根据配方，将以上组分按比例称量，加入球磨机球磨30分钟，过滤，抽入分散罐高速剪切3分钟后经砂磨机充分研磨，控制固体组分粒子直径在2微米以内，研磨结束后搅拌均匀，即得悬浮剂产品。
制剂实施例3
12％氟唑菌酰羟胺·噻呋酰胺水分散粒剂的制备方法：按质量百分比。
氟唑菌酰羟胺：2％；噻呋酰胺：10％；木质素磺酸钠：6％；聚乙烯醇：4％；硫酸铵：8％；白炭黑：10％；高岭土：余量；
制备方法：将以上组分按配方比例加入混合机混合均匀后进行气流粉碎，粉碎完成后加入少量纯化水充分搅拌均匀，挤压造粒，烘干后即可得水分散粒剂产品。
制剂实施例4
8％氟唑菌酰羟胺·噻呋酰胺悬浮种衣剂的制备，按质量百分比。
氟唑菌酰羟胺4％，噻呋酰胺4％，黄原胶：3％，分散剂FS3000：8％，5十二烷基硫酸钠：4％，木质素磺酸钠3％，丙三醇：3％，膨润土：5％，埃里特无水快T：2％，成膜剂：3％，染料：2％，水余量。
制备方法：根据配方，将以上组分(成膜剂、染料除外)按比例称量，加入球磨机球磨60min，过滤，抽入分散罐高速剪切3min后经砂磨机充分研磨，控制固体组分粒子直径在1μm以内，研磨结束后搅拌均匀，并加入成膜剂和染料，即得悬浮种衣剂产品。
实施例3：氟唑菌酰羟胺和噻呋酰胺对栝楼蔓枯病的田间防控实验。
2020，2021年度分别开展栝楼蔓枯病防控试验。将2021年度试验数据整理如下，实验分别使用实施列2即20％氟唑菌酰羟胺·噻呋酰胺悬浮剂、20％氟唑菌酰羟胺悬浮剂、30％噻呋酰胺悬浮剂、及25％嘧菌酯悬浮剂。试验栝楼品种为“皖蒌9号”，试验地点位于安徽省农业科学院岗集实验生产基地的栝楼田内进行，每亩用水量30公斤，栝楼于生长开花前期(5.20号)进行药剂防控，30天后进行病情调查(表2)。
表2不同复配剂型对栝楼蔓枯病的防控效果
大田试验结果表明，由氟唑菌酰羟胺和噻呋酰胺对栝楼蔓枯病具有较显著的防控效果，防控效果好于嘧菌酯。按增效配比组合形成的农药剂型对栝楼蔓枯病整体防控效果更优，防控效果高于单个剂型。根据田间调查，在试验剂量范围内，作物生长正常，未见植株产生药害及异常现象，对栝楼安全。
实施例4：氟唑菌酰羟胺和噻呋酰胺对西瓜蔓枯病的田间防控实验。
2020，2021年度分别开展西瓜蔓枯病防控试验。将2021年度试验数据整理如下，实验分别使用实施列1即18％氟唑菌酰羟胺·噻呋酰胺水分散粒剂，20％氟唑菌酰羟胺悬浮剂、30％噻呋酰胺悬浮剂，及25％嘧菌酯悬浮剂。试验西瓜品种为“早佳8424”，试验地点位于安徽省农业科学院岗集实验生产基地的西瓜大棚进行，每亩用水量30公斤，于西瓜苗定植后30天进行第一次药剂防控，第一次防控10天后进行第二次药剂防控，第二次药剂防控后30天进行病情调查(表3)。
表3不同复配剂型对西瓜蔓枯病的防控效果
大棚试验结果表明，由氟唑菌酰羟胺和噻呋酰胺对西瓜蔓枯病具有较显著的防控效果，防控效果好于嘧菌酯。按增效配比组合形成的农药剂型对西瓜蔓枯病整体防控效果更优，防控效果高于单个剂型。根据田间调查，在试验剂量范围内，作物生长正常，未见植株产生药害及异常现象，对西瓜全。
最后，还需要注意的是，以上列举的仅是本发明的若干个具体实施例。显然，本发明不限于以上实施例，还可以有很多变形。本领域的普通技术人员能从本发明公开的内同直接导出或联想到的所有变形，均认为是本发明的保护范围。
Claims (3)
1.一种用于防控瓜类蔓枯病的杀菌组合物用于防治瓜类蔓枯病的用途，其特征在于：所述杀菌组合物由氟唑菌酰羟胺和噻呋酰胺组成，氟唑菌酰羟胺和噻呋酰胺的质量比为5:1～1:5。
2.根据权利要求1所述的用途，所述的氟唑菌酰羟胺和噻呋酰胺的有效成分占杀菌组合物总质量的1%～80%，通过添加适量的农用杀菌剂助剂，制备成悬浮剂、可湿性粉剂、微胶囊剂、水分散性粒剂或悬浮种衣剂。
3.一种如权利要求1-2任一项中所述的用途，其特征在于：同时兼防白粉病、叶斑病、褐斑病或灰霉病的真菌病害。
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| CN103385247A (zh) * | 2012-05-10 | 2013-11-13 | 陕西韦尔奇作物保护有限公司 | 一种含氟唑菌酰胺与甲氧基丙烯酸酯类的杀菌组合物 |
| CN103416428A (zh) * | 2012-05-26 | 2013-12-04 | 陕西韦尔奇作物保护有限公司 | 一种含氟唑菌酰胺的杀菌组合物 |
| WO2015074614A1 (zh) * | 2013-11-25 | 2015-05-28 | 中国中化股份有限公司 | 一种吡唑酰胺类化合物及其用途 |
| CN104663684A (zh) * | 2015-02-13 | 2015-06-03 | 安徽省农业科学院植物保护与农产品质量安全研究所 | 一种含氟唑菌苯胺和噻呋酰胺的杀菌组合物 |
| WO2015157005A1 (en) * | 2014-04-10 | 2015-10-15 | E I Du Pont De Nemours And Company | Substituted tolyl fungicide mixtures |
| CN109566625A (zh) * | 2017-09-29 | 2019-04-05 | 江苏龙灯化学有限公司 | 一种杀菌组合物 |
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| CN103385247A (zh) * | 2012-05-10 | 2013-11-13 | 陕西韦尔奇作物保护有限公司 | 一种含氟唑菌酰胺与甲氧基丙烯酸酯类的杀菌组合物 |
| CN103416428A (zh) * | 2012-05-26 | 2013-12-04 | 陕西韦尔奇作物保护有限公司 | 一种含氟唑菌酰胺的杀菌组合物 |
| WO2015074614A1 (zh) * | 2013-11-25 | 2015-05-28 | 中国中化股份有限公司 | 一种吡唑酰胺类化合物及其用途 |
| WO2015157005A1 (en) * | 2014-04-10 | 2015-10-15 | E I Du Pont De Nemours And Company | Substituted tolyl fungicide mixtures |
| CN104663684A (zh) * | 2015-02-13 | 2015-06-03 | 安徽省农业科学院植物保护与农产品质量安全研究所 | 一种含氟唑菌苯胺和噻呋酰胺的杀菌组合物 |
| CN109566625A (zh) * | 2017-09-29 | 2019-04-05 | 江苏龙灯化学有限公司 | 一种杀菌组合物 |
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