CN101263821A - 一种杀菌剂组合物 - Google Patents
一种杀菌剂组合物 Download PDFInfo
- Publication number
- CN101263821A CN101263821A CNA2007101868933A CN200710186893A CN101263821A CN 101263821 A CN101263821 A CN 101263821A CN A2007101868933 A CNA2007101868933 A CN A2007101868933A CN 200710186893 A CN200710186893 A CN 200710186893A CN 101263821 A CN101263821 A CN 101263821A
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- CN
- China
- Prior art keywords
- prochloraz
- composition
- carbendazim
- weight portions
- sterilization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 claims abstract description 18
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
一种杀菌组合物，包含咪鲜胺、多菌灵、春雷霉素为有效成份组成的三元农药复配制剂，咪鲜胺、多菌灵、春雷霉素三者之间的重量比为(1～30)∶(1～30)∶(1～30)。该制剂广泛应用于谷类、水稻、蔬菜、果树和经济作物的病菌防治。对作物具有保护和治疗作用，表现出极强的杀菌活性。试验验证表明该组合物具有杀菌谱广、增效作用显著、对作物及环境使用安全等特点。
Description
技术领域
本发明涉及一种具有增效作用的杀菌剂组合物，主要用于谷类、水稻、蔬菜、水果等作物的真菌病害防治，对作物具有治疗和保护作用，表现出极强的抗菌和杀菌作用。该杀菌剂组合物有别于现有的其他杀菌剂组合物。
技术背景
施用化学药剂是防治植物真菌危害最为有效的手段，但长期或重复施用某单一活性化合物来防治有害真菌在很多情况下导致真菌菌株产生适应性变异，使药剂的防效降低甚至无效。为降低抗性真菌菌株选择性的危险性，目前通常使用的方法是筛选出不同活性的化合物的混合物来防治有害真菌。开发新品杀菌剂价格不断攀升，而相比之下，开发与研究高效、低毒、低残留的复配与混配具有投资少、研制周期短而收到国内外重视，纷纷加大开发研制力度。多菌灵、咪鲜胺、春雷霉素都是农业生产上非常有效的杀菌剂。这三种杀菌剂对于子囊菌纲和半知菌类中大多数病原真菌有效，三者之间的作用机理各不相同，多菌灵作用机理主要是通过干扰细菌的有丝分裂中纺锤体的形成，影响细胞分裂，从而达到杀菌的目的，对作物具有保护和治疗作用。咪鲜胺铜盐的杀菌机理主要是通过影响麦角甾醇生物合成，使菌体细胞膜的功能受到破坏，最终导致细胞死亡。春雷霉素是通过干扰氨基酸代谢的酯酶系统，从而影响蛋白质的合成，抑制菌丝伸长和造成细胞颗粒化达到杀菌的目的。通过将具有不同作用机理的活性化合物进行组合，具有扩大杀菌谱，提高防治效果、延长施药适期、减少用药量、减少残留、延缓真菌耐药性和抗药性的发生与发展等积极特点。
发明内容
本发明的目的：针对上述不足之处，通过将咪鲜胺、多菌灵、春雷霉素三种活性成分进行组合，提供一种具有协同增效作用的杀菌剂组合物。试验结果表明：本发明的组合物增效作用明显，持效期长，对作物具有保护和预防作用，而且咪鲜胺、多菌灵及春雷霉素三者之间无交互抗性。
咪鲜胺(英文通用名称Prochloraz)，化学名称(式I)：N-丙基-N-[2-(2，4，6-三氯苯氧基)乙基]-咪唑-1-甲酰胺
适合于本发明的咪鲜胺金属盐类化合物的金属离子可以选择元素周期表中第一至第二过度族元素，尤其是锰、锌、铜，根据情况需要，金属离子可以以它们可能呈现的各种化合价存在。例如，选择金属离子锰的盐类化合物，即，N-丙基-N-[2-(2，4，6-三氯苯氧基)乙基]-1-H-咪唑-1-甲酰胺-氯化锰(如式II)。
多菌灵(英文通用名称carbendazim)，化学名称(式III)：N-(2-苯骈咪唑基)氨基甲酸甲酯
春雷霉素(英文通用名称Kasugamycin)，化学名称(式IV)：(5-氨-3-甲基-6-(2，3，4，5，6-五羟基环已基氧化)吡喃-3-基)氨基-2-亚氨乙酸
本发明的具体方案为：一种相互间具有增效作用的的三元杀菌剂组合物，由下述组分组成：咪鲜胺、多菌灵和春雷霉素以及农药的常规助剂组成。
本发明的组合物中，活性组分a和b重量比为(1～30)∶(1-30)∶(1-30)，优选为(1～20)∶(1-20)∶(1-20)。
本发明的混合物以组合物的形式使用，使用时通常与其他载体、表面活性剂等常用助剂一起施用，这些常规农药助剂在农药领域内都是已知的。
本发明的活性组分咪鲜胺、多菌灵和春雷霉素占药剂总重量的5～95％。
适合于本发明的固体载体，如用于可湿性粉剂和水分散粒剂的通常是天然矿物填料，例如滑石、高岭土，蒙脱石或活性白土。为了管理物理性能也可以加入高分散性硅酸或高分散性吸附聚合物。合适的粒状吸附载体是多孔型的，如浮石、皂土或膨润土；合适的非吸附载体是例如方解石或砂。另外，可以使用大量的无机性质或有机性质的预制成粒状的材料，特别是白云石。
根据本发明三组分的化学性质，合适的表面活性剂为木质素磺酸、萘磺酸、苯酚磺酸、二丁基萘磺酸的碱金属盐、碱土金属盐和胺盐，烷基芳基磺酸盐，烷基硫酸盐，烷基磺酸盐，脂肪醇硫酸盐，脂肪酸和硫酸化脂肪醇乙二醇醚，还有磺化萘和萘衍生物与甲醛的缩合物，萘或萘磺酸与苯酚和甲醛的缩合物，聚氧乙烯辛基苯基醚，乙氧基化异辛基酚，辛基酚，壬基酚，烷基芳基聚乙二醇醚，三丁基苯聚乙二醇醚，三硬脂基苯基聚乙二醇醚，烷基芳基聚醚醇，乙氧基化蓖麻油，聚氧乙烯烷基醚，氧化乙烯缩合物、乙氧基化聚氧丙烯，月桂酸聚乙二醇醚缩醛，山梨醇酯，木质素亚硫酸盐废液和甲基纤维素。
本发明的组合物能以不变的形式使用，或者优选地与配置工艺中通常使用的添加剂一起使用，因此这些化合物能以已知的方式进行配置，例如制成可湿性粉剂、水分散粒剂、悬浮剂。根据这些组合物所具有的性质，可以根据所要达到的目的和环境情况选择如喷雾、弥雾、撒播、泼浇等之类的施用方法。
作为固体形式的组合物，可提及的有下列几种：水分散粒剂(其活性成分的含量一般比较高，通常在30～90重量份之间)，通常是通过可湿性粉末型组合物在合适的颗粒体系中的附聚作用加以制备，制得该剂型。
可湿性粉剂一般用这样的方法制备，即以使其含有3～90重量份的活性成分为准，除固体载体外，它们一般含有0～7重量份的湿润剂，3～10重量份的分散剂，必要时，再含有0～10重量份的一种或多种其它的添加剂。如染料、着色剂、渗透剂、粘合剂或抗结块剂等。
作为液体形式的组合物，可以加工成悬浮剂，其可以通过如下的方法来制备，即以得到不形成沉积物的稳定的流体为准，它们一般含有4～65重量份的活性成分，0.5～45重量份的表面活性剂，0～10重量份适当的诸如染料、着色剂、抗泡沫剂、防蚀剂、稳定剂和渗透剂及粘合剂等的添加剂，载体可以是水或有机液体，活性成分难溶或不溶于水中，可将某些固体有机物质或无机盐溶于液体中以有助于沉积物的形成或作为水的防冻剂。
本发明的组合物有效成分施用量通常是70～600克/公顷，优选80～550克/公顷。
具有增效作用的杀菌剂组合物，兼有保护、铲除和治疗活性，防治谷类、水稻、果树(柑橘、苹果、梨、葡萄)、蔬菜和经济作物(如油菜)等作物的真菌病害，如麦类赤霉病、白粉病菌；水稻稻瘟病、纹枯病、细菌性褐条病；黄瓜枯萎病、细菌性角斑病；葡萄灰霉病、霜霉病、炭疽病；苹果轮纹病；柑橘溃疡病；油菜菌核病等。经过测试证明本发明的组合物具有化学性质稳定、增效明显，对防治对象表现明显的增效及互补作用。
因此，本发明的杀菌组合物表现出以下几方面的优点：1.本发明的组合物在一定的配比范围之内表现出一定的增效作用，提高了防治效果，扩大了杀菌谱；2.该组合物中各单剂的作用机制各不相同，不存在相互间交互抗性的问题，所以，该组合物的应用可以达到延缓病原物抗性的发生和发展，有助于延长该制剂的使用效果，降低病原物产生选择性抗性的几率；3.提高了安全性，对作物、环境的影响大大降低。
下面实施例并非限制本发明，而只是用来说明本发明在实际应用中是如何来实现的。
实施例
一、剂型制备实施例
1、水分散粒剂
咪鲜胺锰盐 11.0重量份
多菌灵 24.0重量份
春雷霉素 10.0重量份
聚乙烯醇， 2.0重量份
2，2’-二萘基甲烷-6，6’-二磺酸钠 4.0重量份
油酰甲基牛磺酸钠 4.0重量份
碳酸钙 5.0重量份
水 余量
将上述原料在水中研磨制得所需的粒径，调整其浓度和黏度，得到喷雾用浆料，然后将浆料定量送进干燥塔内进行喷雾干燥，得到该产品。
以上水分散粒剂也可通过如下方式来加工：
2、水分散粒剂
咪鲜胺铜盐 38.0重量份
多菌灵 41.0重量份
春雷霉素 10.0重量份
月桂硫酸钠 2.0重量份
聚乙烯醇 1.0重量份
木质磺酸钙 2.0重量份
高岭土 余量
将上述成分混合后，在栓型碟式磨粉机中磨成细粉，将粉末在流化床中通过喷洒作为粒化液体的水使之粒化。
3、可湿性粉剂
咪鲜胺铜盐 36.0重量份
春雷霉素 13.0重量份
多菌灵 16.0重量份
木质素磺酸钠 4.0重量份
聚氧乙烯辛基苯基醚 3.0重量份
烷基聚氧乙基醚磺酸盐 5.0重量份
凹凸棒土 余量
有效成分与助剂彻底混合，并将其在合适的磨中彻底研磨，得到的可湿性粉剂可用水稀释成需要浓度的悬浮液。
4、悬浮剂
咪鲜胺 16.0重量份
春雷霉素 5.0重量份
多菌灵 14.0重量份
聚丙烯酸钠 2.0重量份
丙二醇 5.0重量份
木质素磺酸盐 11.0重量份
辛基酚聚乙二醇醚(11-14摩尔环氧乙烷)6.0重量份
水 余量
将磨得很细的有效成分与助剂彻底混合，得到的悬浮剂可用水稀释成任何需要浓度的悬浮液。这样的稀释液可通过喷洒，泼浇或浸渍方法用于处理生长的植物和种子，保护它们免受微生物侵染。
二、应用实施例
实施例1.离体生物活性
采用菌体生长速率法(mycelium growth rate test)测定制剂实施例1(45％水分散粒剂)、制剂实施例4(35％悬浮剂)对苹果轮纹病菌的联合毒力。将供试药剂稀释至设计浓度，取1毫升加入培养皿内，再加入9毫升PSA培养基，摇匀后制备成最终浓度稀释10倍的含药平板。以加入1毫升灭菌水作空白对照。用直径4毫米打孔器沿供试菌丛外缘打取菌盘，置于含药平板内，24±1℃黑暗培养72小时，计量各处理菌盘扩展直径，计算菌体生长抑制百分率，按浓度对数——抑制率几率值法计算药剂有效中浓度(EC50)，进一步采用孙云沛法计算共毒系数。结果表明两混剂共毒系数均明显大于100，表示该混剂有增效作用。试验结果见表1
表1.对苹果轮纹病菌的联合毒力试验结果
| 药种 | 毒力回归式 | EC50(ug/ml) | 共毒系数 |
| 春雷霉素 | Y＝2.36541+1.35452X | 0.983992 | |
| 咪鲜胺锰盐 | Y＝1.52142+0.30214X | 1.157527 |
| 多菌灵 | Y＝0.76593+1.57592X | 2.203243 | |
| 实施例1(75％水分散粒剂) | Y＝1.52676+2.85314X | 0.329218 | 161.9094 |
| 实施例4(35％悬浮剂) | Y＝3.25429+0.93542X | 0.596037 | 135.0863 |
实施例2.温室盆栽试验(防治黄瓜灰霉病试验结果)
试验作物在温室内培养至2-3叶期幼苗，按设计浓度对幼苗叶片进行喷雾处理，药剂处理24小时后接种测试病原菌。然后将幼苗在2±1℃下进行保湿培养，在不施药的空白对照充分发病后进行结果调查。病害分级、防治效果计算方法均按中华人民共和国国家标准“农药田间药效试验准则”进行。试验结果表明：施用本发明的组合物，其防治效果相对于两组分单独施用具有明显的增效效果。试验结果见表2
表2.防治黄瓜灰霉病试验结果
实施例3.田间试验(对油菜菌核病的田间药效试验)
对油菜菌核病的田间药效试验在陆地栽培地进行，油菜试验地由于连续多年使用多菌灵单剂防治油菜菌核病，对多菌灵单剂表现出一定的抗性。供试药剂为实施例1(45％水分散粒剂)。试验共设3个剂量，4次重复，以施清水作空白对照。试验田均为自然发病并在发病初期施药。当空白对照充分发病时进行病情调查。病害分级、防效计算方法均按中华人民共和国国家标准“农药田间药效试验准则”进行。试验结果表明，本发明的组合物对防治油菜菌核病具有优异的防治效果，而且对作物生长无任何的影响。试验结果见表3
表3.对油菜菌核病田间药效防治效果
实施例4.田间试验(对水稻穗颈瘟的田间药效试验)
试验地前茬为小麦，施药时水层深约1.4cm，水稻品种为盐稻9号。试验区土壤类型为水稻勤泥土，pH值7.4，常年地下水位60cm，地势平坦，灌溉条件良好。于水稻破口初期5天时施药一次，喷药量以水稻叶面和稻杆滴水为止。防治穗茎瘟的效果见表4。
表4.对水稻穗颈瘟田间药效防治效果
Claims (4)
1、一种杀菌组合物，其特征在于含咪鲜胺、多菌灵、春雷霉素为活性成分组成的三元复配制剂，三组活性成分之间的重量比为(1～30)∶(1～30)∶(1～30)，组合物中三组活性成分的累计重量占制剂总重量比的5～95％。
2、根据权利要求1的杀菌合物，其特征在于咪鲜胺、多菌灵和春雷霉素之间的重量比为(1～20)∶(1～20)∶(1～20)。
3、根据权利要求1的杀菌合物，其特征在于所述的咪鲜胺可以是咪鲜胺金属盐类化合物，选自咪鲜胺锰盐、咪鲜胺锌盐或咪鲜胺铜盐中的一种化合物。
4、根据权利要求1的杀菌合物，其特征在于具有增效作用的组合物应用于防治谷类、水稻、蔬菜、果树和经济作物等作物的真菌危害。
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|---|---|---|---|---|
| CN102805095A (zh) * | 2012-08-13 | 2012-12-05 | 浙江农林大学 | 含纳他霉素的复配杀菌剂及其用途 |
| CN102823612A (zh) * | 2012-09-26 | 2012-12-19 | 贵州大学 | 防治水稻稻瘟病的农药 |
| CN103070175A (zh) * | 2013-01-30 | 2013-05-01 | 浙江省桐庐汇丰生物化工有限公司 | 一种含啶酰菌胺与春雷霉素的复配农药及其应用 |
| CN103070175B (zh) * | 2013-01-30 | 2014-06-25 | 浙江省桐庐汇丰生物化工有限公司 | 一种含啶酰菌胺与春雷霉素的复配农药及其应用 |
| CN103798273A (zh) * | 2014-02-18 | 2014-05-21 | 中国水稻研究所 | 一种含硫酸链霉素的复配农药及其应用 |
| CN103798273B (zh) * | 2014-02-18 | 2016-07-06 | 中国水稻研究所 | 一种含硫酸链霉素的复配农药及其应用 |
| CN109430275A (zh) * | 2018-10-25 | 2019-03-08 | 中国农业科学院植物保护研究所 | 具有杀菌活性的农业用杀菌剂及应用 |
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| CN101263821B (zh) | 2011-12-28 |
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