CN105409992A - Sterilization composite and application thereof - Google Patents
Sterilization composite and application thereof Download PDFInfo
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- CN105409992A CN105409992A CN201511028686.6A CN201511028686A CN105409992A CN 105409992 A CN105409992 A CN 105409992A CN 201511028686 A CN201511028686 A CN 201511028686A CN 105409992 A CN105409992 A CN 105409992A
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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
- A01N47/08—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 the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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Abstract
本发明属于农用杀菌剂领域,具体地说涉及一种含有吡唑醚菌酯和啶氧菌酯的杀菌组合物及其应用。所述杀菌组合物的有效成分为吡唑醚菌酯与啶氧菌酯,剂型为悬浮剂、水分散粒剂,二者重量比为1:20~15:1,优选5:1~1:8。其优点和有益效果如下:1.杀菌范围广;2.持效期长;3.低毒,无残留,无公害,对环境安全;4.使用复合制剂,两种杀菌剂的用量均比单一使用时降低,从而提高了杀菌效果,增加了安全性,减少了环境污染。The invention belongs to the field of agricultural fungicides, in particular to a fungicidal composition containing pyraclostrobin and picoxystrobin and an application thereof. The active ingredients of the fungicidal composition are pyraclostrobin and picoxystrobin, and the dosage forms are suspension concentrate and water dispersible granule, and the weight ratio of the two is 1:20~15:1, preferably 5:1~1: 8. Its advantages and beneficial effects are as follows: 1. Wide bactericidal range; 2. Long duration; 3. Low toxicity, no residue, no pollution, safe for the environment; When used, it is lowered, thereby improving the bactericidal effect, increasing safety and reducing environmental pollution.
Description
技术领域technical field
本发明属于农用杀菌剂领域,具体地说涉及一种含有吡唑醚菌酯和啶氧菌酯的杀菌组合物及其应用。The invention belongs to the field of agricultural fungicides, in particular to a fungicidal composition containing pyraclostrobin and picoxystrobin and an application thereof.
背景技术Background technique
吡唑醚菌酯为新型广谱杀菌剂,作用机理:为线粒体呼吸抑制剂,即通过在细胞色素合成中阻止电子转移,具有保护、治疗、叶片渗透传导作用。吡唑醚菌酯除对真菌有较强的抑制作用外,对作物的生长也有明显的促进作用,能够明显改善作物的长势,提高免疫力,更好的防御病害。吡唑醚菌酯对鱼剧毒,对鸟、蜜蜂、蚯蚓低毒。在产品标签上注明药械不得在池塘等水源和水体中洗涤,施药残液不得倒入水源和水体中。由于吡唑醚菌酯独特的作用机理和对作物生长的促进作用,同时对其他杀菌剂具抗性的病菌有效,本剂有很大的发展余地。Pyraclostrobin is a new type of broad-spectrum fungicide, and its mechanism of action is that it is a mitochondrial respiration inhibitor, that is, it has the functions of protection, treatment, and leaf penetration by preventing electron transfer during cytochrome synthesis. In addition to its strong inhibitory effect on fungi, pyraclostrobin can also significantly promote the growth of crops, which can significantly improve the growth of crops, improve immunity, and better defend against diseases. Pyraclostrobin is highly toxic to fish, but low toxic to birds, bees and earthworms. It should be indicated on the product label that medical equipment should not be washed in ponds and other water sources and water bodies, and that pesticide residues should not be poured into water sources and water bodies. Due to the unique mechanism of action of pyraclostrobin and the promotion of crop growth, it is also effective against bacteria resistant to other fungicides, so this agent has great room for development.
啶氧菌酯是内吸性杀菌剂,防治对象广谱,主要用于防治麦类的叶面病害如叶枯病、叶锈病、颖枯病、褐斑病、白粉病等,与其他甲氧基丙烯酸酯类杀菌剂相比,啶氧菌酯对小麦叶祜病、网斑病和云纹病有更强的治疗效果。作用机理同为线粒体呼吸抑制剂,即通过在细胞色素b和C1间电子转移抑制线粒体的呼吸。防治对14-脱甲基化酶抑制剂、苯甲酰胺类、三羧酰胺类和苯并咪唑类产生抗性的菌株有效。啶氧菌酯一旦被叶片吸收,就会在木质部中移动,随水流在运输系统中流动;它也在叶片表面的气相中流动并随着从气相中吸收进入叶片后又在木质部中流动。无雨条件下用啶氧菌酯[250g(a.i.)/hm2]喷雾处理的作物和将同样喷雾处理后2h的作物暴露于降雨量为10mm、长达1h进行比较,结果表明两者对大麦叶枯病的防治效果是一致的。正是由于啶氧菌酯的内吸活性和熏蒸活性,因而施药后,有效成分能有效再分配及充分传递,因此啶氧菌酯比商品化的嘧菌酯和肟菌酯有更好的治疗活性。Picoxystrobin is a systemic fungicide with a broad spectrum of control objects. It is mainly used to control wheat foliar diseases such as leaf blight, leaf rust, glume blight, brown spot, powdery mildew, etc., and other methoxy Compared with acrylate-based fungicides, picoxystrobin has a stronger therapeutic effect on wheat leaf spot, net spot and moire. The mechanism of action is the same as the inhibitor of mitochondrial respiration, that is, the respiration of mitochondria is inhibited by electron transfer between cytochrome b and C1. It is effective in controlling strains resistant to 14-demethylase inhibitors, benzamides, tricarboxamides and benzimidazoles. Once taken up by the leaves, picoxystrobin moves in the xylem, following the water flow in the transport system; it also flows in the gas phase on the leaf surface and flows in the xylem after being absorbed into the leaves from the gas phase. A comparison of crops sprayed with picoxystrobin [250g(ai)/hm 2 ] under no-rain conditions and crops exposed to 10mm of rainfall for 1h after the same spray treatment 2h showed both effects on barley The control effect of leaf blight is consistent. It is precisely because of the systemic activity and fumigation activity of picoxystrobin that the active ingredients can be effectively redistributed and fully delivered after application. Therefore, picoxystrobin has a better effect than commercial azoxystrobin and trifloxystrobin. Therapeutic activity.
小麦白粉病,禾本科布氏白粉菌小麦专化型;学名:Blumeriagraminis(DC.)Speer=ErysipegraminisDC.、E.graminisDC.f.sp.triticl。Marchal;是一种世界性病害,在各主要产麦国均有分布,我国山东沿海、四川、贵州、云南发生普遍,为害也重。近年来该病在东北、华北、西北麦区,亦有日趋严重之势。该病可侵害小麦植株地上部各器官,但以叶片和叶鞘为主,发病重时颖壳和芒也可受害。Wheat powdery mildew, gramineous powdery mildew wheat specialization type; Scientific name: Blumeria graminis (DC.) Speer=Erysipe graminis DC., E. graminis DC.f.sp.triticl. Marchal is a worldwide disease, which is distributed in all major wheat-producing countries. It is common in Shandong coastal areas, Sichuan, Guizhou, and Yunnan, and the damage is also serious. In recent years, the disease has also become more and more serious in the Northeast, North China, and Northwest wheat regions. The disease can infect the above-ground organs of wheat plants, but mainly leaves and leaf sheaths, and glumes and awns can also be affected when the disease is severe.
含有单一活性组分的杀菌剂品种在农用杀菌剂防治上往往存在不同程度的缺陷,如杀菌范围窄,防治效果差,施药剂量大易产生抗药性,施用次数多加重环境污染等。对于防治农业上产生抗性的病菌,一种办法是推出新的与现有品种无交互抗性的新成分。但是,新的有效成分的开发成本高,开发周期长,而且永远都跟不上病菌产生抗性的速度。其他的办法比如作物布局调整、不同农药轮换等,在实际操作的过程中,很难真正起到明显的效果。Fungicide varieties containing a single active component often have different degrees of defects in the control of agricultural fungicides, such as narrow bactericidal range, poor control effect, large application doses are easy to produce drug resistance, and frequent application increases environmental pollution. One way to control agriculturally resistant pathogens is to introduce new ingredients that are not cross-resistant with existing varieties. However, the development cost of new active ingredients is high, the development cycle is long, and the speed of resistance of bacteria can never be kept up. Other methods, such as crop layout adjustment, rotation of different pesticides, etc., are difficult to achieve obvious effects in actual operation.
不同品种成分进行复配,是防治抗性病菌最常见的方法。不同成分进行复配,可以提高防治效果,扩大杀菌范围,减少有效成分的用量,节约用药成本,降低环境污染,是综合防治病害的重要手段。Combination of ingredients from different varieties is the most common method for controlling resistant pathogens. Compounding different ingredients can improve the control effect, expand the scope of sterilization, reduce the amount of active ingredients, save drug costs, and reduce environmental pollution. It is an important means of comprehensive disease prevention and control.
发明内容Contents of the invention
本发明的目的是提供一种杀菌活性高效、持效期长、速效性高、低毒、环保的含有吡唑醚菌酯和啶氧菌酯的杀菌组合物及其应用。The object of the present invention is to provide a bactericidal composition containing pyraclostrobin and picoxystrobin with high bactericidal activity, long duration, high quick-acting, low toxicity and environmental protection and its application.
本发明的技术方案如下:Technical scheme of the present invention is as follows:
一种杀菌组合物,其有效成分为吡唑醚菌酯与啶氧菌酯,剂型为悬浮剂、水分散粒剂。A bactericidal composition, the active ingredients of which are pyraclostrobin and picoxystrobin, and the formulations are suspension concentrate and water dispersible granule.
所述有效成分吡唑醚菌酯与啶氧菌酯的重量比为1:20~15:1,优选5:1~1:8。The weight ratio of the active ingredient pyraclostrobin to picoxystrobin is 1:20-15:1, preferably 5:1-1:8.
所述有效成分吡唑醚菌酯与啶氧菌酯在所述杀菌组合物中的重量百分含量为10%~80%。The weight percentage of the active ingredients pyraclostrobin and picoxystrobin in the bactericidal composition is 10% to 80%.
所述杀菌组合物中还包括载体和助剂。The bactericidal composition also includes carriers and auxiliary agents.
所述载体选自水、填料中的一种或多种。The carrier is selected from one or more of water and fillers.
所述助剂包括表面活性剂,所述表面活性剂选自乳化剂、分散剂、润湿剂或渗透剂中的一种或多种。The auxiliary agent includes a surfactant, and the surfactant is selected from one or more of an emulsifying agent, a dispersing agent, a wetting agent or a penetrating agent.
所述助剂还包括其他功能性助剂,所述其他功能性助剂选自防冻剂、增稠剂、稳定剂、崩解剂或消泡剂中一种或多种。The auxiliary agent also includes other functional auxiliary agents, and the other functional auxiliary agents are selected from one or more of antifreeze agents, thickeners, stabilizers, disintegrants or defoamers.
一种所述杀菌组合物在防治小麦白粉病上的应用。An application of the bactericidal composition in preventing and treating wheat powdery mildew.
本发明具有的优点和有益效果:1.杀菌范围广;2.持效期长;3.低毒,无残留,无公害,对环境安全;4.使用复合制剂,两种杀菌剂的用量均比单一使用时降低,从而提高了杀菌效果,增加了安全性,减少了环境污染。The advantages and beneficial effects of the present invention: 1. wide range of sterilization; 2. long duration; 3. low toxicity, no residue, no pollution, safe for the environment; It is lower than when it is used alone, thereby improving the bactericidal effect, increasing safety and reducing environmental pollution.
具体实施方式detailed description
以下结合实施例具体说明本发明。但本发明绝非仅仅限于以下这些实施例。配方中百分比均为重量百分比,所使用的原药以及助剂均从其他厂家购买。The present invention will be described in detail below in conjunction with the examples. However, the present invention is by no means limited to the following examples. The percentages in the formula are all percentages by weight, and the original drugs and auxiliary agents used are all purchased from other manufacturers.
配方筛选如下:Recipe screening is as follows:
吡唑醚菌酯、啶氧菌酯两种有效成分的杀菌活性很高,针对两种成分的作用特点,将室内生测的对象定位为小麦白粉病,具体试验情况以及结果如下:The two active ingredients, pyraclostrobin and picoxystrobin, have high bactericidal activity. According to the characteristics of the two ingredients, the object of the indoor biotest is positioned as wheat powdery mildew. The specific test conditions and results are as follows:
实验用药采用95%吡唑醚菌酯和95%啶氧菌酯原药,使用丙酮将原药溶解,配制成所需要的制剂(根据设定的配比浓度,配制成所需浓度药液备用,所使用的原药及助剂均为其他厂家购买)。The experimental drug used 95% pyraclostrobin and 95% picoxystrobin original drug, and used acetone to dissolve the original drug, and prepared the required preparation (according to the set ratio concentration, the required concentration of the drug solution was prepared for use) , the original drugs and additives used are purchased from other manufacturers).
室内生测的方法为:采用盆栽法,用喷雾法将药剂均匀喷洒于备用的小麦苗上,自然晾干。试验设不含药剂的处理作空白对照。将发病小麦叶片上24h内产生的白粉病菌新鲜孢子均匀抖落接种于处理的2-3叶期盆栽小麦苗上。每处理不少于3盆,每盆10株。保护性试验在药剂处理后24h接种;治疗性试验在药剂处理前24h接种,然后置适宜条件下培养。根据空白对照发病情况分级调查。采用如下分级方法:0级:无病;1级:病斑面积占整片面积的5%以下;3级:病斑面积占整片面积的6%~15%;5级:病斑面积占整片面积的16%~25%;7级:病斑面积占整片面积的26%~50%;9级:病斑面积占整片面积的50%以上。The indoor bioassay method is as follows: the potted method is adopted, and the chemical agent is evenly sprayed on the spare wheat seedlings by spraying method, and then dried naturally. In the experiment, the treatment without drug was used as blank control. The fresh spores of powdery mildew fungus produced on the diseased wheat leaves within 24 hours were evenly shaken off and inoculated on the treated potted wheat seedlings at the 2-3 leaf stage. No less than 3 pots per treatment, 10 plants per pot. The protective test was inoculated 24 hours after the drug treatment; the curative test was inoculated 24 hours before the drug treatment, and then cultured under suitable conditions. According to the incidence of the blank control graded investigation. The following grading method was adopted: grade 0: no disease; grade 1: lesion area accounted for less than 5% of the entire area; grade 3: lesion area accounted for 6% to 15% of the entire area; 16% to 25% of the entire patch area; Grade 7: the lesion area accounts for 26% to 50% of the entire patch area; Grade 9: the lesion area accounts for more than 50% of the entire patch area.
根据调查数据,计算各处理的病情指数和防治效果。According to the survey data, the disease index and control effect of each treatment were calculated.
病情指数按公式(1)计算,计算结果保留小数点后两位:The condition index is calculated according to the formula (1), and the calculation result has two decimal places:
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。In the formula: x—sickness index; Ni—the number of diseased leaves at all levels; i—the value of relative grade; N—the total number of leaves under investigation.
防治效果按公式(2)计算:The control effect is calculated according to the formula (2):
式中:P—防治效果,单位为百分率(%);CK—空白对照病情指数;PT—药剂处理病情指数。In the formula: P—control effect, the unit is percentage (%); CK—blank control disease index; PT—pharmaceutical treatment disease index.
根据各药剂浓度对数值及对应的防效几率值作回归分析,计算各药剂的EC50、EC90等值及其95%置信限。进行药剂联合毒力测定时,根据孙云沛法求出共毒系数。According to the logarithmic value of each agent concentration and the corresponding probability value of control effect, the regression analysis was carried out to calculate the EC50, EC90 equivalent value and 95% confidence limit of each agent. In the determination of drug joint toxicity, the co-toxicity coefficient was calculated according to Sun Yunpei's method.
混配制剂的联合毒力采用孙云沛的共毒系数方法表示:The joint toxicity of the mixed preparation is expressed by Sun Yunpei's co-toxicity coefficient method:
混配制剂的理论毒力指数TTI=Σ(某药的毒力指数ATI×在混剂中该药有效成分的百分率)。The theoretical toxicity index TTI of the mixed preparation = Σ (toxicity index ATI of a certain drug × the percentage of the active ingredient of the drug in the mixed preparation).
CTC大于120时为增效作用,小于80时为拮抗作用,80-120时为加和作用。When the CTC is greater than 120, it is a synergistic effect, when it is less than 80, it is an antagonistic effect, and when it is 80-120, it is an additive effect.
表1不同配比对小麦白粉病的毒力测定结果Table 1 Toxicity test results of different mixtures against wheat powdery mildew
分析上述数据测定结果表明,吡唑醚菌酯与啶氧菌酯不同比例复配时,所有复配配方的共毒系数分别均大于120,都具有明显的增效作用。说明将两种有效成分复配后,能够有很好的增效作用。其中配比五的共毒系数更是达到了176.27,为所有配比中最高。The analysis results of the above data show that when pyraclostrobin and picoxystrobin are compounded in different proportions, the co-toxicity coefficients of all the compound formulas are respectively greater than 120, and all have obvious synergistic effects. It shows that after compounding the two active ingredients, it can have a good synergistic effect. Among them, the co-toxicity coefficient of ratio five even reached 176.27, the highest among all ratios.
配方实例如下:The recipe example is as follows:
实例一:51%吡唑醚菌酯·啶氧菌酯悬浮剂Example 1: 51% pyraclostrobin·picoxystrobin suspension concentrate
实例二:46.5%吡唑醚菌酯·啶氧菌酯水分散粒剂Example 2: 46.5% pyraclostrobin · picoxystrobin water dispersible granules
实例三:22%吡唑醚菌酯·啶氧菌酯悬浮剂Example 3: 22% pyraclostrobin·picoxystrobin suspension concentrate
实例四:18%吡唑醚菌酯·啶氧菌酯水分散粒剂Example 4: 18% pyraclostrobin · picoxystrobin water dispersible granules
实例五:30%吡唑醚菌酯·啶氧菌酯悬浮剂Example 5: 30% pyraclostrobin·picoxystrobin suspension concentrate
实例六:24%吡唑醚菌酯·啶氧菌酯水分散粒剂Example 6: 24% pyraclostrobin · picoxystrobin water dispersible granules
实例七:11%吡唑醚菌酯·啶氧菌酯悬浮剂Example 7: 11% pyraclostrobin·picoxystrobin suspension concentrate
实例八:31%吡唑醚菌酯·啶氧菌酯水分散粒剂Example 8: 31% pyraclostrobin · picoxystrobin water dispersible granules
实例九:25.5%吡唑醚菌酯·啶氧菌酯悬浮剂Example 9: 25.5% pyraclostrobin·picoxystrobin suspension concentrate
按照上述九个实例,进行30%吡唑醚菌酯·啶氧菌酯悬浮剂以及其他复配配方的田间防治小麦白粉病的试验,同时通过与15%吡唑醚菌酯悬浮剂、250g/L啶氧菌酯悬浮剂的效果对比,验证复配后的增效效果。试验地点为河南省周口市淮阳县,时间为2014年3月20日及3月27号共施药两次,试验共四个处理,每个处理三个重复,每重复定6丛,小区随机排列,小区面积15m2,所有小区的种植习惯均与当地的种植习惯相同,记录施药当天和其后一周的天气资料,具体如下:According to above-mentioned nine examples, carry out the field control wheat powdery mildew test of 30% pyraclostrobin · picoxystrobin suspending agent and other compound formulations, pass simultaneously with 15% pyraclostrobin suspending concentrate, 250g/ Comparison of the effect of L picoxystrobin suspension concentrate to verify the synergistic effect after compounding. The test site is Huaiyang County, Zhoukou City, Henan Province. The time was March 20 and March 27, 2014, and the pesticide was applied twice. There were four treatments in the test, and each treatment was replicated three times. Each replicate had 6 clusters. Arranged randomly, the area of the plot is 15m 2 , the planting habits of all plots are the same as the local planting habits, and the weather data on the day of spraying and the following week are recorded, as follows:
表2试验期间气象资料Table 2 Meteorological data during the test period
调查标准为:未施药前先调查1次,然后每次施药后隔7天调查1次,每重复随机调查40株小麦(查3个相邻蘖上部3片叶)。根据《农药田间药效试验标准》中相关标准进行记载。实验数据采用邓肯式新复极差检测法(DMRT)。The survey standard is: survey once before spraying, and then survey once every 7 days after spraying, and randomly survey 40 wheat plants for each repetition (check the upper 3 leaves of 3 adjacent tillers). It is recorded according to the relevant standards in the "Pesticide Field Efficacy Test Standards". The experimental data adopts Duncan's new multiple range detection method (DMRT).
表3不同处理对小麦白粉病的防治效果Table 3 Control effect of different treatments on wheat powdery mildew
从表3试验结果表明,施药后实施药剂对小麦白粉病的防治效果明显高于对比药剂,二次施药7天后,实施药剂对白粉病的防治效果仍然保持在70-85%之间,其中实例五的防效最高为82.91%。这表明吡唑醚菌酯与啶氧菌酯复配杀菌剂具有较好的增效作用,而且持效时间明显长于单一药剂。实验表明,该复配组合物明显降低药剂使用量,减少了生产成本、农药残留和环境污染。另外,试验期间田间观察,实施例药剂各处理药液对作物生长无影响,对周围有益生物安全,与环境相容性好。由此可见,吡唑醚菌酯与啶氧菌酯是一个理想复配杀菌产品。From table 3 test result shows, after spraying, the control effect of medicament to wheat powdery mildew is obviously higher than that of comparison medicament, and after 7 days of secondary spraying, the control effect of medicament to powdery mildew still remains between 70-85%. Wherein the control effect of example five is the highest 82.91%. This shows that pyraclostrobin and picoxystrobin compound fungicides have a better synergistic effect, and the duration of effect is significantly longer than that of a single agent. Experiments show that the compound composition obviously reduces the dosage of chemicals used, reduces production costs, pesticide residues and environmental pollution. In addition, according to field observations during the test, each treatment solution of the medicaments in the examples has no effect on crop growth, is beneficial to the surrounding biological safety, and has good compatibility with the environment. It can be seen that pyraclostrobin and picoxystrobin are an ideal compound sterilization product.
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| CN108651497A (en) * | 2018-06-21 | 2018-10-16 | 浙江新农化工股份有限公司 | Pyraclostrobin-containing and alkene oxime amine bactericidal composition and application thereof and agriculture chemicals fungicide |
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| CN103651368A (en) * | 2013-12-13 | 2014-03-26 | 广西田园生化股份有限公司 | Ultra-low-volume liquid containing picoxystrobin and preparation method of ultra-low-volume liquid |
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| CN103355343A (en) * | 2013-07-26 | 2013-10-23 | 海南正业中农高科股份有限公司 | Agricultural compositions containing sulfur |
| CN103651368A (en) * | 2013-12-13 | 2014-03-26 | 广西田园生化股份有限公司 | Ultra-low-volume liquid containing picoxystrobin and preparation method of ultra-low-volume liquid |
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| CN108651497A (en) * | 2018-06-21 | 2018-10-16 | 浙江新农化工股份有限公司 | Pyraclostrobin-containing and alkene oxime amine bactericidal composition and application thereof and agriculture chemicals fungicide |
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