CN111657296A - 一种含草铵膦的除草组合物 - Google Patents
一种含草铵膦的除草组合物 Download PDFInfo
- Publication number
- CN111657296A CN111657296A CN202010570838.XA CN202010570838A CN111657296A CN 111657296 A CN111657296 A CN 111657296A CN 202010570838 A CN202010570838 A CN 202010570838A CN 111657296 A CN111657296 A CN 111657296A
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- China
- Prior art keywords
- glufosinate
- ammonium
- fluoroglycofen
- flumioxazin
- ethyl
- 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.)
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- FOUWCSDKDDHKQP-UHFFFAOYSA-N flumioxazin Chemical compound FC1=CC=2OCC(=O)N(CC#C)C=2C=C1N(C1=O)C(=O)C2=C1CCCC2 FOUWCSDKDDHKQP-UHFFFAOYSA-N 0.000 claims abstract description 21
- IPPAUTOBDWNELX-UHFFFAOYSA-N (2-ethoxy-2-oxoethyl) 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate Chemical group C1=C([N+]([O-])=O)C(C(=O)OCC(=O)OCC)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 IPPAUTOBDWNELX-UHFFFAOYSA-N 0.000 claims abstract description 18
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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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/48—Nitro-carboxylic acids; Derivatives thereof
-
- 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
- A01N43/72—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
- A01N43/84—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 six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及一种专门用于柑橘园及非耕地的除草组合物，所述除草组合物至少包含草铵膦、乙羧氟草醚和丙炔氟草胺三种组分，活性成分质量比为(1‑50)：(1‑50)：(1‑50)，优选为(1‑10)：(1‑10)：(1‑10)。所述除草组合物按照本技术领域技术人员所公知的方法可以配制的制剂剂型包括水剂、悬浮剂、悬乳剂、可分散油悬浮剂、可湿性粉剂、水分散粒剂、颗粒剂和微囊悬浮‑悬浮剂，活性成分在制剂中的重量百分含量为1％‑80％，优选为5％～75％。本发明还涉及上述组合物在防除柑橘园及非耕地杂草中的应用。
Description
技术领域
本发明涉及一种除草组合物，由活性成分草铵膦、乙羧氟草醚和丙炔氟草胺组成，属于复配农药复配技术领域。
背景技术
丙炔氟草胺，英文通用名flumioxazin，化学名称：7-氟-6-(3,4,5,6-四氢)苯二甲酰亚氨基-4-(2-丙炔基)-1,4-苯并噁嗪-3(2H)-酮，结构上属环状亚胺类除草剂。丙炔氟草胺为由幼芽和叶片吸收的除草剂，作土壤处理可有效防除1年生阔叶杂草和部分禾本科杂草，在环境中易降解，对后茬作物安全。大豆、花生对其有很好的耐药性。玉米、小麦、大麦、水稻具有中等忍耐性。
乙羧氟草醚，英文通用名Fluoroglycofen，化学名称：0-[5-(2-氯-a,a,a-三氟-对-甲苯氧基)-2-硝基苯甲酰基]羟基乙酸乙酯，结构上属二苯醚类除草剂，作用机理属原卟啉氧化酶抑制剂。用于防除大豆田中大多数阔叶杂草，虽然该药剂芽前施用对敏感的双子叶杂草也有一定活性，但剂量必须高于芽后剂量的2-10倍。该药剂防除窄叶或多年生杂草无效。适用于小麦、大麦、花生、大豆和稻田除草。可防除阔叶杂草，尤其是猪殃殃、婆婆纳、堇菜、苍耳属和甘薯杂草。
草铵膦，英文通用名Glufosinate ammonium，化学名称：2-氨基-4-[羟基(甲基)膦酰基]丁酸铵，结构上属有机磷类除草剂，作用机理属谷氨酰胺合成抑制剂，非选择性触杀除草剂。有一定内吸作用，可用于果园、葡萄园、非耕地除草，也可用于马铃薯地防除一年生或多年生双子叶及禾本科杂草和莎草等。
目前市面上专门开发用于柑橘园和非耕地的除草剂较少，因此，开发一种更专用于柑橘园和非耕地防除常见杂草的混合除草剂非常有必要。
发明内容
本发明的目的在于提供一种专门用于柑橘园和非耕地的除草组合物，所述除草组合物至少包含草铵膦、乙羧氟草醚和丙炔氟草胺三种组分。
本发明的另一目的在于提供上述组合物在防除柑橘园和非耕地杂草中的应用。
为了克服现有单一制剂或两元复配的缺陷，本发明除草组合物的技术方案是这样解决的：
A)第一活性成分草铵膦；
B)第二活性成分乙羧氟草醚；
C)第三活性成分丙炔氟草胺。
第一活性成分、第二活性成分与第三活性成分质量比为(1-50)：(1-50)：(1-50)，优选为(1-10)：(1-10)：(1-10)。
本发明一种包含草铵膦的除草组合物按照本技术领域技术人员所公知的方法可以配制的制剂剂型包括水剂、悬浮剂、悬乳剂、可分散油悬浮剂、可湿性粉剂、水分散粒剂、颗粒剂和微囊悬浮-悬浮剂，活性成分在制剂中的重量百分含量为1％-80％，优选为5％～75％。
对水剂，可选用的助剂包括：乳化剂如十二烷基苯磺酸钙、烷基酚甲醛树脂聚氧乙烯醚、农乳2201#、山梨醇酐单硬脂酸酯、失水山梨醇单硬脂酸酯聚氧乙烯醚、壬基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、苯乙基苯酚聚氧乙烯聚氧丙烯醚、农乳600#、农乳400#、十二烷基二甲基苄基氯化铵等；溶剂水为去离子水。
对悬浮剂，可选用的助剂包括：分散剂如聚羧酸盐、木质素磺酸盐、烷基萘甲醛缩合物磺酸盐、烷基酚聚氧乙烯基醚磷酸酯、烷基酚聚氧乙烯基醚磺酸盐、苯乙基酚聚氧乙烯基醚磷酸酯、烷基聚氧乙烯醚磺酸盐、聚氧乙烯聚氧丙烯基醚嵌段共聚物、拉开粉、十二烷基聚氧乙烯醚磷酸酯等中的一种或多种；润湿剂如烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐、苯乙基酚聚氧乙烯基醚磷酸酯、烷基硫酸盐、烷基磺酸盐、烷基萘磺酸盐、烷基酚甲醛树脂聚氧乙烯醚、三苯乙基苯酚聚氧丙烯聚氧乙烯嵌段聚合物等中的一种或多种；增稠剂如黄原胶、聚乙烯醇、膨润土、硅酸镁铝、羧甲基纤维素、羧乙基纤维素、甲基纤维素等中的一种或多种；防腐剂如甲醛、苯甲酸、苯甲酸钠、山梨酸钾、异噻唑啉酮等中的一种或多种；消泡剂如硅油、硅酮类化合物、C10-20饱和脂肪酸类化合物、C8-10脂肪醇类、己醇、丁醇、辛醇等中的一种或多种；防冻剂如乙二醇、丙二醇、丙三醇、聚乙二醇、山梨醇、尿素、无机盐类等中的一种或多种；水为去离子水。
对悬乳剂，可选用的助剂包括：乳化剂如十二烷基苯磺酸钙(农乳500#)、农乳700#、农乳2201、斯盘-60#、乳化剂T-60(通用名：失水山梨醇单硬酯酸酯聚氧乙烯醚)、TX-10(通用名：辛基酚聚氧乙烯(10)醚)、农乳1601#、农乳600#、农乳400#等中的一种或多种；分散剂如聚羧酸盐、木质素磺酸盐、烷基萘磺酸盐等中的一种或多种；溶剂如邻苯二甲酸二甲酯、邻苯二甲酸二丁酯、乙酸乙酯、苯甲酸甲酯等中的一种或多种；消泡剂如硅油、硅酮类化合物、C10-20饱和脂肪酸类化合物、C8-10脂肪醇类、己醇、丁醇、辛醇等中的一种或多种；增稠剂如白炭黑、聚乙烯醇、膨润土、硅酸镁铝等中的一种或多种；防冻剂如乙二醇、丙二醇、甘油、尿素、无机盐类如氯化钠等中的一种或多种；水为去离子水。
对可分散油悬浮剂，可选用的助剂包括：分散剂如聚羧酸盐、烷基萘磺酸盐、TERSPERSE2425(美国亨斯迈公司出品，烷基萘磺酸盐类)中的一种或多种；乳化剂如农乳700#(通用名：烷基酚甲醛聚氧乙烯醚)、农乳2201、斯盘-60(通用名：山梨醇酐单硬脂酸酯)、吐温-60(通用名：失水山梨醇脂肪酸酯聚氧乙烯醚)、农乳1601#(通用名：三苯乙基苯酚聚氧丙烯聚氧乙烯嵌段聚合物)、TERSPERSE4894(美国亨斯迈公司出品)、TERSPERSE2500(美国亨斯迈公司出品)中的一种或多种；润湿剂如烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐、烷基酚聚氧乙烯醚磷酸酯、苯乙基酚聚氧乙烯基醚磷酸酯、烷基硫酸盐、烷基磺酸盐、萘磺酸盐、TERSPERSE2500(美国亨斯迈公司出品)中一种或多种；增稠剂如白炭黑、聚乙烯醇、膨润土、硅酸镁铝中的一种或多种；防冻剂如乙二醇、丙二醇、甘油、尿素、无机盐类如氯化钠中的一种或多种；分散介质如大豆油、菜籽油、玉米油、油酸甲酯、蓖麻油中的一种或多种。
对可湿性粉剂，可选用的助剂包括：分散剂如聚羧酸盐、木质素磺酸盐、聚氧乙烯聚氧丙烯基醚嵌段共聚物、烷基萘甲醛缩合物磺酸盐、烷基酚聚氧乙烯基醚磷酸酯、脂肪醇聚氧乙烯醚磷酸酯、烷基酚聚氧乙烯基醚磺酸盐等中的一种或多种；润湿剂如烷基硫酸盐、烷基磺酸盐、烷基萘磺酸盐等中的一种或多种；填料如硫酸铵、尿素、蔗糖、葡萄糖、硅藻土、高岭土、白炭黑、轻钙、滑石粉、凹凸棒土、陶土等中的一种或多种。
对水分散粒剂，可选用的助剂包括：分散剂如聚羧酸盐(TERSPERSE2700、T36、GY-D06等)、木质素磺酸盐、烷基萘磺酸盐等中的一种或多种；润湿剂如烷基硫酸盐、烷基磺酸盐、萘磺酸盐等中的一种或多种；崩解剂如硫酸铵、硫酸钠、聚乙烯吡咯烷酮、淀粉及其衍生物、膨润土等中的一种或多种；粘结剂如淀粉、葡萄糖、聚乙烯醇、聚乙二醇、羧甲基纤维素钠、蔗糖等中的一种或多种；填料如硅藻土、高岭土、白炭黑、轻钙、滑石粉、凹凸棒土、陶土等中的一种或多种。
对颗粒剂，可选用的助剂包括：载体如粘土、高岭土、滑石、碳酸钙、玉米淀粉、硅酸铝等中的一种或多种；分散剂如聚羧酸盐、木质素磺酸盐、烷基萘磺酸盐等中的一种或多种；润湿剂如烷基硫酸盐、烷基磺酸盐、萘磺酸盐等中的一种或多种；粘合剂如聚乙烯醇、糊精、聚乙烯吡咯烷酮等中的一种或多种。
对微囊悬浮-悬浮剂，可选用的助剂包括：崩解剂如膨润土、尿素、硫酸铵、聚乙烯吡咯烷酮、葡萄糖、碳酸氢钠中的一种或多种；防腐剂如甲醛、苯甲酸、苯甲酸钠、山梨酸钾、异噻唑啉酮等中的一种或多种；乳化剂如脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯醚、十二烷基苯磺酸钙、烷基酚聚氧乙烯醚、苯乙烯基苯酚聚氧乙烯醚、蓖麻油聚氧乙烯醚、山梨醇酐单硬脂酸酯、失水山梨醇单硬脂酸酯聚氧乙烯醚、脂肪酸聚氧乙烯醚磷酸酯等中的一种或多种；分散剂如聚羧酸盐、木质素磺酸盐、烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐(SOPA)、萘和烷基萘甲醛缩合物磺酸盐类、EO-PO嵌段聚醚类、烷基酚聚氧乙烯基醚磷酸酯、烷基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯、脂肪胺聚氧乙烯醚、甘油脂肪酸酯聚氧乙烯醚等中的一种或多种；润湿剂如十二烷基硫酸钠、十二烷基苯磺酸钠、拉开粉BX、湿润渗透剂F、萘磺酸盐甲醛缩合物等中的一种或多种；防冻剂如尿素、乙二醇、丙二醇、丙三醇等中的一种或多种；增稠剂如黄原胶、羧甲基纤维素、羧乙基纤维素、甲基纤维素、硅酸镁铝、聚乙烯醇等中的一种或多种；消泡剂如有机硅油、硅酮类化合物、C10-20饱和脂肪酸类化合物、C8-10脂肪醇、酯醚类等中的一种或多种。
上述助剂的可选择范围，本领域技术人员可参照工具书《固体制剂》、《液体制剂》和《农药助剂》等以及现有文献的记载，但具体的助剂选择种类需通过具体剂型加工试验来尝试，并非任选的助剂均能得到均一稳定的制剂。
本发明组分合理，在柑橘园和非耕地使用除草效果好，用药量少，用药成本低，且其活性和除草效果不是各组分活性的简单叠加，而是有显著的增效作用，对作物安全性好，符合农药制剂的安全性要求。
具体实施方式
下面通过联合作用测定来验证草铵膦、乙羧氟草醚和丙炔氟草胺三元复配对柑橘园和非耕地常见杂草防除效果。
室内毒力测定
试验方法参考《中华人民共和国农业行业标准NY/T1155.4—2006农药室内生物测定试验准则除草剂第4部分：活性测定试验茎叶喷雾法》和《中华人民共和国农业行业标准NY/T1155.7—2006农药室内生物测定试验准则除草剂第7部分：混配的联合作用测定》。试验对象为灰绿藜和马唐。
将原药配制成需要的试验药剂，首先将单剂及各复配药剂设置6个不同浓度梯度(在预备试验结果的基础上，根据药剂配比不同，浓度梯度设置亦有所不同，防除率在5％～90％的范围内按等比级数设定)。设清水对照，重复4次。杂草处于两叶或两叶一心期，从低剂量到高剂量分别进行喷雾处理。处理后置于温室内培养观察，以盆钵底部渗灌方式补水。
采用DPS数据处理软件对试验数据进行处理，根据普特喷雾塔的喷液量及转盘面积进行换算，获得各药剂针对不同靶标的ED50值(g/ha)。采用孙云沛共毒系数法评价混剂的联合作用，当CTC大于120，表明混剂具有协同效应，小于120为拮抗作用，介于二者之间为相加作用。
表1草铵膦、乙羧氟草醚和丙炔氟草胺组合灰绿藜的联合作用
表2草铵膦、乙羧氟草醚和丙炔氟草胺组合对马唐的联合作用
| 处理 | ED<sub>50</sub>值(g/ha) | 共毒系数 |
| 草铵膦(a) | 13.63 | |
| 乙羧氟草醚(b) | 14.77 | |
| 丙炔氟草胺(c) | 81.73 | |
| a:b:c＝1:1:1 | 15.33 | 122.99 |
| a:b:c＝1:3:5 | 21.68 | 120.86 |
| a:b:c＝1:5:3 | 15.72 | 125.99 |
| a:b:c＝1:3:1 | 13.26 | 128.03 |
| a:b:c＝5:1:1 | 11.63 | 126.50 |
| a:b:c＝5:1:10 | 22.58 | 120.93 |
| a:b:c＝1:5:10 | 23.46 | 126.29 |
| a:b:c＝1:10:1 | 12.26 | 127.37 |
| CK | - | - |
室内毒力测定结果表明：草铵膦、乙羧氟草醚和丙炔氟草胺按照(1-5)：(1-10)：(1-10)比例混用，对灰绿藜和马唐均有较高的活性，三者组合后可获得协同防效。
制剂实施例
为了更好地说明本发明，下面结合制剂实施例对本发明内容作进一步说明，配方中的百分比均为重量百分比。
实施例1
称取3％草铵膦、9％乙羧氟草醚、15％丙炔氟草胺、6％山梨醇酐单硬脂酸酯、5％肪酸聚氧乙烯酯、1％聚乙烯醇、0.5％乙二醇、2％渗透剂JFC、0.5％苯甲酸钠，去离子水补足余量。将丙炔氟草胺在环己酮中溶解，加入山梨醇酐单硬脂酸酯搅拌均匀成油相；将去离子水和其它助剂经高速剪切均质机混合均匀，再加入乙羧氟草醚原药，在砂磨机中进行砂磨，使悬浮剂粒径D90在5μm以下。将油相、草铵膦原药晶体加入砂磨好的悬浮剂中，在高速剪切下，使药液粒径D90在5μm以下，即可制成27％草铵膦·乙羧氟草醚·丙炔氟草胺悬乳剂。
实施例2
称取10％草铵膦、30％乙羧氟草醚、10％丙炔氟草胺、11％山梨醇酐单硬脂酸酯、5％聚羧酸钠、1.3％硅酸镁铝、0.4％山梨酸钾，大豆油补足余量。将大豆油和其它助剂经高速剪切均质机混合均匀，再加入有效成分，在砂磨机中进行砂磨，使悬浮剂粒径D90在5μm以下，即可制成50％草铵膦·乙羧氟草醚·丙炔氟草胺可分散油悬浮剂。
实施例3
称取3％草铵膦、30％乙羧氟草醚、3％丙炔氟草胺、5％烷基酚聚氧乙烯基醚磷酸酯、6％十二烷基硫酸钠、3％硫酸铵、4％羧甲基纤维素钠，白炭黑补足余量。按上述原料混合均匀，用超微气流粉碎机粉碎并混合均匀，再加水捏合造粒，在沸腾干燥机中干燥、筛分，经检测分析，即可制成36％草铵膦·乙羧氟草醚·丙炔氟草胺水分散粒剂。
田间药效试验
进行制剂实施例防治杂草的田间药效试验，验证该药剂对杂草的防治效果及对作物的安全性。试验药剂及用量如下表。共6个处理，另设空白对照，每处理4次重复，每小区约30㎡，小区随机区组排列，采用扇形喷头进行喷雾，主要避免药剂接触作物。药后30d调查杂草存活情况，并计算株防效和鲜重防效。
试验防治对象为：马唐和灰绿藜。
表3草铵膦、乙羧氟草醚和丙炔氟草胺组合不同制剂及单剂的田间药效试验结果
田间试验结果表明，以上制剂实施例对禾本科杂草和阔叶杂草防治效果好，持效期长，在有效成分用药量比单剂用量少的条件下，对杂草药后30天的平均株防效和鲜重防效均优于对照药剂。
整个生育期内，丙炔氟草胺单剂和本发明的混配制剂对作物安全，未表现出药害现象，说明药剂对作物安全。
综上所述，本发明的组合物是采用三种活性成分复配方案，其活性和除草效果不是各组分活性的简单叠加，与现有的单一制剂或二元复配制剂相比，具有显著的除草效果，增效作用显著，可以延缓抗性，制剂残留量少，对作物无污染，安全性好，符合农药制剂的安全性要求。
Claims (6)
1.一种防除柑橘园及非耕地禾本科和阔叶杂草的方法，其特征在于所述方法包括采用至少包含草铵膦、乙羧氟草醚和丙炔氟草胺的复配除草组合物处理柑橘园及非耕地，目标杂草处于3-4叶期，所述除草组合物中草铵膦、乙羧氟草醚和丙炔氟草胺的质量比为(1-50)：(1-50)：(1-50)。
2.权利要求1所述的方法，其特征在于所述除草组合物中活性成分的重量比优选(1-10)：(1-10)：(1-10)。
3.权利要求1或2所述方法，其特征在于所述除草组合物可以配制的制剂剂型包括水剂、悬浮剂、悬乳剂、可分散油悬浮剂、可湿性粉剂、水分散粒剂、颗粒剂和微囊悬浮-悬浮剂。
4.权利要求1或2所述方法，其特征在于所述除草组合物中活性成分在制剂中的重量百分含量为1％-80％，优选为5％～75％。
5.一种复配除草组合物在防除柑橘园及非耕地禾本科和阔叶杂草的用途，其特征在于所述除草组合物中草铵膦、乙羧氟草醚和丙炔氟草胺的质量比为(1-10)：(1-10)：(1-10)。
6.权利要求1-5任一项所述的除草组合物。
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