WO2015196951A1 - 具有增效作用的杀虫杀螨剂组合物 - Google Patents
具有增效作用的杀虫杀螨剂组合物 Download PDFInfo
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- WO2015196951A1 WO2015196951A1 PCT/CN2015/081921 CN2015081921W WO2015196951A1 WO 2015196951 A1 WO2015196951 A1 WO 2015196951A1 CN 2015081921 W CN2015081921 W CN 2015081921W WO 2015196951 A1 WO2015196951 A1 WO 2015196951A1
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- Prior art keywords
- composition
- avermectin
- composition according
- flumethrin
- acid
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- 150000001555 benzenes Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 231100000517 death Toxicity 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 230000007830 nerve conduction Effects 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- AXKBOWBNOCUNJL-UHFFFAOYSA-M sodium;2-nitrophenolate Chemical compound [Na+].[O-]C1=CC=CC=C1[N+]([O-])=O AXKBOWBNOCUNJL-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
Definitions
- the present invention relates to an insecticidal and acaricidal composition having improved properties, and more particularly to an insecticidal and acaricidal composition comprising flumethrin and avermectin, and belongs to the field of pesticide preparations.
- Acerithrin is a high-efficiency, low-toxic, broad-spectrum, novel pyrethroid-killing insecticide and insecticide. It has good activity against a variety of food-borne pests, and also has good activity against pests and lepidopteran pests such as hibiscus, leaf miner, thrips and aphids. Used in crops such as cotton, fruit trees, soybeans, corn, vegetables, tea, grapes, citrus, and tobacco.
- Abamectin is a class of 16-membered macrolide compounds with insecticidal, acaricidal and nematicidal activity produced by fermentation of Streptomyces avermitilis in Streptomyces.
- Abamectin has stomach poisoning and contact killing on mites and insects and cannot kill eggs.
- the mechanism of action differs from that of general insecticides in that it interferes with neurophysiological activities and stimulates the release of gamma-aminobutyric acid, which inhibits the nerve conduction of arthropods.
- Adult mites, nymphs and insect larvae are paralyzed after contact with avermectin, inactive, not feeding, and die after 2 to 4 days. The avermectin lethal effect is slower because it does not cause rapid dehydration of insects.
- the purpose of the invention is to screen the two insecticidal and acaricidal agents with different action principles for the resistance problem of the insecticide and acaricide in the practical application, so as to improve the effect of prevention and treatment, reduce the application amount and expand the use. range.
- the present invention provides a group of insecticidal and acaricidal compositions comprising two active ingredients A and B, active ingredient A being flumethrin and active ingredient B being avermectin.
- the inventors found through experiments that the above-mentioned insecticidal composition has obvious synergistic effect, and the application amount is reduced, which can reduce the use cost.
- the compounds containing component A and component B have different structural types and different mechanisms of action. The combination of the two can broaden the spectrum of action and can delay the generation of insect resistance to a certain extent, and there is no cross-resistance between component A and component B.
- compositions comprising two active ingredients A and B and their use in controlling agricultural pests in the agricultural sector.
- the composition of the present invention comprises two active components A and B, and the weight ratio between the two components is from 1:50 to 50:1, preferably from 1:30 to 30:1, more preferably from 1:20 to 20. :1, still more preferably 10:1 to 1:1 or 1:10 to 1:1.
- the two active components A and B can be selected from 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1 : 1, 1, 2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 and other more specific ratios.
- the composition may be prepared by using the active component together with the pesticide-acceptable adjuvant to prepare any dosage form suitable for agricultural use. Specifically, it may be supplemented with the active ingredient and the auxiliary agent, solvent, commonly used in the pesticide preparation.
- the carrier auxiliary component is formulated into various dosage forms suitable for use in agriculture.
- the mass content of the active ingredient is from 1 to 99%, preferably from 1 to 90%, further preferably from 5 to 85%, most preferably from 10 to 55%.
- composition of the present invention can be prepared into various dosage forms by known methods, and the active ingredient and auxiliary agents such as a solvent, a solid carrier, and, if necessary, a surfactant or other components (e.g., solvent, carrier, etc.) can be used.
- the active ingredient and auxiliary agents such as a solvent, a solid carrier, and, if necessary, a surfactant or other components (e.g., solvent, carrier, etc.) can be used.
- the mixture is uniformly mixed and ground to prepare a desired dosage form.
- auxiliaries may be solid or liquid, they are usually materials commonly used in the processing of dosage forms, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, adhesives, surfaces.
- the active agent or fertilizer may be selected one or more.
- the above solvent may be selected from aromatic hydrocarbons, preferably containing from 8 to 12 carbon atoms, such as a mixture of xylenes or substituted benzenes, phthalates such as dibutyl phthalate or dicaprylic acid, aliphatic hydrocarbons such as rings.
- aromatic hydrocarbons preferably containing from 8 to 12 carbon atoms, such as a mixture of xylenes or substituted benzenes, phthalates such as dibutyl phthalate or dicaprylic acid, aliphatic hydrocarbons such as rings.
- Alkenes or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl
- ketones such as cyclohexanone
- highly polar solvents such as N-methyl-2 Pyrrolidone, dimethyl sulfoxide or dimethylformamide
- vegetable or vegetable oils such as soybean oil.
- the abovementioned carriers are typically natural mineral fillers such as talc, kaolin, montmorillonite or activated clay.
- a highly dispersible silicic acid or a highly dispersible adsorbent polymer carrier such as a particulate adsorbent carrier or a non-adsorbing carrier, and a suitable particulate adsorbent carrier is porous, such as pumice, bentonite or Bentonite; a suitable non-adsorbing carrier such as calcite or sand.
- a large amount of pre-granulated materials of inorganic or organic nature can be used as a carrier, in particular dolomite.
- Suitable surfactants are lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, alkaline earth metal or amine salts, alkylarylsulfonates, alkyl groups Sulfates, alkyl sulfonates, fatty alcohol sulphates, fatty acids and sulfated fatty alcohol glycol ethers, as well as condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, naphthalene or naphthalene sulfonic acid with phenol and formaldehyde Shrink Compound, polyoxyethylene octyl phenyl ether, ethoxylated isooctyl phenol, octyl phenol, nonyl phenol, alkyl aryl polyglycol ether, tributyl benzene poly
- the method of application of the compositions of the present invention comprises the use of the compositions of the present invention in aerial parts of plants, including leaves or foliage.
- the plant's growth site such as wheat
- the plant's growth site such as wheat
- the composition may be applied to the soil in solid form, such as in the form of granules (soil application), the composition may be passed from the soil to the plant through the roots of the plant.
- In vivo systemic action
- compositions may be applied only by the active ingredient or may be used in combination with the additives, and thus the compositions of the present invention may be prepared in various dosage forms such as wettable powders, water-dispersible granules, aqueous emulsions, microemulsions.
- the compositions may be applied by spraying, misting, dusting, spreading or pouring, and the like.
- the two active ingredients in the compositions of the present invention exhibit synergistic effects and are more pronounced than the individual activities of the individual compounds.
- the synergistic effect is manifested by allowing for a reduced application rate, a broader insecticidal spectrum, a quicker effect, a more durable control effect, better control of the pest by only one or a few applications, and a widening of the possible application intervals. These characteristics are very important to solve the ubiquitous resistance problem of a single pesticide.
- the insecticidal composition of the invention can be applied to the control of crop pests in the agricultural field, in particular to various plant diseases in various crops such as wheat, cotton, corn, soybean, tea, vegetables, fruit trees (especially citrus, etc.). It has good activity and also has good activity against sucker mouthworms and lepidopteran pests such as hibiscus, leaf miner, thrips, aphids, etc., especially for crops caused by red spiders or small green leafhoppers. Pest has excellent performance.
- the other characteristics of this product are mainly as follows: 1. It can be applied to various possible application methods such as spraying, seed dressing and mixed soil spreading; 2. The chemical composition of the two single agents of the composition is very different. The mechanism is completely different, there is no cross-resistance, and the resistance problem caused by the separate use of the two single agents can be delayed; 3. The compounding of the composition of the invention has obvious synergistic effect, and the crop is safe and effective. It has been proved by experiments that the composition of the invention has stable chemical properties, remarkable synergistic effect, and exhibits obvious synergistic effect and complementary effect on the control object.
- the active ingredients of flumethrin and avermectin are mixed with the dispersing agent, stabilizer, antifoaming agent and solvent in the proportion of the formula, ground in a sanding kettle, and then sent to a homomixer. Mix well to get the finished product.
- Example 1 31% flumethrin avermectin suspension
- Example 2 31% flumethrin avermectin suspension
- Example 3 11% flumethrin avermectin microemulsion
- Example 4 11% flumethrin avermectin microemulsion
- Example 5 10% flumethrin avermectin microemulsion
- the active ingredient flumethrin and avermectin are mixed with the solvent and the auxiliary agent under mechanical agitation, then the emulsifier and the stabilizer are added to be evenly stirred, and finally water is added at 100-12000 rpm. Stir at a speed of 10-30 minutes to make it a homogeneous milky product.
- Example 6 21% flumethrin avermectin water emulsion
- Example 7 21% flumethrin avermectin water emulsion
- Example 1 Determination of virulence test of citrus red spider with flumethrin and avermectin
- the leaves without application of insecticide were cut into 5cm in diameter, and the test agents were sprayed evenly on the positive and negative sides of the leaves with a sprayer. After drying, they were transferred to the culture dish and connected to the 2nd instar larvae. Each treatment was 50 times and repeated 4 times. And with water control.
- the rice was reared at room temperature, 75%-85% relative humidity at 25 °C, and the new rice leaves treated with the drug were replaced every 12 hours. The number of deaths was checked after 48 hours, the mortality was calculated, and the mortality was corrected. Lethal concentration.
- Percentage of flumethrin according to the active ingredient avermectin ratio: 50:1, 30:1, 20:1, 10:1, 1:1, 1:10, 1:20, 1:30, 1 : 50 test, according to Sun Yunpei method to calculate the virulence index of the drug (CTC).
- Measured virulence index (ATI) (standard drug LC50 / test drug LC50) * 100
- Theoretical virulence index (TTI) A virulence index * Percentage of A in the mixture + B virulence index * Percentage of B in the mixture
- CTC Co-toxicity coefficient [mixture measured virulence index (ATI) / mixed theory virulence index (TTI)] * 100
- CTC ⁇ 80 the composition showed antagonism, 80 ⁇ CTC ⁇ 120, the composition showed an additive effect, CTC ⁇ 120, and the composition showed synergistic effect.
- the field efficacy test was repeated 4 times for each treatment, and the whole plant was evenly sprayed at the peak of the occurrence of the damage.
- Each treatment plot immediately took 5 points, and 10 plants were calibrated at each point.
- the number of insect populations was investigated before application, and the number of live insects was recorded 5 days after application, and the rate of reduction of insects was calculated. The effect of treatment.
- the test crops were investigated for signs of phytotoxicity. Determine the safety of the agent.
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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
本发明提供了一种杀虫杀螨剂组合物,该组合物包含两种有效成分A和B,其中活性组分A为氟丙菊酯,活性组分B为选自阿维菌素,两组分之间的重量比为1:50~50:1,本发明还提供了该组合物的制备方法及用途。试验结果表明,本发明提供的上述杀虫组合物增效明显,且能减少使用量,降低防治成本。该杀虫杀螨组合物能有效防治果树、蔬菜及经济作物上的多种害虫。通过将不同作用机制和作用方式的杀虫剂进行复配,有效降低各单剂的施用量,对于扩大杀虫谱和延缓害虫抗药性以及提高防治效果等方面具有很好的作用。
Description
本发明涉及一种具有改进性能的杀虫杀螨组合物,具体地说是涉及一种包含氟丙菊酯和阿维菌素的杀虫杀螨组合物,属于农药制剂领域。
氟丙菊酯(acrinathrin)属于高效、低毒、广谱、新型的拟除虫菊酯类杀螨、杀虫剂。对多种食植性害螨肯具有良好的活性,并对刺吸口器害虫和鳞翅目害虫,如木虱、潜叶蛾、蓟马、蚜虫等也具有良好的活性。用于棉花、果树、大豆、玉米、蔬菜、茶叶、葡萄、柑橘、烟草等作物。
阿维菌素(Abamectin)是一类具有杀虫、杀螨、杀线虫活性的十六元大环内酯化合物,由链霉菌中灰色链霉菌Streptomyces avermitilis发酵产生。阿维菌素对螨类和昆虫具有胃毒和触杀作用,不能杀卵。作用机制与一般杀虫剂不同的是干扰神经生理活动,刺激释放γ-氨基丁酸,而氨基丁酸对节肢动物的神经传导有抑制作用。螨类成虫、若虫和昆虫幼虫与阿维菌素接触后即出现麻痹症状,不活动、不取食,2~4天后死亡。因不引起昆虫迅速脱水,所以阿维菌素致死作用较缓慢。
现已有研究表明,长期重复且专一施用一种活性化合物来防治害虫在很多情况下将导致害虫的抗药性增强,为降低害虫抗药性,目前通常使用不同活性化合物的混合物来防治害虫。通过将具有不同作用机理的活性化合物进行组合,可延缓抗性产生,降低施用量,提高防治效果,并减少防治成本。
发明内容
本发明的目的是:针对杀虫杀螨剂在实际应用中抗性问题,筛选出两种不同作用原理的杀虫杀螨剂进行复配,以提高作用防治效果,降低施药量,扩大使用范围。
为实现上述目的,本发明提供了一组杀虫杀螨组合物,该组合物包含两种有效成分A和B,活性组分A为氟丙菊酯,活性组分B为阿维菌素。发明人通过试验发现,上述杀虫组合物增效明显,施用量减少,可降低使用成本。含有组分A与组分B的化合物结构类型不同,作用机制各异,
两者复配能够扩大作用谱,并且可以在一定程度上延缓昆虫抗性的产生,且组分A与组分B之间无交互抗性。
本发明提供包含两种有效成分A和B的组合物以及其在农业领域防治农作物虫害的应用。
本发明的组合物包含A和B两种活性组分,两组分之间的重量比为1:50~50:1,优选重量比1:30~30:1,进一步优选1:20~20:1,更进一步优选10:1~1:1或者1:10~1:1。在一些具体实施方式中,两种活性组分A和B可选用9:1、8:1、7:1、6:1、5:1、4:1、3:1、2:1、1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9等更具体的配比。
该组合物可以以活性组分辅以农药上可接受的辅料制成适合农业使用的任意一种剂型,具体的,它可以以活性组分并辅以农药制剂中通常使用的助剂、溶剂、载体辅助成分以做成各种适合在农业中使用的剂型。
当本组合物制成某一具体剂型时,其中活性成分的的质量含量为1~99%,优选1~90%,进一步优选5~85%,最优选10~55%。
可用已知的方法可以将本发明的组合物制备成各种剂型,可以将有效成分与助剂,如溶剂、固体载体,需要时可以与表面活性剂或其他组分(如溶剂、载体等)一起均匀混合、研磨,制备成所需要的剂型。
合适的助剂可以是固体或液体,它们通常是剂型加工过程中常用的物质,例如天然的或再生的矿物质,溶剂、分散剂、润湿剂、胶粘剂、增稠剂、粘合剂、表面活性剂或肥料,可择一种选用,也可择多种选用。
上述的溶剂可选自芳香烃,优选含8-12个碳原子,如二甲苯混合物或取代的苯,酞酸酯类,如酞酸二丁酯或酞酸二辛酸,脂肪烃类,如环已烷或石蜡,醇和乙二醇和它们的醚和酯,如乙醇,乙二醇,乙二醇单甲基;酮类,如环已酮,强极性的溶剂,如N-甲基-2-吡咯烷酮,二甲基亚砜或二甲基甲酰胺,和植物油或植物油,如大豆油。
上述的载体(特别是固体载体),如用于粉剂和可分散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。为了管理组合物的物理性能,也可以加入高分散性硅酸或高分散性吸附聚合物载体,例如粒状吸附载体或非吸附载体,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作为载体,特别是白云石。
根据本发明的组合物中的有效成分的化学性质,合适的表面活性剂为木质素磺酸、萘磺酸、苯酚磺酸、碱土金属盐或胺盐,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。
本发明组合物的施用方法包括将本发明的组合物用于植物生长的地上部分,包括叶部或叶面。可以将植物的生长场所,如小麦,用组合物的液体制剂浸湿,或者将组合物以固体形式施用于土壤中,如以颗粒形式(土壤施用),组合物可以由土壤经植物根部进入植物体内(内吸作用)。
这些组合物可以仅仅包含活性成分进行施用,也可以与添加剂一起混合使用,因此本发明的组合物可以制备成各种剂型,例如可湿性粉剂、水分散粒剂、水乳剂、微乳剂。根据这些组合物的性质以及施用组合物所要达到的目的和环境情况,可以选择将组合物以喷雾、弥雾、喷粉、撒播或泼浇等之类的方法施用。
本发明的组合物中两种有效成分表现为增效效果,比单个化合物的单独活性更为显著。增效效果表现为允许施用量减少、更宽的杀虫谱、见效快、更持久的防治效果、通过仅仅一次或少数几次施用更好的控制害虫、以及加宽了可能的施用间隔时间。这些特性对解决杀虫剂单剂普遍存在的抗性问题是非常重要的。
本发明的杀虫组合物可应用于农业领域防治农作物虫害,特别是应用在小麦、棉花、玉米、大豆、茶、蔬菜、果树(特别是柑橘等)等各种农作物上多种食植性害螨肯具有良好的活性,并对刺吸口器害虫和鳞翅目害虫,如木虱、潜叶蛾、蓟马、蚜虫等也具有良好的活性,尤其是对红蜘蛛或小绿叶蝉引起的农作物虫害具有优异的性能。
本品表现出的其它特点主要表现为:1、可应用于喷雾、拌种、混土撒播等各种可能的施药方式;2、本组合物的两个单剂化学结构差异很大,作用机理完全不同,不存在交互抗性,可延缓两单剂单独使用所产生的抗性问题;3、本发明的组合物混配具有明显的增效作用,对作物安全、防效好。经试验证明,本发明组合物化学性质稳定,增效显著,对防治对象表现出明显的增效以及互补作用。
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明,凡在本发明的构思前提下对本发明制备方法的简单改进都属于本发明的保护范围之内。
以下实施例所有配方中百分比均为重量百分比。本发明组合物各种制剂的加工工艺均为现有技术,根据不同情况可以有所变化。
一、剂型制备实施例
(一)悬浮剂的加工及实施例
将活性成分氟丙菊酯和阿维菌素与分散剂、稳定剂、消泡剂和溶剂等各组分按配方的比例混合,放入砂磨釜内研磨后,送入均质混合器内混匀即得成品。
实施例1:31%氟丙菊酯·阿维菌素悬浮剂
氟丙菊酯30%,阿维菌素1%,木质素磺酸钠8%,膨润土4%,黄原胶1%,有机硅消泡剂2%,大豆油补足至100%。
实施例2:31%氟丙菊酯·阿维菌素悬浮剂
氟丙菊酯1%,阿维菌素30%,萘磺酸甲醛缩合物8%,硅藻土5%,硅酸镁铝2%,二氯乙烷补足至100%。
(二)微乳剂的加工及实施例
将活性成分氟丙菊酯与阿维菌素在溶剂中完全溶解后,进行搅拌,同时加入乳化剂、增效助剂和抗冻剂,待上述体系混匀后,再将水慢慢加入上述混合液中,充分搅拌后即可配成不同含量的微乳剂。
实施例3:11%氟丙菊酯·阿维菌素微乳剂
氟丙菊酯10%,阿维菌素1%,丙酮15%,复硝酚钠0.5%,烷基聚氧乙烯醚和壬基酚聚氧乙烯醚5%,丙二醇1%,尿素2%,水补足至100%。
实施例4:11%氟丙菊酯·阿维菌素微乳剂
氟丙菊酯1%,阿维菌素10%,脂肪酸聚氧乙烯酯和苯乙基酚聚氧乙烯醚4%,丙三醇2%,甲醇11%,氮酮1%,水补足至100%。
实施例5:10%氟丙菊酯·阿维菌素微乳剂
氟丙菊酯5%,阿维菌素5%,丙二醇1%,烷基苯磺酸盐和烷基萘磺酸盐13%,噻酮1%,乙酸乙酯11%,水补足至100%。
(三)水乳剂的加工及实施例
在乳化釜中,将活性成分氟丙菊酯和阿维菌素与溶剂、助剂在机械搅拌下混合均匀,然后投入乳化剂和稳定剂搅拌均匀,最后加入水,在100-12000转/分钟的转速下搅拌10-30分钟,使之成为均匀乳状的产品。
实施例6:21%氟丙菊酯·阿维菌素水乳剂
氟丙菊酯20%,阿维菌素1%,N-邻苯二甲酸二甲酯4%,壬基酚苯氧乙烯醚3%,2,6-二叔丁基-4-甲基苯酚2%,乙二醇3%,聚乙烯醇1%,苯甲酸钠1%,有机硅消泡剂0.8%,水补足至100%。
实施例7:21%氟丙菊酯·阿维菌素水乳剂
氟丙菊酯1%,阿维菌素20%,丁基羟基茴香醚4%,聚异丁二酸酐-聚乙二醇共聚物3%,丙二醇2%,黄原胶3%,聚乙烯醇1%,有机硅消泡剂1.2%,水补足至100%。
实施例8 50%氟丙菊酯·阿维菌素水乳剂
氟丙菊酯49%,阿维菌素1%,聚氧乙烯嵌段共聚物3%,丙二醇1%,黄原胶2%,聚异丁二酸酐-聚乙二醇共聚物3%,有机硅消泡剂1.2%,水补足至100%。
实施例9 50%氟丙菊酯·阿维菌素水乳剂
氟丙菊酯1%,阿维菌素49%,N-十二烷基吡咯烷酮2%,蓖麻油聚氧乙烯醚1%,丙三醇3%,聚乙烯醇1.2%,苯甲酸钠1%,异辛醇2%,水补足至100%。-
二、药效验证试验
(一)室内毒力活性测定
实施例1 氟丙菊酯与阿维菌素复配对柑橘红蜘蛛毒力测定试验
1.1供试药剂
氟丙菊酯原药、阿维菌素原药
1.2供试虫源
柑橘红蜘蛛
1.3测定方法
无施用过杀虫剂的叶片剪成直径5cm,供试药剂分别用喷雾器均匀喷在菜叶正、反面,晾干后移入培养皿,接入2龄幼虫,每处理50头,重复4次,并以清水对照。于25℃室温、75%-85%相对湿度下饲养,每隔12h更换药剂处理过的新水稻叶片,48h后检查死亡数,计算死亡率,并以对照的死亡率进行校正,以此求得致死中浓度。
1.4数据分析
按有效成分百分比氟丙菊酯:阿维菌素配比为:50:1、30:1、20:1、10:1、1:1、1:10、1:20、1:30、1:50进行试验,依孙云沛法计算药剂的毒力指数级共毒系数(CTC)。
实测毒力指数(ATI)=(标准药剂LC50/供试药剂LC50)*100
理论毒力指数(TTI)=A药剂毒力指数*混剂中A的百分含量+B药剂毒力指数*混剂中B的百分含量
共毒系数(CTC)=[混剂实测毒力指数(ATI)/混剂理论毒力指数(TTI)]*100
CTC≤80,组合物表现为拮抗作用,80<CTC<120,组合物表现为相加作用,CTC≥120,组合物表现为增效作用。
表1 氟丙菊酯、阿维菌素及其不同配比复配对柑橘红蜘蛛毒力测定结果分析
结果(表1)表明,氟丙菊酯与阿维菌素复配对柑橘红蜘蛛的防治效果显著提高,说明二者复配对柑橘红蜘蛛有显著的防治作用。尤其是氟丙菊酯与阿维菌素配比在1:20~20:1之间,氟丙菊酯与阿维菌素的共毒系数均在160以上,增效作用明显。
实施例2 氟丙菊酯与阿维菌素复配对茶小绿叶蝉毒力测定试验
表2 氟丙菊酯与阿维菌素复配对茶小绿叶蝉毒力测定
结果(表2)表明,氟丙菊酯与阿维菌素复配对茶小绿叶蝉的防治效果显著提高,说明二者复配对茶小绿叶蝉具有显著的防治作用,尤其是氟丙菊酯与阿维菌素配比在1:20~20:1之间,氟丙菊酯与阿维菌素的共毒系数均在140以上,增效作用明显。
(二)田间药效验证试验
田间药效试验每个处理重复4次,于螨害发生高峰期全株均匀喷雾。每处理小区随即取5点,每点标定10棵植株,施药前调查虫口基数,施药后5天记载残留活虫数,计算虫口减退率,即防
治效果。同时调查供试作物有无药害症状。确定药剂的安全性。
预期防效(%)=X+Y-XY/100(其中,X,Y为单剂防效)
表3.氟丙菊酯与阿维菌素复配对柑橘红蜘蛛的田间防效试验结果
测定结果(表3)表明,氟丙菊酯与阿维菌素复配对防治柑橘红蜘蛛的防效明显提高,说明二者复配对柑橘红蜘蛛有显著的协同增效作用。 在整个试验过程中,在本发明组合物制剂的用量范围内,未发现对柑橘生长的药害现象,说明本发明的组合物对柑橘生长是安全的。
Claims (10)
- 具有增效作用的杀虫杀螨剂组合物,其特征在于该组合物包含A和B两种活性组分,其中活性组分A为氟丙菊酯,活性组分B为阿维菌素,两组分之间的重量比为1:50~50:1。
- 根据权利要求1所述组合物,其特征在于活性组分A氟丙菊酯与活性组分B阿维菌素的重量比为1:30~30:1。
- 根据权利要求1或2所述组合物,其特征在于活性组分A氟丙菊酯与活性组分B阿维菌素的重量比为1:20~20:1。
- 根据权利要求1、2或3所述的组合物,其特征在于该组合物以活性组分辅以农药上可接受的辅料制成适合农业使用的任意一种剂型。
- 根据权利要求4所述的组合物,其特征在于该组合物的剂型中活性组分的质量含量为5~85%。
- 根据权利要求4所述的组合物,其特征在于所述农药上可接受的辅料包括助剂、溶剂或载体辅助成分;其中所述助剂选自矿物质、溶剂、分散剂、润湿剂、胶粘剂、增稠剂、粘合剂、表面活性剂或肥料中的一种或几种。
- 根据权利要求4或5所述的组合物,其特征在于所述溶剂选自二甲苯、酞酸二丁酯、酞酸二辛酸、环已烷、石蜡、乙醇,乙二醇、乙二醇单甲基、环已酮、N-甲基-2-吡咯烷酮、二甲基亚砜、二甲基甲酰胺或大豆油;所述载体选自滑石、高岭土、蒙脱石、活性白土、浮石、皂土、膨润土、方解石、砂或白云石;所述表面活性剂为木质素磺酸、萘磺酸、苯酚磺酸、碱土金属盐、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、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或甲基纤维素。
- 根据权利要求4或5所述的组合物,其特征在于所述剂型为可湿性粉剂、水分散粒剂、水乳剂、微乳剂或悬浮剂。
- 权利要求1至5任一项所述的组合物在农业领域防治农作物虫害的应用。
- 根据权利要求9所述的应用,其特征在于所述农作物虫害为木虱、潜叶蛾、蓟马、蚜虫、红蜘蛛或小绿叶蝉引起的农作物虫害。
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CN114568440A (zh) * | 2022-04-07 | 2022-06-03 | 山东亿嘉农化有限公司 | 一种包含氟吡菌酰胺和咯菌腈的杀菌组合物及其应用 |
CN115281187A (zh) * | 2022-08-11 | 2022-11-04 | 北京广源益农化学有限责任公司 | 一种稳定的农药增效剂及其制备方法 |
CN116250540A (zh) * | 2023-02-07 | 2023-06-13 | 广西壮族自治区亚热带作物研究所(广西亚热带农产品加工研究所) | 一种防治澳洲坚果蓟马的生物农药 |
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CN106035365A (zh) * | 2016-05-31 | 2016-10-26 | 刘慎权 | 一种防治棉象鼻虫的组合物及其制备方法 |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000002453A1 (en) * | 1998-07-07 | 2000-01-20 | Novartis Ag | Pesticidal composition comprising emamectin |
CN101185440A (zh) * | 2007-12-18 | 2008-05-28 | 张少武 | 一种含有阿维菌素的复配杀虫剂 |
CN104082335A (zh) * | 2014-06-22 | 2014-10-08 | 江苏辉丰农化股份有限公司 | 具有增效作用的杀虫杀螨剂组合物 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1287783A (zh) * | 1999-09-14 | 2001-03-21 | 浙江威尔达化工有限公司 | 含阿维菌素和菊酯类复合杀虫微乳剂 |
CN1226928C (zh) * | 2002-10-11 | 2005-11-16 | 华中农业大学 | 阿菊水分散粒剂及其生产方法 |
JP2006131515A (ja) * | 2004-11-04 | 2006-05-25 | Nippon Nohyaku Co Ltd | 農園芸有害生物防除剤組成物及びその使用方法 |
CN101790990B (zh) * | 2010-03-30 | 2012-11-28 | 中国石油大学(华东) | 一种高效浓缩型阿维菌素-高效氯氰菊酯水乳剂及其制备方法 |
-
2014
- 2014-06-22 CN CN201410281327.0A patent/CN104082335B/zh active Active
-
2015
- 2015-06-19 WO PCT/CN2015/081921 patent/WO2015196951A1/zh active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000002453A1 (en) * | 1998-07-07 | 2000-01-20 | Novartis Ag | Pesticidal composition comprising emamectin |
CN101185440A (zh) * | 2007-12-18 | 2008-05-28 | 张少武 | 一种含有阿维菌素的复配杀虫剂 |
CN104082335A (zh) * | 2014-06-22 | 2014-10-08 | 江苏辉丰农化股份有限公司 | 具有增效作用的杀虫杀螨剂组合物 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114568440A (zh) * | 2022-04-07 | 2022-06-03 | 山东亿嘉农化有限公司 | 一种包含氟吡菌酰胺和咯菌腈的杀菌组合物及其应用 |
CN114568440B (zh) * | 2022-04-07 | 2023-08-25 | 山东亿嘉农化有限公司 | 一种包含氟吡菌酰胺和咯菌腈的杀菌组合物及其应用 |
CN115281187A (zh) * | 2022-08-11 | 2022-11-04 | 北京广源益农化学有限责任公司 | 一种稳定的农药增效剂及其制备方法 |
CN115281187B (zh) * | 2022-08-11 | 2023-11-24 | 北京广源益农化学有限责任公司 | 一种稳定的农药增效剂及其制备方法 |
CN116250540A (zh) * | 2023-02-07 | 2023-06-13 | 广西壮族自治区亚热带作物研究所(广西亚热带农产品加工研究所) | 一种防治澳洲坚果蓟马的生物农药 |
CN116250540B (zh) * | 2023-02-07 | 2025-02-07 | 广西壮族自治区亚热带作物研究所(广西亚热带农产品加工研究所) | 一种防治澳洲坚果蓟马的生物农药 |
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CN104082335B (zh) | 2016-06-01 |
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