CN102228056A - Pesticide composition containing sulfur-fluorine oxime ether and part of organophosphorus pesticides - Google Patents

Pesticide composition containing sulfur-fluorine oxime ether and part of organophosphorus pesticides Download PDF

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CN102228056A
CN102228056A CN2011101477885A CN201110147788A CN102228056A CN 102228056 A CN102228056 A CN 102228056A CN 2011101477885 A CN2011101477885 A CN 2011101477885A CN 201110147788 A CN201110147788 A CN 201110147788A CN 102228056 A CN102228056 A CN 102228056A
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pesticidal combination
sufluoxime
pesticide composition
pesticide
profenofos
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CN102228056B (en
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杜秀斌
葛尧伦
韩先正
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Hailir Pesticides and Chemicals Group Co Ltd
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Hailir Pesticides and Chemicals Group Co Ltd
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Abstract

The invention relates to a pesticide composition in the field of pesticide compounding. The pesticide composition is characterized in that the pesticide composition comprises the active ingredients such as sulfur-fluorine oxime ether and an organophosphorus pesticide; the weight ratio of the two active ingredients is (0.1-50): (1-80), preferably (0.1-35): (5-50); the total mass percentage of the active ingredients in the pesticide composition is 1-90%, preferably 7-60%; the pesticide composition also comprises auxiliary ingredients which are allowed to be used in the pesticide and can be accepted; and the pesticide composition can be prepared into emulsifiable concentrates, emulsion in water, microemulsion, water dispersible granules, wettable powder and suspending agents by the known method.

Description

A kind of Pesticidal combination that contains sufluoxime and part organophosphorus insecticide
Technical field
The present invention relates to the agriculture chemical compounding technical field, be specifically related to a kind of Pesticidal combination that contains sufluoxime and part organophosphorus insecticide.
Background technology
Sufluoxime is national southern agricultural chemicals initiative Hunan, center base Hunan Chemical Research Institute autonomous Design in 2002, the synthetic non-ester class pyrethroid novel pesticide of formulating out with independent intellectual property right, the research and development code name is a HNPC-sufluoxime 2005, chemical name: 1-(3-fluoro-4-chlorphenyl)-2-methylmercaptan ethyl ketoxime-O-(2-methyl biphenyl-3-methyl) ether, its structural formula is:
Figure BDA0000065877110000011
Sufluoxime can effectively be prevented and treated tea tree insect, tea caterpillar, tea lesser leafhopper, tea chi Qu, oranges and tangerines insect leaf miner and vegetable-crop pest-insect, cabbage caterpillar etc., and insecticidal spectrum is wide, and effect rapidly.Toxicity and residual result of the test show, sufluoxime belongs to low toxicity, low-residual, to the environmentally friendly compound of non-target organism safety.
Domestic patent about sufluoxime, ZL99115557.2, denomination of invention is " biocidal alkyl-replacement (mixing)-aryl-ketoxime-O-ether and intermediate ketone, oxime compound and preparation method thereof ", ZL200310110647.1, denomination of invention is " sulfur-bearing of desinsection, sterilization, an oxime-containing ether compound ".Mainly oximido ether compounds such as sufluoxime and intermediate and preparation method etc. are protected in these two patents; also has the protection of some single agent formulation aspects simultaneously; but not mentioned and other desinsections or bactericide compounded composition; ZL200810032165.1; mention the desinsection patent protection that sufluoxime and macrolides compound are composite in " Pesticidal combination of insecticide sufluoxime ", but the compound synergic effect of other classification compounds is not possessed some special knowledge or mention.
Described part organophosphorus insecticide is chlopyrifos, phoxim, Profenofos, Hostathion, diazinon, the high-efficiency low-toxicity organophosphorus insecticide, and tagging and stomach toxicity, most of no systemic action, insecticidal spectrum is wide, and the power of knocking down is strong, and is very effective to lepidopterous larvae.Make work in the field, because of to photo-labile, understand very fast decomposition failure, so the lasting period is very short, residual danger is minimum, the general longevity of residure 2-3 of foliar spray days; But this medicine applies in the soil, and its lasting period is very long, can reach 1-2 month.Be suitable for preventing and treating soil insect, the grub, the mole cricket that particularly prevent and treat peanut, soybean, wheat have good effect.Larva to the multiple lepidoptera pests of crops such as the peanut of causing harm, wheat, paddy rice, cotton, corn, fruit tree, vegetables, mulberry, tea also has the good action effect, and worm's ovum is also had certain lethal effect, also is suitable for preventing and treating warehouse and sanitary insect pest.
Single insecticide is used repeatedly, insect is easy to generate pesticide resistance, the insecticide consumption is increased, increase the desinsection cost, the natural enemy of a large amount of kill pests, cause high poison, consumption big, residual many, drug effect is poor, contaminated environment, especially organophosphorus insecticide, use in a large number for a long time, insect has produced pesticide resistance in various degree, the problems referred to above occur more so.And with both there not being cross resistance, the discrepant again agricultural chemicals of the mechanism of action rationally is mixed, be a kind of means effectively that overcome the above problems, and the R﹠D cycle is short, environmental sound, be more suitable for the more limited development resources of domestic agricultural chemicals company's utilization and do association area research, through the research staff of our company the research in composite field unexpected find with sufluoxime and part organophosphorus insecticides be active ingredient by a certain percentage two yuan be mixed, has the notable synergistic effect, can there be interior absorption or the not strong problem of interior absorption by fine solution organophosphorus insecticide, and dosage still less, lasting period is longer, residual quantity is lower, the more environmental protection of high preventive effect, and composite between these two kinds of agricultural chemicals do not see relevant report so far.
Summary of the invention
Based on above background of invention, through the long-term screening study of the research staff of our company in the agriculture chemical compounding field, be devoted to solve that the organophosphorus insecticide drug effect descends, drug cost increases, the problem that environmental pressure is big, a kind of agricultural insecticide composition of high-efficiency environment friendly has been proposed finally, this Pesticidal combination be with (A) sufluoxime and (B) the part organophosphorus insecticide be that two yuan of carrying out of active ingredient are mixed, wherein the part organophosphorus insecticide be in chlopyrifos, phoxim, Profenofos, Hostathion, the diazinon any one.
Above-mentioned with (A) sufluoxime and (B) one of any in part organophosphorus insecticide chlopyrifos, phoxim, Profenofos, Hostathion, the diazinon be that active ingredient is carried out two yuan of Pesticidal combinations that are mixed, wherein the percentage by weight of effective constituents A and B is 0.1~50: 1~80 in this Pesticidal combination.
Described with (A) sufluoxime and (B) one of any in part organophosphorus insecticide chlopyrifos, phoxim, Profenofos, Hostathion, the diazinon be that active ingredient is carried out two yuan of Pesticidal combinations that are mixed, infer that through the checking of determination experiments such as virulence and land for growing field crops wherein the percentage by weight of effective constituents A and B can be preferably 0.1~35: 5~50 in this Pesticidal combination.
The formulation that described Pesticidal combination of the present invention can be prepared according to the known method of those skilled in the art of the present technique is missible oil, aqueous emulsion, microemulsion, water-dispersible granules, wetting powder and suspending agent, sufluoxime and the part organophosphorus insecticide percentage that accounts for gross weight in preparation is 1%-90% in the described Pesticidal combination of the present invention, preferred 7%-60%.
Described Pesticidal combination of the present invention has obvious synergistic effect, can significantly reduce dosage, reduce drug cost, and well solve the resistance of organophosphorus insecticide and do not had interior suction or the weak problem of interior absorption, delay the generation of pest resistance to insecticide, and can be used for the improvement of resistant insect.Enlarged insecticidal spectrum, insect to multiple class all has good preventive effect, and residual quantity is low, the complementation that quick-acting and lasting effect are very high, this composition two specific characters are had concurrently, prolonged the life-span of organophosphorus insecticide on market, this has its own strategic significance in agricultural chemicals research and development field, alleviated external agricultural chemicals giant and constantly released the impact of new drug centering traditional Chinese medicines enterprises, for the fast development of domestic agricultural chemicals enterprise has been striven for the regular hour with the external agricultural chemicals giant that contends with.
Described Pesticidal combination of the present invention is caused harm in control aspect the multiple lepidoptera pests of crops such as peanut, wheat, paddy rice, cotton, corn, fruit tree, vegetables, mulberry, tea, and better effects is all arranged, especially in the larva control, and the effect excellence.In addition worm's ovum also there is certain lethal effect, also is suitable for preventing and treating the insect of warehouse and health class.
Embodiment:
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention describes with following specific embodiment, but the present invention is limited to these examples absolutely not.The following stated only is the present invention embodiment preferably, only is used to explain the present invention, can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that all any modifications of being made within the spirit and principles in the present invention, be equal to replacement and improvement etc., all should be included within protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with appended claims.
Simple formulation embodiment following (below be in the formulation embodiment solvent and formulation method):
Effective constituents A is selected from sufluoxime in the following embodiment, and active ingredient B is selected from chlopyrifos, phoxim, Profenofos, Hostathion, the diazinon one of any.
One of technical scheme of the present invention, described Pesticidal combination are aqueous emulsion, and the percentage by weight of component is:
Figure BDA0000065877110000031
The concrete production stage of this aqueous emulsion is: at first former medicine A is added with B, solvent and emulsifier, cosolvent and be in the same place, make and be dissolved into uniform oil phase; With part water, antifreeze, other insecticides adjuvant such as antimicrobial mixes into uniform water; When the reactor high speed stirs, oil phase is added water, slowly add water, open clipper and carry out high speed shear, and add remaining water, shear half an hour approximately, form the aqueous emulsion of oil-in-water type until reaching the phase inversion point.Promptly can be made into the aqueous emulsion of the present composition.
Two of technical scheme of the present invention, when described Pesticidal combination was microemulsion, the percentage by weight of component was:
Figure BDA0000065877110000032
Figure BDA0000065877110000041
The concrete production stage of this microemulsion is: former medicine A, B are dissolved fully with cosolvent, add other compositions such as emulsifier, antifreezing agent stabilizing agent again, evenly mix, add entry at last, can be made into microemulsion after fully stirring.
Three of technical scheme of the present invention, described Pesticidal combination are cream preparation, and the mass percent of component is:
Figure BDA0000065877110000042
The concrete production stage of this cream preparation adds emulsifier, the synergist back that stirs after the dissolving fully again and becomes the oily liquids of transparent and homogeneous for earlier effective constituents A, B being added in the solvent, and can promptly can be made into the cream preparation of the present composition.
Four of technical scheme of the present invention, described Pesticidal combination are suspending agent, and the percentage by weight of component is:
Figure BDA0000065877110000043
The concrete production stage of this suspending agent is earlier other auxiliary agents to be mixed, and mixes through high speed shear, adds effective constituents A, B, and abrading-ball is 2~3 hours in ball crusher, makes a diameter all below 5um, promptly can be made into the suspending agent preparation of the present composition.
Five of technical scheme of the present invention, described Pesticidal combination is a wetting powder, the percentage by weight of component is:
Figure BDA0000065877110000044
The concrete production stage of this wetting powder is: by above-mentioned prescription effective constituents A, B and dispersant, wetting agent and filler are mixed, in stirred tank, evenly stir, behind airslide disintegrating mill, mixing, promptly can be made into the wetting powder of the present composition.
Six of technical scheme of the present invention, described Pesticidal combination are water dispersible granules, and the percentage by weight of component is:
Figure BDA0000065877110000051
The concrete production stage of this water dispersible granules is: by above-mentioned prescription effective constituents A, B and dispersant, wetting agent, disintegrant and filler are mixed, pulverize with micro jet, through mediating, add then and carry out granulation, drying, screening in the fluidized bed prilling dryer after sample analysis, promptly can be made into the water dispersible granules of the present composition.
Emulsifier is alkylbenzene naphthalene sulfonate, alkylphenol polyoxyethylene phosphate, diphenyl phenol polyethenoxy polyethenoxy ether, styrenated phenol APEO, alkylphenol polyoxyethylene formaldehyde condensation products, diphenyl phenol polyethenoxy polyformaldehyde condensation product, castor oil ethylene oxide adduct and derivative thereof, for example farming breast 300, farming breast 500, farming breast 600, Nongru-700, agricultural newborn SorplKS, OX2511, NNO, NP series etc., emulsifier can be one or more mixture.
Dispersant has one or several the mixture in lignosulfonates, fatty acid amide N methyl taurine sodium salt, alkylphenol polyoxyethylene sulphate, lignosulfite, fatty acid ester sulphate, polyoxyethylene polyoxypropylene block copolymer, alkylphenol polyoxyethylene, the fatty alcohol-polyoxyethylene ether.
Wetting agent is one or several the mixture in fatty acid amide N methyl taurine sodium salt, lignosulfonates, alkylphenol polyoxyethylene sulphate, petroleum sodium sulfonate, alkylnaphthalene sulfonate, fatty acid ester sulphate, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, lignosulfite, the withered powder of tea, the spaonin powder.
Thickener is one or more the mixture in CMC, polyvinyl alcohol, xanthans, gum Arabic, sodium alginate, polyvinylpyrrolidone, bentonite, aluminium-magnesium silicate, the gypsum.
Penetrating agent is one or both the mixture among Laurocapram, the JFC.
Defoamer can be one or more the mixture in organic silicone oil, methyl alcohol, ethanol, the epoxidized soybean oil.
Antifreezing agent is one or more the mixture in ethylene glycol, propane diols, glycerine, polyethylene glycol, the sorbierite.
PH value conditioning agent is one or more the mixture in sodium hydroxide, potassium hydroxide, ammoniacal liquor, hydrochloric acid, acetic acid, phosphoric acid or the citric acid.
Solvent and cosolvent have one or more the mixture in water, methyl alcohol, ethanol, butanols, ethylene glycol, propane diols, glycerine, polyethylene glycol, acetone, cyclohexanone, pyrrolidones, toluene, dimethylbenzene, ethyl acetate, dimethyl formamide (DMF), the dimethyl sulfoxide (DMSO) (DMSO).
Disintegrant can be one or more the mixture in urea, magnesium chloride, aluminium chloride, sodium chloride, ammonium sulfate, the bentonite.
Carrier is one or more the mixture in kaolin, diatomite, atlapulgite, white carbon black, clay, precipitated calcium carbonate, talcum powder, the montmorillonite.
Indoor biometrics screening and field experiment:
The method that the present invention adopts indoor bioassay and field trial to combine goes to prove the synergistic effect of the present composition.If no special instructions, the ratio of below mentioning (comprising percentage) all is a mass ratio.
Determination of activity example 1:
(1) test medicine
The former medicine of 96% sufluoxime, Hunan Chemical Research Institute, the former medicine of 90% Profenofos, Shandong Ke Yuan chemical industry Co., Ltd.
Earlier with the former medicine of acetone solution, according to the result of preliminary experiment an amount of former medicine is made into 5 different proportionings, it is stand-by with acetone each processing to be diluted to 5 series concentration gradients respectively again.
(2) subjects
Indoor Turnip Sprouts are raised continuously the third-instar larvae of the diamond-back moth in 10 generations, temperature (25 ± 2) ℃, relative moisture 50% ± 4%, periodicity of illumination 14/10h (L/D).
(3) test method
Adopt dip method with two former medicines all with the small amount of acetone dissolving, be diluted to into 5 dense solution of equal difference again with 0.1% Tween solution, be diluted in the beaker with standby, and in contrast with clear water.With of the same size three age diamondback moth larvae in the soup that soaks the worm cage, flood 5S, inhale and to go to be placed in the culture dish that diameter is 9cm behind the unnecessary soup, be placed with fresh cabbage leaves in the ware and add a cover.Every concentration is handled 10, repeats 4 times, establishes blank, keeps checking lethality behind the 24h in (27 ± 1) ℃ illumination box, and it is dead touching the polypide nonresponder with group pin.Lethality Abbott formula correction, again according to the concentration logarithm---the lethality probit value is analyzed (Bliss) method, obtains virulence regression equation and puts dead middle amount LC 50Value.
(4) data statistics and analysis
According to the toxicity test result of single agent, be 16% quality than sufluoxime by active ingredient: Profenofos was respectively 2: 14, and 4: 12,6: 10,8: 8,10: 6.Adopt above-mentioned 1.3 methods to carry out toxicity test, calculate LC 50, and press the abundant method of Sun Yun and calculate co-toxicity coefficient (CTC).Co-toxicity coefficient CTC, computing formula is as follows: (with the Profenofos is the standard medicament, and its toxicity index is 100):
The LC of the toxicity index of sufluoxime (TI)=Profenofos 50The LC of/sufluoxime 50* 100
The LC of actual toxicity index (ATI)=Profenofos of M 50The LC of/M 50* 100
TI * P the sufluoxime of the TI * P Profenofos+sufluoxime of theoretical toxicity index (TTI)=Profenofos of M
TTI * 100 of the ATI/M of the co-toxicity coefficient of M (CTC)=M
In the formula:
M is a sufluoxime and the mixture of the different proportionings of Profenofos
The P sufluoxime is sufluoxime shared ratio in mixture
The P Profenofos is Profenofos shared ratio in mixture
(5) toxicity test result and analysis
Table 1 Profenofos, sufluoxime are to the indoor measurement result of diamond-back moth
Figure BDA0000065877110000071
As can be seen from the table, in being mixed of different proportion, its co-toxicity coefficient shows certain synergistic effect, wherein sufluoxime all greater than 120: Profenofos is that synergistic effect in 4: 12 o'clock is the most obvious, and co-toxicity coefficient is 177.67.Result of the test shows that sufluoxime, two kinds of medicaments of Profenofos all have higher activity to diamond-back moth under indoor conditions, and the result of the test of different proportionings shows, in active ingredient ratio sufluoxime: Profenofos is 2: 14; 4: 12; 6: 10; 8: 8; When respectively diluting all show stronger synergistic effect at 10: 6, wherein with sufluoxime: Profenofos is 4: 12 o'clock, and synergistic effect is best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 4: 12 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
Field experiment control diamond-back moth
(1) test method
Test is sprayed medicine 1 time altogether, and the dispenser date is June 21.Wild cabbage this moment balling not as yet.The diamondback moth larvae major part was in for 2~3 length of times.Weather is cloudy calm during the spray medicine.With the agricultural board level pressure of profit knapsack hand sprayer each is handled even spraying, leave dual sides all requires to be sprayed with the effect soup.Every sub-district soup 2L.
(2) investigation method
Investigate each sub-district and fix 15 strain wild cabbages, write down the larva quantity on whole blades as the investigation strain.Investigate the insect population radix before spraying medicine, respectively 3,7 days and investigation in 10 days borer population alive behind the spray medicine.This test is investigated 4 times altogether.
(3) drug effect computational methods
Insect population borer population * 100 of living before rate (%)=(borer population of living after borer population one dispenser of living before the dispenser)/dispenser of going down
Preventive effect (%)=(the treatment region insect population rate of going down-check plot insect population go down rate)/(100-according to district's insect population go down rate) * 100
(4) poisoning investigation method
Continuous 10d range estimation medicament does not have poisoning to produce the wild cabbage well-grown to crop after the dispenser.
(5) field control effectiveness test result of the test
Table 2 is handled chemical control diamond-back moth field control effectiveness test result
Figure BDA0000065877110000081
As can be seen from Table 2, the Mixed Pharmacy of different proportion, carry out field experiment by different consumptions, its control efficiency to the wild cabbage diamond-back moth all is better than contrasting medicament behind the medicine, 4% sufluoxime+12% Profenofos behind medicine 10 days, insecticidal effect is respectively 92.67%, 93.84% and 94.82%, and insecticidal effect increases along with the increase of consumption, and difference reaches extremely remarkable between each consumption processing insecticidal effect.According to field range estimation, in the test dose scope, plant growth is normal, and each is handled medicament and poisoning phenomenon to wild cabbage all do not occur, illustrates that it is safe to wild cabbage.In process of the test, testing crew finds that it also has favorable effect to insects such as trialeurodes vaporariorums.Advise that the insecticide different with the mechanism of action mixes use to delay the generation of pest resistance to insecticide.
To sum up result of the test checking several times, the present invention contains sufluoxime and part organophosphorus insecticide chlopyrifos, phoxim, Profenofos, Hostathion, carry out two yuan of Pesticidal combinations that are mixed for active ingredient one of arbitrarily in the diazinon, eliminate aphis anti-, Homoptera suckings pest such as leafhopper reach diamond-back moth, beet armyworm, prodenia litura, cotton bollworm, preventive effect is remarkable during lepidopterous insects such as mealybug class, to the target crop safety, compare with single agent, Pesticidal combination of the present invention has mechanism of action uniqueness, consumption is few, and quick-acting is good, lasting period is long, the advantage of environmental protection.So, in research and development of the present invention and popularization the important social meaning is arranged, can produce very big economic benefit.

Claims (6)

1. agricultural insecticide composition is characterized in that: this Pesticidal combination be with one of any in (A) sufluoxime and (B) part organophosphorus insecticide chlopyrifos, phoxim, Profenofos, Hostathion, the diazinon be that two yuan of carrying out of active ingredient are mixed.
2. Pesticidal combination according to claim 1 is characterized in that: the percentage by weight of effective constituents A and B is 0.1~50: 1~80 in this Pesticidal combination.
3. Pesticidal combination according to claim 1 is characterized in that: the percentage by weight of effective constituents A and B is preferably 0.1~35 in this Pesticidal combination: 5~50.
4. Pesticidal combination according to claim 1 is characterized in that: effective constituents A and the B gross mass percentage composition in preparation is 1%-90%.
5. Pesticidal combination according to claim 1 is characterized in that: effective constituents A and the B gross mass percentage composition in preparation is preferably 7%-60%.
6. Pesticidal combination according to claim 1 is characterized in that: the formulation that Pesticidal combination of the present invention can be prepared according to the known method of those skilled in the art of the present technique is missible oil, aqueous emulsion, microemulsion, water-dispersible granules, wetting powder and suspending agent.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103004866A (en) * 2012-12-26 2013-04-03 湖南海利化工股份有限公司 Insecticidal composition containing sufluoxime ether and pirimiphos-methyl
CN103734180A (en) * 2013-12-30 2014-04-23 孙蒙蒙 Bactericidal and insecticidal composite containing sulfur-fluorine oxime ether
CN104255779A (en) * 2014-09-15 2015-01-07 青岛润鑫伟业科贸有限公司 Efficient insecticide containing cypermethrin, phoxim, cyromazine and sulfur-fluorine oxime ether
CN104322545A (en) * 2014-09-30 2015-02-04 青岛康合伟业商贸有限公司 High-efficient pesticide containing thiofluoro oxime ether, sulfoxaflor, dinotefuran and chlorpyrifos

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CN1528143A (en) * 2003-09-26 2004-09-15 湖南化工研究院 Composition containing non-fatty oxime ether pyrethrin insecticide
CN101336634A (en) * 2008-08-27 2009-01-07 国家农药创制工程技术研究中心 Insecticidal composition of sufluoxime
CN101755827A (en) * 2009-10-29 2010-06-30 深圳诺普信农化股份有限公司 Insecticidal composition with synergy effect

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CN1050811A (en) * 1989-10-10 1991-04-24 山东省农药研究所 Methyldicyanogen chrysanthemum ester organic phosphorus pesticide compounding agent
CN1528143A (en) * 2003-09-26 2004-09-15 湖南化工研究院 Composition containing non-fatty oxime ether pyrethrin insecticide
CN101336634A (en) * 2008-08-27 2009-01-07 国家农药创制工程技术研究中心 Insecticidal composition of sufluoxime
CN101755827A (en) * 2009-10-29 2010-06-30 深圳诺普信农化股份有限公司 Insecticidal composition with synergy effect

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103004866A (en) * 2012-12-26 2013-04-03 湖南海利化工股份有限公司 Insecticidal composition containing sufluoxime ether and pirimiphos-methyl
CN103004866B (en) * 2012-12-26 2014-07-02 湖南海利化工股份有限公司 Insecticidal composition containing sufluoxime ether and pirimiphos-methyl
CN103734180A (en) * 2013-12-30 2014-04-23 孙蒙蒙 Bactericidal and insecticidal composite containing sulfur-fluorine oxime ether
CN103734180B (en) * 2013-12-30 2015-12-30 刘一平 A kind of Fungicidal insecticidal composition containing sufluoxime
CN104255779A (en) * 2014-09-15 2015-01-07 青岛润鑫伟业科贸有限公司 Efficient insecticide containing cypermethrin, phoxim, cyromazine and sulfur-fluorine oxime ether
CN104322545A (en) * 2014-09-30 2015-02-04 青岛康合伟业商贸有限公司 High-efficient pesticide containing thiofluoro oxime ether, sulfoxaflor, dinotefuran and chlorpyrifos

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