CN103039512B - Agricultural insecticidal composition containing chlorpyrifos and ZJ4042 - Google Patents

Agricultural insecticidal composition containing chlorpyrifos and ZJ4042 Download PDF

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CN103039512B
CN103039512B CN201310003110.9A CN201310003110A CN103039512B CN 103039512 B CN103039512 B CN 103039512B CN 201310003110 A CN201310003110 A CN 201310003110A CN 103039512 B CN103039512 B CN 103039512B
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pest
insecticide
chlopyrifos
active ingredient
pesticidal
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CN103039512A (en
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邢家华
朱冰春
袁静
陈杰
孔小林
张晓铭
胡冬松
韦伟
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Corp
Sinochem Lantian Co Ltd
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
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Abstract

The invention discloses an insecticidal composition for agricultural insects, which contains two active ingredients: the first active ingredient is chlopyrifos, the second active ingredient is 3-chlorine-N<1>-(2-methyl-4-heptafluoroisopropyl phenyl)-N<2>-(1-methyl-1-cyano ethyl) phthalic diamide, and the weight ratio of the first active ingredient to the second active ingredient is (1-50):(20-1). The insecticidal composition is suitable for controlling insects such as crop prodenia litura, beet armyworms, plutella xylostella, chilo suppressalis walkers, rice leaf rollers and cotton bollworms, and is superior to a single insecticide in quick-acting property and persistent-acting property; the use amount and the use cost of the insecticide are reduced; and the environmental protection and comprehensive control of the agricultural insects are facilitated.

Description

The agricultural pesticide composition of a kind of containing chlopyrifos and ZJ4042
Technical field
The invention belongs to pesticide field, be specifically related to a kind of by chlopyrifos and the chloro-N of 3- 1-(2-methyl-4-sevoflurane isopropyl base)-N 2composite high-efficiency low-toxicity agricultural pesticide composition and the insecticide thereof forming of-(1-methyl isophthalic acid-cyano ethyl) phthalic amide.
Background technology
The resistance problem of pest is a global problem.Along with Chemical Control of Harmful Insects increase and the non-science of continuity, agricultural chemicals usage amount use agricultural chemicals, pest resistance is day by day serious, the pest species that produces resistance is on the increase.The Lepidoptera class pest of particularly causing harm serious to agricultural production, resistance level is higher, and resistance development speed is relatively very fast.Meanwhile, high-intensity use agricultural chemicals, causes that Practice for Pesticide Residue in Agricultural Products exceeds standard, environmental pollution and the increase of peasant's drug cost etc., is unfavorable for agricultural sustainable development.Therefore, the pesticide of efficient, the low toxicity of research and development, environmental protection has positive effect to agricultural sustainable development.
Chlopyrifos is acetylcholinesteraseinhibitors inhibitors, belongs to thiophosphate insecticides, has stomach toxicity, tags, fumigates triple role, and multiple lepidoptera pest on paddy rice, wheat, cotton, vegetables, tea tree is all had to favorable effect.Chlorpyrifos mixture is good by compatibility, can be obvious with multiple Mixture Use of Insecticides and synergistic effect.
The chloro-N of 3- 1-(2-methyl-4-sevoflurane isopropyl base)-N 2-(1-methyl isophthalic acid-cyano ethyl) phthalic amide (hereinafter to be referred as " ZJ4042 "), shown in structural formula following (I):
Figure BDA00002700767400011
The insecticidal activity of this compound and the fipronil bisamide of recent development substantially suitable.Fipronil bisamide, English common name (flubendiamide) is researched and developed by Nihon Nihyaku Co., Ltd, chemical name is the iodo-N-(2-first sulfonephthalein of 3-base-1,1-dimethyl ethyl group-N-{ 4-" 1; 2; 2,2-tetrafluoro-1-(trifluoromethyl) ethyl-o-tolyl } phthalamide, molecular formula is: C 23h 22f 7n 2o 4, belong to Novel ortho benzenedicarboxamide insecticides, activate calcium release channel in blue Buddhist nun's alkali recipient cell, cause the property out of control of storing calcium ion to discharge, be at present few in number compounds that acts on blue Buddhist nun's alkali (Ryanodine) acceptor of insect cell.Lepidoptera pest is had to wide spectrum preventive effect, produce without cross resistance with existing insecticide, be suitable for very much the control of the insect of existing insecticide generation resistance.
When chlopyrifos and ZJ4042 use separately, drug cost is higher, limited to a certain extent it and applied, and long-term use separately easily causes pest resistance degree constantly to increase.The mixture of different pesticide species is common methods of the agriculture resistant insect of control.Screening by formulation of pesticide, filter out rational formula, can effectively improve actual control efficiency, reduce dosage, reduce costs, delay the generation of pest resistance to insecticide, extend the service life of medicament, is the important means of integrated pest management.
The mixture of chlopyrifos and ZJ4042 is prevented and treated the Lepidoptera class pests such as prodenia litura, beet armyworm, diamond-back moth, striped rice borer, rice leaf roller, cotton bollworm and be there is no at present report and application.
Summary of the invention
The object of the present invention is to provide a kind of efficient, low toxicity and lasting period are long, can effectively prevent and treat crops Lepidoptera class pest agricultural pesticide composition and insecticide thereof.
For reaching goal of the invention the technical solution used in the present invention be:
For a Pesticidal combination for pest, contain two kinds of active components, the first active component is chlopyrifos, second active ingredient is the chloro-N of 3- 1-(2-methyl-4-sevoflurane isopropyl base)-N 2-(1-methyl isophthalic acid-cyano ethyl) phthalic amide, the weight ratio that described the first active component and the second activity become is 1~50:20~1.
The weight ratio that above-mentioned the first active component and the second activity become is preferably 1~20:20~1, and more preferably 1~10:10~1, is particularly preferably 1~5:5~1.
The present invention also provides a kind of insecticide for pest, contains by weight 5~90% above-mentioned Pesticidal combinations, and all the other are the upper acceptable carrier of agricultural and auxiliary agent.As preferred mode, in described insecticide, contain 20~70% above-mentioned Pesticidal combinations, be particularly preferably the Pesticidal combination that contains 20~40% in insecticide.
Carrier of the present invention can be solid or liquid, and any carrier that is generally used for preparing insecticides all can use.
Suitable solid carrier comprises: mineral substance, plant, synthetic filling class and inorganic salts.Wherein mineral substance comprises silicates, carbonate, Sulfates and oxide-based.Silicates is kaolin such as, sepiolite, nacrite, imvite, mica, vermiculite, pyrophyllite, talcum.Carbonate is for example: calcium carbonate, dolomite.Sulfates is as ammonium sulfate, sodium sulphate, calcium sulphate.Oxide-based as quicklime, magnesium lime, diatomite.Plant is for example: citrus pulp, corncob cellulose, rice husk powder, rice husk, large soya bean stem meal, tobacco powder, walnut shell, sawdust.Synthetic filling class is as winnofil hydrate, winnofil, white carbon.Inorganic salts is potassium chloride such as, sodium chloride.
Liquid-carrier comprises water and organic solvent.In the time that active ingredient is aqueous emulsion or suspension emulsion, organic solvent plays solubilising and antifreeze effect.Suitable organic solvent comprises aromatic hydrocarbons, for example benzene, dimethylbenzene, toluene, alkylbenzene, Fluhyzon and chlorinated aromatic hydrocarbons; Chlorinated aliphatic hydrocarbon, for example vinyl chloride, chloroform, carrene, chloroform, carbon tetrachloride and many chloroethanes; Aliphatic hydrocarbon, for example petroleum distillate, cyclohexane, light mineral oil and paraffin.Alcohols is methyl alcohol such as, ethanol, isopropyl alcohol, butanols, isobutanol, ethylene glycol, propane diols, glycerine, fatty alcohol etc.; Ethers is Propylene Glycol ether for example, ethohexadiol ether, benzinum.Ketone is acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone and different fluorine that ketone, N-methyl-pyrrolidones for example; Special solvent also has dimethyl formamide, dimethyl sulfoxide (DMSO), polyethylene glycol, nitrile; Vegetable oil and the vegetable oil that methylates.Above-mentioned organic solvent both can be used alone, but also also mix together, and can also mix together with water.
Auxiliary agent of the present invention can comprise one or more in surfactant, defoamer, thickener, suspending agent and antifreezing agent as required, can also comprise as required other auxiliary agents that the industry is conventional.
Surfactant can be emulsifier, dispersant, stabilizing agent or wetting agent; Can be ionic or nonionic.Suitable surfactant comprises: the sodium salt of polyacrylic acid and lignin sulfonic acid and calcium salt; In molecule, contain the fatty acid of at least 12 carbon atoms or fatty amine and oxirane and/polycondensation product of expoxy propane; The fatty acid ester of glycerine, dodecanol-1, tetradecanol-1, sorbierite, sucrose or pentaerythrite; And the polycondensation product of they and oxirane and/or expoxy propane; The sulphate of their polycondensation product or sulfonate; In molecule, at least containing the sulfuric acid of 10 carbon atoms or the alkali metal of sulfonic acid or alkali salt, is preferably sodium salt, as the sodium salt of lauryl sodium sulfate, Teepol, sulfonated castor oil, alkylaryl sodium sulfonate and neopelex; The copolymer of polymer, oxirane and the expoxy propane of oxirane.
Emulsifier comprises nonionic emulsifier and anionic emulsifier.The preferred polyoxyethylene nonylphenol ether of nonionic emulsifier, fatty alcohol-polyoxyethylene ether, styryl phenyl APEO, alkyl phenol formaldehyde resin polyoxyethylene ether, terminal hydroxy group polyoxyethylene poly-oxygen propylene aether, styryl phenol formaldehyde resin polyoxyethylene poly-oxygen propylene aether, castor oil polyoxyethylene ether.Anionic emulsifier mainly comprises calcium dodecyl benzene sulfonate, triphen ethyl phenol polyoxy ether phosphate amine salt, polyoxyethylene nonylphenol ether phosphate amine salt, castor oil polyoxyethylene ether phosphate amine salt.
Dispersant of the present invention comprises: acrylate homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, rosin segmented APEO polyoxypropylene ether sulfonate, terminal hydroxy group polyoxyethylene poly-oxygen propylene aether block copolymer, triphen ethyl phenol polyoxyethylene ether phosphate, fatty alcohol-polyoxyethylene ether phosphoric acid, to one or more in hydroxyphenyl lignin sulfonic acid sodium salt.
Wetting agent of the present invention comprises: fatty alcohol-polyoxyethylene ether, naphthalene sulfonate, lauryl sodium sulfate, one or more combinations in alkyl phenol resin polyoxyethylene ether sulfate.
Thickener of the present invention comprises xanthans, aluminium-magnesium silicate, sodium alginate, sodium carboxymethylcellulose, gum Arabic, gelatin, one or more in polyvinyl alcohol.Defoamer of the present invention is preferably: bubble enemy, silicone, C 8~10fatty alcohol, C 10~20saturated fat acids and acid amides etc.
Insecticide of the present invention can be mixed with suspending agent, missible oil, wetting powder, oil suspending agent, water-dispersible granules according to the general method in this area.
Pesticidal combination provided by the invention and insecticide are suitable for preventing and treating Lepidoptera class pest, and described Lepidoptera class pest comprises prodenia litura, beet armyworm, diamond-back moth, striped rice borer, rice leaf roller, cotton bollworm.Be particularly suitable for preventing and treating the Lepidoptera class pest in vegetables, paddy rice and cotton.
Pesticidal combination of the present invention and insecticide have following advantage compared to existing technology:
(1) in composition, two kinds of active components are composite necessarily showing good synergistic effect in ratio range, mix the insecticidal effect of composition afterwards and are significantly improved compared with its single dose, and have the advantages that quick-acting is good and lasting effect is long;
(2) reduce using dosage, reduced peasant's drug cost;
(3) utilize two kinds of active components to carry out reasonably mixture to the different mode of action of insect, the different mechanism of action, both extended agricultural chemicals service life, delay again the generation of pest resistance to insecticide.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these embodiments.One skilled in the art would recognize that the present invention contained all alternatives, improvement project and the equivalents that within the scope of claims, may comprise.
In following embodiment material prescription select can suit measures to local conditions, on result without substantial impact.In these embodiments, unless otherwise indicated, all percentage is all weight percentage.
The inventor has carried out Toxicity Determination test to chlopyrifos and ZJ4042 mixture.
Test is evaluated SOP(insecticide volume with reference to pesticide indoor bioassay test rule (agricultural industry criteria NY/T1154.7-2006) and initiative pesticide bioactivity), adopt infusion process.
Synergy adopts following method to calculate:
The content (%) of toxicity index × A of theoretical mixed toxicity index (TTI)=A in mixed
The content (%) of toxicity index × B of+B in mixed
Figure BDA00002700767400042
If co-toxicity coefficient is greater than 120, showing has synergistic effect; If be less than 80, be indicated as antagonism; Be less than 120 if be greater than 80, be indicated as summation action.
Embodiment 1:ZJ4042 and chlopyrifos mixture
Table 1 ZJ4042 and chlopyrifos are to the effect of wild cabbage diamond-back moth Plutella xylostella synergy
Process Proportioning LC 50(mg/L) Actual measurement toxicity index Theoretical toxicity index Co-toxicity coefficient
Chlopyrifos - 18.32 1.42 ? ?
ZJ4042 - 0.26 100.00 ? ?
Chlopyrifos: ZJ4042 50:1 5.24 4.96 3.35 148.02
Chlopyrifos: ZJ4042 20:1 2.78 9.35 6.11 152.98
Chlopyrifos: ZJ4042 1:1 0.35 74.29 50.71 146.49
Chlopyrifos: ZJ4042 1:10 0.19 136.84 91.04 150.31
Chlopyrifos: ZJ4042 1:20 0.19 136.84 95.31 143.58
Table 2 ZJ4042 and chlopyrifos are to the effect of rice leaf roller Cnaphalocrocis medinalis synergy
Process Proportioning LC 50(mg/L) Actual measurement toxicity index Theoretical toxicity index Co-toxicity coefficient
Chlopyrifos - 3.26 140.80 ? ?
ZJ4042 - 4.59 100.00 ? ?
Chlopyrifos: ZJ4042 50:1 2.48 185.08 140.00 132.20
Chlopyrifos: ZJ4042 20:1 2.37 193.67 138.85 139.48
Chlopyrifos: ZJ4042 1:1 2.81 163.35 120.40 135.67
Chlopyrifos: ZJ4042 1:10 3.21 142.99 103.71 137.88
Chlopyrifos: ZJ4042 1:20 3.27 140.37 101.94 137.69
Can find out from result of the test table 1,2, chlopyrifos and ZJ4042,1~50:20~1(by weight) scope in, co-toxicity coefficient is all greater than 120, and wild cabbage diamond-back moth and paddy rice rice leaf roller are all shown as to synergistic effect.Chlopyrifos and ZJ4042 mixture have reasonability and feasibility.
Embodiment 2 (20% chlopyrifos ZJ4042 suspending agent)
By chlopyrifos 18%, ZJ40422%, emulsifier 1601#(styryl phenol polyoxyethylene poly-oxygen propylene aether) 10%, dispersant SOPA mono-27043%, bentonite 2%, xanthans 0.1%, silicone defoaming agent 0.4%, glycerine 5%, surplus is deionized water.Above-mentioned formula is pulverized in proportion in advance, then added in sand mill and grind, after high shear mixing, allotment makes 20% chlopyrifos ZJ4042 suspending agent.
This embodiment is applied to control wild cabbage diamond-back moth.20% chlopyrifos ZJ4042 suspending agent is watered even spraying by 10 grams/acre in wild cabbage diamondback moth larvae occurance peak, and after medicine, the preventive effect of 3 days, 7 days is respectively 93.9%, 95.3%.Contrast single dose 48% chlorpyrifos ec (formulation rate is 50 grams/acre), 20%ZJ4042 suspending agent (formulation rate is 10 grams/acre) are by same method dispenser, after medicine, the preventive effect of 3 days is respectively 60.7%, 87.1%, and after medicine, the preventive effect of 7 days is respectively 55.2%, 89.2%.After chlopyrifos and ZJ4042 mixture, synergistic effect is obvious, and preventive effect is better than single dose.
Embodiment 3 (20% chlopyrifos ZJ4042 missible oil)
By chlopyrifos 15%, ZJ40425%, calcium dodecyl benzene sulfonate 6%, triphen ethyl phenol APEO 6%, NMP8%, surplus is dimethylbenzene.By above-mentioned formula mixing and stirring in proportion.
This embodiment is applied to control wild cabbage prodenia litura.20% chlopyrifos ZJ4042 missible oil is watered even spraying by 10 grams/acre in wild cabbage Spodoptera litura larvae occurrence in peak period, and after medicine, 3 days, 7 days preventive effects are respectively 93.7%, 95.9%.Contrast single dose 48% chlorpyrifos ec (formulation rate is 50 grams/acre), 20%ZJ4042 suspending agent (formulation rate is 10 grams/acre) are by same method dispenser, after medicine, the preventive effect of 3 days is respectively 65.7%, 85.1%, and after medicine, the preventive effect of 7 days is respectively 68.3%, 86.4%.After chlopyrifos and ZJ4042 mixture, synergistic effect is obvious, and preventive effect is better than single dose, and quick-acting and lasting effect are also better than single dose, and dosage reduces than single dose.
Embodiment 4 (70% chlopyrifos ZJ4042 water-dispersible granules)
By chlopyrifos 55%, ZJ404215%, lauryl sodium sulfate 6%, poly-shuttle hydrochlorate 4%, sodium chloride 8%, polyethylene glycol 3%, surplus is kaolin.By above-mentioned formula, dry pulverization process, granulation, dry, screening make 70% chlopyrifos ZJ4042 water-dispersible granules in proportion.
This embodiment is applied to control striped rice borer.70% chlopyrifos ZJ4042 water-dispersible granules is watered even spraying by 10 grams/acre in the striped rice borer ovum hatching peak phase, and after medicine, 7 days, 14 days preventive effects are respectively 88.9%, 90.3%.Contrast single dose 48% chlorpyrifos ec (formulation rate is 50 grams/acre), 20%ZJ4042 suspending agent (formulation rate is 10 grams/acre) are by same method dispenser, after medicine, the preventive effect of 7 days is respectively 52.7%, 80.2%, and after medicine, the preventive effect of 14 days is respectively 61.5%, 81.3%.After chlopyrifos and ZJ4042 mixture, synergistic effect is obvious, and preventive effect is better than single dose, and quick-acting and lasting effect are also better than single dose.
Embodiment 5 (40% chlopyrifos ZJ4042 wetting powder)
By chlopyrifos 35%, ZJ40425%, lauryl sodium sulfate 6%, poly-shuttle hydrochlorate 4%, sodium chloride 8%, polyethylene glycol 3%, surplus is kaolin.By above-mentioned formula, dry pulverization process, granulation, dry, screening make 40% chlopyrifos ZJ4042 wetting powder in proportion.
This embodiment is applied to control rice leaf roller.40% chlopyrifos ZJ4042 wetting powder is watered even spraying by 10 grams/acre in rice leaf roller low instar larvae occurrence in peak period, and after medicine, the preventive effect of 7 days, 14 days is respectively 92.2%, 94.7%.Contrast single dose 48% chlorpyrifos ec (formulation rate is 50 grams/acre), by same method dispenser, after medicine, the preventive effect of 7 days is respectively 53.8%, 82.9% to 20%ZJ4042 suspending agent (formulation rate is 10 grams/acre), after medicine, the preventive effect of 14 days is 63.5%, 86.7%.After chlopyrifos and ZJ4042 mixture, synergistic effect is obvious, and preventive effect is better than single dose, and quick-acting and lasting effect are also better than single dose.Embodiment 6 (20% chlopyrifos ZJ4042 oil suspending agent)
Chlopyrifos 15%, ZJ40425%, castor oil polyoxyethylene ether 13%, tristyrylphenol polyoxyethylene ether phosphate 3%, organobentonite 1%, methyl oleate is mended to 100%.After above-mentioned formula is mixed, sand milling is to certain particle diameter.
This embodiment is applied to control cotton bollworm.20% chlopyrifos ZJ4042 oil suspending agent is watered even spraying by 10 grams/acre in cotton bollworm larvae occurance peak, and after medicine, 3 days, 7 days preventive effects are respectively 93.7%, 98.4%.Contrast single dose 48% chlorpyrifos ec (formulation rate is 50 grams/acre), by same method dispenser, after medicine, the preventive effect of 3 days is respectively 60.8%, 83.9% to 20%ZJ4042 suspending agent (formulation rate is 10 grams/acre), after medicine, the preventive effect of 7 days is 67.5%, 88.6%.After chlopyrifos and ZJ4042 mixture, synergistic effect is obvious, and preventive effect is better than single dose.

Claims (10)

1. for a Pesticidal combination for pest, it is characterized in that containing two kinds of active components, the first active component is chlopyrifos, and second active ingredient is the chloro-N of 3- 1-(2-methyl-4-sevoflurane isopropyl base)-N 2-(1-methyl isophthalic acid-cyano ethyl) phthalic amide, the weight ratio that described the first active component and second active ingredient are is 1~50:20~1.
2. according to the Pesticidal combination for pest claimed in claim 1, it is characterized in that the weight ratio that described the first active component and second active ingredient are is 1~20:20~1.
3. according to the Pesticidal combination for pest claimed in claim 2, it is characterized in that the weight ratio that described the first active component and second active ingredient are is 1~10:10~1.
4. according to the Pesticidal combination for pest claimed in claim 3, it is characterized in that the weight ratio that described the first active component and second active ingredient are is 1~5:5~1.
5. for an insecticide for pest, it is characterized in that containing by weight 5~90% Pesticidal combinations claimed in claim 1, all the other are the upper acceptable carrier of agricultural and auxiliary agent.
6. according to the insecticide for pest claimed in claim 5, it is characterized in that containing by weight 20~70% Pesticidal combinations claimed in claim 1.
7. according to the insecticide for pest claimed in claim 6, it is characterized in that containing by weight 20~40% Pesticidal combinations claimed in claim 1.
8. according to the insecticide for pest claimed in claim 5, it is characterized in that described insecticide can be mixed with suspending agent, missible oil, wetting powder, water-dispersible granules.
9. according to the purposes of Pesticidal combination claimed in claim 1, it is characterized in that preventing and treating Lepidoptera class pest, described Lepidoptera class pest comprises prodenia litura, beet armyworm, diamond-back moth, striped rice borer, rice leaf roller, cotton bollworm.
10. according to the purposes of Pesticidal combination claimed in claim 9, it is characterized in that preventing and treating the Lepidoptera class pest in vegetables, paddy rice and cotton.
CN201310003110.9A 2013-01-05 2013-01-05 Agricultural insecticidal composition containing chlorpyrifos and ZJ4042 Active CN103039512B (en)

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US9549552B2 (en) * 2013-04-19 2017-01-24 Bayer Cropscience Aktiengesellschaft Active compound combinations having insecticidal properties
BR112015025780A2 (en) * 2013-04-19 2017-07-25 Bayer Cropscience Ag active compound combinations having insecticidal properties
CN103947669A (en) * 2014-05-21 2014-07-30 北京燕化永乐生物科技股份有限公司 Compound insecticide
CN104186471B (en) * 2014-08-04 2017-11-28 广东中迅农科股份有限公司 A kind of composition pesticide containing chlorine fluorine cyanogen insect amide and methoxyfenozide
CN104161043A (en) * 2014-08-08 2014-11-26 北京燕化永乐生物科技股份有限公司 Insecticidal composition
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CN105475346B (en) * 2014-09-19 2017-12-12 江苏龙灯化学有限公司 A kind of Pesticidal combination
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Patentee after: Sinochem Lantian Co., Ltd.

Co-patentee after: Sinochem Corporation

Address before: 310051 Binjiang District Jiangnan Road, Zhejiang, No. 96, No.

Co-patentee before: Zhejiang Research Institute of Chemical Industry, Ltd.

Patentee before: Sinochem Lantian Co., Ltd.