CN103621535A - Synergistic insect disinfestation composition containing clothianidin and chlorantraniliprole, and application thereof - Google Patents

Synergistic insect disinfestation composition containing clothianidin and chlorantraniliprole, and application thereof Download PDF

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Publication number
CN103621535A
CN103621535A CN201210310659.8A CN201210310659A CN103621535A CN 103621535 A CN103621535 A CN 103621535A CN 201210310659 A CN201210310659 A CN 201210310659A CN 103621535 A CN103621535 A CN 103621535A
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clothianidin
rynaxypyr
insecticidal compositions
synergistic insecticidal
synergistic
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陈文明
袁竹青
彭永强
吴敏
沈海峰
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Nanjing Huazhou Pharmaceutical Co Ltd
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Nanjing Huazhou Pharmaceutical Co Ltd
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Abstract

The present invention discloses a synergistic insect disinfestation composition containing clothianidin and chlorantraniliprole, and an application thereof. The synergistic insect disinfestation composition adopts clothianidin and chlorantraniliprole as main effective components, wherein a weight ratio of the clothianidin to the chlorantraniliprole is 1-100:0.5-80. The synergistic insect disinfestation composition has effects of prevention and control spectrum expanding, synergy and medication cost reduction, can be prepared into an emulsifiable concentrate, wettable powder, a microemulsion, an aqueous emulsion, a suspending agent and water dispersible granules, and is provided for preventing and controlling Lepidoptera, Hemiptera, Hymenoptera, Coleoptera and a plurality of pests.

Description

The Synergistic insecticidal compositions of a kind of clothianidin-containing and Rynaxypyr and application thereof
Technical field
The invention belongs to the pesticide field that contains heterocyclic compound, be specifically related to a kind of Pesticidal combination and application thereof that clothianidin and Rynaxypyr be main active ingredient of take.
Background technology
Clothianidin (Clothianidin), chemical name: E)-1-(the chloro-1,3-thiazoles-5-of 2-ylmethyl)-3-methyl-2-nitroguanidine; Chemical molecular formula: C 6h 8clN 5o 2s; Sterling outward appearance is white crystals, 176.8 ℃ of fusing points, vapour pressure (20 ℃) 3.8 * 10-11Pa, solvability (g/L, 25 ℃): 0.327 (20 ℃) in water, in ethyl acetate 2.03, <0.00104 in normal heptane, in dimethylbenzene 0.0128, in carrene 1.32, in octanol 0.938, in acetone 15.2, in methyl alcohol 6.26.Structural formula:
Figure BDA00002069261400011
Clothianidin acute oral toxicity, rat male and female: LD50 > 5000mg/kg, acute dermal toxicity: rat male and female: LD50 > 2000mg/kg, inhales people's toxicity: rat male and female, 6.1mg/L.Clothianidin belongs to anabasine insecticide, be a kind of activity high, there is interior absorption, tag and the broad spectrum pesticide of stomach poison function.Shi Wu field company is after Nitenpyram (nitenpyram), and another nicotinic insecticide of discovery, belongs to the second generation.The mechanism of action is in conjunction with the nAChR that is positioned at neural post-synapse.Be applicable to foliar spray, soil treatment effect, show good quick-acting, the lasting period is about 7 days.Be mainly used in paddy rice, vegetables, fruit tree and other crop, control Semiptera, coleoptera, diptera and some lepidoptera pest.
Rynaxypyr (chlorantraniliprole), the bromo-N-[4-chloro-2-methyl-6-[(of chemical name: 3-methyl-carbamoyl) benzene]-1-(3-chloropyridine-2-yl)-1-hydrogen-pyridine-5-formamide, structural formula is:
Figure BDA00002069261400021
Rynaxypyr belongs to O-formammidotiazol-benzamide insecticide.Be mainly to activate blue Buddhist nun's alkali acceptor, discharge the calcium ion of storing in smooth muscle and striated muscle cell, cause that muscle regulates weak, paralysis, until last insect is dead.Rynaxypyr high-efficiency broad spectrum, all has good control effect to lepidopterous Noctuidae, Pyralidae, Carposinidae, tortricid, miller Ke, diamond-back moth section, Gelechidae, Gracilariidae etc., can also control coleoptera Culculionidae, Chrysomelidae; Diptera Agromyzidae; The multiple non-lepidoptera pest such as Bemisia tabaci.This active ingredient shows mammal and the extremely significant selective difference of the blue Buddhist nun's alkali of insect acceptor, has greatly improved mammal and other vertebrate safeties.
Often there is defect in the clothianidin of single component or Rynaxypyr: use is easily developed immunity to drugs continuously, and insecticidal spectrum is narrow, can not provide comprehensive protection for crop, and peasant's drug cost is high in agricultural chemicals control of insect.
Summary of the invention
The Synergistic insecticidal compositions that the object of this invention is to provide a kind of clothianidin-containing and Rynaxypyr, said composition can be used for preventing and treating various agricultural insect, for example, in control paddy rice rice leaf roller, striped rice borer, paddy stem borer, pink rice borer, rice plant skipper, can prevent and treat rice fulgorid again, rice silk worm is first-class, can reach the effect that a drug is prevented and treated dissimilar insect.
The Synergistic insecticidal compositions that another object of the present invention is to provide clothianidin-containing and Rynaxypyr is prevented and treated the application in the insecticidal materials of one or more insects in resistance Lepidoptera, Semiptera, Hymenoptera or coleoptera in preparation.
The present invention adopts following technical scheme:
The Synergistic insecticidal compositions of a kind of clothianidin-containing and Rynaxypyr, it take clothianidin and Rynaxypyr is main active ingredient, wherein, the weight ratio of clothianidin and Rynaxypyr is 1 ~ 100:0.5 ~ 80, be preferably 1 ~ 60:1 ~ 70,1 ~ 30:1 ~ 30 more preferably, more further preferred 1 ~ 10:1 ~ 10, the weight ratio of clothianidin and Rynaxypyr is 1:1 ~ 10 most preferably.This Synergistic insecticidal compositions can only contain active ingredient clothianidin and Rynaxypyr, also can when using or prepare, in active component, add other components, and the effective ingredient of above-mentioned Insecticidal combinations is present in composition with synergy effective dose.
At the Synergistic insecticidal compositions of clothianidin-containing of the present invention and Rynaxypyr, the two weight percentage in this Synergistic insecticidal compositions of clothianidin and Rynaxypyr is 2% ~ 80%, is preferably 8% ~ 60%, and optimum is 20% ~ 40%." % " of the present invention is mass percent.
The Synergistic insecticidal compositions of above-mentioned clothianidin-containing and Rynaxypyr be take clothianidin and Rynaxypyr and is mixed with any one formulation allowing on agricultural chemicals as main active ingredient (active component) and insecticides adjuvant, excipients.The preferred pulvis of formulation, wetting powder, suspending agent, missible oil and water dispersion granule.
Aforementionedly can be applicable to the not special restriction of insecticides adjuvant of the present invention, include, but are not limited to calcium dodecyl benzene sulfonate, alkylphenol polyoxyethylene, the rare block compound of polyoxyethylene polyoxy third (as agriculture breast 33 #), polyoxyethylene nonylphenol ether etc., aforementionedly can be applicable to the not special restriction of insecticides adjuvant of the present invention, include, but are not limited to cyclohexanone, dimethylbenzene, solvent naphtha, water, antifreezing agent (as propane diols), deionized water etc.Above auxiliary agent, excipient and the upper known auxiliary material of other agricultural can alone or and use.
Application in the insecticidal materials of above-mentioned clothianidin-containing and the Synergistic insecticidal compositions of Rynaxypyr one or more insects in preparation control Lepidoptera, Semiptera, Hymenoptera or coleoptera.Especially the effect of preventing and treating in the insecticidal materials of rice hoppers, rice leaf roller or vegetables thrips in preparation is remarkable.
Synergistic insecticidal compositions antagonism lepidoptera pest of the present invention has significant preventive effect, especially for the easy various pests that produces resistance such as rice leaf roller, striped rice borer, paddy stem borer, pink rice borer, rice fulgorid, has good preventive effect; And suppress insect to the pesticide resistance generation of unitary agent (clothianidin or Rynaxypyr) and can prevent and treat Semiptera insect as thrips, aleyrodid, leafhopper etc. simultaneously.
The insecticidal materials of being prepared by the Synergistic insecticidal compositions of described clothianidin-containing and Rynaxypyr is when preventing and treating resistance Lepidoptera, Hymenoptera or coleopteran pest, can prevent and treat Semiptera insect again, to rice hoppers, cotton bollworm and thrips, reach the effect that a medicine is controlled more especially.
Pesticidal combination of the present invention compared with prior art, produces following beneficial effect: (1) is compared with single dose, and said composition insect has notable synergistic, has obviously improved control efficiency; (2) one medicines are controlled more, and a dispenser can prevent and treat various pests simultaneously, reduce control recruitment cost; (3) alternative high-toxic pesticide, and significantly reduce field dosage, effectively reduce environmental pollution and residue of pesticide; (4) have concurrently quick-acting and long-acting; (5) compare with clothianidin single dose, produce and use cost reduction; (6) suppressing insect strengthens the resistance of agricultural chemicals;
Embodiment
Below in conjunction with embodiment, the invention will be further described, but do not limit the present invention in any way.
Embodiments of the invention are the methods that adopt indoor bioassay and field trial to combine.First by indoor bioassay, the co-toxicity coefficient after clear and definite two kinds of medicaments are composite by a certain percentage; On this basis, then carry out field trial.
Embodiment 1:
Take 30g clothianidin and Rynaxypyr, calcium dodecyl benzene sulfonate 4g, phenethyl phenol polyethenoxy ether 3g, vegetable oil to 100g.The method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and makes the clothianidin Rynaxypyr missible oil that main active ingredient weight percentage is 30%.The concrete ratio of clothianidin and Rynaxypyr is in Table 1.
Adopt rice stem infusion process to measure clothianidin and Rynaxypyr and the virulence of composite sample to rice hoppers thereof, every processing repeats 3 times, and every concentration is processed 30, uses LC 50value is pressed the abundant method of Sun Yun and is calculated co-toxicity coefficient:
Table 1 clothianidin, Rynaxypyr and composite sample thereof are to the toxicity test of rice hoppers and co-toxicity coefficient
Figure BDA00002069261400041
In table, data show, after clothianidin and Rynaxypyr are mixed, rice hoppers are had to synergistic effect, and four proportioning co-toxicity coefficients listed in table are all much larger than 120, so clothianidin and Rynaxypyr are mixed and have significant synergies.Wherein when the ratio of Rynaxypyr and clothianidin is 2.5:1, be mixed and kill the synergistic effect maximum of rice hoppers, co-toxicity coefficient is 198.41.
Embodiment 2:
Taking clothianidin, Rynaxypyr adopts conventional formulation method to be mixed with by different proportion the clothianidin Rynaxypyr missible oil that main active ingredient weight percentage is 30%.Concrete ratio is in Table 2.
Adopt feed to add malicious method and measure clothianidin and Rynaxypyr and the virulence of composite sample to rice leaf roller thereof, every processing repeats 3 times, uses LC 50value is pressed the abundant method of Sun Yun and is calculated co-toxicity coefficient:
Table 2 clothianidin, Rynaxypyr and composite sample thereof are to the toxicity test of rice leaf roller and co-toxicity coefficient
Figure BDA00002069261400042
In table, data show, after clothianidin and Rynaxypyr are mixed, rice leaf roller are had to synergistic effect, and four proportioning co-toxicity coefficients listed in table are all much larger than 120, so clothianidin and Rynaxypyr are mixed and have significant synergies.Wherein when the ratio of clothianidin and Rynaxypyr is 1:5, be mixed and kill the synergistic effect maximum of rice leaf roller, co-toxicity coefficient is 201.38.
Embodiment 3:
Take 4g clothianidin, 20g Rynaxypyr, calcium dodecyl benzene sulfonate 4g, phenethyl phenol polyethenoxy ether 3g, dimethylbenzene to 100g, the method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and forms the clothianidin Rynaxypyr missible oil that main active ingredient weight percentage is 24%.
Adopt 3 sample product of embodiment to carry out the field trial of control in field rice hoppers, contrast medicament is 15% clothianidin EC and 22% Rynaxypyr SC, and concrete consumption is in Table 3, every mu of water consumption is 30kg, looks into 7 days after medicine 3 days, 14 days, 28 days results, result of the test is in Table 3:
The field test results of table 3 example 3 samples to rice hoppers
Figure BDA00002069261400051
3 pairs of rice hoppers of example have fabulous quick-acting as can be seen from Table 3, and the lasting period is more intense, in field performance well, are the outstanding medicaments of preventing and treating rice hoppers.
Embodiment 4:
Adopt 3 sample product of embodiment to carry out the field trial of control in field rice leaf roller, contrast medicament is 15% clothianidin EC and 22% Rynaxypyr SC, and concrete consumption is in Table 3, every mu of water consumption is 30kg, looks into 7 days after medicine 3 days, 14 days, 28 days results, result of the test is in Table 4:
The field test results of table 4 example 3 samples to rice leaf roller
Figure BDA00002069261400052
Example 3 samples have fabulous effect to rice leaf roller as can be seen from Table 4, and the lasting period is long, in field performance well, are the outstanding medicaments that prevents rice leaf roller.
Through indoor synergism test, measure and show: by clothianidin and Rynaxypyr built agent, rice hoppers and rice leaf roller are all had to significant synergistic insecticidal action; Field control effectiveness test equally also shows that all built agents of the present invention are all significantly higher than the effect of corresponding single dose agricultural chemicals to the insecticidal effect of rice hoppers and rice leaf roller.
Embodiment 5:
Take 0.2g clothianidin, 20g Rynaxypyr, lignin 10g, Negel 2g, with kaolin, add to 100g, above raw material is mixed in micronizer, form the clothianidin Rynaxypyr wetting powder that main active ingredient weight percentage is 20.2%.
Embodiment 6:
Take 78g clothianidin, 0.5g Rynaxypyr, calcium dodecyl benzene sulfonate 8g, phenethyl phenol polyethenoxy ether 6g, dimethylbenzene and add to 100g, the method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and forms the clothianidin Rynaxypyr missible oil that main active ingredient weight percentage is 78.5%.
Embodiment 7:
Take 2g clothianidin, 10g Rynaxypyr, nonyl phenol phosphate 5g, alkylphenol polyoxyethylene 4g, n-butanol 3g, the dimethylbenzene of 30g and the pyrrolidones of 20g, the xanthans of 0.1g, all the other waters are supplied 100g, n-butanol and water-soluble solution form water, and all the other component mix and blends form oil phases, go in slowly water being added to oil phase under clipper effect, and continue to shear 10 ~ 30 minutes, form the clothianidin chlorantraniliprole water emulsion that main active ingredient weight percentage is 12%.
Embodiment 8:
Take 10g clothianidin, 30g Rynaxypyr, calcium dodecyl benzene sulfonate 5g, alkylphenol polyoxyethylene 4g, the solvent xylene of 30g and the pyrrolidones of 15g, all the other waters complement to 100g, former medicine, solvent, emulsifier, cosolvent mix and blend form homogeneous phase transparent solution, then slowly add water and stir to form clear solution, be the clothianidin Rynaxypyr microemulsion that main active ingredient weight percentage is 40%.
Embodiment 9:
Take 4g clothianidin, 4g Rynaxypyr, calcium dodecyl benzene sulfonate 5g, phenethyl phenol polyethenoxy ether 3g, dimethylbenzene to 100g.The method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and forms the clothianidin Rynaxypyr missible oil that main active ingredient weight percentage is 8%.
Embodiment 10:
Take 3g clothianidin, 30g Rynaxypyr, sodium lignin sulfonate 3g, polyoxyethylene poly-oxygen propylene aether and sulphate 4g thereof, xanthans 0.2g, ethylene glycol 10g, silica ethane 0.1g, aluminium-magnesium silicate 0.5g, water is supplied 100g, forms the clothianidin Rynaxypyr suspending agent that main active ingredient weight percentage is 33% under the effect of sand mill.
Embodiment 11:
Take 5g clothianidin, 60g Rynaxypyr, alkylphenol polyoxyethylene 14g, phenethyl phenol polyethenoxy ether 15g, dimethylbenzene to 100g, the method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and forms the clothianidin Rynaxypyr missible oil that main active ingredient weight percentage is 65%.
Embodiment 12:
Take 45g clothianidin, 5g Rynaxypyr, sodium lignin sulfonate 8g, lauryl sodium sulfate 2g, ammonium sulfate 5g, polyvinyl alcohol 5g, borax 2g, kaolin 28g, forms by the method for water dispersion granule the clothianidin Rynaxypyr water dispersible granules that main active ingredient weight percentage is 50% by above raw material.
Embodiment 13:
Take 25g clothianidin, 25g Rynaxypyr, alkylphenol polyoxyethylene 14g, phenethyl phenol polyethenoxy ether 15g, dimethylbenzene to 100g, the method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and forms the clothianidin Rynaxypyr missible oil that main active ingredient weight percentage is 50%.

Claims (10)

1. a Synergistic insecticidal compositions for clothianidin-containing and Rynaxypyr, is characterized in that it is main active ingredient that this Synergistic insecticidal compositions be take clothianidin and Rynaxypyr, and wherein, the weight ratio of clothianidin and Rynaxypyr is 1 ~ 100:0.5 ~ 80.
2. the Synergistic insecticidal compositions of clothianidin-containing according to claim 1 and Rynaxypyr, is characterized in that the effective ingredient clothianidin of this Pesticidal combination and the weight ratio of Rynaxypyr are 1 ~ 60:1 ~ 70.
3. the Synergistic insecticidal compositions of clothianidin-containing according to claim 2 and Rynaxypyr, is characterized in that the effective ingredient clothianidin of this Pesticidal combination and the weight ratio of Rynaxypyr are 1 ~ 30:1 ~ 30.
4. the Synergistic insecticidal compositions of clothianidin-containing according to claim 3 and Rynaxypyr, is characterized in that the effective ingredient clothianidin of this Pesticidal combination and the weight ratio of Rynaxypyr are 1 ~ 10:1 ~ 10.
5. the Synergistic insecticidal compositions of clothianidin-containing according to claim 1 and Rynaxypyr, is characterized in that the two weight percentage in this Synergistic insecticidal compositions of clothianidin and Rynaxypyr is 2% ~ 80%.
6. the Synergistic insecticidal compositions of clothianidin-containing according to claim 5 and Rynaxypyr, is characterized in that the two weight percentage in this Synergistic insecticidal compositions of clothianidin and Rynaxypyr is 8% ~ 60%.
7. the Synergistic insecticidal compositions of clothianidin-containing according to claim 1 and Rynaxypyr, is characterized in that this Synergistic insecticidal compositions take clothianidin and Rynaxypyr and be mixed with any one formulation allowing on agricultural chemicals as main active ingredient and insecticides adjuvant, excipients.
8. the Synergistic insecticidal compositions of clothianidin-containing according to claim 7 and Rynaxypyr, is characterized in that described formulation is missible oil, wetting powder, microemulsion, aqueous emulsion, suspending agent or water dispersion granule.
9. the application in the insecticidal materials of the Synergistic insecticidal compositions of clothianidin-containing claimed in claim 1 and Rynaxypyr one or more insects in preparation control Lepidoptera, Semiptera, Hymenoptera or coleoptera.
10. application according to claim 9, the Synergistic insecticidal compositions that it is characterized in that clothianidin-containing and Rynaxypyr is prevented and treated the application in the insecticidal materials of rice hoppers, rice leaf roller or vegetables thrips in preparation.
CN201210310659.8A 2012-08-29 2012-08-29 Synergistic insect disinfestation composition containing clothianidin and chlorantraniliprole, and application thereof Pending CN103621535A (en)

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Cited By (13)

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CN104206395A (en) * 2014-09-23 2014-12-17 江苏丘陵地区镇江农业科学研究所 Compound pesticide containing chlorantraniliprole, thifluzamide and polyving akohol, preparation method and application thereof
CN104798805A (en) * 2015-03-26 2015-07-29 河北博嘉农业有限公司 Insecticide composition for corn
CN105557735A (en) * 2014-10-15 2016-05-11 陕西美邦农药有限公司 Insecticidal composition containing N-(2-tert-butylamineformoxyl-4-chloro-6-methylphenyl)-1-(3-chloropyridine-2-pyridinyl)-3-fluoro-methoxy-1H-pyrazole-5-carboxamide
CN105746567A (en) * 2016-03-31 2016-07-13 杭州宇龙化工有限公司 Agricultural insecticidal composition and application thereof
CN106386846A (en) * 2015-08-01 2017-02-15 华中农业大学 Insecticidal composition containing clothianidin, chlopyrifos and chlorantraniliprole, and preparation method thereof
CN109006830A (en) * 2018-08-16 2018-12-18 江苏明德立达作物科技有限公司 A kind of granular insecticide and preparation method thereof
CN111226920A (en) * 2020-04-13 2020-06-05 河南小龙人农业科技有限公司 Insecticidal granule containing chlorantraniliprole and clothianidin
CN112273379A (en) * 2020-10-30 2021-01-29 中诚国联(河南)生物科技有限公司 Preparation method of slow-release fertilizer granules containing chlorantraniliprole and clothianidin
CN112471157A (en) * 2020-11-27 2021-03-12 山东仕邦农化有限公司 7% Chlorantrodia, clothianidin and pyrazole seed treatment suspending agent
CN112956480A (en) * 2021-02-04 2021-06-15 四川眉山凯尔化工有限公司 Pesticide raw material formula
CN113207897A (en) * 2021-05-10 2021-08-06 河南农王实业有限公司 Insecticide composition containing metalaxyl-M and application thereof
CN113480358A (en) * 2021-07-20 2021-10-08 河北禾润生物科技有限公司 Pesticide-fertilizer composition and application thereof
CN114698643A (en) * 2022-03-23 2022-07-05 河南农王实业有限公司 Agricultural composition containing clothianidin

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CN102273440A (en) * 2011-09-13 2011-12-14 广西田园生化股份有限公司 Ultralow volume liquid containing clothianidin

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CN102273440A (en) * 2011-09-13 2011-12-14 广西田园生化股份有限公司 Ultralow volume liquid containing clothianidin

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104206395A (en) * 2014-09-23 2014-12-17 江苏丘陵地区镇江农业科学研究所 Compound pesticide containing chlorantraniliprole, thifluzamide and polyving akohol, preparation method and application thereof
CN105557735A (en) * 2014-10-15 2016-05-11 陕西美邦农药有限公司 Insecticidal composition containing N-(2-tert-butylamineformoxyl-4-chloro-6-methylphenyl)-1-(3-chloropyridine-2-pyridinyl)-3-fluoro-methoxy-1H-pyrazole-5-carboxamide
CN104798805A (en) * 2015-03-26 2015-07-29 河北博嘉农业有限公司 Insecticide composition for corn
CN106386846A (en) * 2015-08-01 2017-02-15 华中农业大学 Insecticidal composition containing clothianidin, chlopyrifos and chlorantraniliprole, and preparation method thereof
CN105746567A (en) * 2016-03-31 2016-07-13 杭州宇龙化工有限公司 Agricultural insecticidal composition and application thereof
CN105746567B (en) * 2016-03-31 2018-03-02 杭州宇龙化工有限公司 A kind of agricultural pesticide composition and application thereof
CN109006830A (en) * 2018-08-16 2018-12-18 江苏明德立达作物科技有限公司 A kind of granular insecticide and preparation method thereof
CN111226920A (en) * 2020-04-13 2020-06-05 河南小龙人农业科技有限公司 Insecticidal granule containing chlorantraniliprole and clothianidin
CN112273379A (en) * 2020-10-30 2021-01-29 中诚国联(河南)生物科技有限公司 Preparation method of slow-release fertilizer granules containing chlorantraniliprole and clothianidin
CN112471157A (en) * 2020-11-27 2021-03-12 山东仕邦农化有限公司 7% Chlorantrodia, clothianidin and pyrazole seed treatment suspending agent
CN112956480A (en) * 2021-02-04 2021-06-15 四川眉山凯尔化工有限公司 Pesticide raw material formula
CN113207897A (en) * 2021-05-10 2021-08-06 河南农王实业有限公司 Insecticide composition containing metalaxyl-M and application thereof
CN113480358A (en) * 2021-07-20 2021-10-08 河北禾润生物科技有限公司 Pesticide-fertilizer composition and application thereof
CN114698643A (en) * 2022-03-23 2022-07-05 河南农王实业有限公司 Agricultural composition containing clothianidin

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Application publication date: 20140312