CN1836513A - Mixed insecticide composition containing fipronil - Google Patents
Mixed insecticide composition containing fipronil Download PDFInfo
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- CN1836513A CN1836513A CN 200510059055 CN200510059055A CN1836513A CN 1836513 A CN1836513 A CN 1836513A CN 200510059055 CN200510059055 CN 200510059055 CN 200510059055 A CN200510059055 A CN 200510059055A CN 1836513 A CN1836513 A CN 1836513A
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Abstract
The re-compounded pesticide composition includes fipronil in the weight ratio to other component of 0.02-50, and at least one of the following pesticides: lambda-cyhalothrin, fenpropathrin, cycloprothrin, esfenvalerate, etofenprox, etc. It may have functional assistant, diluent or carrier added to compound into oil emulsion, soluble liquid, super low capacity sprayed agent, water emulsion, microemulsion or other preparation forms. It has wide pesticidal spectrum, high activity, low cost, less resistance and other features, and may be applied in preventing and controlling pests of rice, vegetable, cotton, corn, fruit tree, tobacco and other crops.
Description
Technical field
The present invention relates to contain the complex insecticidal composition of fluorine worm nitrile, and the preparation of the various formulations of said composition and application technology.Particularly, the present invention relates to fluorine worm nitrile and at least a insecticide that is selected from pyrethroid, organic phosphates, carbamates and pyridines carries out composite Pesticidal combination.
Background technology
The emphasis that the resistance problem of insecticide has become agricultural chemicals circle plant protection circle in recent years to pay close attention to.According to interrelated data, the pyrethroid insecticides resistance development is very fast, and wherein cotton bollworm has reached 228.2 times to the resistance of sumicidin, and Biphenthrin is minimum, also has more than 10 times.Other agricultural chemicals also all produce resistance to some extent because of using all the year round.
In contrast, at present also being in the fluorine worm nitrile in the stage of applying is a kind of new drug, it is wide spectrum, the efficient pesticides of at first being developed by French Luo Na-Rhone-Poulenc, chemical name is (R, S)-and 5-amino-1-(2,6-dichloromethyl phenyl)-4-trifluoromethanesulpacidc acidc benzene pyridine-3-nitrile, general Fipronil by name, commodity are called Regent (sharp strength spy), are a kind of Phenylpyrazole insecticides.External commodity preparation has 5%regent suspending agent, 0.3%regent granule, 5%regent seed dressing and 80%regent water dispersible granules etc.The Pesticidal combination of Deng Ji fluorine-containing worm nitrile has 10.33% fluorine nitrile phonamiphos granule (LS20004) at home, 50% chlorophos fluorine nitrile missible oil (LS20010664), 3.5% fluorine nitrile bromo milk oil (LS20020325), 21% fluorine nitrile azoles Emulphors oil (LS20020326) (LS20020721), 36% fluorine nitrile acetyl first missible oil (LS20021611,20031597), 15% fluorine nitrile well wetting powder (LS991543).Fluorine worm nitrile and preparation thereof have tag, stomach toxicity and moderate systemic action, insecticidal spectrum is wide, be mainly used in the control of insect of various crop such as paddy rice, corn, cotton, banana, vegetables, potato, peanut, beet, tobacco, soybean, Semiptera, Lepidoptera, coleoptera, thrips insect are had high preventive effect.In addition, there is not cross resistance between fluorine worm nitrile and the most of insecticides tested, and the insecticidal activity height, the insect that organic phosphor, carbamate, pyrethroid insectide is produced resistance can effectively be controlled.Fluorine worm nitrile is called as the high-tech insecticide of a new generation in the world.Yet, rely on import because the source of fluorine worm nitrile is most, cost an arm and a leg, about 4 yuan, limited its application at home as the cost per mu of control snout moth's larva to a great extent, particularly be difficult to promote in some economically less developed regions.In addition, fluorine worm nitrile is to some pest, and is on the low side as the preventive effect to paddy stem borer.
The China's economic national conditions both be fit in order to overcome above-mentioned defective and exploitation, have high preventive effect and resist or the agricultural fungicides kind of delaying drug resistance, the researcher in this field has carried out extensive studies, particularly utilize two kinds of different insecticide compounds of mechanism of action may increase the application point of medicine to insect, thereby produce this mechanism of synergistic effect, research and develop out the composition of multiple fluorine worm nitrile and another kind of pesticide compositional, referring to Chinese patent application open source literature such as CN99114151, CN00112280, CN99114445, CN00112689, CN98115768, CN00132045, CN99126078 etc., related another kind of insecticide is the desinsection list in these documents, cartap, chlopyrifos, Hostathion, chlorophos, orthene, cyfloxylate, cis-, trans-cypermethrin, Imidacloprid, bacillus thuringiensis,Bt, rotenone, DDVP, nimbin etc.But above-mentioned these complex preparations still exist not enough on control efficiency, therefore still need to provide price cheaper and more effective product.
The present inventor finds under study for action: fluorine worm nitrile mechanism of action uniqueness, it is a GABA chloride channel inhibitor, play insecticidal action by the chloride metabolism that hinders the control of insect γ-An Jidingsuan, and pyrethroid insecticides is to act on the neurilemmal sodium-ion channel of insect, suppress the aixs cylinder conduction, kill pests.Organophosphorus insecticide is again the inhibitor of insect cholinesterase, and mechanism of action is all inequality, so this insecticides and Firponil compounded, has synergistic effect.Simultaneously, fluorine worm nitrile costs an arm and a leg, and the pyrethroid that it and mu consumption is few makes up, or makes up with low-cost organic phosphor, carbamates, all can reduce consumption, reduce cost.
For this reason, the inventor is through a large amount of research and test, filtered out with Firponil compounded after can reach synergy, doublely control, reduce fluorine worm nitrile mu consumption, reduce cost, resist pesticide resistance, delay pyrethroid, organic phosphates, carbamates and the nicotinic insecticide of purposes such as pesticide resistance, and prepare the complex insecticidal composition and the formulation thereof of fluorine worm nitrile and other insecticides, thereby the present invention has been proposed.
Summary of the invention
One of purpose of the present invention provides and a kind ofly contains fluorine worm nitrile and be selected from the Pesticidal combination of the insecticide of at least a pyrethroid, organic phosphates, carbamates and nicotinoids as active component.
Another object of the present invention is the combination with this effective active composition, is equipped with appropriate functional auxiliary agent, diluent or carrier etc. and makes operable formulation product.
Specifically, the invention provides a kind of Pesticidal combination, comprise active components A and active component B, wherein active components A is a fluorine worm nitrile, and active component B is at least a following insecticide: the pyrethroid insecticides, chlorpyrifos-methyl, Bassa, Acetamiprid and the chlorine methamidophos that are selected from gamma cyhalothrin, fenpropathrin, cycloprothrin, esfenvalerate, ether chrysanthemum ester and silafluofene; The weight ratio of active components A and active component B is 1: 50～50: 1.
In above-mentioned Pesticidal combination of the present invention, the chemical name of fluorine worm nitrile (Fipronil) be (R, S)-5-amino-1-(2,6-dichloromethyl phenyl)-4-trifluoromethanesulpacidc acidc benzene pyridine-3-nitrile, commodity are called Regent (sharp strength spy);
The molecular formula of gamma cyhalothrin (lambda-cyhalothrin) is C23H19O3NClF3, chemical name is alpha-cyano-3-benzyloxy phenoxy base-3-(2-chloro-3,3,3-three fluoro-1-acrylic)-2,2-dimethyl cyclopropane carboxylic acid ester consists of (Z)-(1R, 3R), S-ester and (Z)-(1S, 3S), 1: 1 mixture of R-ester;
The molecular formula of fenpropathrin (fenpropathrin) is C22H23NO3, and chemical name is alpha-cyano-3-phenoxy benzyl-2,2,3,3-tetramethyl-ring propane carbonyl acid ester;
The molecular formula of cycloprothrin (cycloprothrin) is C26H21Cl2NO4, chemical name be alpha-cyano-3 '-phenoxy benzyl (R, S)-2,2-chloro-1-(4-ethoxyphenyl)-2,2-dichloro cyclopropanecarboxylcompound;
The molecular formula of esfenvalerate (Esfenvalerate) is C25H22CLNO3, and chemical name is S-alpha-cyano-3-phenoxy benzyl (S)-2 (4-chlorphenyl)-3 Methylbutanoic acid ester;
The molecular formula of ether chrysanthemum ester (etofenprox) is C25H28O3, and chemical name is 2-(4-ethoxyl phenenyl)-2-methyl-propyl-3-benzyloxy phenoxy base ether;
The molecular formula of silafluofene (silafluofen) is C25H29FO2Si, and chemical name is (4-ethoxybenzene) [4-fluoro-(3-phenoxy group benzene) propyl group] dimethylsilane;
The molecular formula of chlorpyrifos-methyl (chlorpyrifos-methyl) is C7H7Cl3NO3PS, chemical name: O, O-dimethyl-O-(3,5, the 6-trichloro-2-pyridyl) thiophosphate;
The molecular formula of Bassa (fenobucarb) is C12H17NO2, and chemical name is 2-secondary butyl phenenyl-N-methyl carbamate;
The molecular formula of Acetamiprid (acetamiprid) is C10H11ClN4, and chemical name is E-N '-[(6-chloro-3-pyridine radicals) methyl]-N^ (2)-cyano group-N '-methylacetamide;
The chemical name of chlorine methamidophos is O, S-dimethyl (2,2,2-three chloro-1-hydroxyl-ethyls) thio-phosphamide.
The various insecticides that above-mentioned active components A and active component B can select are well known in the art, can obtain as former medicine by various commercial channel.
Separately amount of application and both portfolio ratios and synergy degree when the consumption of active components A and active component B depends on independent use in the Pesticidal combination of the present invention.The weight ratio of active components A and active component B is 1: 50～50: 1, and preferred proportion is 1: 30～30: 1, and optimal proportion is 1: 20～20: 1.
The weight content of active component in the Pesticidal combination of the present invention (A+B) accounts for 0.1% to 95% of composition total weight.
For example, can suitably in Pesticidal combination of the present invention, be added into other adjuvant components, be made into missible oil, soluble liquid, ultra low volume spraying agent, aqueous emulsion, microemulsion, suspending agent, wetting powder, water dispersible granules, dry suspending agent, granule.
In these preparations, except that active component, all contain surfactant, and also can contain thinner such as water, solvent or cosolvent according to different dosage form, and carrier (filler) etc.Add antifreeze, thickener, stabilizing agent, disintegrant, defoamer, preservative, binding agent and toner etc. in case of necessity.
Surfactant can serve as emulsifier, dispersant, wetting agent or bleeding agent.Can be nonionic with ionic, also can be two or more compound uses.Described emulsifier is selected from alkylphenol-polyethenoxy (polyoxypropylene) ether, benzylphenol APEO, phenethyl phenol polyethenoxy ether, fatty alcohol-polyoxyethylene ether, polyoxyethylene carboxylate, phenethyl phenol polyethenoxy polyethenoxy ether, castor oil ethylene oxide adduct, alkylphenol polyoxyethylene formaldehyde condensation products, and the phosphate of these compounds, alkyl benzene sulphonate (sodium salt or calcium salt) or directly use commercially available emulsifier monomer and composite product.Described dispersant; wetting agent; bleeding agent is lignosulfonates (sodium salt or calcium salts); Negel; condensation compound of methyl naphthalene sulfonic acid and formaldehyde sulphate; naphthalene sulfonic acid-formaldehyde condensation product; methanonaphthalene sodium sulfonate dibutyl naphthalene sulfonic acid-formaldehyde condensation product; N-methyl fatty acyl group sodium taurocholate; alkylphenol polyoxyethylene formaldehyde condensation products sulphate; alkylphenol polyoxyethylene formaldehyde phosphate; the withered powder of tea; saponin; lignosulfite; aliphatic alcohol sulfate; lauryl sodium sulfate; alkylbenzenesulfonate; penetrant t; bleeding agent OT; fatty acid amide-N methyl taurine sodium salt; sodium sulfate of polyethenoxy ether of fatty alcohol; draw back powder and JFC etc.; can use separately, also can compoundly use.The weight percentage of described surfactant comprise complex insecticidal composition is 1～40%.Penetrant t in the above-mentioned substance, bleeding agent OT, JFC are materials well known in the art, there is production marketing the domestic market.
Described organic solvent and cosolvent are selected from toluene, dimethylbenzene, chlorobenzene, solvent naphtha, alpha-methyl-naphthalene, turpentine oil, carrene, chloroform, methyl alcohol, ethanol, isopropyl alcohol, butanols, isoamyl alcohol, cyclohexanone, isophorone, acetophenone, ethyl acetate, butyl acetate, N, dinethylformamide, dimethyl sulfoxide (DMSO), methyl cellosolve, ethyl cellosolve etc.
Described carrier (filler) is white carbon, precipitated calcium carbonate, potter's clay, attapulgite, kaolin, diatomite, swollen ravine soil, sepiolite, zeolite, river sand, quartz sand or talcum powder, or the like, can use separately, also can two kinds or above mixing use.
Described antifreeze is: ethylene glycol, glycerine, propane diols, urea, glycerine, ether diglycol, diglycol, polyethylene glycol or isopropyl alcohol etc.
Described stabilizing agent has: antioxidant BHT, triphenyl phosphite, epoxychloropropane, tributyl phosphate, triethanolamine, diethanol amine, can use separately, also can mix use.
Described thickener has: gum Arabic, sodium carboxymethylcellulose, xanthans, Magnesiumaluminumsilicate, hydroxyethylcellulose, polyvinyl alcohol, PAA, bentonite, silicic acid, can use separately, and also can two or more mixing use.
Described disintegrant has sodium alginate, sodium carboxymethyl starch, ammonium sulfate, bentonite, urea, calcium chloride.
Described defoamer has: bubble enemy, silicone, C
8-10Fatty alcohol, C
10-20Saturated fat acids (as capric acid, stearic acid etc.) and amide-type.
Described binding agent is starch, dextrin, gum Arabic, soybean protein, gelatine, sodium sulphate, gypsum, polyvinyl alcohol, polyethylene glycol, rosin, paraffin, sodium carboxymethylcellulose, sodium silicate.Can use separately, also can two or morely use with.
Can contain toner in the preparation, inorganic pigment iron oxide for example, titanium oxide or Prussia orchid; Organic dyestuff is as A Lizhalin, azo dyes, metal phthalocyanine or kiton colors.In water-base preparation, for preventing moldy metamorphism, need add a certain amount of preservative of people, described preservative has Sodium Benzoate, polyformaldehyde, sorbitol, formalin, citric acid, to yl benzoic acid methyl esters, O-SyL sodium, 1,2-benzisothiazole-3-ketone (code name BIT).
According to the preparation type difference, the weight percentage of active component is distinguished to some extent: active component accounts for 0.1%～50% in missible oil, the soluble liquid, is preferably 1%～40%; In the ultra low volume spraying agent, active component accounts for 0.1～25%, is preferably 0.2～15% (w/w); In microemulsion, aqueous emulsion, the suspension emulsion, active component accounts for 0.5～40%, and preferable content is 5～25%; Active component accounts for 5～90% in wettable powder granula, water dispersible granules, the dried suspension emulsion, is preferably 10～80%; Directly in the granule of Shi Yonging, active component is 0.3～20%, is preferably 0.3～10%.
The processing technology of the various preparations of the present composition and equipment are known.
(1) processing of missible oil, soluble liquid, ultra low volume spraying agent:
Press formula rate, the active components A and the active component B of capacity is dissolved in the solvent, add surfactant (using after the heating for dissolving in case of necessity) and other components, mix and get final product.
Process equipment mainly is to mix still, can adopt enamel reaction still, stainless steel stirred tank, is not particularly limited.
(2) processing of microemulsion, aqueous emulsion:
Oil phase preparation: press formula rate, active components A and active component B are dissolved in solvent and the cosolvent, add surfactant, mix.
The water preparation: water-soluble component and water are mixed, and the surfactant that will be insoluble in oil phase in case of necessity adds water.
Oil phase is added aqueous phase or water is added in the oil phase, the limit edged stirs, and makes microemulsion or aqueous emulsion.
According to the kind difference, water only is a water sometimes, does not need special preparation.
Process equipment mainly is to mix still, during the preparation aqueous emulsion, must adopt even matter mixer to carry out water, oil phase mixing, and oil phase can be prepared with enamel reaction still.The available even matter mixer of the preparation of microemulsion, also available other stirring mixers.
(3) processing of suspending agent:
Press formula rate, with the active components A and the active component B of capacity, surfactant, after thickener, carrier or filler and part water mix, through high speed shear, the wet method sand milling, semi-finished product, add water after the analysis and mix to filter and get product.
Capital equipment is: batching still, colloid mill or even matter mixer, sand mill.
(4) processing of wetting powder, water dispersible granules:
Active components A and B, auxiliary agent, filler are mixed the mixed again wetting powder that gets behind comminution by gas stream in proportion.
Active components A and B, auxiliary agent and filler are mixed in proportion; through comminution by gas stream; add 15～20% water then, make the water dispersible granules product through kneading, granulation, drying, screening, maybe the powder that will pulverize water spray, granulation, dry in the fluidized granulating machine goes on foot successfully.Go out sieve behind the machine the water dispersible granules product.
Capital equipment: mixer, airslide disintegrating mill, kneader, Squeezinggranulator.Drying equipment (can be drying room, fluid-bed drying), or fluidized granulating machine, screening machine.
(5) do the processing of outstanding agent: after active components A and B, auxiliary agent, filler are mixed by proportioning, carry out the slurry that the wet method sand milling obtains,, make and do outstanding agent through mist projection granulating.
Capital equipment.Except that the suspending agent process equipment, also need autoclave pressure, sponging granulator and cleaner.
Pesticidal combination of the present invention can be used by commonsense method, as adds water spray and make cauline leaf and handle, but also root is executed.Main as on the various crop such as paddy rice, vegetables, cotton, corn, fruit tree, tobacco, soybean, potato, peanut, be used for lepidopterous insects striped rice borer, paddy stem borer, pink rice borer, rice leaf roller, corn borer, cotton bollworm, diamond-back moth, oriental tobacco budworm, Homoptera insect small brown rice planthopper, aphid, plant hopper, brown planthopper, scale insect, leafhopper, the orthopteran locust, the control of various pests such as coleopteron grub.
Embodiment
The present invention is elaborated with following specific embodiment, but the present invention only limits to these examples absolutely not.Percentage all is weight percentage in all prescriptions.
Emulsifier farming newborn 2201#, 0203B, 0201B are homemade Compositional type emulsifier kinds well known in the art, and domestic most auxiliary agents produce house all this trade mark product, and market is on sale.YUS-SC3 is the fair product of sending out chemical industry in Shanghai, and main component is the phosphoric acid salt anion surfactant, and SC-101 is the product of Nanjing rising sun chemical industry, is mainly used in the preparation of agricultural chemicals suspension agent, and market is on sale.
1. embodiment 1-7 (missible oil)
| Sequence number | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| The A+B total content | 5％ | 2.5％ | 5％ | 6％ | 10％ | 10％ | 15％ |
| A: fluorine worm nitrile | 4％ | 2％ | 4％ | 5％ | 8.5％ | 8％ | 13％ |
| B: gamma cyhalothrin | 0.5％ | 1％ | 1％ | 1.5％ | 2％ | 2％ | |
| B: silafluofene | 1％ | ||||||
| Alkyl benzene calcium sulfonate | 3.0％ | 5.0％ | |||||
| The phenethyl phenol polyethenoxy ether | 5％ | 5.0％ | 7.0％ | ||||
| The phenethyl phenol polyethenoxy ether | 3.0％ | 5.0％ | |||||
| The newborn 2201# of farming | 3％ | 5.0％ | 3.0％ | 5.0％ | |||
| Alkyl benzene calcium sulfonate (70%) | 6.0％ | ||||||
| The alkylphenol polyoxyethylene formaldehyde condensation products | 1.0％ | ||||||
| Phenethyl phenol polyethenoxy polyethenoxy ether | 8.0％ | 8.0％ | |||||
| DMSO | 2.0％ | 2.0％ | 4.0％ | ||||
| DMF | 10％ | 2.0％ | 4.0％ | ||||
| Dimethylbenzene | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% |
2. embodiment 8-16 (missible oil)
| Sequence number | 8# | 9# | 10# | 11# | 12# | 13# | 14# | 15# | 16# |
| The A+B total content | 5％ | 5％ | 10％ | 5％ | 10％ | 8％ | 10％ | 5％ | 10％ |
| A: fluorine worm nitrile | 2.5％ | 2.5％ | 4.0％ | 2.5％ | 4.0％ | 3.0％ | 4.0％ | 4.0％ | 8.5％ |
| B: fenpropathrin | 2.5％ | 5.0％ | 6.0％ | ||||||
| B: cycloprothrin | 2.5％ | 6.0％ | |||||||
| B: ether chrysanthemum ester | 5.0％ | 6.0％ | |||||||
| B: esfenvalerate | 1.0％ | 1.5％ | |||||||
| Alkyl benzene calcium sulfonate | 5.0％ | 5.0％ | 5.0％ | 6.0％ | |||||
| Alkyl benzene calcium sulfonate (70%) | 4.0％ | 2.0％ | 4.0％ | ||||||
| The phenethyl phenol polyethenoxy ether | 8.0％ | 8.0％ | 8.0％ | ||||||
| The phenethyl phenol polyethenoxy ether | 8.0％ | 8.0％ | |||||||
| Phenethyl phenol polyethenoxy polyethenoxy ether | 8.0％ | 4.0％ | 8.0％ | 9.0％ | |||||
| The newborn 2201# of farming | 7.0％ | 8.0％ | 7.0％ | ||||||
| Polyoxyethylene nonylphenol ether | 2.0％ | 2.0％ | |||||||
| Cyclohexanone | 5.0％ | 10.0％ | |||||||
| Ethyl acetate | 10.0％ | ||||||||
| Dimethylbenzene | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% |
3. embodiment 17-24 (missible oil)
| Sequence number | 17# | 18# | 19# | 20# | 21# | 22# | 23# | 24# |
| The A+B total content | 30％ | 50％ | 25％ | 40％ | 30％ | 50％ | 4％ | 9％ |
| A: fluorine worm nitrile | 1.50％ | 3.0％ | 2.0％ | 4.0％ | 4.0％ | 5.0％ | 3.0％ | 7.5％ |
| B: chlorine methamidophos | 28.50％ | 47.0％ | ||||||
| B: chlorpyrifos-methyl | 23.0％ | 36.0％ | ||||||
| B: Bassa | 26.0％ | 45.0％ | ||||||
| B: Acetamiprid | 1.0％ | 1.5％ | ||||||
| Alkyl benzene calcium sulfonate | 2.0％ | 5.0％ | 5.0％ | 4.0％ | ||||
| The phenethyl phenol polyethenoxy ether | 8.0％ | |||||||
| Phenethyl phenol polyethenoxy polyethenoxy ether | 10.0％ | 10.0％ | 10.0％ | |||||
| 0201B | 4.0％ | 3.0％ | ||||||
| 0203B | 6.0％ | 7.0％ | ||||||
| Methyl alcohol | 5.0 | 5.0％ | 10.0％ | |||||
| Carrene | 5.0 | 10％ | 5.0％ | 5.0％ | ||||
| Ethyl acetate | 5.0％ | 10％ | 15.0％ | |||||
| Dimethylbenzene | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% |
4. embodiment 25-33 (microemulsion)
| Sequence number | 25# | 26# | 27# | 28# | 29# | 30# | 31# | 32# | 33# |
| The A+B total content | 3％ | 5％ | 10％ | 10％ | 5％ | 10％ | 6％ | 10％ | 5％ |
| A: fluorine worm nitrile | 2.3％ | 4.0％ | 8.5％ | 4.0％ | 2.5％ | 4.0％ | 3.0％ | 4.0％ | 4.0％ |
| B: gamma cyhalothrin | 0.7％ | 1.0％ | 1.5％ | ||||||
| B: fenpropathrin | 6.0％ | ||||||||
| B: cycloprothrin | 2.5％ | 6.0％ | |||||||
| B: ether chrysanthemum ester | 3.0％ | 6.0％ | |||||||
| B: esfenvalerate | 1.0％ | ||||||||
| Methyl alcohol | 5.0％ | 5.0％ | 5.0％ | ||||||
| Cyclohexanone | 10.0％ | 10.0％ | 15.0％ | 10.0％ | 5.0％ | 10.0％ | |||
| DMF | 15.0％ | 5.0％ | 10.0％ | 8.0％ | 10.0％ | 15.0％ | |||
| Cyclohexanol | 5.0％ | 5.0％ | |||||||
| Ethylene glycol | 5.0％ | 5.0％ | 5.0％ | 10.0％ | |||||
| Glycerine | 5.0％ | 10.0％ | 5.0％ | 5.0％ | |||||
| Phenethyl phenol polyoxydivinyl ether | 10.0％ | 10.0％ | 10.0％ | 10.0％ | 5.0％ | ||||
| Alkyl benzene calcium sulfonate | 2.0％ | 3.0％ | 3.0％ | 5.0％ | |||||
| Phenethyl phenol polyethenoxy polyethenoxy ether | 12.0％ | 15.0％ | 15.0％ | 5.0％ | 20.0％ | 5.0％ | |||
| The alkylphenol polyoxyethylene formaldehyde condensation products | 10.0％ | 8.0％ | 5.0％ | 5.0％ | 5.0％ | ||||
| Water | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% |
5. embodiment 34-39 (microemulsion)
| Sequence number | 34# | 35# | 36# | 37# | 38# | 39# |
| The A+B total content | 5％ | 8％ | 20％ | 15％ | 30％ | 15％ |
| A: fluorine worm nitrile | 4.0％ | 6.0％ | 2.0％ | 2.5％ | 3.0％ | 4.0％ |
| B: silafluofene | 1.0％ | 2.0％ | ||||
| B: chlorpyrifos-methyl | 18.0％ | |||||
| B: Bassa | 12.5％ | 27.0％ | ||||
| B: Acetamiprid | 1.0％ | |||||
| Cyclohexanone | 10.0％ | 15.0％ | 10.0％ | 10.0％ | ||
| DMF | 15.0％ | 1.5％ | ||||
| Cellosolve | 5.0％ | 10.0％ | ||||
| Propane diols | 5.0％ | 5.0％ | 5.0％ | |||
| Glycerine | 5.0％ | 5.0％ | 10.0％ | |||
| The newborn 2201# of farming | 5.0％ | 10.0％ | 5.0％ | |||
| Phenethyl phenol polyethenoxy polyethenoxy ether | 10.0％ | 15.0％ | 5.0％ | 15.0％ | 10.0％ | |
| The phenethyl phenol polyethenoxy ether | 15.0％ | 5.0％ |
| Alkyl benzene calcium sulfonate | 5.0％ | 5.0％ | 5.0％ | |||
| Water | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% |
6. embodiment 40-48 (aqueous emulsion)
| Sequence number | 40# | 41# | 42# | 43# | 44# | 45# | 46# | 47# | 48# |
| The A+B total content | 3％ | 5％ | 10％ | 10％ | 5％ | 10％ | 10％ | 5％ | 5％ |
| A: fluorine worm nitrile | 4.0％ | 8.5％ | 13.0％ | 4.0％ | 3.0％ | 4.0％ | 5.0％ | 2.0％ | 4.0％ |
| B: gamma cyhalothrin | 1.0％ | 1.5％ | 2.0％ | ||||||
| B: fenpropathrin | 6.0％ | ||||||||
| B: cycloprothrin | 2.0％ | 6.0％ | |||||||
| B: ether chrysanthemum ester | 5.0％ | 3.0％ | |||||||
| B: esfenvalerate | 1.0％ | ||||||||
| Alkyl phenol polyoxy alkene polyethenoxy ether | 1.0％ | 2.0％ | 5.0％ | 6.0％ | 5.0％ | 3.0％ | |||
| The phenyl phenol APEO | 7.0％ | 3.0％ | 2.0％ | 3.0％ | 4.0％ | ||||
| Castor oil polyoxyethylene ether | 4.0％ | 7.0％ | 2.0％ | 10.0％ | 3.0％ | 2.0％ | 6.0％ | ||
| Calcium dodecyl benzene sulfonate | 3.0％ | 1.0％ | |||||||
| Dimethylbenzene | 10.0％ | 15.0％ | 15.0％ | 10.0％ | |||||
| Alpha-methyl-naphthalene | 20.0％ | 15.0％ | |||||||
| Toluene | 15.0％ | 10.0％ | 10.0％ | ||||||
| Ethylene glycol | 5.0％ | 5.0％ | 5.0％ | 5.0％ | |||||
| Glycerine | 5.0％ | 5.0％ | 5.0％ | 5.0％ | |||||
| Urea | 2.0％ | 2.0％ | |||||||
| Water | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% |
7. embodiment 49-55 (aqueous emulsion)
| Sequence number | 49# | 50# | 51# | 52# | 53# | 54# | 55# |
| The A+B total content | 10％ | 18％ | 30％ | 20％ | 40％ | 5％ | 10％ |
| A: fluorine worm nitrile | 8％ | 15％ | 3％ | 2％ | 5％ | 4％ | 7.5％ |
| B: silafluofene | 2％ | 3％ | |||||
| B: chlorpyrifos-methyl | 27％ | ||||||
| B: Bassa | 18％ | 35％ | |||||
| B: Acetamiprid | 1％ | 2.5％ | |||||
| The phenethyl phenol polyethenoxy ether | 2％ | 5％ | |||||
| Alkylphenol polyoxyethylene | 2％ | 5％ | 5％ | 5％ | |||
| Castor oil polyoxyethylene ether | 5％ | 6％ | 5％ | 10％ | |||
| Alkyl phenol polyoxy alkene polyethenoxy ether | 5％ | 3％ | 5％ | ||||
| Calcium dodecyl benzene sulfonate | 2％ | 1％ | |||||
| Dimethylbenzene | 10％ | 15 | 10％ | 15％ |
| Toluene | 15％ | 15％ | 20％ | ||||
| Ethylene glycol | 5％ | 5％ | 10％ | 10％ | |||
| Propane diols | 5％ | 5％ | 5％ | ||||
| Water | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% |
8. embodiment 56-64 (suspending agent)
| Sequence number | 56# | 57# | 58# | 59# | 60# | 61# | 62# | 63# | 64# |
| The A+B total content | 5％ | 10％ | 20％ | 15％ | 10％ | 20％ | 10％ | 5％ | 10％ |
| A: fluorine worm nitrile | 4％ | 7.5％ | 17.5％ | 6％ | 3％ | 8％ | 4％ | 4％ | 7.5％ |
| The B gamma cyhalothrin | 1％ | 2.5％ | 2.5％ | ||||||
| B: fenpropathrin | 9％ | ||||||||
| B: cycloprothrin | 7％ | 12％ | |||||||
| B: ether chrysanthemum ester | 6％ | ||||||||
| B: esfenvalerate | 1％ | 2.5％ | |||||||
| Calcium lignosulfonate | 3％ | 5％ | 2％ | ||||||
| Sodium lignin sulfonate | 4％ | 2％ | 1％ | ||||||
| Methyl naphthalene sulfonate formaldehyde condensate | 1％ | 3％ | 1％ | 2％ | |||||
| The withered powder of tea | 1％ | 2％ | 2％ | 2％ | |||||
| The nekal formaldehyde condensation products | |||||||||
| YUS-SC3 | 3％ | 4％ | 1％ | ||||||
| SC-101 | 1％ | 3％ | 3％ | ||||||
| White carbon black | 2％ | 1％ | 1％ | 3％ | |||||
| Bentonite | 2％ | 1％ | 2％ | ||||||
| Xanthans | 0.5％ | 0.3％ | 0.5％ | 0.5％ | |||||
| Magnesiumaluminumsilicate | 1％ | 2％ | 1％ | 2％ | 1％ | 1％ | 2％ | ||
| Ethylene glycol | 5％ | 5％ | 5％ | 5％ | |||||
| Glycerine | 5％ | 5％ | 5％ | 5％ | 5％ | ||||
| Sodium Benzoate | 1％ | 0.5％ | 1％ | 1％ | |||||
| Organic silicone | A little | A little | A little | A little | A little | A little | A little | A little | A little |
| Water | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% |
9. embodiment 65-76 (wetting powder, water dispersible granules)
| Formulation | Wetting powder | Water dispersible granules | ||||||||||
| Sequence number | 65# | 66# | 67# | 68# | 69# | 70# | 71# | 72# | 73# | 74# | 75# | 76# |
| The A+B total content | 10％ | 25％ | 20％ | 10％ | 30％ | 50％ | 80％ | 70％ | 75％ | 80％ | 60％ | 60％ |
| A: fluorine worm nitrile | 8％ | 21％ | 8％ | 8％ | 4％ | 5％ | 70％ | 60％ | 35％ | 65％ | 55％ | 10％ |
| B: silafluofene | 5％ | |||||||||||
| B: gamma cyhalothrin | 2％ | 4％ | 10％ | 10％ | ||||||||
| B: cycloprothrin | 12％ | 40％ | ||||||||||
| B: esfenvalerate | 2％ | 15％ | ||||||||||
| B: chlorine methamidophos | 26％ | |||||||||||
| B: Bassa | 45％ | 50％ | ||||||||||
| Calcium lignosulfonate | 5％ | 5％ | 5％ | 10％ | 5％ | 4％ | 5％ | |||||
| Negel | 5％ | 4％ | 5％ | 10％ | 4％ | 6％ | 10％ | 2％ | ||||
| The withered powder of tea | 8％ | 7％ | 5％ | 5％ | 5％ | 5％ | 5％ | 10％ | ||||
| Lauryl sodium sulfate | 0.5％ | 0.5％ | 1.0％ | 2％ | 2％ | 1％ | 1％ | |||||
| Draw back powder | 0.6％ | 0.4％ | 1.0％ | 1.0％ | 1.0％ | |||||||
| Sodium carboxymethyl starch | 2％ | 2％ | ||||||||||
| Sodium alginate | 2％ | 3％ | 3％ | |||||||||
| Magnesiumaluminumsilicate | 2％ | 2％ | ||||||||||
| Sodium carboxymethylcellulose | 1％ | 1％ | ||||||||||
| N-methyl acetyl sodium taurocholate | 4％ | 4％ | ||||||||||
| White carbon | 5％ | 5％ | 5％ | 2％ | 2％ | |||||||
| Bentonite | 10％ | 15％ | 10％ | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | |||
| Attapulgite | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% | Supply 100% |
10. embodiment 77-88 (soluble liquid, ultra low volume spraying agent)
| Formulation | Soluble liquid | The ultra low volume spraying agent | ||||||||||
| Sequence number | 77# | 78# | 79# | 80# | 81# | 82# | 83# | 84# | 85# | 86# | 87# | 88# |
| The A+B total content | 10％ | 15％ | 10％ | 5％ | 6％ | 30％ | 0.3％ | 0.6％ | 0.4％ | 0.3％ | 0.3％ | 5％ |
| A: fluorine worm nitrile | 8％ | 5％ | 8％ | 4％ | 4％ | 2％ | 0.2％ | 0.3％ | 0.3％ | 0.2％ | 0.2％ | 0.2％ |
| B: gamma cyhalothrin | 2％ | 0.1％ | ||||||||||
| B: cycloprothrin | 10％ | 0.3％ | ||||||||||
| B: esfenvalerate | 2％ | 0.1％ | ||||||||||
| B: silafluofene | 1％ | 0.1％ | ||||||||||
| B: Acetamiprid | 2％ | 0.1％ | ||||||||||
| B: Bassa | 28％ | 4.8％ | ||||||||||
| The phenethyl phenol polyethenoxy ether | 15％ | 15％ | 10％ | 10％ | 10％ | 5％ | 5％ | 5％ | ||||
| Alkylphenol polyoxyethylene | 10％ | 10％ | 5％ | 3％ | ||||||||
| Fatty alcohol-polyoxyethylene ether | 5％ | 10％ | 10％ | 3％ | 5％ | |||||||
| The alkylphenol polyoxyethylene formaldehyde condensation products | 10 | 1％ | 3％ | 2％ | ||||||||
| The newborn 2201# of farming | 15％ | 6％ | 10％ | |||||||||
| Cyclohexanone | 15％ | 10％ | 15％ | 2％ | 3％ | |||||||
| Ethylene glycol-ether | 20％ | 10％ | 10％ | 5％ | 10％ | |||||||
| Isophorone | 10％ | 5％ | 2％ | 5％ | ||||||||
| Solvent naphtha | 20％ | Supply 100% | ||||||||||
| Diesel oil | Supply 100% | Supply 100% | Supply 100% | |||||||||
| DMF | Supply 100% | Supply 100% | Supply 100% | 20％ | Supply 100% | 5％ | 5％ | |||||
| Methyl alcohol | Supply 100% | Supply 100% | ||||||||||
| Methyl naphthalene | 10％ | 10％ | 5％ | |||||||||
| Turpentine oil | Supply 100% | Supply 100% |
Measured the test of pesticide effectiveness result of composition pesticide of the present invention by following embodiment.
Fluorine worm nitrile is a kind of Phenylpyrazole insecticides, the desinsection wide spectrum, to insect based on stomach poison function, have concurrently and tag and certain systemic function, its insecticidal mechanism is to hinder the chloride metabolism of insect γ-An Jidingsuan control, therefore various pests such as Lepidoptera, coleoptera, orthoptera there is very high insecticidal activity, crop is not had poisoning.This medicament can impose on soil, but also foliar spray.And pyrethroid insecticides such as gamma cyhalothrin belong to never poison, and knockdown effect is more outstanding.Has repellent, knock down and kills three kinds of not same-actions.Fluorine worm nitrile and pyrethroid insecticides are composite, are difficult for producing cross resistance.Through the field application test, has the notable synergistic effect.And characteristics such as consumption is few, control efficiency is obvious, safety height.Concrete test is as follows:
Embodiment 89: the composite control efficiency to the lepidopterous insects striped rice borer of fluorine worm nitrile and pyrethroid insecticides cycloprothrin
The test site is located at Anhui and grand-mother's bridge town, county Sheng Wang village one paddy field, and kind is excellent No. 6 hybrid rice of gold, and test is established 8 processed group, repeated for four times, and district's group is arranged at random.Spraying time is in August, 2003, every 667m
2Convert 50 kilograms of the water yields, spray medicine with manual sprayer heading stage in the paddy rice cut, controlling object is a second generation striped rice borer.Adopt five point samplings to investigate withered calculation in 10 days after the dispenser, calculate control efficiency.Investigate 10 clumps at every.
| The medicament title | Consumption (gai/hm 2) | Withered heart rate (%) | Preventive effect (%) |
| 5% fluorine worm nitrile SC | 22.5 | 6.2 | 67.2 |
| 5% fluorine worm nitrile SC | 30 | 5.1 | 73.0 |
| 10% cycloprothrin SC | 60 | 8.6 | 54.5 |
| 10% cycloprothrin SC | 100 | 5.6 | 70.3 |
| 6% (fluorine worm nitrile+cycloprothrin) ME | 15+30 | 2.4 | 87.3 |
| 6% (fluorine worm nitrile+cycloprothrin) ME | 30+60 | 1.9 | 89.9 |
| 6% (fluorine worm nitrile+cycloprothrin) ME | 30+75 | 1.6 | 91.5 |
| Clear water | 18.9 |
Embodiment 90: fluorine worm nitrile and pyrethroid insecticides high-efficient lambda-cyhalothrin compound are to the control efficiency of lepidopterous insects diamond-back moth
Test fluorine worm nitrile and high-efficient lambda-cyhalothrin compound control efficiency to Wild cabbage type Chinese cabbage diamond-back moth in Anhui Province and test in a county level in September, 2003.Eight processing are established in test altogether, four repetitions, and district's group is arranged at random.The dispenser phase is a 1-3 prelarva in age, every 667m
2Convert 60 kilograms of the water yields, spray medicine with manual sprayer.10 strains are investigated in every sub-district.7 days investigation prevention effects behind the medicine.
| The medicament title | Consumption (gai/hm 2) | The insect population rate (%) that goes down | Proofread and correct preventive effect (%) |
| 5% fluorine worm nitrile SC | 15 | 73.2 | 84.3 |
| 5% fluorine worm nitrile SC | 22.5 | 79.3 | 87.9 |
| 2.5% gamma cyhalothrin EC (weight/capacity) | 10 | 59.7 | 76.8 |
| 2.5% gamma cyhalothrin EC (weight/capacity) | 15 | 68.1 | 81.3 |
| 10% (fluorine worm nitrile+gamma cyhalothrin) SC | 7.5+5 | 65.5 | 79.8 |
| 10% (fluorine worm nitrile+gamma cyhalothrin) SC | 10+10 | 81.9 | 89.4 |
| 10% (fluorine worm nitrile+gamma cyhalothrin) SC | 20+15 | 94.8 | 97.0 |
| Clear water | -70.8 |
Embodiment 91: the composite control efficiency to lepidopterous insects cotton cotton bollworm of fluorine worm nitrile and organophosphorus insecticides chlorpyrifos-methyl
In August, 2003 is in Wangjiang County, Anhui Province test fluorine worm nitrile and the composite control efficiency to the cotton cotton bollworm of chlorpyrifos-methyl.Seven processing are established in test altogether, four repetitions, and district's group is arranged at random.The dispenser phase is the cotton bollworm occurance peak, sprayed before 3 ages.Every 667m
2Convert 50 kilograms of the water yields, spray medicine with manual sprayer.10 strains are investigated in every sub-district.Investigation in 7 days behind the medicine.
| The medicament title | Consumption (gai/hm 2) | The insect population rate (%) that goes down | Proofread and correct preventive effect (%) |
| 5% fluorine worm nitrile SC | 25 | 69.8 | 82.0 |
| 5% fluorine worm nitrile SC | 35 | 75.4 | 85.3 |
| 40% chlorpyrifos-methyl EC | 400 | 73.5 | 84.2 |
| 40% chlorpyrifos-methyl EC | 600 | 79.2 | 87.6 |
| 20% (fluorine worm nitrile+chlorpyrifos-methyl) ME | 25+225 | 85.5 | 91.3 |
| 20% (fluorine worm nitrile+chlorpyrifos-methyl) ME | 35+315 | 89.3 | 93.6 |
| Clear water | -68.0 |
Embodiment 92: the composite control efficiency to the Homoptera insect wheat aphid of fluorine worm nitrile and nicotinic insecticide Acetamiprid
In August, 2004 is in Maanshan City, Anhui Province Yushan District good mountain area test fluorine worm nitrile and the composite control efficiency to wheat aphid of Acetamiprid.Wheat is in the fringe phase during test, and aphid is medium occurrence degree.Soil fertility is general, and soil property belongs to yellow soil.Seven processing are established in test, four repetitions, and district's group is arranged at random.Every 667m
2Convert 60 kilograms of the water yields, the manual sprayer spraying.5 samplings of every sub-district diagonal are taked in field investigation, get 10 fringes at every, decide fringe.7 days preventive effects are as follows behind the medicine:
| The medicament title | Consumption (gai/hm 2) | The insect population rate (%) that goes down | Proofread and correct preventive effect (%) |
| 5% fluorine worm nitrile SC | 25 | 83.2 | 90.5 |
| 5% fluorine worm nitrile SC | 30 | 85.6 | 91.9 |
| 3% Acetamiprid EC | 9 | 89.5 | 94.1 |
| 3% Acetamiprid EC | 13.5 | 91.6 | 95.3 |
| 10% (fluorine worm nitrile+Acetamiprid) EC | 20+10 | 97.4 | 98.6 |
| 10% (fluorine worm nitrile+Acetamiprid) EC | 27+13.5 | 100 | 100.0 |
| Clear water | -77.5 |
Claims (12)
1. complex insecticidal composition, comprise active components A and active component B, wherein active components A is a fluorine worm nitrile, active component B is at least a following insecticide: the pyrethroid insecticides that is selected from gamma cyhalothrin, fenpropathrin, cycloprothrin, esfenvalerate, ether chrysanthemum ester and silafluofene, chlorpyrifos-methyl, Bassa, Acetamiprid and chlorine methamidophos; The weight ratio of active components A and active component B is 1: 50～50: 1.
2. complex insecticidal composition according to claim 1 is characterized in that, the weight ratio of described active components A and active component B is 1: 30～30: 1.
3. complex insecticidal composition according to claim 1 is characterized in that, the weight ratio of described active components A and active component B is 1: 20～20: 1.
4. according to any described complex insecticidal composition of claim 1～3, it is characterized in that, also comprise insecticides adjuvant in the described complex insecticidal composition, the weight percentage of described active components A+B accounts for 0.1～95% of complex insecticidal composition gross weight, and described insecticides adjuvant accounts for 5～99.9% of complex insecticidal composition gross weight.
5. complex insecticidal composition according to claim 4, it is characterized in that, described insecticides adjuvant is a surfactant, perhaps is surfactant and at least a auxiliary agent that is selected from filler, water, organic solvent or cosolvent, antifreeze, thickener, stabilizing agent, disintegrant, defoamer, preservative, binding agent, the toner.
6. according to the described complex insecticidal composition of claim 5, it is characterized in that: described surfactant is selected from following one or more: alkylphenol polyoxyethylene, alkyl phenol polyethenoxy ether, benzylphenol APEO, phenethyl phenol polyethenoxy ether, fatty alcohol-polyoxyethylene ether, polyoxyethylene carboxylate, phenethyl phenol polyethenoxy polyethenoxy ether, castor oil ethylene oxide adduct, alkylphenol polyoxyethylene formaldehyde condensation products, and the phosphate of these compounds, alkylbenzenesulfonate; Lignosulfonates, Negel, condensation compound of methyl naphthalene sulfonic acid and formaldehyde sulphate, naphthalene sulfonic acid-formaldehyde condensation product, methanonaphthalene sodium sulfonate dibutyl naphthalene sulfonic acid-formaldehyde condensation product, N-methyl fatty acyl group sodium taurocholate, alkylphenol polyoxyethylene formaldehyde condensation products sulphate, alkylphenol polyoxyethylene formaldehyde phosphate, the withered powder of tea, saponin, lignosulfite, aliphatic alcohol sulfate, lauryl sodium sulfate, alkylbenzenesulfonate, penetrant t, bleeding agent OT, fatty acid amide-N methyl taurine sodium salt, sodium sulfate of polyethenoxy ether of fatty alcohol, draw back powder and JFC; The weight percentage of described surfactant in complex insecticidal composition is 1～40%.
7. complex insecticidal composition according to claim 4, it is characterized in that it is one of following that the formulation of described complex insecticidal composition is selected from: missible oil, soluble liquid, ultra low volume spraying agent, aqueous emulsion, microemulsion, suspending agent, wetting powder, water dispersible granules, dry suspending agent and granule.
8. complex insecticidal composition according to claim 7 is characterized in that, the formulation of described complex insecticidal composition is missible oil or soluble liquid, and in this complex insecticidal composition, the weight percentage of active components A+B is 0.1%～50%.
9. complex insecticidal composition according to claim 7 is characterized in that, the formulation of described complex insecticidal composition is the ultra low volume spraying agent, and in this complex insecticidal composition, the weight percentage of active components A+B is 0.1～25%.
10. complex insecticidal composition according to claim 7 is characterized in that, the formulation of described complex insecticidal composition is microemulsion, aqueous emulsion or suspension emulsion, and in this complex insecticidal composition, the weight percentage of active components A+B is 0.5～40%.
11. complex insecticidal composition according to claim 7, it is characterized in that, the formulation of described complex insecticidal composition is wettable powder granula, water dispersible granules or dried suspension emulsion, and in this complex insecticidal composition, the weight percentage of active components A+B is 5～90%.
12. complex insecticidal composition according to claim 7 is characterized in that, the formulation of described complex insecticidal composition is the granule that directly uses, and in this complex insecticidal composition, the weight percentage of active components A+B is 0.3～20%.
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| CNA2008100087461A Division CN101292665A (en) | 2005-03-21 | 2005-03-21 | Complex insecticidal composition of fipronil and acetamiprid |
| CNA2008100087476A Division CN101292666A (en) | 2005-03-21 | 2005-03-21 | Complex insecticidal composition of fipronil and methyl chlorpyrifos, chlorine methamidophos |
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| CN106797948A (en) * | 2015-11-26 | 2017-06-06 | 陕西韦尔奇作物保护有限公司 | A kind of Pesticidal combination of the nitrile of worm containing acetyl and gamma cyhalothrin |
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