CN104872170B - Gamma cyhalothrin emamectin-benzoate aqueous microsphere shot agent - Google Patents
Gamma cyhalothrin emamectin-benzoate aqueous microsphere shot agent Download PDFInfo
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- CN104872170B CN104872170B CN201510317988.9A CN201510317988A CN104872170B CN 104872170 B CN104872170 B CN 104872170B CN 201510317988 A CN201510317988 A CN 201510317988A CN 104872170 B CN104872170 B CN 104872170B
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- emamectin
- benzoate
- gamma cyhalothrin
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- microballoon
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Abstract
The present invention relates to a kind of gamma cyhalothrin/emamectin-benzoate aqueous microsphere shot agent.The water dispersible granules are mainly made up of gamma cyhalothrin and emamectin-benzoate 50% ~ 80%, wetting agent 1% ~ 5%, dispersant 3% ~ 10%, disintegrant 1% ~ 5%, binding agent 0.5% ~ 4%, defoamer 0% ~ 3%, balance carriers.The aqueous microsphere shot agent can be applied to cauliflower, wild cabbage, Chinese cabbage, cotton, soybean etc., there is remarkable result to the preventing and treating of diamondback moth, beet armyworm, cabbage caterpillar etc., while having the advantages that strong drug action, had good sustained release effect, low photodissociation, extension lasting period, low toxicity, storage convenient transportation, environmental protection.
Description
Technical field
The invention belongs to the preparation field of pesticidal preparations, and in particular to a kind of gamma cyhalothrin/methylamino Avermectin
Plain benzoate aqueous microsphere shot agent.
Background technology
Gamma cyhalothrin, English name is λ-Cyhalothrin, and chemical name is 3- (2- chloro- 3,3,3- trifluoropropyls
Alkenyl) -2,2- dimethyl cyclopropane carboxylic acid's alpha-cyano -3- phenoxybenzyl esters.Gamma cyhalothrin belongs to never poison, effect
In the periphery of insect and central nervous system, it can suppress the conduction at insect neural axon position, change neu to ion
Permeability, cause insect paralysis by stimulating nerve cell to cause reignition, the characteristics of with knocking down fast.Efficient chlorine fluorine
The main effect model of Cyano chrysanthemate is to tag and stomach toxicity, and bioactivity is high, and insecticidal range is wide, to Lepidoptera, Semiptera, elytrum
Mesh, Thysanoptera, Hymenoptera, Orthoptera, the various pests of Diptera are effective.
Emamectin-benzoate(Emamectin benzoate), English name is Emamectin benzoate, generally simple
Referred to as emamectin benzoate.It is a kind of antibiotic compound obtained from AVM is chemically modified.Emamectin benzoate can increase
The unstrung effects such as strong glutamic acid, GABA (GABA), cause a large amount of Cl- Enter in cell through cell membrane, cell
Various functions reduction, and the regular event potential conductance of nervous system is destroyed, cause poisoning insect larva to be benumbed, stop
Take food.The main effect model of emamectin benzoate is stomach toxicity, while having action of contace poison, has bioactivity very high, particularly to squama
Wing mesh and the preventing and treating of Diptera class pest are splendid, such as bollworm, beet armyworm, diamondback moth, tomato hawkmoth, cabbage heart snout moth's larva, potato first
Worm, wild cabbage horizontal stripe snout moth's larva etc..Emamectin benzoate is used as biogenic pesticide, and its security is good, using universal in the production of green agricultural product.
Although gamma cyhalothrin and emamectin benzoate belong to high activity agricultural chemicals, due to Irrational Use of Drugs, two kinds of agricultures
The resistance problem of medicine is also increasingly severe, and dosage increases rapid.Gamma cyhalothrin and emamectin benzoate are multiple according to a certain percentage
With with obvious synergistic effect, so as to reduce formulation rate, and delay drug-fast generation and further development.In the market
The several gamma cyhalothrins and the complex preparation of emamectin benzoate for occurring are mainly aqueous emulsion, microemulsion, missible oil.Wherein missible oil system
Agent organic solvent content is higher, and emulsifier content is higher in aqueous emulsion and microemulsion, has larger pollution to environment, and this three
Plant formulation and be liquid preparation, not readily transportable and storage does not meet the developing direction of pesticidal preparations curable type.And these three
Dosage form product does not solve the fast shortcoming of emamectin benzoate degraded, especially emamectin benzoate easily photodissociation, if be formed without microballoon carried out
If protection, the lasting period of medicine is easily had a strong impact on because of photodissociation in field.In addition, at present other people study and apply be
Pesticide water dispersible granules or agricultural chemicals microballoon suspending agent.Water dispersible granules are that pesticide active ingredient directly is processed into water dispersible granules
(It is curable type agent type), water dispersible granules can directly use in production(Sprayed after dilute with water).But directly emamectin benzoate is had
The shortcoming that effect composition is processed into water dispersible granules is the defect that dosage form of water dispersible granule can not solve the easy photodissociation of emamectin benzoate, and if
By agricultural chemicals(Emamectin benzoate)Agricultural chemicals microballoon is prepared into if being wrapped in microballoon, the defect of the easy photodissociation of emamectin benzoate can be effectively solved;And
And agricultural chemicals(Emamectin benzoate)Microballoon also have sustained release extension drug action, but agricultural chemicals microballoon can not in production directly use, it is necessary to
It is prepared into agricultural chemicals microballoon suspending agent(It is liquid dosage form)Could directly be used on reproduction(Sprayed after dilute with water), and agricultural chemicals is micro-
Ball suspending agent(It is liquid dosage form)Not readily transportable and storage.Therefore, first dimension is solved by preparing agricultural chemicals aqueous microsphere shot agent
The easy photodissociation defect of salt, and with sustained release extension drug action, meanwhile, can be sprayed after direct dilute with water in production again and used.
The present invention is exactly the microballoon for first pesticide active ingredient being made with sustained release and being slowed down degradation(Will agricultural chemicals be wrapped in microballoon
In), then the microballoon is made the water dispersible granules of curable type again.
The content of the invention
The purpose of the present invention is directed to the deficiency of existing water dispersible granules, there is provided a kind of gamma cyhalothrin/methylamino
Abamectin benzoate aqueous microsphere shot agent.Obtained aqueous microsphere shot agent of the invention, can improve drug effect, expand desinsection
Spectrum, with slow releasing function, extension drug effect, reduce photodissociation, without organic solvent, and be curable type preparation, be readily transported storage and
Environmentally friendly low-residual.
The technical solution adopted by the present invention is as follows:
A kind of gamma cyhalothrin/emamectin-benzoate aqueous microsphere shot agent, each component quality hundred
Ratio is divided to be calculated as:Gamma cyhalothrin/emamectin-benzoate microballoon 50% ~ 80%, wetting agent 1% ~ 5%, dispersant
3% ~ 10%, disintegrant 1% ~ 5%, binding agent 0.5% ~ 4%, defoamer 0% ~ 3%, balance of carrier.
Described gamma cyhalothrin/emamectin-benzoate aqueous microsphere shot agent, each component presses matter
Amount percentages are preferably:Gamma cyhalothrin/emamectin-benzoate microballoon 60% ~ 75%, wetting agent 2% ~
4%th, dispersant 4% ~ 8%, disintegrant 2% ~ 4%, binding agent 1% ~ 2.5%, defoamer 1% ~ 2%, balance of carrier.
In described gamma cyhalothrin/emamectin-benzoate microballoon, gamma cyhalothrin and first
Amino abamectin benzoate mass ratio is 0.1 ~ 35:35 ~ 0.1, core is with wall material mass ratio:1:1~4;Emulsifier solution
Middle emulsifying agent mass-volume concentration is:5~25 g/L.
In described gamma cyhalothrin/emamectin-benzoate microballoon, gamma cyhalothrin and first
Amino abamectin benzoate mass ratio is preferably 1 ~ 30:30~1;Core is preferably with wall material mass ratio:1:2~3;Emulsifying agent
Emulsifying agent mass-volume concentration is preferably in solution:10~20 g/L.
The wetting agent is the one kind or many in lauryl sodium sulfate, pull open powder, Terwet 1004, Morwet EFW
Kind.
During the dispersant is sodium lignin sulfonate, NNO, Dispersant MF, Morwet D-425, Tersperse 2700
One or more.
The disintegrant is one or more in sodium sulphate, ammonium sulfate, sodium chloride, aluminium chloride, urea.
The binding agent is one or more in polyvinyl alcohol, polyethylene glycol, Arabic gum, carboxymethylcellulose calcium.
Described carrier is one or more in white carbon, bentonite, kaolin, diatomite.
The defoamer is one or more in DF- 66, DF- 160, DF-1561.
A kind of microballoon of gamma cyhalothrin and emamectin benzoate compounding, its preparation process is as follows:
The gamma cyhalothrin for mixing according to a certain percentage and emamectin benzoate that will be completely dissolved with organic solvent(Core)
And PLA(Wall material)Add in emulsifier aqueous solution, stirred to organic solvent after high speed shear and volatilized completely, then suction filtration, dry
It is dry, collect microsphere powder.
Described organic solvent is one or more in dichloromethane, chloroform, acetone, ether.
Described emulsifying agent is one or more in gelatin, Arabic gum, polyvinyl alcohol, sodium carboxymethylcellulose.
, to be prepared under best composition mass ratio, microballoon is theoretical to carry medicine for the gamma cyhalothrin and emamectin benzoate microballoon
Amount(Active ingredient gross mass accounts for microspheres quality percentage, is determined by core wall material ratio)It is 25.0% ~ 33.3%.
Gamma cyhalothrin and emamectin benzoate compounding aqueous microsphere shot agent preparation method are as follows:
Each composition is included by mass percentage:Gamma cyhalothrin and emamectin benzoate compounding microballoon 50% ~ 80%, wetting agent 1%
~ 5%, dispersant 5% ~ 12%, disintegrant 1% ~ 5%, binding agent 0.5% ~ 4%, defoamer 0% ~ 3%, balance of carrier;By all the components
Crushed with airslide disintegrating mill after fully mixing, granulated using rotary table granulation method, by drying.Screening obtains aqueous microsphere shot
Agent.
The present invention has advantages below compared with the prior art:
(1)Compounding microballoon is configured to water dispersible granules by the present invention, and organic solvent has been free of in preparation, is being produced and is being made
Small to environment and operator's harm during, security is good, and due to being that molecule preparation is readily transported and stores;
(2)Compounding microballoon is configured to water dispersible granules by the present invention, is not only overcome and is directly added emamectin benzoate-chlorfenapyr active ingredient
Work causes the unabiding defect of pesticide efficacy into the easy photodissociation of emamectin benzoate during water dispersible granules, and emamectin benzoate compounding microballoon can not be
The shortcoming directly used in production;A kind of aqueous microsphere shot for using that can be sprayed after direct dilute with water in production has been obtained
Agent, possesses prominent progress;
(3)Obtained aqueous microsphere shot footpath of the invention, it is identical with emamectin benzoate compounding mass ratio in gamma cyhalothrin
In the case of, compared with commercially available first ties up chlorine fluorine aqueous emulsion high, compounding moisture is calculated according to the abundant co-toxicity coefficient methods of Sun Yun
Shot agent is far longer than 120 relative to the co-toxicity coefficient of aqueous emulsion, with obvious synergistic effect.
Specific embodiment
By embodiment, the present invention will be further described, but the present invention is not limited by following examples.
Embodiment 1
Gamma cyhalothrin and emamectin benzoate total content are the water dispersible granules of 5wt%
By gamma cyhalothrin and emamectin benzoate according to mass ratio 4:1 mixing, it is 1 to dissolve mass ratio with dichloromethane:3
Core and wall material, core wall material solution are added in the polyvinyl alcohol water solution of the g/L of mass-volume concentration 10, after high speed shear
Stirring to organic solvent volatilizees completely, then suction filtration, drying, collects microsphere powder.Microballoon drugloading rate is 23.5% after measured, i.e.,
About 23.5 grams of active ingredient gross mass in per hectogram microballoon, condition is different with batch prepare the actual drugloading rate of thus obtained microsphere have it is micro-
Small difference.
Weigh raw material components(Mass percent meter):Gamma cyhalothrin and emamectin benzoate compounding microballoon about 21.3%, wetting
Agent Terwet 1,004 2%, dispersant Tersperse 2,700 4%, disintegrant sodium sulphate 3%, binding agent polyvinyl alcohol 1.5%, disappear
Infusion DF-66 1%, kaolin polishing.Crushed with airslide disintegrating mill after all the components are fully mixed, made using rotary table granulation method
Grain, by drying.Screening obtains aqueous microsphere shot agent.Using leaching leaf feeding method pair:1) the 5% of the present embodiment efficient chlorine fluorine cyanogen
Chrysanthemum ester emamectin benzoate aqueous microsphere shot agent(Gamma cyhalothrin and emamectin benzoate mass ratio 4:1), 2) commercially available 5% first dimension
Chlorine fluorine aqueous emulsion high(Gamma cyhalothrin and emamectin benzoate mass ratio 4:1), 3) commercially available 5.0% gamma cyhalothrin micro emulsion
4 kinds of preparations such as agent, 1.5% 4) commercially available emamectin-benzoate missible oil have carried out Toxicity Determination, according to 48h
The death rate afterwards calculates LC50Value, LC of four kinds of preparations to diamondback moth50Respectively 18.22,17.96,160.0,6.345 mg/L,
Be can be seen that from toxicity test result:In the case of gamma cyhalothrin and emamectin benzoate compound quality than identical, the present invention
Formulation products and commercially available 5% first to tie up chlorine fluorine aqueous emulsion high close to the indoor virulence of diamondback moth, according to the abundant co-toxicity coefficients of Sun Yun
It is 150.3 that method is calculated compound water dispersible granule relative to two kinds of co-toxicity coefficients of single dose, with obvious synergistic effect.
Embodiment 2
Gamma cyhalothrin and emamectin benzoate total content are the water dispersible granules of 10wt%
By gamma cyhalothrin and emamectin benzoate according to mass ratio 10:1 mixing, it is 1 to dissolve mass ratio with chloroform:3
Core and wall material, core wall material solution is added in the Arabic gum aqueous solution of the g/L of mass-volume concentration 10, high speed shear
After stir to organic solvent and volatilize completely, microsphere powder is collected in then suction filtration, drying.Microballoon drugloading rate is about after measured
23.0%, i.e., 23.0 grams of active ingredient gross mass in every hectogram microballoon, condition is different with batch to prepare the actual drugloading rate of thus obtained microsphere
Have minute differences.
Weigh raw material components(Mass percent meter):Gamma cyhalothrin and emamectin benzoate compounding microballoon 43.5%, wetting agent
Lauryl sodium sulfate 3%, dispersant NNO 6%, disintegrant ammonium sulfate 3%, binding agent Arabic gum 2%, defoamer DF-160
1.5%th, diatomite polishing.Crushed with airslide disintegrating mill after all the components are fully mixed, granulated using rotary table granulation method, passed through
Dry.Screening obtains aqueous microsphere shot agent.Toxicity Determination is carried out to the present embodiment using leaching leaf feeding method, this reality is measured
Apply LC of the example to diamondback moth50It is 32.55 mg/L, co-toxicity coefficient is 153.5, with notable synergistic effect.
Embodiment 3
Gamma cyhalothrin and emamectin benzoate total content are the water dispersible granules of 15wt%
By gamma cyhalothrin and emamectin benzoate according to mass ratio 2:3 mixing, are 1 with ether dissolution mass ratio:3 core
And wall material, core wall material solution is added to the gelatin-gum arabic of the g/L of mass-volume concentration 10(Mass ratio 1:1)The aqueous solution
In, stirred to organic solvent after high speed shear and volatilized completely, then suction filtration, drying, collect microsphere powder.Microballoon carries medicine after measured
Amount about 23.3%, i.e., 23.3 grams of active ingredient gross mass in every hectogram microballoon, condition is different with batch to prepare thus obtained microsphere reality
Drugloading rate has minute differences.
Weigh raw material components(Mass percent meter):Gamma cyhalothrin and emamectin benzoate compounding microballoon 64.4%, wetting agent
Morwet EFW 4%, dispersant Morwet D-425 8%, disintegrant urea 3%, binding agent Arabic gum 2%, defoamer DF-
1561 2%, white carbon polishing.Crushed with airslide disintegrating mill after all the components are fully mixed, granulated using rotary table granulation method, warp
Cross and dry.Screening obtains aqueous microsphere shot agent.Toxicity Determination is carried out to the present embodiment using leaching leaf feeding method, this is measured
LC of the embodiment to diamondback moth50It is 8.02 mg/L, co-toxicity coefficient is 128.5, with notable synergistic effect.
Embodiment 4
Gamma cyhalothrin and emamectin benzoate total content are the water dispersible granules of 20wt%
By gamma cyhalothrin and emamectin benzoate according to mass ratio 5:1 mixing, it is 1 to dissolve mass ratio with dichloromethane:2
Core and wall material, core wall material solution is added in the aqueous gelatin solution of the g/L of mass-volume concentration 20, is stirred after high speed shear
Volatilized completely to organic solvent, then suction filtration, drying, collect microsphere powder.Microballoon drugloading rate is about 31.5% after measured, i.e., often
31.5 grams of active ingredient gross mass in hectogram microballoon, the condition actual drugloading rate of thus obtained microsphere for preparing different with batch has small difference
Not.
Weigh raw material components(Mass percent meter):Gamma cyhalothrin and emamectin benzoate compounding microballoon 63.5%, wetting agent
Pull open powder 4%, dispersant sodium lignin sulfonate-NNO(Mass ratio 1:1)7%th, disintegrant aluminium chloride 3%, binding agent carboxymethyl cellulose
Element 1.5%, defoamer DF- 160 2%, bentonite polishing.Crushed with airslide disintegrating mill after all the components are fully mixed, used
Rotary table granulation method is granulated, by drying.Screening obtains aqueous microsphere shot agent.Room is carried out to the present embodiment using leaching leaf feeding method
Interior toxicity test, measures LC of the present embodiment to diamondback moth50It is 22.07 mg/L, co-toxicity coefficient is 143.9, with notable synergistic
Effect.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (1)
1. a kind of gamma cyhalothrin/emamectin-benzoate aqueous microsphere shot agent, it is characterised in that:Microballoon
Each component mass percent is calculated as in water dispersible granules:Gamma cyhalothrin and emamectin benzoate compounding microballoon 43.5%, wetting agent ten
Sodium dialkyl sulfate 3%, dispersant NNO 6%, disintegrant ammonium sulfate 3%, binding agent Arabic gum 2%, defoamer DF-160
1.5%th, balance of diatomite;In described gamma cyhalothrin/emamectin-benzoate microballoon, efficient chlorine fluorine
Cyano chrysanthemate and emamectin-benzoate mass ratio are 10:1, core is with wall material mass ratio:1:3;Emulsifier solution
Middle emulsifying agent mass-volume concentration is:10 g/L.
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CN111011368A (en) * | 2019-11-11 | 2020-04-17 | 南京华洲药业有限公司 | Composite insecticidal and acaricidal nano-water agent containing efficient cyhalothrin and emamectin benzoate and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101720777A (en) * | 2009-12-06 | 2010-06-09 | 山西科锋农业科技有限公司 | Emamectin benzoate and efficient cyfluthrin pesticide mixture preparation |
CN102696640A (en) * | 2012-06-15 | 2012-10-03 | 福建农林大学 | Emamectin benzoate polylactic acid microsphere suspension and preparation method thereof |
CN103798232A (en) * | 2012-11-14 | 2014-05-21 | 中国农业科学院植物保护研究所 | Emamectin benzoate microsphere and preparation method thereof |
CN103828801A (en) * | 2014-01-15 | 2014-06-04 | 福建农林大学 | Spinosyn/emamectin benzoate microsphere and preparation method thereof |
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2015
- 2015-06-11 CN CN201510317988.9A patent/CN104872170B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101720777A (en) * | 2009-12-06 | 2010-06-09 | 山西科锋农业科技有限公司 | Emamectin benzoate and efficient cyfluthrin pesticide mixture preparation |
CN102696640A (en) * | 2012-06-15 | 2012-10-03 | 福建农林大学 | Emamectin benzoate polylactic acid microsphere suspension and preparation method thereof |
CN103798232A (en) * | 2012-11-14 | 2014-05-21 | 中国农业科学院植物保护研究所 | Emamectin benzoate microsphere and preparation method thereof |
CN103828801A (en) * | 2014-01-15 | 2014-06-04 | 福建农林大学 | Spinosyn/emamectin benzoate microsphere and preparation method thereof |
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