Summary of the invention
The object of the invention is: for insecticide resistance problem in actual applications, the insecticide that filters out two kinds of different desinsection principles carries out composite, to improve insecticide control effect, reduce formulation rate, expand the scope of application.
For achieving the above object, the invention provides one group of Pesticidal combination, said composition comprises two kinds of effective constituents A and B, and active component A is fipronil bisamide, and active component B is the one being selected from gamma cyhalothrin, carbosulfan, orthene.Inventor finds by test, and above-mentioned Pesticidal combination synergy is obvious, and amount of application reduces, and can reduce use cost.Contain component A different from the compound structure type of B component, mechanism of action is different, and both are composite can expand insecticidal spectrum, and can delay to a certain extent the generation of insect-resistant, and between component A and B component without cross resistance.
The invention provides the preparation method who comprises two kinds of effective constituents A and B Pesticidal combination and the application that prevents and treats crop pests at agriculture field.
It is characterized in that described composition comprises A and two kinds of active components of B, the weight ratio between two components is 1:60~60:1, preferred weight ratio 1:40~40:1.
This Pesticidal combination also contains normally used auxiliary agent in pesticidal preparations, solvent, carrier auxiliary element to make the various formulations that are adapted at using in agricultural.
Available known method can be prepared into various formulations by composition of the present invention, can, by active ingredient and auxiliary agent, as solvent, solid carrier, can evenly mix together with surfactant, grinds while needs, is prepared into needed formulation.
Suitable auxiliary agent can be solid or liquid, and they are conventional material in formulation process normally, for example mineral matter natural or regeneration, solvent, dispersant, wetting agent, adhesive, thickener, adhesive or fertilizer.
Above-mentioned solvent can be selected from aromatic hydrocarbon, preferably containing 8-12 carbon atom, as the benzene of xylene mixture or replacement, phthalate, as Dibutyl phthalate or phthalandione two sad, fat hydrocarbon, as thiacyclohexane or paraffin, ether and the ester of alcohol and ethylene glycol and they, as ethanol, ethylene glycol, ethylene glycol monomethyl; Ketone, as cyclohexanone, the solvent of strong polarity, as METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO) or dimethyl formamide, and vegetable oil or vegetable oil, as soybean oil.
Above-mentioned solid carrier, as for example, for pulvis with dispersible the normally natural minerals filler of agent, talcum, kaolin, montmorillonite or atlapulgite.In order to manage the physical property of composition, also can add polymolecularity silicic acid or polymolecularity adsorpting polymerization thing carrier, for example granular absorption carrier or non-absorption carrier, suitable granular absorption carrier is porous type, as float stone, bentonite or bentonite; Suitable non-absorption carrier is as calcite or sand.In addition, can use the granular material of being prefabricated into of a large amount of inorganic in nature or organic nature as carrier, particularly dolomite.
According to the chemical property of the active ingredient in composition of the present invention, suitable surfactant is lignin sulfonic acid, naphthalene sulfonic acids, phenolsulfonic acid, alkali salt or amine salt, alkylaryl sulfonates, alkyl sulfate, alkylsulfonate, aliphatic alcohol sulfate, fatty acid and sulphated fatty alcohol glycol ether, also has the condensation product of sulfonated naphthalene and naphthalene derivatives and formaldehyde, the condensation product of naphthalene or naphthalene sulfonic acids and phenol and formaldehyde, NONIN HS 240, ethoxylation isooctylphenol, octyl phenol, nonyl phenol, alkylaryl polyglycol ether, tributyl benzene polyglycol ether, three stearyl phenyl polyglycol ethers, alkyl aryl polyether alcohol, ethoxylated castor oil, polyoxyethylene alkyl ether, ethylene oxide condensation product, ethoxylation polyoxypropylene, lauric acid polyglycol ether acetal, sorbitol ester, lignin sulfite waste liquor and methylcellulose.
The application process of the present composition comprises the acrial part for plant growth by composition of the present invention, comprises leaf portion or blade face.Can be by the growth place of plant, as rice field, soak with the liquid preparation of composition, or composition is applied in soil with solid form, as with particle form (soil application), composition can be by soil in plant root enters plant corpus (systemic action).
These compositions can only comprise active component and use, also can mix together with additive, therefore composition of the present invention can be prepared into various formulations, for example wetting powder, suspending agent, oil-suspending agent, water dispersible granules, aqueous emulsion, microemulsion.According to the character of these compositions and use object and the ambient conditions that composition will reach, can select composition with spraying, atomizing, dust, broadcast sowing or sprinkle the method for watering etc. and so on and use.
In composition of the present invention, two kinds of active ingredients show as synergistic effect, more more remarkable than the independent activity of individualized compound.Synergistic effect shows as and allows that amount of application reduces, wider insecticidal spectrum, instant effect, more lasting control efficiency, by only once or minority use several times better Control pests and widened the possible administration interval time.These characteristics are very important to solving the ubiquitous resistance problem of insecticide single dose.
Pesticidal combination of the present invention is applied on the various crops such as paddy rice, wheat, cotton, corn, soybean, vegetables, fruit tree.It is applied to the insects such as control Lepidoptera, Homoptera, coleoptera, diptera, especially remarkable to snout moth's larva, rice leaf roller, diamond-back moth, cabbage caterpillar, rice fulgorid, aphid, prodenia litura, Bemisia tabaci texts.
Other feature main manifestations that this product shows is: 1, can be applicable to spraying, seed dressing, mixed soil and the various possible insecticide-applying way such as broadcast sowing; 2, two of this composition single dose chemical constitutions are widely different, and the mechanism of action is completely different, does not have cross resistance, can delay two single doses and use separately the resistance problem producing; 3, composition mixture of the present invention has obvious synergistic effect, good to crop safety, preventive effect.Through evidence, present composition stable chemical nature, synergy is remarkable, and controlling object is shown to obvious synergy and complementation.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention, all under design prerequisite of the present invention, preparation method's of the present invention simple modifications is all belonged to protection scope of the present invention within.
In all formulas of following examples, percentage is all weight percentage.The processing technology of the various preparations of the present composition is prior art, can change to some extent according to different situations.
One, formulation Preparation Example
(1) processing of water dispersible granules and embodiment
By the one in active component fipronil bisamide and gamma cyhalothrin, carbosulfan, orthene, mix in the ratio of formula with auxiliary agent and filler, become wetting powder through air-flow crushing, add again a certain amount of water mixing extruder grain, after drying screening, make water dispersible granules product.
Embodiment 1:61% fipronil bisamide gamma cyhalothrin water dispersible granules (60:1)
Fipronil bisamide 60%, gamma cyhalothrin 1%, Negel 4%, dodecyl sodium sulfate 3%, ammonium sulfate 3%, precipitated calcium carbonate complements to 100%.
Embodiment 2:58% fipronil bisamide gamma cyhalothrin water dispersible granules (1:57)
Fipronil bisamide 1%, gamma cyhalothrin 57%, sodium lignin sulfonate 5%, methyl naphthalene sulfonate formaldehyde condensate 7%, lauryl sodium sulfate 3%, diatomite complements to 100%.
Embodiment 3:56% fipronil bisamide carbosulfan water dispersible granules (55:1)
Fipronil bisamide 55%, carbosulfan 1%, sodium lignin sulfonate 6%, dodecyl sodium sulfate 3%, xanthans 1%, sodium carboxymethyl starch 1%, attapulgite complements to 100%.
Embodiment 4:61% fipronil bisamide carbosulfan water dispersible granules (1:60)
Fipronil bisamide 1%, carbosulfan 60%, ammonium sulfate 1%, sodium alginate 2%, methyl naphthalene sulfonate formaldehyde condensate 1%, organic silicone 1%, bentonite complements to 100%.
Embodiment 5:60% fipronil bisamide orthene water dispersible granules (59:1)
Fipronil bisamide 59%, orthene 1%, dodecyl sodium sulfate 2%, Negel 2%, ammonium sulfate 3%, precipitated calcium carbonate complements to 100%.
Embodiment 6:55% fipronil bisamide orthene water dispersible granules (1:54)
Fipronil bisamide 1%, orthene 54%, methyl naphthalene sulfonate formaldehyde condensate 5%, sodium lignin sulfonate 4%, lauryl sodium sulfate 3%, diatomite complements to 100%.
(2) processing of suspending agent and embodiment
By the one in active component fipronil bisamide and gamma cyhalothrin, carbosulfan, orthene, mix in the ratio of formula with each component such as dispersant, wetting agent, thickener and water, after sand milling and/or high speed shear, obtain semi-finished product, after analysis, add water mix filter get product.
Embodiment 7:31% fipronil bisamide gamma cyhalothrin suspending agent (30:1)
Fipronil bisamide 30%, gamma cyhalothrin 1%, sodium lignin sulfonate 7%, xanthans 0.8%, bentonite 3%, Magnesiumaluminumsilicate 1%, ethylene glycol 4%, water complements to 100%.
Embodiment 8:21% fipronil bisamide gamma cyhalothrin suspending agent (1:20)
Fipronil bisamide 1%, gamma cyhalothrin 20%, methyl naphthalene sulfonate formaldehyde condensate 6%, bentonite 4%, glycerine 5%, water complements to 100%.
Embodiment 9:33% fipronil bisamide carbosulfan suspending agent (10:1)
Fipronil bisamide 30%, carbosulfan 3%, aliphatic alcohol polyoxyvinethene phosphate 7%, white carbon 3%, glycerine 6%, Sodium Benzoate 2%, water complements to 100%.
Embodiment 10:33% fipronil bisamide carbosulfan suspending agent (1:10)
Fipronil bisamide 3%, carbosulfan 30%, sodium lignin sulfonate 7%, white carbon 3%, ethylene glycol 6%, xanthans 1%, water complements to 100%.
Embodiment 11:40% fipronil bisamide orthene suspending agent (1:1)
Fipronil bisamide 20%, orthene 20%, aliphatic alcohol polyoxyvinethene phosphate 7%, white carbon 3%, glycerine 6%, Sodium Benzoate 2%, water complements to 100%.
Embodiment 12:30% fipronil bisamide orthene suspending agent (2:1)
Fipronil bisamide 20%, orthene 10%, sodium lignin sulfonate 7%, white carbon 3%, ethylene glycol 6%, xanthans 1%, water complements to 100%.
(3) processing of wetting powder and embodiment
Active component fipronil bisamide A is fully mixed with various auxiliary agents and filler etc. in proportion with the one in B active component gamma cyhalothrin, carbosulfan, orthene, after ultra-fine pulverizer disintegrating, make wetting powder.
Embodiment 13:90% fipronil bisamide gamma cyhalothrin wetting powder (2:88)
Fipronil bisamide 2%, gamma cyhalothrin 88%, calcium lignosulfonate 2%, neopelex 1%, bentonite 2%, attapulgite complements to 100%.
Embodiment 14:88% fipronil bisamide gamma cyhalothrin wetting powder (86:2)
Fipronil bisamide 86%, gamma cyhalothrin 2%, alkyl polyoxy ethyl ether sulfonate 1%, pulls open powder 2%, bentonite 1.5%, white carbon 2%, diatomite complements to 100%.
Embodiment 15:88% fipronil bisamide carbosulfan wetting powder (86:2)
Fipronil bisamide 86%, carbosulfan 2%, NONIN HS 240 2%, sodium lignin sulfonate 6%, white carbon 4%, diatomite complements to 100%.
Embodiment 16:70% fipronil bisamide carbosulfan wetting powder (1:1)
Fipronil bisamide 35%, carbosulfan 35%, calcium lignosulfonate 7%, white carbon 5%, neopelex 3%, attapulgite complements to 100%.
Embodiment 17:85% fipronil bisamide orthene wetting powder (83:2)
Fipronil bisamide 83%, orthene 2%, NONIN HS 240 1%, sodium lignin sulfonate 2%, white carbon 3%, diatomite complements to 100%.
Embodiment 18:78% fipronil bisamide orthene wetting powder (2:76)
Fipronil bisamide 2%, orthene 76%, neopelex 3%, white carbon 5%, calcium lignosulfonate 7%, attapulgite complements to 100%.
(4) processing of microemulsion and embodiment
After one in active component fipronil bisamide A and active component B gamma cyhalothrin, carbosulfan, orthene is dissolved completely in solvent, stir, add emulsifier, builder and antifreeze simultaneously, after above-mentioned system mixes, again water is slowly added in above-mentioned mixed liquor, after fully stirring, can be made into the microemulsion of different content.
Embodiment 19:20% fipronil bisamide gamma cyhalothrin microemulsion (1:1)
Fipronil bisamide 10%, gamma cyhalothrin 10%, acetone 15%, compound sodium nitrophenolate 0.5%, alkyl polyoxyethylene ether and polyoxyethylene nonylphenol ether 5%, propane diols 1%, urea 2%, water complements to 100%.
Embodiment 20:21% fipronil bisamide gamma cyhalothrin microemulsion (20:1)
Fipronil bisamide 20%, gamma cyhalothrin 1%, polyoxyethylene carboxylate and phenethyl phenol polyethenoxy ether 4%, glycerine 2%, methyl alcohol 11%, azone 1%, water complements to 100%.
Embodiment 21:19% fipronil bisamide carbosulfan microemulsion (1:18)
Fipronil bisamide 1%, carbosulfan 18%, alkylbenzenesulfonate and alkylnaphthalene sulfonate 16%, thiophene ketone 1%, ethyl acetate 16%, propane diols 1%, water complements to 100%.
Embodiment 22:21% fipronil bisamide carbosulfan microemulsion (20:1)
Fipronil bisamide 20%, carbosulfan 1%, calcium dodecyl benzene sulfonate 8%, thiophene ketone 0.5%, sorbic acid 14%, polyethylene glycol 3%, water complements to 100%.
Embodiment 23:18% fipronil bisamide orthene microemulsion (1:2)
Fipronil bisamide 6%, orthene 12%, acetone 15%, compound sodium nitrophenolate 0.5%, alkyl polyoxyethylene ether and polyoxyethylene nonylphenol ether 5%, propane diols 1%, urea 2%, water complements to 100%.
Embodiment 24:21% fipronil bisamide orthene microemulsion (20:1)
Fipronil bisamide 20%, orthene 1%, polyoxyethylene carboxylate and phenethyl phenol polyethenoxy ether 4%, glycerine 2%, methyl alcohol 11%, azone 1%, water complements to 100%.
(5) processing of aqueous emulsion and embodiment
In emulsifying kettle, active component fipronil bisamide A is mixed with solvent, auxiliary agent with the one in B active component gamma cyhalothrin, carbosulfan, orthene under mechanical agitation, then drop into emulsifier and stabilizing agent stirs, finally add water, under the rotating speed of 100-12000 rev/min, stir 10-30 minute, make it to become the product of even emulsus.
Embodiment 25:22% fipronil bisamide gamma cyhalothrin aqueous emulsion (10:1)
Fipronil bisamide 20%, gamma cyhalothrin 2%, N-repefral 4%, nonyl phenol benzene oxygen vinethene 3%, 2,6-di-tert-butyl-4-methy phenol 2%, ethylene glycol 3%, polyvinyl alcohol 1%, Sodium Benzoate 1%, silicone defoaming agent 0.8%, water complements to 100%.
Embodiment 26:44% fipronil bisamide gamma cyhalothrin aqueous emulsion (1:10)
Fipronil bisamide 4%, gamma cyhalothrin 40%, butylated hydroxy anisole 4%, poly-isosuccinic acid acid anhydride-ethylene glycol copolymer 3%, propane diols 2%, xanthans 3%, polyvinyl alcohol 1%, silicone defoaming agent 1.2%, water complements to 100%.
Embodiment 27:25% fipronil bisamide aqueous carbosulfan emulsion (4:1)
Fipronil bisamide 20%, carbosulfan 5%, polyoxyethylene block copolymer 3%, propane diols 1%, xanthans 2%, poly-isosuccinic acid acid anhydride-ethylene glycol copolymer 3%, silicone defoaming agent 1.2%, water complements to 100%.
Embodiment 28:31% fipronil bisamide aqueous carbosulfan emulsion (1:30)
Fipronil bisamide 1%, carbosulfan 30%, N-dodecylpyrrolidone 2%, castor oil polyoxyethylene ether 1%, glycerine 3%, polyvinyl alcohol 1.2%, Sodium Benzoate 1%, isooctanol 2%, water complements to 100%.
Embodiment 29:21% fipronil bisamide orthene aqueous emulsion (1:20)
Fipronil bisamide 1%, orthene 20%, 2,6-di-tert-butyl-4-methy phenol 1%, nonyl phenol benzene oxygen vinethene 2%, ethylene glycol 3%, Sodium Benzoate 1%, N-repefral 2%, polyvinyl alcohol 1%, silicone defoaming agent 1%, water complements to 100%.
Embodiment 30:22% fipronil bisamide orthene aqueous emulsion (1:10)
Fipronil bisamide 2%, orthene 20%, propane diols 2%, butylated hydroxy anisole 3%, poly-isosuccinic acid acid anhydride-ethylene glycol copolymer 3%, xanthans 3%, polyvinyl alcohol 1%, silicone defoaming agent 1.2%, water complements to 100%.
(6) processing of oil-suspending agent and embodiment
Each components such as active component fipronil bisamide A and a kind of and dispersant, stabilizing agent, defoamer and solvent in B active component gamma cyhalothrin, carbosulfan, orthene are mixed in the ratio of formula, put into after the grinding of sand milling still, send in mixer for well-distribution and mix and get product.
Embodiment 31:31% fipronil bisamide gamma cyhalothrin oil-suspending agent 1:30
Fipronil bisamide 1%, gamma cyhalothrin 30%, sodium lignin sulfonate 8%, bentonite 4%, xanthans 1%, silicone defoaming agent 2%, soybean oil complements to 100%.
Embodiment 32:45% fipronil bisamide gamma cyhalothrin oil-suspending agent (1:2)
Fipronil bisamide 15%, gamma cyhalothrin 30%, pulls open powder 8%, bentonite 5%, organic silicone 2%, machine oil complements to 100%.
Embodiment 33:30% fipronil bisamide carbosulfan oil-suspending agent (2:1)
Fipronil bisamide 20%, carbosulfan 10%, naphthalene sulfonic acid-formaldehyde condensation product 8%, diatomite 5%, aluminium-magnesium silicate 2%, dichloroethane complements to 100%.
Embodiment 34:41% fipronil bisamide carbosulfan oil-suspending agent (1:40)
Fipronil bisamide 1%, carbosulfan 40%, sodium lignin sulfonate 11%, aerosil 4%, aluminium-magnesium silicate 2%, castor oil complements to 100%.
Embodiment 35:22% fipronil bisamide orthene oil-suspending agent (1:10)
Fipronil bisamide 2%, orthene 20%, silicone defoaming agent 1%, bentonite 3%, sodium lignin sulfonate 7%, xanthans 1%, soybean oil complements to 100%.
Embodiment 36:22% fipronil bisamide orthene oil-suspending agent (10:1)
Fipronil bisamide 20%, orthene 2%, bentonite 3%, pulls open powder 7%, organic silicone 2%, machine oil complements to 100%.
Two, drug effect demonstration test
(1) indoor virulence determination of activity
Embodiment 1 fipronil bisamide and high-efficient lambda-cyhalothrin compound are to diamond-back moth toxicity test test on wild cabbage
1.1 reagent agent
The former medicine of fipronil bisamide, the former medicine of gamma cyhalothrin, fipronil bisamide and gamma cyhalothrin different proportion mixed agent
1.2 for examination worm source
Diamondback moth larvae
1.3 assay method
Be cut into diameter 5cm without the cabbage leaves of using insecticide, reagent agent is evenly sprayed on dish leaf positive and negative with sprayer respectively, dries rear immigration culture dish, access 2 instar larvaes, and 50 of every processing, repeat 4 times, and contrast with clear water.Under 25 DEG C of room temperatures, 75%-85% relative moisture, raise, change every 12h the new cabbage leaves that chemicals treatment is crossed, after 48h, check death toll, calculate lethality, and proofread and correct with the lethality of contrast, try to achieve the lethal concentration of 50 with this.
1.4 data analysis
By active ingredient percentage fipronil bisamide: gamma cyhalothrin proportioning is: 60:1,40:1,20:1,10:1,1:1,1:10,1:20,1:40,1:60 test, calculate the toxicity index level co-toxicity coefficient (CTC) of medicament according to the abundant method of Sun Yun.
Actual measurement toxicity index (ATI)=(standard medicament LC50/ reagent agent LC50) * 100
The percentage composition of B in percentage composition+B medicament toxicity index * mixture of A in theoretical toxicity index (TTI)=A medicament toxicity index * mixture
Co-toxicity coefficient (CTC)=[theoretical toxicity index of mixture actual measurement toxicity index (ATI)/mixture (TTI)] * 100
CTC≤80, composition performance is antagonism, 80 < CTC < 120, composition performance is summation action, CTC >=120, composition performance is synergistic effect.
Table 1 fipronil bisamide, gamma cyhalothrin and different proportioning thereof are composite to the interpretation of result of wild cabbage diamond-back moth toxicity test
Result (table 1) shows, fipronil bisamide and high-efficient lambda-cyhalothrin compound significantly improve the control efficiency of wild cabbage diamond-back moth, illustrates that the two compositely has significant preventive and therapeutic effect to diamond-back moth.Especially fipronil bisamide and gamma cyhalothrin proportioning are between 1:40~40:1, and the co-toxicity coefficient of fipronil bisamide and gamma cyhalothrin is all more than 130, and synergistic effect is obvious.
Embodiment 2 fipronil bisamides and carbosulfan are composite to be tested rice-stem borer toxicity test
Table 2 fipronil bisamide, carbosulfan and different proportioning thereof are composite to the interpretation of result of striped rice borer toxicity test
Result (table 2) shows, the composite control efficiency to striped rice borer of fipronil bisamide and carbosulfan significantly improves, illustrate that the two compositely has significant preventive and therapeutic effect to striped rice borer, especially fipronil bisamide and carbosulfan proportioning are between 1:40~40:1, the co-toxicity coefficient of fipronil bisamide and carbosulfan is all more than 130, and synergistic effect is obvious.
3, fipronil bisamide and orthene are composite tests cotton aphid toxicity test
Table 3 fipronil bisamide, orthene and different proportioning thereof are composite to the interpretation of result of aphid toxicity test
Result (table 3) shows, the composite control efficiency to aphid of fipronil bisamide and orthene significantly improves, illustrate that the two compositely has significant synergies to anti-eliminating aphis, especially fipronil bisamide and orthene proportioning are between 1:40~40:1, the co-toxicity coefficient of fipronil bisamide and orthene is all more than 130, and synergistic effect is obvious.
(2) field efficacy demonstration test
Test method: carry out immediately dispenser at the insect pest initial stage, before dispenser, check borer population alive on each community, within before dispenser and after dispenser 7 days, investigate borer population alive on every community, calculate insect population decline rate and control efficiency, pilot survey adopts 5 point sampling methods, every 1 strain, 5 strains of every community, each 1 of upper, middle and lower blade is got respectively in every strain, blade overturn gently, and the one-tenth borer population on statistics blade.Investigation radix before dispenser, after medicine, 7d respectively investigates insect population number, calculates insect population decline rate and control efficiency.
(1) fipronil bisamide and the field control effectiveness test of gamma cyhalothrin mixture to wild cabbage diamond-back moth
Table 4 fipronil bisamide and gamma cyhalothrin mixture are to diamond-back moth control efficiency
As can be seen from Table 4, fipronil bisamide and high-efficient lambda-cyhalothrin compound can effectively be prevented and treated wild cabbage diamond-back moth, and control efficiency is better than the preventive effect of single dose, illustrate that the two composite preventive effect to diamond-back moth has significant synergistic effect.
(2) fipronil bisamide and the field control effectiveness test of carbosulfan mixture to rice-stem borer
Table 5 fipronil bisamide and the control efficiency of carbosulfan mixture to rice-stem borer
As can be seen from Table 5, fipronil bisamide and carbosulfan are composite can effectively prevent and treat rice-stem borer, and both built agent preventive effects are all higher than single dose, illustrates that the two compositely has significant synergistic effect to control rice-stem borer.
(3) fipronil bisamide and the field control effectiveness test of orthene mixture to cotton aphid
Table 6 fipronil bisamide and the control efficiency of orthene mixture to cotton aphid
As can be seen from Table 6, fipronil bisamide and orthene are composite can effectively prevent and treat cotton aphid, and both composite preventive effects are higher than single dose, illustrates that the two compositely has significant synergistic effect to prevention and control of aphides.