Background technology
Tolfenpyrad (Tolfenpyrad), chemical name: 4-chloro-3-ethyl-1-methyl-N-{[4-(4-methylphenoxy) phenyl]-methyl }-1H pyrazoles-5-carboxylic acid amides, be the off-white color pressed powder, density (25 ℃): 1.18g/cm, vapour pressure (25 ℃):<5 * 10Pa.Solvability (25 ℃): water 0.037mg/L, n-hexane 7.41g/L, toluene 366g/L, methyl alcohol 59.6g/L.Distribution coefficient (n-octyl alcohol/water) (25 ℃): log Pow 5.61.Structural formula is:
The acute toxicity of Tolfenpyrad preparation is: rat oral LD50 102 (hero), 83 (female) mg/kg; Its mouse oral LD50104 (hero), 108 (female) mg/kg.Acute dermal toxicity is relatively low, to rat, mouse LD50 all>2000mg/kg.Lagophthalmos eyeball and skin there is moderate spread effect.
Tolfenpyrad is the novel pyrazole heterocyclic insecticidal/acaricidal agent of former Mitsubishi chemical company (its agricultural chemicals partly now belong to Japanese agricultural chemicals company) exploitation, its main mechanism is the oxidative phosphorylation that stops insect, also has ovicidal, presses down food, oviposition deterrence and bactericidal action.
Beta-cypermethrin (theta-cypermethrin), chemical name: (S)-alpha-cyano-3-phenoxy benzyl (1R, 3S)-3-(2, the 2-dichloroethylene) 2.2-dimethyl cyclopropane carboxylic acid ester and (R)-alpha-cyano-3-phenoxy benzyl (1S, 3R)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester, structural formula is:
Beta-cypermethrin belongs to third generation pyrethroid insecticides, be mainly used in the controls of the agriculture and forestry injurious insect such as field crop, economic crops, vegetables, fruit tree and the domestic hygiene insects such as vegetables, mosquito class bedbug and have that virus killing is efficient, wide spectrum, to people and animals' low toxicity, effect rapidly, the characteristics such as holding effect is long, have and tag and stomach toxicity, ovicidal, insect there are the effects such as antifeedant activity, more to light, thermally-stabilised.Resistance of rainwater washing against has special efficacy to the insect that organophosphorous pesticide has reached resistance especially.
Often there is defective in the insecticide variety that contains single component in the agricultural chemicals control of insect: use is developed immunity to drugs easily continuously, and insecticidal spectrum is narrow, can not provide comprehensive protection for crop, and peasant's drug cost is high.Being combined in to a certain extent and can overcoming to a certain extent above-mentioned shortcoming by two kinds or various active components in the coming year.Have two kinds of synergistic effect or the combination of two or more active components and be mixed, can improve preventive effect, reduce active ingredient ground dosage, save cost, slow down pest resistance occur, and can the expanding prevention spectrum, play that many worms are double to be controlled, reduce peasant's use cost.
Summary of the invention
The purpose of this invention is to provide a kind of Synergistic insecticidal compositions that contains Tolfenpyrad and beta-cypermethrin.
Another object of the present invention provides the Synergistic insecticidal compositions that contains Tolfenpyrad and beta-cypermethrin and prevents and treats application in the insecticidal materials of one or more insects in resistance Lepidoptera, Homoptera, Hymenoptera or the coleoptera in preparation.
Said composition can be used for preventing and treating the various agricultural insect, and such as vegetables diamond-back moth, cotton cotton bollworm, beet armyworm, cabbage caterpillar etc. can reach the effect that a drug is prevented and treated dissimilar insects.
The present invention adopts following technical scheme:
A kind of Synergistic insecticidal compositions that contains Tolfenpyrad and beta-cypermethrin, it is take Tolfenpyrad and beta-cypermethrin as main active ingredient, and wherein, the weight ratio of Tolfenpyrad and beta-cypermethrin is 0.1~80: 0.5~80.Be preferably 1~60: 1~70, more preferably 1~30: 1~30.The effective ingredient of above-mentioned Insecticidal combinations is present in the composition with the synergy effective dose.
At the Synergistic insecticidal compositions that contains Tolfenpyrad and beta-cypermethrin of the present invention, the two weight percentage in this Synergistic insecticidal compositions of Tolfenpyrad and beta-cypermethrin is 2%~80%, be preferably 8%~60%, optimum is 20%~40%.
The above-mentioned Synergistic insecticidal compositions that contains Tolfenpyrad and beta-cypermethrin take Tolfenpyrad and beta-cypermethrin as main active ingredient (active component) and insecticides adjuvant, excipients be mixed with any one formulation that allows on the agricultural chemicals.The preferred missible oil of formulation, wetting powder, microemulsion, aqueous emulsion, suspending agent or water dispersible granules.
Described auxiliary agent can adopt calcium dodecyl benzene sulfonate, alkylphenol polyoxyethylene, polyoxyethylene polyoxy third rare block compound (such as farming breast 33
#), polyoxyethylene nonylphenol ether etc., excipient comprises cyclohexanone, dimethylbenzene, solvent naphtha, water, antifreezing agent (such as propane diols), deionized water etc.Above auxiliary agent, excipient and the upper known auxiliary material of other agricultural can alone or and usefulness.
Application in the insecticidal materials of the above-mentioned Synergistic insecticidal compositions that contains Tolfenpyrad and beta-cypermethrin one or more insects in preparation control Lepidoptera, Homoptera, Hymenoptera or coleoptera reaches the effect that a medicine is controlled more.Especially the effect in the insecticidal materials of the cotton cotton bollworm, beet armyworm, cabbage caterpillar or the diamond-back moth that prepare the easy generation of control resistance is remarkable, and suppresses insect to the pesticide resistance generation of unitary agent (Tolfenpyrad or beta-cypermethrin).
Pesticidal combination of the present invention compared with prior art, produce following beneficial effect: (1) is compared with single dose, the said composition insect has notable synergistic, has obviously improved control efficiency; (2) one medicines are controlled more, and a dispenser can prevent and treat various pests simultaneously, reduce control recruitment cost; (3) alternative high-toxic pesticide, and significantly reduce the field dosage, effective environmental contamination reduction and residue of pesticide; (4) have concurrently quick-acting and long-acting; (5) compare with the Tolfenpyrad single dose, produce and the use cost reduction; (6) suppress insect to the resistance enhancing of agricultural chemicals.
Embodiment
Embodiments of the invention are the methods that adopt indoor bioassay and field trial to combine.First by indoor bioassay, the co-toxicity coefficient after clear and definite two kinds of medicaments are composite by a certain percentage; On this basis, carry out again field trial.
Embodiment 1:
Taking by weighing Tolfenpyrad, beta-cypermethrin, to adopt the conventional formulation method to be mixed with main active ingredient weight percentage by different proportion be 30% Tolfenpyrad beta-cypermethrin missible oil.Concrete ratio sees Table 1.
Adopt feed to add malicious method and measure Tolfenpyrad and beta-cypermethrin and composite sample thereof to the virulence of cotton cotton bollworm, every processing repeats 3 times, and every concentration is processed 30, uses LC
50Value is pressed the abundant method of Sun Yun and is calculated co-toxicity coefficient:
Table 1 Tolfenpyrad, beta-cypermethrin and composite sample thereof are to toxicity test and the co-toxicity coefficient of cotton cotton bollworm
Data show in the table, Tolfenpyrad and beta-cypermethrin are mixed and rear the cotton cotton bollworm are had synergistic effect, four listed in table proportioning co-toxicity coefficients are all greater than 100, so Tolfenpyrad and beta-cypermethrin are mixed and have significant synergies.The synergistic effect maximum that wherein is mixed when the ratio of beta-cypermethrin and Tolfenpyrad is 10: 1 and kills the cotton cotton bollworm, co-toxicity coefficient is 139.4.
Embodiment 2:
Taking by weighing Tolfenpyrad, beta-cypermethrin, to adopt the conventional formulation method to be mixed with main active ingredient weight percentage by different proportion be 30% Tolfenpyrad beta-cypermethrin missible oil.Concrete ratio sees Table 2.
Adopt rice stem infusion process to measure Tolfenpyrad and beta-cypermethrin and composite sample thereof to the virulence of diamond-back moth, every processing repeats 3 times, uses LC
50Value is pressed the abundant method of Sun Yun and is calculated co-toxicity coefficient:
Table 2 Tolfenpyrad, beta-cypermethrin and composite sample thereof are to toxicity test and the co-toxicity coefficient of diamond-back moth
Data show in the table, and Tolfenpyrad and beta-cypermethrin are mixed and rear diamond-back moth are had synergistic effect, and four listed in table proportioning co-toxicity coefficients are all greater than 100, so Tolfenpyrad and beta-cypermethrin are mixed and have significant synergies.The synergistic effect maximum that wherein is mixed when the ratio of Tolfenpyrad and beta-cypermethrin is 1: 10 and kills diamond-back moth, co-toxicity coefficient is 141.8.
Embodiment 3:
Take by weighing 5g Tolfenpyrad, 20g beta-cypermethrin, calcium dodecyl benzene sulfonate 4g, phenethyl phenol polyethenoxy ether 3g, add dimethylbenzene to 100g, the method that above raw material is prepared missible oil routinely drops in the mixing kettle mixes, and forms main active ingredient weight percentage and be 25% Tolfenpyrad beta-cypermethrin missible oil.
Adopt 3 sample product of embodiment to carry out the field trial of control in field cotton cotton bollworm, the contrast medicament is 15% Tolfenpyrad EC (missible oil) and 5% beta-cypermethrin EC, and concrete consumption sees Table 3, every mu of water consumption is 30kg, looks into 7 days behind the medicine 3 days, 14 days, 28 days results.Do blank with clear water, result of the test sees Table 3:
Table 3 example 3 samples are to the field test results of cotton cotton bollworm
3 pairs of cotton cotton bollworms of example have fabulous quick-acting as can be seen from Table 3, and the lasting period is more intense, in the field performance well, are the outstanding medicaments of control cotton cotton bollworm.
Embodiment 4:
Adopt 3 sample product of embodiment to carry out the field trial of control in field vegetables diamond-back moth, the contrast medicament is 15% Tolfenpyrad EC and 5% beta-cypermethrin EC, and concrete consumption sees Table 3, every mu of water consumption is 30kg, looks into 7 days behind the medicine 3 days, 14 days, 28 days results.Do blank with clear water, result of the test sees Table 4:
Table 4 example 3 samples are to the field test results of diamond-back moth
Example 3 samples have fabulous effect to diamond-back moth as can be seen from Table 4, and the lasting period is long, in the field performance well, are the outstanding medicaments that prevents diamond-back moth.
Show through indoor synergism test mensuration: by Tolfenpyrad and beta-cypermethrin built agent cotton cotton bollworm and diamond-back moth are all had significant synergistic insecticidal action; Field control effectiveness test shows that equally also all built agents of the present invention all are significantly higher than the effect of corresponding single dose agricultural chemicals to the insecticidal effect of cotton cotton bollworm and diamond-back moth.
Embodiment 5:
Take by weighing 0.2g Tolfenpyrad, 19.8g beta-cypermethrin, lignin 10g, Negel 2g, add to 100g with kaolin, above raw material is mixed in micronizer, form main active ingredient weight percentage and be 20% Tolfenpyrad beta-cypermethrin wetting powder.
Embodiment 6:
Take by weighing 78g Tolfenpyrad, 0.5g beta-cypermethrin, calcium dodecyl benzene sulfonate 8g, phenethyl phenol polyethenoxy ether 6g, dimethylbenzene and add to 100g, the method that above raw material is prepared missible oil routinely drops in the mixing kettle mixes, and forms main active ingredient weight percentage and be 78.5% Tolfenpyrad beta-cypermethrin missible oil.
Embodiment 7:
Take by weighing 2g Tolfenpyrad, 10g beta-cypermethrin, nonyl phenol phosphate 5g, alkylphenol polyoxyethylene 4g, n-butanol 3g, the dimethylbenzene of 30g and the pyrrolidones of 20g, 0.1g xanthans, all the other waters are supplied 100g, n-butanol and water-soluble solution form water, all the other component mix and blends form oil phase, under the clipper effect, slowly water is added in the oil phase and go, and continue to shear 10~30 minutes, form main active ingredient weight percentage and be 12% Tolfenpyrad beta-cypermethrin aqueous emulsion.
Embodiment 8:
Take by weighing 10g Tolfenpyrad, 30g beta-cypermethrin, calcium dodecyl benzene sulfonate 5g, alkylphenol polyoxyethylene 4g, the solvent xylene of 30g and the pyrrolidones of 15g, all the other waters complement to 100g, former medicine, solvent, emulsifier, cosolvent mix and blend form homogeneous phase transparent solution, then slowly add entry and stir to form clear solution, be main active ingredient weight percentage and be 40% Tolfenpyrad beta-cypermethrin microemulsion.
Embodiment 9:
Take by weighing 4g Tolfenpyrad, 4g beta-cypermethrin, calcium dodecyl benzene sulfonate 5g, phenethyl phenol polyethenoxy ether 3g, dimethylbenzene to 100g.The method that above raw material is prepared missible oil routinely drops in the mixing kettle mixes, and forms main active ingredient weight percentage and be 8% Tolfenpyrad beta-cypermethrin missible oil.
Embodiment 10:
Take by weighing 3g Tolfenpyrad, 30g beta-cypermethrin, sodium lignin sulfonate 3g, polyoxyethylene poly-oxygen propylene aether and sulphate 4g thereof, xanthans 0.2g, ethylene glycol 10g, silica ethane 0.1g, aluminium-magnesium silicate 0.5g, water is supplied 100g, and the main active ingredient weight percentage of formation is 33% Tolfenpyrad beta-cypermethrin suspending agent under the effect of sand mill.
Embodiment 11:
Take by weighing 5g Tolfenpyrad, 55g beta-cypermethrin, alkylphenol polyoxyethylene 14g, phenethyl phenol polyethenoxy ether 15g, dimethylbenzene to 100g, the method that above raw material is prepared missible oil routinely drops in the mixing kettle mixes, and forms main active ingredient weight percentage and be 60% Tolfenpyrad beta-cypermethrin missible oil.
Embodiment 12:
Take by weighing 45g Tolfenpyrad, 5g beta-cypermethrin, sodium lignin sulfonate 8g, lauryl sodium sulfate 2g, ammonium sulfate 5g, polyvinyl alcohol 5g, borax 2g, kaolin 28g, it is 50% Tolfenpyrad beta-cypermethrin water dispersible granules that above raw material is formed main active ingredient weight percentage by the method for water dispersion granule.
Embodiment 13:
Take by weighing 30g Tolfenpyrad, 1g beta-cypermethrin, alkylphenol polyoxyethylene 14g, phenethyl phenol polyethenoxy ether 15g, dimethylbenzene to 100g, the method that above raw material is prepared missible oil routinely drops in the mixing kettle mixes, and forms main active ingredient weight percentage and be 31% Tolfenpyrad beta-cypermethrin missible oil.
Embodiment 14:
Take by weighing 60g Tolfenpyrad, 1g beta-cypermethrin, alkylphenol polyoxyethylene 14g, phenethyl phenol polyethenoxy ether 15g, dimethylbenzene to 100g, the method that above raw material is prepared missible oil routinely drops in the mixing kettle mixes, and forms main active ingredient weight percentage and be 61% Tolfenpyrad beta-cypermethrin missible oil.
Embodiment 15:
Take by weighing 1g Tolfenpyrad, 70g beta-cypermethrin, alkylphenol polyoxyethylene 10g, phenethyl phenol polyethenoxy ether 10g, dimethylbenzene to 100g, the method that above raw material is prepared missible oil routinely drops in the mixing kettle mixes, and forms main active ingredient weight percentage and be 71% Tolfenpyrad beta-cypermethrin missible oil.