WO2018171817A1 - 含螺环醚类衍生物的杀螨组合物 - Google Patents

含螺环醚类衍生物的杀螨组合物 Download PDF

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WO2018171817A1
WO2018171817A1 PCT/CN2018/087839 CN2018087839W WO2018171817A1 WO 2018171817 A1 WO2018171817 A1 WO 2018171817A1 CN 2018087839 W CN2018087839 W CN 2018087839W WO 2018171817 A1 WO2018171817 A1 WO 2018171817A1
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Prior art keywords
active ingredient
group
mass ratio
acaricide
water
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PCT/CN2018/087839
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English (en)
French (fr)
Inventor
许天明
袁静
胡冬松
钟良坤
邢家华
魏优昌
黄红英
郁季平
Original Assignee
浙江省化工研究院有限公司
中化蓝天集团有限公司
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Priority claimed from CN201710177859.3A external-priority patent/CN108617675A/zh
Priority claimed from CN201710177980.6A external-priority patent/CN108617685A/zh
Priority claimed from CN201710180372.0A external-priority patent/CN108617677A/zh
Priority claimed from CN201710231751.8A external-priority patent/CN108684702A/zh
Priority claimed from CN201710231720.2A external-priority patent/CN108684694A/zh
Application filed by 浙江省化工研究院有限公司, 中化蓝天集团有限公司 filed Critical 浙江省化工研究院有限公司
Publication of WO2018171817A1 publication Critical patent/WO2018171817A1/zh
Priority to ZA2019/06960A priority Critical patent/ZA201906960B/en

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  • the present invention relates to a pesticidal composition, and more particularly to a miticide composition.
  • the agricultural pests are small in size, fast in reproduction, adaptable and easy to produce resistance, and are one of the most difficult pests to control. It is an important organism of fruit trees, vegetables, and agricultural and forestry crops. It mainly harms leaves and also harms young shoots, flower buds and fruits. After the number of insect populations increases sharply, the plants often cause defoliation, and growth is inhibited or even died. The crops in the affected areas tend to be shorter, and the quality and yield are significantly reduced.
  • Spiroether derivatives as shown in the following structural formulas A-7, A-8 and A-10, have the same mechanism of action as spiroesters, mainly inhibiting fat synthesis in harmful sputum, and existing acaricides No cross-resistance, suitable for use in the control of harmful mites that are resistant to existing acaricides. Moreover, it has a wide spectrum of killing and adaptability. It has good control effect on red spider, yellow spider, rust tick, sassafras, cinnabar and leaf mites, and can be used for fruit trees such as citrus and grapes.
  • the egg-killing effect is particularly excellent, and it also has a good contact effect on the young cockroaches, and the long-lasting effect can control the damage of citrus full-claws for 40-50 days. .
  • a composition comprising two active ingredients, the first active ingredient comprising at least one selected from the group consisting of the following compounds A-7, A-8 and A-10, the second active ingredient comprising At least one selected from the group consisting of avermectin, emamectin, spinosyn, spinetoram, ivermectin, milbemycin, avermectin, and milavirin,
  • the present invention provides a composition comprising two active ingredients, wherein: the first active ingredient may be at least one selected from the group consisting of a compound selected from the group consisting of A-7, a compound represented by A-8 and a compound represented by A-10.
  • the second active ingredient may be selected from the group consisting of avermectin, emamectin, spinosyn, ethyl spinosyn, ivermectin, milbemycin, avermectin and imipenem. At least one of the primes.
  • composition provided by the present invention has no particular requirement for the ratio of the two active ingredients.
  • the two active ingredients can be mixed in any ratio.
  • the mass ratio of the first active ingredient to the second active ingredient is from 50:1 to 1:50.
  • the mass ratio of the first active ingredient to the second active ingredient is from 20:1 to 1:20.
  • the mass ratio of the first active ingredient to the second active ingredient is from 20:1 to 1:6.
  • the first active ingredient includes one or more selected from the group consisting of a compound represented by A-7, a compound represented by A-8, and a compound represented by A-10, the first active ingredient may be included in any ratio between the compounds. presence.
  • the second active ingredient comprises a selected from the group consisting of avermectin, emamectin, spinosyn, spinetoram, ivermectin, milbemycin, avermectin and imipenem
  • the one selected from the group consisting of avermectin, emamectin, spinosyn, ethyl spinosyn, ivermectin, milbemycin, avermectin, and milavirin Two or three of them may exist in any ratio.
  • the present invention can also adopt the following technical solutions:
  • a composition comprising two active ingredients, the first active ingredient comprising at least one selected from the group consisting of the following compounds A-7, A-8 and A-10, the second active ingredient comprising At least one selected from the group consisting of oxazolidine, thioxanthone, and tetrazine,
  • the present invention provides a composition comprising two active ingredients, wherein: the first active ingredient may be at least one selected from the group consisting of a compound selected from the group consisting of A-7, a compound represented by A-8 and a compound represented by A-10.
  • the second active ingredient may be at least one selected from the group consisting of etoxazole, thiazolone and tetrahydropyridazine.
  • composition provided by the present invention has no particular requirement for the ratio of the two active ingredients.
  • the two active ingredients can be mixed in any ratio.
  • the mass ratio of the first active ingredient to the second active ingredient is from 50:1 to 1:50.
  • the mass ratio of the first active ingredient to the second active ingredient is from 20:1 to 1:20.
  • the mass ratio of the first active ingredient to the second active ingredient is from 9:1 to 1:9.
  • the first active ingredient includes one or more selected from the group consisting of a compound represented by A-7, a compound represented by A-8, and a compound represented by A-10, the first active ingredient may be included in any ratio between the compounds. presence.
  • the second active ingredient comprises one or more selected from the group consisting of etoxazole, thiazolone and tetrazine
  • the two or three selected from the group consisting of etoxazole, thiazolone and tetrazine There can be any ratio between them.
  • the present invention can also adopt the following technical solutions:
  • a composition comprising two active ingredients, the first active ingredient comprising at least one selected from the group consisting of the following compounds A-7, A-8 and A-10, the second active ingredient comprising At least one selected from the group consisting of quinone, quinacridone, oxazolidinyl ester, pyrimidine, and pyridoxamine,
  • the present invention provides a composition comprising two active ingredients, wherein: the first active ingredient may be at least one selected from the group consisting of a compound selected from the group consisting of A-7, a compound represented by A-8 and a compound represented by A-10.
  • the second active ingredient may be at least one selected from the group consisting of quinone, quinacridone, oxazolidinyl ester, pyrimidine, and pyridoxamine.
  • composition provided by the present invention has no particular requirement for the ratio of the two active ingredients.
  • the two active ingredients can be mixed in any ratio.
  • the mass ratio of the first active ingredient to the second active ingredient is from 50:1 to 1:50.
  • the mass ratio of the first active ingredient to the second active ingredient is from 20:1 to 1:20.
  • the mass ratio of the first active ingredient to the second active ingredient is from 9:1 to 1:9.
  • the first active ingredient includes one or more selected from the group consisting of a compound represented by A-7, a compound represented by A-8, and a compound represented by A-10, the first active ingredient may be included in any ratio between the compounds. presence.
  • the second active ingredient comprises one or more selected from the group consisting of oxime, quinacridone, oxazolidine, pyridoxine and pyridoxamine
  • the one selected from the group consisting of oxime, quinacridone, and oxazolidine Two, three or more of the pyrimidin and pyridoxamine may be present in any ratio.
  • the present invention can also adopt the following technical solutions:
  • a composition comprising two active ingredients, the first active ingredient comprising at least one selected from the group consisting of the following compounds A-7, A-8 and A-10, the second active ingredient comprising Botanical pesticides,
  • the mass ratio of the first active ingredient to the second active ingredient is from 50:1 to 1:50.
  • the present invention provides a composition, wherein the first active ingredient comprises at least one selected from the group consisting of the above compounds A-7, A-8 and A-10, that is, may be selected from the above A-7, A- One, two or three of the compounds shown in 8 and A-10.
  • the present invention provides a composition comprising the plant-derived insecticide.
  • the plant-derived insecticide may be a plant-derived insecticide commonly used in the industry.
  • the plant-derived insecticide is selected from the group consisting of azadirachtin, cucurbitine, matrine, tea saponin, rotenone, nicotine, oxymatrine, nocturnin-III, blood base, At least one of eucalyptus, celangulin, osthole, avermectin, artemisinin, basalin, eucalyptol and quercetin.
  • the plant-derived insecticide is selected from at least one of azadirachtin, cucurbitine, matrine, tea saponin, rotenone, and nicotine.
  • composition provided by the present invention has a mass ratio of the first active ingredient to the second active ingredient.
  • the two active ingredients can be mixed in any ratio.
  • the mass ratio of the first active ingredient to the second active ingredient is from 50:1 to 1:50.
  • the mass ratio of the first active ingredient to the second active ingredient is from 10:1 to 1:20.
  • the mass ratio of the first active ingredient to the second active ingredient is from 5:1 to 1:20.
  • the present invention can also adopt the following technical solutions:
  • a composition comprising two active ingredients, the first active ingredient comprising at least one selected from the group consisting of the following compounds A-7, A-8 and A-10, the second active ingredient comprising Organotin acaricide,
  • the mass ratio of the first active ingredient to the second active ingredient is from 50:1 to 1:50.
  • the present invention provides a composition, wherein the first active ingredient comprises at least one selected from the group consisting of the above compounds A-7, A-8 and A-10, that is, may be selected from the above A-7, A- One, two or three of the compounds shown in 8 and A-10.
  • the present invention provides a composition comprising the organotin-based acaricide.
  • the organotin acaricide may be an organotin acaricide commonly used in the industry.
  • the organotin-based acaricide is selected from at least one of triazolium tin, phenbutyltin, tricyclotin, and triphosphorus.
  • composition provided by the present invention has a mass ratio of the first active ingredient to the second active ingredient.
  • the two active ingredients can be mixed in any ratio.
  • the mass ratio of the first active ingredient to the second active ingredient is from 50:1 to 1:50.
  • the mass ratio of the first active ingredient to the second active ingredient is from 20:1 to 1:20.
  • the mass ratio of the first active ingredient to the second active ingredient is from 5:1 to 1:10.
  • the present invention can also adopt the following technical solutions:
  • a composition comprising two active ingredients, the first active ingredient comprising at least one selected from the group consisting of the following compounds A-7, A-8 and A-10, the second active ingredient comprising Organic sulfur acaricide,
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:50 to 50:1.
  • the present invention provides a composition, wherein the first active ingredient comprises at least one selected from the group consisting of the above compounds A-7, A-8 and A-10, that is, may be selected from the above A-7, A- One, two or three of the compounds shown in 8 and A-10.
  • the first active ingredient comprises an organic sulfur acaricide.
  • the organic sulfur acaricide may be an organic sulfur acaricide commonly used in the industry.
  • the organosulfur acaricide is at least one selected from the group consisting of acetylene, dibutyl ether urea, acaricidal ester and acaricidal thioether.
  • composition provided by the present invention has a mass ratio of the first active ingredient to the second active ingredient.
  • the two active ingredients can be mixed in any ratio.
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:50 to 50:1.
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:20 to 20:1.
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:20 to 10:1.
  • the present invention can also adopt the following technical solutions:
  • a composition comprising two active ingredients, the first active ingredient comprising at least one selected from the group consisting of the following compounds A-7, A-8 and A-10, the second active ingredient comprising Pyrethroid pesticides,
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:50 to 50:1.
  • the present invention provides a composition, wherein the first active ingredient comprises at least one selected from the group consisting of the above compounds A-7, A-8 and A-10, that is, may be selected from the above A-7, A- One, two or three of the compounds shown in 8 and A-10.
  • the second active ingredient comprises a pyrethroid pesticide.
  • the pyrethroid pesticide may be a pyrethroid pesticide commonly used in the industry.
  • the pyrethroid pesticide is selected from the group consisting of fenpropathrin, bifenthrin, deltamethrin, cypermethrin, fenvalerate, cyhalothrin, lambda-cypermethrin, beta-cypermethrin, At least one of flumethrin, propythrin, and tetrafluthrin.
  • the pyrethroid pesticide is at least one selected from the group consisting of fenpropathrin, bifenthrin and lambda cyhalothrin.
  • composition provided by the present invention has a mass ratio of the first active ingredient to the second active ingredient.
  • the two active ingredients can be mixed in any ratio.
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:50 to 50:1.
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:20 to 20:1.
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:9 to 9:1.
  • the present invention can also adopt the following technical solutions:
  • a composition comprising two active ingredients, the first active ingredient comprising at least one selected from the group consisting of the following compounds A-7, A-8 and A-10, the second active ingredient comprising Biphenyl ester,
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:50 to 50:1.
  • the present invention provides a composition, wherein the first active ingredient comprises at least one selected from the group consisting of the above compounds A-7, A-8 and A-10, that is, may be selected from the above A-7, A- One, two or three of the compounds shown in 8 and A-10.
  • the present invention provides a composition comprising a diphenyl decyl ester.
  • composition provided by the present invention has a mass ratio of the first active ingredient to the second active ingredient.
  • the two active ingredients can be mixed in any ratio.
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:50 to 50:1.
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:20 to 20:1.
  • the mass ratio of the first active ingredient to the second active ingredient is from 1:9 to 9:1.
  • the present invention also provides an acaricide comprising 0.1% by weight or more of the above composition containing two active ingredients.
  • the acaricide comprises from 1% to 80% by weight of the above-mentioned composition containing the two active ingredients according to claim 1.
  • the acaricide provided by the present invention may further comprise, in addition to the above composition, a carrier and an adjuvant which are generally acceptable for the preparation of an insecticidal and acaricidal composition.
  • the carrier may be solid or liquid.
  • Suitable solid carriers include: minerals, plants, synthetic fillers, and inorganic salts.
  • minerals include silicates, carbonates, sulfates and oxides.
  • Silicates such as kaolin, sepiolite, pearlite, montmorillonite, mica, vermiculite, pyrophyllite, talc.
  • Carbonates such as calcium carbonate and dolomite.
  • Sulfates such as ammonium sulfate, sodium sulfate, and calcium sulfate.
  • Oxides such as quicklime, magnesium lime, diatomaceous earth.
  • Plants such as: citrus slag, corn cob core, chaff powder, rice husk, soybean stalk powder, tobacco powder, walnut shell, sawn wood powder.
  • Synthetic fillers such as precipitated calcium carbonate hydrate, precipitated calcium carbonate, white carbon black.
  • Inorganic salts such as potassium chloride and sodium chloride.
  • the liquid carrier includes water and an organic solvent.
  • Suitable organic solvents include: aromatic hydrocarbons such as benzene, xylene, toluene, alkylbenzenes, alkylnaphthalenes and chlorinated aromatic hydrocarbons; chlorinated aliphatic hydrocarbons such as vinyl chloride, chloroform, dichloromethane, chloroform, tetrachlorinated Carbon and polychloroethane; aliphatic hydrocarbons such as petroleum distillates, cyclohexane, light mineral oils and paraffins; alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, Glycerol, fatty alcohol, etc.; ethers, such as methyl glycol ether, ethyl glycol ether, petroleum
  • the auxiliary agent of the present invention may include at least one selected from the group consisting of a surfactant, an antifoaming agent, a thickener, a suspending agent, and an antifreezing agent as needed, and may further include other auxiliary agents commonly used in the industry as needed.
  • the surfactant may be an emulsifier, a dispersant, a stabilizer or a wetting agent, or it may be ionic or nonionic.
  • Suitable surfactants include: sodium and calcium salts of polyacrylic acid and lignosulfonic acid; polycondensation products of fatty acids or fatty amines having at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; glycerin, Fatty acid esters of dodecanol-1, myristyl alcohol-1, sorbitol, sucrose or pentaerythritol; and their polycondensation products with ethylene oxide and/or propylene oxide; sulfates of their polycondensation products or a sulfonate; an alkali metal or alkaline earth metal salt of sulfuric acid or a sulfonic acid having at least 10 carbon atoms in the molecule, preferably a sodium salt such as sodium lauryl sulfate
  • Emulsifiers include nonionic emulsifiers and commercially available emulsifiers.
  • the nonionic emulsifier is preferably a polyoxyethylene fatty acid ester, a polyoxyethylene fatty alcohol ether, and a polyoxyethylene fatty ammonia, such as ethoxylated castor oil, polyoxyethylene (n 20 ) phenethyl phenol ether ether oleate, Alkyl aryl polyoxyethylene polyoxypropylene ether, alkyl aryl formaldehyde resin polyoxyethylene ether, tristyryl phenol polyoxyethylene (n 20 ), ether phosphorylated triethanolamine salt, diphenylethyl phenol group polymerization An oxyethylene ether (n 18 ) formaldehyde condensate, diphenylphenol polyoxyethylene (n 18 ) polyoxypropylene ether (n 20 ), or the like.
  • emulsifiers include: agricultural milk 0201B, agricultural milk 0203B, agricultural milk 100 # , agricultural milk 500 # , agricultural milk 600 # , agricultural milk 600-2 # , agricultural milk 1601, agricultural milk 2201, agricultural milk NP-10 , Agricultural Milk NP-15, Agricultural Milk 507 # , Agricultural Milk OX-635, Agricultural Milk OX-622, Agricultural Milk OX-653, Agricultural Milk OX-667, Agricultural Milk CS-7, Ning Milk 36 # .
  • the dispersing agent of the invention comprises: sodium lignosulfonate, pull-opening powder, calcium lignosulfonate, methylnaphthalenesulfonic acid formaldehyde condensate, naphthalenesulfonic acid formaldehyde condensate, sodium methylene naphthalene sulfonate, oil Sodium acid methylaminoethyl sulfonate, epoxy polyether, p-tert-butyl ether, dibutyl naphthalenesulfonic acid formaldehyde condensate, phosphate such as sodium hexametaphosphate, alkylphenol polyoxyethylene phosphate, alkane Phenolic polyoxyethylene ether formaldehyde condensate sulfate, N-methyl-fatty acyl-taurine sodium alkylphenol polyoxyethylene ether formaldehyde condensate, aralkyl phenol polyoxyethylene ether phosphat
  • the humectant of the present invention comprises: sodium lauryl sulfate, sodium alkyl polyoxyethylene ether sulfate, octylphenol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, Sodium alkane sulfonate, sodium dodecyl benzene sulfonate, sodium alkylnaphthalene sulfonate, alkyl succinic acid sulfonate, sodium laureth polyoxyethylene ether sulfonate, sodium alkyl alkanoate taurate, Fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester polyoxyethylene ether and the like.
  • the thickening agent of the present invention may be synthetic, such as carboxymethyl alcohol, polyvinyl alcohol or polyvinyl acetate; or it may be a natural water-soluble polymer such as xanthan gum, gelatin or gum arabic. , polyvinylpyrrolidone, magnesium aluminum silicate, polyvinyl alcohol, polyethylene glycol, phenolic resin, shellac, carboxymethyl cellulose and sodium alginate.
  • the antifoaming agent of the present invention is preferably a foaming agent, a silicone, a C 8-10 fatty alcohol, a C 10-20 saturated fatty acid, an amide or the like.
  • the acaricides of the present invention may be formulated as emulsifiable concentrates, suspensions, suspoemulsions, microemulsions, aqueous emulsions, wettable powders, soluble powders, granules or capsules.
  • the cream, suspension, suspoemulsion, microemulsion, aqueous emulsion, dispersible oil suspension, wettable powder, soluble powder, granule or capsule contains 0.1% or more of the above two A composition of active ingredients.
  • the acaricide when it is a wettable powder, it comprises, by weight percentage, 0.1% to 80% of the composition containing the two active ingredients, 2% to 10% of the wetting agent, 5% to 10% of the dispersing agent, and the filler 8 ⁇ 90%.
  • the acaricide when it is a suspending agent, it comprises, by weight percentage, 0.1% to 60% of a composition containing two active ingredients, 1% to 5% of a wetting agent, 1% to 8% of a dispersing agent, and a thickener. 0.1% to 1%, antifreeze 2% to 5%, and water to 100%.
  • the acaricide When the acaricide is a microemulsion, it comprises, by weight percentage, 0.1% to 40% of the composition containing the two active ingredients, 1% to 12% of the emulsifier, 0% to 10% of the auxiliary solvent, and the stabilizer 0. % to 5%, solvent 0% to 40%, and water to 100%.
  • the acaricide when it is an aqueous emulsion, it comprises, by weight percentage, 0.1% to 80% of the composition containing the two active ingredients, 1% to 20% of the emulsifier, 0% to 15% of the auxiliary solvent, and the stabilizer 0. % to 5%, solvent 10% to 40%, and water to 100%.
  • the acaricide When the acaricide is a suspoemulsion, it comprises, by weight percentage, 0.1% to 50% of the composition containing the two active ingredients, 1% to 5% of the solvent, 1% to 5% of the dispersing agent, and 1% of the emulsifier. ⁇ 10%, wetting agent 1% ⁇ 5%, stabilizer 1% ⁇ 5%, antifreeze 0% ⁇ 5%, thickener 0% ⁇ 5%, antifoaming agent 0% ⁇ 5%, water up to 100%.
  • the composition comprises: 0.1% to 80% of the composition containing the two active ingredients, 0% to 2% of the surfactant, 1% to 15% of the humectant,
  • the dispersing agent is 1% to 15%
  • the disintegrant is 1% to 10%
  • the stabilizer is 0% to 5%
  • the filler is added to 100%.
  • the acaricide when it is a microcapsule suspending agent, it comprises, by weight percentage, 0.1% to 40% of the composition containing the two active ingredients, 1% to 20% of the emulsifier, 1% to 20% of the solvent, and thickening.
  • Agent 0% to 10%, antifreeze 0% to 10%, stabilizer 0% to 5%, antifoaming agent 0% to 5%, microcapsule carrier 1% to 10%, water to 100%.
  • the acaricide when it is a dispersible oil suspending agent, it comprises, by weight percentage, 0.1% to 40% of the composition of the two active ingredients, 1% to 20% of the emulsifier, and 1% to 5% of the dispersing agent.
  • the thickener is 0.5% to 3%, and the carrier oil phase is added to 100%.
  • composition containing the two active ingredients of the present invention can be directly prepared into a finished preparation form, that is, each substance in the composition has been mixed and used directly for insecticide; the ingredients of the composition can also be provided by a separate preparation, before use.
  • the concentrate of the invention is typically mixed with water to provide the desired concentration of active material.
  • the invention also encompasses the use of a composition comprising two active ingredients of the invention for controlling agricultural and forestry pests.
  • the composition containing the two active ingredients provided by the present invention is suitable for controlling agricultural pests. It is particularly suitable for controlling a variety of important agricultural pests such as cotton leafhopper, vegetable leafhopper, hawthorn leafhopper, citrus scorpion, citrus rust, apple leaf mites, diptera, alfalfa, whitefly and the like.
  • crops such as: fruit trees such as apples, pears, citrus lychees, etc.; cereals such as wheat, rice, etc.; beans such as soybeans, kidney beans, etc.; vegetables such as cabbage, broccoli, cabbage, rape , tomatoes, peppers, etc.; flowers such as rose, cotton, tea trees.
  • the application site of the acaricide according to the present invention is farmland, orchard or warehouse.
  • composition or acaricide containing the two active ingredients of the present invention can be applied in a usual manner, such as pouring, spraying, and spraying.
  • the application rate varies with climatic conditions or crop conditions, and the application time may be before or after the pest damage.
  • the duration of protection is usually related to the amount of individual compounds in the composition and also to external factors, such as climate, but the effects of climate can be mitigated by the use of appropriate dosage forms.
  • composition containing the two active ingredients of the present invention can also be used in combination with other compounds having insecticidal, herbicidal and bactericidal properties, and also with nematicides, protective agents, growth regulators, phytonutrients or soil conditioners. Mixed use.
  • the two active ingredients show a strong synergistic effect, and the mixed composition has a significantly higher killing effect than the single agent, and can kill eggs, young clams, nymphs and mites, and has a long-lasting effect. Characteristics of the period;
  • the ratio of the solid preparations is a percentage by weight
  • the ratio of the liquid preparations is a volume percentage
  • the treatment amount of the biologically active portion is an effective content, that is, an "active ingredient ratio”.
  • the solvent, the original drug and the emulsifier are respectively added, and the mixture is uniformly mixed, and if necessary, heated and dissolved in a water bath to obtain a transparent emulsifiable concentrate.
  • Example 1-1 20% EC, the ratio of active ingredients was 9:1
  • Example 1-2 30% emulsifiable concentrate, active ingredient ratio 5:1
  • A-8 it is also possible to replace A-8 with one of the spiro ether compounds described in the cost specification.
  • Abamectin can be replaced with emamectin, spinosyn, spinosyn, Iverm
  • melanomycin, milbemycin, avermectin, and militacin forms a new emulsifiable concentrate.
  • the original drug, various additives and fillers are thoroughly mixed, and after being crushed by an ultrafine pulverizer, the processed product is obtained.
  • A-8 it is also possible to replace A-8 with one of the spiro ether compounds described in the cost specification.
  • Abamectin can be replaced with emamectin, spinosyn, spinosyn, Iverm
  • melanomycin, milbemycin, avermectin, and imipenem forms a new wettable powder product.
  • the original drug and the powder carrier, the wetting spreader and the binder are mixed and pulverized, and then kneaded by water, and then added to a granulator equipped with a sieve of a certain size for granulation. It is then dried and sieved (by screen area) to obtain a granulated product.
  • A-8 it is also possible to replace A-8 with one of the spiro ether compounds described in the cost specification.
  • Abamectin can be replaced with emamectin, spinosyn, spinosyn, Iverm
  • melanomycin, milbemycin, avermectin, and imipenem forms a new water-dispersible granule product.
  • the original drug, dispersant, wetting agent, suspending agent and antifreeze are mixed uniformly with water as medium, and then added to the sand mill for sanding to a certain particle size filtration and then added with thickener. Cut and mix evenly.
  • EW alkylnaphthalene sulfonate and anionic wetting agent mixture
  • EW alkylnaphthalene sulfonate and anionic wetting agent mixture
  • A-8 it is also possible to replace A-8 with one of the spiro ether compounds described in the cost specification.
  • Abamectin can be replaced with emamectin, spinosyn, spinosyn, Iverm
  • melanomycin, milbemycin, avermectin, and imipenem forms a new suspension product.
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and water and ethylene glycol are mixed and stirred to form an aqueous phase, and the oil phase is slowly added to the water phase under high shear conditions, that is, A water emulsion is available.
  • A-8 it is also possible to replace A-8 with one of the spiro ether compounds described in the cost specification.
  • Abamectin can be replaced with emamectin, spinosyn, spinosyn, Iverm
  • melanomycin, milbemycin, avermectin, and milbecin forms a new aqueous emulsion product.
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and the water is gradually added to the oil phase, and stirred until uniform and transparent.
  • Example 1-11 10% microemulsion
  • A-8 it is also possible to replace A-8 with one of the spiro ether compounds described in the cost specification.
  • Abamectin can be replaced with emamectin, spinosyn, spinosyn, Iverm
  • melanomycin, milbemycin, avermectin, and militacin forms a new microemulsion product.
  • spiro ether compounds and avermectin, emamectin, spinosyn, ethyl spinosyn, ivermectin, milbemycin, avermectin, imipenem A large number of formula screening tests were carried out on the virulence of the composition of the pigment. The test was carried out with reference to the pesticide bioassay test guidelines for pesticides (agricultural industry standard NY/T1154.7-2006) and the creation of pesticide bioactivity evaluation SOP (insecticide rolls) using a spray method. The test with avermectin was carried out by cutting the leaves of broad bean leaves and inserting them into a glass bottle with water. Receive a certain number of members.
  • the mites were removed, and the leaves with enough eggs were sprayed, and the leaves were placed in ampoules and allowed to dry naturally. Incubate in an observation room (25 ⁇ 2 ° C, humidity 70% to 80%, 16h light / d). The test was repeated 3 times, and a blank control was set up, and the whole of the control was investigated after incubation. When the investigation is conducted, it cannot be hatched as a dead insect.
  • the test with the spinosyn was to cut the handle of the broad bean leaves and insert them into a glass bottle with water. Receive a certain number of members. After 24 hours of spawning, the mites were removed, and the eggs were all incubated for 48 hours, then sprayed and dried naturally.
  • Theoretical mixed virulence index (TTI) virulence index of A ⁇ A content in mixed use (%)
  • the co-toxicity coefficient is greater than 120, it indicates synergistic effect; if less than 80, it indicates antagonism; if greater than 80 is less than 120, it indicates additive effect.
  • Example 1-14 A-9 and avermectin combined synergism
  • Avermectin - 0.0366 872.40 A-9 - 0.3193 100.00
  • Avermectin: A-9 6:1 0.0297 1074.07 762.06 140.94 Avermectin: A-9 3:1 0.0328 972.56 679.30 143.17
  • Example 1-15 A-10 and avermectin combined synergism
  • Test results 7 days, 14 days, 21 days after the drug, the control effects of the mixed preparations on citrus red spider were 95.6%-97.8%, 96.9%-98.4% and 96.8%-97.9%, respectively. Better than 1.8% avermectin EC, 20% A-8 suspending agent, 20% A-9 suspending agent and 20% A-10 suspending agent.
  • Example 1-20 field efficacy test on apple red spider
  • the control effect on apple red spider was determined under field conditions.
  • the test site is located in Anzhuang Town, Feicheng City, Shandong province.
  • the variety is Xinhongxing, and the row spacing is 3m*4m.
  • the application rate was 1150 kg/hm 2 .
  • the results were investigated 7 days, 14 days, and 21 days after the drug.
  • the apple leaves in each test plot were marked with 5 fixed points according to the east, south, west and north, and 2 plots were surveyed in each plot. The number of live insects per plant was investigated.
  • apple red spiders were 97.6%-99.4%, 95.1%-99.5% and 94.2%-97.7%, respectively, 7 days, 14 days and 21 days after the drug treatment.
  • the effect of controlling apple red spider was better than 1.8. % avermectin EC, 20% A-8 suspension, 20% A-9 suspension and 20% A-10 suspension.
  • composition provided by the present invention not only has obvious synergistic effect on the control of citrus red spider and apple red spider, but also has better effect than single agent, and can reduce the dosage and delay the drug resistance caused by a single agent.
  • the solvent, the original drug and the emulsifier are separately added, and the mixture is uniformly mixed, and if necessary, heated and dissolved in a water bath to obtain a transparent emulsifiable concentrate.
  • Example 2-1 20% emulsifiable concentrate
  • Example 2-2 20% EC
  • the original drug, various additives and fillers are thoroughly mixed, and after being crushed by an ultrafine pulverizer, the processed product is obtained.
  • Example 2-3 40% wettable powder
  • A-8 with one of A-7, A-10 described in the cost specification, and ethazole may be replaced with one of thiazolone or tetrazine to form a new wettable powder product.
  • the original drug and the powder carrier, the wetting spreader and the binder are mixed and pulverized, and then kneaded by water, and then added to a granulator equipped with a sieve of a certain size for granulation. It is then dried and sieved (by screen area) to obtain a granulated product.
  • Example 2-5 40% water-dispersible granules
  • the original drug, dispersant, wetting agent, suspending agent and antifreeze are mixed uniformly with water as medium, and then added to the sand mill for sanding to a certain particle size filtration and then added with thickener. Cut and mix evenly.
  • EW alkylnaphthalene sulfonate and anionic wetting agent mixture
  • EW alkyl naphthalene sulfonate and anionic wetting agent mixture
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and water and ethylene glycol are mixed and stirred to form an aqueous phase, and the oil phase is slowly added to the water phase under high shear conditions, that is, A water emulsion is available.
  • Example 2-9 20% water emulsion
  • Example 2-10 20% water emulsion
  • A-8 with one of A-7, A-10 described in the cost specification, and ethazole may be replaced with one of thiazolone or tetrazine to form a new aqueous emulsion product.
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and the water is gradually added to the oil phase, and stirred until uniform and transparent.
  • Example 2-12 20% microemulsion
  • A-8 with one of A-7, A-10 described in the cost specification, and ethazole may be replaced with one of thiazolone or tetrazine to form a new microemulsion product.
  • the active component, the dispersing agent, the emulsifier, the thickener and the carrier oil are uniformly mixed, added to a sand mill, and ground to a certain particle size.
  • Example 2-13 10% dispersible oil suspension agent
  • Theoretical mixed virulence index (TTI) virulence index of A ⁇ A content in mixed use (%)
  • the co-toxicity coefficient is greater than 120, it indicates synergistic effect; if less than 80, it indicates antagonism; if greater than 80 is less than 120, it indicates additive effect.
  • Example 2-14 A-8 combined with etoxazole synergistic effect
  • Example 2-16 A-10 combined with oxazole synergistic effect
  • Test results 7 days, 14 days, 21 days after the drug, the control effects of the mixed preparations on citrus red spider were 95.9%-99.6%, 96.4%-99.2% and 95.2%-99.4%, respectively.
  • the control effect on apple red spider was determined under field conditions.
  • the application rate was 1150 kg/hm 2 .
  • the results were investigated 7 days, 14 days, and 21 days after the drug.
  • the apple leaves in each test plot were marked with 5 fixed points according to the east, south, west and north, and 2 plots were surveyed in each plot. The number of live insects per plant was investigated.
  • apple red spiders were 95.2%-99.3%, 95.7%-99.1% and 94.3%-99.2% at 7 days, 14 days and 21 days after the drug, respectively.
  • the effect of controlling apple red spider was better than 11 % oxazolidine suspension, 5% thiaxanone wettable powder, 20% A-8 suspension, 20% A-7 suspension and 20% A-10 suspension.
  • acaricidal composition provided by the present invention not only has a significant synergistic effect against citrus red spider, but is superior to A-7, A-9, A-10, etoxazole or thiabendone alone. It can reduce the amount of drug used and delay the drug resistance caused by a single agent.
  • the solvent, the original drug and the emulsifier are separately added, and the mixture is uniformly mixed, and if necessary, heated and dissolved in a water bath to obtain a transparent emulsifiable concentrate.
  • Example 3-1 15% emulsifiable concentrate
  • the original drug, various additives and fillers are thoroughly mixed, and after being crushed by an ultrafine pulverizer, the processed product is obtained.
  • Example 3-3 40% wettable powder
  • Example 3-4 40% wettable powder
  • the original drug and the powder carrier, the wetting spreader and the binder are mixed and pulverized, and then kneaded by water, and then added to a granulator equipped with a sieve of a certain size for granulation. It is then dried and sieved (by screen area) to obtain a granulated product.
  • Example 3-5 60% water-dispersible granules
  • A-8 40%, bismuth 20%, sodium lignosulfonate 15%, methyl naphthalene sulfonate formaldehyde condensate 5%, epoxy polyether 5%, bentonite 10%, kaolin to 100%.
  • the original drug, dispersant, wetting agent, suspending agent and antifreeze are mixed uniformly with water as medium, and then added to the sand mill for sanding to a certain particle size filtration and then added with thickener. Cut and mix evenly.
  • A-8 10%, ⁇ 10%, sodium lignin sulfonate 5%, white carbon black 0.3%, alkyl naphthalene sulfonate and anionic wetting agent mixture (EFW) 2.0%, potassium dihydrogen phosphate 0.2 %, ethylene glycol 4%, tributyl phosphate 0.2%, water to 100%.
  • EW alkyl naphthalene sulfonate and anionic wetting agent mixture
  • EW alkyl naphthalene sulfonate and anionic wetting agent mixture
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and water and ethylene glycol are mixed and stirred to form an aqueous phase, and the oil phase is slowly added to the water phase under high shear conditions, that is, A water emulsion is available.
  • Example 3-9 20% water emulsion
  • Example 3-10 31.5% water emulsion
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and the water is gradually added to the oil phase, and stirred until uniform and transparent.
  • Example 3-12 20% microemulsion
  • a large number of formulation screening tests were conducted. .
  • the test was carried out with reference to the pesticide bioassay test guidelines for pesticides (agricultural industry standard NY/T1154.7-2006) and the creation of pesticide bioactivity evaluation SOP (insecticide rolls) using a spray method.
  • the broad bean leaves were cut with a handle and inserted into a glass bottle with water. Receive a certain number of members.
  • Theoretical mixed virulence index (TTI) virulence index of A ⁇ A content in mixed use (%)
  • the co-toxicity coefficient is greater than 120, it indicates synergistic effect; if less than 80, it indicates antagonism; if greater than 80 is less than 120, it indicates additive effect.
  • Azathioprine A-10 3:1 0.812 40.52 26.93 150.45 Azathioprine: A-10 1:1 0.427 77.05 51.29 150.23 Azathioprine: A-10 1:3 0.308 106.82 75.64 141.21 Azathioprine: A-10 1:5 0.276 119.20 83.76 142.31 Azathioprine: A-10 1:7 0.263 125.10 87.82 142.44 Azathioprine: A-10 1:9 0.257 128.02 90.26 141.83 Azathioprine: A-10 1:20 0.265 124.15 95.36 130.19 Azathioprine: A-10 1:50 0.279 117.92 98.09 120.22
  • the control effect on apple red spider was determined under field conditions.
  • the test site is located in Anzhuang Town, Feicheng City, Shandong province.
  • the variety is Xinhongxing, and the row spacing is 3m*4m.
  • the application rate was 1150 kg/hm 2 .
  • the results were investigated 7 days, 14 days, and 21 days after the drug.
  • the apple leaves in each test plot were marked with 5 fixed points according to the east, south, west and north, and 2 plots were surveyed in each plot. The number of live insects per plant was investigated.
  • apple red spiders were 96.4%-98.4%, 96.5%-99.8% and 96.3%-98.6% after 7 days, 14 days and 21 days, respectively.
  • the effect of controlling apple red spiders was better than 20. % ⁇ ⁇ wettable powder, 5% oxazolidine suspending agent, 20% A-8 suspending agent, 20% A-9 suspending agent and 20% A-10 suspending agent. .
  • the active composition provided by the present invention not only has a remarkable synergistic effect on the control of citrus red spider, but also has better effect than using A-8, A-9, A-10, scorpion or oxazolidinate alone. Moreover, it can reduce the amount of drug used and delay the drug resistance caused by a single agent.
  • the solvent, the original drug and the emulsifier are separately added, and the mixture is uniformly mixed, and if necessary, heated and dissolved in a water bath to obtain a transparent emulsifiable concentrate.
  • Example 4-1 15% emulsifiable concentrate
  • Example 4-2 20% emulsifiable concentrate
  • A-7 10%, azadirachtin 10%, agricultural milk 2201# 6%, agricultural milk 0201B 8%, cyclohexanone 8%, solvent oil 150 to 100%.
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8 and A-10 described in the cost specification.
  • Azadirachtin can be replaced with cucurbitine, matrine, tea saponin, rotenone, and tobacco.
  • One of the bases forms a new cream product.
  • the original drug, various additives and fillers are thoroughly mixed, and after being crushed by an ultrafine pulverizer, the processed product is obtained.
  • Example 4-3 40% wettable powder
  • Example 4-4 50% wettable powder
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8 and A-10 described in the cost specification.
  • Azadirachtin can be replaced with cucurbitine, matrine, tea saponin, rotenone, and tobacco.
  • One of the bases forms a new wettable powder product.
  • the original drug and the powder carrier, the wetting spreader and the binder are mixed and pulverized, and then kneaded by water, and then added to a granulator equipped with a sieve of a certain size for granulation. It is then dried and sieved (by screen area) to obtain a granulated product.
  • Example 4-5 40% water-dispersible granules
  • A-7 10%, azadirachtin 30%, N-methyl-oleoyl-taurate sodium 8%, naphtholsulfonic acid formaldehyde condensate 10%, soluble starch 8%, sodium sulfate 10%, kaolin supplemented to 100%.
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8 and A-10 described in the cost specification.
  • Azadirachtin can be replaced with cucurbitine, matrine, tea saponin, rotenone, and tobacco.
  • One of the bases forms a new water-dispersible granule product.
  • the original drug, dispersant, wetting agent, suspending agent and antifreeze are mixed uniformly with water as medium, and then added to the sand mill for sanding to a certain particle size filtration and then added with thickener. Cut and mix evenly.
  • EW alkylnaphthalene sulfonate and anionic wetting agent mixture
  • A-7 20%, azadirachtin 30%, sodium methylnaphthalene sulfonate formaldehyde condensate 2.5%, alkylnaphthalene sulfonate and anionic wetting agent mixture (EFW) 2.0%, agricultural milk OX-656 3.0% , glycerol 4%, tributyl phosphate 0.2%, water to 100%.
  • EW alkylnaphthalene sulfonate and anionic wetting agent mixture
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8 and A-10 described in the cost specification.
  • Azadirachtin can be replaced with cucurbitine, matrine, tea saponin, rotenone, and tobacco.
  • One of the bases forms a new suspension product.
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and water and ethylene glycol are mixed and stirred to form an aqueous phase, and the oil phase is slowly added to the water phase under high shear conditions, that is, A water emulsion is available.
  • Example 4-10 25% water emulsion
  • A-7 10%, azadirachtin 15%, solvent oil S-150 30%, triphenylethylphenol polyoxyethylene ether phosphate 4%, hydroxyl terminated polyoxyethylene polyoxypropylene ether block copolymer 5%, Ethylene glycol 3%, water to 100%.
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8 and A-10 described in the cost specification.
  • Azadirachtin can be replaced with cucurbitine, matrine, tea saponin, rotenone, and tobacco.
  • One of the bases forms a new aqueous emulsion product.
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and the water is gradually added to the oil phase, and stirred until uniform and transparent.
  • Example 4-11 8% microemulsion
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8 and A-10 described in the cost specification.
  • Azadirachtin can be replaced with cucurbitine, matrine, tea saponin, rotenone, and tobacco.
  • One of the bases forms a new microemulsion product.
  • the original drug, the dispersing agent, the emulsifier, the thickener and the oil phase carrier are mixed and stirred uniformly, and then added to a sand mill to be ground to a certain particle size.
  • A-7 10%, azadirachtin 20%, triphenylethylphenol polyoxyethylene ether phosphate 3%, fatty alcohol polyoxyethylene ether 14%, organic bentonite 1.5%, methyl oleate to 100%.
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8 and A-10 described in the cost specification.
  • Azadirachtin can be replaced with cucurbitine, matrine, tea saponin, rotenone, and tobacco.
  • One of the bases forms a new dispersible oil suspension product.
  • the mites were removed, and the eggs were all incubated for 48 hours, then sprayed and dried naturally. Incubate in an observation room (25 ⁇ 2 ° C, humidity 70% to 80%, 16h light / d). The test was repeated 3 times, and a blank control was set up, and the investigation was conducted 48 hours later. During the investigation, it was impossible to crawl normally as a dead insect.
  • the test with the cucurbitine mixture was carried out by cutting the leaves of the broad bean leaves and inserting them into a glass bottle filled with water. Receive a certain number of members. After 24 hours of spawning, the mites were removed, and the leaves with enough eggs were sprayed, and the leaves were placed in ampoules and allowed to dry naturally.
  • Theoretical mixed virulence index (TTI) virulence index of A ⁇ A content in mixed use (%)
  • the co-toxicity coefficient is greater than 120, it indicates synergistic effect; if less than 80, it indicates antagonism; if greater than 80 is less than 120, it indicates additive effect.
  • Example 4-19 A-8 combined with cucurbitine synergistic effect (Tetranychus cinnabarinus)
  • Example 4-20 A-10 combined with cucurbitine synergistic effect (Tetranychus cinnabarinus)
  • Test results 7 days, 14 days, 21 days after the drug, the control effects of the mixed preparations on citrus scorpion were 96.2%-98.2%, 97.1%-98.6% and 96.4%-97.2%, respectively.
  • the effect of Xenopus was better than 0.3% azadirachtin EC, 20% A-7 suspension, 20% A-8 suspension and 20% A-10 suspension.
  • the control effect on the whole clawed cockroach of apple was determined under field conditions.
  • the test was carried out according to the “Pesticide Field Efficacy Test Guidelines (I) – Acaricide Control of Apple Leafhopper GB/T 17980.7-2000”.
  • the test site is located in Anzhuang Town, Feicheng City, Shandong province.
  • the variety is Xinhongxing, and the plant spacing is 3m. *4m.
  • the application rate was 1150 L/hm 2 .
  • the results were investigated 7 days, 14 days, and 21 days after the drug.
  • the apple leaves in each test plot were marked with 5 fixed points according to the east, south, west and north, and 2 plots were surveyed in each plot. The number of live insects per plant was investigated.
  • composition provided by the present invention has obvious synergistic effect on the control of citrus whole claw mites and apple whole scorpion mites, and the effect is better than using A-7, A-8, A-10 or Azadirachtin can also reduce the amount of drug used and delay the drug resistance caused by a single agent.
  • the fifth group is a group consisting of:
  • the solvent, the original drug and the emulsifier are separately added, and the mixture is uniformly mixed, and if necessary, heated and dissolved in a water bath to obtain a transparent emulsifiable concentrate.
  • Example 5-1 10% emulsifiable concentrate
  • Example 5-2 20% emulsifiable concentrate
  • the original drug, various additives and fillers are thoroughly mixed, and after being crushed by an ultrafine pulverizer, the processed product is obtained.
  • Example 5-3 60% wettable powder
  • Example 5-4 70% wettable powder
  • A-7 10%, triazolyl 60%, sodium dodecylbenzene sulfonate 2%, p-tert-butyl ether 2%, white carbon black 5%, sodium lignosulfonate 10%, light calcium carbonate complement To 100%.
  • the original drug and the powder carrier, the wetting spreader and the binder are mixed and pulverized, and then kneaded by water, and then added to a granulator equipped with a sieve of a certain size for granulation. It is then dried and sieved (by screen area) to obtain a granulated product.
  • Example 5-5 40% water-dispersible granules
  • A-7 10%, triazolyl 30%, N-methyl-oleoyl-taurate sodium 8%, naphtholsulfonic acid formaldehyde condensate 10%, soluble starch 8%, sodium sulfate 10%, kaolin supplemented to 100%.
  • A-7 25%, triazolyl 25%, sodium lignosulfonate 15%, methyl naphthalenesulfonate sodium formaldehyde condensate 5%, epoxy polyether 5%, bentonite 10%, kaolin to 100%.
  • A-7 with one of the spiro ether compounds A-8 and A-10 described in the specification, and the triazole tin can be replaced with one of phenbutyltin, tricyclotin and triphosphorus.
  • a new water-dispersible granule product is formed.
  • the original drug, dispersant, wetting agent, suspending agent and antifreeze are mixed uniformly with water as medium, and then added to the sand mill for sanding to a certain particle size filtration and then added with thickener. Cut and mix evenly.
  • EW alkyl naphthalene sulfonate and anionic wetting agent mixture
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and water and ethylene glycol are mixed and stirred to form an aqueous phase, and the oil phase is slowly added to the water phase under high shear conditions, that is, A water emulsion is available.
  • Example 5-10 25% water emulsion
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and the water is gradually added to the oil phase, and stirred until uniform and transparent.
  • A-7 2%, triazole tin 6%, isopropanol 10%, solvent oil S-150 15%, calcium dodecylbenzenesulfonate 2%, styryl phenyl polyoxyethylene ether 18%, water Make up to 100%.
  • the original drug, the dispersing agent, the emulsifier, the thickener and the oil phase carrier are mixed and stirred uniformly, and then added to a sand mill to be ground to a certain particle size.
  • A-7 10%, triazolyl 20%, triphenylethylphenol polyoxyethylene ether phosphate 3%, fatty alcohol polyoxyethylene ether 14%, organic bentonite 1.5%, methyl oleate to 100%.
  • A-7 with one of the spiro ether compounds A-8 and A-10 described in the specification, and the triazole tin can be replaced with one of phenbutyltin, tricyclotin and triphosphorus.
  • a new dispersible oil suspension product is formed.
  • the mites were removed, and the eggs were all incubated for 48 hours, then sprayed and dried naturally. Incubate in an observation room (25 ⁇ 2 ° C, humidity 70% to 80%, 16h light / d). The test was repeated 3 times, and a blank control was set up, and the investigation was conducted 48 hours later. During the investigation, it was impossible to crawl normally as a dead insect.
  • the test object is an egg
  • the broad bean leaves are cut with a handle and inserted into a glass bottle filled with water. Receive a certain number of members.
  • the mites were removed, and the leaves with enough eggs were sprayed, and the leaves were placed in ampoules and allowed to dry naturally.
  • Theoretical mixed virulence index (TTI) virulence index of A ⁇ A content in mixed use (%)
  • the co-toxicity coefficient is greater than 120, it indicates synergistic effect; if less than 80, it indicates antagonism; if greater than 80 is less than 120, it indicates additive effect.
  • composition provided by the present invention exhibits synergistic effect on both the cinnabar and the eggs, and has a significant synergistic effect in the range of mass ratio of 1:20 to 20:1.
  • the synergistic effect is most pronounced in the range of mass ratio 1:10 to 5:1. It is scientific and rational to mix and control spiro ether compounds with organotin acaricides.
  • Test results 7 days, 14 days, 21 days after the drug, the control effects of the mixed preparations on citrus scorpion were 96.4%-98.1%, 97.0%-98.5% and 96.5%-97.6%, respectively.
  • the effect of Xenopus was better than 25% triazolyl wettable powder, 20% A-7 suspension, 20% A-8 suspension and 20% A-10 suspension.
  • the control effect on the whole clawed cockroach of apple was determined under field conditions.
  • the test was carried out according to the “Pesticide Field Efficacy Test Guidelines (I) – Acaricide Control of Apple Leafhopper GB/T 17980.7-2000”. The results were investigated 7 days, 14 days, and 21 days after the drug.
  • the apple leaves in each test plot were marked with 5 fixed points according to the east, south, west and north, and 2 plots were surveyed in each plot. The number of live insects per plant was investigated.
  • composition provided by the present invention not only has obvious synergistic effect on the control of citrus squamosa and apple whole scorpion scorpion, but has quicker effect and sustained effect than A-7 and A-8 alone.
  • A-10 or triazolium can reduce the amount of drug use, delaying the drug resistance caused by a single agent.
  • Theoretical mixed virulence index (TTI) virulence index of A ⁇ A content in mixed use (%)
  • the co-toxicity coefficient is greater than 120, it indicates synergistic effect; if less than 80, it indicates antagonism; if greater than 80 is less than 120, it indicates additive effect.
  • A-7 alkyne 5:1 2.2215 973.77 543.54 179.15 A-7: alkyne 10:1 2.2547 959.44 583.86 164.33 A-7: alkyne 20:1 2.5342 853.62 606.90 140.65 A-7: alkyne 50:1 2.7313 792.02 621.81 127.37
  • A-8 Dibutyl ether urea 1:5 1.2428 2433.03 1572.14 154.76 A-8: Dibutyl ether urea 1:1 0.4527 6679.41 4516.43 147.89 A-8: Dibutyl ether urea 5:1 0.2719 11120.89 7460.71 149.06 A-8: Dibutyl ether urea 10:1 0.2568 11774.81 8129.86 144.83 A-8: Dibutyl ether urea 20:1 0.2671 11320.74 8512.24 132.99 A-8: Dibutyl ether urea 50:1 0.2822 10,714.99 8759.66 122.32
  • composition provided by the present invention exhibits synergistic effect on both the cinnabar and the eggs, and has a significant synergistic effect in the range of mass ratio of 1:20 to 20:1.
  • the synergistic effect is most significant in the range of 1:20 to 10:1. It is scientifically reasonable to mix spiro ether compounds with organic sulfur acaricides to control pests.
  • the solvent, the original drug and the emulsifier are separately added, and the mixture is uniformly mixed, and if necessary, heated and dissolved in a water bath to obtain a transparent emulsifiable concentrate.
  • Example 6-7 20% emulsifiable concentrate
  • A-7 10%, acetylene 10%, agricultural milk 0203B 5%, agricultural milk 0201B 10%, cyclohexanone 8%, solvent oil 150 made up to 100%.
  • the original drug, various additives and fillers are thoroughly mixed, and after being crushed by an ultrafine pulverizer, the processed product is obtained.
  • A-7 60%, acetylene 10%, sodium dodecyl benzene sulfonate 2%, p-tert-butyl ether 2%, white carbon black 5%, sodium lignosulfonate 10%, light calcium carbonate complement To 100%.
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8, A-10 described in the cost specification, and the alkyne can be replaced with one of dibutyl ether urea, fentanyl ester and acaricidal thioether. A new wettable powder product is formed.
  • the original drug and the powder carrier, the wetting spreader and the binder are mixed and pulverized, and then kneaded by water, and then added to a granulator equipped with a sieve of a certain size for granulation. It is then dried and sieved (by screen area) to obtain a granulated product.
  • Example 6-11 40% water-dispersible granules
  • A-7 10%, acetylene 30%, N-methyl-oleoyl-taurate sodium 8%, naphtholsulfonic acid formaldehyde condensate 10%, soluble starch 8%, sodium sulfate 10%, kaolin supplemented to 100%.
  • Example 6-12 55% water-dispersible granules
  • A-7 50%, acetylene 5%, sodium lignosulfonate 15%, methyl naphthalene sulfonate formaldehyde condensate 5%, epoxy polyether 5%, bentonite 10%, kaolin supplement to 100%.
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8, A-10 described in the cost specification, and the alkyne can be replaced with one of dibutyl ether urea, fentanyl ester and acaricidal thioether. A new water-dispersible granule product is formed.
  • the original drug, dispersant, wetting agent, suspending agent and antifreeze are mixed uniformly with water as medium, and then added to the sand mill for sanding to a certain particle size filtration and then added with thickener. Cut and mix evenly.
  • A-7 25%, acetylene 5%, sodium lignin sulfonate 5%, white carbon black 0.3%, alkylnaphthalene sulfonate and anionic wetting agent mixture (EFW) 2.0%, potassium dihydrogen phosphate 0.2 %, ethylene glycol 4%, tributyl phosphate 0.2%, water to 100%.
  • EW alkylnaphthalene sulfonate and anionic wetting agent mixture
  • A-7 5%, acetylene 35%, methyl naphthalene sulfonate formaldehyde condensate 2.5%, alkyl naphthalene sulfonate and anionic wetting agent mixture (EFW) 2.0%, agricultural milk OX-656 3.0% , glycerol 4%, tributyl phosphate 0.2%, water to 100%.
  • EW alkyl naphthalene sulfonate and anionic wetting agent mixture
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and water and ethylene glycol are mixed and stirred to form an aqueous phase, and the oil phase is slowly added to the water phase under high shear conditions, that is, A water emulsion is available.
  • A-7 10%, acetylene 10%, solvent oil S-150 30%, triphenylethyl phenol polyoxyethylene ether phosphate 4%, hydroxyl terminated polyoxyethylene polyoxypropylene ether block copolymer 5%, Ethylene glycol 3%, water to 100%.
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and the water is gradually added to the oil phase, and stirred until uniform and transparent.
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8, A-10 described in the cost specification, and the alkyne can be replaced with one of dibutyl ether urea, fentanyl ester and acaricidal thioether. Form new microemulsion products.
  • the original drug, the dispersing agent, the emulsifier, the thickener and the oil phase carrier are mixed and stirred uniformly, and then added to a sand mill to be ground to a certain particle size.
  • Example 6-20 30% dispersible oil suspension agent
  • A-7 it is also possible to replace A-7 with one of the spiro ether compounds A-8, A-10 described in the cost specification, and the alkyne can be replaced with one of dibutyl ether urea, fentanyl ester and acaricidal thioether. A new dispersible oil suspension product is formed.
  • Test results 7 days, 14 days, 21 days after the drug, the control effects of the mixed preparations on citrus scorpion were 97.5%-98.6%, 98.0%-99.4% and 96.8%-97.7%, respectively.
  • the effect of Xenopus was better than that of 73% acetylene emulsifiable concentrate, 20% A-7 suspension, 20% A-8 suspension, and 20% A-10 suspension.
  • the control effect on the whole clawed cockroach of apple was determined under field conditions.
  • the test was carried out according to the “Pesticide Field Efficacy Test Guidelines (I) – Acaricide Control of Apple Leafhopper GB/T 17980.7-2000”. The results were investigated 7 days, 14 days, and 21 days after the drug.
  • the apple leaves in each test plot were marked with 5 fixed points according to the east, south, west and north, and 2 plots were surveyed in each plot. The number of live insects per plant was investigated.
  • composition provided by the present invention not only has a significant synergistic effect on the control of citrus scorpion and the whole claw scorpion, but is superior to the use of A-7, A-8, A-10 or acetylene alone. Moreover, it can reduce the amount of drug used and delay the drug resistance caused by a single agent.
  • the solvent, the original drug and the emulsifier are separately added, and the mixture is uniformly mixed, and if necessary, heated and dissolved in a water bath to obtain a transparent emulsifiable concentrate.
  • Example 7-1 10% emulsifiable concentrate
  • Example 7-2 25% emulsifiable concentrate
  • the original drug, various additives and fillers are thoroughly mixed, and after being crushed by an ultrafine pulverizer, the processed product is obtained.
  • Example 7-3 30% wettable powder
  • Example 7-4 50% wettable powder
  • the original drug and the powder carrier, the wetting agent, the dispersing agent and the binder are mixed and pulverized, and then kneaded by water, and then added to a granulator equipped with a sieve of a certain size for granulation. Then, it is dried and sieved (in the range of the sieve) to obtain a granulated product or a granulated product obtained by spray granulation after wet pulverization and sieving.
  • Example 7-5 40% water-dispersible granules
  • A-7 40%, fenpropathrin 10%, alkyl sulfate 3%, maleic acid homopolymer sodium salt 5%, kaolin supplement to 100%.
  • the original drug, dispersant, wetting agent, suspending agent and antifreeze are mixed uniformly with water as medium, and then added to the sand mill for sanding to a certain particle size filtration and then added with thickener. Cut and mix evenly.
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and water and ethylene glycol are mixed and stirred to form an aqueous phase, and the oil phase is slowly added to the water phase under high shear conditions, that is, A water emulsion is available.
  • Example 7-10 25% water emulsion
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and the water is gradually added to the oil phase, and stirred until uniform and transparent.
  • Example 7-11 5% microemulsion
  • A-7 2.5%, fenpropathrin 2.5%, isopropanol 10%, solvent oil S-150 15%, calcium dodecylbenzenesulfonate 2%, styryl phenyl ethoxylate 18%, Water is added to 100%.
  • the active component, the dispersing agent, the emulsifier, the thickener and the carrier oil are uniformly mixed, added to a sand mill, and ground to a certain particle size.
  • Example 7-13 10% dispersible oil suspension
  • A-8, a wetting agent, a dispersing agent, water, and the like are disposed in an aqueous suspension phase, and fenpropathrin, an emulsifier, and a solvent are formulated into an oil phase.
  • the oil phase is added to the aqueous suspension phase under high shear or agitation to obtain a suspoemulsion.
  • Theoretical mixed virulence index (TTI) virulence index of A ⁇ A content in mixed use (%)
  • the co-toxicity coefficient is greater than 120, it indicates synergistic effect; if less than 80, it indicates antagonism; if greater than 80 is less than 120, it indicates additive effect.
  • Example 7-21 A-10 combined with bifenthrin synergistic effect
  • Test results 7 days, 14 days, 21 days after drug administration, the control effects of the mixed preparations on citrus red spider were 96.5% ⁇ 99.6%, 97.1% ⁇ 99.2% and 96.9% ⁇ 99.7%, respectively.
  • 20% fenpropathrin emulsifiable concentrate 20% A-7 suspension, 20% A-8 suspension and 20% A-10 suspension.
  • the control effect on apple red spider was determined under field conditions.
  • the test site is located in Anzhuang Town, Feicheng City, Shandong province.
  • the variety is Xinhongxing, and the row spacing is 3m*4m.
  • the application rate was 1150 kg/hm 2 .
  • the results were investigated 7 days, 14 days, and 21 days after the drug.
  • the apple leaves in each test plot were marked with 5 fixed points according to the east, south, west and north, and 2 plots were surveyed in each plot. The number of live insects per plant was investigated.
  • Test results 7 days, 14 days, 21 days after the drug, the control effects of the mixed preparations on apple red spider were 96.5% ⁇ 99.7%, 95.9% ⁇ 99.4% and 96.2% ⁇ 99.6%, respectively.
  • 20% fenpropathrin emulsifiable concentrate 20% A-8 suspending agent, 20% A-9 suspending agent and 20% A-10 suspending agent.
  • composition provided by the present invention not only has a remarkable synergistic effect for controlling citrus red spider and apple red spider, but is superior to A-7, A-8, A-10 and fenpropathrin alone, and It can reduce the amount of drug used and delay the drug resistance caused by a single agent.
  • the solvent, the original drug and the emulsifier are separately added, and the mixture is uniformly mixed, and if necessary, heated and dissolved in a water bath to obtain a transparent emulsifiable concentrate.
  • Example 8-1 50% emulsifiable concentrate
  • A-7 25%, biphenyl phthalate 25%, calcium dodecyl benzene sulfonate 6%, triphenylethyl phenol polyoxyethylene ether 9%, cyclohexanone 10%, solvent oil 150 to 100%.
  • Example 8-2 70% emulsifiable concentrate
  • the original drug, various additives and fillers are thoroughly mixed, and after being crushed by an ultrafine pulverizer, the processed product is obtained.
  • Example 8-3 60% wettable powder
  • Example 8-4 80% wettable powder
  • A-7 10%, biphenyl decyl ester 70%, sodium lauryl sulfate 2%, naphthalene sulfonic acid formaldehyde condensate sodium salt 8%, light calcium carbonate complement to 100%.
  • the original drug and the powder carrier, the wetting agent, the dispersing agent and the binder are mixed and pulverized, and then kneaded by water, and then added to a granulator equipped with a sieve of a certain size for granulation. Then, it is dried and sieved (in the range of the sieve) to obtain a granulated product or a granulated product obtained by spray granulation after wet pulverization and sieving.
  • Example 8-5 40% water-dispersible granules
  • A-7 10%, biphenyl decyl ester 30%, naphthalene sulfonate sodium salt 2%, naphthalene sulfonic acid formaldehyde condensate sodium salt 10%, soluble starch 8%, sodium sulfate 10%, kaolin clay to 100%.
  • the original drug, dispersant, wetting agent, suspending agent and antifreeze are mixed uniformly with water as medium, and then added to the sand mill for sanding to a certain particle size filtration and then added with thickener. Cut and mix evenly.
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and water and ethylene glycol are mixed and stirred to form an aqueous phase, and the oil phase is slowly added to the water phase under high shear conditions, that is, A water emulsion is available.
  • Example 8-10 25% water emulsion
  • the original drug, solvent and emulsifier are mixed and stirred to form a uniform oil phase, and the water is gradually added to the oil phase, and stirred until uniform and transparent.
  • the active component, the dispersing agent, the emulsifier, the thickener and the carrier oil are uniformly mixed, added to a sand mill, and ground to a certain particle size.
  • the test was carried out with reference to the pesticide bioassay test guidelines for pesticides (agricultural industry standard NY/T1154.7-2006) and the creation of pesticide bioactivity evaluation SOP (insecticide rolls) using a spray method.
  • the test was carried out by mixing the biphenyl phthalate with the handle of the broad bean leaves and inserting it into a glass bottle with water. Receive a certain number of members. After 24 hours of spawning, the mites were removed, and the eggs were all incubated for 48 hours, then sprayed and dried naturally.
  • Theoretical mixed virulence index (TTI) virulence index of A ⁇ A content in mixed use (%)
  • the co-toxicity coefficient is greater than 120, it indicates synergistic effect; if less than 80, it indicates antagonism; if greater than 80 is less than 120, it indicates additive effect.
  • A-7 Diphenyl decyl ester 2:1 0.31 109.7 88.46 123.98 A-7: Diphenyl decyl ester 1:1 0.31 109.7 82.69 132.63 A-7: Diphenyl decyl ester 1:2 0.21 161.9 120.35 134.53 A-7: Diphenyl decyl ester 1:3 0.17 200.0 135.03 148.11 A-7: Diphenyl decyl ester 1:4 0.23 147.8 113.90 129.79
  • Test results 7 days, 14 days, 21 days after the drug, the control effects of the mixed preparations on citrus red spider were 96.2%-99.2%, 96.8%-99.6% and 96.5%-99.7%, respectively. Better than 24% biphenyl ester suspension, 20% A-7 suspension, 20% A-8 suspension and 20% A-10 suspension.
  • the control effect on apple red spider was determined under field conditions.
  • the test site is located in Anzhuang Town, Feicheng City, Shandong province.
  • the variety is Xinhongxing, and the row spacing is 3m*4m.
  • the application rate was 1150 kg/hm 2 .
  • the results were investigated 7 days, 14 days, and 21 days after the drug.
  • the apple leaves in each test plot were marked with 5 fixed points according to the east, south, west and north, and 2 plots were surveyed in each plot. The number of live insects per plant was investigated.
  • composition provided by the present invention has obvious synergistic effect on controlling citrus red spider and apple red spider, and the effect is better than using A-7, A-8, A-10 and biphenyl phthalate alone. Reduce the amount of medication and delay the drug resistance caused by a single agent.

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Abstract

本发明提供了一种杀螨组合物，含有两种活性成分，第一种活性成分包括选自A-7、A-8和A-10所示化合物中的至少一种，第二种活性成分选自第一组至第八组中的一组。本发明提供的杀螨组合物能够提高防效、降低农用成本、延缓害虫抗药性的产生。

Description

含螺环醚类衍生物的杀螨组合物 技术领域
本发明涉及一种杀虫组合物，尤其涉及一种杀螨组合物。
背景技术
农业害螨体积小、繁殖快、适应性强、易产生抗性，是最难防治的有害生物之一。害螨是果树、蔬菜、农林作物的重要生物，主要危害叶片，也危害嫩梢、花蕾和果实。虫口数量急剧增加后，常造成植株落叶，生长受抑制甚至枯死。被害区的作物往往稍矮，品质和产量明显下降。
螺环醚类衍生物，如下文结构式A-7、A-8和A-10所示，与螺螨酯作用机制相同，主要是抑制有害螨体内的脂肪合成，与现有杀螨剂之间无交互抗性，适用于用来防治对现有杀螨剂产生抗性的有害螨类。而且其杀螨谱广、适应性强，对红蜘蛛、黄蜘蛛、锈壁虱、茶黄螨、朱砂叶螨和二斑叶螨等均有很好防效，可用于柑桔、葡萄等果树和茄子、辣椒、番茄等茄科作物的螨害治理；杀卵效果特别优异，同时对幼若螨也有良好的触杀作用，而且持效期长能控制柑桔全爪螨危害达40-50天。
在实际使用中，长期使用单一杀螨剂品种，易造成害螨对单一杀螨剂产生抗性的问题。开发新的杀螨组合物是解决延缓杀螨剂使用寿命和减缓害螨对单一杀螨剂的抗性发展的方法之一。
发明内容
本发明的目的在于提供杀螨组合物，能够提高防效、降低农用成本、延缓害虫抗药性的产生。
本发明提供如下技术方案：
一种组合物，所述组合物含有两种活性成分，第一种活性成分包括选自以下A-7、A-8和A-10所示化合物中的至少一种，第二种活性成分包括选自阿维菌素、甲氨基阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素和弥拜菌素中的至少一种，
Figure PCTCN2018087839-appb-000001
本发明提供的组合物，含有两种活性成分，其中：第一种活性成分可以是包括选自A-7 所示化合物、A-8所示化合物和A-10所示化合物中的至少一种；第二种活性成分可以是包括选自阿维菌素、甲氨基阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素和弥拜菌素中的至少一种。
本发明提供的组合物，对于两种活性成分的配比没有特别要求。理论上，两种活性成分可以以任何配比混合。
优选的是，所述第一种活性成分与第二种活性成分的质量配比为50:1～1:50。
进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为20:1～1:20。
更进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为20:1～1:6。
当第一种活性成分包括选自A-7所示化合物、A-8所示化合物和A-10所示化合物中的一种以上时，第一种活性成分包括的化合物之间可以以任何比例存在。
当第二种活性成分包括选自阿维菌素、甲氨基阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素和弥拜菌素中的一种以上时，所述选自阿维菌素、甲氨基阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素和弥拜菌素中的两种或三种之间可以以任何比例存在。
为了解决上述问题，本发明还可以采用如下技术方案：
一种组合物，所述组合物含有两种活性成分，第一种活性成分包括选自以下A-7、A-8和A-10所示化合物中的至少一种，第二种活性成分包括选自乙螨唑、噻螨酮和四螨嗪中的至少一种，
Figure PCTCN2018087839-appb-000002
本发明提供的组合物，含有两种活性成分，其中：第一种活性成分可以是包括选自A-7所示化合物、A-8所示化合物和A-10所示化合物中的至少一种；第二种活性成分可以是包括选自乙螨唑、噻螨酮和四螨嗪中的至少一种。
本发明提供的组合物，对于两种活性成分的配比没有特别要求。理论上，两种活性成分可以以任何配比混合。
优选的是，所述第一种活性成分与第二种活性成分的质量配比为50:1～1:50。
进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为20:1～1:20。
更进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为9:1～1:9。
当第一种活性成分包括选自A-7所示化合物、A-8所示化合物和A-10所示化合物中的一种以上时，第一种活性成分包括的化合物之间可以以任何比例存在。
当第二种活性成分包括选自乙螨唑、噻螨酮和四螨嗪中的一种以上时，所述选自乙螨唑、噻螨酮和四螨嗪中的两种或三种之间可以以任何比例存在。
为了解决上述问题，本发明还可以采用如下技术方案：
一种组合物，所述组合物含有两种活性成分，第一种活性成分包括选自以下A-7、A-8和A-10所示化合物中的至少一种，第二种活性成分包括选自哒螨灵、喹螨醚、唑螨酯、嘧螨醚和吡螨胺中的至少一种，
Figure PCTCN2018087839-appb-000003
本发明提供的组合物，含有两种活性成分，其中：第一种活性成分可以是包括选自A-7所示化合物、A-8所示化合物和A-10所示化合物中的至少一种；第二种活性成分可以是包括选自哒螨灵、喹螨醚、唑螨酯、嘧螨醚和吡螨胺中的至少一种。
本发明提供的组合物，对于两种活性成分的配比没有特别要求。理论上，两种活性成分可以以任何配比混合。
优选的是，所述第一种活性成分与第二种活性成分的质量配比为50:1～1:50。
进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为20:1～1:20。
更进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为9:1～1:9。
当第一种活性成分包括选自A-7所示化合物、A-8所示化合物和A-10所示化合物中的一种以上时，第一种活性成分包括的化合物之间可以以任何比例存在。
当第二种活性成分包括选自哒螨灵、喹螨醚、唑螨酯、嘧螨醚和吡螨胺中的一种以上时，所述选自哒螨灵、喹螨醚、唑螨酯、嘧螨醚和吡螨胺中的两种、三种或三种以上之间可以以任何比例存在。
为了解决上述问题，本发明还可以采用如下技术方案：
一种组合物，所述组合物含有两种活性成分，第一种活性成分包括选自以下A-7、A-8和A-10所示化合物中的至少一种，第二种活性成分包括植物源杀虫剂，
Figure PCTCN2018087839-appb-000004
所述第一种活性成分与第二种活性成分的质量配比为50:1～1:50。
本发明提供的组合物，所述第一种活性成分包括选自以上A-7、A-8和A-10所示化合物中的至少一种，即可以是选自以上A-7、A-8和A-10所示化合物中的一种、两种或三种。
本发明提供的组合物，所述第一种活性成分包括植物源杀虫剂。
所述植物源杀虫剂，可以是本行业常用的植物源杀虫剂。
优选的是，所述植物源杀虫剂选自印楝素、藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱、氧化苦参碱、闹羊花素-III、血根碱、桉叶素、苦皮藤素、蛇床子素、除虫菌素、茴蒿素、百部碱、桉叶素和楝素中的至少一种。
进一步优选的是，所述植物源杀虫剂选自印楝素、藜芦碱、苦参碱、茶皂素、鱼藤酮和烟碱中的至少一种。
本发明提供的组合物，所述第一种活性成分与第二种活性成分的质量配比，原则上两种活性成分可以按照任意比例混合。
优选的是，所述第一种活性成分与第二种活性成分的质量配比为50:1～1:50。
进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为10:1～1:20。
最优选的是，所述第一种活性成分与第二种活性成分的质量配比为5:1～1:20。
为了解决上述问题，本发明还可以采用如下技术方案：
一种组合物，所述组合物含有两种活性成分，第一种活性成分包括选自以下A-7、A-8和A-10所示化合物中的至少一种，第二种活性成分包括有机锡类杀螨剂，
Figure PCTCN2018087839-appb-000005
所述第一种活性成分与第二种活性成分的质量配比为50:1～1:50。
本发明提供的组合物，所述第一种活性成分包括选自以上A-7、A-8和A-10所示化合物中的至少一种，即可以是选自以上A-7、A-8和A-10所示化合物中的一种、两种或三种。
本发明提供的组合物，所述第一种活性成分包括有机锡类杀螨剂。
所述有机锡类杀螨剂，可以是本行业常用的有机锡类杀螨剂。
优选的是，所述有机锡类杀螨剂选自三唑锡、苯丁锡、三环锡和三磷锡中的至少一种。
本发明提供的组合物，所述第一种活性成分与第二种活性成分的质量配比，原则上两种活性成分可以按照任意比例混合。
优选的是，所述第一种活性成分与第二种活性成分的质量配比为50:1～1:50。
进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为20:1～1:20。
最优选的是，所述第一种活性成分与第二种活性成分的质量配比为5:1～1:10。
为了解决上述问题，本发明还可以采用如下技术方案：
一种组合物，所述组合物含有两种活性成分，第一种活性成分包括选自以下A-7、A-8和A-10所示化合物中的至少一种，第二种活性成分包括有机硫杀螨剂，
Figure PCTCN2018087839-appb-000006
所述第一种活性成分与第二种活性成分的质量配比为1:50～50:1。
本发明提供的组合物，所述第一种活性成分包括选自以上A-7、A-8和A-10所示化合物中的至少一种，即可以是选自以上A-7、A-8和A-10所示化合物中的一种、两种或三种。
本发明提供的组合物，所述第一种活性成分包括有机硫杀螨剂。
所述有机硫杀螨剂，可以是本行业常用的有机硫类杀螨剂。
优选的是，所述有机硫杀螨剂选自炔螨特、丁醚脲、杀螨酯和杀螨硫醚中的至少一种。
本发明提供的组合物，所述第一种活性成分与第二种活性成分的质量配比，原则上两种活性成分可以按照任意比例混合。
优选的是，所述第一种活性成分与第二种活性成分的质量配比为1:50～50:1。
进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为1:20～20:1。
最优选的是，所述第一种活性成分与第二种活性成分的质量配比为1:20～10:1。
为了解决上述问题，本发明还可以采用如下技术方案：
一种组合物，所述组合物含有两种活性成分，第一种活性成分包括选自以下A-7、A-8和A-10所示化合物中的至少一种，第二种活性成分包括菊酯类农药，
Figure PCTCN2018087839-appb-000007
所述第一种活性成分与第二种活性成分的质量配比为1:50～50:1。
本发明提供的组合物，所述第一种活性成分包括选自以上A-7、A-8和A-10所示化合物中的至少一种，即可以是选自以上A-7、A-8和A-10所示化合物中的一种、两种或三种。
本发明提供的组合物，所述第二种活性成分包括菊酯类农药。
所述菊酯类农药，可以是本行业常用的菊酯类农药。
优选的是，所述菊酯类农药选自甲氰菊酯、联苯菊酯、溴氰菊酯、氯氰菊酯、氰戊菊酯、氯氟氰菊酯、高效氯氟氰菊酯、高效氯氰菊酯、氟硅菊酯、炔丙菊酯和四氟醚菊酯中的至少一种。
进一步优选的是，所述菊酯类农药选自甲氰菊酯、联苯菊酯和高效氯氟氰菊酯中的至少一种。
本发明提供的组合物，所述第一种活性成分与第二种活性成分的质量配比，原则上两种活性成分可以按照任意比例混合。
优选的是，所述第一种活性成分与第二种活性成分的质量配比为1:50～50:1。
进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为1:20～20:1。
最优选的是，所述第一种活性成分与第二种活性成分的质量配比为1:9～9:1。
为了解决上述问题，本发明还可以采用如下技术方案：
一种组合物，所述组合物含有两种活性成分，第一种活性成分包括选自以下A-7、A-8和A-10所示化合物中的至少一种，第二种活性成分包括联苯肼酯，
Figure PCTCN2018087839-appb-000008
所述第一种活性成分与第二种活性成分的质量配比为1:50～50:1。
本发明提供的组合物，所述第一种活性成分包括选自以上A-7、A-8和A-10所示化合物中的至少一种，即可以是选自以上A-7、A-8和A-10所示化合物中的一种、两种或三种。
本发明提供的组合物，所述第二种活性成分包括联苯肼酯。
本发明提供的组合物，所述第一种活性成分与第二种活性成分的质量配比，原则上两种活性成分可以按照任意比例混合。
优选的是，所述第一种活性成分与第二种活性成分的质量配比为1:50～50:1。
进一步优选的是，所述第一种活性成分与第二种活性成分的质量配比为1:20～20:1。
最优选的是，所述第一种活性成分与第二种活性成分的质量配比为1:9～9:1。
本发明还提供一种杀螨剂，所述杀螨剂以重量计含有0.1％以上的上述含有两种活性成分的组合物。
优选的是，所述杀螨剂以重量计含有1％～80％的权利要求1所述的上述含有两种活性成分的组合物。
本发明提供的杀螨剂，除上述组合物外，还可以进一步的包括农药上可以接受的、通常用于配制杀虫杀螨组合物的载体和助剂。所述载体可以是固体的，也可以是液体的。
合适的固体载体包括：矿物类、植物类、合成填料类和无机盐类。其中矿物类包括硅酸盐类、碳酸盐类、硫酸盐类和氧化物类。硅酸盐类例如高岭土、海泡石、珍珠陶土、蒙脱土、云母、蛭石、叶蜡石、滑石。碳酸盐类例如：碳酸钙、白云石。硫酸盐类如硫酸铵、硫酸钠、硫酸钙。氧化物类如生石灰、镁石灰、硅藻土。植物类例如：柑橘渣、玉米棒芯、谷壳粉、稻壳、大豆秸粉、烟草粉、胡桃壳、锯木粉。合成填料类如沉淀碳酸钙水合物、沉淀碳酸钙、白炭黑。无机盐类例如氯化钾、氯化钠。
液体载体包括水和有机溶剂。当有效成分为水乳剂或悬乳剂时，有机溶剂起到增溶和防冻作用。合适的有机溶剂包括：芳烃，例如苯、二甲苯、甲苯、烷基苯、烷基萘和氯代芳烃；氯代脂肪烃，例如氯乙烯、三氯甲烷、二氯甲烷、氯仿、四氯化碳和多氯乙烷；脂肪烃，例 如石油馏分、环己烷、轻质矿物油和石蜡；醇类，例如甲醇、乙醇、异丙醇、丁醇、异丁醇，乙二醇、丙二醇、丙三醇、脂肪醇等；醚类，例如甲基乙二醇醚、乙基乙二醇醚、石油醚；酮类，例如丙酮、甲乙酮、甲基异丁基酮、环己酮、异氟尔酮、N-甲基-吡咯烷酮；特种溶剂，例如二甲基甲酰胺、二甲基亚砜、聚乙二醇、已腈；植物油及甲基化植物油。上述有机溶剂既可以单独使用，也可以混合使用，还可以与水一起混合使用。
本发明所述助剂可以根据需要包括选自表面活性剂、消泡剂、增稠剂、助悬剂和防冻剂中的至少一种，还可以根据需要包括本行业常用的其他助剂。
表面活性剂可以是乳化剂、分散剂、稳定剂或湿润剂，也可以是离子型的或非离子型的。合适的表面活性剂包括：聚丙烯酸和木质素磺酸的钠盐和钙盐；分子中含有至少12个碳原子的脂肪酸或脂肪胺与环氧乙烷和/环氧丙烷的缩聚产物；甘油、十二烷醇-1、十四烷醇-1、山梨醇、蔗糖或季戊四醇的脂肪酸酯；及它们与环氧乙烷和/或环氧丙烷的缩聚产物；它们的缩聚产物的硫酸盐或磺酸盐；在分子中至少含有10个碳原子的硫酸或磺酸的碱金属或碱土金属盐，较佳的为钠盐，如十二烷基硫酸钠、仲烷基硫酸钠、磺化蓖麻油的钠盐、烷芳基磺酸钠和十二烷基苯磺酸钠；环氧乙烷的聚合物、环氧乙烷和环氧丙烷的共聚物。
乳化剂包括非离子型乳化剂和市售的乳化剂。非离子型乳化剂优选聚氧乙烯脂肪酸脂、聚氧乙烯脂肪醇醚和聚氧乙烯脂肪氨，例如乙氧基化蓖麻油、聚氧乙烯(n 20)苯乙基酚基醚油酸酯、烷基芳基聚氧乙烯聚氧丙烯醚、烷基芳基甲醛树脂聚氧乙烯醚、三苯乙烯基酚聚氧乙烯(n 20)，醚磷酸化三乙醇胺盐、二苯乙基酚基聚氧乙烯醚(n 18)甲醛缩合物、二苯基酚聚氧乙烯(n 18)聚氧丙烯醚(n 20)等。市售的乳化剂包括：农乳0201B、农乳0203B、农乳100 #、农乳500 #、农乳600 #、农乳600-2 #、农乳1601、农乳2201、农乳NP-10、农乳NP-15、农乳507 #、农乳OX-635、农乳OX-622、农乳OX-653、农乳OX-667、农乳CS-7、宁乳36 #。
本发明所述的分散剂包括：木质素磺酸钠、拉开粉、木质素磺酸钙、甲基萘磺酸甲醛缩合物、萘磺酸甲醛缩合物、亚甲基萘磺酸钠、油酸甲基氨基乙基磺酸钠、环氧聚醚、对叔丁基醚、二丁基萘磺酸甲醛缩合物、磷酸盐如六偏磷酸钠、烷基酚聚氧乙烯基磷酸盐、烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐、N-甲基-脂肪酰基-牛磺酸钠烷基酚聚氧乙烯醚甲醛缩合物、芳烷基酚聚氧乙烯醚磷酸酯烷基酚聚氧乙烯醚、蓖麻油环氧乙烷加成物、环氧乙烷-环氧丙烷嵌段共聚物烷基酚聚氧乙烯醚甲醛缩合物、烷基酚聚氧乙烯聚氧丙烯醚和甲基纤维素。
本发明所述的湿润剂包括：月桂醇硫酸钠、烷基醇聚氧乙烯基醚硫酸钠、辛基酚聚氧乙烯基醚硫酸盐、烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐、烷基磺酸钠、十二烷基苯磺酸钠、烷基萘磺酸钠、烷基丁二酸磺酸盐、月桂醇聚氧乙烯基醚磺酸钠、烷酰胺基牛磺酸钠、脂肪醇聚氧乙烯基醚、烷基酚聚氧乙烯基醚、聚氧乙烯聚氧丙烯嵌段聚合物、失水山梨醇脂肪酸 酯聚氧乙烯基醚等。
本发明所述的增稠剂，既可以是人工合成的，例如羧甲基醇、聚乙烯醇或聚乙酸乙烯酯；也可以是天然的水溶性聚合物，例如黄原胶、明胶、阿拉伯树胶、聚乙烯吡咯烷酮、硅酸铝镁、聚乙烯醇、聚乙二醇、酚醛树脂、虫胶、羧甲基纤维素和海藻酸钠等。
本发明所述的消泡剂优选为：泡敌、硅酮类、C 8～10脂肪醇、C 10～20饱和脂肪酸类及酰胺等。
本发明所述的杀螨剂可以被配制成乳油、悬浮剂、悬乳剂、微乳剂、水乳剂、可湿性粉剂、可溶性粉剂、颗粒剂或胶囊剂。当被配制成制剂时，所述乳油、悬浮剂、悬乳剂、微乳剂、水乳剂、可分散油悬浮剂、可湿性粉剂、可溶性粉剂、颗粒剂或胶囊剂中含有0.1％以上的上述含有两种活性成分的组合物。
当所述杀螨剂为可湿性粉剂时，以重量百分比计含有：含有两种活性成分的组合物0.1％～80％、湿润剂2％～10％、分散剂5％～10％、填料8～90％。
当所述杀螨剂为悬浮剂时，以重量百分比计含有：含有两种活性成分的组合物0.1％～60％、湿润剂1％～5％、分散剂1％～8％、增稠剂0.1％～1％、防冻剂2％～5％、水补齐至100％。
当所述杀螨剂为微乳剂时，以重量百分比计含有：含有两种活性成分的组合物0.1％～40％、乳化剂1％～12％、助溶剂0％～10％、稳定剂0％～5％、溶剂0％～40％、水补齐至100％。
当所述杀螨剂为水乳剂时，以重量百分比计含有：含有两种活性成分的组合物0.1％～80％、乳化剂1％～20％、助溶剂0％～15％、稳定剂0％～5％、溶剂10％～40％、水补齐至100％。
当所述杀螨剂为悬乳剂时，以重量百分比计含有：含有两种活性成分的组合物0.1％～50％、溶剂1％～5％、分散剂1％～5％、乳化剂1％～10％、湿润剂1％～5％、稳定剂1％～5％、防冻剂0％～5％、增稠剂0％～5％、消泡剂0％～5％、水补齐至100％。
当所述杀螨剂为水分散粒剂时，以重量百分比计含有：含有两种活性成分的组合物0.1％～80％、表面活性剂0％～2％、湿润剂1％～15％、分散剂1％～15％、崩解剂1％～10％、稳定剂0％～5％、填料补齐至100％。
当所述杀螨剂为微胶囊悬浮剂时，以重量百分比计含有：含有两种活性成分的组合物0.1％～40％、乳化剂1％～20％、溶剂1％～20％、增稠剂0％～10％、防冻剂0％～10％、稳定剂0％～5％、消泡剂0％～5％、微囊载体1％～10％、水补齐至100％。
当所述杀螨剂为可分散油悬浮剂时，以重量百分比计含有：两种活性成分的组合物0.1％～40％、乳化剂1％～20％、分散剂1％～5％、增稠剂0.5％～3％、载体油相补充至100％。
本发明所述的含有两种活性成分的组合物可以直接制成成品制剂形式，即组合物中各物质已经混合，直接用于杀虫；组合物的成分也可以以由单独制剂提供，使用前在桶(罐)中直接混合。本发明的浓缩物通常与水混合得到所需活性物质的浓度。
本发明还包括本发明所述含有两种活性成分的组合物在控制农林害虫上的用途。本发明提供的含有两种活性成分的组合物适合用于防治农业害螨。具体适合于防治多种重要的农业害虫如棉花叶螨、蔬菜叶螨、山楂叶螨、柑橘全爪螨、柑橘锈螨、苹果叶螨、二斑叶螨、瘿螨、粉螨等。也适合用于防治以下作物中的害螨，例如：果树如苹果、梨、柑桔荔枝等；禾谷类如小麦、水稻等；豆类如大豆、菜豆等；蔬菜如甘蓝、花椰菜、白菜、油菜、番茄、辣椒等；花卉如月季等；棉花，茶树。
本发明所述的杀螨剂施用场所为农田、果园或仓库等。
本发明所述的含有两种活性成分的组合物或杀螨剂可以按普通的方法施用，如浇注、喷射、喷雾。施用量随气候条件或作物状态变化，施用时间可以在害虫危害之前或之后。保护作用的持续时间通常与组合物中单个化合物的含量有关，也与外界因素相关，例如气候，但通过使用适当的剂型可以减缓气候的影响。
本发明所述的含有两种活性成分的组合物也可以与其它具有杀虫、除草、杀菌性能的化合物混合使用，也可以与杀线虫剂、防护剂、生长调节剂、植物营养素或土壤调节剂混合使用。
本发明提供的含有两种活性成分的组合物相比现有技术，具有以下优点：
(1)两种活性成分表现出极强的增效作用，混合后的组合物杀螨效果较其单剂有明显的提高，能够杀死卵、幼螨、若螨和成螨，具有持效期长的特点；
(2)降低了使用剂量，减少农民用药成本；
(3)利用两种活性成分对害螨不同的作用方式、不同的作用机理进行合理地混配，既延长了农药使用寿命，又延缓害螨抗药性的产生。
具体实施方式
下面结合具体实施例来对本发明进行进一步说明，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。
以下实施例中，固体制剂的配比均为重量百分比，液体制剂的配比均为体积百分比，生物活性部分的处理剂量均为有效含量，即“有效成分比”。
第一组：
一、制剂的配制
1、乳油的配制
按配方要求，分别加入溶剂、原药、乳化剂，混合均匀，必要时用水浴加热溶解，即得 到透明状乳油。
实施例1-1、20％乳油，有效成分比9:1
A-8 18％，阿维菌素2％，农乳0203B 6％，农乳0201B 9％，环己酮8％，溶剂油150补足至100％。
实施例1-2、30％乳油，有效成分比5:1
A-8 25％，阿维菌素5％，农乳2201#6％，农乳0201B 8％，环己酮8％，溶剂油150补足至100％。
还可以将A-8替换成本说明书所描述的螺环醚类化合物中的一种，阿维菌素可替换为甲氨基阿阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素、弥拜菌素中的一种形成新的乳油产品。
2、可湿性粉剂的配制
按配方要求，将原药、各种助剂及填料等充分混合，经超细粉碎机粉碎后，即得到加工产品。
实施例1-3、50％可湿性粉剂
A-8 45％，阿维菌素5％，十二烷基苯磺酸钠1.8％，对叔丁基醚2％，白碳黑10％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
实施例1-4、40％可湿性粉剂
A-8 38％，阿维菌素2％，十二烷基苯磺酸钠2％，对叔丁基醚2％，白碳黑5％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
还可以将A-8替换成本说明书所描述的螺环醚类化合物中的一种，阿维菌素可替换为甲氨基阿阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素、弥拜菌素中的一种形成新的可湿性粉剂产品。
3、水分散性粒剂的配制
将原药和粉状载体、润湿展着剂及粘结剂等进行混合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒。然后再经干燥、筛分(按筛网范围)即得颗粒状产品。
实施例1-5、40％水分散性粒剂
A-8 38％，阿维菌素2％，N-甲基-油酰基-牛磺酸钠8％，萘酚磺酸甲醛缩合物10％，可溶性淀粉8％，硫酸钠10％，高岭土补足至100％。
实施例1-6、32％水分散性粒剂
A-8 30％，阿维菌素2％，木质素磺酸钠15％，甲基萘磺酸钠甲醛缩合物5％，环氧聚醚5％，膨润土10％，高岭土补足至100％。
还可以将A-8替换成本说明书所描述的螺环醚类化合物中的一种，阿维菌素可替换为甲氨基阿阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素、弥拜菌素中的一种形成新的水分散性粒剂产品。
4、悬浮剂的配制
按配方要求，以水为介质，将原药、分散剂、润湿剂，助悬剂和防冻剂等混合均匀后加入砂磨机中，进行砂磨至一定的粒径过滤后加入增稠剂剪切搅拌均匀即可。
实施例1-7、20％悬浮剂
A-8 18％，阿维菌素2％，木质素磺酸钠5％，白碳黑0.3％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，磷酸二氢钾0.2％，乙二醇4％，磷酸三丁酯0.2％，水补足至100％。
实施例1-8、20％悬浮剂
A-8 19％，阿维菌素1％，甲基萘磺酸钠甲醛缩合物2.5％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，农乳OX-656 3.0％，丙三醇4％，磷酸三丁酯0.2％，水补足至100％。
还可以将A-8替换成本说明书所描述的螺环醚类化合物中的一种，阿维菌素可替换为甲氨基阿阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素、弥拜菌素中的一种形成新的悬浮剂产品。
5、水乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水，乙二醇混合搅拌配成水相，在高剪切的条件下，将油相缓慢的加入到水相中，即可得到水乳剂。
实施例1-9、14％水乳剂
A-8 12％，阿维菌素2％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯3％，苯乙烯基苯酚甲醛树脂聚氧乙烯聚氧丙烯醚5％，丙二醇3％，水补至100％。
实施例1-10、16％水乳剂
A-8 15％，阿维菌素1％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯4％，端羟基聚氧乙烯聚氧丙烯醚嵌段共聚物5％，乙二醇3％，水补至100％。
还可以将A-8替换成本说明书所描述的螺环醚类化合物中的一种，阿维菌素可替换为甲氨基阿阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素、弥拜菌素中的一种形成新的水乳剂产品。
6、微乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水逐渐加入到油相中，搅拌至均一透明即可。
实施例1-11、10％微乳剂
ZJ-1 9％，阿维菌素1％，异丙醇10％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，苯乙烯基苯基聚氧乙烯醚19％，水补至100％。
实施例1-12、6％微乳剂
A-8 5％，阿维菌素1％，N-辛基吡咯烷酮6％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，烷基酚甲醛树脂聚氧乙烯醚16％，水补至100％。
还可以将A-8替换成本说明书所描述的螺环醚类化合物中的一种，阿维菌素可替换为甲氨基阿阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素、弥拜菌素中的一种形成新的微乳剂产品。
二、室内生物活性测定
为了进一步了解螺环醚类化合物与阿维菌素、甲氨基阿阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素、弥拜菌素的组合物对害虫的毒力，进行了大量配方筛选试验。试验参照杀虫剂农药室内生物测定试验准则(农业行业标准NY/T1154.7-2006)和创制农药生物活性评价SOP(杀虫剂卷)，采用喷雾法。与阿维菌素混配试验为将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，将带有足够多卵的叶片喷雾处理，将叶片重新置于安培瓶中，自然晾干。置于观察室(25±2℃、湿度70％～80％、16h光照/d)内培养。试验重复3次，并设空白对照，待对照全部孵化后进行调查。调查时以不能孵化视为死虫。与多杀菌素混配试验为将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，待卵全部孵化48h后进行喷雾处理，自然晾干。置于观察室(25±2℃、湿度70％～80％、16h光照/d)内培养。试验重复3次，并设空白对照，48h后进行调查。调查时以不能正常爬行为死虫。
Figure PCTCN2018087839-appb-000009
理论混用毒力指数(TTI)＝A的毒力指数×A在混用中的含量(％)
+B的毒力指数×B在混用中的含量(％)
Figure PCTCN2018087839-appb-000010
共毒系数若大于120，表明有增效作用；若小于80，表明为拮抗作用；若大于80小于120，表明为相加作用。
结果表明：螺环醚类化合物与阿维菌素、甲氨基阿阿维菌素、多杀菌素、乙基多杀菌素、 伊维菌素、米尔贝霉素、天维菌素、弥拜菌素混配对供试靶标均有很高的活性，混配后表现出显著的增效作用。
实施例1-13、A-8与阿维菌素联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
阿维菌素 - 0.0389 964.27    
A-8 - 0.3751 100.00    
阿维菌素：A-8 50:1 0.0328 1143.29 947.32 120.69
阿维菌素：A-8 20:1 0.0331 1132.93 923.11 122.73
阿维菌素：A-8 12:1 0.0319 1175.55 897.79 130.94
阿维菌素：A-8 9:1 0.0325 1153.85 877.84 131.44
阿维菌素：A-8 6:1 0.0311 1205.79 840.80 143.41
阿维菌素：A-8 3:1 0.0351 1068.38 748.20 142.79
阿维菌素：A-8 1:1 0.0486 771.60 532.13 145.00
阿维菌素：A-8 1:3 0.0824 455.10 316.07 143.99
阿维菌素：A-8 1:6 0.1124 333.63 223.47 149.30
阿维菌素：A-8 1:9 0.1355 276.75 186.43 148.45
阿维菌素：A-8 1:12 0.1524 246.06 166.48 147.80
阿维菌素：A-8 1:20 0.1796 208.80 141.16 147.92
阿维菌素：A-8 1:50 0.2514 149.16 116.95 127.55
实施例1-14、A-9与阿维菌素联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
阿维菌素 - 0.0366 872.40    
A-9 - 0.3193 100.00    
阿维菌素：A-9 50:1 0.0306 1042.48 857.26 121.61
阿维菌素：A-9 20:1 0.0311 1025.72 835.62 122.75
阿维菌素：A-9 12:1 0.0299 1066.89 812.99 131.23
阿维菌素：A-9 9:1 0.0292 1092.47 795.16 137.39
阿维菌素：A-9 6:1 0.0297 1074.07 762.06 140.94
阿维菌素：A-9 3:1 0.0328 972.56 679.30 143.17
阿维菌素：A-9 1:1 0.0466 684.55 486.20 140.80
阿维菌素：A-9 1:3 0.0764 417.54 293.10 142.46
阿维菌素：A-9 1:6 0.1051 303.52 210.34 144.30
阿维菌素：A-9 1:9 0.1234 258.51 177.24 145.85
阿维菌素：A-9 1:12 0.1362 234.21 159.42 146.92
阿维菌素：A-9 1:20 0.1601 199.25 136.78 145.67
阿维菌素：A-9 1:50 0.2072 153.96 115.15 133.71
实施例1-15、A-10与阿维菌素联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
阿维菌素 - 0.0397 1066.75    
A-10 - 0.4235 100.00    
阿维菌素：A-10 50:1 0.0335 1262.69 1047.79 120.51
阿维菌素：A-10 20:1 0.0339 1247.79 1020.71 122.25
阿维菌素：A-10 12:1 0.0324 1305.56 992.39 131.56
阿维菌素：A-10 9:1 0.0321 1317.76 970.08 135.84
阿维菌素：A-10 6:1 0.0325 1301.54 928.64 140.15
阿维菌素：A-10 3:1 0.0371 1140.16 825.06 138.19
阿维菌素：A-10 1:1 0.0523 808.80 583.38 138.64
阿维菌素：A-10 1:3 0.0864 489.58 341.69 143.28
阿维菌素：A-10 1:6 0.1234 342.79 238.11 143.96
阿维菌素：A-10 1:9 0.1507 280.69 196.68 142.72
阿维菌素：A-10 1:12 0.1681 251.64 174.37 144.32
阿维菌素：A-10 1:20 0.1974 214.29 146.04 146.74
阿维菌素：A-10 1:50 0.2741 154.32 118.96 129.73
实施例1-16、A-8与多杀菌素联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
多杀菌素 - 1.762 19.35 - -
A-8 - 0.341 100.00 - -
多杀菌素：A-8 50:1 1.354 25.18 20.93 120.30
多杀菌素：A-8 20:1 1.234 27.63 23.19 119.15
多杀菌素：A-8 12:1 1.022 33.37 25.56 130.56
多杀菌素：A-8 9:1 0.875 38.97 27.42 142.14
多杀菌素：A-8 6:1 0.799 42.68 30.87 138.23
多杀菌素：A-8 3:1 0.621 54.91 39.51 138.96
多杀菌素：A-8 1:1 0.401 85.04 59.68 142.50
多杀菌素：A-8 1:3 0.305 111.80 79.84 140.04
多杀菌素：A-8 1:6 0.268 127.24 88.48 143.81
多杀菌素：A-8 1:9 0.253 134.78 91.94 146.61
多杀菌素：A-8 1:12 0.251 135.86 93.80 144.84
多杀菌素：A-8 1:20 0.243 140.33 96.16 145.93
多杀菌素：A-8 1:50 0.264 129.17 98.42 131.24
实施例1-17、A-9与多杀菌素联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
多杀菌素 - 1.937 21.79 - -
A-9 - 0.422 100.00 - -
多杀菌素：A-9 50:1 1.498 28.17 23.32 120.80
多杀菌素：A-9 20:1 1.335 31.61 25.51 123.91
多杀菌素：A-9 12:1 1.175 35.91 27.80 129.18
多杀菌素：A-9 9:1 1.021 41.33 29.61 139.60
多杀菌素：A-9 6:1 0.924 45.67 32.96 138.57
多杀菌素：A-9 3:1 0.736 57.34 41.34 138.70
多杀菌素：A-9 1:1 0.498 84.74 60.89 139.16
多杀菌素：A-9 1:3 0.371 113.75 80.45 141.39
多杀菌素：A-9 1:6 0.324 130.25 88.83 146.63
多杀菌素：A-9 1:9 0.311 135.69 92.18 147.20
多杀菌素：A-9 1:12 0.304 138.82 93.98 147.70
多杀菌素：A-9 1:20 0.3 140.67 96.28 146.11
多杀菌素：A-9 1:50 0.324 130.25 98.47 132.28
实施例1-18、A-10与多杀菌素联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
多杀菌素 - 1.664 19.65    
A-10 - 0.327 100.00    
多杀菌素：A-10 50:1 1.261 25.93 21.23 122.16
多杀菌素：A-10 20:1 1.159 28.21 23.48 120.17
多杀菌素：A-10 12:1 0.961 34.03 25.83 131.72
多杀菌素：A-10 9:1 0.851 38.43 27.69 138.79
多杀菌素：A-10 6:1 0.748 43.72 31.13 140.43
多杀菌素：A-10 3:1 0.587 55.71 39.74 140.18
多杀菌素：A-10 1:1 0.389 84.06 59.83 140.51
多杀菌素：A-10 1:3 0.288 113.54 79.91 142.08
多杀菌素：A-10 1:6 1.964 166.70 113.82 146.46
多杀菌素：A-10 1:9 2.057 159.16 109.68 145.12
多杀菌素：A-10 1:12 2.104 155.61 107.44 144.83
多杀菌素：A-10 1:20 2.141 152.92 104.61 146.18
多杀菌素：A-10 1:50 2.434 134.51 101.90 132.01
三、田间小区防治效果
实施例1-19、对柑橘红蜘蛛的田间药效试验
在田间条件下测定对柑橘红蜘蛛的防治效果。试验根据“农药田间药效试验准则(一)——杀虫剂防治柑橘红蜘蛛”的规定进行，每试验小区柑橘叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天，各混配制剂对柑橘红蜘蛛防效分别为95.6％-97.8％、96.9％-98.4％和96.8％-97.9％，防治柑橘红蜘蛛效果均好于1.8％阿维菌素乳油、20％A-8悬浮剂、20％A-9悬浮剂和20％A-10悬浮剂。
对柑橘红蜘蛛的田间药效试验结果
Figure PCTCN2018087839-appb-000011
实施例1-20、对苹果红蜘蛛的田间药效试验
在田间条件下测定对苹果红蜘蛛的防治效果。试验地位于山东省肥城安庄镇，品种为新红星，株行距3m*4m。施药量为1150kg/hm 2。药后7天、14天、21天调查结果。每试验小区苹果叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天对苹果红蜘蛛防效分别为97.6％-99.4％、95.1％-99.5％和94.2％-97.7％，防治苹果红蜘蛛效果均好于好于1.8％阿维菌素乳油、20％A-8悬浮剂、20％A-9悬浮剂和20％A-10悬浮剂。
对苹果红蜘蛛的田间药效试验结果
Figure PCTCN2018087839-appb-000012
Figure PCTCN2018087839-appb-000013
从以上数据可知，本发明提供的组合物，不仅对于防治柑橘红蜘蛛和苹果红蜘蛛具有明显的协同作用且效果优于单剂，而且能够减少用药量、延缓单一药剂带来的抗药性问题。
第二组：
一、组合物的制备与生物活性实例
1、乳油的配制
按配方要求，分别加入溶剂、原药、乳化剂，混合均匀，必要时用水浴加热溶解，即得到透明状乳油。
实施例2-1、20％乳油
A-8 10％，乙螨唑10％，农乳0203B 6％，农乳0201B 9％，环己酮8％，溶剂油150补足至100％。
实施例2-2、20％乳油
A-8 15％，乙螨唑5％，农乳2201# 6％，农乳0201B 8％，环己酮8％，溶剂油150补足至100％。
还可以将A-8替换成本说明书所描述的A-7、A-10中的一种，乙螨唑可替换为噻螨酮或四螨嗪中的一种形成新的乳油产品。
2、可湿性粉剂的配制
按配方要求，将原药、各种助剂及填料等充分混合，经超细粉碎机粉碎后，即得到加工产品。
实施例2-3、40％可湿性粉剂
A-8 30％，乙螨唑10％，十二烷基苯磺酸钠1.8％，对叔丁基醚2％，白碳黑10％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
实施例2-4、30％可湿性粉剂
A-8 20％，乙螨唑10％，十二烷基苯磺酸钠2％，对叔丁基醚2％，白碳黑5％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
还可以将A-8替换成本说明书所描述的A-7、A-10中的一种，乙螨唑可替换为噻螨酮或四螨嗪中的一种形成新的可湿性粉剂产品。
3水分散性粒剂的配制
将原药和粉状载体、润湿展着剂及粘结剂等进行混合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒。然后再经干燥、筛分(按筛网范围)即得颗粒状产品。
实施例2-5、40％水分散性粒剂
A-8 30％，乙螨唑10％，N-甲基-油酰基-牛磺酸钠8％，萘酚磺酸甲醛缩合物10％，可溶性淀粉8％，硫酸钠10％，高岭土补足至100％。
实施例2-6、60％水分散性粒剂
A-8 50％，乙螨唑10％，木质素磺酸钠15％，甲基萘磺酸钠甲醛缩合物5％，环氧聚醚5％，膨润土10％，高岭土补足至100％。
还可以将A-8替换成本说明书所描述的A-7、A-10中的一种，乙螨唑可替换为噻螨酮或四螨嗪中的一种形成新的水分散性粒剂产品。
4悬浮剂的配制
按配方要求，以水为介质，将原药、分散剂、润湿剂，助悬剂和防冻剂等混合均匀后加入砂磨机中，进行砂磨至一定的粒径过滤后加入增稠剂剪切搅拌均匀即可。
实施例2-7、40％悬浮剂
A-8 30％，乙螨唑10％，木质素磺酸钠5％，白碳黑0.3％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，磷酸二氢钾0.2％，乙二醇4％，磷酸三丁酯0.2％，水补足至100％。
实施例2-8、25％悬浮剂
A-8 20％，乙螨唑5％，甲基萘磺酸钠甲醛缩合物2.5％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，农乳OX-656 3.0％，丙三醇4％，磷酸三丁酯0.2％，水补足至100％。
还可以将A-8替换成本说明书所描述的A-7、A-10中的一种，乙螨唑可替换为噻螨酮或四螨嗪中的一种形成新的悬浮剂产品。
5水乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水，乙二醇混合搅拌配成水相，在高剪切的条件下，将油相缓慢的加入到水相中，即可得到水乳剂。
实施例2-9、20％水乳剂
A-8 15％，乙螨唑5％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯3％，苯乙烯 基苯酚甲醛树脂聚氧乙烯聚氧丙烯醚5％，丙二醇3％，水补至100％。
实施例2-10、20％水乳剂
A-8 10％，乙螨唑10％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯4％，端羟基聚氧乙烯聚氧丙烯醚嵌段共聚物5％，乙二醇3％，水补至100％。
还可以将A-8替换成本说明书所描述的A-7、A-10中的一种，乙螨唑可替换为噻螨酮或四螨嗪中的一种形成新的水乳剂产品。
6微乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水逐渐加入到油相中，搅拌至均一透明即可。
实施例2-11、25％微乳剂
A-8 20％，乙螨唑5％，异丙醇10％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，苯乙烯基苯基聚氧乙烯醚19％，水补至100％。
实施例2-12、20％微乳剂
A-8 10％，乙螨唑10％，N-辛基吡咯烷酮6％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，烷基酚甲醛树脂聚氧乙烯醚16％，水补至100％。
还可以将A-8替换成本说明书所描述的A-7、A-10中的一种，乙螨唑可替换为噻螨酮或四螨嗪中的一种形成新的微乳剂产品。
7可分散油悬浮剂的配制
将活性组分、分散剂、乳化剂、增稠剂和载体油相混合均匀后，加入到砂磨机中，研磨至一定的粒径即可。
实施例2-13、10％可分散油悬浮剂
A-8 5％，乙螨唑5％，烷基酚聚氧乙烯醚磷酸酯2％，蓖麻油聚氧乙烯醚13％，有机膨润土2％，油酸甲酯补齐至100％。
A-8 10％,乙螨唑20％，三苯乙基酚聚氧乙烯醚磷酸酯3％，脂肪醇聚氧乙烯醚14％，有机膨润土1.5％，油酸甲酯补齐至100％。
二、室内生物活性测定
为了进一步了解A-7、A-10与乙螨唑、噻螨酮或四螨嗪的组合物对害虫的毒力，进行了大量配方筛选试验。试验参照杀虫剂农药室内生物测定试验准则(农业行业标准NY/T1154.7-2006)和创制农药生物活性评价SOP(杀虫剂卷)，采用喷雾法。将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，将带有 足够多卵的叶片喷雾处理，将叶片重新置于安培瓶中，自然晾干。置于观察室(25±2℃、湿度70％～80％、16h光照/d)内培养。试验重复4次，并设空白对照，待对照全部孵化后进行调查。调查时以不能孵化视为死虫。
Figure PCTCN2018087839-appb-000014
理论混用毒力指数(TTI)＝A的毒力指数×A在混用中的含量(％)
+B的毒力指数×B在混用中的含量(％)
Figure PCTCN2018087839-appb-000015
共毒系数若大于120，表明有增效作用；若小于80，表明为拮抗作用；若大于80小于120，表明为相加作用。
结果表明：试验结果：A-7、A-8或A-10与乙螨唑或噻螨酮混配对供试靶标均有很高的活性，混配后表现出显著的增效作用。
实施例2-14、A-8与乙螨唑联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
Figure PCTCN2018087839-appb-000016
Figure PCTCN2018087839-appb-000017
实施例2-15、A-7与乙螨唑联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
Figure PCTCN2018087839-appb-000018
实施例2-16、A-10与乙螨唑联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
Figure PCTCN2018087839-appb-000019
实施例2-17、A-8与噻螨酮联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
Figure PCTCN2018087839-appb-000020
Figure PCTCN2018087839-appb-000021
实施例2-18、A-7与噻螨酮联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
Figure PCTCN2018087839-appb-000022
Figure PCTCN2018087839-appb-000023
实施例2-19、A-10与噻螨酮联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
Figure PCTCN2018087839-appb-000024
Figure PCTCN2018087839-appb-000025
三、田间小区防治试验
实验例2-20、对柑橘红蜘蛛的田间药效试验
在田间条件下测定对柑橘红蜘蛛的防治效果。试验根据“农药田间药效试验准则(一)——杀虫剂防治柑橘红蜘蛛”的规定进行，每试验小区柑橘叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天，各混配制剂对柑橘红蜘蛛防效分别为95.9％-99.6％、96.4％-99.2％和95.2％-99.4％，防治柑橘红蜘蛛效果均好于11％乙螨唑悬浮剂、5％噻螨酮可湿性粉剂、20％A-8悬浮剂、20％A-7悬浮剂和20％A-10悬浮剂。
对柑橘红蜘蛛的田间药效试验结果
Figure PCTCN2018087839-appb-000026
Figure PCTCN2018087839-appb-000027
实验例2-21、对苹果红蜘蛛的田间药效试验
在田间条件下测定对苹果红蜘蛛的防治效果。施药量为1150kg/hm 2。药后7天、14天、21天调查结果。每试验小区苹果叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天对苹果红蜘蛛防效分别为95.2％-99.3％、95.7％-99.1％和94.3％-99.2％，防治苹果红蜘蛛效果均好于好于11％乙螨唑悬浮剂、5％噻螨酮可湿性粉剂、20％A-8悬浮剂、20％A-7悬浮剂和20％A-10悬浮剂。
对苹果红蜘蛛的田间药效试验结果
Figure PCTCN2018087839-appb-000028
Figure PCTCN2018087839-appb-000029
以上数据说明，本发明提供的杀螨组合物不仅对于防治柑橘红蜘蛛具有明显的协同作用，效果优于单独使用A-7、A-9、A-10、乙螨唑或噻螨酮，而且能够减少用药量、延缓单一药剂带来的抗药性问题。
第三组：
一、制剂制备
1、乳油的配制
按配方要求，分别加入溶剂、原药、乳化剂，混合均匀，必要时用水浴加热溶解，即得到透明状乳油。
实施例3-1、15％乳油
A-8 5％，哒螨灵10％，农乳0203B 6％，农乳0201B 9％，环己酮8％，溶剂油150补足至100％。
实施例3-2、20％乳油
A-8 10％，哒螨灵10％，农乳2201# 6％，农乳0201B 8％，环己酮8％，溶剂油150补足至100％。
还可以将A-8替换成本说明书所描述的螺环醚类衍生物中的一种，哒螨灵可替换为喹螨醚、唑螨酯、嘧螨醚、吡螨胺中的一种形成新的乳油产品。
2、可湿性粉剂的配制
按配方要求，将原药、各种助剂及填料等充分混合，经超细粉碎机粉碎后，即得到加工产品。
实施例3-3、40％可湿性粉剂
A-8 30％，哒螨灵10％，十二烷基苯磺酸钠1.8％，对叔丁基醚2％，白碳黑10％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
实施例3-4、40％可湿性粉剂
A-8 20％，哒螨灵20％，十二烷基苯磺酸钠2％，对叔丁基醚2％，白碳黑5％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
还可以将A-8替换成本说明书所描述的螺环醚类衍生物中的一种，哒螨灵可替换为喹螨醚、唑螨酯、嘧螨醚、吡螨胺中的一种形成新的可湿性粉剂产品。
3、水分散性粒剂的配制
将原药和粉状载体、润湿展着剂及粘结剂等进行混合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒。然后再经干燥、筛分(按筛网范围)即得颗粒状产品。
实施例3-5、60％水分散性粒剂
A-8 30％，哒螨灵30％，N-甲基-油酰基-牛磺酸钠8％，萘酚磺酸甲醛缩合物10％，可溶性淀粉8％，硫酸钠10％，高岭土补足至100％。
实施例3-6、60％水分散性粒剂
A-8 40％，哒螨灵20％，木质素磺酸钠15％，甲基萘磺酸钠甲醛缩合物5％，环氧聚醚5％，膨润土10％，高岭土补足至100％。
还可以将A-8替换成本说明书所描述的螺环醚类衍生物中的一种，哒螨灵可替换为喹螨醚、唑螨酯、嘧螨醚、吡螨胺中的一种形成新的水分散性粒剂产品。
4、悬浮剂的配制
按配方要求，以水为介质，将原药、分散剂、润湿剂，助悬剂和防冻剂等混合均匀后加入砂磨机中，进行砂磨至一定的粒径过滤后加入增稠剂剪切搅拌均匀即可。
实施例3-7、20％悬浮剂
A-8 10％，哒螨灵10％，木质素磺酸钠5％，白碳黑0.3％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，磷酸二氢钾0.2％，乙二醇4％，磷酸三丁酯0.2％，水补足至100％。
实施例3-8、30％悬浮剂
A-8 10％，哒螨灵20％，甲基萘磺酸钠甲醛缩合物2.5％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，农乳OX-656 3.0％，丙三醇4％，磷酸三丁酯0.2％，水补足至100％。
还可以将A-8替换成本说明书所描述的螺环醚类衍生物中的一种，哒螨灵可替换为喹螨醚、唑螨酯、嘧螨醚、吡螨胺中的一种形成新的悬浮剂产品。
5、水乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水，乙二醇混合搅拌配成水相，在高剪切的条件下，将油相缓慢的加入到水相中，即可得到水乳剂。
实施例3-9、20％水乳剂
A-8 5％，哒螨灵15％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯3％，苯乙烯基苯酚甲醛树脂聚氧乙烯聚氧丙烯醚5％，丙二醇3％，水补至100％。
实施例3-10、31.5％水乳剂
A-8 30％，哒螨灵1.5％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯4％，端羟基聚氧乙烯聚氧丙烯醚嵌段共聚物5％，乙二醇3％，水补至100％。
还可以将A-8替换成本说明书所描述的螺环醚类衍生物中的一种，哒螨灵可替换为喹螨 醚、唑螨酯、嘧螨醚、吡螨胺中的一种形成新的水乳剂产品。
6、微乳剂的配制
将原药、溶剂、乳化剂混合搅拌均匀配成均一油相，将水逐渐加入到油相中，搅拌至均一透明即可。
实施例3-11、25％微乳剂
A-8 20％，哒螨灵5％，异丙醇10％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，苯乙烯基苯基聚氧乙烯醚19％，水补至100％。
实施例3-12、20％微乳剂
A-8 10％，哒螨灵10％，N-辛基吡咯烷酮6％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，烷基酚甲醛树脂聚氧乙烯醚16％，水补至100％。
还可以将A-8替换成本说明书所描述的螺环醚类衍生物中的一种，哒螨灵可替换为喹螨醚、唑螨酯、嘧螨醚、吡螨胺中的一种形成新的微乳剂产品。
二、室内生物活性测定
为了进一步了解螺环醚类衍生物与选自哒螨灵、喹螨醚、唑螨酯、嘧螨醚和吡螨胺中至少一种的组合物对害虫的毒力，进行了大量配方筛选试验。试验参照杀虫剂农药室内生物测定试验准则(农业行业标准NY/T1154.7-2006)和创制农药生物活性评价SOP(杀虫剂卷)，采用喷雾法。将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，将带有足够多卵的叶片喷雾处理，将叶片重新置于安培瓶中，自然晾干。置于观察室(25±21℃、湿度70％～80％、16h光照/d)内培养。试验重复4次，并设空白对照，待对照全部孵化后进行调查。调查时以不能孵化视为死虫。
Figure PCTCN2018087839-appb-000030
理论混用毒力指数(TTI)＝A的毒力指数×A在混用中的含量(％)
+B的毒力指数×B在混用中的含量(％)
Figure PCTCN2018087839-appb-000031
共毒系数若大于120，表明有增效作用；若小于80，表明为拮抗作用；若大于80小于120，表明为相加作用。
结果表明：试验结果：螺环醚类衍生物与哒螨灵、喹螨醚、唑螨酯、嘧螨醚、吡螨胺混 配对供试靶标均有很高的活性，混配后表现出显著的增效作用。
实施例3-13、A-8与哒螨灵联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
哒螨灵 - 0.678 46.31 - -
A-8 - 0.314 100.00 - -
哒螨灵：A-8 50:1 0.549 57.19 47.37 120.75
哒螨灵：A-8 20:1 0.491 63.95 48.87 130.86
哒螨灵：A-8 9:1 0.432 72.69 51.68 140.64
哒螨灵：A-8 7:1 0.405 77.53 53.02 146.22
哒螨灵：A-8 5:1 0.398 78.89 55.26 142.77
哒螨灵：A-8 3:1 0.354 88.70 59.73 148.49
哒螨灵：A-8 1:1 0.288 109.03 73.16 149.03
哒螨灵：A-8 1:3 0.246 127.64 86.58 147.43
哒螨灵：A-8 1:5 0.237 132.49 91.05 145.51
哒螨灵：A-8 1:7 0.232 135.34 93.29 145.08
哒螨灵：A-8 1:9 0.237 132.49 94.63 140.01
哒螨灵：A-8 1:20 0.244 128.69 97.44 132.06
哒螨灵：A-8 1:50 0.261 120.31 98.95 121.59
实施例3-14、A-9与哒螨灵联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
哒螨灵 - 0.594 62.63 - -
A-9 - 0.372 100.00 - -
哒螨灵：A-9 50:1 0.486 76.54 63.36 120.81
哒螨灵：A-9 20:1 0.441 84.35 64.41 130.97
哒螨灵：A-9 9:1 0.396 93.94 66.36 141.55
哒螨灵：A-9 7:1 0.372 100.00 67.30 148.59
哒螨灵：A-9 5:1 0.373 99.73 68.86 144.84
哒螨灵：A-9 3:1 0.343 108.45 71.97 150.70
哒螨灵：A-9 1:1 0.302 123.18 81.31 151.49
哒螨灵：A-9 1:3 0.291 127.84 90.66 141.01
哒螨灵：A-9 1:5 0.274 135.77 93.77 144.79
哒螨灵：A-9 1:7 0.273 136.26 95.33 142.94
哒螨灵：A-9 1:9 0.275 135.27 96.26 140.52
哒螨灵：A-9 1:20 0.288 129.17 98.22 131.51
哒螨灵：A-9 1:50 0.311 119.61 99.27 120.50
实施例3-15、A-10与哒螨灵联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
哒螨灵 - 0.524 64.31 - -
A-10 - 0.337 100.00 - -
哒螨灵：A-10 50:1 0.431 78.19 65.01 120.27
哒螨灵：A-10 20:1 0.391 86.19 66.01 130.57
哒螨灵：A-10 9:1 0.351 96.01 67.88 141.44
哒螨灵：A-10 7:1 0.336 100.30 68.77 145.84
哒螨灵：A-10 5:1 0.322 104.66 70.26 148.96
哒螨灵：A-10 3:1 0.305 110.49 73.23 150.87
哒螨灵：A-10 1:1 0.271 124.35 82.16 151.36
哒螨灵：A-10 1:3 0.254 132.68 91.08 145.67
哒螨灵：A-10 1:5 0.252 133.73 94.05 142.19
哒螨灵：A-10 1:7 0.249 135.34 95.54 141.66
哒螨灵：A-10 1:9 0.248 135.89 96.43 140.92
哒螨灵：A-10 1:20 0.261 129.12 98.30 131.35
哒螨灵：A-10 1:50 0.281 119.93 99.30 120.77
实施例3-16、A-8与唑螨酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
唑螨酯 - 13.548 2.40 - -
A-8 - 0.325 100.00 - -
唑螨酯：A-8 50:1 6.301 5.16 4.31 119.60
唑螨酯：A-8 20:1 3.502 9.28 7.05 131.70
唑螨酯：A-8 9:1 1.911 17.01 12.16 139.87
唑螨酯：A-8 7:1 1.547 21.01 14.60 143.90
唑螨酯：A-8 5:1 1.238 26.25 18.67 140.64
唑螨酯：A-8 3:1 0.811 40.07 26.80 149.53
唑螨酯：A-8 1:1 0.421 77.20 51.20 150.78
唑螨酯：A-8 1:3 0.305 106.56 75.60 140.95
唑螨酯：A-8 1:5 0.273 119.05 83.73 142.18
唑螨酯：A-8 1:7 0.263 123.57 87.80 140.75
唑螨酯：A-8 1:9 0.254 127.95 90.24 141.79
唑螨酯：A-8 1:20 0.259 125.48 95.35 131.60
唑螨酯：A-8 1:50 0.274 118.61 98.09 120.93
实施例3-17、A-9与唑螨酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
唑螨酯 - 15.217 2.36 - -
A-9 - 0.359 100.00 - -
唑螨酯：A-9 50:1 6.923 5.19 4.27 121.34
唑螨酯：A-9 20:1 3.914 9.17 7.01 130.87
唑螨酯：A-9 9:1 2.12 16.93 12.12 139.68
唑螨酯：A-9 7:1 1.752 20.49 14.56 140.69
唑螨酯：A-9 5:1 1.334 26.91 18.63 144.43
唑螨酯：A-9 3:1 0.878 40.89 26.77 152.74
唑螨酯：A-9 1:1 0.465 77.20 51.18 150.85
唑螨酯：A-9 1:3 0.339 105.90 75.59 140.10
唑螨酯：A-9 1:5 0.302 118.87 83.73 141.98
唑螨酯：A-9 1:7 0.287 125.09 87.79 142.48
唑螨酯：A-9 1:9 0.281 127.76 90.24 141.58
唑螨酯：A-9 1:20 0.287 125.09 95.35 131.19
唑螨酯：A-9 1:50 0.305 117.70 98.09 120.00
实施例3-18、A-10与唑螨酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
唑螨酯 - 12.782 2.57 - -
A-10 - 0.329 100.00 - -
唑螨酯：A-10 50:1 5.998 5.49 4.48 122.32
唑螨酯：A-10 20:1 3.456 9.52 7.21 131.97
唑螨酯：A-10 9:1 1.897 17.34 12.32 140.81
唑螨酯：A-10 7:1 1.563 21.05 14.75 142.69
唑螨酯：A-10 5:1 1.241 26.51 18.81 140.93
唑螨酯：A-10 3:1 0.812 40.52 26.93 150.45
唑螨酯：A-10 1:1 0.427 77.05 51.29 150.23
唑螨酯：A-10 1:3 0.308 106.82 75.64 141.21
唑螨酯：A-10 1:5 0.276 119.20 83.76 142.31
唑螨酯：A-10 1:7 0.263 125.10 87.82 142.44
唑螨酯：A-10 1:9 0.257 128.02 90.26 141.83
唑螨酯：A-10 1:20 0.265 124.15 95.36 130.19
唑螨酯：A-10 1:50 0.279 117.92 98.09 120.22
三、田间小区防治试验
实施例3-19、对柑橘红蜘蛛的田间药效试验
在田间条件下测定对柑橘红蜘蛛的防治效果。试验根据“农药田间药效试验准则(一)——杀虫剂防治柑橘红蜘蛛”的规定进行，每试验小区柑橘叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天，各混配制剂对柑橘红蜘蛛防效分别为97.4％～99.3％、97.7％～99.5％和97.3％～99.5％，防治柑橘红蜘蛛效果均好于20％哒螨灵可湿性粉剂、5％唑螨酯悬浮剂、20％的A-8悬浮剂、20％的A-9悬浮剂和20％的A-10悬浮剂。
对柑橘红蜘蛛的田间药效试验结果
Figure PCTCN2018087839-appb-000032
Figure PCTCN2018087839-appb-000033
实施例3-20、对苹果红蜘蛛的田间药效试验
在田间条件下测定对苹果红蜘蛛的防治效果。试验地位于山东省肥城安庄镇，品种为新红星，株行距3m*4m。施药量为1150kg/hm 2。药后7天、14天、21天调查结果。每试验小区苹果叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天对苹果红蜘蛛防效分别为96.4％～98.4％、96.5％～98.9％和96.3％～98.5％，防治苹果红蜘蛛效果均好于好于20％哒螨灵可湿性粉剂、5％唑螨酯悬浮剂、20％的A-8悬浮剂、20％的A-9悬浮剂和20％的A-10悬浮剂。。
对苹果红蜘蛛的田间药效试验结果
Figure PCTCN2018087839-appb-000034
Figure PCTCN2018087839-appb-000035
从以上数据可以看出，本发明提供的活性组合物不仅对于防治柑橘红蜘蛛具有明显的协同作用且效果优于单独使用A-8、A-9、A-10、哒螨灵或唑螨酯，而且能够减少用药量、延缓单一药剂带来的抗药性问题。
第四组：
一、组合物的制备
1、乳油的配制
按配方要求，分别加入溶剂、原药、乳化剂，混合均匀，必要时用水浴加热溶解，即得到透明状乳油。
实施例4-1、15％乳油
A-7 5％，印楝素10％，农乳0203B 6％，农乳0201B 9％，环己酮8％，溶剂油150补足至100％。
实施例4-2、20％乳油
A-7 10％，印楝素10％，农乳2201# 6％，农乳0201B 8％，环己酮8％，溶剂油150补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，印楝素可替换为藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱中的一种形成新的乳油产品。
2、可湿性粉剂的配制
按配方要求，将原药、各种助剂及填料等充分混合，经超细粉碎机粉碎后，即得到加工产品。
实施例4-3、40％可湿性粉剂
A-7 15％，印楝素25％，十二烷基苯磺酸钠1.8％，对叔丁基醚2％，白碳黑10％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
实施例4-4、50％可湿性粉剂
A-7 20％，印楝素30％，十二烷基苯磺酸钠2％，对叔丁基醚2％，白碳黑5％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，印楝素可替换为藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱中的一种形成新的可湿性粉剂产品。
3、水分散性粒剂的配制
将原药和粉状载体、润湿展着剂及粘结剂等进行混合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒。然后再经干燥、筛分(按筛网范围)即得颗粒状产品。
实施例4-5、40％水分散性粒剂
A-7 10％，印楝素30％，N-甲基-油酰基-牛磺酸钠8％，萘酚磺酸甲醛缩合物10％，可溶性淀粉8％，硫酸钠10％，高岭土补足至100％。
实施例4-6、50％水分散性粒剂
A-7 25％，印楝素25％，木质素磺酸钠15％，甲基萘磺酸钠甲醛缩合物5％，环氧聚醚5％，膨润土10％，高岭土补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，印楝素可替换为藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱中的一种形成新的水分散性粒剂产品。
4、悬浮剂的配制
按配方要求，以水为介质，将原药、分散剂、润湿剂，助悬剂和防冻剂等混合均匀后加入砂磨机中，进行砂磨至一定的粒径过滤后加入增稠剂剪切搅拌均匀即可。
实施例4-7、30％悬浮剂
A-7 15％，印楝素15％，木质素磺酸钠5％，白碳黑0.3％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，磷酸二氢钾0.2％，乙二醇4％，磷酸三丁酯0.2％，水补足至100％。
实施例4-8、50％悬浮剂
A-7 20％，印楝素30％，甲基萘磺酸钠甲醛缩合物2.5％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，农乳OX-656 3.0％，丙三醇4％，磷酸三丁酯0.2％，水补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，印楝素可替换为藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱中的一种形成新的悬浮剂产品。
5、水乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水，乙二醇混合搅拌配成水相，在高剪切的条件下，将油相缓慢的加入到水相中，即可得到水乳剂。
实施例4-9、15％水乳剂
A-7 5％，印楝素10％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯3％，苯乙烯基苯酚甲醛树脂聚氧乙烯聚氧丙烯醚5％，丙二醇3％，水补至100％。
实施例4-10、25％水乳剂
A-7 10％，印楝素15％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯4％，端羟基聚氧乙烯聚氧丙烯醚嵌段共聚物5％，乙二醇3％，水补至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，印楝素可替换为藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱中的一种形成新的水乳剂产品。
6、微乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水逐渐加入到油相中，搅拌至均一透明即可。
实施例4-11、8％微乳剂
A-7 2％，印楝素6％，异丙醇10％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，苯乙烯基苯基聚氧乙烯醚18％，水补至100％。
实施例4-12、15％微乳剂
A-7 5％，印楝素10％，N-辛基吡咯烷酮6％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，烷基酚甲醛树脂聚氧乙烯醚15％，水补至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，印楝素可替换为藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱中的一种形成新的微乳剂产品。
7、可分散油悬浮剂的配制
将原药，分散剂，乳化剂、增稠剂和油相载体混合搅拌均匀后，加入砂磨机，研磨至一定的粒径即可。
实施例4-13、10％可分散油悬浮剂
A-7 5％，印楝素5％，烷基酚聚氧乙烯醚磷酸酯2％，蓖麻油聚氧乙烯醚13％，有机膨润土2％，油酸甲酯补齐至100％。
实施例4-14、30％可分散油悬浮剂
A-7 10％，印楝素20％，三苯乙基酚聚氧乙烯醚磷酸酯3％，脂肪醇聚氧乙烯醚14％，有机膨润土1.5％，油酸甲酯补齐至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，印楝素可替换为藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱中的一种形成新的可分散油悬浮剂产品。
二、室内生物活性测定
为了进一步了解螺环醚类化合物与印楝素、藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱的组合物对害虫的毒力，进行了大量配方筛选试验。试验参照杀虫剂农药室内生物测定试验准则(农业行业标准NY/T1154.7-2006)和创制农药生物活性评价SOP(杀虫剂卷)，采用喷雾法。与印楝素混配试验为将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，待卵全部孵化48h后进行喷雾处理，自然晾干。置于观察室(25±2℃、湿度70％～80％、16h光照/d)内培养。试验重复3次，并设空白对照，48h后进行调查。调查时以不能正常爬行为死虫。与藜芦碱混配试验为将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，将带有足够多卵的叶片喷雾处理，将叶片重新置于安培瓶中，自然晾干。置于观察室(25±2℃、湿度70％～80％、16h光照/d)内培养。试验重复3次，并设空白对照，待对照全部孵化后进行调查。调查时以不能孵化视为死虫。
Figure PCTCN2018087839-appb-000036
理论混用毒力指数(TTI)＝A的毒力指数×A在混用中的含量(％)
+B的毒力指数×B在混用中的含量(％)
Figure PCTCN2018087839-appb-000037
共毒系数若大于120，表明有增效作用；若小于80，表明为拮抗作用；若大于80小于120，表明为相加作用。
结果表明：螺环醚类化合物与印楝素、藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱混配对供试靶标均有很高的活性，混配后表现出显著的增效作用。
实施例4-15、A-7与印楝素联合增效作用(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
印楝素 - 0.5178 686.06 - -
A-7 - 3.5524 100.00 - -
印楝素：A-7 1:50 2.5801 137.68 111.49 123.49
印楝素：A-7 1:20 2.2132 160.51 127.91 125.49
印楝素：A-7 1:10 1.8611 190.88 153.28 124.53
印楝素：A-7 1:5 1.3205 269.02 197.68 136.09
印楝素：A-7 1:1 0.6912 513.95 393.03 130.77
印楝素：A-7 5:1 0.4421 803.53 588.38 136.57
印楝素：A-7 10:1 0.4005 886.99 632.78 140.17
印楝素：A-7 20:1 0.4003 887.43 658.15 134.84
印楝素：A-7 50:1 0.4101 866.23 674.57 128.41
实施例4-16、A-8与印楝素联合增效作用(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
印楝素 - 0.5153 612.21 - -
A-8 - 3.1547 100.00 - -
印楝素：A-8 1:50 2.3153 136.25 110.04 123.82
印楝素：A-8 1:20 2.1105 149.48 124.39 120.17
印楝素：A-8 1:10 1.5412 204.69 146.56 139.66
印楝素：A-8 1:5 1.1908 264.92 185.37 142.92
印楝素：A-8 1:1 0.6204 508.49 356.10 142.79
印楝素：A-8 5:1 0.4102 769.06 526.84 145.98
印楝素：A-8 10:1 0.4211 749.16 565.64 132.44
印楝素：A-8 20:1 0.4205 750.23 587.82 127.63
印楝素：A-8 50:1 0.4313 731.44 602.16 121.47
实施例4-17、A-10与印楝素联合增效作用(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
印楝素 - 0.5211 656.61 - -
A-10 - 3.4216 100.00 - -
印楝素：A-10 1:50 2.4811 137.91 110.91 124.34
印楝素：A-10 1:20 2.1937 155.97 126.51 123.29
印楝素：A-10 1:10 1.8437 185.58 150.60 123.23
印楝素：A-10 1:5 1.3201 259.19 192.77 134.46
印楝素：A-10 1:1 0.6559 521.66 378.31 137.90
印楝素：A-10 5:1 0.4495 761.20 563.84 135.00
印楝素：A-10 10:1 0.4304 794.98 606.01 131.18
印楝素：A-10 20:1 0.4024 850.30 630.11 134.95
印楝素：A-10 50:1 0.4067 841.31 645.70 130.29
实施例4-18、A-7与藜芦碱联合增效作用(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
藜芦碱 - 0.3152 111.87 - -
A-7 - 0.3526 100.00 - -
藜芦碱：A-7 1:50 0.2737 128.83 100.23 128.53
藜芦碱：A-7 1:20 0.2625 134.32 100.57 133.57
藜芦碱：A-7 1:10 0.2716 129.82 101.08 128.44
藜芦碱：A-7 1:5 0.2659 132.61 101.98 130.03
藜芦碱：A-7 1:1 0.2564 137.52 105.93 129.82
藜芦碱：A-7 5:1 0.2209 159.62 109.89 145.26
藜芦碱：A-7 10:1 0.2226 158.40 110.79 142.98
藜芦碱：A-7 20:1 0.2316 152.25 111.30 136.79
藜芦碱：A-7 50:1 0.2424 145.46 111.63 130.30
实施例4-19、A-8与藜芦碱联合增效作用(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
藜芦碱 - 0.3153 105.23 - -
A-8 - 0.3318 100.00 - -
藜芦碱：A-8 1:50 0.2734 121.36 100.10 121.24
藜芦碱：A-8 1:20 0.2546 130.32 100.25 130.00
藜芦碱：A-8 1:10 0.2414 137.45 100.48 136.80
藜芦碱：A-8 1:5 0.2617 126.79 100.87 125.69
藜芦碱：A-8 1:1 0.2418 137.22 102.62 133.72
藜芦碱：A-8 5:1 0.2231 148.72 104.36 142.51
藜芦碱：A-8 10:1 0.2119 156.58 104.76 149.47
藜芦碱：A-8 20:1 0.2235 148.46 104.98 141.41
藜芦碱：A-8 50:1 0.2349 141.25 105.13 134.36
实施例4-20、A-10与藜芦碱联合增效作用(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
藜芦碱 - 0.3098 111.39 - -
A-10 - 0.3451 100.00 - -
藜芦碱：A-10 1:50 0.2776 124.32 100.22 124.04
藜芦碱：A-10 1:20 0.2737 126.09 100.54 125.41
藜芦碱：A-10 1:10 0.2567 134.44 101.04 133.06
藜芦碱：A-10 1:5 0.2549 135.39 101.90 132.86
藜芦碱：A-10 1:1 0.2334 147.86 105.70 139.89
藜芦碱：A-10 5:1 0.2327 148.30 109.50 135.44
藜芦碱：A-10 10:1 0.2316 149.01 110.36 135.02
藜芦碱：A-10 20:1 0.2346 147.10 110.85 132.70
藜芦碱：A-10 50:1 0.2537 136.03 111.17 122.36
三、田间小区防治效果
实施例4-21、对柑桔全爪螨(Panonychus citri)的田间药效试验
在田间条件下测定对柑桔全爪螨的防治效果。试验根据“农药田间药效试验准则(一)——杀螨剂剂防治桔全爪螨GB/T 17980.11-2000”的规定进行，每试验小区柑桔叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天，各混配制剂对柑桔全爪螨防效分别为96.2％-98.2％、97.1％-98.6％和96.4％-97.2％，防治柑桔全爪螨效果均好于0.3％印楝素乳油、20％A-7悬浮剂、20％A-8悬浮剂和20％A-10悬浮剂。
对柑桔全爪螨的田间药效试验结果
Figure PCTCN2018087839-appb-000038
Figure PCTCN2018087839-appb-000039
实施例4-22、对苹果全爪螨(Panonychus ulmi)的田间药效试验
在田间条件下测定对苹果全爪螨的防治效果。试验根据“农药田间药效试验准则(一)——杀螨剂防治苹果叶螨GB/T 17980.7-2000”的规定进行，试验地位于山东省肥城安庄镇，品种为新红星，株行距3m*4m。施药量为1150L/hm 2。药后7天、14天、21天调查结果。每试验小区苹果叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天对苹果全爪螨防效分别为97.6％-98.5％、96.7％-98.3％和95.1％-98.2％，防治苹果全爪螨效果均好于好于0.3％印楝素乳油、20％A-7悬浮剂、20％A-8悬浮剂和20％A-10悬浮剂。
对苹果全爪螨的田间药效试验结果
Figure PCTCN2018087839-appb-000040
从以上实施例数据可知，本发明提供的组合物对于柑桔全爪螨和苹果全爪螨的防治具有明显的增效作用，效果优于单独使用A-7、A-8、A-10或印楝素，此外还能够减少用药量、延缓单一药剂带来的抗药性问题。
第五组：
一、组合物的制备
1、乳油的配制
按配方要求，分别加入溶剂、原药、乳化剂，混合均匀，必要时用水浴加热溶解，即得到透明状乳油。
实施例5-1、10％乳油
A-7 5％，三唑锡5％，农乳0203B 6％，农乳0201B 9％，环己酮8％，溶剂油150补足至100％。
实施例5-2、20％乳油
A-7 15％，三唑锡5％，农乳2201# 6％，农乳0201B 8％，环己酮8％，溶剂油150补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，三唑锡可替换为苯丁锡、三环锡和三磷锡中的一种形成新的乳油产品。
2、可湿性粉剂的配制
按配方要求，将原药、各种助剂及填料等充分混合，经超细粉碎机粉碎后，即得到加工产品。
实施例5-3、60％可湿性粉剂
A-7 15％，三唑锡45％，十二烷基苯磺酸钠1.8％，对叔丁基醚2％，白碳黑10％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
实施例5-4、70％可湿性粉剂
A-7 10％，三唑锡60％，十二烷基苯磺酸钠2％，对叔丁基醚2％，白碳黑5％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，三唑锡可替换为苯丁锡、三环锡和三磷锡中的一种形成新的可湿性粉剂产品。
3、水分散性粒剂的配制
将原药和粉状载体、润湿展着剂及粘结剂等进行混合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒。然后再经干燥、筛分(按筛网范围)即得颗粒状产品。
实施例5-5、40％水分散性粒剂
A-7 10％，三唑锡30％，N-甲基-油酰基-牛磺酸钠8％，萘酚磺酸甲醛缩合物10％，可溶性淀粉8％，硫酸钠10％，高岭土补足至100％。
实施例5-6、50％水分散性粒剂
A-7 25％，三唑锡25％，木质素磺酸钠15％，甲基萘磺酸钠甲醛缩合物5％，环氧聚醚5％，膨润土10％，高岭土补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，三唑锡可替换为苯丁锡、三环锡和三磷锡中的一种形成新的水分散性粒剂产品。
4、悬浮剂的配制
按配方要求，以水为介质，将原药、分散剂、润湿剂，助悬剂和防冻剂等混合均匀后加入砂磨机中，进行砂磨至一定的粒径过滤后加入增稠剂剪切搅拌均匀即可。
实施例5-7、30％悬浮剂
A-7 25％，三唑锡5％，木质素磺酸钠5％，白碳黑0.3％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，磷酸二氢钾0.2％，乙二醇4％，磷酸三丁酯0.2％，水补足至100％。
实施例5-8、65％悬浮剂
A-7 5％，三唑锡60％，甲基萘磺酸钠甲醛缩合物2.5％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，农乳OX-656 3.0％，丙三醇4％，磷酸三丁酯0.2％，水补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，三唑锡可替换为苯丁锡、三环锡和三磷锡中的一种形成新的悬浮剂产品。
5、水乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水，乙二醇混合搅拌配成水相，在高剪切的条件下，将油相缓慢的加入到水相中，即可得到水乳剂。
实施例5-9、15％水乳剂
A-7 5％，三唑锡10％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯3％，苯乙烯基苯酚甲醛树脂聚氧乙烯聚氧丙烯醚5％，丙二醇3％，水补至100％。
实施例5-10、25％水乳剂
A-7 15％，三唑锡10％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯4％，端羟基聚氧乙烯聚氧丙烯醚嵌段共聚物5％，乙二醇3％，水补至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，三唑锡可替换为苯丁锡、三环锡和三磷锡中的一种形成新的水乳剂产品。
6、微乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水逐渐加入到油相中，搅拌至均一透明即可。
实施例5-11、8％微乳剂
A-7 2％，三唑锡6％，异丙醇10％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，苯乙烯基苯基聚氧乙烯醚18％，水补至100％。
实施例5-12、15％微乳剂
A-7 5％，三唑锡10％，N-辛基吡咯烷酮6％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，烷基酚甲醛树脂聚氧乙烯醚15％，水补至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，三唑锡可 替换为苯丁锡、三环锡和三磷锡中的一种形成新的微乳剂产品。
7、可分散油悬浮剂的配制
将原药，分散剂，乳化剂、增稠剂和油相载体混合搅拌均匀后，加入砂磨机，研磨至一定的粒径即可。
实施例5-13、10％可分散油悬浮剂
A-7 5％，三唑锡5％，烷基酚聚氧乙烯醚磷酸酯2％，蓖麻油聚氧乙烯醚13％，有机膨润土2％，油酸甲酯补齐至100％。
实施例5-14、30％可分散油悬浮剂
A-7 10％，三唑锡20％，三苯乙基酚聚氧乙烯醚磷酸酯3％，脂肪醇聚氧乙烯醚14％，有机膨润土1.5％，油酸甲酯补齐至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，三唑锡可替换为苯丁锡、三环锡和三磷锡中的一种形成新的可分散油悬浮剂产品。
二、室内生物活性测定
为了进一步了解螺环醚类化合物与有机锡类类杀螨剂三唑锡、苯丁锡、三环锡和三磷锡的组合物对害虫的毒力，进行了大量配方筛选试验。试验参照杀虫剂农药室内生物测定试验准则(农业行业标准NY/T1154.7-2006)和创制农药生物活性评价SOP(杀虫剂卷)，采用喷雾法。供试靶标为朱砂叶螨(Tetranychus cinnabarinus)若螨和卵。测试对象为若螨时，将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，待卵全部孵化48h后进行喷雾处理，自然晾干。置于观察室(25±2℃、湿度70％～80％、16h光照/d)内培养。试验重复3次，并设空白对照，48h后进行调查。调查时以不能正常爬行为死虫。测试对象为卵时，将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，将带有足够多卵的叶片喷雾处理，将叶片重新置于安培瓶中，自然晾干。置于观察室(25±2℃、湿度70％～80％、16h光照/d)内培养。试验重复3次，并设空白对照，待对照全部孵化后进行调查。调查时以不能孵化视为死虫。
Figure PCTCN2018087839-appb-000041
理论混用毒力指数(TTI)＝A的毒力指数×A在混用中的含量(％)
+B的毒力指数×B在混用中的含量(％)
Figure PCTCN2018087839-appb-000042
共毒系数若大于120，表明有增效作用；若小于80，表明为拮抗作用；若大于80小于120，表明为相加作用。
实施例5-15、A-7与苯丁锡对朱砂叶螨-若螨的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-7 - 3.2325 672.41 - -
苯丁锡 - 21.7356 100.00 - -
A-7：苯丁锡 1:50 14.0365 154.85 111.22 139.22
A-7：苯丁锡 1:20 12.0285 180.70 127.26 142.00
A-7：苯丁锡 1:10 8.6257 251.99 152.04 165.74
A-7：苯丁锡 1:5 6.3128 344.31 195.40 176.21
A-7：苯丁锡 1:1 3.2542 667.92 386.20 172.95
A-7：苯丁锡 5:1 2.2243 977.19 577.01 169.35
A-7：苯丁锡 10:1 2.2514 965.43 620.37 155.62
A-7：苯丁锡 20:1 2.3251 934.82 645.15 144.90
A-7：苯丁锡 50:1 2.5637 847.82 661.18 128.23
实施例5-16、A-8与苯丁锡对朱砂叶螨-若螨的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-8 - 3.1142 719.34 - -
苯丁锡 - 22.4017 100.00 - -
A-8：苯丁锡 1:50 14.2122 157.62 112.14 140.55
A-8：苯丁锡 1:20 11.1157 201.53 129.49 155.63
A-8：苯丁锡 1:10 8.6782 258.14 156.30 165.15
A-8：苯丁锡 1:5 6.2479 358.55 203.22 176.43
A-8：苯丁锡 1:1 3.0514 734.14 409.67 179.20
A-8：苯丁锡 5:1 2.1363 1048.62 616.12 170.20
A-8：苯丁锡 10:1 2.2136 1012.00 663.04 152.63
A-8：苯丁锡 20:1 2.1251 1054.15 689.85 152.81
A-8：苯丁锡 50:1 2.4147 927.72 707.20 131.18
实施例5-17、A-10与苯丁锡对朱砂叶螨-若螨的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-10 - 3.2533 680.93 - -
苯丁锡 - 22.1527 100.00 - -
A-10：苯丁锡 1:50 14.2648 155.30 111.39 139.42
A-10：苯丁锡 1:20 11.4528 193.43 127.66 151.51
A-10：苯丁锡 1:10 8.8711 249.72 152.81 163.42
A-10：苯丁锡 1:5 6.8426 323.75 196.82 164.49
A-10：苯丁锡 1:1 3.3473 661.81 390.47 169.49
A-10：苯丁锡 5:1 2.2359 990.77 584.11 169.62
A-10：苯丁锡 10:1 2.2774 972.72 628.12 154.86
A-10：苯丁锡 20:1 2.4155 917.11 653.27 140.39
A-10：苯丁锡 50:1 2.5872 856.24 669.54 127.89
实施例5-18、A-7与三唑锡对朱砂叶螨-卵的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-7 - 0.3328 7956.19 - -
三唑锡 - 26.4782 100.00 - -
A-7：三唑锡 1:50 8.0158 330.33 254.04 130.03
A-7：三唑锡 1:20 3.8252 692.20 474.10 146.00
A-7：三唑锡 1:10 2.0637 1283.05 814.20 157.58
A-7：三唑锡 1:5 1.1471 2308.27 1409.36 163.78
A-7：三唑锡 1:1 0.3965 6677.98 4028.09 165.79
A-7：三唑锡 5:1 0.2356 11238.62 6646.82 169.08
A-7：三唑锡 10:1 0.2522 10498.89 7241.99 144.97
A-7：三唑锡 20:1 0.2452 10798.61 7582.09 142.42
A-7：三唑锡 50:1 0.2656 9969.20 7802.15 127.78
实施例5-19、A-8与三唑锡对朱砂叶螨-卵的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-8 - 0.3152 8574.65 - -
三唑锡 - 27.0273 100.00 - -
A-8：三唑锡 1:50 7.8068 346.20 266.17 130.07
A-8：三唑锡 1:20 3.7458 721.54 503.55 143.29
A-8：三唑锡 1:10 1.9867 1360.41 870.42 156.29
A-8：三唑锡 1:5 1.0587 2552.88 1512.44 168.79
A-8：三唑锡 1:1 0.3871 6981.99 4337.33 160.97
A-8：三唑锡 5:1 0.2297 11766.35 7162.21 164.28
A-8：三唑锡 10:1 0.2378 11365.56 7804.23 145.63
A-8：三唑锡 20:1 0.2354 11481.44 8171.10 140.51
A-8：三唑锡 50:1 0.2554 10582.34 8408.48 125.85
实施例5-20、A-10与三唑锡对朱砂叶螨-卵的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-10 - 0.3422 7854.35 - -
三唑锡 - 26.8776 100.00 - -
A-10：三唑锡 1:50 7.7712 345.86 252.05 137.22
A-10：三唑锡 1:20 3.6258 741.29 469.25 157.97
A-10：三唑锡 1:10 2.0215 1329.59 804.94 165.18
A-10：三唑锡 1:5 1.1844 2269.30 1392.39 162.98
A-10：三唑锡 1:1 0.4054 6629.90 3977.18 166.70
A-10：三唑锡 5:1 0.2498 10759.65 6561.96 163.97
A-10：三唑锡 10:1 0.2401 11194.34 7149.41 156.58
A-10：三唑锡 20:1 0.2439 11019.93 7485.10 147.22
A-10：三唑锡 50:1 0.2781 9664.72 7702.31 125.48
从以上实施例数据可知，本发明提供的组合物对朱砂叶螨若螨和卵均表现为增效作用，其中在质量比为1:20～20:1的范围内具有明显增效作用，以质量比为1:10～5:1的范围内增效作用最为显著。螺环醚类化合物与有机锡类杀螨剂混配防治害螨具有科学合理性。
三、田间小区防治效果
实施例5-21、对柑桔全爪螨(Panonychus citri)的田间药效试验
在田间条件下测定对柑桔全爪螨的防治效果。试验根据“农药田间药效试验准则(一)——杀螨剂剂防治桔全爪螨GB/T 17980.11-2000”的规定进行，每试验小区柑桔叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天，各混配制剂对柑桔全爪螨防效分别为96.4％-98.1％、 97.0％-98.5％和96.5％-97.6％，防治柑桔全爪螨效果均好于25％三唑锡可湿性粉剂、20％A-7悬浮剂、20％A-8悬浮剂和20％A-10悬浮剂。
对柑桔全爪螨的田间药效试验结果
Figure PCTCN2018087839-appb-000043
实施例5-22、对苹果全爪螨(Panonychus ulmi)的田间药效试验
在田间条件下测定对苹果全爪螨的防治效果。试验根据“农药田间药效试验准则(一)——杀螨剂防治苹果叶螨GB/T 17980.7-2000”的规定进行。药后7天、14天、21天调查结果。每试验小区苹果叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天对苹果全爪螨防效分别为97.8％-99.2％、96.3％-99.7％和95.4％-98.3％，防治苹果全爪螨效果均好于好于25％三唑锡可湿性粉剂、20％A-7悬浮剂、20％A-8悬浮剂和20％A-10悬浮剂。
对苹果全爪螨的田间药效试验结果
Figure PCTCN2018087839-appb-000044
从以上实施例数据可知，本发明提供的组合物不仅对于防治柑桔全爪螨和苹果全爪螨具有明显的增效作用，速效性和持效性优于单独使用A-7、A-8、A-10或三唑锡，而且能够减少用药量、延缓单一药剂带来的抗药性问题。
第六组：
一、组合物室内生物活性测定
为了进一步了解螺环醚类化合物与有机硫杀螨剂的组合物对害虫的毒力，进行了大量配方筛选试验。试验参照杀虫剂农药室内生物测定试验准则(农业行业标准NY/T1154.7-2006)和创制农药生物活性评价SOP(杀虫剂卷)，采用喷雾法。与有机硫杀螨剂混配试验为将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，待卵全部孵化48h后进行喷雾处理，自然晾干。置于观察室(25±2℃、湿度70％～80％、16h光照/d)内培养。试验重复3次，并设空白对照，48h后进行调查。调查时以不能正常爬行为死虫。与丁醚脲混配试验为将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，将带有足够多卵的叶片喷雾处理，将叶片重新置于安培瓶中，自然晾干。置于观察室(25±2℃、湿度70％～80％、16h光照/d)内培养。试验重复3次，并设空白对照，待对照全部孵化后进行调查。调查时以不能孵化视为死虫。
Figure PCTCN2018087839-appb-000045
理论混用毒力指数(TTI)＝A的毒力指数×A在混用中的含量(％)
+B的毒力指数×B在混用中的含量(％)
Figure PCTCN2018087839-appb-000046
共毒系数若大于120，表明有增效作用；若小于80，表明为拮抗作用；若大于80小于120，表明为相加作用。
实施例6-1、A-7与炔螨特组合物对朱砂叶螨-若螨的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-7 - 3.4215 632.25 - -
炔螨特 - 21.6324 100.00 - -
A-7：炔螨特 1:50 14.0218 154.28 110.44 139.70
A-7：炔螨特 1:20 11.0562 195.66 125.35 156.10
A-7：炔螨特 1:10 8.6217 250.91 148.39 169.09
A-7：炔螨特 1:5 6.3557 340.36 188.71 180.36
A-7：炔螨特 1:1 3.2542 664.75 366.12 181.56
A-7：炔螨特 5:1 2.2215 973.77 543.54 179.15
A-7：炔螨特 10:1 2.2547 959.44 583.86 164.33
A-7：炔螨特 20:1 2.5342 853.62 606.90 140.65
A-7：炔螨特 50:1 2.7313 792.02 621.81 127.37
实施例6-2、A-8与炔螨特组合物对朱砂叶螨-若螨的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-8 - 3.1748 707.25 - -
炔螨特 - 22.4537 100.00 - -
A-8：炔螨特 1:50 14.2213 157.89 111.91 141.09
A-8：炔螨特 1:20 11.3745 197.40 128.92 153.13
A-8：炔螨特 1:10 8.9217 251.68 155.20 162.16
A-8：炔螨特 1:5 6.9683 322.23 201.21 160.15
A-8：炔螨特 1:1 3.3124 677.87 403.62 167.95
A-8：炔螨特 5:1 2.2472 999.19 606.04 164.87
A-8：炔螨特 10:1 2.2674 990.28 652.04 151.87
A-8：炔螨特 20:1 2.3351 961.57 678.33 141.76
A-8：炔螨特 50:1 2.5115 894.04 695.34 128.58
实施例6-3、A-10与炔螨特组合物对朱砂叶螨-若螨的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-10 - 3.2533 680.98 - -
炔螨特 - 22.1542 100.00 - -
A-10：炔螨特 1:50 13.5648 163.32 111.39 146.62
A-10：炔螨特 1:20 11.4582 193.35 127.67 151.45
A-10：炔螨特 1:10 8.8711 249.73 152.82 163.42
A-10：炔螨特 1:5 6.8426 323.77 196.83 164.49
A-10：炔螨特 1:1 3.3473 661.85 390.49 169.49
A-10：炔螨特 5:1 2.2359 990.84 584.15 169.62
A-10：炔螨特 10:1 2.2774 972.78 628.16 154.86
A-10：炔螨特 20:1 2.4158 917.05 653.31 140.37
A-10：炔螨特 50:1 2.5472 869.75 669.58 129.89
实施例6-4、A-7与丁醚脲组合物对朱砂叶螨-卵的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-7 - 0.3523 8413.71 - -
丁醚脲 - 29.6415 100.00 - -
A-7：丁醚脲 1:50 8.3236 356.11 263.01 135.40
A-7：丁醚脲 1:20 3.7786 784.46 495.89 158.19
A-7：丁醚脲 1:10 2.2356 1325.89 855.79 154.93
A-7：丁醚脲 1:5 1.2689 2336.00 1485.62 157.24
A-7：丁醚脲 1:1 0.4358 6801.63 4256.85 159.78
A-7：丁醚脲 5:1 0.2683 11047.89 7028.09 157.20
A-7：丁醚脲 10:1 0.2607 11369.97 7657.92 148.47
A-7：丁醚脲 20:1 0.2624 11296.30 8017.82 140.89
A-7：丁醚脲 50:1 0.2741 10814.12 8250.70 131.07
实施例6-5、A-8与丁醚脲组合物对朱砂叶螨-卵的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-8 - 0.3385 8932.85 - -
丁醚脲 - 30.2377 100.00 - -
A-8：丁醚脲 1:50 8.0752 374.45 273.19 137.06
A-8：丁醚脲 1:20 4.0125 753.59 520.61 144.75
A-8：丁醚脲 1:10 2.1154 1429.41 902.99 158.30
A-8：丁醚脲 1:5 1.2428 2433.03 1572.14 154.76
A-8：丁醚脲 1:1 0.4527 6679.41 4516.43 147.89
A-8：丁醚脲 5:1 0.2719 11120.89 7460.71 149.06
A-8：丁醚脲 10:1 0.2568 11774.81 8129.86 144.83
A-8：丁醚脲 20:1 0.2671 11320.74 8512.24 132.99
A-8：丁醚脲 50:1 0.2822 10714.99 8759.66 122.32
实施例6-6、A-10与丁醚脲组合物对朱砂叶螨-卵的联合增效作用结果
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-10 - 0.3425 8359.91 - -
丁醚脲 - 28.6327 100.00 - -
A-10：丁醚脲 1:50 7.9637 359.54 261.96 137.25
A-10：丁醚脲 1:20 4.1158 695.68 493.33 141.02
A-10：丁醚脲 1:10 2.1786 1314.27 850.90 154.46
A-10：丁醚脲 1:5 1.2377 2313.38 1476.65 156.66
A-10：丁醚脲 1:1 0.4387 6526.72 4229.96 154.30
A-10：丁醚脲 5:1 0.2634 10870.43 6983.26 155.66
A-10：丁醚脲 10:1 0.2521 11357.68 7609.01 149.27
A-10：丁醚脲 20:1 0.2638 10853.94 7966.58 136.24
A-10：丁醚脲 50:1 0.2728 10495.86 8197.95 128.03
从以上实施例数据可知，本发明提供的组合物对朱砂叶螨若螨和卵均表现为增效作用，其中在质量比为1:20～20:1的范围内具有明显增效作用，以质量比为1:20～10:1的范围内增效作用最为显著。螺环醚类化合物与有机硫类杀螨剂混配防治害螨具有科学合理性。
二、制剂制备
1、乳油的配制
按配方要求，分别加入溶剂、原药、乳化剂，混合均匀，必要时用水浴加热溶解，即得到透明状乳油。
实施例6-7、20％乳油
A-7 10％，炔螨特10％，农乳0203B 5％，农乳0201B 10％，环己酮8％，溶剂油150补足至100％。
实施例6-8、63％乳油
A-7 3％，炔螨特60％，农乳2201# 6％，农乳0201B 8％，环己酮10％，溶剂油150补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，炔螨特可替换为丁醚脲、杀螨酯和杀螨硫醚中的一种形成新的乳油产品。
2、可湿性粉剂的配制
按配方要求，将原药、各种助剂及填料等充分混合，经超细粉碎机粉碎后，即得到加工产品。
实施例6-9、60％可湿性粉剂
A-7 15％，炔螨特45％，十二烷基苯磺酸钠1.8％，对叔丁基醚2％，白碳黑10％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
实施例6-10、70％可湿性粉剂
A-7 60％，炔螨特10％，十二烷基苯磺酸钠2％，对叔丁基醚2％，白碳黑5％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，炔螨特可替换为丁醚脲、杀螨酯和杀螨硫醚中的一种形成新的可湿性粉剂产品。
3、水分散性粒剂的配制
将原药和粉状载体、润湿展着剂及粘结剂等进行混合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒。然后再经干燥、筛分(按筛网范围)即得颗粒状产品。
实施例6-11、40％水分散性粒剂
A-7 10％，炔螨特30％，N-甲基-油酰基-牛磺酸钠8％，萘酚磺酸甲醛缩合物10％，可溶性淀粉8％，硫酸钠10％，高岭土补足至100％。
实施例6-12、55％水分散性粒剂
A-7 50％，炔螨特5％，木质素磺酸钠15％，甲基萘磺酸钠甲醛缩合物5％，环氧聚醚5％，膨润土10％，高岭土补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，炔螨特可替换为丁醚脲、杀螨酯和杀螨硫醚中的一种形成新的水分散性粒剂产品。
4、悬浮剂的配制
按配方要求，以水为介质，将原药、分散剂、润湿剂，助悬剂和防冻剂等混合均匀后加入砂磨机中，进行砂磨至一定的粒径过滤后加入增稠剂剪切搅拌均匀即可。
实施例6-13、30％悬浮剂
A-7 25％，炔螨特5％，木质素磺酸钠5％，白碳黑0.3％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，磷酸二氢钾0.2％，乙二醇4％，磷酸三丁酯0.2％，水补足至100％。
实施例6-14、40％悬浮剂
A-7 5％，炔螨特35％，甲基萘磺酸钠甲醛缩合物2.5％，烷基萘磺酸盐和阴离子润湿剂的混合物(EFW)2.0％，农乳OX-656 3.0％，丙三醇4％，磷酸三丁酯0.2％，水补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，炔螨特可替换为丁醚脲、杀螨酯和杀螨硫醚中的一种形成新的悬浮剂产品。
5、水乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水，乙二醇混合搅拌配成水相，在高剪切的条件下，将油相缓慢的加入到水相中，即可得到水乳剂。
实施例6-15、15％水乳剂
A-7 5％，炔螨特10％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯3％，苯乙烯基苯酚甲醛树脂聚氧乙烯聚氧丙烯醚5％，丙二醇3％，水补至100％。
实施例6-16、20％水乳剂
A-7 10％，炔螨特10％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯4％，端羟基聚氧乙烯聚氧丙烯醚嵌段共聚物5％，乙二醇3％，水补至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，炔螨特可替换为丁醚脲、杀螨酯和杀螨硫醚中的一种形成新的水乳剂产品。
6、微乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水逐渐加入到油相中，搅拌至均一透明即可。
实施例6-17、10％微乳剂
A-7 5％，炔螨特5％，异丙醇10％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，苯乙烯基苯基聚氧乙烯醚18％，水补至100％。
实施例6-18、15％微乳剂
A-7 5％，炔螨特10％，N-辛基吡咯烷酮6％，溶剂油S-150 15％，十二烷基苯磺酸钙2％， 烷基酚甲醛树脂聚氧乙烯醚15％，水补至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，炔螨特可替换为丁醚脲、杀螨酯和杀螨硫醚中的一种形成新的微乳剂产品。
7、可分散油悬浮剂的配制
将原药，分散剂，乳化剂、增稠剂和油相载体混合搅拌均匀后，加入砂磨机，研磨至一定的粒径即可。
实施例6-19、15％可分散油悬浮剂
A-7 5％，炔螨特10％，烷基酚聚氧乙烯醚磷酸酯2％，蓖麻油聚氧乙烯醚13％，有机膨润土2％，油酸甲酯补齐至100％。
实施例6-20、30％可分散油悬浮剂
A-7 5％，炔螨特25％，三苯乙基酚聚氧乙烯醚磷酸酯3％，脂肪醇聚氧乙烯醚14％，有机膨润土1.5％，油酸甲酯补齐至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，炔螨特可替换为丁醚脲、杀螨酯和杀螨硫醚中的一种形成新的可分散油悬浮剂产品。
三、田间小区防治效果
实施例6-21、对柑桔全爪螨(Panonychus citri)的田间药效试验
在田间条件下测定对柑桔全爪螨的防治效果。试验根据“农药田间药效试验准则(一)——杀螨剂剂防治桔全爪螨GB/T 17980.11-2000”的规定进行，每试验小区柑桔叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天，各混配制剂对柑桔全爪螨防效分别为97.5％-98.6％、98.0％-99.4％和96.8％-97.7％，防治柑桔全爪螨效果均好于73％炔螨特乳油、20％A-7悬浮剂、20％A-8悬浮剂和20％A-10悬浮剂。
对柑桔全爪螨的田间药效试验结果
Figure PCTCN2018087839-appb-000047
Figure PCTCN2018087839-appb-000048
实施例6-22、对苹果全爪螨(Panonychus ulmi)的田间药效试验
在田间条件下测定对苹果全爪螨的防治效果。试验根据“农药田间药效试验准则(一)——杀螨剂防治苹果叶螨GB/T 17980.7-2000”的规定进行。药后7天、14天、21天调查结果。每试验小区苹果叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天对苹果全爪螨防效分别为97.6％-98.2％、98.4％-99.3％和95.8％-97.8％，防治苹果全爪螨效果均好于好于73％炔螨特乳油、20％A-7悬浮剂、20％A-8悬浮剂和20％A-10悬浮剂。
对苹果全爪螨的田间药效试验结果
Figure PCTCN2018087839-appb-000049
以上数据说明，本发明提供的组合物不仅对于防治柑桔全爪螨和苹果全爪螨具有明显的增效作用，效果优于单独使用A-7、A-8、A-10或炔螨特，而且能够减少用药量、延缓单一药剂带来的抗药性问题。
第七组：
一、制剂的制备
1、乳油的配制
按配方要求，分别加入溶剂、原药、乳化剂，混合均匀，必要时用水浴加热溶解，即得到透明状乳油。
实施例7-1、10％乳油
A-7 6％，甲氰菊酯4％，十二烷基苯磺酸钙6％，三苯乙基酚聚氧乙烯醚9％，环己酮10％，溶剂油150补足至100％。
实施例7-2、25％乳油
A-7 15％，甲氰菊酯10％，十二烷基苯磺酸钙5％，烷基酚聚氧乙烯醚8％，环己酮8％，溶剂油150补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，将甲氰菊酯换成所述菊酯类农药活性成分中的一种形成新的乳油产品。
2、可湿性粉剂的配制
按配方要求，将原药、各种助剂及填料等充分混合，经超细粉碎机粉碎后，即得到加工产品。
实施例7-3、30％可湿性粉剂
A-7 15％，甲氰菊酯15％，十二烷基硫酸钠2％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
实施例7-4、50％可湿性粉剂
A-7 30％，甲氰菊酯20％，十二烷基硫酸钠2％，萘磺酸甲醛缩合物钠盐8％，轻质碳酸钙补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，将甲氰菊酯换成所述菊酯类农药活性成分中的一种形成新的可湿性粉剂产品。
3、水分散性粒剂的配制
将原药和粉状载体、润湿剂、分散剂及粘结剂等进行混合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒。然后再经干燥、筛分(按筛网范围)即得颗粒状产品或经湿法粉碎后进行喷雾造粒，筛分后得到的颗粒剂产品。
实施例7-5、40％水分散性粒剂
A-7 30％，甲氰菊酯10％，萘磺酸钠盐2％，萘磺酸甲醛缩合物钠盐10％，可溶性淀粉8％，硫酸钠10％，高岭土补足至100％。
实施例7-6、50％水分散性粒剂
A-7 40％，甲氰菊酯10％，烷基硫酸盐3％，马来酸均聚物钠盐5％，高岭土补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，将甲氰菊酯换成所述菊酯类农药活性成分中的一种形成新的水分散性粒剂产品。
4、悬浮剂的配制
按配方要求，以水为介质，将原药、分散剂、润湿剂，助悬剂和防冻剂等混合均匀后加入砂磨机中，进行砂磨至一定的粒径过滤后加入增稠剂剪切搅拌均匀即可。
实施例7-7、30％悬浮剂
A-7 25％，甲氰菊酯5％，脂肪醇聚氧乙烯醚1％，三苯乙基酚聚氧乙烯醚磷酸化三乙胺盐3％，磷酸二氢钾0.2％，乙二醇4％，磷酸三丁酯0.2％，黄原胶0.2％，水补足至100％。
实施例7-8、50％悬浮剂
A-7 30％，甲氰菊酯20％，端羟基聚氧乙烯醚聚氧丙烯醚嵌段共聚物2.5％，丙烯酸均聚物钠盐4％，丙二醇4％，黄原胶0.2％，水补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，将甲氰菊酯换成所述菊酯类农药活性成分中的一种形成新的悬浮剂产品
5、水乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水，乙二醇混合搅拌配成水相，在高剪切的条件下，将油相缓慢的加入到水相中，即可得到水乳剂。
实施例7-9、20％水乳剂
A-7 5％，甲氰菊酯15％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯3％，苯乙烯基苯酚甲醛树脂聚氧乙烯聚氧丙烯醚5％，丙二醇3％，水补至100％。
实施例7-10、25％水乳剂
A-7 15％，甲氰菊酯10％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯4％，端羟基聚氧乙烯聚氧丙烯醚嵌段共聚物5％，乙二醇3％，水补至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，将甲氰菊 酯换成所述菊酯类农药活性成分中的一种形成新的水乳剂产品。
6、微乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水逐渐加入到油相中，搅拌至均一透明即可。
实施例7-11、5％微乳剂
A-7 2.5％，甲氰菊酯2.5％，异丙醇10％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，苯乙烯基苯基聚氧乙烯醚18％，水补至100％。
实施例7-12、15％微乳剂
A-7 5％，甲氰菊酯10％，N-辛基吡咯烷酮6％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，烷基酚甲醛树脂聚氧乙烯醚15％，水补至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，将甲氰菊酯换成所述菊酯类农药活性成分中的一种形成新的微乳剂产品。
7、可分散油悬浮剂的配制
将活性组分、分散剂、乳化剂、增稠剂和载体油相混合均匀后，加入到砂磨机中，研磨至一定的粒径即可。
实施例7-13、10％可分散油悬浮剂
A-8 5％，甲氰菊酯5％，烷基酚聚氧乙烯醚磷酸酯2％，蓖麻油聚氧乙烯醚13％，有机膨润土2％，油酸甲酯补齐至100％。
实施例7-14、30％可分散油悬浮剂
A-8 10％，甲氰菊酯20％，三苯乙基酚聚氧乙烯醚磷酸酯3％，脂肪醇聚氧乙烯醚14％，有机膨润土1.5％，油酸甲酯补齐至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，将甲氰菊酯换成所述菊酯类农药活性成分中的一种形成新的油悬浮剂产品。
8、悬乳剂
将A-8、润湿剂，分散剂、水等配置成水悬浮相，将甲氰菊酯、乳化剂、溶剂配制成油 相。在高剪切或搅拌的条件下，将油相加入到水悬浮相中，得到悬乳剂。
实施例7-15、30％悬乳剂
A-8 20％，甲氰菊酯10％，端羟基环氧乙烷环氧丙烷嵌段聚醚2％，马来酸均聚物钠盐3％、溶剂油S-150 15％，水补充至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种，将甲氰菊酯换成所述菊酯类农药活性成分中的一种形成新的悬乳剂产品。
二、室内生物活性测定
为了进一步了解螺环醚类化合物与甲氰菊酯的组合物对害虫的毒力，进行了大量配方筛选试验。试验参照杀虫剂农药室内生物测定试验准则(农业行业标准NY/T1154.7-2006)和创制农药生物活性评价SOP(杀虫剂卷)，采用喷雾法。与甲氰菊酯混配试验为将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，待卵全部孵化48h后进行喷雾处理，自然晾干。置于观察室(25±2℃、湿度70％-80％、16h光照/d)内培养。试验重复3次，并设空白对照，48h后进行调查。调查时以不能正常爬行为死虫。
Figure PCTCN2018087839-appb-000050
理论混用毒力指数(TTI)＝A的毒力指数×A在混用中的含量(％)
+B的毒力指数×B在混用中的含量(％)
Figure PCTCN2018087839-appb-000051
共毒系数若大于120，表明有增效作用；若小于80，表明为拮抗作用；若大于80小于120，表明为相加作用。
结果表明：螺环醚类化合物与菊酯类农药混配对供试靶标均有很高的活性，混配后表现出显著的增效作用。
实施例7-16、A-7与甲氰菊酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-7 - 0.35 100 - -
甲氰菊酯 - 1.12 31.25 - -
A-7：甲氰菊酯 4:1 0.28 125.0 86.25 144.93
A-7：甲氰菊酯 3:1 0.31 112.9 82.81 136.34
A-7：甲氰菊酯 2:1 0.35 100.0 77.08 129.73
A-7：甲氰菊酯 1:1 0.39 89.7 65.63 136.75
A-7：甲氰菊酯 1:2 0.27 129.6 93.75 138.27
A-7：甲氰菊酯 1:3 0.22 159.1 115.93 137.23
A-7：甲氰菊酯 1:4 0.28 125.0 102.58 121.86
实施例7-17、A-8与甲氰菊酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-8 - 0.36 100 - -
甲氰菊酯 - 1.12 32.14 - -
A8：甲氰菊酯 4:1 0.26 138.5 86.43 160.20
A8：甲氰菊酯 3:1 0.32 112.5 83.04 135.48
A8：甲氰菊酯 2:1 0.33 109.1 77.38 140.98
A8：甲氰菊酯 1:1 0.41 87.8 66.07 132.89
A8：甲氰菊酯 1:2 0.29 124.1 103.02 120.50
A8：甲氰菊酯 1:3 0.22 163.6 118.99 137.52
A8：甲氰菊酯 1:4 0.23 156.5 109.77 142.59
实施例7-18、A-10与甲氰菊酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-10 - 0.34 100 - -
甲氰菊酯 - 1.12 30.36 - -
A10：甲氰菊酯 4:1 0.29 117.2 86.07 136.21
A10：甲氰菊酯 3:1 0.3 113.3 82.59 137.23
A10：甲氰菊酯 2:1 0.28 121.4 76.79 158.14
A10：甲氰菊酯 1:1 0.37 91.9 65.18 140.98
A10：甲氰菊酯 1:2 0.26 130.8 88.28 148.13
A10：甲氰菊酯 1:3 0.23 147.8 114.31 129.32
A10：甲氰菊酯 1:4 0.21 161.9 119.81 135.14
实施例7-19、A-7与联苯菊酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-7 - 0.35 100 - -
联苯菊酯 - 3.63 9.64 - -
A7：联苯菊酯 4:1 0.31 112.9 81.93 137.81
A7：联苯菊酯 3:1 0.32 109.4 77.41 141.29
A7：联苯菊酯 2:1 0.34 102.9 69.88 147.31
A7：联苯菊酯 1:1 0.49 71.4 54.82 130.29
A7：联苯菊酯 1:2 0.35 100.0 78.48 127.42
A7：联苯菊酯 1:3 0.26 134.6 110.26 122.09
A7：联苯菊酯 1:4 0.27 129.6 104.23 124.37
实施例7-20、A-8与联苯菊酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-8 - 0.33 100    
联苯菊酯 - 3.63 9.09    
A8：联苯菊酯 4:1 0.29 113.8 81.82 139.08
A8：联苯菊酯 3:1 0.31 106.5 77.27 137.76
A8：联苯菊酯 2:1 0.3 110.0 69.70 157.83
A8：联苯菊酯 1:1 0.45 73.3 54.55 134.44
A8：联苯菊酯 1:2 0.31 106.5 78.89 134.93
A8：联苯菊酯 1:3 0.23 143.5 108.29 132.50
A8：联苯菊酯 1:4 0.25 132.0 109.29 120.78
实施例7-21、A-10与联苯菊酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-10 - 0.36 100 - -
联苯菊酯 - 3.63 9.92 - -
A10：联苯菊酯 4:1 0.31 116.1 81.98 141.65
A10：联苯菊酯 3:1 0.35 102.9 77.48 132.75
A10：联苯菊酯 2:1 0.38 94.7 69.97 135.39
A10：联苯菊酯 1:1 0.49 73.5 54.96 133.68
A10：联苯菊酯 1:2 0.33 109.1 80.73 135.14
A10：联苯菊酯 1:3 0.28 128.6 106.18 121.09
A10：联苯菊酯 1:4 0.29 124.1 96.36 128.83
三、田间小区防治效果
实施例7-22、对柑橘红蜘蛛的田间药效试验
在田间条件下测定对柑橘红蜘蛛的防治效果。试验根据“农药田间药效试验准则(一)——杀虫剂防治柑橘红蜘蛛”的规定进行，每试验小区柑橘叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天，各混配制剂对柑橘红蜘蛛防效分别为96.5％～99.6％、97.1％～99.2％和96.9％～99.7％，防治柑橘红蜘蛛效果均好于20％甲氰菊酯乳油、20％A-7悬浮剂、20％A-8悬浮剂和20％A-10悬浮剂。
对柑橘红蜘蛛的田间药效试验结果表
Figure PCTCN2018087839-appb-000052
Figure PCTCN2018087839-appb-000053
实施例7-23、对苹果红蜘蛛的田间药效试验
在田间条件下测定对苹果红蜘蛛的防治效果。试验地位于山东省肥城安庄镇，品种为新红星，株行距3m*4m。施药量为1150kg/hm 2。药后7天、14天、21天调查结果。每试验小区苹果叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天，各混配制剂对苹果红蜘蛛防效分别为96.5％～99.7％、95.9％～99.4％和96.2％～99.6％，防治苹果红蜘蛛效果均好于好于20％甲氰菊酯乳油、20％A-8悬浮剂、20％A-9悬浮剂和20％A-10悬浮剂。
对苹果红蜘蛛的田间药效试验结果
Figure PCTCN2018087839-appb-000054
从以上数据可知，本发明提供的组合物不仅对于防治柑橘红蜘蛛和苹果红蜘蛛具有明显的协同作用，效果优于单独使用A-7、A-8、A-10和甲氰菊酯，而且能够减少用药量、延缓单一药剂带来的抗药性问题。
第八组：
一、组合物的制备
1、乳油的配制
按配方要求，分别加入溶剂、原药、乳化剂，混合均匀，必要时用水浴加热溶解，即得到透明状乳油。
实施例8-1、50％乳油
A-7 25％，联苯肼酯25％，十二烷基苯磺酸钙6％，三苯乙基酚聚氧乙烯醚9％，环己酮10％，溶剂油150补足至100％。
实施例8-2、70％乳油
A-7 20％，联苯肼酯50％，十二烷基苯磺酸钙5％，烷基酚聚氧乙烯醚8％，环己酮8％，溶剂油150补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种形成新的乳油产品。
2、可湿性粉剂的配制
按配方要求，将原药、各种助剂及填料等充分混合，经超细粉碎机粉碎后，即得到加工产品。
实施例8-3、60％可湿性粉剂
A-7 15％，联苯肼酯45％，十二烷基硫酸钠2％，木质素磺酸钠10％，轻质碳酸钙补足至100％。
实施例8-4、80％可湿性粉剂
A-7 10％，联苯肼酯70％，十二烷基硫酸钠2％，萘磺酸甲醛缩合物钠盐8％，轻质碳酸钙补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种形成新的可湿性粉剂产品。
3、水分散性粒剂的配制
将原药和粉状载体、润湿剂、分散剂及粘结剂等进行混合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒。然后再经干燥、筛分(按筛网范围)即得颗粒状产品或经湿法粉碎后进行喷雾造粒，筛分后得到的颗粒剂产品。
实施例8-5、40％水分散性粒剂
A-7 10％，联苯肼酯30％，萘磺酸钠盐2％，萘磺酸甲醛缩合物钠盐10％，可溶性淀粉8％，硫酸钠10％，高岭土补足至100％。
实施例8-6、50％水分散性粒剂
A-7 25％，联苯肼酯25％，烷基硫酸盐3％，马来酸均聚物钠盐5％，高岭土补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种形成新的水分散性粒剂产品。
4、悬浮剂的配制
按配方要求，以水为介质，将原药、分散剂、润湿剂，助悬剂和防冻剂等混合均匀后加入砂磨机中，进行砂磨至一定的粒径过滤后加入增稠剂剪切搅拌均匀即可。
实施例8-7、30％悬浮剂
A-7 25％，联苯肼酯5％，脂肪醇聚氧乙烯醚1％，三苯乙基酚聚氧乙烯醚磷酸化三乙胺盐3％，磷酸二氢钾0.2％，乙二醇4％，磷酸三丁酯0.2％，黄原胶0.2％，水补足至100％。
实施例8-8、50％悬浮剂
A-7 20％，联苯肼酯30％，端羟基聚氧乙烯醚聚氧丙烯醚嵌段共聚物2.5％，丙烯酸均聚物钠盐4％，丙二醇4％，黄原胶0.2％，水补足至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种形成新的悬浮剂产品。
5、水乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水，乙二醇混合搅拌配成水相，在高剪切的条件下，将油相缓慢的加入到水相中，即可得到水乳剂。
实施例8-9、15％水乳剂
A-7 5％，联苯肼酯10％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯3％，苯乙烯基苯酚甲醛树脂聚氧乙烯聚氧丙烯醚5％，丙二醇3％，水补至100％。
实施例8-10、25％水乳剂
A-7 15％，联苯肼酯10％，溶剂油S-150 30％，三苯乙基酚聚氧乙烯醚磷酸酯4％，端羟基聚氧乙烯聚氧丙烯醚嵌段共聚物5％，乙二醇3％，水补至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种形成新的水乳剂产品。
6、微乳剂的配制
将原药，溶剂，乳化剂混合搅拌均匀配成均一油相，将水逐渐加入到油相中，搅拌至均一透明即可。
实施例8-11、8％微乳剂
A-7 2％，联苯肼酯6％，异丙醇10％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，苯乙烯基苯基聚氧乙烯醚18％，水补至100％。
实施例8-12、15％微乳剂
A-7 5％，联苯肼酯10％，N-辛基吡咯烷酮6％，溶剂油S-150 15％，十二烷基苯磺酸钙2％，烷基酚甲醛树脂聚氧乙烯醚15％，水补至100％。
还可以将A-7替换成本说明书所描述的螺环醚类化合物A-8、A-10中的一种形成新的微乳剂产品。
7、可分散油悬浮剂的配制
将活性组分、分散剂、乳化剂、增稠剂和载体油相混合均匀后，加入到砂磨机中，研磨至一定的粒径即可。
实施例8-13、10％可分散油悬浮剂
A-8 5％，联苯肼酯5％，烷基酚聚氧乙烯醚磷酸酯2％，蓖麻油聚氧乙烯醚13％，有机膨润土2％，油酸甲酯补齐至100％。
实施例8-14、30％可分散油悬浮剂
A-8 10％，联苯肼酯20％，三苯乙基酚聚氧乙烯醚磷酸酯3％，脂肪醇聚氧乙烯醚14％，有机膨润土1.5％，油酸甲酯补齐至100％。
二、室内生物活性测定
为了进一步了解螺环醚类化合物与联苯肼酯的组合物对害虫的毒力，进行了大量配方筛选试验。试验参照杀虫剂农药室内生物测定试验准则(农业行业标准NY/T1154.7-2006)和创制农药生物活性评价SOP(杀虫剂卷)，采用喷雾法。与联苯肼酯混配试验为将蚕豆叶片带柄剪下，插于加水的玻璃瓶中。接一定数量的成螨。待成螨产卵24h后，去除成螨，待卵全部孵化48h后进行喷雾处理，自然晾干。置于观察室(25±2℃、湿度70％～80％、16h光照/d)内培养。试验重复3次，并设空白对照，48h后进行调查。调查时以不能正常爬行为死虫。
Figure PCTCN2018087839-appb-000055
理论混用毒力指数(TTI)＝A的毒力指数×A在混用中的含量(％)
+B的毒力指数×B在混用中的含量(％)
Figure PCTCN2018087839-appb-000056
共毒系数若大于120，表明有增效作用；若小于80，表明为拮抗作用；若大于80小于120，表明为相加作用。
结果表明：螺环醚类化合物与联苯肼酯混配对供试靶标均有很高的活性，混配后表现出显著的增效作用。
实施例8-15、A-7与联苯肼酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-7 - 0.34 100 - -
联苯肼酯 - 0.52 65.38 - -
A-7：联苯肼酯 4:1 0.23 147.8 93.08 158.82
A-7：联苯肼酯 3:1 0.26 130.8 91.35 143.16
A-7：联苯肼酯 2:1 0.31 109.7 88.46 123.98
A-7：联苯肼酯 1:1 0.31 109.7 82.69 132.63
A-7：联苯肼酯 1:2 0.21 161.9 120.35 134.53
A-7：联苯肼酯 1:3 0.17 200.0 135.03 148.11
A-7：联苯肼酯 1:4 0.23 147.8 113.90 129.79
实施例8-16、A-8与联苯肼酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-8 - 0.36 100 - -
联苯肼酯 - 0.52 69.23 - -
A8：联苯肼酯 4:1 0.27 133.3 93.85 142.08
A8：联苯肼酯 3:1 0.25 144.0 92.31 156.00
A8：联苯肼酯 2:1 0.33 109.1 89.74 121.56
A8：联苯肼酯 1:1 0.31 116.1 84.62 137.24
A8：联苯肼酯 1:2 0.24 150.0 111.97 133.97
A8：联苯肼酯 1:3 0.21 171.4 141.33 121.29
A8：联苯肼酯 1:4 0.23 156.5 116.07 134.85
实施例8-17、A-10与联苯肼酯联合增效作用
(朱砂叶螨Tetranychus cinnabarinus)
处理 配比 LC 50(mg/L) 实测毒力指数 理论毒力指数 共毒系数
A-10 - 0.35 100 - -
联苯肼酯 - 0.52 67.31 - -
A10：联苯肼酯 4:1 0.26 134.6 93.46 144.03
A10：联苯肼酯 3:1 0.27 129.6 91.83 141.17
A10：联苯肼酯 2:1 0.31 112.9 89.10 126.71
A10：联苯肼酯 1:1 0.28 125.0 83.65 149.43
A10：联苯肼酯 1:2 0.25 140.0 112.18 124.80
A10：联苯肼酯 1:3 0.2 175.0 130.88 133.71
A10：联苯肼酯 1:4 0.24 145.8 116.25 125.45
三、田间小区防治效果
实施例8-18、对柑橘红蜘蛛的田间药效试验
在田间条件下测定对柑橘红蜘蛛的防治效果。试验根据“农药田间药效试验准则(一)——杀虫剂防治柑橘红蜘蛛”的规定进行，每试验小区柑橘叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天，各混配制剂对柑橘红蜘蛛防效分别为96.2％～99.2％、96.8％～99.6％和96.5％～99.7％，防治柑橘红蜘蛛效果均好于24％联苯肼酯悬浮剂、20％A-7悬浮剂、20％A-8悬浮剂和20％A-10悬浮剂。
对柑橘红蜘蛛的田间药效试验结果
Figure PCTCN2018087839-appb-000057
实施例8-19、对苹果红蜘蛛的田间药效试验
在田间条件下测定对苹果红蜘蛛的防治效果。试验地位于山东省肥城安庄镇，品种为新红星，株行距3m*4m。施药量为1150kg/hm 2。药后7天、14天、21天调查结果。每试验小区苹果叶片采用5个定点按东、南、西、北5个方位标记，每小区调查2株，调查每株上所有活虫数。
试验结果：药后7天、14天、21天，各混配制剂对苹果红蜘蛛防效分别为97.4％～99.4％、96.5％～99.7％和96.4％～98.9％，防治苹果红蜘蛛效果均好于好于24％联苯肼酯悬浮剂、20％A-8悬浮剂、20％A-9悬浮剂和20％A-10悬浮剂。
对苹果红蜘蛛的田间药效试验结果
Figure PCTCN2018087839-appb-000058
从以上数据可知，本发明提供的组合物对于防治柑橘红蜘蛛和苹果红蜘蛛具有明显的协同作用，效果优于单独使用A-7、A-8、A-10和联苯肼酯，从而能够减少用药量、延缓单一药剂带来的抗药性问题。

Claims (14)

  1. 一种组合物，其特征在于，所述组合物含有两种活性成分，第一种活性成分包括选自以下A-7、A-8和A-10所示化合物中的至少一种，第二种活性成分选自第一组至第八组中的一组；
    Figure PCTCN2018087839-appb-100001
    所述第一组包括选自阿维菌素、甲氨基阿维菌素、多杀菌素、乙基多杀菌素、伊维菌素、米尔贝霉素、天维菌素和弥拜菌素中的至少一种；
    所述第二组包括选自乙螨唑、噻螨酮和四螨嗪中的至少一种；
    所述第三组包括选自哒螨灵、喹螨醚、唑螨酯、嘧螨醚和吡螨胺中的至少一种；
    所述第四组包括植物源杀虫剂；
    所述第五组包括有机锡类杀螨剂；
    所述第六组包括有机硫杀螨剂；
    所述第七组包括菊酯类农药；
    所述第八组包括联苯肼酯。
  2. 按照权利要求1所述的组合物，其特征在于，所述第一种活性成分与第二种活性成分的质量配比为50:1～1:50。
  3. 按照权利要求2所述的组合物，其特征在于，当第二种活性成分选自第一组时，所述第一种活性成分与第二种活性成分的质量配比为20:1～1:12；
    当第二种活性成分选自第二组时，所述第一种活性成分与第二种活性成分的质量配比为20:1～1:20；
    当第二种活性成分选自第三组时，所述第一种活性成分与第二种活性成分的质量配比为20:1～1:20；
    当第二种活性成分选自第四组时，所述第一种活性成分与第二种活性成分的质量配比为10:1～1:20；
    当第二种活性成分选自第五组时，所述第一种活性成分与第二种活性成分的质量配比为20:1～1:20；
    当第二种活性成分选自第六组时，所述第一种活性成分与第二种活性成分的质量配比为 1:20～20:1；
    当第二种活性成分选自第七组时，所述第一种活性成分与第二种活性成分的质量配比为1:20～20:1；
    当第二种活性成分选自第八组时，所述第一种活性成分与第二种活性成分的质量配比为1:20～20:1。
  4. 按照权利要求3所述的组合物，其特征在于，当第二种活性成分选自第一组时，所述第一种活性成分与第二种活性成分的质量配比为20:1～1:6；
    当第二种活性成分选自第二组时，所述第一种活性成分与第二种活性成分的质量配比为9:1～1:9；
    当第二种活性成分选自第三组时，所述第一种活性成分与第二种活性成分的质量配比为9:1～1:9；
    当第二种活性成分选自第四组时，所述第一种活性成分与第二种活性成分的质量配比为5:1～1:20；
    当第二种活性成分选自第五组时，所述第一种活性成分与第二种活性成分的质量配比为5:1～1:10；
    当第二种活性成分选自第六组时，所述第一种活性成分与第二种活性成分的质量配比为1:20～10:1；
    当第二种活性成分选自第七组时，所述第一种活性成分与第二种活性成分的质量配比为1:9～9:1；
    当第二种活性成分选自第八组时，所述第一种活性成分与第二种活性成分的质量配比为1:9～9:1。
  5. 按照权利要求1所述的组合物，其特征在于，所述植物源杀虫剂选自印楝素、藜芦碱、苦参碱、茶皂素、鱼藤酮、烟碱、氧化苦参碱、闹羊花素-III、血根碱、桉叶素、苦皮藤素、蛇床子素、除虫菌素、茴蒿素、百部碱、桉叶素和楝素中的至少一种。
  6. 按照权利要求5所述的组合物，其特征在于，所述植物源杀虫剂选自印楝素、藜芦碱、苦参碱、茶皂素、鱼藤酮和烟碱中的至少一种。
  7. 按照权利要求1所述的组合物，其特征在于，所述有机锡类杀螨剂选自三唑锡、苯丁锡、三环锡和三磷锡中的至少一种。
  8. 按照权利要求1所述的组合物，其特征在于，所述有机硫杀螨剂选自炔螨特、丁醚脲、杀螨酯和杀螨硫醚中的至少一种。
  9. 按照权利要求1所述的组合物，其特征在于，所述菊酯类农药选自甲氰菊酯、联苯菊酯、溴氰菊酯、氯氰菊酯、氰戊菊酯、氯氟氰菊酯、高效氯氟氰菊酯、高效氯氰菊酯、氟硅菊酯、炔丙菊酯和四氟醚菊酯中的至少一种。
  10. 按照权利要求9所述的组合物，其特征在于，所述菊酯类农药选自甲氰菊酯、联苯菊酯和高效氯氟氰菊酯中的至少一种。
  11. 一种杀螨剂，其特征在于，所述杀螨剂以重量计含有0.1％以上的权利要求1所述的组合物。
  12. 按照权利要求11所述的杀螨剂，其特征在于，所述杀螨剂以重量计含有1％～80％的权利要求1所述的组合物。
  13. 按照权利要求11所述的杀螨剂，其特征在于，所述杀螨剂配制成乳油、悬浮剂、悬乳剂、微乳剂、水乳剂、可分散油悬浮剂、可湿性粉剂、可溶性粉剂、颗粒剂或胶囊剂。
  14. 按照权利要求1所述的组合物，其特征在于，所述组合物用于防治农业害螨。
PCT/CN2018/087839 2017-03-23 2018-05-22 含螺环醚类衍生物的杀螨组合物 WO2018171817A1 (zh)

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