Acaricidal composition containing tianweimectin B and etoxazole

Abstract

The invention discloses an agricultural acaricidal composition, comprising two active components, wherein the first active component is tianweimectin B, and the other active component is etoxazole. The acaricidal composition of the invention may further contain a carrier and an adjuvant. The composition may be formulated into an emulsifiable concentrate, a suspension, a microemulsion, an aqueous emulsion, a wettable powder, a soluble powder, a water-dispersible granule, a granule or a capsule. The acaricidal composition of the invention has a significant synergistic effect, can kill eggs, young mites, nymph mites and adult mites, and can delay the resistance problem caused by a single agent, and has a high preventive effect on mites on fruit trees, cotton and tea trees.

Description

[Technical field]

[0001] The invention relates to an agricultural acaricidal composition, in particular to an acaricidal composition containing tebuconazole B and etoxazole and application thereof. [Background technology]

[0002] Agricultural pest mites are small in size, reproduce quickly, have strong adaptability, and are prone to resistance. They are one of the most difficult pests to control. Pest mites are important organisms for fruit trees, vegetables, and agricultural and forestry crops. They mainly harm leaves, but also tender shoots, flower buds, and fruits. A sharp increase in the number of insects often causes plant leaf fall, growth inhibition, and even death. Long-term use of a single acaricide variety can easily lead to the rapid development of resistance. Therefore, it is of great significance to develop and prepare acaricide compositions to prolong the service life of acaricides and slow down the development of resistance of pest mites to single acaricides.

[0003] Molecular formula of Tianweimectin B: C 46 H 70 O 14 , relative molecular mass: 847.05.

[0004] Has the following structural formula

[0005]

[0006] Tianweimectin B is obtained by separating and purifying the secondary metabolites of MHJ1011. Tianweimectin B has high activity against pests, including cinnabarinus spider mite, two-spotted spider mite, citrus red spider, striped stem borer, cotton bollworm, armyworm and pine wood nematode, and has reduced toxicity to aquatic organisms.

[0007] Etoxazole, chemical name: (RS)-5-tert-butyl-2-[2-(2,6-difluorophenyl)-4,5-dihydro-1,3-oxazol-4-yl]phenethyl ether, molecular formula: C 21 H 23 F 2 NO 2 , molecular weight: 359.41, structural formula:

[0008]

[0009] Etoxazole is a new acaricide with a special structure developed by Sumitomo Chemical Co., Ltd. of Japan. Its mode of action is to inhibit the embryo formation of mite eggs and the molting process from young mites to adult mites. It is effective against eggs and young mites, but not against adult mites. Therefore, the best time to prevent and control it is the early stage of mite damage. This agent is highly rain-resistant and has a lasting effect of up to 50 days. It has excellent control effects on mites such as spider mites, early spider mites, panonychus mites, two-spotted spider mites, and cinnabar spider mites in crops such as citrus, cotton, apples, flowers, and vegetables.

[0010] The present invention finds that the compounding of tianweimectin B and etoxazole can reduce the amount of pesticides used, significantly improve the mite killing effect, reduce environmental pollution, and solve the problem that the mites are prone to resistance to a single pesticide. At present, the compounding and application of tianweimectin B and etoxazole have not been disclosed at home and abroad. [Summary of the invention]

[0011] The object of the present invention is to provide a preparation and application of a composition containing acaricides tianweimectin B and etoxazole, wherein the composition can fully utilize the significant synergistic effect produced by mixing the two active components, improve the prevention effect, reduce agricultural costs, and delay the development of pest resistance.

[0012] To achieve the purpose of the invention, the present invention provides an agricultural acaricide composition, wherein the effective active ingredients of the composition are tianweimectin B and etoxazole.

[0013] Preferably, the mass ratio of tianweimectin B to etoxazole is 1:50-50:1.

[0014] Particularly preferably, the mass ratio of tianweimectin B to etoxazole is 1:12 to 9:1.

[0015] The present invention also provides an agricultural acaricide, which contains the acaricide composition according to any one of claims 1 to 3 in a mass concentration of 0.5 to 95%.

[0016] Preferably, the agricultural acaricide contains the acaricide composition according to any one of claims 1 to 3 at a mass concentration of 8 to 50%.

[0017] Optionally, the agricultural acaricide further contains a carrier and / or adjuvant acceptable in pesticides.

[0018] Preferably, the auxiliary agent is a surfactant.

[0019] Optionally, the agricultural acaricide is in the form of emulsifiable concentrate, suspension, microemulsion, aqueous emulsion, wettable powder, soluble powder, water-dispersible granules, granules or capsules.

[0020] The present invention also relates to the application of the above-mentioned acaricide composition or acaricide in preventing and controlling harmful mites of crops, especially fruit trees, cotton and tea trees.

[0021] The invention provides an agricultural acaricidal composition, characterized in that the effective active ingredients of the composition are tianbamectin B and etoxazole; the mass ratio of tianbamectin B to etoxazole is 1:12 to 9:1.

[0022] The agricultural acaricidal composition as described above is characterized in that the content of tianweimectin B in the composition is 1-5%, and the content of etoxazole is 1-30%.

[0023] The agricultural acaricide composition as described above is characterized in that the composition is in the form of a suspension or a microemulsion.

[0024] The agricultural acaricidal composition as described above is characterized in that the suspension contains 1-5% of tianweimectin B, 1-30% of etoxazole, 1-8% of sodium lignin sulfonate, and 2.0% of a mixture of alkylnaphthalene sulfonate and anionic wetting agent (Morwet EFW).

[0025] The agricultural acaricidal composition as described above is characterized in that the suspension contains 2% of tianweimectin B, 10% of etoxazole, 5% of sodium lignin sulfonate, and 2.0% of a mixture of alkylnaphthalene sulfonate and anionic wetting agent (Morwet EFW).

[0026] The agricultural acaricidal composition as described above is characterized in that the microemulsion contains 1-5% of tianweimectin B, 1-30% of etoxazole, 1-15% of N-methylpyrrolidone, 1-6% of solvent oil S-150, 8-20% of methyl oleate, 0-5% of calcium dodecylbenzene sulfonate, and 8-25% of terminal hydroxyl polyoxyethylene polyoxypropylene ether.

[0027] The agricultural acaricidal composition as described above is characterized in that the microemulsion contains 1-5% of tianweimectin B, 1-30% of etoxazole, 5-15% of isopropyl alcohol, 1-6% of solvent oil S-150, 8-20% of methyl oleate, 0-5% of calcium dodecylbenzenesulfonate, and 8-25% of styrylphenyl polyoxyethylene ether.

[0028] The agricultural acaricidal composition as described above is characterized in that the microemulsion contains 2% of tianweimectin B, 8% of etoxazole, 6% of N-methylpyrrolidone, 3% of solvent oil S-150, 12% of methyl oleate, 2% of calcium dodecylbenzenesulfonate, 18% of terminal hydroxyl polyoxyethylene polyoxypropylene ether, and water is added to 100%.

[0029] The agricultural acaricidal composition as described above is characterized in that the microemulsion contains 2% of tianweimectin B, 10% of etoxazole, 10% of isopropyl alcohol, 3% of solvent oil S-150, 12% of methyl oleate, 2% of calcium dodecylbenzenesulfonate, 19% of styrylphenyl polyoxyethylene ether, and water is added to 100%.

[0030] Use of the acaricidal composition as described above in controlling red spider mites.

[0031] The technical solution of the present invention will be described in more detail below.

[0032] An agricultural acaricidal composition, wherein the effective active ingredients of the composition are tianweimectin B and etoxazole, and the mass ratio is preferably 1:50-50:1, and more preferably 1:12 to 9:1.

[0033] The above-mentioned acaricide composition can be used to prepare acaricide, and the acaricide can further contain a carrier, and the carrier can be solid or liquid, and any carrier acceptable in pesticides and commonly used in preparing acaricide compositions can be used.

[0034] Suitable solid carriers include: minerals, plants, synthetic fillers and inorganic salts. Minerals include silicates, carbonates, sulfates and oxides. Silicates include kaolin, sepiolite, pearl clay, montmorillonite, mica, vermiculite, pyrophyllite, talc. Carbonates include: calcium carbonate, dolomite. Sulfates include ammonium sulfate, sodium sulfate, calcium sulfate. Oxides include quicklime, magnesium lime, diatomaceous earth. Plants include: citrus residues, corn cobs, husk powder, rice husk, soybean straw powder, tobacco powder, walnut shells, sawdust. Synthetic fillers include precipitated calcium carbonate hydrate, precipitated calcium carbonate, white carbon black. Inorganic salts include potassium chloride, sodium chloride.

[0035] Liquid carriers include water and organic solvents. When the active ingredient is an aqueous emulsion or a suspoemulsion, the organic solvent plays a solubilizing and antifreezing role. 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, carbon tetrachloride and polychlorinated ethanes; aliphatic hydrocarbons, such as petroleum fractions, cyclohexane, light mineral oil and paraffin. Alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, glycerol, fatty alcohols, etc.; ethers such as methyl glycol ether, ethyl glycol ether, petroleum ether. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, N-methyl-pyrrolidone; special solvents also include dimethylformamide, dimethyl sulfoxide, polyethylene glycol, cyanonitrile; vegetable oils and methylated vegetable oils. The above organic solvents may be used alone or in combination, or may be mixed with water.

[0036] The auxiliary agent of the present invention may include one or more of a surfactant, a defoamer, a thickener, a suspending agent and an antifreeze agent as required, and may also include other auxiliary agents commonly used in the industry as required.

[0037] The surfactant may be an emulsifier, dispersant, stabilizer or wetting agent; it may be ionic or nonionic. Suitable surfactants include: sodium and calcium salts of polyacrylic acid and lignin sulfonic acid; condensation products of fatty acids or fatty amines containing at least 12 carbon atoms in the molecule with ethylene oxide and / or propylene oxide; fatty acid esters of glycerol, dodecanol-1, tetradecanol-1, sorbitol, sucrose or pentaerythritol; and their condensation products with ethylene oxide and / or propylene oxide; sulfates or sulfonates of their condensation products; alkali metal or alkaline earth metal salts of sulfuric acid or sulfonic acid containing at least 10 carbon atoms in the molecule, preferably sodium salts, such as sodium dodecyl sulfate, sodium secondary alkyl sulfate, sodium salt of sulfonated castor oil, sodium alkyl aryl sulfonate and sodium dodecylbenzene sulfonate; polymers of ethylene oxide, copolymers of ethylene oxide and propylene oxide.

[0038] Emulsifiers include nonionic emulsifiers and commercially available emulsifiers. Nonionic emulsifiers are preferably polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers and polyoxyethylene fatty amines, such as ethoxylated castor oil, polyoxyethylene (n 20 ) phenethylphenol ether oleate, alkyl aryl polyoxyethylene polyoxypropylene ether, alkyl aryl formaldehyde resin polyoxyethylene ether, tristyrylphenol polyoxyethylene (n 20 ), ether phosphorylated triethanolamine salt, diphenylethylphenol polyoxyethylene ether (n 18 ) formaldehyde condensation products, diphenylphenol polyoxyethylene (n 18 ) Polyoxypropylene ether (n 20 ) etc. Commercially available emulsifiers include: Nongru 0201B, Nongru 0203B, Nongru 100 # 、Nongru 500 # 、Nongru 600 # 、Nongru 600-2 # 、Nongru 1601、Nongru 2201、Nongru NP-10、Nongru NP-15、Nongru 507 # 、Nongru OX-635、Nongru OX-622、Nongru OX-653、Nongru OX-667、Nongru CS-7、Ningru 36 # .

[0039] The dispersant of the present invention comprises: sodium lignin sulfonate, pull-opening powder, calcium lignin sulfonate, methylnaphthalene sulfonic acid formaldehyde condensate, naphthalene sulfonic acid formaldehyde condensate, sodium methylenenaphthalene sulfonate, sodium oleic acid methylaminoethyl sulfonate, epoxy polyether, p-tert-butyl ether, dibutylnaphthalene sulfonic acid formaldehyde condensate, phosphate such as sodium hexametaphosphate, alkylphenol polyoxyethylene phosphate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, N-methyl-fatty acyl-taurate sodium alkylphenol polyoxyethylene ether formaldehyde condensate, aromatic alkylphenol polyoxyethylene ether phosphate alkylphenol polyoxyethylene ether, castor oil ethylene oxide adduct, ethylene oxide-propylene oxide block copolymer alkylphenol polyoxyethylene ether formaldehyde condensate, alkylphenol polyoxyethylene polyoxypropylene ether and methylcellulose.

[0040] The wetting agent described in the present invention includes: sodium lauryl sulfate, sodium alkyl alcohol polyoxyethylene ether sulfate, octylphenol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkyl sodium sulfonate, sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, alkyl succinic acid sulfonate, sodium lauryl alcohol polyoxyethylene ether sulfonate, sodium alkanecarboxamide taurine, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester polyoxyethylene ether, etc.

[0041] The thickener described in the present invention can be either artificially synthesized, such as carboxymethyl alcohol, polyvinyl alcohol or polyvinyl acetate; or it can be a natural water-soluble polymer, such as xanthan gum, gelatin, gum arabic, polyvinyl pyrrolidone, magnesium aluminum silicate, polyvinyl alcohol, polyethylene glycol, phenolic resin, shellac, carboxymethyl cellulose and sodium alginate.

[0042] The defoaming agent of the present invention is preferably: foam enemy, silicone, C 8～10 Fatty alcohol, C 10～20 Saturated fatty acids and amides, etc.

[0043] The present invention also provides an agricultural acaricide containing the agricultural acaricide composition, wherein the amount of the acaricide composition contained is preferably 0.5 to 95% of the total weight based on the active components.

[0044] The agricultural acaricide composition of the present invention can be formulated into liquid, emulsifiable concentrate, suspension, microemulsion, aqueous emulsion, powder, wettable powder, soluble powder, water-dispersible granule, granule or capsule, etc. These preparations can be prepared by common methods.

[0045] The agricultural acaricide composition of the present invention can be directly prepared into a finished product formulation, that is, the various substances in the composition have been mixed and directly used for insecticide; the components of the composition can also be provided as separate formulations and directly mixed in a barrel (tank) before use. The concentrate of the present invention is usually mixed with water to obtain the desired concentration of active substances.

[0046] The agricultural acaricide composition of the present invention is particularly suitable for preventing and controlling citrus red spiders, apple red spiders, cotton red spiders, and tea tree red spiders; and is suitable for citrus, apples, cotton, tea trees, and the like.

[0047] The agricultural acaricide of the present invention is applied to farmland, orchard and the like.

[0048] The agricultural acaricide composition of the present invention can be applied by common methods, such as pouring, spraying, and spraying. The application amount varies with climatic conditions or crop status, and the application time can be before or after the pest damage. The duration of the protective effect is usually related to the content of the individual compounds in the composition, and is also related to external factors, such as climate, but the influence of climate can be mitigated by using an appropriate formulation.

[0049] The agricultural acaricide composition of the present invention can also be used in combination with other compounds having insecticidal, weeding and fungicidal properties, or in combination with nematicides, protective agents, growth regulators, plant nutrients or soil conditioners.

[0050] The advantages of the present invention are that the two acaricides in the composition show a strong synergistic effect within a certain ratio range, and the acaricidal effect of the mixed composition is significantly improved compared with that of a single agent, and can kill eggs, young mites, nymphs and adult mites, and has the characteristics of a long lasting effect; the dosage used is reduced, and the cost of farmers for using pesticides is reduced; the two pesticides are reasonably mixed by using different action modes and different action mechanisms on harmful mites, which not only prolongs the service life of the pesticides, but also delays the generation of drug resistance of harmful mites. [Specific implementation method]

[0051] The present invention is further described below in conjunction with specific embodiments, but the present invention is not limited to these specific embodiments. Those skilled in the art should recognize that the present invention covers all possible alternatives, improvements and equivalents within the scope of the claims.

[0052] In the invention, all percentages in the proportions of solid preparations are weight percentages, and all percentages in the proportions of liquid preparations are volume percentages; the treatment doses of the biologically active parts are all effective contents; unless otherwise specified, the "effective ingredient ratio" is the "effective ingredient ratio of oxadiazine B and etoxazole".

[0053] 1. Preparation of the composition and biological activity examples

[0054] 1. Preparation of emulsifiable concentrate

[0055] According to the formula requirements, add the solvent, original drug and emulsifier respectively, mix them evenly, and heat in a water bath to dissolve if necessary to obtain a transparent emulsifiable concentrate.

[0056] Example 1 Concentration 25.5% emulsifiable concentrate, active ingredient ratio 1:50

[0057] Tianweimectin B 0.5%, etoxazole 25%, Nongru 2201# 7.5%, Nongru 600# 4.5%, dimethylformamide 8%, solvent oil 150 is supplemented to 100% (S-150#) (The main component of S-150# solvent oil is tetramethylbenzene, produced and sold by Jiangsu Hualun Chemical Co., Ltd.).

[0058] Example 2: 15% emulsifiable concentrate, effective ingredient ratio 1:4

[0059] Tianweimectin B 3%, etoxazole 12%, Nongru 500# 5%, Nongru 0201B 10%, dimethylformamide 12%, solvent oil 150 (S-150#) are supplemented to 100%.

[0060] Example 3 12% emulsifiable concentrate, active ingredient ratio 1:5

[0061] Tianweimectin B 2%, etoxazole 10%, Nongru 0203B 6%, Nongru 0201B 9%, cyclohexanone 8%, solvent oil 150 to 100%.

[0062] Example 4 20% emulsifiable concentrate, active ingredient ratio 1:9

[0063] Tianweimectin B 2%, etoxazole 18%, Nongru 2201# 6%, Nongru 0201B 8%, cyclohexanone 8%, solvent oil 150 is made up to 100%.

[0064] 2 Preparation of wettable powder

[0065] According to the formula requirements, the original drug, various additives and fillers are fully mixed and crushed by an ultra-fine grinder to obtain the processed product.

[0066] Example 5: 10% wettable powder, active ingredient ratio 1:1

[0067] Tianweimectin B 5%, etoxazole 5%, sodium dodecylbenzene sulfonate 2.0%, white carbon black 5%, sodium lignin sulfonate 10%, light calcium carbonate is supplemented to 100%.

[0068] Example 6: 10% wettable powder, active ingredient ratio 9:1

[0069] Tianweimectin B 9%, etoxazole 1%, sodium lauryl sulfate 1.5%, naphthalenesulfonic acid formaldehyde condensate 5%, sodium lignin sulfonate 3%, white carbon black 8%, light calcium carbonate is supplemented to 100%.

[0070] Example 7: 25% wettable powder, active ingredient ratio 1:4

[0071] Tianweimectin B 5%, etoxazole 20%, sodium dodecylbenzene sulfonate 1.8%, p-tert-butyl ether 2%, white carbon black 10%, sodium lignin sulfonate 10%, and light calcium carbonate is supplemented to 100%.

[0072] Example 8: 40% wettable powder, active ingredient ratio 1:3

[0073] Tianweimucin B 10%, etoxazole 30%, sodium dodecylbenzene sulfonate 2%, p-tert-butyl ether 3%, white carbon black 6%, sodium lignin sulfonate 7%, light calcium carbonate is supplemented to 100%.

[0074] Example 9: 31.5% wettable powder, active ingredient ratio 1:20

[0075] Tianweimectin B 1.5%, etoxazole 30%, sodium dodecylbenzene sulfonate 2%, p-tert-butyl ether 2%, white carbon black 5%, sodium lignin sulfonate 10%, and light calcium carbonate is supplemented to 100%.

[0076] 3. Preparation of water dispersible granules

[0077] The original drug, powdered carrier, wetting agent, and binder are mixed and crushed, and then water is added and kneaded, and then added into a granulator equipped with a certain specification of screen for granulation. Then, it is dried and sieved (according to the range of the screen) to obtain a granular product.

[0078] Example 10: 8% water-dispersible granules, active ingredient ratio 1:3

[0079] Tianweimectin B 2%, etoxazole 6%, sodium lignin sulfonate 15%, sodium methylnaphthalene sulfonate formaldehyde condensate 5%, epoxy polyether 5%, bentonite 10%, kaolin is made up to 100%.

[0080] Example 11: 50% water dispersible granules, active ingredient ratio 1:4

[0081] Tianweimectin B 10%, etoxazole 40%, sodium lignin sulfonate 12%, sodium methylnaphthalene sulfonate formaldehyde condensate 5%, epoxy polyether 3%, bentonite 10%, kaolin to 100%. Example 12 Concentration 48% water-dispersible granules, active ingredient ratio 1:5

[0082] Tianweimectin B 8%, etoxazole 40%, sodium N-methyl-oleoyl-taurate 8%, naphtholsulfonic acid formaldehyde condensate 10%, soluble starch 8%, sodium sulfate 10%, kaolin is supplemented to 100%.

[0083] Example 13: 35% water-dispersible granules, active ingredient ratio 1:6

[0084] Tianweimectin B 5%, etoxazole 30%, sodium lignin sulfonate 15%, sodium methylnaphthalene sulfonate formaldehyde condensate 5%, epoxy polyether 5%, bentonite 10%, kaolin is made up to 100%.

[0085] 4. Preparation of suspension

[0086] According to the formula requirements, use water as the medium, mix the original drug, dispersant, wetting agent, suspending agent and antifreeze evenly, then add them into the sand mill, grind to a certain particle size, filter, add the thickener, shear and stir evenly.

[0087] Example 14: 10% suspension, active ingredient ratio 9:1

[0088] Tianweimectin B 9%, etoxazole 1%, pull open powder 1.5%, Soproplot SC 3%, xanthan gum 0.15%, magnesium aluminum silicate 1.0%, 418G 0.3%, BIT 0.05%, ethylene glycol 3%, water makes up to 100%.

[0089] Example 15 Concentration 20% suspension, active ingredient ratio 1:3

[0090] Tianweimectin B 5%, etoxazole 15%, sodium lignin sulfonate 5%, white carbon black 0.5%, sodium methylnaphthalene sulfonate formaldehyde condensate 2.0%, potassium dihydrogen phosphate 0.2%, ethylene glycol 4%, tributyl phosphate 0.2%, water is made up to 100%.

[0091] Example 16 Concentration 20% suspension, active ingredient ratio 1:4

[0092] Tianweimectin B 4%, etoxazole 16%, sodium methylnaphthalene sulfonate formaldehyde condensate 2.5%, agricultural milk OX-656 5.0%, glycerol 4%, tributyl phosphate 0.2%, water is made up to 100%.

[0093] Example 17: 12% suspension, active ingredient ratio 1:5

[0094] Tianweimectin B 2%, etoxazole 10%, sodium lignin sulfonate 5%, white carbon black 0.3%, a mixture of alkyl naphthalene sulfonate and anionic wetting agent (EFW) 2.0%, potassium dihydrogen phosphate 0.2%, ethylene glycol 4%, tributyl phosphate 0.2%, and water is added to 100%.

[0095] Example 18: 35% suspension, active ingredient ratio 1:6

[0096] Tianweimectin B 5%, etoxazole 30%, sodium methyl naphthalene sulfonate formaldehyde condensate 2.5%, a mixture of alkyl naphthalene sulfonate and anionic wetting agent (EFW) 2.0%, agricultural milk OX-656 3.0%, glycerol 4%, tributyl phosphate 0.2%, water is supplemented to 100%.

[0097] Example 19: 25.5% concentration suspension, active ingredient ratio 1:50

[0098] Tianweimectin B 0.5%, etoxazole 25%, sodium methyl naphthalene sulfonate formaldehyde condensate 2.5%, a mixture of alkyl naphthalene sulfonate and anionic wetting agent (EFW) 2.0%, agricultural milk OX-656 3.0%, glycerol 4%, tributyl phosphate 0.2%, water is supplemented to 100%.

[0099] 5. Preparation of water emulsion

[0100] The original drug, solvent and emulsifier are mixed and stirred evenly to form a uniform oil phase, and water and ethylene glycol are mixed and stirred to form a water phase. Under high shear conditions, the oil phase is slowly added to the water phase to obtain an aqueous emulsion.

[0101] Example 20: 20% aqueous emulsion, active ingredient ratio 9:1

[0102] Tianweimectin B 9%, etoxazole 1%, solvent oil S-150 30%, calcium dodecylbenzene sulfonate 3%, polyoxyethylene styrylphenyl ether 6%, ethylene glycol 3%, water to 100%.

[0103] Example 21: 10% aqueous emulsion, active ingredient ratio 1:4

[0104] Tianweimectin B 2%, etoxazole 8%, solvent oil S-150 30%, triphenylphenol polyoxyethylene ether phosphate 4%, terminal hydroxyl polyoxyethylene polyoxypropylene ether block copolymer 5%, ethylene glycol 3%, water to 100%.

[0105] Example 22: 18% aqueous emulsion, active ingredient ratio 1:5

[0106] Tianweimectin B 3%, etoxazole 15%, solvent oil S-150 30%, triphenyl phenol polyoxyethylene ether phosphate 3%, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether 5%, propylene glycol 3%, water to 100%.

[0107] Example 23: 10.5% aqueous emulsion, active ingredient ratio 20:1

[0108] Tianweimectin B 10%, etoxazole 0.5%, solvent oil S-150 30%, triphenylphenol polyoxyethylene ether phosphate 4%, terminal hydroxyl polyoxyethylene polyoxypropylene ether block copolymer 5%, ethylene glycol 3%, water to 100%.

[0109] Example 24: 21% aqueous emulsion, active ingredient ratio 1:20

[0110] Tianweimectin B 1%, etoxazole 20%, solvent oil S-150 30%, triphenyl phenol polyoxyethylene ether phosphate 3%, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether 5%, propylene glycol 3%, water to 100%.

[0111] 6Microemulsion processing technology:

[0112] Mix the original drug, solvent, emulsifier, co-emulsifier, etc. to form a uniform oil phase. Gradually add water to the oil phase and stir until it is uniform and transparent.

[0113] Although different solvents, emulsifiers, etc. can be used to prepare microemulsions, the stability of microemulsions is different. Some microemulsions quickly break, become turbid, and stratify, and their stability does not exceed 7 days. Through a large number of experiments to select suitable excipients, the following microemulsions with a concentration of 10%-14% and a stability of more than 7 days were obtained.

[0114] Example 25: 10% microemulsion, active ingredient ratio 1:4

[0115] Tianweimectin B 2%, etoxazole 8%, N-methylpyrrolidone 6%, solvent oil S-150 15%, calcium dodecylbenzene sulfonate 2%, terminal hydroxy polyoxyethylene polyoxypropylene ether 18%, water to 100%.

[0116] Example 26: 12% microemulsion, active ingredient ratio 1:5

[0117] Tianweimectin B 2%, etoxazole 10%, isopropyl alcohol 10%, solvent oil S-150 15%, calcium dodecylbenzene sulfonate 2%, styrylphenyl polyoxyethylene ether 19%, water to 100%.

[0118] Example 27: 14% microemulsion, active ingredient ratio 1:6

[0119] Tianweimectin B 2%, etoxazole 12%, N-octyl pyrrolidone 6%, solvent oil S-150 15%, calcium dodecylbenzene sulfonate 2%, alkylphenol formaldehyde resin polyoxyethylene ether 16%, water to 100%.

[0120] Example 28: 10% microemulsion, active ingredient ratio 1:9

[0121] Tianweimectin B 1%, etoxazole 9%, isopropyl alcohol 10%, solvent oil S-150 15%, calcium dodecylbenzene sulfonate 2%, styrylphenyl polyoxyethylene ether 19%, water to 100%.

[0122] Experimental Example 1

[0123] Indoor biological activity assay

[0124] In order to further understand the toxicity of the combination of tianweimectin B and etoxazole to pests, a large number of formulation screening tests were conducted. The test was based on the guidelines for indoor bioassay tests of insecticides (agricultural industry standard NY / T1154.7-2006) and the SOP for the evaluation of the biological activity of pesticides (pesticide volume), and the leaf immersion method was used. Cut the broad bean leaves with the stalks and insert them into a glass bottle with water. A certain number of adult mites were collected. After the adult mites laid eggs for 24 hours, the adult mites were removed, and the leaves with enough eggs were immersed in the liquid for 10 seconds. The excess liquid was quickly absorbed with absorbent paper, and the leaves were placed back in the ampoule bottle and dried naturally. They were placed in an observation room (25±2℃, humidity 70%~80%, 16h light / d) for cultivation. The test was repeated 3 times, and a blank control was set up. After all the controls were hatched, an investigation was conducted. During the investigation, those that failed to hatch were considered dead insects.

[0125]

[0126] Theoretical toxicity index (TTI) = toxicity index of A × content of A in the mixture (%)

[0127] + Toxicity index of B × content of B in the mixture (%)

[0128]

[0129] If the co-toxicity coefficient is greater than 120, it indicates a synergistic effect; if it is less than 80, it indicates an antagonistic effect; if it is greater than 80 and less than 120, it indicates an additive effect.

[0130] The results show that: Test results: The mixture of Tianweimectin B and etoxazole has high activity against the test targets. After Tianweimectin B and etoxazole are mixed, when Tianweimectin B: etoxazole is 50:1, 20:1, 1:20, 1:50, it shows an additive effect, and when it is 9:1-1:12, it shows a significant synergistic effect. When Tianweimectin B: etoxazole = 1:4, the co-toxicity coefficient is the largest and the synergistic effect is the most significant. The results are detailed in Example 20.

[0131] Experimental Example 1 Synergistic effect of oxadiazine B and etoxazole

[0132] (Tetranychus cinnabarinus)

[0133]

[0134]

[0135] 7. Control effect in field plots

[0136] Experimental Example 2 Field test of the efficacy of a mixture of avermectin B and etoxazole against citrus spider mites

[0137] The control effects of 12% tianweixanthin B·etoxazole suspension, 10% tianweixanthin B·etoxazole microemulsion, 12% tianweixanthin B·etoxazole microemulsion, and 35% tianweixanthin B·etoxazole water dispersible granules in the formulation examples on citrus red spider mites were determined under field conditions. The citrus was cultivated in the open field and the seedlings were 10 years old. The application rate was 900kg / hm 2 . 2% Tianweimectin B microemulsion: 13.3mg / L; 110g / L etoxazole suspension: 20mg / L. Use the "Hemei" HM-16A backpack electric sprayer to spray the leaves of the plants evenly. 4 replicates, arranged in random blocks. Survey results 3 days, 7 days, 14 days, and 21 days after the drug was applied. According to the provisions of "Pesticide Field Efficacy Test Guidelines (I) - Insecticide Control of Citrus Red Spider", 5 fixed points were used to mark the citrus leaves in each test area according to the 5 directions of east, south, west, and north. Two plants were surveyed in each area, and the number of all live insects on each plant was investigated.

[0138] Test results: 3 days, 7 days, 14 days, 21 days after application, the control effects of 12% Tianweimectin B·etoxazole suspension, 10% Tianweimectin B·etoxazole microemulsion, 12% Tianweimectin B·etoxazole microemulsion, and 35% Tianweimectin B·etoxazole water dispersible granules on citrus red spider were 91.30%-94.73%, 90.33%-96.07%, 90.98%-95.34%, and 86.15%-92.51%, respectively, and the control effects of citrus red spider were better than 110g / L etoxazole suspension 20mg / L and 2% Tianweimectin B microemulsion 13.3mg / L. Tianweimectin B and etoxazole are mixed, which has high control effect on citrus red spider, good rapid effect and long lasting effect.

[0139] Field test results of the mixture of tianweimectin B and etoxazole against citrus red spider mites

[0140]

[0141] Experimental Example 3: Field efficacy test of a mixture of avermectin B and etoxazole against apple red spider mites

[0142] The control effects of 12% tianweixanthin B·etoxazole suspension, 10% tianweixanthin B·etoxazole microemulsion, 12% tianweixanthin B·etoxazole microemulsion, and 35% tianweixanthin B·etoxazole water dispersible granules on apple red spider mites were tested under field conditions. The application rate was 1150kg / hm 2. 2% Tianweimectin B microemulsion: 13.3mg / L; 110g / L etoxazole suspension: 20mg / L. Use "Hemei" HM-16A backpack electric sprayer to spray the leaves of the plants evenly. Repeat 4 times, arranged in random blocks. Survey results 3 days, 7 days, 14 days, and 21 days after the drug. Five fixed points were used to mark the apple leaves in each test area according to the five directions of east, south, west, and north. Two plants were surveyed in each area, and the number of all live insects on each plant was investigated.

[0143] Test results:

[0144] 3 days, 7 days, 14 days and 21 days after application, the control effects of 12% Tianweimectin B·etoxazole suspension, 10% Tianweimectin B·etoxazole microemulsion, 12% Tianweimectin B·etoxazole microemulsion and 35% Tianweimectin B·etoxazole water dispersible granules on citrus red spider were 93.78%-97.26%, 92.84%-96.46%, 93.19%-93.82% and 91.42%-93.08% respectively, and the control effects of citrus red spider were better than 110g / L etoxazole suspension 20mg / L and 2% Tianweimectin B microemulsion 13.3mg / L. Tianweimectin B and etoxazole are mixed, which has high control effect on apple red spider, good rapid effect and long lasting effect.

[0145] Field test on the efficacy of a mixture of tianweimectin B and etoxazole against apple red spider mites

[0146]

[0147] The above data show that the mixture of tianbamectin B and etoxazole has obvious synergistic effect in controlling citrus red spider mites and apple red spider mites, and the effect is better than using tianbamectin B or etoxazole alone, thereby reducing the dosage of medicine and delaying the problem of drug resistance caused by a single agent.

[0148] Through the field efficacy test, it can be seen that at the same dosage of tianweixanthin B and etoxazole, 10% tianweixanthin B·etoxazole microemulsion and 12% tianweixanthin B·etoxazole microemulsion have the best efficacy, which can last for 21 days and still have excellent prevention and control effects.

[0149] Subsequently, due to field use, higher requirements are placed on the stability and anti-photolysis performance of the pharmaceutical preparations, and therefore further studies were conducted on the stability and anti-photolysis performance in Examples 25 and 26.

[0150] At room temperature and a light condition of 1200-1500 LX, the microemulsions in Examples 25 and 26 were subjected to a study on photolysis resistance and stability. Under the above conditions, the microemulsions in Examples 25 and 26 decomposed more than 50% of tianweimectin B in 24 hours.

[0151] According to the previous experimental results, the solvent methyl oleate is beneficial to reduce the degradation rate of tianweimectin B. Therefore, it is considered to replace the solvent oil S-150 in the microemulsion with methyl oleate to improve its anti-photolysis performance and stability. However, the microemulsion prepared by using only methyl oleate is very easy to produce stratification and turbidity. Therefore, it is considered to use methyl oleate and solvent oil S-150 as a mixed solvent, take the formula of Example 25 as the research object, prepare microemulsions with different S-150: methyl oleate ratios, and measure the degradation rate of tianweimectin B and the stability of the microemulsion.

[0152]

[0153] Through the above screening, S-150:methyl oleate=1:4 was determined to be the preferred oil phase solvent.

[0154] Therefore, a microemulsion with the following formula is prepared:

[0155] Example 29: 10% microemulsion, active ingredient ratio 1:4

[0156] Tianweimectin B 2%, etoxazole 8%, N-methylpyrrolidone 6%, solvent oil S-150 3%, methyl oleate 12%, calcium dodecylbenzene sulfonate 2%, terminal hydroxy polyoxyethylene polyoxypropylene ether 18%, water to 100%.

[0157] Example 30: 12% microemulsion, active ingredient ratio 1:5

[0158] Tianweimectin B 2%, etoxazole 10%, isopropyl alcohol 10%, solvent oil S-150 3%, methyl oleate 12%, calcium dodecylbenzenesulfonate 2%, styrylphenyl polyoxyethylene ether 19%, water to 100%.

[0159] According to the method of Experimental Examples 2 and 3, the microemulsions of Examples 29 and 30 were subjected to field efficacy tests against citrus red spider and apple red spider (21 days), and the following results were obtained:

[0160]

[0161] It can be seen that the microemulsions of Examples 29 and 30 not only improve the stability, but also improve the acaricidal effect for 21 days.

[0162] The above description is a general description of the present invention. According to the situation or actual needs, changes in form and substitution of equivalents can be made. Although specific terms are used herein, these terms are intended to describe rather than limit the purpose. Those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. An agricultural acaricidal composition, characterized in that The effective active ingredients of the composition are tianbamectin B and etoxazole; the mass ratio of tianbamectin B to etoxazole is 1:12 to 9:1, the content of tianbamectin B in the composition is 1-5%, and the content of etoxazole is 1-30%.

2. The agricultural acaricidal composition according to claim 1, characterized in that The dosage form of the composition is a suspension or a microemulsion.

3. The agricultural acaricidal composition according to claim 2, characterized in that The suspending agent comprises 1-5% of tianweimectin B, 1-30% of etoxazole, 1-8% of sodium lignin sulfonate, and 2.0% of a mixture of alkylnaphthalene sulfonate and anionic wetting agent.

4. The agricultural acaricidal composition according to claim 2, characterized in that The suspension contains 2% of tianweimectin B, 10% of etoxazole, 5% of sodium lignin sulfonate, and 2.0% of a mixture of alkylnaphthalene sulfonate and anionic wetting agent.

5. The agricultural acaricidal composition according to claim 2, characterized in that The microemulsion contains 1-5% of tianweimectin B, 1-30% of etoxazole, 1-15% of N-methylpyrrolidone, 1-6% of solvent oil S-150, 8-20% of methyl oleate, 0-5% of calcium dodecylbenzene sulfonate, and 8-25% of terminal hydroxyl polyoxyethylene polyoxypropylene ether.

6. The agricultural acaricidal composition according to claim 2, characterized in that The microemulsion contains 1-5% of tianweimectin B, 1-30% of etoxazole, 5-15% of isopropyl alcohol, 1-6% of solvent oil S-150, 8-20% of methyl oleate, 0-5% of calcium dodecylbenzene sulfonate, and 8-25% of styrylphenyl polyoxyethylene ether.

7. The agricultural acaricidal composition according to claim 2, characterized in that The microemulsion comprises 2% of tianweimectin B, 8% of etoxazole, 6% of N-methylpyrrolidone, 3% of solvent oil S-150, 12% of methyl oleate, 2% of calcium dodecylbenzene sulfonate, 18% of terminal hydroxyl polyoxyethylene polyoxypropylene ether, and water is added to 100%.

8. The agricultural acaricidal composition according to claim 2, characterized in that The microemulsion comprises 2% of tianweimectin B, 10% of etoxazole, 10% of isopropyl alcohol, 3% of solvent oil S-150, 12% of methyl oleate, 2% of calcium dodecylbenzenesulfonate, 19% of styrylphenyl polyoxyethylene ether, and water is added to 100%.

9. Use of the acaricidal composition according to any one of claims 1 to 8 in controlling red spider mites.

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