A pesticide composition containing fluorine-containing acaricide thioether and its application

Abstract

The present application belongs to the technical field of pesticides, and relates to a pesticide composition containing fluorine-containing mite sulfide, which comprises active ingredient A and active ingredient B; the active ingredient A is fluorine-containing mite sulfide, and the active ingredient B is selected from any one of spiroxamine, spirodiclofen and spirodichloride. The pesticide composition or the preparation thereof can enhance the efficacy, expand the mite spectrum, reduce the use cost, reduce the dosage, prolong the effective period and delay the development of drug resistance.

Description

Technical Field

[0001] This invention relates to the field of pesticide compound technology, and in particular to a pesticide composition containing flufenoxuron and its application. Background Technology

[0002] In recent years, with the rapid development of the vegetable planting industry, the types of vegetables and production management conditions have been constantly changing, leading to an increase in the types of vegetable diseases and pests. This has brought many inconveniences to vegetable planting and management, as well as many uncertainties to the safety of vegetables for consumption, posing a serious threat to human life and property.

[0003] Fluorosulfuron has the chemical name (4'-chloro-6-fluoro-4-methyl-[1,1'-biphenyl]-3-yl)(2,2,2-trifluoroethyl) sulfide, and its chemical structure is as follows:

[0004]

[0005] Spirodiclofen, chemically known as [2-oxoylide-3-(2,4,6-trimethylphenyl)-1-oxaspiro[4,4]non-3-en-4-yl]3,3-dimethylbutyrate, is a spirocyclic quaternary ketoacid insecticide and acaricide developed by Bayer AG. It possesses a unique spirocyclic quaternary ketoacid structure, a novel mechanism of action, and excellent insecticidal and acaricidal activity. It is mainly used in cotton, vegetables, and ornamental plants to control piercing-sucking pests, and is very effective against spider mites and whiteflies. The mechanism of action of spirodiclofen involves affecting the development of whiteflies and mites, interfering with their liposome biosynthesis, and also causing ovarian duct closure, reducing the reproductive capacity of whiteflies and mites, and decreasing the number of eggs laid.

[0006] Spirodiclofen diester's chemical name is 3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4,5]dec-3-en-4-yl dibutyl carbonate. Spirodiclofen diester is a non-systemic acaricide that controls eggs, nymphs, and adult females through contact and stomach poisoning. Its mechanism of action is to inhibit fat synthesis and block energy metabolism in the mites, and it does not exhibit severe cross-resistance with conventional acaricides. Spirodiclofen diester is highly effective against species such as *Pterocarya*, *Tetranychus*, *Tetranychus*, and *Gallaria*, and can be used for mite control in crops such as citrus, grapes, eggplant, and peppers.

[0007] In recent years, with the widespread promotion of facility agriculture, mite infestations have shown a trend of increasing severity year by year. Agricultural mites are small in size, reproduce rapidly, have many generations, and are highly adaptable, making them typical pests prone to outbreaks and recognized as one of the most difficult pest communities to control. Long-term, continuous, high-dose use of single chemical agents can easily lead to a series of problems such as pesticide resistance in mites and environmental pollution. Rational compounding or mixing of chemical agents has positive characteristics such as broadening the insecticidal spectrum, improving control efficacy, extending the application period, reducing pesticide dosage, reducing phytotoxicity, reducing residues, and delaying the development of pesticide resistance in pests. The applicant has surprisingly discovered through indoor toxicity experiments and field efficacy trials that the compound combination of flufenoxuron with spirodiclofen or spirodiclofen has a significant synergistic effect, and the pesticide composition and application of the compound combination of flufenoxuron with spirodiclofen or spirodiclofen have not been reported before. Summary of the Invention

[0008] Based on the above, the present invention aims to provide a pesticide composition containing flufenoxuron, mainly used for the control of phytophagous mites. This pesticide composition or its formulation can enhance efficacy, reduce dosage, prolong the duration of action, and delay the development of resistance.

[0009] To achieve the above objectives, the present invention provides the following technical solution: a pesticide composition containing flufenoxuron, wherein the pesticide composition comprises active ingredient A and active ingredient B, wherein active ingredient A is flufenoxuron, and active ingredient B is selected from either spirodiclofen or spirodiclofen diester;

[0010] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:28 to 30:1;

[0011] Furthermore, the mass ratio of flufenoxuron to spirodiclofen is 1:28 to 30:1;

[0012] Furthermore, the mass ratio of flufenoxuron to spirodiclofen is 1:28, 1:14, 1:8, 1:6, 2:3, 5:2, 8:1, 14:1, 20:1, or 30:1.

[0013] Furthermore, the mass ratio of flufenoxuron to spirodiclofen is 1:14 to 20:1;

[0014] Furthermore, the mass ratio of flufenoxuron to spirodiclofen is 1:14, 1:8, 1:6, 2:3, 5:2, 8:1, 14:1, or 20:1.

[0015] Furthermore, the mass ratio of flufenoxuron to spirodimethyl is 1:28 to 28:1;

[0016] Further, the mass ratio of flufenoxuron to spirodimethyl is 1:28; 1:14; 1:8; 2:7; 1:2; 7:2; 14:1; 28:1;

[0017] Furthermore, the mass ratio of flufenoxuron to spirodimethyl is 1:28 to 14:1;

[0018] Furthermore, the mass ratio of flufenoxuron to spirodimethyl is 1:28; 1:14; 1:8; 2:7; 1:2; 7:2; 14:1;

[0019] Furthermore, based on a total weight of 100 wt% of the pesticide composition, the sum of the contents of active ingredient A and active ingredient B in the pesticide composition is 1-95 wt%.

[0020] Furthermore, based on a total weight of 100 wt% of the pesticide composition, the sum of the contents of active ingredient A and active ingredient B in the pesticide composition is 5 to 80 wt%.

[0021] Furthermore, based on a total mass of 100 wt% of the pesticide composition, the sum of the contents of flufenoxuron and spirodiclofen in the pesticide composition is 5 to 45 wt%.

[0022] Further, based on a total mass of 100 wt% of the pesticide composition, the sum of the contents of flufenoxuron and spirodiclofen in the pesticide composition is 5 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, and 45 wt%.

[0023] Furthermore, based on a total mass of 100 wt% of the pesticide composition, the sum of the contents of flufenoxuron and spirodiclofen in the pesticide composition is 5 to 45 wt%.

[0024] Further, based on a total mass of 100 wt% of the pesticide composition, the sum of the contents of flufenoxuron and spirodiclofen in the pesticide composition is 5 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, and 40 wt%.

[0025] Furthermore, in addition to the active ingredient, the pesticide composition also includes agriculturally acceptable auxiliary ingredients, which are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, stabilizers, synergists, or carriers.

[0026] The wetting agent is selected from one or more of the following: alkylbenzene sulfonates, alkylnaphthalene sulfonates, lignin sulfonates, sodium dodecyl sulfate, sodium dioctyl succinate sulfonate, α-olefin sulfonates, alkylphenol polyoxyethylene ethers, castor oil polyoxyethylene ethers, alkylphenol ethoxylates, fatty alcohol ethoxylates, sodium fatty alcohol polyoxyethylene ether sulfate, silkworm excrement, soapberry powder, soapberry powder, SOPA, detergents, emulsifiers 2000 series, and wetting and penetrating agents F; and / or

[0027] The dispersant is selected from one or more of the following: lignin sulfonates, alkyl naphthalene sulfonates formaldehyde condensates, naphthalene sulfonates, tristyrylphenol ethoxylate phosphates, fatty alcohol ethoxylates, alkylphenol polyoxyethylene ethers, alkylphenol polyoxyethylene ether methyl ether condensates sulfates, fatty amine polyoxyethylene ethers, glycerol fatty acid ester polyoxyethylene ethers, polycarboxylates, polyacrylic acids, phosphates, EO-PO block copolymers, and EO-PO graft copolymers; and / or

[0028] The emulsifier is selected from one or more of the following: calcium dodecylbenzenesulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styrene-phenol polyoxyethylene ether, castor oil polyoxyethylene ether, and alkylphenol ether phosphate; and / or

[0029] The thickener is selected from one or more of xanthan gum, organobentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose, and silica; and / or

[0030] The disintegrant is selected from one or more of sodium sulfate, ammonium sulfate, aluminum chloride, sodium chloride, ammonium chloride, bentonite, glucose, sucrose, starch, cellulose, urea, sodium carbonate, sodium bicarbonate, citric acid, and tartaric acid; and / or

[0031] Antifreeze is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons, and inorganic salts; and / or

[0032] Defoamer selected from C 10 -C 20 Saturated fatty acid compounds, silicone oil, silicone compounds, C8-C 10 One or more of the fatty alcohols; and / or

[0033] The solvent is selected from one or more of benzene, toluene, xylene, mesitylene, methanol, ethanol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, cyclohexanone, hydrocarbon carbonates, diesel oil, solvent oil, vegetable oil, vegetable oil derivatives, and water; and / or

[0034] The preservative is selected from one or more of propionic acid, sodium propionate, sorbic acid, sodium sorbate, potassium sorbate, benzoic acid, sodium benzoate, sodium p-hydroxybenzoate, methyl p-hydroxybenzoate, Kathon, and 1,2-benzisothiazolin-3-one; and / or

[0035] The stabilizer is selected from one or more of the following: disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2,6-di-tert-butyl-p-cresol, triethanolamine oleate, epoxidized vegetable oil, kaolin, bentonite, attapulgite, silica, talc, montmorillonite, and starch; and / or

[0036] Synergists are selected from synergistic phosphorus, synergistic ether; and / or

[0037] The carrier is selected from one or more of the following: ammonium salts, ground natural minerals, ground artificial minerals, silicates, resins, waxes, solid fertilizers, water, organic solvents, mineral oils, vegetable oils, and vegetable oil derivatives.

[0038] This invention optimizes the content of active ingredients and adjuvants in the acaricide composition to achieve a better balance between toxicity and residue, thereby enhancing efficacy, reducing dosage, and lowering costs.

[0039] Furthermore, the pesticide composition can be prepared into an agriculturally permissible formulation, wherein the formulation is selected from solid and / or liquid formulations;

[0040] Furthermore, the solid dosage form is selected from wettable powders and water-dispersible granules; the liquid dosage form is selected from emulsifiable concentrates, water-in-oil emulsions, microemulsions, and suspensions.

[0041] The specific implementation scheme of the pesticide formulation prepared by the pesticide composition of the present invention is as follows:

[0042] When the pesticide composition is a wettable powder, the mass parts of the components are: active ingredient A1-40 parts, active ingredient B1-40 parts, dispersant 3-10 parts, wetting agent 1-5 parts, filler, and deionized water to make up the balance.

[0043] The specific production steps of the wettable powder are as follows: the active ingredients, dispersant, wetting agent and filler are mixed according to the above formula, stirred evenly in a stirring tank, and then mixed evenly after air jet pulverization, so as to prepare the wettable powder of the composition of the present invention.

[0044] When the pesticide composition is a water-dispersible granule, the mass fractions of the components are: active ingredient A1-40 parts, active ingredient B1-40 parts, dispersant 3-10 parts, wetting agent 1-10 parts, disintegrant 1-5 parts, and filler balance.

[0045] The specific production steps of the water-dispersible granules are as follows: the active ingredients, dispersant, wetting agent, disintegrant and filler are mixed evenly according to the above formula, pulverized by ultra-micro airflow pulverizer, kneaded, and then added to fluidized bed granulation dryer for granulation, drying, sieving and sampling analysis, and the water-dispersible granules of the composition of the present invention can be produced.

[0046] When the pesticide composition is an emulsifiable concentrate, the mass parts of the components are: active ingredient A 1-40 parts, active ingredient B 1-40 parts, conventional emulsifier 10-30 parts, conventional solvent 20-50 parts, and conventional synergist 1-5 parts.

[0047] The specific production steps of the emulsifiable concentrate formulation are as follows: first, the active ingredient is added to the solvent and completely dissolved, then the emulsifier and synergist are added and stirred evenly to form a uniform and transparent oily liquid, which is then filled into the container to produce the emulsifiable concentrate formulation of the composition of the present invention.

[0048] When the pesticide composition is an emulsion, the mass parts of the components are: active ingredient A1-40 parts, active ingredient B1-40 parts, emulsifier 3-30 parts, solvent 5-15 parts, stabilizer 2-15 parts, antifreeze 1-5 parts, defoamer 0.1-8 parts, thickener 0.2-2 parts, deionized water, and the balance.

[0049] The specific production steps of the water-in-oil emulsion are as follows: the active ingredient, solvent, emulsifier, and cosolvent are added together to dissolve into a uniform oil phase; a portion of deionized water, antifreeze, antimicrobial agent, and other pesticide adjuvants are mixed together to form a uniform aqueous phase; while stirring at high speed in a reaction vessel, the oil phase is added to the aqueous phase, water is slowly added until the phase inversion point is reached, a shearing machine is turned on for high-speed shearing, and the remaining water is added. Shearing is carried out for about half an hour to form an oil-in-water emulsion, which is the water-in-oil emulsion of the composition of the present invention.

[0050] When the pesticide composition is a microemulsion, the mass parts of the components are: active ingredient A1-40 parts, active ingredient B1-40 parts, emulsifier 10-30 parts, antifreeze 1-8 parts, stabilizer 0.5-10 parts, and conventional solvents and cosolvents 20-50 parts.

[0051] The specific production steps of the microemulsion are as follows: the active ingredient is completely dissolved in a cosolvent, then other ingredients such as emulsifier, antifreeze stabilizer, etc. are added, mixed evenly, and finally water is added and stirred thoroughly to form a microemulsion.

[0052] When the pesticide composition is a suspension, the mass parts of the components are as follows: active ingredient A 1-40 parts, active ingredient B 1-40 parts, dispersant 1-10 parts, antifreeze 1-5 parts, thickener 0.1-2 parts, defoamer 0.1-0.8 parts, solvent 0-10 parts, stabilizer 1-5 parts, and deionized water to make up the balance.

[0053] The specific production steps of the suspension are as follows: using glass beads, wet pulverizing with a sand mill until D90 (the particle size of 90% of the particles) < 10 μm can produce the suspension preparation of the composition of the present invention.

[0054] Application of a pesticide composition containing flufenoxuron in the control of phytophagous mites;

[0055] Furthermore, the phytophagous mites mentioned are spider mites, galbidae, and / or eupodidae mites;

[0056] Furthermore, the phytophagous mites mentioned are spider mites;

[0057] Furthermore, the spider mites mentioned are: truncated spider mite, carmine spider mite, citrus spider mite, and two-spotted spider mite;

[0058] Furthermore, the pesticide composition and / or its formulation are applied at an effective dose to the mites that need to be controlled or the medium in which they grow.

[0059] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0060] (1) The compound pesticide of the present invention has a significant synergistic effect in prevention and control;

[0061] (2) It is friendly to crops, non-target organisms and the environment, increases the rapid effect of pesticides on pests, delays the development of pesticide resistance in pests and prolongs the duration of pesticide effect;

[0062] (3) The compound pesticide of the present invention is composed of two agents with different mechanisms of action, and there is no cross-resistance, which is beneficial to delaying the development of pesticide resistance in mites. Detailed Implementation

[0063] To make the technical solution, objectives and advantages of the present invention clearer, the present invention is described with reference to the following specific embodiments. However, the present invention can be implemented in various forms and should not be limited to the embodiments described herein.

[0064] Indoor toxicity testing

[0065] Test insect source: Two-spotted spider mite (raised at the R&D center);

[0066] Test reagents: 98% spirodiclofen technical grade, 95% spirodiclofen technical grade;

[0067] Test material preparation: Select female adult mites that are kept indoors and have the same physiological condition. Cut double-sided tape into 2cm lengths and attach them to one end of a slide. Then select healthy mites and stick their backs onto the double-sided tape. Each slide contains 30 mites. Place them in a container lined with a damp sponge, cover the container, and place it at (25±1)℃. After 2 hours, examine the slide under a microscope, remove any dead or injured individuals, and replenish the slide to contain 30 mites.

[0068] Reagent preparation: The technical grade drug was prepared into a stock solution using acetone. The stock solution was then diluted with a 0.1% Tween-80 aqueous solution to prepare test reagents in different proportions. The specific proportions and concentration gradients are as follows:

[0069] Table 1 Concentration gradients of single and compound agents of flufenoxuron, spirodiclofen, and spirodiclofen diester for various treatments

[0070]

[0071]

[0072] Drug treatment: Immerse the glass slide in the drug solution and gently shake for 5 seconds, then remove it, absorb excess drug solution with absorbent paper, place it in a white porcelain dish lined with a damp sponge, cover with a transparent plastic film, and keep it at (25±1)℃ for observation. Each treatment was repeated 4 times, and a blank control without drug treatment was set up.

[0073] Experimental investigation: The mortality rate of the test insects was checked 48 hours after treatment. The total number of insects and the number of dead insects were recorded, and the mortality rate was calculated.

[0074]

[0075] In the formula:

[0076] P – Mortality rate, expressed as a percentage (%);

[0077] K represents the number of dead insects, in heads;

[0078] N represents the total number of insects treated, in units of heads.

[0079]

[0080] In the formula:

[0081] P1 – Corrected mortality rate, in percentage (%);

[0082] P t —The mortality rate is expressed as a percentage (%).

[0083] P0 – Mortality rate in the blank control group, expressed as a percentage (%).

[0084] If the control mortality rate is <5%, no correction is needed; if the control mortality rate is between 5% and 20%, correction should be performed according to the above formula; if the control mortality rate is >20%, the experiment needs to be repeated.

[0085] The LC ratio of each drug was determined by linear regression analysis between the probability value of mortality and the logarithm of the series concentrations. 50 The co-toxicity coefficient (CTC) of the mixture was calculated using the Sun Yunpei method to evaluate the activity of the test agent against the test insects; the specific calculation formula is as follows:

[0086]

[0087] In the formula:

[0088] ATI – Actual Measured Toxicity Index of Mixtures;

[0089] S – LC50 of standard acaricides 50 The unit is milligrams per liter (mg / L);

[0090] M – LC of the mixture 50 The unit is milligrams per liter (mg / L).

[0091] TTI = TI A *P A +TI B *P B

[0092] In the formula:

[0093] TTI – Theoretical Toxicity Index of Mixtures;

[0094] TI A —A. Toxicity index of drug A;

[0095] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0096] TI B —Toxicity index of drug B;

[0097] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0098]

[0099] In the formula:

[0100] CTC – Cotoxicity Coefficient;

[0101] ATI – Actual Measured Toxicity Index of Mixtures;

[0102] TTI – Theoretical Toxicity Index of Mixtures.

[0103] According to the criteria for classifying combined effects: a co-toxicity coefficient (CTC) ≥ 120 indicates an synergistic effect, a co-toxicity coefficient (CTC) ≤ 80 indicates an antagonistic effect, and 80 < CTC < 120 indicates an additive effect.

[0104] Experimental results:

[0105] Combined toxicity assay of flufenoxuron and spirodiclofen against adult female Tetranychus two-spotted spider mites at different ratios: Table 2 shows the results of flufenoxuron against adult female Tetranychus two-spotted spider mites at different ratios. 50 The value was 4.504 mg / L, and the LC50 value of spirodiclofen against Tetranychus two-spotted mites was... 50 The value was 7.313 mg / L.

[0106] Flufenoxam and spirotetramat exhibit synergistic effects against the two-spotted spider mite in a ratio range of 1:28–30:1. The highest co-toxicity coefficient (198.202) is observed when the ratio of flufenoxam to spirotetramat is 2:3. 50 The value was 2.953 mg / L.

[0107] Table 2. Results of indoor activity assays of the combination of flufenoxuron and spirotetramat against adult female Tetranychus biloba.

[0108]

[0109]

[0110] Combined toxicity assay of different ratios of flufenoxuron and spirodimethyl against adult female Tetranychus two-spotted mites: Table 3 shows the results of spirodimethyl against the LC50 of Tetranychus two-spotted mites. 50 The value was 15.873 mg / L.

[0111] Flufenoxam and spirodiclofen showed a synergistic effect on the control of Tetranychus taeniorhizoma in the range of 1:28 to 28:1. The highest co-toxicity coefficient (219.229) was observed when the ratio of flufenoxam to spirodiclofen was 1:2. 50 The value was 3.932 mg / L.

[0112] Table 3. Results of indoor activity assays of flufenoxuron and spirodimethyl ester combination on adult female Tetranychus biloba.

[0113]

[0114]

[0115] Formulation preparation example

[0116] Preparation Example 1

[0117] 5% Flufenoxam·Spirodiclofen EC (2+3)

[0118] Formula composition: 2% flufenoxuron, 3% spirodiclofen, 12% benzyl dimethylphenol polyoxyethyl ether, 6.5% sodium dodecyl sulfate, 14% fatty alcohol polyoxyethylene ether, 5% soybean oil, and methyl oleate to make up the balance;

[0119] Preparation method: First, add the active ingredient to the solvent and dissolve it completely. Then add the emulsifier and synergist and stir evenly to form a uniform and transparent oily liquid. Fill the container to prepare the emulsifiable concentrate of the composition of the present invention.

[0120] Preparation Example 2

[0121] 15% Flufenoxam·Spirodiclofen Suspension Concentrate (5+10)

[0122] Formula composition: 5% flufenoxuron, 10% spirodiclofen, 3% alkyl naphthalene sulfonate formaldehyde condensate, 0.5% sodium lignosulfonate, 3.5% polyether, 2% sodium dodecyl sulfate, 0.5% silicone defoamer, 0.2% xanthan gum, 1% magnesium aluminum silicate, 4% ethylene glycol, 2% glycerin, 0.5% sodium benzoate, deionized water to 100%;

[0123] Preparation method: Add the active ingredient to the wetting and dispersing agent and defoamer, and wet-mill with glass beads until D is achieved. 90 (90% of the particles have a particle size) <10μm to obtain a pulverized slurry. Thickener, antifreeze, and preservative are added to the pulverized slurry and mixed evenly. Deionized water is added to make up to 100%, and the mixture is sheared at high speed to obtain a suspension.

[0124] Preparation Example 3

[0125] 40% Flufenoxam·Spirodiclofen Water Dispersible Granules (20+20)

[0126] Formula composition: 20% flufenoxuron, 20% spirodiclofen, 8% lignin sulfonate, 2% α-olefin sulfonate, 2% ammonium carbonate, 20% kaolin, bentonite to 100%;

[0127] Preparation method: First, mix evenly, then pulverize to below 15μm using an air jet mill, mix evenly with water, granulate using a rotary granulator, dry at 60℃ until the moisture content is ≤1%, and sieve using 20-mesh and 60-mesh test sieves, discarding the large particles at the top and the dust filtered at the bottom to obtain water-dispersible granules.

[0128] Preparation Example 4

[0129] 6% Flufenoxam·Spiromedimethyl Emulsifiable Concentrate (2+4)

[0130] Formula composition: 2% flufenoxuron, 4% spirodimethyl ester, 13% propylene carbonate, 5.5% sodium dodecylbenzenesulfonate, 10% fatty alcohol polyoxyethylene ether, 4% peanut oil, and methyl oleate to make up the balance;

[0131] Preparation method: First, add the active ingredient to the solvent and dissolve it completely. Then add the emulsifier and synergist and stir evenly to form a uniform and transparent oily liquid. Fill the container to prepare the emulsifiable concentrate of the composition of the present invention.

[0132] Preparation Example 5

[0133] 24% Flufenoxam·Spiromedimethyl Suspension Concentrate (5+19)

[0134] Formula composition: 5% flufenoxuron, 19% spirodimethyl diester, 3% alkylnaphthalene sulfonate formaldehyde condensate, 5% sodium lignosulfonate, 1% EO-PO block copolymer, 2% sodium dodecyl sulfate, 0.5% silicone defoamer, 0.2% xanthan gum, 1% magnesium aluminum silicate, 3% ethylene glycol, 2% glycerin, 0.5% sodium benzoate, deionized water to 100%;

[0135] Preparation method: Add the active ingredient to the wetting and dispersing agent and defoamer, and wet-mill with glass beads until D is achieved. 90 (90% of the particles have a particle size) <10μm to obtain a pulverized slurry. Thickener, antifreeze, and preservative are added to the pulverized slurry and mixed evenly. Deionized water is added to make up to 100%, and the mixture is sheared at high speed to obtain a suspension.

[0136] Preparation Example 6

[0137] 40% Flufenoxam·Spiromedimethyl wettable powder (15+25)

[0138] Formula composition: 15% flufenoxuron, 25% spirodimethyl ester, 15% sodium lignosulfonate, 3% sodium dodecyl sulfate, 6% bentonite, and kaolin to 100%;

[0139] Preparation method: First, pre-crush and mix evenly, then pulverize with an air jet mill until the fineness meets the requirement of at least 98 wt% passing through a 45 μm test sieve to obtain a wettable powder.

[0140] Field Examples

[0141] Field Example 1: Field Control of Strawberry Two-Spotted Spider Mite

[0142] Test crop: Strawberry (Sweet Treasure);

[0143] Test subject: Two-spotted spider mite;

[0144] Experimental Design: The experiment included two treatments: 5% flufenoxuron·spirodiclofen emulsifiable concentrate (2+3) and 15% flufenoxuron·spirodiclofen suspension concentrate (5+10). Control treatments included 20% flufenoxuron suspension concentrate and 240 g / L spirodiclofen suspension concentrate. A water control was also included. A total of 7 treatments were administered, with 4 replicates and 28 plots, each plot measuring 25 m². 2 The randomized block arrangement was used, with each block space having two rows of strawberries between it.

[0145] Table 4. Test reagents and dosages

[0146]

[0147]

[0148] Experimental site and conditions: The experiment was conducted at a strawberry base in Feixian County, Linyi City, Shandong Province. The soil fertility of the experimental site is high, the cultivation and management conditions are good, and it is planted year-round.

[0149] No watering was carried out during the 2021 trial. The day of application was cloudy with a high of 28°C, a low of 15°C, a relative humidity of 52%, and a northeasterly wind of level 3. The weather was mostly cloudy during the trial period.

[0150] No watering was carried out during the 2022 trial. The day of application was sunny with a high of 27°C, a low of 15°C, a relative humidity of 55%, and a southeast wind of level 1. The weather was sunny during the trial.

[0151] Application method, time, and frequency: Use a backpack sprayer (3JWB16A type) for manual spraying, evenly spraying both sides of the leaves. Spray once on the mornings of May 10, 2021, and April 23, 2022.

[0152] Survey method: Five sampling points were taken in each community, with one plant fixed at each point and five leaves with mites fixed at each plant to investigate the number of mites.

[0153] Survey time and frequency: The insect population was surveyed before pesticide application, and then surveyed again on days 1, 7, and 14 after pesticide application, for a total of 4 surveys.

[0154] Methods for calculating drug efficacy:

[0155]

[0156]

[0157] During the experiment, strawberry growth was observed to be good in all treatment plots, and no phytotoxicity was observed in any treatment.

[0158] Results of experiments on the control of strawberry two-spotted spider mite with various treatments:

[0159] As shown in Table 5, the combination of flufenoxuron and spirodiclofen has a good control effect on two-spotted spider mites on strawberries. After 7 days of treatment with active ingredients of 40 and 80 mg / kg, the control effect reached more than 80%.

[0160] When using 5% flufenoxuron-spirotetramat EC (2+3) and 15% flufenoxuron-spirotetramat SC (5+10) for pest control, the active ingredient is 80 mg / kg. One day after application, the control efficacy is over 80%, demonstrating good rapid-acting properties. Seven days after application, the control efficacy is over 94%, with the efficacy continuing to increase. Fourteen days after application, the control efficacy continued to increase. Both 5% flufenoxuron·spirotetramat EC (2+3) and 15% flufenoxuron·spirotetramat SC (5+10), with an active ingredient concentration of 40 mg / kg, achieved control efficacies of over 85%. At an active ingredient concentration of 80 mg / kg, the control efficacies were 90.14% and 91.28%, respectively. The efficacy of 5% flufenoxuron·spirotetramat EC (2+3) and 15% flufenoxuron·spirotetramat SC (5+10) could last up to 14 days, indicating that the combination of flufenoxuron and spirotetramat has a good residual effect in controlling strawberry two-spotted spider mites.

[0161] Table 5. The efficacy of different treatments in controlling strawberry two-spotted spider mite (2021)

[0162]

[0163] Note: The efficacy (%) in the table is the average of each replicate, with a difference at the 0.01% level. The same applies to Table 6 below.

[0164] Table 6 shows that the combination of flufenoxuron and spirodiclofen has a good control effect on two-spotted spider mites on strawberries. After 7 days of treatment with active ingredients of 40 and 80 mg / kg, the control efficacy reached over 80%. When using 5% flufenoxuron·spirodiclofen EC (2+3) and 15% flufenoxuron·spirodiclofen SC (5+10), with an active ingredient of 80 mg / kg, the control efficacy was over 80% one day after application, demonstrating good rapid action. Seven days after application, the control efficacy was over 95%, with the efficacy continuing to increase. Fourteen days after application, the control efficacy continued to increase. The control efficacy of 5% flufenoxuron·spirotetramat EC (2+3) and 15% flufenoxuron·spirotetramat SC (5+10), with an active ingredient concentration of 40 mg / kg, both reached over 93%. At an active ingredient concentration of 80 mg / kg, the control efficacy was 100%. The efficacy of 5% flufenoxuron·spirotetramat EC (2+3) and 15% flufenoxuron·spirotetramat SC (5+10) could last up to 14 days, indicating that the combination of flufenoxuron and spirotetramat has a good residual effect in controlling strawberry two-spotted spider mites.

[0165] Compared with Table 5, the results of the survey on different days after application and the control efficacy of different pesticide concentrations against two-spotted spider mites were similar to the results of the 2021 experiment, indicating that the pesticide has good stability in controlling strawberry two-spotted spider mites.

[0166] Table 6. The efficacy of different treatments in controlling strawberry two-spotted spider mites (2022)

[0167]

[0168] Field Example 2: Field Control of Apple Two-Spotted Spider Mite

[0169] Test crop: Apple (Red Fuji), row spacing 3m × 3m;

[0170] Test subject: Two-spotted spider mite;

[0171] Experimental Design: The experiment included 6% flufenoxuron:spirodimethyl emulsifiable concentrate (2+4) and 40% flufenoxuron:spirodimethyl wettable powder (15+25). Control treatments included 20% flufenoxuron suspension concentrate and 24% spirodimethyl suspension concentrate. A water control was also included. There were a total of 5 treatments, with 4 replicates and 20 plots. Each plot consisted of 2 trees, arranged in a randomized block design with a row of trees between each plot.

[0172] Table 7. Test reagents and dosages

[0173]

[0174] Experimental site: Apple orchard in Liangzhuang Town, Daiyue District, Tai'an City, Shandong Province. The fruit trees in the experimental area are growing in a relatively uniform manner. The two-spotted spider mite has been more prevalent in recent years. The orchard is located in a plain with clay loam soil.

[0175] The experimental site has high soil fertility, good cultivation and management conditions, and is planted year-round.

[0176] No watering was carried out during the 2022 trial period. The pesticide was applied on June 7, 2022. The day of application was sunny with a high of 29°C, a low of 18°C, a relative humidity of 63%, and a southeast wind of level 2. The weather during the trial period was mostly cloudy turning sunny.

[0177] Application method, time, and frequency: Use a motorized sprayer (WL-ABSC type) or manual spraying to evenly spray the entire tree. The amount of pesticide applied should be enough to evenly coat the leaves with a few drops running down. Apply once.

[0178] Survey method: For each tree, five leaf clusters with intact leaves were randomly selected from five directions (east, south, west, north, and center) and tagged. The number of live mites on all leaves was counted. Two experimental trees in each plot were surveyed. Surveys were conducted once before application and again at 2, 10, and 15 days after application.

[0179] Method for calculating drug efficacy: Drug efficacy is calculated using the following formula:

[0180]

[0181]

[0182] During the experiment, the apple trees in each experimental plot grew well, and no pesticide damage was observed in any of the treatments.

[0183] As shown in Table 8, the combination of flufenoxuron and spirodimethyl showed good rapid efficacy in controlling two-spotted spider mites on apples. The control efficacies of 6% flufenoxuron·spirodimethyl emulsifiable concentrate (2+4) and 40% flufenoxuron·spirodimethyl wettable powder (15+25) were 87.5% and 86.7%, respectively. At the 0.01 level, through difference analysis, the combination of flufenoxuron and spirodimethyl was significantly higher than the control single-agent formulations of 20% flufenoxuron suspension and 24% spirodimethyl suspension.

[0184] Table 8. Control efficacy of each treatment against apple two-spotted spider mite 2 days after application.

[0185]

[0186] Note: The efficacy (%) in the table is the average of each replicate, with a difference at the 0.01% level. The same applies to Tables 9 and 10 below.

[0187] As shown in Table 9, the control efficacy of the mixture of flufenoxuron and spirodimethyl on two-spotted spider mites on apples improved over time. Ten days after application, the control efficacies of 6% flufenoxuron·spirodimethyl emulsifiable concentrate (2+4) and 40% flufenoxuron·spirodimethyl wettable powder (15+25) were 91.1% and 90.6%, respectively. At the 0.01 level, the difference analysis showed that the mixture of flufenoxuron and spirodimethyl was significantly higher than the control single-agent formulations of 20% flufenoxuron suspension and 24% spirodimethyl suspension.

[0188] Table 9. Control efficacy of each treatment against apple two-spotted spider mite 10 days after application.

[0189]

[0190] As shown in Table 10, the combination of flufenoxuron and spirodimethyl showed very good sustained efficacy against two-spotted spider mites on apples. The control efficacy of 6% flufenoxuron·spirodimethyl emulsifiable concentrate (2+4) and 40% flufenoxuron·spirodimethyl wettable powder (15+25) was 95.0% and 96.3%, respectively. At the 0.01 level, the difference analysis showed that the combination of flufenoxuron and spirodimethyl was significantly higher than the control single agent 20% flufenoxuron suspension and 24% spirodimethyl suspension.

[0191] Table 10 shows the control efficacy of each treatment against apple two-spotted spider mite 15 days after application.

[0192]

[0193]

[0194] Through indoor toxicity testing and field trials on strawberries and apples, the acaricidal composition of the present invention, formulated with either flufenoxuron or spirodiclofen or spirodiclofen diester, showed good control efficacy against phytophagous mites. The acaricidal composition or formulation obtained by the present invention exhibits significant efficacy, superior to single agents in delaying the development of resistance and prolonging the duration of action. Furthermore, no phytotoxicity was observed in the experiments with the formulated agents, indicating that the improved synergistic effect of the acaricidal composition or formulation reduces production and usage costs while ensuring crop safety.

[0195] The exemplary embodiments have been chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various exemplary embodiments of the invention, as well as various alternatives and modifications. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A pesticidal composition comprising a fluorinated acaricide thioether, characterized by: The pesticide composition comprises active ingredient A and active ingredient B, the active ingredient A is fluorine mite sulfide, the active ingredient B is selected from any one of spirodiclofen, spirodiclofen, the mass ratio of fluorine mite sulfide and spirodiclofen is 1:28-30:1, the mass ratio of fluorine mite sulfide and spirodiclofen is 1:28-28:

1.

2. The pesticidal composition according to claim 1, characterized in that: The mass ratio of fluorine mite sulfide and spirodiclofen is 1:14-20:1; the mass ratio of fluorine mite sulfide and spirodiclofen is 1:28-14:

1.

3. The pesticidal composition according to claim 2, characterized in that: The mass ratio of fluorine mite sulfide and spirodiclofen is 1:14, 1:8, 1:6, 2:3, 5:2, 8:1, 14:1, 20:1; the mass ratio of fluorine mite sulfide and spirodiclofen is 1:28, 1:14, 1:8, 2:7, 1:2, 7:2, 14:

1.

4. The pesticidal composition according to claim 1, characterized in that: The total weight of the pesticide composition is 100wt%, the content of active ingredient A and active ingredient B in the pesticide composition is 1-95wt%.

5. The pesticidal composition according to claim 4, characterized in that: The total content of fluorine mite sulfide and spirodiclofen in the pesticide composition is 5-50wt%; the total content of fluorine mite sulfide and spirodiclofen in the pesticide composition is 5-45wt%.

6. The pesticidal composition according to claim 1, characterized in that: The pesticide composition comprises active ingredient A and active ingredient B, the active ingredient A is fluorine mite sulfide, the active ingredient B is selected from any one of spirodiclofen, spirodiclofen, the mass ratio of fluorine mite sulfide and spirodiclofen is 1:28-30:1, the mass ratio of fluorine mite sulfide and spirodiclofen is 1:28-28:

1.

7. The pesticidal composition according to claim 6, characterized in that: The pesticide composition is prepared into an agricultural permissible preparation form, and the preparation form is selected from wettable powder, water dispersible granule, emulsifiable concentrate, water emulsion, microemulsion or suspension concentrate.

8. Use of a pesticidal composition according to any one of claims 1 to 7 for the control of phytophagous mites, characterized in that: The phytophagous mites are Tetranychus cinnabarinus, Tetranychus urticae, Tetranychus truncatus.

9. Use according to claim 8, characterized in that: The pesticide composition is applied to the medium where the control of the mites or the growth of the mites is needed in an effective dose.

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