A pesticide composition and its application

Abstract

The present invention belongs to the field of pesticide technology and relates to a pesticide composition; the active ingredients of the pesticide composition include active ingredient A and active ingredient B; active ingredient A is a compound of formula (I), and active ingredient B is selected from either etoxazole or diafenthiuron. The pesticide composition or its formulation of the present invention can enhance efficacy, expand the spectrum of acaricides, reduce the population of harmful mites, reduce usage costs, reduce dosage, extend the duration of efficacy, and delay the development of pesticide resistance in harmful mites.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticide compounding, and in particular to a pesticide composition and application thereof. Background Art

[0002] Mite pests are also widespread and rampant in fruit trees and vegetables. Their adaptability and high reproductive rates make them prone to developing pesticide resistance, making their control challenging. The most common mite species in my country is the spider mite (Tetranychus cinnabarinus). With its widespread distribution and varied diet, it can infect hundreds of plant species and has become a significant pest of garden flowers and trees. It primarily damages leaves, stems, and flowers, significantly impacting the ornamental value of flowers and trees. Spider mites primarily target leaves, sucking chlorophyll granules and cellular sap, inhibiting photosynthesis, causing water loss, and reducing nutrient accumulation, resulting in dense white spots on the leaf surface. In severe cases, they can cause premature leaf and fruit drop, impacting the yield and quality of vegetables and fruit trees.

[0003] The chemical name of the compound of formula (I) is (4'-chloro-6-fluoro-4-methyl-[1,1'-biphenyl]-3-yl)(2,2,2-trifluoroethyl) sulfide, and the chemical structure is as follows:

[0004]

[0005] Etoxazole belongs to the diphenyloxazoline acaricide class, CAS number: 153233-91-1; it is a contact acaricide whose mechanism of action is to inhibit the normal molting process of mites and has ovicidal activity. Therefore, it can effectively control the entire juvenile stage of mites (eggs, larvae and nymphs) and also has an infertility effect on female adult mites.

[0006] Diafenthiuron is a new thiourea insecticide and acaricide, CAS number: 80060-09-9. It primarily acts as a contact and stomach poison against pests, with its effectiveness increasing with increasing temperature. It also has moderate ovicidal activity and can control Lepidoptera pests, such as the diamondback moth, and Homoptera pests, such as leafhoppers and spider mites, on a variety of crops and ornamental plants.

[0007] Spider mites damage leaf tissue structure, reducing net photosynthetic rate, transpiration rate, intercellular carbon dioxide concentration, and stomatal conductance. They also suck leaf cell sap, causing numerous white spots and reducing chlorophyll content. The applicant surprisingly discovered through indoor toxicity experiments and field efficacy trials that the combination of the compound of formula (I) with etoxazole or diafenthiuron has a significant synergistic effect on the control of phytophagous spider mites. Furthermore, the pesticide composition and use of the compound of formula (I) with etoxazole or diafenthiuron have not been reported to date. Summary of the Invention

[0008] Based on the above situation, the purpose of the present invention is to provide a pesticide composition, which is mainly used to control phytophagous mites. The pesticide composition or its preparation can enhance the efficacy, reduce the dosage, and at the same time prolong the lasting effect and delay the development of drug resistance.

[0009] In order to achieve the above object, the present invention provides the following technical solution: a pesticide composition comprising an active ingredient A and an active ingredient B, wherein the active ingredient A is a compound of formula (I):

[0010] Active ingredient B is either etoxazole or diafenthiuron;

[0011] Furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1:45 to 36:1;

[0012] Furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1:45, 1:36, 1:32, 1:30, 1:28, 1:24, 1:16, 1:12, 1:10, 1:6, 1:5, 2:5, 1:1, 2:1, 9:4, 5:2, 10:1, 14:1, 15:1, 20:1, 24:1, 28:1, 30:1, and 36:1;

[0013] Furthermore, the mass ratio of the compound of formula (I) to etoxazole is 1:36 to 30:1;

[0014] Furthermore, the mass ratio of the compound of formula (I) to etoxazole is 1:32, 1:30, 1:28, 1:24, 1:16, 1:12, 1:10, 1:6, 1:5, 2:5, 1:1, 2:1, 9:4, 5:2, 10:1, 14:1, 15:1, 20:1, 24:1, 28:1, and 30:1;

[0015] Furthermore, the mass ratio of the compound of formula (I) to etoxazole is 1:24 to 20:1;

[0016] Furthermore, the mass ratio of the compound of formula (I) to etoxazole is 1:24, 1:16, 1:12, 1:10, 1:6, 1:5, 2:5, 1:1, 2:1, 9:4, 5:2, 10:1, 14:1, 15:1, and 20:1;

[0017] Furthermore, the mass ratio of the compound of formula (I) to diafenthiuron is 1:28 to 28:1;

[0018] Furthermore, the mass ratio of the compound of formula (I) to diafenthiuron is 1:28, 1:24, 1:14, 1:10, 1:5, 2:5, 1:1, 5:2, 7:2, 14:1, 15:1, 21:1, and 28:1;

[0019] Furthermore, the mass ratio of the compound of formula (I) to diafenthiuron is 1:28 to 21:1;

[0020] Furthermore, the mass ratio of the compound of formula (I) to diafenthiuron is 1:28, 1:24, 1:14, 1:10, 1:5, 2:5, 1:1, 5:2, 7:2, 14:1, 15:1, and 21:1;

[0021] Furthermore, based on the total weight of the pesticide composition being 100 wt%, the sum of the contents of the active ingredient A and the active ingredient B in the pesticide composition is 0.5 to 95 wt%;

[0022] Furthermore, based on the total weight of the pesticide composition being 100 wt%, the sum of the content of the active ingredient A and the active ingredient B in the pesticide composition is 1 to 80 wt%;

[0023] Furthermore, based on the total mass of the pesticide composition being 100 wt%, the sum of the contents of the compound of formula (I) and etoxazole in the pesticide composition is 2 to 50 wt%;

[0024] Furthermore, based on the total mass of the pesticide composition as 100wt%, the sum of the contents of the compound of formula (I) and etoxazole in the pesticide composition is 5wt%, 15wt%, 20wt%, 25wt%, 30wt%, 40wt%, and 50wt%;

[0025] Furthermore, based on the total mass of the pesticide composition being 100 wt%, the sum of the contents of the compound (I) and diafenthiuron in the pesticide composition is 2 to 60 wt%;

[0026] Furthermore, based on the total mass of the pesticide composition as 100 wt%, the sum of the contents of the compound (I) and diafenthiuron in the pesticide composition is 5 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, and 60 wt%;

[0027] Furthermore, the pesticide composition further comprises, in addition to the active ingredient, agriculturally acceptable auxiliary ingredients, wherein the auxiliary ingredients are selected from one or more of a wetting agent, a dispersant, an emulsifier, a thickener, a disintegrant, an antifreeze agent, a defoaming agent, a solvent, a preservative, a stabilizer, a synergist or a carrier;

[0028] The wetting agent is selected from one or more of alkylbenzene sulfonate, alkylnaphthalene sulfonate, lignin sulfonate, sodium lauryl sulfate, sodium dioctyl sulfosuccinate, alpha olefin sulfonate, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, ethylene glycol polyoxyethylene polyoxypropylene ether, fatty alcohol ethoxylate, isomeric alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether sodium sulfate, silkworm feces, soapberry powder, soapberry powder, SOPA, detergent, emulsifier 2000 series and wetting penetrant F; and / or

[0029] The dispersant is selected from one or more of lignin sulfonate, alkylnaphthalene sulfonate formaldehyde condensate, naphthalene sulfonate, tristyrylphenol ethoxylate phosphate, block polyether phosphate salt, arylphenol polyoxyethylene ether sulfate salt, fatty alcohol ethoxylate, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether methyl ether condensate sulfate, fatty amine polyoxyethylene ether, glycerol fatty acid ester polyoxyethylene ether, polycarboxylates, polyacrylic acids, phosphates, EO-PO block copolymers and EO-PO graft copolymers; and / or

[0030] The emulsifier is selected from one or more of calcium dodecylbenzenesulfonate, dodecylbenzenesulfonamide, alkylphenol formaldehyde resin polyoxyethylene ether, phenylethylphenol polyoxyethylene polyoxypropylene ether, benzylphenol polyoxyethylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styrylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylphenol ether phosphate and styrylphenol polyoxyethylene ether phosphate; and / or

[0031] The thickener is selected from one or more of xanthan gum, organobentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose and white carbon black; and / or

[0032] Disintegrants: The disintegrants are 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

[0033] The antifreeze agent is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons and inorganic salts; and / or

[0034] Defoaming agent selected from C 10 -C 20 Saturated fatty acid compounds, silicone oil, silicone compounds, C8-C 10 One or more of fatty alcohols; and / or

[0035] The solvent is selected from one or more of benzene, toluene, xylene, trimethylbenzene, durene, methanol, ethanol, isopropyl alcohol, n-butanol, isooctyl alcohol, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyldecylamide, N-methylpyrrolidone, cyclohexanone, propylene carbonate, alkylene carbonate, diesel, solvent oil, vegetable oil, vegetable oil derivatives and water; and / or

[0036] The preservative is selected from one or more of propionic acid, sodium propionic acid, sorbic acid, sodium sorbic acid, potassium sorbic acid, benzoic acid, sodium benzoic acid, sodium p-hydroxybenzoic acid, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, isothiazolinones, benzimidazoles, iodopropargyls, pyridinethiones, kasone and 1,2-benzisothiazolin-3-one; and / or

[0037] The stabilizer is selected from one or more of 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, white carbon black, talc, montmorillonite and starch; and / or

[0038] Synergists are selected from synergistic phosphorus, synergistic ether, synergistic amine; and / or

[0039] The carrier is selected from one or more of ammonium salts, ground natural minerals, ground artificial minerals, silicates, resins, waxes, solid fertilizers, water, organic solvents, mineral oils, vegetable oils and vegetable oil derivatives.

[0040] The present invention optimizes the content of active ingredients and adjuvants in the acaricidal composition to achieve a better balance between toxicity and residue, thereby enhancing efficacy, reducing dosage and lowering costs.

[0041] Furthermore, the pesticide composition can be prepared into an agriculturally acceptable formulation, wherein the formulation is selected from a solid formulation and / or a liquid formulation;

[0042] Furthermore, the solid preparation includes powders, granules, pellets, tablets, strips, wettable powders, oil-dispersible powders, emulsion powders, water-dispersible granules, emulsion granules, water-dispersible tablets, soluble powders, soluble tablets or soluble granules;

[0043] Furthermore, the liquid preparation includes a soluble solution, a soluble gel, an oil, a film-spreading oil, an emulsifiable concentrate, a latex, a dispersible liquid, an ointment, an aqueous emulsion, an oil emulsion, a microemulsion, a fat, a suspension, a microcapsule suspension, an oil suspension, a dispersible oil suspension, a suspoemulsion, a microcapsule suspension-suspension, a microcapsule suspension-water emulsion or a microcapsule suspension-suspoemulsion;

[0044] Furthermore, the solid preparation is selected from wettable powders and water-dispersible granules; the liquid preparation is selected from soluble concentrates, emulsifiable concentrates, aqueous emulsions, suspensions, suspoemulsions, microemulsions, and dispersible oil suspensions;

[0045] Furthermore, when the pesticide composition is a wettable powder, the components by mass are: 1 to 40 parts of active ingredient A, 1 to 40 parts of active ingredient B, 3 to 10 parts of dispersant, 1 to 5 parts of wetting agent, and the balance is made up of fillers; the wettable powder preparation method is to pre-crush the active ingredients and other adjuvants and mix them evenly, and then grind them with a jet mill to a fineness that meets the requirement of at least 98wt% passing a 45μm test sieve to obtain a wettable powder product.

[0046] When the pesticide composition is a water-dispersible granule, the components by weight are: 1-40 parts of active ingredient A, 1-40 parts of active ingredient B, 3-20 parts of dispersant, 1-10 parts of wetting agent, 1-5 parts of disintegrant, and the balance is made up of fillers. The water-dispersible granules are prepared by adding the active ingredients to a carrier according to the formula ratio, adding a surfactant and other functional additives thereto, mixing, air flow pulverizing, adding 10-25% of water, and then kneading, granulating, drying, and sieving to obtain the water-dispersible granule product.

[0047] When the pesticide composition is an emulsifiable concentrate preparation, the components by mass are: 1-40 parts of active ingredient A, 1-40 parts of active ingredient B, 5-30 parts of emulsifier, 0-5 parts of synergist, and the balance is made up of solvent. The emulsifiable concentrate preparation method comprises the following steps: adding the active ingredients into a solvent according to the formula proportions in the embodiment, adding a surfactant and other functional additives thereto, and stirring and mixing the mixture in a stirring mixing kettle to obtain an emulsifiable concentrate product.

[0048] When the pesticide composition is an aqueous emulsion, the components by mass are: 1-40 parts of active ingredient A, 1-40 parts of active ingredient B, 3-30 parts of emulsifier, 5-50 parts of solvent, 2-15 parts of stabilizer, 1-5 parts of antifreeze, 0.1-8 parts of defoamer, 0.2-2 parts of thickener, and deionized water making up the balance. The aqueous emulsion is prepared by dissolving the active ingredient in a solvent according to the formula ratio in the embodiment, adding an emulsifier to dissolve the active ingredient into a uniform oil phase, mixing deionized water and antifreeze together to form a uniform aqueous phase; adding the aqueous phase to the oil phase, stirring evenly, adding the defoamer, and subjecting to high-speed shearing to form a well-dispersed aqueous emulsion product.

[0049] When the pesticide composition is a suspension concentrate, the components by weight are as follows: 1-40 parts of active ingredient A, 1-40 parts of active ingredient B, 1-15 parts of wetting and dispersing agent, 1-5 parts of antifreeze agent, 0.1-2 parts of thickener, 0.1-0.8 parts of defoamer, 0-10 parts of solvent, 0-5 parts of stabilizer, and the balance is made up of deionized water. The suspension concentrate is prepared by placing the active ingredient, surfactant and other functional additives in a reaction kettle in order according to the formula ratio, adding water to mix uniformly, subjecting the mixture to high-speed shearing, wet sand grinding, and finally filtering the mixture to obtain the suspension concentrate product.

[0050] When the pesticide composition is a suspoemulsion, the components are as follows by weight: active ingredient A 1-40 parts, active ingredient B 1-40 parts, emulsifier 1-10 parts, dispersant 1-10 parts, antifreeze 1-5 parts, thickener 0.1-2 parts, defoamer 0.1-0.8 parts, solvent 1-40 parts, stabilizer 0-5 parts, and deionized water makes up the balance; the preparation method of the suspoemulsion is as follows: according to the formula ratio, the active ingredient A is completely dissolved in the solvent, the emulsifier is added to form an oil phase; the active ingredient B is mixed with the wetting dispersant, antifreeze, defoamer, deionized water, etc. by wet sand grinding until D 90 The suspension mother liquid is prepared by adding the oil phase into the suspension mother liquid and stirring evenly, and then adding the thickener and stirring and shearing evenly to prepare the suspoemulsion preparation of the composition of the present invention.

[0051] When the pesticide composition is a microemulsion, the components by weight are: 1-40 parts of active ingredient A, 1-40 parts of active ingredient B, 8-30 parts of emulsifier, 5-15 parts of solvent, 2-15 parts of stabilizer, 1-5 parts of antifreeze, 0.1-8 parts of defoamer, and deionized water makes up the balance. The preparation method of the microemulsion comprises the following steps: dissolving the active ingredient in a solvent according to the formula proportions in the embodiment, adding an emulsifier to dissolve the active ingredient into a uniform oil phase, mixing deionized water and antifreeze together to form a uniform water phase; adding the water phase into the oil phase, or vice versa, and stirring evenly to form a microemulsion product.

[0052] The present invention also discloses the use of the above-mentioned pesticide composition for controlling harmful mites;

[0053] Furthermore, the harmful mites are of the family Tetranychidae, the family Acaridae and / or the family Eupodidae;

[0054] Furthermore, the harmful mites are of the family Tetranychus;

[0055] Furthermore, the pest mites of the family Tetranychus are: Panonychus citri McGregor, Eotetranychus kankitus (Ehara), Phyllocoptes oleivora, Tetranychus cinnabarinus (Boisduval), and Tetranychus urticae Koch.

[0056] Furthermore, the pesticide composition and / or its preparation is applied at an effective dose to the harmful mites to be controlled or the medium in which they grow.

[0057] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0058] (1) The compound pesticide of the present invention has a significant synergistic effect on the prevention and control effect;

[0059] (2) The compound pesticide of the present invention is a compound of two pesticides with different action mechanisms, has no cross-resistance, and is beneficial for delaying the development of pesticide resistance in pest mites.

[0060] (3) It is environmentally friendly, safe and efficient, and its promotion and application will have huge economic and social benefits. DETAILED DESCRIPTION

[0061] In order to make the technical solutions, objectives and advantages of the present invention more clearly understood, 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.

[0062] Indoor toxicity assay

[0063] Insect sources for testing: Tetranychus cinnabarinus and Panonychus citri;

[0064] Test agents: 97% etoxazole technical, 97% diafenthiuron technical, 96% compound of formula (I);

[0065] Material Preparation: Select nymphs of mites raised indoors and in consistent physiological condition. Cut double-sided tape into 2 cm lengths and attach to one end of a glass slide. Select healthy mites and attach their backs to the tape, 30 per slide. Place 30 mites in a container lined with a damp sponge, cover, and store at (25 ± 1)°C. After 2 hours, examine under a microscope, remove dead and injured individuals, and replenish the remaining 30 mites per slide.

[0066] Preparation of drugs: The original drug was prepared into a mother solution with acetone, and the mother solution was prepared into test drugs in different proportions with 0.1% Tween-80 aqueous solution.

[0067] Chemical treatment: Immerse the glass slide in the drug solution and shake it gently for 5 seconds, then take it out and absorb the excess drug solution with absorbent paper. Place it on a white porcelain plate with a wet sponge, cover it with a plastic film with good light transmittance, and place it at (25±1)℃ for observation.

[0068] Experimental repetition: Each treatment was repeated 4 times, and a treatment without drug was set as a blank control.

[0069] Test investigation: 48 hours after treatment, check the mortality of test insects, record the total number of mites and the number of dead mites, and calculate the mortality rate:

[0070]

[0071] Where:

[0072] P——mortality rate, in percentage (%);

[0073] K——indicates the number of dead mites, the unit is head;

[0074] N——represents the total number of mites treated, in heads.

[0075]

[0076] Where:

[0077] P1——adjusted mortality rate, in percentage (%);

[0078] P t ——Treatment mortality rate, expressed in percentage (%);

[0079] P0 - blank control mortality rate, in percentage (%).

[0080] If the control mortality rate is less than 5%, no correction is required; if the control mortality rate is between 5% and 20%, correction should be made according to the above formula; if the control mortality rate is greater than 20%, the test needs to be repeated.

[0081] The LC value of each drug was calculated by linear regression analysis between the probability value of mortality and the logarithmic value of the serial concentration (DPS data processing system). 50 The co-toxicity coefficient (CTC) of the mixture was calculated using the Sun Yunpei method to evaluate the activity of the test agents against the test insects. The specific calculation formula is as follows:

[0082]

[0083] Where:

[0084] ATI - measured toxicity index of mixture;

[0085] S——LC of standard acaricide 50 , the unit is milligrams per liter (mg / L);

[0086] M——LC of the mixture 50 , the unit is milligrams per liter (mg / L).

[0087] TTI=TI A *P A +TI B *P B

[0088] Where:

[0089] TTI – Theoretical Toxicity Index of Mixtures;

[0090] TI A ——Agent toxicity index;

[0091] P A ——The percentage of agent A in the mixture, in percentage (%);

[0092] TI B ——Toxicity index of agent B;

[0093] P B ——The percentage of agent B in the mixture, in percentage (%).

[0094]

[0095] Where:

[0096] CTC – Co-toxicity coefficient;

[0097] ATI - measured toxicity index of mixture;

[0098] TTI - Theoretical Toxicity Index of Mixture.

[0099] According to the classification standard of joint effects: a co-toxicity coefficient (CTC) ≥ 120 indicates a synergistic effect, a co-toxicity coefficient (CTC) ≤ 80 indicates an antagonistic effect, and a co-toxicity coefficient (CTC) 80 < 120 indicates an additive effect.

[0100] Test results:

[0101] The combined toxicity test of different ratios of the compound of formula (I) and etoxazole on Tetranychus cinnabarinus (nymphs) was as follows: The results in Table 1 show that the compound of formula (I) has a strong effect on Tetranychus cinnabarinus LC 50 The value is 1.094 mg / L, and the LC value of etoxazole for Tetranychus cinnabarinus is 1.094 mg / L. 50 The value is 4.594 mg / L.

[0102] The compound of formula (I) and etoxazole have a synergistic effect on the control of Tetranychus cinnabarinus in the range of 1:36 to 30:1. The mass ratio of the compound of formula (I) to etoxazole is 1:24 to 20:1, the co-toxicity coefficient is greater than 130, and the synergistic effect is significant. When the compound of formula (I) and etoxazole = 2:1, the co-toxicity coefficient is the highest, which is 196.044, LC 50 The value is 0.748mg / L.

[0103] Table 1 Indoor activity test results of compound of formula (I) combined with etoxazole against Tetranychus cinnabarinus (nymphs)

[0104]

[0105]

[0106] The combined toxicity test of different ratios of the compound of formula (I) and etoxazole on Panonychus citri (nymph) was as follows: The results in Table 2 show that the compound of formula (I) has a strong effect on Panonychus citri LC. 50 The value is 2.523mg / L, and the LC value of etoxazole against citrus mites is 2.523mg / L. 50 The value is 39.806 mg / L. The compound of formula (I) and etoxazole have a synergistic effect on the prevention of citrus mites in the range of 1:32 to 24:1. The mass ratio of the compound of formula (I) to etoxazole is 1:32 to 14:1, the co-toxicity coefficient is greater than 140, and the synergistic effect is significant. When the compound of formula (I) and etoxazole = 9:4, the co-toxicity coefficient is the highest, which is 221.711, LC 50 The value is 1.598mg / L.

[0107] Table 2 Indoor activity test results of compound of formula (I) combined with etoxazole against Panonychus citri (nymph)

[0108]

[0109]

[0110] The combined toxicity test of different ratios of the compound of formula (I) and diafenthiuron against Tetranychus cinnabarinus (nymph): The results in Table 3 show that diafenthiuron has a strong effect on Tetranychus cinnabarinus LC 50 The value is 6.466 mg / L. The compound of formula (I) and diafenthiuron have a synergistic effect on the control of Tetranychus cinnabarinus in the range of 1:28 to 28:1. When the compound of formula (I) and diafenthiuron = 2:5, the co-toxicity coefficient is the highest, which is 248.308. LC 50 The value is 1.083mg / L.

[0111] Table 3 Indoor activity test results of compound of formula (I) combined with diafenthiuron against Tetranychus cinnabarinus (nymphs)

[0112]

[0113] The combined toxicity test of different ratios of the compound of formula (I) and diafenthiuron against Panonychus citri (nymph): The results in Table 4 show that diafenthiuron has a strong effect on the LC of Tetranychus cinnabarinus. 50 The value is 16.925 mg / L. The compound of formula (I) and diafenthiuron have a synergistic effect on the control of citrus mites in the range of 1:28 to 21:1. When the compound of formula (I) and diafenthiuron = 7:2, the co-toxicity coefficient is the highest, which is 212.625. LC 50 The value is 1.463 mg / L.

[0114] Table 4 Indoor activity test results of compound of formula (I) combined with diafenthiuron against Panonychus citri (nymph)

[0115]

[0116] Preparation Example

[0117] Preparation Example 1

[0118] 9% Formula (Ⅰ) compound·Ethioxazole emulsifiable concentrate (6+3)

[0119] Formula composition: 6% of compound of formula (I), 3% of etoxazole, 12% of castor oil polyoxyethylene ether, 3% of calcium dodecylbenzenesulfonate, 15% of fatty alcohol polyoxyethylene ether, 6% of corn oil, 30% of cyclohexanone, and methyl oleate to make up the balance;

[0120] Preparation method: first add the active ingredient into the solvent and dissolve it completely, then add the emulsifier and stir evenly to form a uniform and transparent oily liquid, and then fill it to prepare the emulsifiable concentrate preparation of the composition of the present invention.

[0121] Preparation Example 2

[0122] 7% compound of formula (I)·difenthuron emulsifiable concentrate (2+5)

[0123] Formula composition: 2% of compound of formula (I), 5% of diafenthiuron, 15% of propylene carbonate, 3% of calcium dodecylbenzenesulfonate, 12% of styrylphenol polyoxyethylene ether, 15% of cyclohexanone, and the balance made up of solvent oil;

[0124] Preparation method: Same as Preparation Example 1.

[0125] Preparation Example 3

[0126] 22% Formula (I) compound·Ethioxazole suspension (15+7)

[0127] Formula composition: 15% compound of formula (I), 7% etoxazole, 5% polycarboxylate, 3% EO-PO block copolymer, 0.5% naphthalenesulfonate, 0.5% organosilicon defoamer, 0.2% xanthan gum, 1% magnesium aluminum silicate, 4% ethylene glycol, 0.5% sodium benzoate, and deionized water to 100%;

[0128] Preparation method: Add a wetting and dispersing agent and a defoamer to a measured amount of deionized water and mix thoroughly. Then, add the active ingredient and mix thoroughly. Wet-grind the mixture using a sand mill with zirconium beads until the D90 (90% particle size) is less than 5 μm to obtain a pulverized slurry. Add a thickener, antifreeze agent, and preservative to the pulverized slurry and mix thoroughly. Add deionized water to 100% and high-speed shear to obtain a suspension concentrate.

[0129] Preparation Example 4

[0130] 25% compound of formula (I)·difenthionyl suspension (7+18)

[0131] Formula composition: 7% of compound of formula (I), 18% of diafenthiuron, 3% of alkylnaphthalene sulfonate formaldehyde condensate, 3% of polycarboxylate, 2% of EO-PO block copolymer, 2% of fatty alcohol polyoxyethylene ether phosphate, 1% of dioctyl sodium sulfosuccinate, 0.5% of organosilicon defoamer, 0.2% of xanthan gum, 1% of magnesium aluminum silicate, 5% of ethylene glycol, 0.15% of methyl parahydroxybenzoate, and deionized water to 100%;

[0132] Preparation method: Same as Preparation Example 3.

[0133] Preparation Example 5

[0134] 45% Formula (I) compound·Ethioxazole water dispersible granules (25+20)

[0135] Formula composition: 25% of compound of formula (I), 20% of etoxazole, 8% of lignin sulfonate, 2% of α-olefin sulfonate, 8% of alkylnaphthalene sulfonate formaldehyde condensate, 2% of ammonium sulfate, 2.5% of sodium lauryl sulfate, 20% of kaolin, 15% of white carbon black, and bentonite added to 100%;

[0136] Preparation method: First mix evenly, then grind to less than 15μm by air flow mill, mix evenly with water, granulate by rotary granulator, dry at 60℃ to a moisture content of ≤3%, select 20 mesh and 60 mesh test sieves for sieving, discard the large particles on the top and the dust filtered at the bottom to prepare water dispersible granules.

[0137] Preparation Example 6

[0138] 40% formula (Ⅰ) compound·Ethioxazole wettable powder (25+15)

[0139] Formula composition: 25% of compound of formula (I), 15% of etoxazole, 1% of alkylphenol polyoxyethylene ether methyl ether condensate sulfate, 15% of lignin sulfonate sodium salt, 2.5% of sodium lauryl sulfate, 10% of white carbon black, 8% of bentonite, and kaolin added to 100%;

[0140] Preparation method: pre-crush and mix evenly, then grind by air flow mill to a fineness that satisfies the requirement that at least 98 wt% passes through a 45 μm test sieve to obtain a wettable powder.

[0141] Preparation Example 7

[0142] 42% compound of formula (I)·difenthion wettable powder (18+24)

[0143] Formula composition: 18% of the compound of formula (I), 24% of diafenthiuron, 15% of sodium lignin sulfonate, 2.5% of sodium lauryl sulfate, 4% of naphthalene sulfonate, 6% of bentonite, 5% of white carbon black, and kaolin added to 100%;

[0144] Preparation method: pre-crush and mix evenly, then grind by air flow mill to a fineness that satisfies the requirement that at least 98 wt% passes through a 45 μm test sieve to obtain a wettable powder.

[0145] Field Example 1

[0146] Control of potato spider mites in the field

[0147] Test crops: potato (Zhongshu No. 2);

[0148] Test subjects: Tetranychus cinnabarinus;

[0149] Experimental design: 22% Formula (I) compound·etoxazole suspension (15+7), 25% Formula (I) compound·diafenthiuron suspension (7+18), 110 g / L etoxazole suspension, 50% diafenthiuron suspension, 20% Formula (I) compound suspension as control treatments, and a separate water control. A total of 6 treatments, 4 replicates, 24 plots, each plot area 15 m 2 , using random block arrangement, with one row of potatoes between each plot.

[0150] Table 5 Test agents and dosage

[0151]

[0152] Experimental location and conditions: The experiment was set up in the vegetable plantation of Haidu College in Laiyang City, Yantai. The soil fertility of the experimental site is high and the cultivation and management conditions are good.

[0153] The pesticide was applied on July 7, 2022. It was cloudy on the day of application, with a maximum temperature of 30°C, a minimum temperature of 21°C, a relative humidity of 52%, and a northwest wind of level 2. It was sunny during the test.

[0154] Application method, time and frequency: Use a backpack sprayer for manual spraying, spray evenly on the front and back of the leaves, with a water consumption of 45L per mu.

[0155] Survey method: Sampling was carried out at 5 points in each plot, 2 plants were fixed at each point, and 4 leaves with mites were fixed on each plant to investigate the insect population.

[0156] Survey time and frequency: Survey the insect population base before spraying, and survey once 3 days and 10 days after spraying, for a total of 3 surveys.

[0157] Calculation method of drug efficacy: The drug efficacy is calculated according to the following formula:

[0158]

[0159]

[0160] Survey on the number of tubers per plant: During the potato maturity period, 20 potato plants were selected from the middle of each plot, and the number of tubers per plant was counted after digging.

[0161] During the experiment, potatoes in each treatment plot grew well and no phytotoxicity was observed in any treatment.

[0162] The test results of each treatment agent on potato two-spotted spider mite:

[0163] As shown in Table 6, the compound of formula (I) mixed with etoxazole and diafenthiuron has a good control effect on potato spider mites. At the dosage of 40 and 50 mg / kg of active ingredient, the control effect reached more than 85% three days after treatment, showing good rapidity.

[0164] Ten days after application, the control effect of the compound of formula (I) mixed with etoxazole and diafenthiuron was above 95%, the efficacy continued to increase, and the effect lasted for a long time.

[0165] Table 6 The control effect of different pesticides on potato spider mites

[0166]

[0167] Note: The protective efficacy (%) in the table is the average value of each replicate, and the difference is at the 0.05% level.

[0168] Potatoes primarily rely on photosynthesis in their aboveground stems and leaves to produce dry matter for underground growth. Tetranychus cinnabarinus pierces and sucks moisture from potato stems and leaves, causing loss of green color and whitening in the affected areas. The leaf surface develops dense, pale spots and curls and turns yellow. Tetranychus cinnabarinus has a certain impact on potato yield. Treatment with different pesticides can reduce the number of mites and mitigate their damage to potatoes. As shown in Table 7, a mixture of the compound of formula (I) with etoxazole and diafenthiuron has a yield-promoting effect on potatoes.

[0169] Table 7 Effects of different pesticide treatments on the number of tubers per potato plant

[0170]

[0171] Note: The number of tubers per plant in the table is the average of each replicate, and the difference is at the 0.05% level.

[0172] Indoor toxicity assays and field tests on potatoes have shown that the acaricidal composition described herein, comprising a compound of formula (I) and either etoxazole or diafenthiuron, exhibits excellent control efficacy against phytophagous mites, particularly Tetranychus cinnabarinus. The resulting pesticide composition or formulation exhibits significant control efficacy, outperforming single agents in delaying the development of resistance and prolonging the effectiveness. Furthermore, no crop damage was observed with the combined formulation, demonstrating that the improved synergistic acaricidal efficacy of the resulting pesticide composition or formulation can reduce production and use costs, while maintaining crop safety.

[0173] Field Example 2

[0174] Field trials on the efficacy of pesticides against citrus red spider mites

[0175] Test crops: Citrus (Wogan);

[0176] Test subjects: Citrus spider mite;

[0177] Experimental Design: 22% Formula (I) compound + etoxazole suspension concentrate (15+7), 25% Formula (I) compound + diafenthiuron suspension concentrate (7+18), 110 g / L etoxazole suspension concentrate, 50% diafenthiuron suspension concentrate, and 20% Formula (I) compound suspension concentrate as controls. A water control was also used. Six treatments, three replicates, and 18 plots were used. Each plot contained two trees, using a randomized block arrangement, with each plot separated by a row of fruit trees.

[0178] Table 8 Test agents and dosage

[0179]

[0180] The test site was a citrus orchard in Shuangqiao Town, Wuming District, Nanning City, Guangxi Zhuang Autonomous Region. Citrus trees in the test area grew uniformly, but citrus spider mite infestations have been severe in recent years. The soil fertility of the test site was high, and cultivation and management conditions were favorable, with year-round planting.

[0181] The pesticide was applied on October 12, 2022. It was sunny on the day of application, with the highest temperature of 29°C, the lowest temperature of 17°C, and the northeast wind at level 2. It was sunny during the test.

[0182] Application method, timing, and frequency: Use a motorized sprayer (WL-ABSC) and manually apply spray evenly throughout the tree. Based on field conditions and farmer water usage habits, use 1.8 L of water per citrus tree. Apply enough to ensure even coverage of the leaves with slight dripping. Apply once.

[0183] Survey Method: Randomly select a point on each citrus plant in the east, west, south, north, and center directions. Mark a branch at each point and record the total number of live citrus red spider mites on leaves on the marked branches (starting with the top leaf, with at least five leaves). Focus on adult and nymph mites (observe with a magnifying glass). Surveys should be conducted before, 3 days after, and 10 days after treatment.

[0184] Calculation method of drug efficacy: The drug efficacy is calculated according to the following formula:

[0185]

[0186]

[0187] During the experiment, the citrus trees in each experimental plot grew well and no phytotoxicity was observed in any treatment.

[0188] Field trial results show:

[0189] As can be seen from Table 9, the mixture of the compound of formula (I) with etoxazole and diafenthiuron has a good control effect on citrus red spider mites, showing good fast-acting property. Three days after application, the control efficacy of 22% formula (I) compound·etoxazole suspension concentrate (15+7) and 25% formula (I) compound·diafenthiuron suspension concentrate (7+18) against citrus red spider mites were 94.57% and 95.42%, respectively. At the 0.05 level, through difference analysis, the mixed preparation of the compound of formula (I) with etoxazole and diafenthiuron was significantly higher than the control single-dose 110 g / L etoxazole suspension concentrate, 50% diafenthiuron suspension concentrate, and 20% formula (I) compound suspension concentrate.

[0190] Table 9 Control effect of each treatment on citrus red spider mites 3 days after application

[0191]

[0192] Note: The protective effect (%) in the table is the average value of each replicate, with the difference at the 0.05% level. The same applies to the following tables.

[0193] As can be seen from Table 10, as time goes by, the control effect of the compound of formula (I) mixed with etoxazole and diafenthiuron on citrus red spider mites increases and the duration of effect is long. Ten days after application, the control effects of 22% compound of formula (I)·etoxazole suspension concentrate (15+7) and 25% compound of formula (I)·diafenthiuron suspension concentrate (7+18) were 98.37% and 98.16%, respectively. At the 0.05 level, through difference analysis, at the 0.05 level, the mixed preparation of the compound of formula (I) with etoxazole and diafenthiuron was significantly higher than the control single-dose 110 g / L etoxazole suspension concentrate, 50% diafenthiuron suspension concentrate, and 20% compound of formula (I) suspension concentrate.

[0194] Table 10 Control effect of each treatment on citrus red spider mites 10 days after application

[0195]

[0196] Note: The protective effect (%) in the table is the average value of each replicate, with the difference at the 0.05% level. The same applies to the following tables.

[0197] Indoor toxicity assays and field tests on citrus fruits have shown that the acaricidal composition of the present invention, formulated with either the compound of formula (I) and either etoxazole or diafenthiuron, exhibits excellent control efficacy against phytophagous mites. The resulting acaricidal composition or formulation exhibits significant control efficacy, outperforming single agents in delaying the development of resistance and prolonging the effectiveness. Furthermore, no crop damage was observed with the combined formulation, demonstrating that the enhanced synergistic acaricidal efficacy of the resulting acaricidal composition or formulation can reduce production and use costs, while maintaining crop safety.

[0198] The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various exemplary embodiments of the present invention and various options and modifications. Such modifications or improvements made without departing from the spirit of the present invention are all within the scope of protection claimed in the present invention.

Claims

1. A pesticide composition, characterized in that: The pesticide composition comprises active ingredient A and active ingredient B, wherein active ingredient A is a compound of formula (I): (I), active ingredient B is etoxazole, and the mass ratio of the compound of formula (I) to etoxazole is 1:36~30:

1.

2. The pesticide composition according to claim 1, characterized in that The mass ratio of the compound of formula (I) to etoxazole is 1:24~20:

1.

3. The pesticide composition according to claim 2, characterized in that The mass ratio of the compound of formula (I) to etoxazole is 1:24, 1:16, 1:12, 1:10, 1:6, 1:5, 2:5, 1:1, 2:1, 9:4, 5:2, 10:1, 14:1, 15:1, and 20:

1.

4. The pesticide composition according to claim 1, characterized in that Based on the total weight of the pesticide composition as 100 wt%, the sum of the contents of the active ingredient A and the active ingredient B in the pesticide composition is 1 to 80 wt%.

5. The pesticide composition according to claim 4, characterized in that Based on the total mass of the pesticide composition as 100wt%, the sum of the contents of the compound of formula (I) and etoxazole in the pesticide composition is 2-50wt%.

6. The pesticide composition according to claim 1, characterized in that In addition to the active ingredients, 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, defoaming agents, solvents, preservatives, stabilizers, synergists or carriers.

7. The pesticide composition according to claim 6, characterized in that The pesticide composition can be prepared into an agriculturally acceptable formulation, and the formulation is selected from a solid formulation and / or a liquid formulation.

8. The pesticide composition according to claim 7, characterized in that The solid preparation is selected from wettable powders and water-dispersible granules; the liquid preparation is selected from soluble solutions, emulsifiable concentrates, aqueous emulsions, suspensions, suspoemulsions, microemulsions, and dispersible oil suspensions.

9. Use of the pesticide composition according to any one of claims 1 to 8 for controlling pest mites, characterized in that: The harmful mites are herbivorous mites; the herbivorous mites are Panonychus citri and Tetranychus cinnabarinus.

10. The use according to claim 9, characterized in that The pesticide composition and / or its preparation is applied at an effective dose to the pest mites to be controlled or the medium where they grow.

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