Pesticide composition and application thereof
By using (4'-chloro-6-fluoro-4-methyl-[1,1'-biphenyl]-3-yl)(2,2,2-trifluoroethyl)sulfide ether in pesticide compositions Combination with ethiazole or terethurea, optimized dosage form, solved the problem of poor control of cinnabar spider mite in the existing technology, achieved efficient and lasting effect on the control of venomous mites, and reduced drug resistance and production costs. .
Patent Information
- Application Number
- CN202310665060.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-06-07
- Publication Date
- 2024-12-10
- Estimated Expiration
- 2043-06-07
AI Technical Summary
The prior art is difficult to effectively prevent and control mite pests, especially cinnabar spider mites, which are seriously harmful to fruit trees, vegetables, etc. and are prone to drug resistance. The existing pesticide compositions have limited control effects on them.
Provided is a pesticide composition comprising active ingredient A being (4'-chloro-6-fluoro-4-methyl-[1,1'-biphenyl]-3-yl)(2,2,2-trifluoro Ethyl)sulfide and active ingredient B are ethiazole or butyl ether urea, with a mass ratio of 1:45 to 36:1. By optimizing the active ingredients and additive content in the acaric composition, it is prepared into different dosage forms to enhance the Effectiveness, reduce dosage and delay resistance.
It significantly enhances the prevention and control effect of plant-based mites, extends the durability of drug efficacy, and reduces the risk of drug resistance. In the experiment, no drug damage to crops was found, reducing production costs.
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Abstract
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 very widespread and rampant in the harm of fruit trees, vegetables, etc., and they have the characteristics of strong adaptability and high reproduction rate, and are prone to drug resistance, which makes it difficult to prevent and control. The main species of harmful mites in my country is the cinnabar spider mite, which is widely distributed and has a mixed diet. It can harm hundreds of plants and has become one of the important pests that harm garden flowers and trees. It mainly damages the leaves, stems, flowers and other parts of the plant, which has a certain impact on the ornamental value of flowers and trees. Spider mites mainly harm leaves, sucking their chlorophyll particles and cell fluid, inhibiting photosynthesis, causing water loss, reducing nutrient accumulation, and causing dense white spots on the leaf surface. In severe cases, it can also cause leaves and fruits to fall prematurely, affecting 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] Ethoxazole belongs to the diphenyloxazoline acaricide, CAS number: 153233-91-1; it is a contact acaricide, its mechanism of action is to inhibit the normal molting process of mites and has ovicidal activity, so it can effectively control the entire young stage of mites (eggs, young mites and nymphs), and also has a sterilizing effect on female adult mites.
[0006] Difenacarb is a new type of thiourea insecticide and acaricide, CAS No. 80060-09-9, which has two main effects on pests: contact killing and stomach poisoning, and the effect is better as the temperature increases. It has a certain ovicidal activity and can control lepidopteran pests, such as diamondback moth, and homopteran pests, such as leafhoppers and spider mites, on a variety of crops and ornamental plants.
[0007] Spider mites destroy the tissue structure of leaves, reduce the net photosynthetic rate, transpiration rate, intercellular carbon dioxide concentration, stomatal conductance of leaves, and also suck leaf cell sap, causing many white spots on leaves and reducing chlorophyll content. The applicant surprisingly found through indoor toxicity experiments and field efficacy tests 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, and the pesticide composition of the compound of formula (I) with etoxazole or diafenthiuron and its application have not been reported yet. 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 for controlling 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, the pesticide composition comprises 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 any one of 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] Further, 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, 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, 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, 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, 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, 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 contents 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%, 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 100wt%, the sum of the contents of the compound (I) and diafenthiuron in the pesticide composition is 5wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 60wt%;
[0027] Furthermore, the pesticide composition includes agriculturally acceptable auxiliary ingredients in addition to the active ingredients, and the auxiliary ingredients are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, stabilizers, synergists or carriers;
[0028] The wetting agent is selected from one or more of alkylbenzene sulfonate, alkylnaphthalene sulfonate, lignin sulfonate, sodium dodecyl sulfate, sodium dioctyl succinate sulfonate, 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, saponin 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 acid, phosphates, EO-PO block copolymers and EO-PO graft copolymers; and / or
[0030] The emulsifier is selected from one or more of calcium dodecylbenzene sulfonate, dodecylbenzene sulfonate amine, 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] The defoamer is 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, isopropanol, 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] The synergist is 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 invention optimizes the content of active ingredients and auxiliary agents in the acaricide composition to achieve a better balance between toxicity and residue, thereby enhancing the efficacy, reducing the dosage and lowering the cost.
[0041] Furthermore, the pesticide composition can be prepared into a formulation form permitted in agriculture, and the formulation form 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] Further, 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 solutions, emulsifiable concentrates, aqueous emulsions, suspensions, suspoemulsions, microemulsions, and dispersible oil suspensions;
[0045] Furthermore, when the pesticide composition is a wettable powder, the mass proportions of the components are: 1-40 parts of active ingredient A, 1-40 parts of active ingredient B, 3-10 parts of dispersant, 1-5 parts of wetting agent, and the balance is made up of fillers; the preparation method of the wettable powder is to pre-crush the active ingredient and other auxiliary agents and mix them evenly, and then grind them by a jet mill to a fineness that meets the requirement that at least 98wt% passes through a 45μm test sieve to obtain a wettable powder product.
[0046] When the pesticide composition is a water-dispersible granule, the mass proportions of the components 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 preparation method of the water-dispersible granule is to add the active ingredient into a carrier according to the formula ratio, add a surfactant and other functional additives thereto, mix, add 10-25% of water after air flow pulverization, and then knead, granulate, dry and sieve to obtain a water-dispersible granule product.
[0047] When the pesticide composition is an emulsifiable concentrate preparation, the mass proportions of the components 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 solvent makes up the balance; the emulsifiable concentrate preparation method is to add the active ingredients into the solvent according to the formula ratio of the embodiment, and add surfactants and other functional additives thereto, and stir and mix them evenly in a stirring mixing kettle to obtain an emulsifiable concentrate product.
[0048] When the pesticide composition is an aqueous emulsion, the mass fractions of the components 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 makes up the balance; the preparation method of the aqueous emulsion is to dissolve the active ingredient in the solvent according to the formula ratio of the embodiment, add the emulsifier to dissolve it into a uniform oil phase, mix the deionized water and the antifreeze together to form a uniform water phase; add the water phase into the oil phase, stir evenly, add the defoamer, and form a well-dispersed aqueous emulsion product through high-speed shearing.
[0049] When the pesticide composition is a suspension concentrate, the mass proportions of the components are: 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 preparation method of the suspension concentrate is to place the active ingredient, surfactant and other functional additives in a reaction kettle in sequence according to the formula ratio, add water to mix evenly, and then perform high-speed shearing, wet sand grinding, and finally filter to obtain the suspension concentrate product.
[0050] When the pesticide composition is a suspoemulsion, the mass fractions of the components are: 1-40 parts of active ingredient A, 1-40 parts of active ingredient B, 1-10 parts of emulsifier, 1-10 parts of dispersant, 1-5 parts of antifreeze, 0.1-2 parts of thickener, 0.1-0.8 parts of defoamer, 1-40 parts of solvent, 0-5 parts of stabilizer, and deionized water makes up the balance; the preparation method of the suspoemulsion is to completely dissolve the active ingredient A with the solvent according to the formula ratio, add the emulsifier to form the oil phase; wet-grind the active ingredient B with the wetting dispersant, antifreeze, defoamer, deionized water, etc. to D 90 The suspension mother liquid is prepared by mixing 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 mass fractions of the components 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 is to dissolve the active ingredient in the solvent according to the formula ratio of the embodiment, add the emulsifier to dissolve it into a uniform oil phase, mix the deionized water and the antifreeze together to form a uniform water phase; add the water phase into the oil phase, or add the oil phase into the water phase, and stir evenly to form a microemulsion product.
[0052] The present invention also discloses the use of the above-mentioned pesticide composition in preventing and controlling harmful mites;
[0053] Furthermore, the harmful mites are from the family Tetranychidae, the family Acaridae and / or the family Eupodidae;
[0054] Furthermore, the harmful mites are harmful mites 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), 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 to 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 control effect;
[0059] (2) The compound pesticide of the present invention is compounded from two pesticides with different action mechanisms, has no cross-resistance, and is beneficial for delaying the development of pesticide resistance in harmful 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 the following specific embodiments, but the present invention can be implemented in various forms and should not be limited by the embodiments described herein.
[0062] Indoor toxicity assay
[0063] Test insect sources: Tetranychus cinnabarinus and Panonychus citri;
[0064] Test agents: 97% etoxazole technical, 97% diafenthiuron technical, 96% compound of formula (Ⅰ);
[0065] Preparation of test materials: Select nymphs raised indoors and in the same physiological state. Cut double-sided tape into 2 cm long pieces and stick them on one end of the slide. Then select healthy mites and stick their backs on the double-sided tape. Put 30 mites per slide in a container padded with a wet sponge, cover it with a lid, and place it at (25±1)℃. After 2 hours, examine under a microscope, remove dead and injured individuals, and make up 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 chemical solution and shake it gently for 5 seconds, then take it out and absorb the excess chemical solution with absorbent paper. Place it on a white porcelain plate lined with a wet sponge, cover it with a light-transmitting plastic film, 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 death 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 as 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 of each drug was calculated by linear regression analysis between the probability value of mortality and the logarithmic value of the series concentration (DPS data processing system). 50 The Sun Yunpei method was used to calculate the co-toxicity coefficient (CTC) of the mixture to evaluate the activity of the test agent against the test insects; the specific calculation formula is as follows:
[0082]
[0083] Where:
[0084] ATI——Actual 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 ——A: toxicity index of the agent;
[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——Actual Toxicity Index of Mixture;
[0098] TTI - Theoretical Toxicity Index of Mixture.
[0099] According to the classification standard of combined 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 < CTC < 120 indicates an additive effect.
[0100] Test results:
[0101] The combined toxicity test of different ratios of the compound of formula (I) and etoxazole against Tetranychus cinnabarinus (nymphs) is shown in Table 1. 50 The value is 1.094mg / L, and the LC value of etoxazole against Tetranychus cinnabarinus 50 The value is 4.594mg / 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 (nymph)
[0104]
[0105]
[0106] The combined toxicity test of different ratios of the compound of formula (I) and etoxazole against Panonychus citri (nymph) is shown in Table 2. 50 The value is 2.523mg / L, and the LC value of etoxazole against citrus mites is 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) was as follows: The results in Table 3 show that diafenthiuron has a strong toxicity against 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 (nymph)
[0112]
[0113] The combined toxicity test of different ratios of the compound of formula (I) and diafenthiuron against Panonychus citri (nymph) is shown in Table 4. 50 The value is 16.925 mg / L. The compound of formula (I) and diafenthiuron have a synergistic effect on the prevention 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 1.463mg / 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·Ethioprine EC (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 makes up the balance;
[0120] Preparation method: firstly add the active ingredient into the solvent and completely dissolve it, then add the emulsifier and the like 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)·dimethoxyfenuron emulsifiable concentrate (2+5)
[0123] Formula composition: 2% of the 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 is made up of solvent oil;
[0124] Preparation method: Same as Preparation Example 1.
[0125] Preparation Example 3
[0126] 22% Formula (Ⅰ) compound·Ethioprine suspension (15+7)
[0127] Formula composition: 15% of compound of formula (I), 7% of etoxazole, 5% of polycarboxylate, 3% of EO-PO block copolymer, 0.5% of naphthalenesulfonate, 0.5% of organosilicon defoamer, 0.2% of xanthan gum, 1% of magnesium aluminum silicate, 4% of ethylene glycol, 0.5% of sodium benzoate, and deionized water is added to 100%;
[0128] Preparation method: add a wetting dispersant and a defoamer to the measured deionized water and stir evenly, then add the active ingredient and stir evenly, use zirconium beads and a sand mill to wet grind until D90 (90% of the particle size) is less than 5μm to obtain a crushed slurry. Add a thickener, an antifreeze agent, and a preservative to the crushed slurry and mix evenly, add deionized water to 100%, and high-speed shear to obtain a suspension.
[0129] Preparation Example 4
[0130] 25% compound of formula (I)· diafenthiuron suspension (7+18)
[0131] Formula composition: 7% of compound of formula (I), 18% of dimethoate urea, 3% of alkylnaphthalene sulfonate formaldehyde condensate, 3% of polycarboxylate, 2% of EO-PO block copolymer, 2% of fatty alcohol polyoxyethylene ether phosphate, 1% of sodium dioctyl succinate sulfonate, 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 is added to 100%;
[0132] Preparation method: Same as Preparation Example 3.
[0133] Preparation Example 5
[0134] 45% Formula (Ⅰ) compound·Ethioprine 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, and prepare water-dispersible granules.
[0137] Preparation Example 6
[0138] 40% compound of formula (Ⅰ) · etoxazole wettable powder (25+15)
[0139] Formula composition: 25% of the 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 dodecyl 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 98wt% passes through a 45μm test sieve to obtain a wettable powder.
[0141] Preparation Example 7
[0142] 42% compound of formula (I)·Diafenthiuron 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 98wt% passes through a 45μm 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·difenthuron suspension (7+18), 110 g / L etoxazole suspension, 50% difenthuron suspension, 20% formula (Ⅰ) compound suspension as control treatment, and clear water control. A total of 6 treatments, 4 replicates, 24 plots, plot area of 15m 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 was high and the cultivation and management conditions were good.
[0153] The pesticide was applied on July 7, 2022. It was cloudy on the day of application, with the highest temperature of 30℃, the lowest temperature of 21℃, the relative humidity of 52%, and the northwest wind of level 2. It was sunny during the test.
[0154] Application method, time and frequency: Use a backpack sprayer and spray manually, 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 can be seen from Table 6, the compound of formula (I) mixed with etoxazole and diafenthiuron has a good control effect on potato spider mites. The effective ingredient dosage is 40 and 50 mg / kg, and the control effect reaches more than 85% 3 days after treatment, with good quick effect.
[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 had a good lasting effect.
[0165] Table 6 The efficacy of different pesticides in preventing potato spider mites
[0166]
[0167] Note: The protective effect (%) in the table is the average value of each replicate, and the difference is at the 0.05% level.
[0168] Potatoes mainly rely on photosynthesis of the aboveground stems and leaves to produce dry matter for underground growth. Cinnabarin spider mites suck the stems and leaves of potatoes, reducing the moisture content of the affected parts, causing them to lose green color and turn white. The leaf surface shows dense pale spots and curls and turns yellow. Cinnabarin spider mites have a certain impact on potato yield. Using different agents to treat can reduce the number of cinnabarin spider mites and reduce the damage to potatoes by cinnabarin spider mites. As shown in Table 7, the compound of formula (I) mixed with etoxazole and dithiocarb 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] Through indoor toxicity determination and field potato tests, the acaricidal composition of the present invention, which is a compound of the compound of formula (I) and either etoxazole or diafenthiuron, shows good control effect on phytophagous pest mites, especially Tetranychus cinnabarinus. The pesticide composition or its preparation obtained by compounding of the present invention has significant control effect, and is superior to a single agent in delaying the development of drug resistance and prolonging the lasting effect. In addition, no phytotoxicity of the compound agent to crops was found in the test, indicating that when the acaricidal synergistic synergy of the obtained pesticide composition or preparation is improved, the production cost and the use cost can be reduced, and it is safe for crops.
[0173] Field Example 2
[0174] Field test 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 (15+7), 25% formula (Ⅰ) compound·difenuron suspension (7+18), 110 g / L etoxazole suspension, 50% difenuron suspension, 20% formula (Ⅰ) compound suspension as control treatment, and water control. A total of 6 treatments, 3 repetitions, 18 plots, 2 trees per plot, randomized block arrangement, each plot separated by a row of fruit trees.
[0178] Table 8 Test agents and dosage
[0179]
[0180] Test location: Citrus orchard in Shuangqiao Town, Wuming District, Nanning City, Guangxi Province. The growth of citrus trees in the test area is basically the same, and citrus red spider mites have occurred more severely in recent years. The soil fertility of the test site is high, the cultivation and management conditions are good, and it is planted all year round.
[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, time and frequency: Use a motorized sprayer (WL-ABSC model) and manually spray the whole tree evenly. According to the actual field conditions and farmers' water consumption habits, the water consumption per citrus tree is determined to be 1.8L, and the amount of application is determined to be evenly applied to the leaves with a little dripping. Apply once.
[0183] Survey method: Randomly select one point from the east, west, south, north and center of each citrus plant, mark a branch at each point, and record the number of all living citrus red spider mites on the leaves of the marked branches (starting from the top leaf, no less than 5 leaves). Mainly investigate adult mites and nymph mites (can be observed with a magnifying glass). Survey once before and 3d and 10d after the drug.
[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] The results of the field trials showed that:
[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 rapid effectiveness. 3 days after application, the control effects of 22% compound of formula (I)·etoxazole suspension (15+7) and 25% compound of formula (I)·diafenthiuron suspension (7+18) on 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 of 110 g / L etoxazole suspension, 50% diafenthiuron suspension, and 20% suspension of the compound of formula (I).
[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, and the difference is 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) with etoxazole and diafenthiuron on citrus red spider mites increases and the duration of effect is long. 10 days after application, the control effects of 22% compound of formula (I)·etoxazole suspension (15+7) and 25% compound of formula (I)·diafenthiuron suspension (7+18) are 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 is significantly higher than the control single-dose 110 g / L etoxazole suspension, 50% diafenthiuron suspension, and 20% suspension of the compound of formula (I).
[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, and the difference is at the 0.05% level. The same applies to the following tables.
[0197] Through indoor toxicity determination and field tests on citrus, the acaricidal composition of the compound of formula (I) of the present invention and any one of etoxazole and diafenthiuron showed good control effect on phytophagous mites. The acaricidal composition or its preparation obtained by compounding of the present invention has significant control effect, and is superior to a single agent in delaying the development of drug resistance and prolonging the lasting effect. In addition, no phytotoxicity of the compounded agent to crops was found in the test, indicating that when the acaricidal synergistic synergy of the obtained acaricidal composition or preparation is improved, the production cost and use cost can be reduced, and it is safe for crops.
[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 selections and changes. These modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.
Claims
1. A pesticide composition, characterized in that: The pesticide composition comprises an active ingredient A and an active ingredient B, wherein the active ingredient A is a compound of formula (I): The active ingredient B is either etoxazole or diafenthiuron.
2. The pesticide composition according to claim 1, characterized in that The mass ratio of the active ingredient A to the active ingredient B is 1:45 to 36:
1.
3. The pesticide composition according to claim 1, characterized in that The mass ratio of the compound of formula (I) to etoxazole is 1:36 to 30:1, and the mass ratio of the compound of formula (I) to diafenthiuron is 1:28 to 28:
1.
4. The pesticide composition according to any one of claims 1 to 5, characterized in that Based on the total weight of the pesticide composition as 100wt%, the sum of the contents of the active ingredient A and the active ingredient B in the pesticide composition is 0.5 to 95wt%, preferably 1 to 80wt%; Preferably, 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%; Preferably, based on the total mass of the pesticide composition being 100 wt%, the sum of the contents of the compound of formula (I) and diafenthiuron in the pesticide composition is 2 to 60 wt%.
5. 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, defoamers, solvents, preservatives, stabilizers, synergists or carriers.
6. The pesticide composition according to claim 5, characterized in that The pesticide composition can be prepared into a formulation form permitted in agriculture, and the formulation form is selected from a solid formulation and / or a liquid formulation.
7. The pesticide composition according to claim 6, 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.
8. Use of the pesticide composition according to any one of claims 1 to 7 for controlling harmful mites.
9. The use according to claim 8, characterized in that: The harmful mites are herbivorous mites; preferably, the herbivorous mites are Panonychus citri, Tetranychus citri, Tetranychus cinnabarinus, and Tetranychus urticae.
10. The use according to claim 8, characterized in that: The pesticide composition and / or its preparation is applied at an effective dose to the harmful mites to be controlled or the medium where they grow.
Citation Information
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