A pesticide composition and use thereof

Abstract

The application belongs to the technical field of pesticide mite killing, and discloses a pesticide composition and application thereof. The pesticide composition comprises active ingredient A and active ingredient B. The active ingredient A is (4'-chloro-6-fluoro-4-methyl-[1,1'-biphenyl]-3-yl)(2,2,2-trifluoroethyl) sulfide. The active ingredient B is any one of spirodiclofen or bifenazate. The mass ratio of the active ingredient A to the active ingredient B is 1:52-45:1. The pesticide composition has good control effect on citrus leaf mite and two-spotted spider mite, is fast-acting, and has long effective period.

Description

[0001] This invention application is a divisional application of application number CN202310543087.6, filed on May 15, 2023, entitled "A pesticide composition and its application". Technical Field

[0002] This invention belongs to the field of pesticide acaricide technology, and discloses a pesticide composition and its application. Background Technology

[0003] (4'-Chloro-6-fluoro-4-methyl-[1,1'-biphenyl]-3-yl)(2,2,2-trifluoroethyl) sulfide is a biphenyl sulfide acaricide with excellent control effects against common plant mites. Its structural formula is shown below:

[0004] .

[0005] Spirodiclofen is a highly effective and low-toxicity acaricide developed by Bayer. It primarily inhibits fat synthesis in mites, blocking energy metabolism. It is effective at all developmental stages of mites, especially eggs and nymphs, and also has a certain inhibitory effect on the reproduction of adult female mites. Its structural formula is as follows:

[0006] .

[0007] Biphenylhydrazine, chemically known as isopropyl 3-(4-methoxybiphenyl-3-yl)hydrazinocarbamate, is an acaricide that primarily acts on the Qo site of cytochrome b complex III in the electron transport chain. This drug is effective against all developmental stages of spider mites. Its structural formula is as follows:

[0008] .

[0009] Due to the extensive field production methods, farmers use a large amount of insecticides and acaricides, which has led to varying degrees of resistance in field mite populations to common acaricides. Therefore, developing acaricides that have a significant synergistic effect on mites and can reduce the dosage of pesticides used is an important trend in current agricultural development. Summary of the Invention

[0010] To address the problems in the prior art, this invention provides a pesticide composition that exhibits excellent control effects against mites, particularly showing a significant synergistic effect against common crop mites such as the two-spotted spider mite and the citrus parsnipus mite. This composition reduces the dosage of pesticides used, has excellent rapid action, and a long-lasting effect.

[0011] The present invention also provides various formulations of the pesticide composition for the control of two-spotted spider mites and citrus parsnip mites.

[0012] To achieve the above objectives, the present invention adopts the following technical solution: a pesticide composition comprising active ingredient A and active ingredient B, wherein active ingredient A is (4'-chloro-6-fluoro-4-methyl-[1,1'-biphenyl]-3-yl)(2,2,2-trifluoroethyl) sulfide, and active ingredient B is either spirodiclofen or bifenazate.

[0013] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:52 to 45:1;

[0014] Furthermore, the active ingredient B is spirodiclofen, and the mass ratio of active ingredient A to active ingredient B is 1:52~44:1;

[0015] The active ingredient B is biphenylhydrazine ester, and the mass ratio of active ingredient A to active ingredient B is 1:35~40:1.

[0016] Furthermore, the active ingredient B is spirodiclofen, and the mass ratio of active ingredient A to active ingredient B is 1:33~38:1;

[0017] The active ingredient B is biphenylhydrazine ester, and the mass ratio of active ingredient A to active ingredient B is 1:30~40:1.

[0018] Furthermore, based on a total weight of 100 wt%, the total weight of active ingredient A and active ingredient B accounts for 0.1 wt% to 80 wt% of the total weight of the pesticide composition.

[0019] Furthermore, the pesticide composition, in addition to the active ingredient, also includes auxiliary ingredients, which are selected from one or more of the following: wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, stabilizers, synergists, or carriers.

[0020] Further, the wetting agent is selected from one or more of 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

[0021] The dispersant is selected from one or more of the following: lignin sulfonate, alkyl naphthalene sulfonate formaldehyde condensate, naphthalene sulfonate, tristyrylphenol ethoxylate phosphate, 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

[0022] The thickener is selected from one or more of xanthan gum, polyvinyl alcohol, organobentonite, magnesium aluminum silicate, and carboxymethyl cellulose; and / or

[0023] 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

[0024] The emulsifier is selected from one or more of the following: fatty alcohol polyoxyethylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, phenethylphenol polyoxyethylene polyoxypropylene ether, alkylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, alkylbenzene sulfonate, styrene-phenol polyoxyethylene ether, and fatty acid polyoxyethylene ester; and / or

[0025] The defoamer is selected from silicone oil, C 10 ~C 20 Saturated fatty acid compounds, C8-C 10 One or more of fatty alcohols or silicone compounds; and / or

[0026] The preservative is selected from one or more of sorbic acid, sodium sorbate, potassium sorbate, benzoic acid, sodium benzoate, sodium p-hydroxybenzoate, and methyl p-hydroxybenzoate; and / or

[0027] 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, and epoxidized vegetable oil; and / or

[0028] The synergist is selected from synergistic phosphorus, synergistic ether; and / or

[0029] The carrier is selected from one or more of kaolin, bentonite, attapulgite, light calcium carbonate, diatomaceous earth, and precipitated silica; and / or

[0030] The solvent is selected from one or more of benzene, toluene, xylene, methanol, ethanol, isopropanol, n-butanol, diesel oil, N,N-dimethylformamide, cyclohexanone, ethyl acetate, N-methylpyrrolidone, propanol, butanol, ethylene glycol, diethylene glycol, ethylene glycol methyl ether, butyl ether, solvent oil, vegetable oil, vegetable oil derivatives, and deionized water; and / or

[0031] All of the above auxiliary ingredients are commercially available.

[0032] Furthermore, the pesticide composition can be prepared into a formulation that is either a solid formulation or a liquid formulation;

[0033] Furthermore, the liquid formulation is selected from soluble concentrates, soluble gels, oils, spreading oils, emulsions, latexes, dispersible liquids, ointments, water emulsions, oil emulsions, microemulsions, lipid suspensions, microcapsule suspensions, oil suspensions, dispersible oil suspensions, suspension emulsions, microcapsule suspension-suspension, microcapsule suspension-water emulsions, or microcapsule suspension-suspension emulsions; the solid formulation is selected from powders, granules, balls, tablets, strips, wettable powders, oil-dispersible powders, emulsion powders, water-dispersible granules, emulsion granules, water-dispersible tablets, soluble powders, soluble tablets, or soluble granules.

[0034] Furthermore, the solid formulation is a water-dispersible granule, and the liquid formulation is a suspension, water-emulsion, microemulsion, emulsifiable concentrate, dispersible oil suspension, or suspension emulsion.

[0035] The present invention also discloses the application of the pesticide composition and its formulation as described above for the control of mites.

[0036] Furthermore, the harmful mites are spider mites; the spider mites are *Tetranychus citrus*, *Tetranychus appleensis*, *Tetranychus two-spotted*, or *Tetranychus carmineus*.

[0037] Furthermore, the spider mites mentioned are *Tetranychus citrus* and *Tetranychus two-spotted*.

[0038] The beneficial effects of this invention are as follows:

[0039] 1. The pesticide composition of the present invention has a significant synergistic effect on common plant mites, especially against two-spotted spider mites and citrus parsnipus mites, which can effectively reduce the number of pesticide applications and the amount of single agent used.

[0040] 2. The pesticide composition of the present invention is composed of active ingredients with different mechanisms of action, which effectively slows down the development of pesticide resistance in mites. Detailed Implementation

[0041] To make the technical solution, objectives and advantages of the present invention clearer, the present invention is described in the following specific embodiments. However, the present invention can be implemented in various forms and should not be limited to the embodiments described herein.

[0042] Examples of some related formulation preparations:

[0043]

[0044] Indoor toxicity testing.

[0045] Example 1: Indoor activity ratio screening test.

[0046] Experimental targets: two-spotted spider mite nymphs and citrus paronychia nymphs.

[0047] Test reference: NY / T 1154.13-2008 "Guidelines for Indoor Bioassay Testing of Pesticides - Insecticides - Part 13: Leaf Disc Spraying Method".

[0048] Experimental Methods: Leaves of green beans and citrus trees that had not been treated with any pesticides were selected and perforated to create leaf discs. Two leaf discs were placed face down in humidified petri dishes, and 15 nymphs were transferred to each disc. After the mites stabilized, the spray was applied using a potter's sprayer, increasing the concentration from low to high. Each treatment used 1.5 mL of spray, allowing 1 minute of settling time. Each treatment was repeated four times. The control area was treated with water.

[0049] After treatment, the test mites were transferred to a temperature of (25±1)℃ and a photoperiod of L:D=(16:8)h for rearing and observation. Each treatment was repeated 4 times, and a treatment without the drug (containing all organic solvents and emulsifiers) was set up as a blank control. After 48h of drug treatment, the mortality of nymphs was checked, and the total number of mites and the number of dead mites were recorded.

[0050] According to statistics and analysis:

[0051] Calculate the mortality rate for each treatment based on the survey data. Use the following formula:

[0052] In the formula:

[0053] P — Mortality rate, expressed as a percentage (%);

[0054] K —This indicates the number of dead insects, expressed in heads;

[0055] N — This indicates the total number of insects treated, in units of heads.

[0056] In the formula:

[0057] P 1 —Adjusted mortality rate, in percentages (%);

[0058] P t —The mortality rate is expressed as a percentage (%).

[0059] P 0 — Mortality rate in blank control group, expressed as a percentage (%).

[0060] 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 corrected mortality rate formula; if the control mortality rate is >20%, the trial needs to be repeated.

[0061] The obtained experimental data were analyzed using the DPS statistical analysis system to determine the toxicity regression equation, correlation coefficient, and LC. 50 The value is used to evaluate the activity of the test reagent on the biological sample.

[0062] The co-toxicity coefficient (CTC value) of the mixture is calculated using the following formula:

[0063] In the formula:

[0064] ATI —Measured toxicity index of the mixture;

[0065] S LC of standard acaricides 50 The unit is milligrams per liter (mg / L);

[0066] M LC of the mixture 50 The unit is milligrams per liter (mg / L).

[0067] In the formula:

[0068] TTI —Theoretical toxicity index of the mixture;

[0069] TI A —A. Toxicity index of drug A;

[0070] P A —The percentage content of drug A in the mixture, expressed as a percentage (%).

[0071] TI B —Toxicity index of drug B;

[0072] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0073] In the formula:

[0074] CTC —Cotoxicity coefficient;

[0075] ATI —Measured toxicity index of the mixture;

[0076] TTI —Theoretical toxicity index of mixed preparations.

[0077] Co-toxicity coefficient of compound CTC ≥120 exhibits a synergistic effect; CTC≤80 It exhibits antagonistic effects; 80 < CTC <120 exhibits an additive effect.

[0078] The results of the relevant indoor activity tests are shown in the table below:

[0079] Table 1. Indoor bioactivity test of active ingredient A combined with spirodiclofen on nymphs of Tetranychus bisa.

[0080] Test reagents <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Active ingredient A 3.5397 100.000 / / Spirodiclofen (Active Ingredient B) 9.5504 37.063 / / A:B=1:52 7.3840 47.937 38.251 125.324 A:B=1:45 6.1355 57.692 38.432 150.117 A:B=1:38 5.6599 62.540 38.677 161.698 A:B=1:16 5.0581 69.981 40.766 171.667 A:B=1:8 4.5743 77.382 44.056 175.644 A:B=2:5 3.4673 102.088 55.045 185.462 A:B=6:1 2.3524 150.472 91.009 165.337 A:B=18:1 2.3736 149.128 96.688 154.237 A:B=29:1 2.4530 144.301 97.902 147.393 A:B=35:1 2.5907 136.631 98.252 139.062 A:B=44:1 2.9614 119.528 98.601 121.223

[0081] The indoor activity tests are shown in Table 1. The combination of active ingredient A and spirodiclofen, within a reasonable range, showed a significant synergistic effect against Tetranychus tinctoria. The mass ratio of active ingredient A to spirodiclofen was 1:52~44:1, with a co-toxicity coefficient greater than 120, indicating a synergistic effect.

[0082] Table 2. Indoor bioactivity test of active ingredient A combined with biphenylhydrazine on two-spotted spider mite nymphs.

[0083] Test reagents <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Active ingredient A 3.5397 100.000 / / Biphenylhydrazine (Active Ingredient B) 3.5637 99.327 / / A:B=1:45 3.0115 117.539 99.341 118.319 A:B=1:30 2.7745 127.580 99.348 128.417 A:B=1:15 2.4350 145.368 99.369 146.291 A:B=1:6 2.2714 155.838 99.423 156.743 A:B=1:2 2.0257 174.740 99.551 175.528 A:B=2:1 2.0985 168.678 99.776 169.057 A:B=5:1 2.2303 158.710 99.888 158.888 A:B=10:1 2.4299 145.673 99.939 145.762 A:B=20:1 2.5983 136.231 99.968 136.275 A:B=30:1 2.6980 131.197 99.978 131.226 A:B=40:1 2.8170 125.655 99.984 125.676

[0084] The results of the indoor activity test are shown in Table 2. When active ingredient A is combined with biphenylhydrazine at a mass ratio of 1:30 to 40:1, the co-toxicity coefficient is greater than 120, which shows a synergistic effect on two-spotted spider mites.

[0085] Table 3. Indoor bioactivity assay of active ingredient A combined with spirodiclofen against citrus pseudococcus nymphs.

[0086] Test reagents <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Active ingredient A 2.5649 83.329 / / Spirodiclofen (Active Ingredient B) 2.1373 100.000 / / A:B=1:48 2.0198 105.817 99.660 106.179 A:B=1:33 1.7041 125.421 99.510 126.039 A:B=1:24 1.6099 132.760 99.333 133.651 A:B=1:16 1.5095 141.590 99.019 142.992 A:B=1:8 1.4335 149.097 98.148 151.911 A:B=1:1 1.3119 162.916 91.664 177.731 A:B=6:1 1.4459 147.818 85.710 172.462 A:B=12:1 1.5945 134.042 84.611 158.421 A:B=24:1 1.8213 117.350 83.996 139.710 A:B=38:1 2.1178 100.921 83.756 120.493 A:B=45:1 2.2742 93.980 83.691 112.294

[0087] The results of the indoor activity test are shown in Table 3. The mass ratio of active ingredient A to spirodiclofen was 1:33~38:1, and the co-toxicity coefficient was greater than 120. The combined effect on citrus parchoides showed a synergistic effect.

[0088] Table 4. Indoor bioactivity test of active ingredient A combined with biphenylhydrazine on nymphs of *Pachycarpus citrinum*.

[0089] Test reagents <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Active ingredient A 2.5649 65.355 / / Biphenylhydrazine (Active Ingredient B) 1.6763 100.000 / / A:B=1:35 1.3994 119.787 99.038 120.951 A:B=1:22 1.1722 143.005 98.494 145.192 A:B=1:15 1.0788 155.386 97.835 158.825 A:B=1:7 0.9815 170.790 95.669 178.521 A:B=3:2 1.0343 162.071 79.213 204.601 A:B=7:1 1.3085 128.109 69.686 183.837 A:B=14:1 1.4753 113.624 67.665 167.922 A:B=28:1 1.6942 98.943 66.550 148.675 A:B=40:1 1.9278 86.954 66.200 131.350

[0090] The results of the indoor activity test are shown in Table 4. The mass ratio of active ingredient A to biphenylhydrazine ester was 1:35~40:1, and the co-toxicity coefficient was greater than 120. The combined effect on citrus parchoides showed a synergistic effect.

[0091] Field efficacy verification test.

[0092] Example 2: Field experiment on the control of two-spotted spider mite on loofah.

[0093] This experiment was conducted in accordance with GB / T 17980.17-2000 "Guidelines for Field Efficacy Tests of Pesticides (I) Acaricides for the Control of Spider Mites in Legumes and Vegetables".

[0094] The experiment was conducted in Zhangqiao Village, Shouguang City, Shandong Province, where the soil fertility was moderate to high.

[0095] Experimental crop: loofah.

[0096] Experimental target: Two-spotted spider mite.

[0097] Experimental Design: The experimental plots, control plots, and blank control plots were arranged in a randomized block design. All experimental plots had uniform cultivation conditions, consistent with local scientific agricultural practices. The area of ​​each experimental plot was 30 m². 2 Each treatment was repeated 4 times.

[0098] Application time: Apply the pesticide once on September 20, 2022, using 45 kg of water per mu. Spray once when the mites reach the control threshold (i.e., about 10% of the leaves have 3 to 10 adult nymphs per leaf).

[0099] Experimental survey time: 20 leaves were taken from each plot to count the number of adult mites and nymphs. A baseline survey was conducted before the experiment, and surveys were conducted 3, 7 and 14 days after the application of the pesticide.

[0100] Methods for calculating drug efficacy:

[0101]

[0102] Table 5 Results of field trials for controlling two-spotted spider mites on loofah

[0103]

[0104] The results of field efficacy trials for controlling two-spotted spider mites (Table 5) show that the pesticide composition of the present invention has a good control effect on two-spotted spider mites on loofah, and has good rapid effect and long-lasting effect.

[0105] Example 3: Field trial for controlling citrus spider mites

[0106] Refer to GB / T 17980.11-2000 "Guidelines for Field Efficacy Testing of Pesticides (I) Acaricides for the Control of Citrus Paronychia".

[0107] Experimental location: Shuangqiao Town, Wuming District, Nanning City, Guangxi Zhuang Autonomous Region. The trees in each plot of the experimental site were of the same age and had basically the same crown size.

[0108] Experimental crop: Citrus.

[0109] Experimental target: Citrus spider mite.

[0110] Experimental pesticides: Each experimental plot consisted of 2 fruit trees, with each treatment replicated 4 times. The experimental pesticide, control pesticide, and blank control plots were arranged in a randomized block design.

[0111] Application time: Apply the pesticide once on October 28, 2022. Apply 1.5L of pesticide per tree. Use an electric sprayer to apply the pesticide to the whole citrus tree. Apply the pesticide until the leaves are wet but not dripping.

[0112] Survey method: For each plot, tender shoots were marked in five directions (east, west, south, north, and center) on the tree. The number of active mites on a total of 20 leaves was investigated. The leaf surface was directly observed using a handheld magnifying glass, and the number of mites was counted.

[0113] Survey time and frequency: Surveys were conducted 3 days and 15 days after treatment, and the number of active mites was recorded.

[0114] Methods for calculating drug efficacy:

[0115]

[0116] The results of the field efficacy trials are shown in the table below:

[0117] Table 6 Results of field trials for controlling citrus spider mites

[0118]

[0119] The results of the field efficacy control test (Table 6) show that the pesticide composition of the present invention has a good control effect on citrus red spider mite. Three days after application, the control efficacy of Preparation Example 2 and Preparation Example 5 against citrus spider mites is higher than 90%.

[0120] No phytotoxicity was found in the target crops or adverse effects on non-target organisms during the above field trials.

[0121] Although the present invention has been described in detail above with general description and specific embodiments, some modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention are within the scope of protection claimed by 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 (4'-chloro-6-fluoro-4-methyl-[1,1'-biphenyl]-3-yl)(2,2,2-trifluoroethyl) sulfide, and active ingredient B is biphenylhydrazine ester, and the mass ratio of active ingredient A to active ingredient B is 1:35~40:

1.

2. The pesticide composition according to claim 1, characterized in that, The mass ratio of active ingredient A to active ingredient B is 1:30 to 40:

1.

3. The pesticide composition according to claim 1, characterized in that, The total weight of the pesticide composition is 100 wt%, and the total weight of active ingredient A and active ingredient B accounts for 0.1 wt% to 80 wt% of the total weight of the pesticide composition.

4. The pesticide composition according to claim 1, characterized in that, In addition to the active ingredient, the pesticide composition also includes auxiliary ingredients, which are selected from one or more of the following: wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, stabilizers, synergists, or carriers.

5. The pesticide composition according to claim 1, characterized in that, The pesticide composition is prepared into a formulation in the form of a solid or liquid formulation.

6. The pesticide composition according to claim 5, characterized in that, The solid formulation is a water-dispersible granule, and the liquid formulation is a suspension, water emulsion, microemulsion, emulsifiable concentrate, dispersible oil suspension, or suspension emulsion.

7. The application of the pesticide composition according to any one of claims 1-6 for the control of mites, characterized in that, The mites mentioned are two-spotted spider mites and citrus parsnip.

Images