A pesticide composition and use thereof

Abstract

The present application belongs to the technical field of pesticide acaricidal technology, and discloses a pesticide composition and application thereof, which comprises a compound of formula I and mineral oil, wherein the mass ratio of the compound of formula I to the mineral oil is 1:35-36:1, and the pesticide preparation prepared by using the compound of formula I, the mineral oil and an acceptable auxiliary component in the pesticide field is also provided.The pesticide composition of the present application is used for preventing and treating various plant harmful mites, has a significant synergistic effect, can effectively delay the generation and development of the resistance of the harmful mites, and reduces the use amount of the pesticide.

Description

Technical Field

[0001] This invention belongs to the field of pesticide acaricide technology, and discloses a pesticide composition and its uses. Background Technology

[0002] Mites, belonging to the class Arachnida, are mainly distributed in temperate regions and are a significant pest group affecting fruit trees such as citrus and lemon. They typically cause direct damage by damaging the plant epidermis with their mouthparts and sucking plant sap. They can also act as vectors for viruses, spreading viral diseases and causing indirect damage, leading to substantial economic losses. Mites are characterized by large populations, short growth cycles, strong adaptability, and difficulty in control. In agricultural production, mite control primarily relies on chemical control, but long-term use of chemical control has led to resistance in mites to some acaricides. Therefore, developing highly effective, low-toxicity, safe acaricides that are less likely to induce resistance has become a new direction for mite control.

[0003] Mineral oil is an organic pesticide with advantages such as being environmentally friendly, not inducing resistance, leaving no residues, and having low toxicity to beneficial organisms, making it an ideal integrated pest management agent.

[0004] Currently, there are no reports on the application of mineral oil in combination with compounds of formula I, or on the rational use of such combinations for mite control. Researching the efficacy of rational combinations of mineral oil with insecticides and acaricides in controlling mites, and ultimately finding a highly effective, low-toxicity, and environmentally friendly method for mite control, would significantly reduce the impact of mites on agricultural production. This is of great significance for reducing and replacing the use of conventional chemical pesticides and protecting the agricultural ecological environment. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, the present invention provides a pesticide composition. This pesticide composition is prepared by rationally compounding mineral oil with a compound of formula I into a suitable formulation. This pesticide composition has excellent control effects on agricultural, horticultural, and forestry mites, reduces the dosage of pesticides used, and slows down the development of mite resistance.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: a pesticide composition, characterized in that the pesticide composition comprises a compound of formula I and a mineral oil, wherein the compound of formula I is: The mass ratio of mineral oil to mineral oil is 1:35 to 36:1, or any value within the above range.

[0007] Furthermore, the mass ratio of the compound of formula I to the mineral oil is 1:35 to 22:1, or any value within the above range.

[0008] Furthermore, the mass ratio of the compound of formula I to the mineral oil is 1:26 to 18:1, or any value within the above range.

[0009] Furthermore, the mass ratio of the compound of formula I to the mineral oil is 1:15 to 12:1, or any value within the above range.

[0010] Furthermore, the pesticide composition includes, in addition to the active ingredient, pesticide-acceptable auxiliary ingredients, which are fillers and / or surfactants.

[0011] The auxiliary components are selected from one or more of the following: wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, stabilizers, synergists, or carriers.

[0012] 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

[0013] Further, the dispersant is selected from one or more of the following: lignin sulfonate, alkylnaphthalene 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

[0014] Further, the emulsifier is selected from one or more of the following: calcium dodecylbenzenesulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styrene-phenol polyoxyethylene ether, castor oil polyoxyethylene ether, and alkylphenol ether phosphate; and / or

[0015] Furthermore, the thickener is selected from one or more of xanthan gum, organobentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose, and silica; and / or

[0016] Further, 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

[0017] Furthermore, the antifreeze is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons, and inorganic salts; and / or

[0018] Furthermore, the defoamer is selected from C 10 -C 20 Saturated fatty acid compounds, silicone oil, silicone compounds, C8-C 10 One or more of the fatty alcohols; and / or

[0019] Further, the solvent is selected from one or more of benzene, toluene, xylene, mesitylene, methanol, ethanol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, cyclohexanone, hydrocarbon carbonates, diesel oil, solvent oil, vegetable oil, vegetable oil derivatives, and water; and / or

[0020] Further, the preservative is selected from one or more of propionic acid, sodium propionate, sorbic acid, sodium sorbate, potassium sorbate, benzoic acid, sodium benzoate, sodium p-hydroxybenzoate, methyl p-hydroxybenzoate, Kathon, and 1,2-benzisothiazolin-3-one; and / or

[0021] Further, the stabilizer is selected from one or more of the following: disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2,6-di-tert-butyl-p-cresol, triethanolamine oleate, epoxidized vegetable oil, kaolin, bentonite, attapulgite, silica, talc, montmorillonite, and starch; and / or

[0022] Furthermore, the synergist is selected from synergistic phosphorus, synergistic ether; and / or

[0023] Furthermore, the carrier is selected from one or more of the following: ammonium salts, ground natural minerals, ground artificial minerals, silicates, resins, waxes, solid fertilizers, water, organic solvents, mineral oils, vegetable oils, and vegetable oil derivatives.

[0024] Furthermore, the composition can be used to prepare a liquid formulation.

[0025] Furthermore, the formulation is an emulsifiable concentrate, an aqueous emulsion, or a dispersible oil suspension.

[0026] Furthermore, the total weight of the compound of Formula I and the mineral oil accounts for 1% to 80% of the total weight of the pesticide composition.

[0027] The present invention also discloses the use of the pesticide composition described above for the control of plant mites.

[0028] Furthermore, the harmful mites mentioned are spider mites and malariae mites;

[0029] Furthermore, the spider mite pests mentioned are *Tetranychus citrus*, *Tetranychus appleus*, *Tetranychus cinnabarinus*, or *Tetranychus two-spotted*, and the gall mite pests are *Tetranychus rustii*.

[0030] The beneficial effects of this invention are:

[0031] The pesticide composition of the present invention rationally combines organic pesticide mineral oil with compound of formula I. The composition is reasonable, the acaricidal effect is good, the application cost is low, and its acaricidal activity is not a simple superposition of active ingredients, but has a significant synergistic effect. It can delay the development of pesticide resistance in mites, is safe for crops, and meets the safety requirements of pesticide formulations. Detailed Implementation

[0032] To make the technical solution, objectives and advantages of the present invention clearer, the present invention is described with reference to the following specific embodiments. However, the present invention can be implemented in various forms and should not be limited to the embodiments described herein.

[0033] Formulation preparation example:

[0034] Emulsifiable concentrate preparation method: The metered compound of formula I, mineral oil, solvent, and co-solvent are added to a mixing tank and stirred to dissolve. Then, an emulsifier is added, and the remaining solvent is used to make up the balance. The mixture is stirred evenly in a mixing tank and filtered to obtain the emulsifiable concentrate required by this invention.

[0035] Preparation method of water-in-oil emulsion: Dissolve the metered compound of formula I in a solvent, add mineral oil and emulsifier to dissolve into a homogeneous oil phase, mix deionized water, antifreeze and other ingredients together to form a homogeneous aqueous phase; under high-speed shearing, add the oil phase to the aqueous phase, shear until the particle size is qualified, add defoamer, thickener and preservative and stir evenly to form a well-dispersed water-in-oil emulsion product.

[0036] Preparation Example 1: 27% Compound I of Formula 1·Mineral Oil Emulsion (1:26)

[0037] Formula composition: 1% Formula I compound, 26% mineral oil, 18% cyclohexanone, 12% glycerol fatty acid ester polyoxyethylene ether, 2% calcium dodecylbenzenesulfonate, 22% propylene carbonate, xylene to make up the balance.

[0038] Preparation Example 2: 22% Compound I of Formula I·Mineral Oil Emulsion (2:9)

[0039] Formula composition: 4% Formula I compound, 18% mineral oil, 20% cyclohexanone, 15% sorbitan oleate polyoxyethylene ether, 2% calcium dodecylbenzenesulfonate, and methyl oleate to make up the balance.

[0040] Preparation Example 3: 38.5% Compound I of Formula I·Mineral Oil Emulsion (1:10)

[0041] Formulation composition: 3.5% Formula I compound, 35% mineral oil, 13% EO / PO block copolymer, 16% acetophenone, 10% cyclohexanone, 2% calcium dodecylbenzenesulfonate, and trimethylbenzene to make up the balance.

[0042] Preparation Example 4: 34% Compound I of Formula 1·Mineral Oil Emulsion (15:2)

[0043] Formula composition: 30% Formula I compound, 4% mineral oil, 25% propylene glycol methyl ether, 12% phenylethyl phenol polyoxyethylene polyoxypropylene ether, 2% calcium dodecylbenzene sulfonate, 12% cyclohexanone, and methyl oleate to make up the balance.

[0044] Preparation Example 5: 10% Compound I Mineral Oil Water Emulsion (1:9)

[0045] Formula composition: 1% Formula I compound, 9% mineral oil, 5% xylene, 15% cyclohexanone, 2% BHT, 2% polyoxyethylene dehydrated sorbitan monooleate, 5% ethylene oxide-propylene oxide copolymer, 5% propylene glycol, 0.05% silicone defoamer, 0.25% xanthan gum, 0.1% sodium benzoate, deionized water to make up the balance.

[0046] Preparation Example 6: 12% Compound I of Formula I mineral oil water emulsion (1:15)

[0047] Formula composition: 0.75% Formula I compound, 11.25% mineral oil, 3% EO / PO block copolymer, 2% alkylphenol formaldehyde resin polyoxyethylene ether sulfate, 20% cyclohexanone, 0.25% xanthan gum, 5% ethylene glycol, 0.1% potassium benzoate, 0.05% silicone oil, deionized water to make up the balance.

[0048] Preparation Example 7: 13% Compound I of Formula 1 Mineral Oil Water Emulsion (12:1)

[0049] Formula composition: 12% Formula I compound, 1% mineral oil, 8% tristyrene-phenylphenol polyoxyethylene ether polyoxypropylene ether, 1% sodium alkyl polyoxyethylene ether sulfonate, 20% cyclohexanone, 0.25% xanthan gum, 5% glycerol, 0.1% sodium benzoate, 0.04% silicone oil, deionized water to make up the balance.

[0050] Preparation Example 8: 9% Compound I of Formula I·Mineral Oil Water Emulsion (2:1)

[0051] Formula composition: 6% Formula I compound, 3% mineral oil, 8% alkylphenylethylphenol polyoxyethylene polyoxypropylene ether, 2% styrene phenol polyoxyethylene ether sulfate, 20% cyclohexanone, 0.25% xanthan gum, 5% glycerol, 0.1% sodium sorbate, 0.05% silicone oil, deionized water to make up the balance.

[0052] Example 1: Indoor virulence determination of *Pachycerium citrinum*

[0053] Test basis: The test was conducted in accordance with NY / T 1154.12-2008 "Guidelines for the determination of biological activity of pesticides in the laboratory - Insecticides - Part 12: Tetranychus slide immersion method".

[0054] Experimental targets: nymphs of the citrus pteris mites (Panonychus citri) and nymphs of the citrus rust mite (Phyllocoptrutaoleivora).

[0055] Test reagents: Formula I compound technical grade (provided by the R&D Center of Hailier Pharmaceutical Group Co., Ltd.), 99% mineral oil (provided by Hailier Pharmaceutical Group Co., Ltd., PD20121278).

[0056] Test method: The test reagent was diluted to 5 concentrations based on the preliminary test, and each concentration was repeated 4 times.

[0057] Select test mites that are kept indoors and are in the same physiological state. Cut a 2cm piece of double-sided tape and stick it to one end of a glass slide. Select healthy test mites and stick them onto the double-sided tape, 30 mites per slide. After treatment, place the harmful mites in a container lined with a damp sponge, cover it, and place it at (25±1)℃. After 2 hours, examine them under a microscope, remove dead, injured, and inactive individuals, and replenish to 30 mites per slide.

[0058] Immerse the glass slide in the above reagent and gently shake for 5 seconds. Remove the slide, absorb excess reagent with absorbent paper, place it in a white porcelain dish lined with a damp sponge, cover it with a transparent plastic film, and set up a blank control containing no reagent (containing all organic solvents and emulsifiers).

[0059] Rearing and observation: The treated mites were reared and observed in an artificial climate chamber at (25±1)℃ and a relative humidity of 75%–85% under a photoperiod of L:D = (16:8)h. After 48 hours of treatment, the mites were checked for mortality, and the total number of mites and the number of dead mites were recorded.

[0060] Data statistics and analysis:

[0061] Based on the survey data, the corrected mortality rates for each treatment were calculated using the following formula, and the results were rounded to two decimal places.

[0062]

[0063] In the formula:

[0064] P – Mortality rate, expressed as a percentage (%);

[0065] K represents the number of dead insects, in heads;

[0066] N represents the total number of insects treated, in units of heads.

[0067]

[0068] In the formula:

[0069] P1 – Corrected mortality rate, in percentage (%);

[0070] P t —The mortality rate is expressed as a percentage (%).

[0071] P0 – Mortality rate in the blank control group, expressed as a percentage (%).

[0072] 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.

[0073] The DPS statistical analysis system was used to analyze the data and obtain the virulence regression equation, correlation coefficient, and LC. 50 The value is used to evaluate the activity of the test reagent on the biological sample.

[0074] The co-toxicity coefficient (CTC value) of the mixture is calculated using the following formula:

[0075]

[0076] In the formula:

[0077] ATI – Actual Measured Toxicity Index of Mixtures;

[0078] S – LC50 of standard acaricides 50 The unit is milligrams per liter (mg / L);

[0079] M – LC of the mixture 50 The unit is milligrams per liter (mg / L).

[0080] TTI = TI A ×P A +TI B ×P B

[0081] In the formula:

[0082] TTI – Theoretical Toxicity Index of Mixtures;

[0083] TI A —A. Toxicity index of drug A;

[0084] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0085] TI B —Toxicity index of drug B;

[0086] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0087]

[0088] In the formula:

[0089] CTC – Cotoxicity Coefficient;

[0090] ATI – Actual Measured Toxicity Index of Mixtures;

[0091] TTI – Theoretical Toxicity Index of Mixtures.

[0092] The co-toxicity coefficient of the compound is ≥120, which shows a synergistic effect; CTC≤80 shows an antagonistic effect; and 80<CTC<120 shows an additive effect.

[0093] The results of the indoor activity test are shown in the table below:

[0094] Table 1. Results of indoor bioactivity tests of compound I combined with mineral oil on *Pseudomonas citrus*.

[0095]

[0096] Indoor test results showed that the compound of Formula I combined with mineral oil exhibited good biological activity against *Paecilomyces citrus*. When the mass ratio of Formula I to mineral oil was 1:35–20:1, the co-toxicity coefficient against *Paecilomyces citrus* was greater than 120, indicating a synergistic effect. A mass ratio of Formula I to mineral oil of 1:26–18:1 showed a significant synergistic effect, and a mass ratio of Formula I to mineral oil of 1:15–12:1 showed a remarkable synergistic effect.

[0097] Table 2 shows the results of indoor bioactivity tests of compound I combined with mineral oil on citrus rust mites.

[0098]

[0099]

[0100] Indoor test results showed that the compound of Formula I combined with mineral oil exhibited good biological activity against citrus rust mite. When the mass ratio of Formula I compound to mineral oil was 1:35–22:1, the co-toxicity coefficient against citrus rust mite was greater than 120, indicating a synergistic effect. A mass ratio of Formula I compound to mineral oil of 1:16–15:1 showed a significant synergistic effect, and a mass ratio of Formula I compound to mineral oil of 1:9–15:2 showed a remarkable synergistic effect.

[0101] Example 2: Field efficacy trial for controlling citrus pseudomitr

[0102] Experimental site: Citrus orchard in Gaoqiao Town, Lianjiang City, Zhanjiang City, Guangdong Province. The citrus variety used in the experiment was Hongjiang Orange. The trees were 4 years old and growing vigorously. The soil fertility of the experimental site was moderate to high. Fertilizer and water management were consistent in all experimental plots.

[0103] Experimental design: The experiment included 9 treatments, each replicated 4 times. The experiment used a randomized block design, with 3 citrus trees in each plot and a protection row.

[0104] Application time: The experiment was conducted on April 20, 2024, with only one application during the entire application period. Conventional spraying method was used, with a MATABI Super Green 16 backpack hand-operated sprayer with dual nozzles to ensure that all leaves inside and outside the canopy were evenly covered with the pesticide. The blank control was sprayed with an equal amount of water.

[0105] Survey Methods: Before the experiment, two fruit trees were randomly selected from each plot. For each tree, tender shoots were marked with east, south, west, north, and center indicators. The number of active mites on 25 leaves was surveyed, with 50 leaves surveyed per plot. The leaf surface was directly observed using a handheld magnifying glass, and the number of mites was counted. The initial mite population was surveyed before pesticide application, and surveys were conducted again at 3, 10, and 15 days after application, recording the number of active mites.

[0106] Methods for calculating drug efficacy:

[0107]

[0108] Results and analysis of field efficacy trials:

[0109] Table 3 Results of field efficacy trials for controlling *Pseudomonas citrus*

[0110]

[0111]

[0112] Field efficacy trials showed that the combination of compound I and mineral oil at an appropriate mass ratio significantly controlled citrus paronychia. The combination maintained high efficacy even 15 days after application, with a long-lasting effect. Within the above-mentioned reasonable application concentration range, the tested agent had no toxic effects or adverse effects on citrus trees, and showed no significant killing effect on natural enemies such as ladybugs and predatory mites in citrus orchards.

[0113] Example 3: Field efficacy trial for controlling citrus rust mites

[0114] Experimental site: Dongchong Town, Nansha District, Guangzhou City, Guangdong Province. The site is flat, with convenient irrigation and drainage, moderate fertility, and good management conditions. The citrus trees are approximately 4 years old, growing vigorously and showing good growth. All experimental plots maintained the same cultivation and management conditions (soil type, water and fertilizer management, planting density, growth period, water level management, etc.) as the local area. The experimental period was during the fruit enlargement stage.

[0115] Experimental crop: January Red Tangerine.

[0116] Experimental Design: The experiment consisted of 7 treatments, each with 4 replicates, for a total of 28 plots, with 2 trees per plot. A randomized block design was used, with protectant trees between plots. Application was carried out on a sunny, windless day. A spray method was employed. The actual amount of pesticide needed for each plot was diluted with water and applied using a Gongnong-16 backpack sprayer. The amount of pesticide applied was sufficient to moisten the leaves and fruit, with a slight dripping of pesticide from the leaves. One application was performed.

[0117] Experimental survey time and methods: Two trees were fixed for each plot. On each tree, two affected leaves from the same shoot stage were marked from five directions: east, south, west, north, and top center. Two fields of view were surveyed, and the number of live mites was recorded. The initial mite population was surveyed before pesticide application, and the number of surviving mites was surveyed again on the 1st, 7th, 14th, and 21st days after application. The mite population reduction rate and control effect were calculated.

[0118] Safety investigation: Throughout the efficacy test, the test agent was observed periodically to determine whether it caused phytotoxicity to citrus plants or whether it promoted or inhibited growth.

[0119] Methods for calculating drug efficacy:

[0120]

[0121] Results and analysis of field efficacy trials:

[0122] Table 4 Results of field efficacy trials for controlling citrus rust mites

[0123]

[0124]

[0125] The four compound formulations of Formula I plus mineral oil showed a control efficacy of 85.77%–92.23% seven days after application, indicating good rapid-acting properties. Twenty-one days after application, the control efficacy of each compound formulation ranged from 86.31% to 93.71%, indicating that the residual effect of this pesticide combination can last for more than 21 days, requiring only one application per generation to control the damage. Throughout the efficacy test, the tested pesticides showed no phytotoxicity to citrus plants and did not inhibit citrus growth.

[0126] In summary, through indoor activity tests and field trials, the pesticide composition of the present invention has significant control efficacy against target mites, good rapid effect, long-lasting effect, and no phytotoxicity to target crops, making it safe for crops.

[0127] 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 based on the present invention, 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 a compound of formula I and a mineral oil, wherein the compound of formula I is: The mass ratio of (Formula I) to mineral oil is 1:35 to 22:

1.

2. The pesticide composition according to claim 1, characterized in that, The mass ratio of the compound of formula I to mineral oil is 1:26 to 18:

1.

3. The pesticide composition according to claim 2, characterized in that, The mass ratio of the compound of formula I to mineral oil is 1:15 to 12:

1.

4. The pesticide composition according to claim 1, characterized in that, In addition to the active ingredient, the pesticide composition also includes pesticide-acceptable auxiliary components, which are fillers and / or surfactants.

5. The pesticide composition according to claim 1, characterized in that, The formulation prepared from the composition is a liquid formulation.

6. The pesticide composition according to claim 5, characterized in that, The formulation is an emulsifiable concentrate, an aqueous emulsion, or a dispersible oil suspension.

7. The pesticide composition according to claim 1, characterized in that, The total weight of the compound of Formula I and the mineral oil accounts for 1% to 80% of the total weight of the pesticide composition.

8. The use of the pesticide composition according to any one of claims 1-7 for the control of plant mites, characterized in that, The mites mentioned are the citrus parrot mite and the citrus rust mite.

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