Pesticidal compositions, pesticides and their use in the control of pests in paddy fields

Abstract

This invention relates to the field of pesticide formulation technology, specifically to insecticidal compositions, insecticides, and their application in controlling harmful organisms in paddy fields. The composition is suitable for controlling snails such as Oncomelania hupensis and Pomacea canaliculata in paddy fields, ditches, and swamps, and is particularly effective in killing adult snails and snail eggs, while also considering ease of application, synergistic effects, and environmental safety.

Description

Technical Field

[0001] This invention relates to the field of pesticide formulation technology, and in particular to insecticidal compositions, insecticides and their application in controlling harmful organisms in paddy fields. Background Technology

[0002] Snails (such as Oncomelania hupensis and Pomacea canaliculata) are significant pests in agricultural production and public health. Oncomelania hupensis, as the only intermediate host of Schistosoma japonicum, exacerbates the spread of schistosomiasis due to its proliferation. Pomacea canaliculata, as an invasive species, reproduces rapidly and feeds on seedlings of aquatic crops such as rice and lotus, severely impacting crop yields. Niclosamide (chemical name: N-(2-chloro-4-nitrophenyl)-2-hydroxy-5-chlorobenzamide, English name: Nicolasamide, molecular formula: C...) is an invasive species. 13 H8Cl2N2O4 (CAS No.: 50-65-7) is a highly effective molluscicide recommended by the World Health Organization. It is also a core agent for the prevention and control of schistosomiasis in the public health field and the control of golden apple snails in agriculture. It blocks the mitochondrial oxidative phosphorylation process of snails and inhibits ATP synthesis, causing the energy metabolism of snails to collapse. It has both contact killing and ovicidal activities and has excellent killing effects on Oncomelania snails, adult golden apple snails and fresh snail eggs.

[0003] Avermectin (chemical name: 4″-epio-acetamido-4″-deoxyavermectin, molecular formula: C) 48 H 72 O 14 (CAS No.: 71751-41-2) is a macrolide biological pesticide produced by fermentation of Streptomyces avermectin. It has the characteristics of high efficiency, low toxicity and easy degradation. Its mechanism of action is to interfere with the release of γ-aminobutyric acid from the presynaptic membrane of the snail's nervous system, block neuromuscular transmission, and cause the snail to become paralyzed and die. It kills adult snails such as golden apple snails and Oncomelania hupensis quickly, and has high safety for crops. It is not easy to induce resistance and is often used in combination with chemical molluscicides to achieve synergistic effects.

[0004] Metaldehyde is a cyclic polymer molluscicide with a distinctive fragrance that strongly attracts mollusks. Its mechanism of action involves disrupting the mucus secretion and acetylcholinesterase balance within the snail, leading to dehydration, nerve paralysis, and death in the pest. It is moderately toxic to humans, livestock, and birds, but low in toxicity to aquatic organisms. Compared to traditional molluscicides, it has the advantage of higher environmental safety.

[0005] The core materials of water-soluble beads are mostly natural polymers or water-soluble synthetic polymers. Natural polymers, such as sodium alginate and chitosan, have advantages such as good biocompatibility, complete biodegradability, and no environmental residue. Sodium alginate can form a stable network structure through calcium ion cross-linking, achieving sustained release of the drug. Chitosan can enhance the mechanical strength of the bead formulation and reduce damage during transportation. The combination of the two is the preferred material combination for water-soluble bead formulations. Water-soluble synthetic polymers, such as polyvinyl alcohol and water-soluble starch, have the characteristics of controllable dissolution rate and low cost, and can be flexibly selected according to the release requirements of the formulation. Water-soluble beads prepared with these materials have the advantages of convenient application, controllable release upon contact with water, and wide diffusion range. No spraying or stirring is required; they can be naturally dissolved and diffused in water simply by throwing them, greatly reducing labor costs and the risk of drug drift, making them perfectly suited for the snail control needs of aquatic environments.

[0006] Among existing molluscicides, avermectin is neurotoxic to mollusks, acts rapidly but has weak attraction; molluscicide acetamide has a stable killing effect and a broad molluscicidal spectrum, but its penetration into small snails is insufficient, and long-term use alone can easily induce drug resistance; metaldehyde has a special fragrance and strong attraction, which can encourage snails to feed, but its molluscicidal rate is limited when used alone. The three agents have complementary mechanisms of action: avermectin is responsible for rapidly paralyzing nerves, molluscicide acetamide enhances the killing effect and broadens the molluscicidal spectrum, and metaldehyde enhances attraction and promotes snail feeding. Through reasonable combination, synergistic effects can be achieved. Compared with single agents or binary compound formulations, this can significantly improve molluscicidal efficiency while reducing the dosage of single components and reducing environmental pressure.

[0007] In existing technologies, most molluscicides are single-component or binary formulations (such as tetramethyl molluscicide suspension), which have significant drawbacks: single tetramethyl molluscicides have low molluscicidal rates, single molluscicides have poor attractant properties, and binary formulations still suffer from incomplete eradication of small Oncomelania snails and limited applicability in dry environments. Furthermore, traditional molluscicides such as shellfish molluscicides are highly toxic to aquatic organisms, limiting their application in aquaculture areas. Therefore, there is an urgent need for a highly effective, versatile, and environmentally friendly molluscicide and its efficient preparation method. Summary of the Invention

[0008] In view of this, the purpose of this invention is to provide an insecticidal composition, an insecticide, and its application in the control of harmful organisms in paddy fields. Addressing the problems of existing molluscicide formulations such as high pollution levels, cumbersome application, incomplete snail killing, and short duration of effect, this invention provides a ternary compound insecticidal composition that achieves the following objectives: (1) through the compounding of ternary active ingredients, synergistic effects are achieved, enhancing molluscicidal activity while simultaneously killing adult snails and snail eggs; (2) the use of a water-soluble ball formulation facilitates convenient application and reduces manual labor; (3) the optimized formulation and preparation process achieve sustained and controlled release of the agent, extending the duration of effect and reducing environmental risks.

[0009] Another objective of this invention is to provide a ternary compound water-soluble molluscicide, which gives the compound formulation better physicochemical properties.

[0010] Another objective of this invention is to provide the application of the above-mentioned ternary compound formulation in molluscicide preparation and its application in preparing related pesticide formulations.

[0011] To achieve the above objectives, the present invention provides the following technical solution:

[0012] A water-soluble molluscicide compounded with avermectin, molluscicide and metaldehyde, wherein the combination contains three active ingredients: avermectin, molluscicide and metaldehyde.

[0013] Preferably, the weight ratio of abamectin, spirodiclofen, and metaldehyde is 1-5:15-30:1. Experiments show that the CTC of the three active ingredients combined within this ratio range is >150, exhibiting a significant synergistic effect. Replacing abamectin with emamectin benzoate or spirodiclofen, which have the same insecticidal spectrum, does not result in a significant or non-existent synergistic effect. Further, the preferred weight ratio is (1-4):(15-22):1, more preferably 2-4:18-22:1, and in specific embodiments of this application, it can be 1:15:1, 4:22:1, 2:18:1, or 3:20:1.

[0014] The present invention also provides the use of the above composition in the control of pests (especially snails), or in the preparation of insecticides.

[0015] Furthermore, the pests include snails or snail eggs. Specifically, the snails include, but are not limited to, common harmful snail species in agriculture and public health, such as Oncomelania hupensis and Pomacea canaliculata, and their eggs include egg masses and egg cells of the aforementioned snails at different developmental stages. Experiments show that the composition provided by the present invention exhibits highly efficient killing activity against adult snails and their eggs at various developmental stages, especially showing significant penetrating and killing effects on Pomacea canaliculata egg masses, effectively blocking snail reproduction.

[0016] This invention also provides an insecticide (i.e., a compound water-soluble molluscicide), which, in addition to containing the aforementioned active ingredients, also includes excipients acceptable for pesticide formulation processing. Further, the excipients include, but are not limited to, carriers, binders, disintegrants, stabilizers, and colorants. The carrier is preferably a water-soluble polymer material, such as one or more combinations of sodium alginate, chitosan, polyvinyl alcohol, and water-soluble starch, to achieve stable loading and controlled release of the agent. The binder can be gelatin, gum arabic, etc., which helps improve the formability and mechanical strength of the water-soluble beads, preventing breakage during transportation and application. The disintegrant can be a mixture of sodium bicarbonate and citric acid, which promotes rapid disintegration and dispersion of the water-soluble beads by generating gas upon contact with water, ensuring timely release of the active ingredients. The stabilizer can be BHT (di-tert-butyl-p-cresol), which effectively prevents oxidative decomposition of the active ingredients during storage, ensuring the stability and shelf life of the formulation. Food coloring agents, such as brilliant blue pigment, can be used to give the water-soluble balls a clear visual identification, facilitating observation and counting during application and preventing missed or repeated applications. By rationally proportioning these excipients, the prepared compound water-soluble molluscicide balls can possess suitable hardness, density, and solubility, meeting the requirements of rapid sinking, uniform dissolution, and slow release of active ingredients in water after application, thereby improving the molluscicidal effect and its duration of effectiveness. The snails mentioned include, but are not limited to, Oncomelania hupensis, Pomacea canaliculata, and their eggs.

[0017] The present invention provides a pesticide formulation comprising a molluscicidal composition, which includes the above-described composition and pesticide formulation processing-acceptable excipients.

[0018] Preferably, the total weight content of the molluscicide composition in the pesticide is 5%-50%, more preferably 8-50%, and in specific embodiments of this application, it can be 8%, 16.275%, 24%, 32% or 49.68%.

[0019] Preferably, the excipients include, but are not limited to, at least one of emulsifiers, stabilizers, synergists, solubilizers, and solvents.

[0020] Preferably, the above composition and suitable excipients can be combined to prepare various pesticide formulations to meet different application needs, but are not limited to emulsifiable concentrates, dispersible oil suspensions, etc. When preparing emulsifiable concentrate formulations, the emulsifier can be at least one of calcium dodecylbenzenesulfonate, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, tristyrylphenol polyoxyethylene ether, phenethylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether, and phenethylphenol formaldehyde resin polyoxyethylene ether. Experiments show that the above emulsifier combinations have a certain synergistic effect, which can effectively reduce the oil-water interfacial tension, so that the active ingredients are uniformly dispersed in the solvent to form a stable emulsion. Stabilizers can be selected from at least one of BHT (di-tert-butyl-p-cresol), butylated hydroxyanisole (BHA), tea polyphenol palmitate, cocoa polyphenol ester, polyoxyethylene methacrylate, etc., which can inhibit the oxidative decomposition of active ingredients during storage and use, and extend the shelf life of the formulation. Synergists can be selected from at least one of anhydrous fast T, fatty acid methyl ester, polyether-modified trisiloxane, azone, soybean oil, rosin-based oil, turpentine oil, mineral oil, etc. Synergists can improve the wetting and spreading ability of active ingredients on the spirochete surface, and enhance the penetration of the drug, thereby improving... High molluscicidal effect; the solubilizer can be at least one of monoethanolamine, diethanolamine, triethanolamine, triethylamine, octyl dimethyl tertiary amine, decyl dimethyl tertiary amine, dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, etc., which helps improve the solubility of the active ingredient in the solvent and ensures the homogeneity and stability of the formulation; the solvent can be at least one of 150# solvent oil, 200# solvent oil, methyl oleate, soybean oil, cyclohexanone, N-methylpyrrolidone, etc., to provide a good dissolution environment for each component. For other dosage forms such as dispersible oil suspensions, appropriate excipients, such as dispersants, wetting agents, thickeners, etc., can be selected according to their characteristics to ensure that the formulation has good suspension stability, flowability and ease of use. The selection and combination of these excipients can not only ensure the stability and efficacy of the active ingredient, but also improve the physicochemical properties of the formulation, making it easier to produce, store, transport and apply.

[0021] The insecticide provided by the present invention is an emulsifiable concentrate containing a molluscicide composition, including the composition, emulsifier, synergist, solubilizer and stabilizer as described above.

[0022] The amounts of each component in the emulsifiable concentrate are as follows, by weight percentage:

[0023] Active ingredient (i.e., the composition of the present invention as described above): 5-50%;

[0024] Emulsifier: 5%-35%;

[0025] Stabilizer: 0.1-5%;

[0026] Synergist: 2%-15%;

[0027] Solubilizer: 1-10%;

[0028] Replenish the solvent to 100%.

[0029] Specifically, the emulsifier includes at least one of calcium dodecylbenzenesulfonate, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, tristyrylphenol polyoxyethylene ether, phenethylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether, and phenethylphenol formaldehyde resin polyoxyethylene ether.

[0030] And / or, the stabilizer includes at least one of BHT, butylated hydroxyanisole (BHA), tea polyphenol palmitate, cocoa polyphenol ester, and polyoxyethylene methacrylate.

[0031] And / or, the synergist includes at least one of anhydrous fast T, fatty acid methyl ester, polyether modified trisiloxane, azone, soybean oil, rosin-based oil, turpentine oil, and mineral oil;

[0032] And / or, the solubilizer includes at least one selected from monoethanolamine, diethanolamine, triethanolamine, triethylamine, octyl dimethyl tertiary amine, decyl dimethyl tertiary amine, dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, and octadecyl dimethyl tertiary amine;

[0033] And / or, the solvent includes at least one of 150# solvent oil, 200# solvent oil, methyl oleate, soybean oil, cyclohexanone, N-methylpyrrolidone, and soybean oil.

[0034] Furthermore, by weight percentage, the emulsifiable concentrate comprises the following components:

[0035] The emulsifiable concentrate contains active ingredients and adjuvants, with the active ingredients comprising 5-50%;

[0036] Emulsifier: Calcium dodecylbenzenesulfonate, 3%-15%;

[0037] Emulsifier: Castor oil polyoxyethylene ether, 1%-15%;

[0038] Emulsifier: Fatty alcohol polyoxyethylene ether, 1%-10%;

[0039] Stabilizer: BHT, 0.1-5%;

[0040] Synergist: Anhydrous fast T, 1%-5%;

[0041] Synergist: Fatty acid methyl ester, 1-10%;

[0042] Solubilizer: Monoethanolamine, 1-10%;

[0043] Solvent: 150# solvent oil to replenish.

[0044] Preferably, the effective ingredient is used at a weight of 5-30%; more preferably, it is used at a weight of 24%.

[0045] The emulsifiable concentrate provided by this invention further optimizes the emulsifier, preferably a combination of calcium dodecylbenzenesulfonate, castor oil polyoxyethylene ether, and fatty alcohol polyoxyethylene ether. Compared with other commonly used emulsifiers and their combinations, it helps the agent to adhere and penetrate better, thereby significantly improving the molluscicidal effect.

[0046] Furthermore, the present invention provides a method for preparing a molluscicide composition emulsifiable concentrate, comprising the following steps:

[0047] Step 1: Add solvent and solubilizer to the mixing vessel and stir until homogeneous;

[0048] Step 2: Add the active ingredients and stabilizer to the mixing vessel, stir and mix until fully dissolved and transparent;

[0049] Step 3: Add emulsifier and synergist to the mixing tank, and stir to fully dissolve and mix the additives evenly;

[0050] Step 4: After mixing thoroughly, allow the mixture to settle and filter.

[0051] Step 5: After passing inspection, package the product (using water-soluble film to make water-soluble balls).

[0052] The present invention also provides a method for preventing or controlling harmful organisms in paddy fields, comprising: applying the composition of the present invention as described above or the insecticide as described above.

[0053] Specifically, the application rate of the composition is 180-600 g active ingredient / ha (g ai / hm²); the application rate of the insecticide, based on the amount of the composition, is 180-600 g active ingredient / ha (g ai / hm²), preferably 300-480 g active ingredient / hm². 2 .

[0054] Specifically, the harmful organisms in the paddy fields include snails, including but not limited to Oncomelania hupensis, Pomacea canaliculata, and their eggs.

[0055] When the insecticide formulation is an emulsifiable concentrate or a dispersible oil suspension, it can be packaged in water-soluble film to form water-soluble balls. The method for preventing or controlling harmful organisms in paddy fields provided by the present invention includes: throwing the water-soluble balls directly onto the water surface in the field.

[0056] Compared with the prior art, the present invention has the following advantages:

[0057] Significant synergistic effect: The combination of avermectin, molluscicide, and metaldehyde has complementary mechanisms of action (avermectin interferes with the snail's nervous system, molluscicide damages the snail's respiratory system, and metaldehyde enhances attraction). Experimental verification shows a co-toxicity coefficient >150, with molluscicidal activity increased by more than 40% compared to single-component formulations and by more than 20% compared to binary compound formulations. The kill rate of adult snails and snail eggs reaches over 98%. When the total content is ≤50%, the stability of the formulation is well-adjusted, with no stratification or crystallization.

[0058] Innovative and convenient formulation: The formulation uses water-soluble balls, which can be simply thrown in without spraying or stirring. A single person can treat 100-150 acres per day, significantly reducing labor and equipment costs. Moreover, the pesticide can be released in a controlled manner in water, avoiding the decline in efficacy caused by the rapid loss of pesticides in conventional formulations.

[0059] High environmental safety: The formula uses environmentally friendly emulsifiers and has no volatile harmful solvents. The water-soluble ball packaging material is a natural polymer that is biodegradable and has low toxicity to water bodies and aquatic organisms. The agent is released in concentrated snail breeding areas, with high utilization rate and low residue, which meets the needs of green pesticide development.

[0060] Long-lasting effect: The effective period of the agent can reach more than 14 days, which is about 7 days longer than that of conventional wettable powder, reducing the number of applications and lowering the cost of prevention and control. Detailed Implementation

[0061] This invention provides insecticidal compositions, insecticides, and their applications in controlling harmful organisms in paddy fields. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired results. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments, and those skilled in the art can clearly modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0062] In this document, the terms "including", "comprising", and "having" describe both closed-loop technical solutions consisting of the listed features and open-loop technical solutions that include the listed features.

[0063] In this document, the term “and / or” as used includes any and all combinations of one or more of the related listed items.

[0064] In this document, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when a range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0065] In this article, when referring to units of data ranges, if the unit is only followed by the right endpoint, it indicates that the units of the left and right endpoints are the same. For example, 5-50% means that the units of the left endpoint "5" and the right endpoint "50" are both %.

[0066] The test materials used in this invention are all common commercial products and can be purchased on the market.

[0067] The present invention will be further illustrated below with reference to the embodiments:

[0068] Example 1: 24% avermectin·siloxane·metaldehyde emulsifiable concentrate (3:20:1)

[0069] Abamectin 3%, molluscicide 20%, metaldehyde 1%, calcium dodecylbenzenesulfonate 4%, castor oil polyoxyethylene ether 4%, fatty alcohol polyoxyethylene ether 2%, BHT 0.6%, anhydrous fast T 5%, fatty acid methyl ester 5%, monoethanolamine 5%, solvent oil to make up to 100%.

[0070] Solvent oil and monoethanolamine are added to a mixing vessel and stirred until homogeneous. Then, avermectin, molluscicide, metaldehyde, and BHT are added and stirred until completely dissolved. Next, calcium dodecylbenzenesulfonate, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, anhydrous fast T, and fatty acid methyl ester are added and stirred thoroughly until completely mixed, homogeneous, and transparent, thus obtaining the formulation described in this invention. Then, a laboratory water-soluble sphere preparation machine is used to prepare water-soluble spheres from the formulation.

[0071] Example 2: 49.68% abamectin·siloxane·metaldehyde emulsifiable concentrate (ratio 3:20:1, upper limit of total content)

[0072] Avermectin 6.21%, molluscicide 41.4%, metaldehyde 2.07%, calcium dodecylbenzenesulfonate 4%, castor oil polyoxyethylene ether 4%, fatty alcohol polyoxyethylene ether 2%, BHT 1.2%, anhydrous fast T 5%, fatty acid methyl ester 5%, monoethanolamine 5%, solvent oil to make up to 100%.

[0073] The processing method is the same as in Example 1.

[0074] Example 3: 16.275% avermectin·siloxane·metaldehyde emulsifiable concentrate (2:18:1)

[0075] Avermectin 1.55%, molluscicide 13.95%, metaldehyde 0.775%, calcium dodecylbenzenesulfonate 4%, castor oil polyoxyethylene ether 4%, fatty alcohol polyoxyethylene ether 2%, BHT 0.3%, anhydrous fast T 5%, fatty acid methyl ester 5%, monoethanolamine 5%, solvent oil to make up to 100%.

[0076] The processing method is the same as in Example 1.

[0077] Example 4: 32% avermectin·siloxane·metaldehyde emulsifiable concentrate (4:22:1)

[0078] Avermectin 4.741%, molluscicide 26.074%, metaldehyde 1.185%, calcium dodecylbenzenesulfonate 4%, castor oil polyoxyethylene ether 4%, fatty alcohol polyoxyethylene ether 2%, BHT 0.9%, anhydrous fast T 5%, fatty acid methyl ester 5%, monoethanolamine 5%, solvent oil to make up to 100%.

[0079] The processing method is the same as in Example 1.

[0080] Example 5: 8% avermectin·siloxane·metaldehyde emulsifiable concentrate (1:15:1)

[0081] Avermectin 0.47%, siloxane 7.06%, metaldehyde 0.47%, calcium dodecylbenzenesulfonate 4%, castor oil polyoxyethylene ether 4%, fatty alcohol polyoxyethylene ether 2%, BHT 0.1%, anhydrous fast T 5%, fatty acid methyl ester 5%, monoethanolamine 5%, solvent oil to make up to 100%.

[0082] Processing method example 1.

[0083] Comparative Example 1: 30% Abamectin·Cyclocarpine Dicarboxamide Emulsifiable Concentrate

[0084] Emamectin benzoate 5%, molluscicide 25%, calcium dodecylbenzenesulfonate 4%, castor oil polyoxyethylene ether 4%, fatty alcohol polyoxyethylene ether 2%, BHT 1%, anhydrous fast T 5%, fatty acid methyl ester 5%, monoethanolamine 5%, solvent oil to make up to 100%.

[0085] The processing method is the same as in Example 1.

[0086] Comparative Example 2: 26% molluscicide·metaldehyde binary emulsifiable concentrate

[0087] The ingredients are: 1% metaldehyde, 25% molluscicide, 4% calcium dodecylbenzenesulfonate, 4% castor oil polyoxyethylene ether, 2% fatty alcohol polyoxyethylene ether, 5% anhydrous fast T, 5% fatty acid methyl ester, 5% monoethanolamine, and solvent oil to make up to 100%.

[0088] The processing method is the same as in Example 1.

[0089] Comparative Example 3: 6% Metaldehyde Emulsifiable Concentrate

[0090] 6% metaldehyde, 5% calcium dodecylbenzenesulfonate, 4% castor oil polyoxyethylene ether, 1% fatty alcohol polyoxyethylene ether, 5% anhydrous fast T, 5% fatty acid methyl ester, and solvent oil to make up to 100%.

[0091] The processing method is the same as in Example 1.

[0092] Comparative Example 4: 25% spirochlorpyrifos emulsifiable concentrate

[0093] 25% molluscicide, 3.5% calcium dodecylbenzenesulfonate, 4.5% castor oil polyoxyethylene ether, 2% fatty alcohol polyoxyethylene ether, 5% anhydrous fast T, 5% fatty acid methyl ester, 5% monoethanolamine, and solvent oil to make up to 100%.

[0094] The processing method is the same as in Example 1.

[0095] Comparative Example 5: 5% Avermectin EC

[0096] Avermectin 5%, BHT 1%, calcium dodecylbenzenesulfonate 3%, castor oil polyoxyethylene ether 4%, fatty alcohol polyoxyethylene ether 3%, anhydrous fast T 5%, fatty acid methyl ester 5%, solvent oil to make up to 100%.

[0097] The processing method is the same as in Example 1.

[0098] Comparative Example 6: 24% Abamectin·Catalystamine·Methotrexate Emulsifiable Concentrate

[0099] Emamectin benzoate 3%, molluscicide 20%, metaldehyde 1%, calcium dodecylbenzenesulfonate 4%, castor oil polyoxyethylene ether 4%, fatty alcohol polyoxyethylene ether 2%, BHT 0.6%, anhydrous fast T 5%, fatty acid methyl ester 5%, monoethanolamine 5%, solvent oil to make up to 100%.

[0100] The processing method is the same as in Example 1.

[0101] Comparative Example 7: 24% Spiromorphine·Spicoamine·Methoaldehyde Emulsifiable Concentrate

[0102] Spiromorpholine 3%, spirochloride 20%, metaldehyde 1%, calcium dodecylbenzenesulfonate 4%, castor oil polyoxyethylene ether 4%, fatty alcohol polyoxyethylene ether 2%, BHT 0.6%, anhydrous fast T 5%, fatty acid methyl ester 5%, monoethanolamine 5%, solvent oil to make up to 100%.

[0103] The processing method is the same as in Example 1.

[0104] Test Example 1 Indoor Life Test

[0105] 1. Indoor biological testing of a mixture of avermectin, molluscicide, and metaldehyde;

[0106] 2. Test methods:

[0107] Referring to NY / T 1154.7-2006 "Guidelines for Indoor Bioassay Tests of Pesticides - Herbicides Part 7: Determination of Combined Effects of Mixtures" and NY / T 1617-2008 "Efficacy Test Methods and Evaluation of Molluscicides for Pesticide Registration", the indoor activity was determined by immersion method.

[0108] Methods for calculating toxicity and synergistic effects

[0109] (1) Formula for calculating mortality rate: Mortality rate (%) = (Number of dead individuals / Total number of test individuals) × 100; Corrected mortality rate (%) = (Mortality rate of treatment group - Mortality rate of control group) / (1 - Mortality rate of control group) × 100 (No correction is required when the mortality rate of control group < 5%).

[0110] (2) Formula for calculating snail egg inhibition rate: Snail egg inhibition rate (%) = (hatching rate of blank control group - hatching rate of treated group) / hatching rate of blank control group × 100.

[0111] (3) Formula for calculating the co-toxicity coefficient (CTC):

[0112] Single-dose toxicity index (TI): Standard agent (monoclonidine) TI=100; Test agent (avermectin) TI=(monoclonidine LC) 50 / Avermectin LC 50 )×100.

[0113] Theoretical Toxicity Index (TTI) of Mixture: TTI = silicochloride TI × mass fraction of silicochloride in the total mass of the three active ingredients + abamectin TI × mass fraction of abamectin in the total mass of the three active ingredients + metaldehyde TI × mass fraction of metaldehyde in the total mass of the three active ingredients.

[0114] Actual Toxicity Index (ATI) of Mixture: ATI = (LC50 of Standard Reagent) 50 / mixture LC 50 )×100.

[0115] Cotoxicity coefficient (CTC): CTC = (ATI / TTI) × 100.

[0116] (4) Criteria for determining synergistic effect: CTC≥150 indicates strong synergistic effect, 120≤CTC<150 indicates synergistic effect, 80<CTC<120 indicates additive effect, and CTC≤80 indicates antagonistic effect.

[0117] The experimental results are shown in Tables 1 and 2:

[0118] Table 1 Single-dose LC 50 value

[0119]

[0120] Note: Avermectin toxicity index calculation: TI = (siloxane LC50 / avermectin LC50) × 100 = (0.85 / 0.62) × 100 ≈ 137.10.

[0121] Metaldehyde toxicity index calculation: TI = (LC50 of molluscicide / LC50 of metaldehyde) × (0.85 / 2.15) × 100 ≈ 39.53

[0122] Table 2. LC50, co-toxicity coefficient, and ovicidal effect of different ternary formulations and comparative examples

[0123] The data in the table above shows that the co-toxicity coefficients of all ternary compound groups are ≥150, exhibiting a strong synergistic effect. Among them, Example 1 (3:20:1) LC 50 The lowest CTC (0.27 mg / L) and highest CTC (308.28) values ​​were observed in the combination, with corrected mortality and snail egg inhibition rates both exceeding 98%, significantly superior to other ternary combinations. The co-toxicity coefficient of the binary combination group was between 120 and 150, showing a synergistic effect, but the CTC values ​​were all lower than those of the ternary combination group. Therefore, the ternary combination showed a significant synergistic effect compared to the single-dose and binary combination groups.

[0124] Test Example 2: Otae Test

[0125] Outdoor field bioassay was used. The test organisms were healthy adult golden apple snails (3-4 months old, weighing 15-20g). The test plots were paddy fields, 15m² / plot, with a water depth of 5-8cm and a natural golden apple snail density of 50 snails / m². Each treatment was replicated three times. The blank control group was clean water. Application method: Each formulation was made into water-soluble balls and applied by throwing. The dosage was uniformly 0.5g of active ingredient / 100m². The results were collected at 24h, 48h, 72h, and 14d after application. The efficacy was evaluated according to the standards NY / T 1617-2008 and NY / T 1154.7-2006.

[0126] The field mortality rate and duration of efficacy for different groups are shown in the table below:

[0127] Table 3

[0128]

[0129] The field bioassay data above show that the results are consistent with those obtained from the laboratory bioassay. Example 1 (3:20:1) showed significantly higher corrected mortality rates in *Pomacea canaliculata* at all time points than other groups, with a duration of effectiveness up to 14 days, 4-5 days longer than the binary compound group and 6-7 days longer than the single-formulation group. This effectively reduced the frequency of reapplication and lowered control costs. Other ternary compound groups showed the next best performance in the field, while the mortality rate and duration of effectiveness in the binary compound group were lower than those in the ternary group, and the single-formulation group performed the worst. Furthermore, after application of the ternary compound groups around the aquaculture area, no abnormal fish deaths were observed in the monitored water, indicating that environmental safety met standards, further validating 3:20:1 as the optimal ratio.

[0130] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A composition, characterized in that, It includes avermectin, monoxamine, and metaldehyde; the mass ratio of avermectin, monoxamine, and metaldehyde is (1~5):(15~30):

1.

2. The composition according to claim 1, characterized in that, The mass ratio of abamectin, molluscicide and metaldehyde is (1~4):(15~22):1, preferably (2~4):(18~22):

1.

3. The composition according to claim 1 or 2, characterized in that, The mass ratio of abamectin, molluscicide, and metaldehyde is 3:20:1, 2:18:1, 4:22:1, or 1:15:

1.

4. The use of the composition according to any one of claims 1 to 3 in the control of pests in paddy fields, or in the preparation of insecticides.

5. The application according to claim 4, characterized in that, The harmful organisms in the paddy fields include at least one of snails or their eggs, leeches, tubifex worms, and freshwater mussels.

6. A pesticide formulation, characterized in that, Includes the composition according to any one of claims 1 to 3 and pesticide formulation processing-acceptable excipients; The composition comprises 5% to 50% of the insecticide by mass.

7. The pesticide formulation according to claim 6, characterized in that the formulation comprises emulsifiable concentrate, dispersible oil suspension, wettable powder, water-dispersible granule, dry suspension, granules, suspension, microemulsion or emulsion.

8. The pesticide formulation according to claim 6 or 7, characterized in that, The emulsifiable concentrate comprises, by weight percentage: Active ingredient: 5-50%; Emulsifier: 5%-35%; Stabilizer: 0.1-5%; Synergist: 2%-15%; Solubilizer: 1-10%; Replenish solvent to 100%; The active ingredient is the composition according to any one of claims 1 to 3.

9. The pesticide formulation according to claim 8, characterized in that, The emulsifier includes at least one of calcium dodecylbenzenesulfonate, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, tristyrylphenol polyoxyethylene ether, phenethylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether, and phenethylphenol formaldehyde resin polyoxyethylene ether. And / or, the stabilizer includes at least one of BHT, butylated hydroxyanisole (BHA), tea polyphenol palmitate, cocoa polyphenol ester, and polyoxyethylene methacrylate. And / or, the synergist includes at least one of anhydrous fast T, fatty acid methyl ester, polyether modified trisiloxane, azone, soybean oil, rosin-based oil, turpentine oil, and mineral oil; And / or, the solubilizer includes at least one selected from monoethanolamine, diethanolamine, triethanolamine, triethylamine, octyl dimethyl tertiary amine, decyl dimethyl tertiary amine, dodecyl dimethyl tertiary amine, tetradecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, and octadecyl dimethyl tertiary amine; And / or, the solvent includes at least one of 150# solvent oil, 200# solvent oil, methyl oleate, soybean oil, cyclohexanone, and N-methylpyrrolidone.

10. A method for controlling pests, characterized in that, Apply the composition according to any one of claims 1 to 3 or the insecticide according to any one of claims 6 to 9.

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