A microcapsule suspension for seed treatment and its preparation method

Abstract

This disclosure relates to a seed treatment microcapsule suspension-suspension containing chlorantraniliprole, fludioxonil, and metalaxyl, and its preparation method. The method includes: 1) dispersing metalaxyl emulsifiable concentrate in an emulsifier solution to obtain a first material; 2) mixing the first material with an aqueous monomer solution to obtain a second material; 3) adjusting the pH of the second material to 3.5-5.0 and performing solidification and condensation to obtain a third material; 4) mixing the third material with a first dispersant, a first thickener, and an antifreeze agent to obtain a metalaxyl microcapsule suspension; 5) mixing the metalaxyl microcapsule suspension with a chlorantraniliprole-fludioxonil suspension, a film-forming agent, and a colorant to form a metalaxyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension. This method can increase the storage stability of the formulation, effectively prolong the effective period of metalaxyl, and at the same time, the combined use of metalaxyl with chlorantraniliprole and fludioxonil broadens the fungicidal spectrum, effectively preventing and controlling various seedling diseases and pests of crops.

Description

Technical Field

[0001] This disclosure relates to the field of pesticide technology, specifically to a seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl, and its preparation method. Background Technology

[0002] Metalaxyl, also known as high-efficiency metalaxyl, is an amide fungicide with a benzene ring as its parent compound. It has high systemic activity and can affect protein complex II (succinate dehydrogenase) in the respiratory electron transport chain of pathogens, thereby achieving a bacteriostatic effect. Metalaxyl can exert its therapeutic effect on all stages of pathogen development in plants, and is extremely effective in treating oomycete diseases. It also has good preventive and control effects against various diseases and pests caused by oomycetes, as well as damping-off and seed rot caused by Phytophthora.

[0003] In practical applications, metalaxyl has poor stability in soil and is prone to degradation, leading to rapid loss and deterioration of its active ingredients, which prevents it from maintaining its antibacterial effect. Furthermore, when used alone, metalaxyl's mechanism of action and effect are relatively simple, which also affects its antibacterial efficacy. Summary of the Invention

[0004] To overcome the problems of existing technologies where metalaxyl cannot exert a sustained antibacterial effect and has a single mode of action and effect, this disclosure provides a seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl, and its preparation method. This microcapsule suspension-suspension agent has good storage stability, rapid and sustained effect, and good control effect.

[0005] To achieve the above objectives, this disclosure provides a method for preparing a microcapsule suspension for seed treatment, wherein the microcapsule suspension contains chlorantraniliprole, fludioxonil, and metalaxyl, and the method includes:

[0006] 1) Disperse metalaxyl emulsifiable concentrate in an emulsifier solution to obtain a first material; wherein the metalaxyl emulsifiable concentrate comprises metalaxyl, a first emulsifier, an organic solvent, and an oily monomer; 2) Mix the first material with an aqueous monomer solution to obtain a second material; 3) Adjust the pH of the second material to 3.5–5.0 and perform solidification and condensation to obtain a third material; 4) Mix the third material with a first dispersant, a first thickener, and an antifreeze agent to obtain a metalaxyl microcapsule suspension; 5) Mix the metalaxyl microcapsule suspension with a chlorantraniliprole-fludioxonil suspension, a first film-forming agent, and a color paste to obtain a metalaxyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0007] Optionally, in step 1), the weight ratio of metalaxyl-containing emulsion, first emulsifier, organic solvent, and oily monomer in the metalaxyl-containing emulsion is 1:(0.05-5):(0.1-10):(0.01-0.2); wherein the first emulsifier includes at least calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, styrene-maleic anhydride copolymer, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, block polyether, alkylphenol polyoxyethylene ether, sorbitan polyoxyethylene polyoxypropylene ether, and sorbitan monostearate polyoxyethylene polyoxypropylene ether. The organic solvent comprises at least one of ethylene ether, sodium lauryl sulfate, polyvinyl alcohol, polycarboxylate, and naphthalene sulfonate; the organic solvent comprises at least one of petroleum ether, ethyl acetate, dichloromethane, chloroform, xylene, and solvent oil; the oily monomer comprises at least one of terephthalic diisocyanate, isophthalic diisocyanate, dodecyl isocyanate, 1,6-hexamethylene diisocyanate, toluene diisocyanate, dimethyl biphenyl diisocyanate, dodecyl chloride, 1,7-heptyl chloride, adipic acid chloride, docosyl chloride, and dichloroformate.

[0008] Optionally, in step 1), the weight ratio of metalaxyl, the first emulsifier, the organic solvent, and the oily monomer in the metalaxyl emulsion is 1:(0.1-1):(1-5):(0.05-0.1); wherein the first emulsifier includes at least one of calcium dodecylbenzenesulfonate, castor oil polyoxyethylene ether, block polyether, and sorbitol polyoxyethylene polyoxypropylene ether; the organic solvent includes at least one of petroleum ether, xylene, and solvent oil; and the oily monomer includes at least one of toluene diisocyanate, dimethyl biphenyl diisocyanate, dodecyl chloride, and dichloroformate.

[0009] Optionally, in step 1), the weight ratio of the metalaxyl emulsion and the emulsifier solution is 1:(0.5-5); the emulsifier solution includes water and a second emulsifier, the weight ratio of water and the second emulsifier is 1:(0.01-1), and the second emulsifier includes at least one of calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, styrene-maleic anhydride copolymer, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, block polyether, alkylphenol polyoxyethylene ether, sorbitan polyoxyethylene polyoxypropylene ether, sorbitan monostearate polyoxyethylene ether, sodium lauryl sulfate, polyvinyl alcohol, polycarboxylate, and naphthalene sulfonate.

[0010] Optionally, in step 2), the weight ratio of the first material to the aqueous monomer solution is 1:(0.5-5); the aqueous monomer solution includes water and aqueous monomers, the weight ratio of water to aqueous monomers is 1:(0.005-0.5), and the aqueous monomers include at least one of ethylene glycol, propylene glycol, glycerol, pentaerythritol, ethylenediamine, and 3-ethylene-4-amine.

[0011] Optionally, the weight ratio of the third material to the first dispersant, the first thickener, and the antifreeze in step 4) is 1:(0.01-0.1):(0.001-0.02):(0.02-0.1); wherein the first dispersant includes at least one of dodecylbenzene sulfonate, methylene bis(naphthalene) sulfonate, sodium formaldehyde condensate of 1-methylnaphthalene sulfonate, benzylnaphthalene sulfonate formaldehyde condensate, lignin sulfonate, desaccharified sodium lignin sulfonate, desaccharified condensed lignin sulfonate, sodium succinate sulfonate, separating powder, polycarboxylate, EO-PO block copolymer, nonylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether; the first thickener includes at least one of magnesium aluminum silicate, xanthan gum, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, bentonite, and silica; and the antifreeze includes at least one of ethylene glycol, 1,2-propanediol, glycerol, and urea.

[0012] Optionally, the weight ratio of the third product to the first dispersant, the first thickener, and the antifreeze in step 4) is 1:(0.02-0.05):(0.002-0.01):(0.05-0.1); wherein the first dispersant includes at least one of methylene bis(naphthalene) sulfonate, lignin sulfonate, polycarboxylate, and EO-PO block copolymer; the first thickener includes at least one of magnesium aluminum silicate, xanthan gum, and silica; and the antifreeze includes at least one of ethylene glycol and 1,2-propanediol.

[0013] Optionally, in step 5), the weight ratio of the metalaxyl microcapsule suspension to the chlorantraniliprole-fludioxonil suspension, the first film-forming agent, and the color paste is 1:(0.1-10):(0.01-0.1):(0.05-0.2); in the chlorantraniliprole-fludioxonil suspension, the weight ratio of chlorantraniliprole to fludioxonil is 1:(0.01-1); the first film-forming agent includes at least one of gum arabic, animal glue, methylcellulose, ethylcellulose, sodium hydroxymethylcellulose, polyvinyl alcohol, polyethylene glycol, polyacrylamide, sodium polyacrylate, homopolymer vinyl acetate, polysaccharide polymers, and cellulose derivatives.

[0014] Optionally, in step 5), when the metalaxyl microcapsule suspension is mixed with the chlorantraniliprole·fludioxonil suspension, a third dispersant is also added, wherein the weight ratio of the metalaxyl microcapsule suspension to the third dispersant is 1:(0.01-0.2); the third dispersant includes at least one of dodecylbenzene sulfonate, methylene bisnaphthalene sulfonate, sodium formaldehyde condensate of 1-methylnaphthalene sulfonate, benzylnaphthalene sulfonate formaldehyde condensate, lignin sulfonate, desugared sodium lignin sulfonate, desugared condensed lignin sulfonate, sodium succinate sulfonate, separating powder, polycarboxylate, EO-PO block copolymer, nonylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.

[0015] This disclosure also provides a seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl, which is prepared by the above-described preparation method.

[0016] Through the above technical solution, the microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl, prepared by the preparation method provided in this disclosure, can form a metalaxyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension agent by adding appropriate and suitable adjuvants. This increases the storage stability of the formulation, effectively prolongs the effective period of metalaxyl, and, when used in combination with chlorantraniliprole and fludioxonil, broadens the fungicidal spectrum, effectively preventing and controlling various seedling diseases and pests of crops.

[0017] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Detailed Implementation

[0018] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit this disclosure.

[0019] The first aspect of this disclosure is: a method for preparing a microcapsule suspension for seed treatment, wherein the microcapsule suspension contains chlorantraniliprole, fludioxonil, and metalaxyl, the method comprising:

[0020] 1) Disperse metalaxyl emulsifiable concentrate in an emulsifier solution to obtain a first material; wherein the metalaxyl emulsifiable concentrate comprises metalaxyl, a first emulsifier, an organic solvent, and an oily monomer; 2) Mix the first material with an aqueous monomer solution to obtain a second material; 3) Adjust the pH of the second material to 3.5–5.0 and perform solidification and condensation to obtain a third material; 4) Mix the third material with a first dispersant, a first thickener, and an antifreeze agent to obtain a metalaxyl microcapsule suspension; 5) Mix the metalaxyl microcapsule suspension with a chlorantraniliprole-fludioxonil suspension, a first film-forming agent, and a color paste to obtain a metalaxyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0021] In the above technical solution, the method of dispersing metalaxyl emulsifiable concentrate in the emulsifier solution can be a general dispersion method in the art. This disclosure does not have any special limitations on it. For example, the mixture can be subjected to high-speed shearing at a rotation speed of 10,000 to 30,000 rpm to ensure that the metalaxyl emulsifiable concentrate is fully dispersed in the emulsifier solution.

[0022] Metalaxyl-M is an amide fungicide with a benzene ring as its parent compound. It exhibits high systemic activity and is also known as high-efficiency metalaxyl. Its CAS Registry Number is 70630-17-0. Its chemical name is N-(2,6-xylyl)-N-(methoxyacetyl)-D-propanol methyl ester, with a relative molecular weight of 279.33. Its structural formula is as follows:

[0023]

[0024] Chlorantraniliprole is a novel o-aminobenzamide insecticide with excellent control efficacy against lepidopteran pests. Its chemical formula is C1. 18 H 14 BRCL2N5O2, chemical name: 3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)benzene]-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide, CAS Registry Number 500008-45-7, its structural formula is as follows:

[0025]

[0026] Fludioxonil is a novel pyrrole-based, non-systemic, broad-spectrum fungicide, also known as fludioxonil or fludioxonil ester, with the chemical formula C. 12 H6F2N2O2, chemical name: 4-(2,2-difluoro-1,3-benzodioxo-4-yl)pyrrole-3-onitrile, CAS Registry Number 131341-86-1, its structural formula is as follows:

[0027]

[0028] The method for preparing a microcapsule suspension-suspension of chlorantraniliprole, fludioxonil, and metalaxyl provided in this disclosure, by adding appropriate and suitable adjuvants, forms a microcapsule suspension-suspension of metalaxyl-fludioxonil-chlorantraniliprole for seed treatment, which increases the storage stability of the formulation, effectively prolongs the duration of action of metalaxyl, and, when used in combination with chlorantraniliprole and fludioxonil, broadens the fungicidal spectrum, effectively preventing and controlling various seedling diseases and pests of crops.

[0029] According to this disclosure, in step 1), the weight ratio of metalaxyl, the first emulsifier, the organic solvent, and the oily monomer in the metalaxyl emulsion can be 1:(0.05-5):(0.1-10):(0.01-0.2); wherein, the first emulsifier may include calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, styrene-maleic anhydride copolymer, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, block polyether, alkylphenol polyoxyethylene ether, sorbitan polyoxyethylene polyoxypropylene ether, sorbitan monostearate polyoxyethylene ether, lauryl alcohol. The organic solvent may include at least one of sodium sulfate, polyvinyl alcohol, polycarboxylate, and naphthalene sulfonate; the organic solvent may include at least one of petroleum ether, ethyl acetate, dichloromethane, chloroform, xylene, and solvent oil; the oily monomer may include at least one of polyisocyanates and polyacrylic chlorides such as terephthalic diisocyanate, isophthalic diisocyanate, dodecyl isocyanate, 1,6-hexamethylene diisocyanate, toluene diisocyanate, dimethyl biphenyl diisocyanate, dodecyl isocyanate, dodecyl chloride, 1,7-heptyl chloride, adipic acid chloride, docosyl chloride, and dichloroformate.

[0030] Preferably, in step 1), the weight ratio of metalaxyl, the first emulsifier, the organic solvent, and the oily monomer in the metalaxyl emulsion is 1:(0.1-1):(1-5):(0.05-0.1); wherein, the first emulsifier may include at least one of calcium dodecylbenzenesulfonate, castor oil polyoxyethylene ether, block polyether, and sorbitol polyoxyethylene polyoxypropylene ether; the organic solvent may include at least one of petroleum ether, xylene, and solvent oil; and the oily monomer may include at least one of toluene diisocyanate, dimethyl biphenyl diisocyanate, dodecyl chloride, and dichloroformate.

[0031] The above-mentioned optimized formulation and types of adjuvants can further improve the stability of metalaxyl in microcapsule suspension, prolong the shelf life of metalaxyl, and extend the duration of action of metalaxyl.

[0032] According to this disclosure, the weight ratio of the metalaxyl emulsion and the emulsifier solution in step 1) can be 1:(0.5-5); the emulsifier solution includes water and a second emulsifier, and the weight ratio of water and the second emulsifier can be 1:(0.01-1). The second emulsifier may include at least one of calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, styrene-maleic anhydride copolymer, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, block polyether, alkylphenol polyoxyethylene ether, sorbitan polyoxyethylene polyoxypropylene ether, sorbitan monostearate polyoxyethylene ether, sodium lauryl sulfate, polyvinyl alcohol, polycarboxylate, and naphthalene sulfonate.

[0033] Preferably, in step 1), the weight ratio of the metalaxyl emulsion and the emulsifier solution is 1:(1-2); the weight ratio of the water and the second emulsifier is 1:(0.05-0.5), and the second emulsifier may include at least one of sodium dodecylbenzenesulfonate, styrene-maleic anhydride copolymer and block polyether.

[0034] The above-mentioned optimized formulation and types of adjuvants can further improve the stability of metalaxyl in microcapsule suspension, prolong the shelf life of metalaxyl, and extend the duration of action of metalaxyl.

[0035] According to this disclosure, by polymerizing oil-soluble monomers and water-soluble monomers on the surface of an emulsion, the encapsulating material is deposited on the surface of the active ingredient core, ultimately forming microcapsules that encapsulate the active ingredient, and under the adjustment of appropriate amounts of adjuvants, a stable microcapsule suspension is formed.

[0036] The solubility of metalaxyl in organic solvents is significantly greater than its solubility in water. Using organic solvents can ensure its complete dissolution, increase the content of active ingredients per unit volume of drug solution, and enhance efficacy. Emulsifiers can increase the stability of metalaxyl emulsion. Oily monomers can polymerize with watery monomers on the emulsion surface, which helps to form stable microcapsule suspensions.

[0037] According to this disclosure, in step 2), the weight ratio of the first material to the aqueous monomer solution can be 1:(0.5-5); the aqueous monomer solution includes water and aqueous monomer, and the weight ratio of water to aqueous monomer can be 1:(0.005-0.5). The aqueous monomer may include at least one of ethylene glycol, propylene glycol, glycerol, pentaerythritol, ethylenediamine, and 3-ethylene-4-amine.

[0038] Preferably, in step 2), the weight ratio of the first material to the aqueous monomer solution is 1:(1-2); the aqueous monomer solution includes water and aqueous monomer, and the weight ratio of water to aqueous monomer can be 1:(0.05-0.2), and the aqueous monomer may include at least one of ethylene glycol, ethylenediamine and 3-ethylene-4-amine.

[0039] The above-mentioned optimized ratios and types of adjuvants can further improve the stability of the metalaxyl-M microcapsule suspension, enabling the microcapsules to better protect the metalaxyl-M and prevent it from being degraded by external conditions. At the same time, it is also conducive to the release of the metalaxyl-M from the microcapsule suspension, preventing the microcapsules from affecting the efficacy of the metalaxyl-M.

[0040] The mixing method of the first material and the aqueous monomer solution can be a general dispersion method in the art, and this disclosure does not have any special limitations on it. For example, the aqueous monomer solution can be added to the first material at a uniform rate under stirring conditions of 200 to 500 rpm for 0.5 to 4 hours at 25 to 35°C.

[0041] According to this disclosure, in step 3), a pH adjuster may be added to adjust the pH value of the second material. The pH adjuster may include at least one of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and ammonium chloride; the concentration of the pH adjuster may be 0.5 to 5% by weight.

[0042] Preferably, in step 3), a pH adjuster is added to adjust the pH value of the second material, wherein the pH adjuster includes at least one of hydrochloric acid and sulfuric acid; and the concentration of the pH adjuster is 1-3% by weight.

[0043] In the preparation of microcapsule suspensions, an appropriate pH value in the solution system can improve the encapsulation rate, uniformity, and shell compactness of the microcapsules, thereby further enhancing the storage stability of the microcapsule suspension. The method of adding a pH adjuster to the second material can be a general dispersion method in the art, and this disclosure does not impose any particular limitations on it. Exemplarily, the pH adjuster can be added uniformly to the second material at a stirring speed of 200–500 rpm over 0.5–1 hour at a temperature of 25–35°C.

[0044] Optionally, the reaction conditions for the curing polycondensation in step 4) are as follows: reaction temperature of 40–60°C, reaction time of 2–5 hours, and stirring speed of 200–400 rpm. After the curing polycondensation is completed, the pH value of the cured polycondensation product is adjusted to neutral.

[0045] After the microcapsules in the Jingjiashuangling microcapsule suspension are encapsulated, phenomena such as microcapsule aggregation, sedimentation, and caking may occur due to subsequent reactions, gravity, and the interaction between cross-linked macromolecular resins. The solidification and condensation step can increase the stability of the microcapsules, and the neutral environment can also further increase the stability of the microcapsules.

[0046] According to this disclosure, the weight ratio of the third material to the first dispersant, the first thickener, and the antifreeze in step 4) can be 1:(0.01-0.1):(0.001-0.02):(0.02-0.1); wherein, the first dispersant may include at least one of dodecylbenzene sulfonate, methylene bis(naphthalene) sulfonate, sodium formaldehyde condensate of 1-methylnaphthalene sulfonate, benzylnaphthalene sulfonate formaldehyde condensate, lignin sulfonate, desugared sodium lignin sulfonate, desugared condensed lignin sulfonate, sodium succinate sulfonate, separating powder, polycarboxylate, EO-PO block copolymer, nonylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether; the first thickener may include at least one of magnesium aluminum silicate, xanthan gum, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, bentonite, and silica; the antifreeze may include at least one of ethylene glycol, 1,2-propanediol, glycerol, and urea.

[0047] Preferably, the weight ratio of the third product to the first dispersant, the first thickener, and the antifreeze in step 4) is 1:(0.02-0.05):(0.002-0.01):(0.05-0.1); wherein the first dispersant may include at least one of methylene bis(naphthalene) sulfonate, lignin sulfonate, polycarboxylate, and EO-PO block copolymer; the first thickener may include at least one of magnesium aluminum silicate, xanthan gum, and silica; and the antifreeze may include ethylene glycol and / or 1,2-propanediol.

[0048] The above-mentioned optimized ratios and types of adjuvants can further improve the stability of the metalaxyl-M microcapsule suspension, enabling the microcapsules to better protect the metalaxyl-M and prevent it from being degraded by external conditions. At the same time, it is also conducive to the release of the metalaxyl-M from the microcapsule suspension, preventing the microcapsules from affecting the efficacy of the metalaxyl-M.

[0049] Mixing the solidified condensation product with appropriate amounts of dispersants, thickeners, antifreeze, and other additives can improve the stability of the suspending agent. The method of mixing the third material with the first dispersant, the first thickener, and the antifreeze in step 4) can be a general dispersion method in the art, and this disclosure does not impose any special limitations on it. For example, the first dispersant, the first thickener, and the antifreeze can be uniformly added to the fourth material under stirring conditions at 25–35°C for 0.5–4 hours, with a stirring speed of 200–500 rpm.

[0050] According to this disclosure, in step 5), the weight ratio of the metalaxyl microcapsule suspension to the chlorantraniliprole-fludioxonil suspension, the first film-forming agent, and the color paste can be 1:(0.1-10):(0.01-0.1):(0.05-0.2); in the chlorantraniliprole-fludioxonil suspension, the weight ratio of chlorantraniliprole to fludioxonil is 1:(0.01-1); the first film-forming agent includes at least one of gum arabic, animal glue, methylcellulose, ethylcellulose, sodium hydroxymethylcellulose, polyvinyl alcohol, polyethylene glycol, polyacrylamide, sodium polyacrylate, homopolymer vinyl acetate, polysaccharide polymers, and cellulose derivatives.

[0051] The first film-forming agent helps the agent adhere to the seed surface, increases the duration of the agent's effectiveness, reduces the amount of agent used, and reduces environmental pollution; the color paste can increase the recognizability of the microcapsule suspension-suspension agent disclosed in this invention, avoid misuse or ingestion by the user, and prevent accidental feeding to animals, thus serving as a warning.

[0052] Preferably, in step 5), the weight ratio of the metalaxyl microcapsule suspension to the chlorantraniliprole-fludioxonil suspension, the first film-forming agent, and the color paste is 1:(1-5):(0.05-0.1):(0.05-0.1); and in the chlorantraniliprole-fludioxonil suspension, the weight ratio of chlorantraniliprole to fludioxonil is 1:(0.1-0.5). The first film-forming agent includes at least one of methylcellulose, sodium carboxymethylcellulose, polyvinyl alcohol, and cellulose derivatives. The color paste may include at least one of red and blue water-soluble color pastes.

[0053] The optimal ratio of the above-mentioned metalaxyl suspension to chlorantraniliprole·fludioxonil suspension enables metalaxyl to exert a better synergistic effect with chlorantraniliprole and fludioxonil, further expanding the fungicidal spectrum, increasing the control effect on various seedling diseases and pests of crops, stimulating crop growth, and promoting crop health.

[0054] Optionally, the preparation step of the chlorantraniliprole·fludioxonil suspension in step 5) may include:

[0055] The chlorantraniliprole, fludioxonil, a second dispersant, a second film-forming agent, a second thickener, and water are sequentially mixed, dispersed, and milled to obtain the chlorantraniliprole·fludioxonil suspension. The weight ratio of the chlorantraniliprole, fludioxonil, second dispersant, second film-forming agent, and second thickener can be 1:(0.01~1):(0.01~0.1):(0.01~0.1):(0.001~0.02), preferably 1:(0.1~0.5):(0.05~0.1):(0.02~0.05):(0.002~0.01). In the chlorantraniliprole·fludioxonil suspension, the average particle size of the suspended particles of chlorantraniliprole and fludioxonil can be 1~5μm, preferably 3~5μm. The second dispersant may include at least one of the following: dodecylbenzene sulfonate, methylene bisnaphthalene sulfonate, sodium formaldehyde condensate of 1-methylnaphthalene sulfonate, benzylnaphthalene sulfonate formaldehyde condensate, lignin sulfonate, desaccharified sodium lignin sulfonate, desaccharified condensed lignin sulfonate, sodium succinate sulfonate, dispersant, polycarboxylate, EO-PO block copolymer, nonylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether; the second film-forming agent may include at least one of the following: gum arabic, animal glue, methylcellulose, ethylcellulose, sodium hydroxymethylcellulose, polyvinyl alcohol, polyethylene glycol, polyacrylamide, sodium polyacrylate, homopolymer vinyl acetate, polysaccharide polymers, and cellulose derivatives; the second thickener may include at least one of the following: magnesium aluminum silicate, xanthan gum, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, bentonite, and silica.

[0056] Further, the preparation step of the chlorantraniliprole·fludioxonil suspension in step 5) may also include: mixing, dispersing and milling fludioxonil and chlorantraniliprole with a second dispersant, a second film-forming agent, a second thickener, a color paste and water in sequence to obtain a chlorantraniliprole·fludioxonil suspension seed coating agent.

[0057] Further, in step 5), when mixing the metalaxyl microcapsule suspension with the chlorantraniliprole·fludioxonil suspension, a third dispersant may be added, wherein the weight ratio of the metalaxyl microcapsule suspension to the third dispersant may be 1:(0.01-0.2); the third dispersant includes at least one of the following: dodecylbenzene sulfonate, methylene bisnaphthalene sulfonate, sodium formaldehyde condensate of 1-methylnaphthalene sulfonate, benzylnaphthalene sulfonate formaldehyde condensate, lignin sulfonate, desugared sodium lignin sulfonate, desugared condensed lignin sulfonate, sodium succinate sulfonate, dispersant, polycarboxylate, EO-PO block copolymer, nonylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.

[0058] The addition of a third dispersant can further improve the stability of the microcapsule suspension-suspension of this invention, prolong the duration of drug action, reduce the dosage and frequency of administration, and protect the environment.

[0059] Furthermore, the weight ratio of the microcapsule suspension to the third dispersant can be 1:(0.02-0.1); the third dispersant may include at least one of dodecylbenzene sulfonate, methylene bisnaphthalene sulfonate, sodium succinate sulfonate, nonylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.

[0060] The above-mentioned preferred ratios and types of adjuvants can further improve the stability of the microcapsule suspension-suspension of this disclosure, prolong the duration of drug action, reduce the dosage and frequency of drug administration, and protect the environment.

[0061] Mixing the metalaxyl-containing microcapsule suspension with the chlorantraniliprole-fludioxonil suspension or with the chlorantraniliprole-fludioxonil suspension seed coating agent, and then adding the first film-forming agent, color paste and the third dispersant, and then mixing and dispersing, can yield a microcapsule suspension-suspension that can be used as a metalaxyl-containing microcapsule suspension-suspension agent containing metalaxyl-containing microcapsule, chlorantraniliprole and fludioxonil.

[0062] A second aspect of this disclosure provides a seed treatment microcapsule suspension-suspension containing chlorantraniliprole, fludioxonil, and metalaxyl, prepared by the above-described method. The microcapsule suspension-suspension containing chlorantraniliprole, fludioxonil, and metalaxyl provided by this disclosure exhibits good storage stability. When used for seed treatment of crops, it demonstrates good control effects against crop diseases and pests, has a broad fungicidal spectrum, and can effectively control various seedling diseases and pests in crops, with rapid and sustained action.

[0063] The present disclosure is further described in detail below through examples, but is not intended to limit the scope of the disclosure.

[0064] In the following embodiments and comparative examples of this disclosure, all raw materials and reagents used were commercially available.

[0065] Example 1

[0066] A seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl was prepared, as follows:

[0067] 1) Metalaxyl, block polyether and toluene diisocyanate are dissolved in xylene to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, block polyether, xylene and toluene diisocyanate is 1:0.5:3:0.05;

[0068] Sodium dodecylbenzenesulfonate was dissolved in water at a weight ratio of 1:0.2 to obtain an emulsifier solution.

[0069] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 20,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:1.5.

[0070] 2) Dissolve ethylenediamine in water at a weight ratio of 1:0.1 to obtain an aqueous monomer solution;

[0071] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:1.5.

[0072] 3) Add 2% hydrochloric acid to the second material above, adjust the pH value to 4.0, and carry out solidification polycondensation at 50°C and 300 rpm for 3 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0073] 4) Mix the above third material with sodium lignosulfonate, magnesium aluminum silicate and ethylene glycol in a weight ratio of 1:0.05:0.005:0.1 to obtain a microcapsule suspension of metalaxyl-methyl.

[0074] 5) Mix and disperse 40% by weight of chlorantraniliprole, 20% by weight of fludioxonil, 4% by weight of methylcellulose, 2% by weight of sodium lignosulfonate, 0.2% by weight of magnesium aluminum silicate and 33.8% by weight of water thoroughly. After uniform dispersion, pass the mixture into a sand mill for sand milling until a suspension with an average particle size of less than 4 micrometers is obtained.

[0075] The above-mentioned metalaxyl-methyl microcapsule suspension was mixed with chlorantraniliprole-fludioxonil suspension, methylcellulose and red soluble pigment in a weight ratio of 1:3:0.1:0.1 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0076] Example 2

[0077] A seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl was prepared, as follows:

[0078] 1) Metalaxyl, calcium dodecylbenzenesulfonate and dimethyl biphenyl diisocyanate were dissolved in petroleum ether to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, calcium dodecylbenzenesulfonate, petroleum ether and dimethyl biphenyl diisocyanate was 1:0.1:1:0.05.

[0079] The styrene-maleic anhydride copolymer was dissolved in water at a weight ratio of 1:0.0.5 to obtain an emulsifier solution.

[0080] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 10,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:1.

[0081] 2) Dissolve ethylene glycol in water at a weight ratio of 1:0.05 to obtain an aqueous monomer solution;

[0082] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:1.

[0083] 3) Add sulfuric acid with a concentration of 1% by weight to the second material above, adjust the pH value to 3.5, and carry out solidification and polycondensation at 40°C and 400 rpm for 4 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0084] 4) The above third material is mixed with methylene bis(naphthalene) sulfonate, xanthan gum and 1,2-propanediol in a weight ratio of 1:0.02:0.002:0.05 to obtain a microcapsule suspension of metalaxyl-methyl.

[0085] 5) Mix and disperse 40% by weight of chlorantraniliprole, 4% by weight of fludioxonil, 2% by weight of sodium carboxymethyl cellulose, 0.8% by weight of methylene bis(naphthalene) sulfonate, 0.08% by weight of xanthan gum and 53.12% by weight of water thoroughly. After uniform dispersion, pass the mixture into a sand mill for sand milling until a suspension with an average particle size of less than 3 micrometers is obtained.

[0086] The above-mentioned metalaxyl-methyl microcapsule suspension was mixed with chlorantraniliprole-fludioxonil suspension, sodium hydroxymethyl cellulose and blue soluble pigment in a weight ratio of 1:1:0.05:0.05 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0087] Example 3

[0088] A seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl was prepared, as follows:

[0089] 1) Metalaxyl, castor oil polyoxyethylene ether and dodecyl chloride are dissolved in solvent oil to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, castor oil polyoxyethylene ether, solvent oil and dodecyl chloride is 1:1:5:0.1;

[0090] An emulsifier solution was prepared by dissolving the block polyether in water at a weight ratio of 1:0.5.

[0091] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 30,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:2.

[0092] 2) Dissolve 3-ethylene-4-amine in water at a weight ratio of 1:0.2 to obtain an aqueous monomer solution;

[0093] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:2.

[0094] 3) Add 3% hydrochloric acid to the second material above, adjust the pH value to 5.0, and carry out solidification polycondensation at 60℃ and 400 rpm for 2 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0095] 4) The above third material is mixed with polycarboxylate, EO-PO block copolymer, silica and 1,2-propanediol in a weight ratio of 1:0.05:0.01:0.1 to obtain metalaxyl-M microcapsule suspension.

[0096] 5) Mix and disperse 40% by weight of chlorantraniliprole, 20% by weight of fludioxonil, 4% by weight of polyvinyl alcohol, 2% by weight of polycarboxylate, 4% by weight of bentonite and 30% by weight of water thoroughly. After uniform dispersion, pass the mixture into a sand mill for sand milling until a suspension with an average particle size of less than 5 micrometers is obtained.

[0097] The above-mentioned metalaxyl-methyl microcapsule suspension was mixed with chlorantraniliprole-fludioxonil suspension, polyvinyl alcohol and red soluble pigment in a weight ratio of 1:5:0.1:0.1 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0098] Example 4

[0099] A seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl was prepared, as follows:

[0100] 1) Metalaxyl-M, sorbitol polyoxyethylene polyoxypropylene ether, and dichloroformate were dissolved in xylene to prepare metalaxyl-M emulsion, wherein the weight ratio of metalaxyl-M, sorbitol polyoxyethylene polyoxypropylene ether, xylene, and dichloroformate was 1:0.3:2:0.05;

[0101] Sodium dodecylbenzenesulfonate was dissolved in water at a weight ratio of 1:0.1 to obtain an emulsifier solution.

[0102] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 15,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:1.25.

[0103] 2) Dissolve ethylenediamine in water at a weight ratio of 1:0.07 to obtain an aqueous monomer solution;

[0104] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:1.25.

[0105] 3) Add 1.5% by weight hydrochloric acid to the second material above, adjust the pH value to 4.5, and carry out solidification polycondensation at 45°C and 250 rpm for 2.5 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0106] 4) The above third material is mixed with EO-PO block copolymer, magnesium aluminum silicate and 1,2-propanediol in a weight ratio of 1:0.03:0.004:0.07 to obtain a microcapsule suspension of metalaxyl-methyl.

[0107] 5) 40 wt% chlorantraniliprole, 12 wt% fludioxonil, 2.8 wt% cellulose derivative, 1.6 wt% EO-PO block copolymer, 0.16 wt% silica and 43.44 wt% water are thoroughly mixed and dispersed. After uniform dispersion, the mixture is fed into a sand mill for sand milling until a suspension with an average particle size of less than 3 micrometers is obtained.

[0108] The above-mentioned metalaxyl-methyl microcapsule suspension was mixed with chlorantraniliprole-fludioxonil suspension, cellulose derivative and blue soluble pigment in a weight ratio of 1:2:0.07:0.07 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0109] Example 5

[0110] A seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl was prepared, as follows:

[0111] 1) Metalaxyl, block polyether and toluene diisocyanate are dissolved in xylene to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, block polyether, xylene and toluene diisocyanate is 1:0.7:4:0.07;

[0112] Sodium dodecylbenzenesulfonate was dissolved in water at a weight ratio of 1:0.3 to obtain an emulsifier solution.

[0113] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 25,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:1.75.

[0114] 2) Dissolve ethylenediamine in water at a weight ratio of 1:0.15 to obtain an aqueous monomer solution;

[0115] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:1.75.

[0116] 3) Add 2.5% by weight sulfuric acid to the second material above, adjust the pH value to 4.0, and carry out solidification polycondensation at 55℃ and 350 rpm for 4 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0117] 4) Mix the above third material with sodium lignosulfonate, magnesium aluminum silicate and ethylene glycol in a weight ratio of 1:0.05:0.007:0.1 to obtain a microcapsule suspension of metalaxyl-methyl.

[0118] 5) 40 wt% chlorantraniliprole, 20 wt% fludioxonil, 4 wt% gum arabic, 2 wt% sodium formaldehyde condensate of 1-methylnaphthalenesulfonate, 0.28 wt% polyethylene glycol and 33.72 wt% water are thoroughly mixed and dispersed. After being evenly dispersed, the mixture is fed into a sand mill for sand milling until a suspension with an average particle size of less than 5 micrometers is obtained, thus obtaining a chlorantraniliprole·fludioxonil suspension.

[0119] The above-mentioned metalaxyl-methyl microcapsule suspension was mixed with chlorantraniliprole-fludioxonil suspension, methylcellulose and red soluble pigment in a weight ratio of 1:4:0.1:0.1 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0120] Example 6

[0121] A seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl was prepared, as follows:

[0122] 1) Metalaxyl, styrene-maleic anhydride copolymer and dodecyl isocyanate were dissolved in ethyl acetate to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, styrene-maleic anhydride copolymer, ethyl acetate and dodecyl isocyanate was 1:0.05:0.1:0.01;

[0123] An emulsifier solution was prepared by dissolving fatty alcohol polyoxyethylene ether in water at a weight ratio of 1:0.01.

[0124] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 20,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:0.5.

[0125] 2) Dissolve propylene glycol in water at a weight ratio of 1:0.005 to obtain an aqueous monomer solution;

[0126] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:0.5.

[0127] 3) Add 0.5% by weight of phosphoric acid to the second material above, adjust the pH value to 3.5, and carry out solidification polycondensation at 40°C and 200 rpm for 2 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0128] 4) The above third material is mixed with dodecylbenzene sulfonate, polyethylene glycol and glycerol in a weight ratio of 1:0.01:0.001:0.02 to obtain the metalaxyl-methyl microcapsule suspension.

[0129] 5) 40% by weight of chlorantraniliprole, 0.4% by weight of fludioxonil, 0.4% by weight of methylcellulose, 0.4% by weight of sodium lignosulfonate, 0.04% by weight of magnesium aluminum silicate and 59.76% by weight of water are thoroughly mixed and dispersed. After being evenly dispersed, the mixture is fed into a sand mill for sand milling until a suspension with an average particle size of less than 1 micrometer is obtained, thus obtaining a chlorantraniliprole·fludioxonil suspension.

[0130] The above-mentioned metalaxyl-methyl microcapsule suspension, chlorantraniliprole-fludioxonil suspension, gum arabic red water-soluble pigment, and nonylphenol polyoxyethylene ether were mixed evenly in a weight ratio of 1:0.1:0.01:0.05:0.01 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension agent.

[0131] Example 7

[0132] A seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl was prepared, as follows:

[0133] 1) Metalaxyl, sodium lauryl sulfate and 1,7-pimecroyl chloride were dissolved in dichloromethane to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, sodium lauryl sulfate, dichloromethane and 1,7-pimecroyl chloride was 1:5:10:0.2;

[0134] Sodium lauryl sulfate was dissolved in water at a weight ratio of 1:1 to prepare an emulsifier solution.

[0135] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 20,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:5.

[0136] 2) Dissolve glycerol in water at a weight ratio of 1:0.5 to obtain an aqueous monomer solution;

[0137] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:5.

[0138] 3) Add acetic acid with a concentration of 5% by weight to the second material above, adjust the pH value to 5.0, and carry out solidification polycondensation at 60°C and 400 rpm for 5 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0139] 4) Mix the above third material with the separating powder, polyvinyl alcohol and urea in sequence at a weight ratio of 1:0.1:0.02:0.1 to obtain the Jingjiashuangling microcapsule suspension.

[0140] 5) Mix and disperse 40% by weight of chlorantraniliprole, 40% by weight of fludioxonil, 4% by weight of methylcellulose, 4% by weight of sodium lignosulfonate, 8% by weight of magnesium aluminum silicate and 4% by weight of water thoroughly. After uniform dispersion, pass the mixture into a sand mill for sand milling until a suspension with an average particle size of less than 5 micrometers is obtained.

[0141] The above-mentioned metalaxyl-methyl microcapsule suspension, chlorantraniliprole-fludioxonil suspension, polyacrylamide, blue water-soluble pigment, and fatty alcohol polyoxyethylene ether were mixed evenly in a weight ratio of 1:10:0.1:0.2:0.2 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension agent.

[0142] Example 8

[0143] A seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl was prepared, as follows:

[0144] 1) Metalaxyl, polyvinyl alcohol and icosyl chloride are dissolved in chloroform to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, polyvinyl alcohol, chloroform and icosyl chloride is 1:0.07:0.5:0.03;

[0145] An emulsifier solution was prepared by dissolving polyvinyl alcohol in water at a weight ratio of 1:0.03.

[0146] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 20,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:1.

[0147] 2) Prepare an aqueous monomer solution by dissolving pentylenetetrol in water at a weight ratio of 1:0.03.

[0148] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:0.75.

[0149] 3) Add 0.75% by weight of ammonium chloride to the second material above, adjust the pH value to 4.0, and carry out solidification polycondensation at 50°C and 300 rpm for 3 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0150] 4) Mix the above third material with nonylphenol polyoxyethylene ether, carboxymethyl cellulose and ethylene glycol in a weight ratio of 1:0.02:0.002:0.1 to obtain the metalaxyl-methyl microcapsule suspension.

[0151] 5) Mix and disperse 40% by weight of chlorantraniliprole, 2% by weight of fludioxonil, 1.2% by weight of methylcellulose, 0.8% by weight of sodium lignosulfonate, 0.08% by weight of magnesium aluminum silicate and 55.92% by weight of water thoroughly. After uniform dispersion, pass the mixture into a sand mill for sand milling until a suspension with an average particle size of less than 2 micrometers is obtained.

[0152] The above-mentioned metalaxyl-methyl microcapsule suspension, chlorantraniliprole-fludioxonil suspension, homopolymer vinyl acetate, blue water-soluble pigment, and sodium succinate sulfonate were mixed evenly in a weight ratio of 1:0.5:0.03:0.05:0.02 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0153] Example 9

[0154] A seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl was prepared, as follows:

[0155] 1) Metalaxyl, alkylphenol polyoxyethylene ether and terephthalic diisocyanate are dissolved in petroleum ether to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, alkylphenol polyoxyethylene ether, petroleum ether and terephthalic diisocyanate is 1:3:7:0.2.

[0156] An emulsifier solution was prepared by dissolving sorbitan monostearate polyoxyethylene ether in water at a weight ratio of 1:0.7.

[0157] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 20,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:3.

[0158] 2) Dissolve ethylenediamine in water at a weight ratio of 1:0.03 to obtain an aqueous monomer solution;

[0159] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:3.

[0160] 3) Add 4% hydrochloric acid to the second material above, adjust the pH value to 4.5, and carry out solidification polycondensation at 55°C and 350 rpm for 4 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0161] 4) Mix the above third material with fatty alcohol polyoxyethylene ether, bentonite and ethylene glycol in a weight ratio of 1:0.07:0.02:0.1 to obtain the metalaxyl-methyl microcapsule suspension.

[0162] 5) Mix and disperse 40% by weight of chlorantraniliprole, 28% by weight of fludioxonil, 4% by weight of methylcellulose, 2.8% by weight of sodium lignosulfonate, 0.8% by weight of magnesium aluminum silicate, and 24.4% by weight of water thoroughly. After uniform dispersion, pass the mixture into a sand mill for sand milling until a suspension with an average particle size of less than 5 micrometers is obtained.

[0163] The above-mentioned metalaxyl-methyl microcapsule suspension, chlorantraniliprole-fludioxonil suspension, polysaccharide polymer, blue water-soluble pigment, and methylene bis(naphthalene) sulfonate were mixed evenly in a weight ratio of 1:7:0.1:0.15:0.2 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension agent.

[0164] Comparative Example 1

[0165] Based on Example 1, the second material obtained during the preparation process was adjusted to pH but not subjected to solidification and condensation. The remaining operations were exactly the same as in Example 1. A microcapsule suspension-suspension agent containing metalaxyl, chlorantraniliprole, and fludioxonil was prepared, as follows:

[0166] 1) Metalaxyl, block polyether and toluene diisocyanate are dissolved in xylene to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, block polyether, xylene and toluene diisocyanate is 1:0.5:3:0.05;

[0167] Sodium dodecylbenzenesulfonate was dissolved in water at a weight ratio of 1:0.2 to obtain an emulsifier solution.

[0168] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 20,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:1.5.

[0169] 2) Dissolve ethylenediamine in water at a weight ratio of 1:0.1 to obtain an aqueous monomer solution;

[0170] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:1.5.

[0171] 3) Add 2% by weight hydrochloric acid to the second material above, adjust the pH value to 4.0, and obtain the third material;

[0172] 4) Mix the above third material with sodium lignosulfonate, magnesium aluminum silicate and ethylene glycol in a weight ratio of 1:0.05:0.005:0.1 to obtain a microcapsule suspension of metalaxyl-methyl.

[0173] 5) Mix and disperse 40% by weight of chlorantraniliprole, 20% by weight of fludioxonil, 4% by weight of methylcellulose, 2% by weight of sodium lignosulfonate, 0.2% by weight of magnesium aluminum silicate and 33.8% by weight of water thoroughly. After uniform dispersion, pass the mixture into a sand mill for sand milling until a suspension with an average particle size of less than 4 micrometers is obtained.

[0174] The above-mentioned metalaxyl-methyl microcapsule suspension was mixed with chlorantraniliprole-fludioxonil suspension, methylcellulose and red soluble pigment in a weight ratio of 1:3:0.1:0.1 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0175] Comparative Example 2

[0176] Based on Example 1, the second material obtained during the preparation process was directly cured into an acetal without adding a pH adjuster. The remaining operations were exactly the same as in Example 1. A microcapsule suspension-suspension agent containing metalaxyl, chlorantraniliprole, and fludioxonil was prepared, as follows:

[0177] 1) Metalaxyl, block polyether and toluene diisocyanate are dissolved in xylene to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, block polyether, xylene and toluene diisocyanate is 1:0.5:3:0.05;

[0178] Sodium dodecylbenzenesulfonate was dissolved in water at a weight ratio of 1:0.2 to obtain an emulsifier solution.

[0179] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 20,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:1.5.

[0180] 2) Dissolve ethylenediamine in water at a weight ratio of 1:0.1 to obtain an aqueous monomer solution;

[0181] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:1.5.

[0182] 3) The second material obtained in step 2) is cured and polycondensed at 50°C and 300 rpm for 3 hours. The pH value of the cured polycondensation product is adjusted to neutral to obtain the third material.

[0183] 4) Mix the above third material with sodium lignosulfonate, magnesium aluminum silicate and ethylene glycol in a weight ratio of 1:0.05:0.005:0.1 to obtain a microcapsule suspension of metalaxyl-methyl.

[0184] 5) Mix and disperse 40% by weight of chlorantraniliprole, 20% by weight of fludioxonil, 4% by weight of methylcellulose, 2% by weight of sodium lignosulfonate, 0.2% by weight of magnesium aluminum silicate and 33.8% by weight of water thoroughly. After uniform dispersion, pass the mixture into a sand mill for sand milling until a suspension with an average particle size of less than 4 micrometers is obtained.

[0185] The above-mentioned metalaxyl-methyl microcapsule suspension was mixed with chlorantraniliprole-fludioxonil suspension, methylcellulose and red soluble pigment in a weight ratio of 1:3:0.1:0.1 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0186] Comparative Example 3

[0187] Based on Example 1, the third material obtained during the preparation process is not mixed with the first dispersant, the first thickener, and the antifreeze, but is directly mixed with the chlorantraniliprole-fludioxonil suspension. The remaining operations are exactly the same as in Example 1, to prepare a microcapsule suspension-suspension containing metalaxyl, chlorantraniliprole, and fludioxonil, as follows:

[0188] 1) Metalaxyl, block polyether and toluene diisocyanate are dissolved in xylene to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, block polyether, xylene and toluene diisocyanate is 1:0.5:3:0.05;

[0189] Sodium dodecylbenzenesulfonate was dissolved in water at a weight ratio of 1:0.2 to obtain an emulsifier solution.

[0190] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 20,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:1.5.

[0191] 2) Dissolve ethylenediamine in water at a weight ratio of 1:0.1 to obtain an aqueous monomer solution;

[0192] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:1.5.

[0193] 3) Add 2% hydrochloric acid to the second material above, adjust the pH value to 4.0, and carry out solidification polycondensation at 50°C and 300 rpm for 3 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0194] 4) 40% by weight of chlorantraniliprole, 20% by weight of fludioxonil, 4% by weight of methylcellulose, 2% by weight of sodium lignosulfonate, 0.2% by weight of magnesium aluminum silicate and 33.8% by weight of water are thoroughly mixed and dispersed. After being evenly dispersed, the mixture is fed into a sand mill for sand milling until a suspension with an average particle size of less than 4 micrometers is obtained.

[0195] The above-mentioned metalaxyl-methyl microcapsule suspension was mixed with chlorantraniliprole-fludioxonil suspension, methylcellulose and red soluble pigment in a weight ratio of 1:3:0.1:0.1 to obtain the metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension.

[0196] Comparative Example 4

[0197] The microcapsule suspension of metalaxyl was prepared according to steps 1) to 4) in Example 1, as follows:

[0198] 1) Metalaxyl, block polyether and toluene diisocyanate are dissolved in xylene to prepare metalaxyl emulsion, wherein the weight ratio of metalaxyl, block polyether, xylene and toluene diisocyanate is 1:0.5:3:0.05;

[0199] Sodium dodecylbenzenesulfonate was dissolved in water at a weight ratio of 1:0.2 to obtain an emulsifier solution.

[0200] The above-mentioned metalaxyl emulsion and emulsifier solution were sheared and mixed evenly at a speed of 20,000 rpm to obtain the first material, wherein the weight ratio of the metalaxyl emulsion and the emulsifier solution was 1:1.5.

[0201] 2) Dissolve ethylenediamine in water at a weight ratio of 1:0.1 to obtain an aqueous monomer solution;

[0202] The second material and the aqueous monomer solution are mixed evenly to obtain the second material, wherein the weight ratio of the first material to the aqueous monomer solution is 1:1.5.

[0203] 3) Add 2% hydrochloric acid to the second material above, adjust the pH value to 4.0, and carry out solidification polycondensation at 50°C and 300 rpm for 3 hours. Adjust the pH value of the solidified polycondensation product to neutral to obtain the third material.

[0204] 4) Mix the above third material with sodium lignosulfonate, magnesium aluminum silicate and ethylene glycol in a weight ratio of 1:0.05:0.005:0.1 to obtain the metalaxyl-mancozeb microcapsule suspension.

[0205] Comparative Example 5

[0206] 40% by weight of chlorantraniliprole, 20% by weight of fludioxonil, 4% by weight of methylcellulose, 2% by weight of sodium lignosulfonate, 0.2% by weight of magnesium aluminum silicate and 33.8% by weight of water were thoroughly mixed and dispersed. After being evenly dispersed, the mixture was fed into a sand mill for sand milling until a suspension with an average particle size of less than 4 micrometers was obtained.

[0207] Comparative Example 6

[0208] 1) 40% by weight of chlorantraniliprole, 20% by weight of fludioxonil, 4% by weight of methylcellulose, 2% by weight of sodium lignosulfonate, 0.2% by weight of magnesium aluminum silicate and 33.8% by weight of water are thoroughly mixed and dispersed. After being evenly dispersed, the mixture is fed into a sand mill for sand milling until a suspension with an average particle size of less than 4 micrometers is obtained.

[0209] 2) Mix the technical grade metalaxyl with the above-mentioned chlorantraniliprole-fludioxonil suspension, methylcellulose and red soluble pigment in a weight ratio of 1:3:0.1:0.1 to obtain a suspension containing chlorantraniliprole, fludioxonil and metalaxyl.

[0210] Test Example 1

[0211] This test example is used to test the thermal storage stability and low temperature stability of the final products obtained in Examples 1-9 and Comparative Examples 1-6.

[0212] Thermal storage stability test: The final products obtained in Examples 1 to 9 and Comparative Examples 1 to 6 were used as samples and placed in containers. After sealing, they were placed in a constant temperature oven at (54±2)℃ and left to stand for 14 days. The suspension rate of each sample was determined according to GB / T14825-2006 standard, and the appearance and flowability were observed. The results are shown in Table 1.

[0213] Low-temperature stability test: The final products obtained in Examples 1-9 and Comparative Examples 1-6 were used as samples and placed in containers. After sealing, they were placed in a (0±2)℃ refrigerator for 1 hour. The mixture was stirred once every 15 minutes for 15 seconds each time. The appearance was observed for any changes. The mixture was placed at (0±2)℃ for another 7 days. Then, it was taken out and allowed to stand at room temperature to recover. The suspension rate of each sample was determined according to GB / T14825-2006 standard. The appearance and flowability were observed. The results are shown in Table 1.

[0214] Table 1. Thermal storage stability and low temperature stability of the tested samples

[0215]

[0216]

[0217] As can be seen from Table 1:

[0218] 1) The test results of Examples 1 to 9 show that the microcapsule suspension-suspension agent containing metalaxyl, chlorantraniliprole and fludioxonil obtained by the preparation method provided in this disclosure has good thermal storage stability and low temperature storage stability.

[0219] 2) The test results of Example 1 and Comparative Example 1 show that the solidification polycondensation step in the preparation method provided in this disclosure can increase the storage stability of the microcapsules;

[0220] 3) The test results of Example 1 and Comparative Example 2 show that, in the preparation method provided by this disclosure, an appropriate solution system pH value can provide the microcapsule encapsulation rate, uniformity and shell compactness, thereby further improving the storage stability of the microcapsule suspension.

[0221] 4) The test results of Example 1 and Comparative Example 3 show that in the preparation method provided in this disclosure, mixing the solidified polycondensation product with appropriate amounts of dispersants, thickeners, antifreeze and other additives can improve the stability of the suspension.

[0222] 5) The test results of Example 1 and Comparative Example 6 show that in the preparation method provided in this disclosure, metalaxyl is first prepared into a metalaxyl microcapsule suspension, which can further enhance the stability of the microcapsule suspension-suspension of metalaxyl, chlorantraniliprole and fludioxonil.

[0223] Test Example 2

[0224] This test example uses the final products obtained in Examples 1-9 and Comparative Examples 1-6 as samples to test the control effect of corn stem rot and grubs (appropriate amount of water can be added to the agent during use). The test site is located in Baoding City, Hebei Province. The selected experimental field has medium soil fertility and is well managed. The corn variety planted is Zhengdan 958. Seeds were treated before sowing with 200-250g (ai) / 100kg of seeds and the drug-to-solution ratio was 1:50. Normal management was carried out after sowing.

[0225] In the experiment, the final products obtained from Examples 1-9 and Comparative Examples 1-6 were mixed with an appropriate amount of water and then used for seed treatment. The blank control was treated with an equal amount of water. Each treatment was repeated 3 times, and a total of 45 plots were planted, with each plot being 66.7㎡. The plots were randomly arranged.

[0226] The emergence rate was investigated 10 days after sowing, the seedling growth was investigated 30 days after sowing, the severity of stem rot was investigated, and the control effect on grubs was investigated. The actual yield was measured at harvest time, and the average yield was calculated.

[0227] Survey Methodology:

[0228] Seedling emergence rate survey: 5 points were randomly selected from each plot, and 10 comparison points were selected from each point to record the seedling emergence status.

[0229] Investigating seedling growth: Five points were randomly selected from each plot, and 10 corn seedlings were taken from each point to measure plant height and fresh weight of 100 seedlings.

[0230] Efficacy survey: Five points were randomly selected from each plot for investigation, with 100 plants taken from each point. The seedlings were dug to a depth of 30cm. The initial insect population was investigated before the pesticide was applied, and the number of residual insects was investigated 30 days after the pesticide was applied. The control efficacy was calculated. The incidence rate was investigated using the softening and hollowing of the stem nodes at the base of the stem as an indicator, and the relative control efficacy was calculated.

[0231] During the harvest season, the actual yield of each plot was measured, and the yield per mu was estimated based on the area.

[0232] The test results are shown in Table 1.

[0233] Relative control efficacy against stem base rot (%) = (PT-CK) / CK×100;

[0234] White grub control efficacy = (PT insect population reduction rate - CK insect population reduction rate) / (100 - CK insect population reduction rate) × 100;

[0235] In the formula: CK—incidence rate in the blank control area;

[0236] PT – Incidence rate in the treatment area.

[0237] Table 2 shows the control efficacy of the test samples against stalk rot and grubs on maize.

[0238]

[0239] As can be seen from Table 2:

[0240] The microcapsule suspension-suspension agent containing metalaxyl, chlorantraniliprole and fludioxonil obtained by the preparation method provided in this disclosure can effectively prevent and control a variety of seedling diseases and pests of crops, and can also stimulate crop growth and promote crop health.

[0241] Test Example 3

[0242] This test example uses the final products obtained in Examples 1-9 and Comparative Examples 1-6 as samples to test the effects on peanut root rot and grubs.

[0243] Experimental location: Baoding City, Hebei Province. The plot has good fertility and is well managed. The variety used is Jihua 16. Before sowing, the seeds were treated with a seed dressing of 200-250g(ai) / 100kg of seeds at a solution ratio of 1:50. After drying, the seeds were sown and managed normally after sowing.

[0244] In the experiment, the final products obtained from Examples 1-9 and Comparative Examples 1-6 were mixed with an appropriate amount of water and then used for seed dressing. The blank control was mixed with an equal amount of water. Each treatment was repeated 3 times, and a total of 45 plots were planted, each plot being 66.7㎡. The plots were randomly arranged.

[0245] Survey Methodology:

[0246] The occurrence of root rot and grubs was investigated 10, 30 and 60 days after peanut emergence. Five random sampling points were used in each treatment area, and 30 plants were investigated in each plot. The seedlings were dug to a depth of 30 cm. The insect population was investigated before the pesticide was applied and the number of residual insects was investigated 30 days after the pesticide was applied. The control efficacy was calculated. The incidence of root rot was investigated and the relative control efficacy was calculated.

[0247] Relative control efficacy against root rot (%) = (PT - CK) / CK × 100;

[0248] White grub control efficacy = (PT insect population reduction rate - CK insect population reduction rate) / (100 - CK insect population reduction rate) × 100;

[0249] In the formula: CK—incidence rate in the blank control area;

[0250] PT – Incidence rate in the treatment area.

[0251] Table 3 shows the control effects of the tested samples on peanut root rot and white grubs.

[0252]

[0253] As can be seen from Table 3:

[0254] 1) The test results of Examples 1 to 9 show that the microcapsule suspension-suspension agent containing metalaxyl, chlorantraniliprole and fludioxonil obtained by the preparation method provided in this disclosure has a slow-release and long-lasting effect in preventing crop diseases and pests.

[0255] 2) The test results of Example 1 and Comparative Examples 1-3 and Comparative Example 6 further demonstrate that the microcapsule suspension-suspension agent containing metalaxyl, chlorantraniliprole and fludioxonil obtained by the preparation method provided in this disclosure has good control effect on multiple crop diseases and pests, and is fast-acting and long-lasting.

[0256] 3) The test results of Example 1, Comparative Example 4, and Comparative Example 5 show that the preparation method provided in this disclosure combines metalaxyl with chlorantraniliprole and fludioxonil to form a microcapsule suspension-suspension agent, which can enhance the efficacy of the drug in controlling crop diseases and pests.

[0257] The microcapsule suspension-suspension of metalaxyl, chlorantraniliprole, and fludioxonil disclosed herein has the advantage of a longer duration of action compared to other formulations of metalaxyl, chlorantraniliprole, and fludioxonil, thereby reducing the frequency and dosage of medication and saving costs; it also contains less organic solvent, which can reduce environmental pollution.

[0258] The method for preparing microcapsule suspensions containing metalaxyl, chlorantraniliprole, and fludioxonil disclosed herein significantly improves the control time of seed dressing agents by encapsulating metalaxyl into capsules, achieving both rapid and sustained effects. When used in combination with chlorantraniliprole and fludioxonil, it broadens the fungicidal spectrum, effectively controlling various seedling diseases and pests of crops, while also stimulating crop growth and promoting crop health.

[0259] The preferred embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0260] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0261] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A method for preparing a microcapsule suspension for seed treatment, characterized in that, The microcapsule suspension-suspension contains chlorantraniliprole, fludioxonil, and metalaxyl, and the method includes: 1) Disperse the metalaxyl emulsion in an emulsifier solution to obtain the first material; wherein the metalaxyl emulsion comprises metalaxyl, a first emulsifier, an organic solvent and an oily monomer; 2) Mix the first material with an aqueous monomer solution to obtain the second material; 3) Adjust the pH of the second material to 3.5–5.0 and perform solidification and polycondensation to obtain the third material; 4) The third material is mixed with the first dispersant, the first thickener and the antifreeze to obtain a metalaxyl-maniol microcapsule suspension; 5) Mix the metalaxyl-methyl micro-suspension agent with chlorantraniliprole-fludioxonil suspension, the first film-forming agent and the color paste to obtain metalaxyl-methyl-fludioxonil-chlorantraniliprole seed treatment microcapsule suspension-suspension agent; Step 1) The weight ratio of metalaxyl, first emulsifier, organic solvent and oily monomer in the metalaxyl emulsion is 1:0.5:3:0.05; wherein, the first emulsifier is block polyether; the organic solvent is xylene; and the oily monomer is toluene diisocyanate. In step 1), the weight ratio of the nail cream emulsion to the emulsifier solution is 1:1.5; the emulsifier solution includes water and a second emulsifier, the weight ratio of water to the second emulsifier is 1:0.2, and the second emulsifier is sodium dodecylbenzene sulfonate; In step 2), the weight ratio of the first material to the aqueous monomer solution is 1:1.5; The aqueous monomer solution comprises water and an aqueous monomer, wherein the weight ratio of water to aqueous monomer is 1:0.1, and the aqueous monomer is ethylenediamine. The reaction conditions for solidification polycondensation described in step 3) are as follows: reaction temperature is 40-60℃, reaction time is 2-5 hours, stirring speed is 200-400 rpm, and after solidification polycondensation is completed, the pH value of the solidified polycondensation product is adjusted to neutral. In step 4), the weight ratio of the third material to the first dispersant, the first thickener, and the antifreeze is 1:(0.02~0.05):(0.002~0.01):(0.05~0.1); where, The first dispersant is lignin sulfonate; The first thickener is magnesium aluminum silicate; The antifreeze is ethylene glycol.

2. The preparation method according to claim 1, characterized in that, In step 5), the weight ratio of the metalaxyl-mancozeb microcapsule suspension to the chlorantraniliprole-fludioxonil suspension, the first film-forming agent, and the color paste is 1:(0.1-10):(0.01-0.1):(0.05-0.2). In the chlorantraniliprole·fludioxonil suspension, the weight ratio of chlorantraniliprole to fludioxonil is 1:(0.01~1). The first film-forming agent includes at least one of gum arabic, animal glue, methylcellulose, ethylcellulose, sodium hydroxymethylcellulose, polyvinyl alcohol, polyethylene glycol, polyacrylamide, sodium polyacrylate, homopolymer vinyl acetate, polysaccharide polymers, and cellulose derivatives.

3. The preparation method according to claim 1, characterized in that, In step 5), when the metalaxyl microcapsule suspension is mixed with the chlorantraniliprole·fludioxonil suspension, a third dispersant is also added, wherein the weight ratio of the metalaxyl microcapsule suspension to the third dispersant is 1:(0.01~0.2); the third dispersant includes at least one of the following: dodecylbenzene sulfonate, methylene bisnaphthalene sulfonate, sodium formaldehyde condensate of 1-methylnaphthalene sulfonate, benzylnaphthalene sulfonate formaldehyde condensate, lignin sulfonate, desugared sodium lignin sulfonate, desugared condensed lignin sulfonate, sodium succinate sulfonate, separating powder, polycarboxylate, EO-PO block copolymer, nonylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.

4. A seed treatment microcapsule suspension-suspension agent containing chlorantraniliprole, fludioxonil, and metalaxyl, obtained by the preparation method according to any one of claims 1 to 3.

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