A composite suspension concentrate of pyraclostrobin and captan and its preparation method

Abstract

The present invention discloses a pyraclostrobin and captan compound suspension and a preparation method thereof. The liquid comprises pyraclostrobin, captan, a wetting dispersant and a composite stabilizer; the composite stabilizer comprises an organic acid or its derivative, and also comprises an ascorbic acid fatty acid ester of formula (I) or its derivative; wherein the mass ratio of the organic acid or its derivative to the ascorbic acid fatty acid ester of formula (I) or its derivative is (0.5-5):1, and the acidity coefficient of the organic acid at 25°C is 2≤pKa≤5; in the compound suspension, the mass ratio of pyraclostrobin to captan is 1:(0.5-10). The present invention adds the composite stabilizer to the pyraclostrobin and captan compound suspension, maintains the pH of the suspension between 4 and 6, reduces the degradation rate of captan, which is as low as 0.5%, and also reduces the degradation rate of other effective active components in the liquid preparation. The present invention also reduces the risk of drug damage to the agent.

Description

Technical Field

[0001] The present invention relates to the field of pesticide preparations, and in particular to a pyraclostrobin and captan compound suspension concentrate and a preparation method thereof. Background Art

[0002] Captan, also known as Captan, is chemically named N-(trichloromethylthio)-cyclohex-4-ene-1,2-dicarboximide. It is a broad-spectrum, low-toxic organosulfur fungicide. Its primary protective effect is supplemented by some therapeutic benefits, making it relatively safe to use. It effectively prevents a wide range of fungal diseases on a variety of crops, and is particularly effective against crops sensitive to copper pesticides. The drug penetrates the cell membranes of pathogens, interfering with both their respiration and cell division. With multiple sites of action, repeated use is unlikely to induce resistance in pathogens, and continuous spraying offers enhanced disease control effectiveness. It is primarily applied by spray, but can also be used as a seed treatment, a post-harvest dip, or as a soil treatment before sowing or planting.

[0003] Pyraclostrobin, also known as pyraclostrobin, is a broad-spectrum methoxyacrylate fungicide developed by BASF in Germany in 1993 and launched in 2002. It acts by inhibiting mitochondrial respiration, preventing mitochondria from producing and supplying the energy required for normal cellular metabolism, ultimately leading to cell death. Pyraclostrobin has a broad spectrum of activity and is widely used in crops such as rice, soybeans, and cucumbers. It controls most diseases of Ascomycetes, Basidiomycetes, Deuteromycetes, and Oomycetes. It has a strong inhibitory effect on spore germination and mycelial growth within leaves, exhibiting protective and therapeutic activity, as well as penetrant and local systemic activity. Its long-lasting effect is significant. At 25°C and a pH of 5–7, pyraclostrobin is stable for over 30 days. For pesticide formulations containing at least the active ingredient captan, those skilled in the art are urgently concerned with the stability of the active ingredient captan in the formulation system, including chemical stability and physical stability. In terms of chemical stability, the degradation rate of captan (2 years) needs to be controlled within 5%. In terms of physical stability, no abnormal phenomena should occur within 2 years. If the formulation is a homogeneous system, no crystallization should occur in the formulation. If the formulation is a non-homogeneous system, the particle size of the microparticles in the formulation remains stable, no obvious crystal growth occurs, no bottoming occurs, no stratification occurs, and the water separation rate or oil separation rate is controlled within the qualified range.

[0004] Clothianidin is a neonicotinoid insecticide that acts similarly to nicotinic acetylcholine receptors and has contact, stomach and systemic activity. Clothianidin is relatively stable at pH 5 to 7 under weakly acidic conditions (50°C) and degrades slowly. It is stable at pH 7 to 9 under weakly alkaline conditions. 501401 days (pH 9, 20°C) (European Union Rev. Rep.).

[0005] Captan is relatively stable under acidic conditions and degrades slowly, but degrades rapidly under alkaline conditions. At 20°C and pH 5, the half-life of captan is DT 50 The half-life of captan at pH 7 is 32.4 hours. 50 The half-life of captan is 8.3 hours at a pH of 10. 50 Captan has good heat stability. Under 80℃, the half-life DT of Captan is less than 2 minutes. 50 More than 4 years. When captan is made into a pesticide formulation, the inventors of the present application also found that a stabilizer must be added to control the degradation rate of captan (2 years) to within 5%. The general treatment method now is acidification treatment, that is, directly adding some organic acids. The inventors of the present application found that, on the one hand, during acidification treatment, the pH must be adjusted to 3 or even 1-2 before the degradation rate (2 years) can be controlled within 5%. During the storage and transportation of liquid pesticide formulations, the liquid formulation is maintained at a pH of 3 or below, that is, under strong acidic conditions. The components of the liquid formulation are prone to oxidation-reduction reactions, molecular ionization, hydrolysis, reactions with packaging materials, and many other phenomena, causing the pH value of the liquid formulation to shift toward a neutral environment, which easily leads to the degradation of captan.

[0006] However, addressing the chemical stability of captan by fine-tuning acidification parameters often results in substandard chemical stability of other active ingredients in the formulation. If the formulation contains other active ingredients, such as pyraclostrobin, adjusting the pH to 3, or even 1-2, will cause the degradation rate of pyraclostrobin in the pesticide formulation to exceed 5% over two years, with degradation rates potentially exceeding 40%. To control the degradation rate of pyraclostrobin in the pesticide formulation to less than 5%, the pH must be adjusted to above 4, meaning between 4 and 6.

[0007] Fine-tuning acidification parameters to address the chemical stability of captan can also easily lead to substandard physical stability in the formulation. If captan is formulated in a heterogeneous system, such as a suspension concentrate or dispersible oil suspension concentrate, the dispersant partially loses its dispersing ability in the weakly acidic system, leading to captan particles sinking to the bottom, crystal growth, and stratification. Furthermore, if the pesticide formulation is a combined system, such as captan and pyraclostrobin, this can be problematic.

[0008] Pyraclostrobin has four crystal forms with a wide range of melting points, ranging from 40°C to 67°C. The physical properties of each crystal form also vary, creating significant challenges for the sand-grinding process of the suspension concentrate, particularly the stability of the formulated formulation. After melting during hot storage, the low-melting-point pyraclostrobin portion of the four crystal forms is already molten. Unconstrained by the existing dispersant, it continuously aggregates and fuses, growing and rapidly settling. During this settling process, it adheres to or adsorbs other component particles, causing both components to precipitate together after the suspension concentrate is subsequently transferred from hot storage to room temperature.

[0009] Those skilled in the art have effectively solved the problem of stable single-dose formula of pyraclostrobin suspension concentrate within 30% content, no crystallization, and no stratification by selecting suitable wetting and dispersing agents, such as polycarboxylate high-efficiency wetting and dispersing agents and sulfonate wetting and dispersing agents, through the multiple anchoring points of the dispersant, dispersing pyraclostrobin particles. However, there is still no better solution for its compound preparation, especially when compounded with captan. The difficulty is that, on the one hand, the commercialized pyraclostrobin technical has a low melting point (pure product 63.7-65.2°C). When it is compounded with other components, the melting point of the mixed components is reduced, which makes the control of sand milling temperature and the selection of high-efficiency wetting and dispersing agents more demanding. At present, it is difficult to ensure that pyraclostrobin compound products in the pesticide formulation industry will not crystallize within two months after being transferred from hot storage to room temperature. The time stability of the formulation products is not guaranteed, and there is a risk of crystallization and return after circulation in the market. On the other hand, since polycarboxylate-based high-efficiency wetting and dispersing agents and sulfonate-based wetting and dispersing agents exhibit excellent wetting and dispersing properties at pH 5-7, their wetting and dispersing properties significantly decrease below pH 3, and decrease to zero below pH 2. Adjusting the pH to below 3 directly impacts the stability of pyraclostrobin, affecting its physical stability by causing pyraclostrobin particles to sink to the bottom, crystal growth, and stratification in the pesticide formulation.

[0010] The Chinese patent for a fungicidal composition containing penconazole and captan and its application (patent application number: CN201410495968.6) uses sodium citrate and resorcinol as stabilizers to prevent degradation of the active ingredients. However, resorcinol is on the list of three types of carcinogens. The chemical properties of resorcinol are similar to those of dibasic acids. It reacts with sodium hydroxide, ammonia water, etc. to form salts. Sodium citrate has the function of regulating acid and base. This patent mainly prevents degradation of the active ingredients by adjusting the pH, but the actual effect is not good, and the ingredients are not universal. The Chinese patent contains a synergistic fungicide composition containing captan (patent application number: CN200710013632.1). In order to prevent the degradation of the active ingredients, the selected stabilizers are ethanolamine, diethanolamine, tributyl phosphate, epichlorohydrin, and triphenyl phosphite. Ethanolamine and diethanolamine have the function of adjusting the acid and base. Tributyl phosphate is a colorless and odorless liquid that is miscible with a variety of organic solvents. It is a plasticizer for nitrocellulose, cellulose acetate, chlorinated rubber and polyvinyl chloride, and a solvent for coatings, inks and adhesives. It is easy to use in water-based liquid preparations. The physical system is unstable. On the other hand, it is difficult to prevent the degradation of active ingredients. Triphenyl phosphite is a reducing agent, but it is too active. The packaging must be sealed during normal storage and must not be exposed to moisture. It should be stored separately from oxidants, acids, alkalis, and food chemicals. On the other hand, it is an oily substance and is insoluble in water. It is soluble in organic solvents such as alcohol, ether, benzene and acetone, which can easily make water-based liquid preparations unstable. Epichlorohydrin is a stabilizer for oxygen-containing substances, but it is a colorless liquid with a chloroform-like odor, is volatile, and is unstable. Secondly, epichlorohydrin is on the list of Class 2A carcinogens. In order to prevent the degradation of the active ingredients, the Chinese patented fungicidal composition containing zinc thiazole (patent application number: CN201010282092.9) uses epoxy soybean oil, epichlorohydrin, triphenyl phosphite, glycidyl ether and / or pentaerythritol as stabilizers. Epoxidized soybean oil has strong lipophilicity and is difficult to emulsify. It has poor affinity with other active ingredients, resulting in poor stabilization effect. Glycidyl ether and / or pentaerythritol are polyether polyols with certain dispersibility, but the stabilization effect is poor. China patents a pesticide bactericidal composition and its application (patent application number: CN202210411587.X). To prevent the degradation of active ingredients, the selected stabilizers are epoxy soybean oil, epichlorohydrin, BHT and triphenyl phosphate. The chemical name of BHT is 2,6-di-tert-butyl-4-methylphenol, which is used as an antioxidant in food processing. On the one hand, BHT is mainly used in the oil and fat field of food to increase the shelf life of oil and fat. It is an excellent antioxidant additive for petroleum products. The antioxidant BHT has the best antioxidant effect when its working temperature is 100 degrees. Many brands have banned their product packaging bags from containing industrial-grade BHT substances. On the other hand, in terms of room temperature antioxidant, due to the strong lipophilicity of BHT, the stability of the active ingredients of water-based liquid preparations, especially hydrophilic active ingredients, is not good.In summary, the stabilizers used in the prior art for captan all have obvious defects, including poor stabilization effect, defects such as being detrimental to the stability of liquid preparations, or being carcinogens.

[0011] Regarding crop damage caused by fungicide applications, pyraclostrobin suspension concentrates (SCs) pose a risk of phytotoxicity during the seedling and nursery period, when crops are experiencing vigorous growth, high temperatures (above 37°C), and high humidity. Using pyraclostrobin at excessive concentrations can cause phytotoxicity, potentially leading to leaf burn. Taking bananas as an example, when both a 25% SC and EC were sprayed at a 375-fold dilution and maintained under the aforementioned growth conditions, severe leaf burn was observed in all treatments. When crops experience phytotoxicity, complex physiological processes undergo changes, including reduced water absorption capacity, resulting in water deficit; disruption of the plasma membrane structure, decreased active transport capacity, increased permeability, and extracellular material leakage; and extensive hydrolysis of carbohydrates and proteins. The production of reactive oxygen species (ROS) is believed to be a key driver of these processes. Under normal conditions, plants can promptly eliminate toxic ROS, keeping them at low levels. However, when phytotoxicity occurs, ROS production accelerates, causing their accumulation and causing oxidative damage. To protect against the toxic effects of ROS, plants have systems in place to eliminate them. The ascorbic acid-glutathione (ASA-GSH) cycle is a key pathway for scavenging ROS free radicals in plants. It is responsible for scavenging H:O· and regulates the body's redox potential, directing signal transduction systems in a direction that is beneficial to plant growth. However, ascorbic acid has a strong reducing property and is easily oxidized to dehydroascorbic acid. This reaction is reversible, and while ascorbic acid and dehydroascorbic acid share the same physiological function, further hydrolysis of dehydroascorbic acid to form diketogulonic acid is irreversible, completely losing its physiological efficacy. Therefore, it is difficult to use ascorbic acid in pesticide formulations.

[0012] In summary, technicians in this field are in urgent need of a stabilizer for liquid preparations containing the active ingredient captan to solve the chemical stability and physical stability problems of the preparation system, as well as to solve the problem of fungicide toxicity and reduce the risk of toxicity that may be caused by the use of fungicides. Summary of the Invention

[0013] The purpose of the present invention is to address the deficiencies in the prior art and provide a composite suspension concentrate of pyraclostrobin and captan and a preparation method thereof, so as to achieve stability of the pesticide active ingredient captan in a liquid preparation at a pH of 4 to 6, especially to maintain stability in a water-based liquid preparation with water as the main dispersion medium, thereby reducing the decomposition of the active ingredient and also avoiding the decomposition of the composite pesticide active ingredient, such as pyraclostrobin, due to low pH, which results in reduced pesticide activity.

[0014] In order to achieve the above-mentioned purpose of one aspect of the present invention, the present invention adopts the following technical solutions:

[0015] A composite stabilizer for a liquid preparation, wherein the liquid preparation contains at least a first active ingredient, wherein the first active ingredient is captan;

[0016] Composite stabilizers include, but are not limited to, organic acids or their derivatives, and also include, but are not limited to, ascorbic acid fatty acid esters of formula (I) or their derivatives;

[0017]

[0018] wherein R is independently a monovalent hydrocarbon group having 9 to 21 carbon atoms;

[0019] The acidity coefficient (25°C) of the organic acid in the liquid preparation is 2≤pKa≤5, and the organic acid or its derivative is any one of an alkyl acid or its derivative, an alkyl diacid or its derivative, an alkyl triacid or its derivative, and an alkylbenzenesulfonic acid or its derivative.

[0020] The inventors of this application also found that free H in organic acids in pesticide formulations + The concentration range of 0.00001 to 0.01 mol / L ensures the stability of the active ingredient captan. However, the larger the organic acid ionization constant, the better the stability. When pKa is less than 5, it is easy to cause a large difference in pH value before and after hot storage (52±2℃, 14 days). When pKa is greater than 5, it cannot guarantee that the free H+ in the pesticide formulation reaches a sufficient concentration.

[0021] Preferably, the mass percentage of the organic acid in the liquid preparation is 0.05-1%.

[0022] And / or in the liquid preparation, the mass ratio of the ascorbic acid fatty acid ester of formula (I) or its derivative to the first active ingredient is (0.05-5):35.

[0023] Preferably, the alkyl acid includes but is not limited to any one of formic acid, acetic acid, propionic acid, and hexenoic acid.

[0024] And / or the derivatives of the alkyl acid include but are not limited to glycolic acid and lactic acid.

[0025] Preferably, the alkyl diacid includes but not limited to butenedioic acid, glutaric acid, adipic acid,

[0026] And / or the derivatives of the alkyl diacid include but are not limited to glutamic acid.

[0027] Preferably, the alkyl triacid includes but is not limited to adipic acid,

[0028] And / or derivatives of the alkyl triacid include but are not limited to citric acid.

[0029] Preferably, the alkylbenzenesulfonic acid includes but is not limited to benzenesulfonic acid, methylbenzenesulfonic acid, and dodecylbenzenesulfonic acid.

[0030] And / or the derivatives of the alkylbenzenesulfonic acid include but are not limited to nitrobenzoic acid.

[0031] Preferably, the ascorbic acid fatty acid ester of formula (I) contains an ascorbic acid group, and the ascorbic acid group is an L-ascorbic acid group;

[0032] And / or the ascorbic acid fatty acid ester derivative of formula (I) contains an ascorbic acid group, and the ascorbic acid group is an L-ascorbic acid group, and the ascorbic acid fatty acid ester derivative of formula (I) is a salt of the ascorbic acid fatty acid ester of formula (I), including but not limited to ammonium salt, sodium salt, potassium salt, and magnesium salt.

[0033] Further, the ascorbic acid fatty acid esters of formula (I) include, but are not limited to, ascorbyl laurate, ascorbyl olivate, ascorbyl palmitate, and ascorbyl stearate;

[0034] And / or ascorbic acid fatty acid ester derivatives of formula (I) include but are not limited to lauroyl ascorbate, olivetyl ascorbate, palmitoyl ascorbate, stearoyl ascorbate.

[0035] Preferably, the liquid preparation contains at least a second pesticide active ingredient, and the second pesticide active ingredient includes but is not limited to pyraclostrobin.

[0036] Preferably, the liquid preparation includes but is not limited to aqueous emulsions, suspensions, seed treatment suspensions, dispersible oil suspensions, oil suspensions, oil preparations, and low-volume liquid preparations;

[0037] Among them, the dispersion medium of the aqueous emulsion is water,

[0038] The dispersion medium of the suspension is water.

[0039] The dispersing medium of seed treatment suspension is water.

[0040] The dispersing medium of the dispersible oil suspension is selected from any one or more of soybean oil, methyl oleate, and rapeseed oil.

[0041] The dispersion medium of the oil suspension is selected from any one or more of soybean oil, methyl oleate, and rapeseed oil.

[0042] The dispersion medium of the oil is selected from any one or more of methyl oleate, toluene, xylene, trimethylbenzene, and solvent oil.

[0043] The dispersion medium of the low-volume liquid is selected from any one or more of toluene, xylene, trimethylbenzene and solvent oil.

[0044] Liquid preparations in which the active ingredients are stably suspended in water-immiscible liquids and used after dilution with water are called dispersible oil suspension concentrates (Oil-based susoension concentrates, oil dispersion), abbreviated as OD. Liquid preparations in which the active ingredients are stably suspended in or partially dissolved in water-immiscible liquids and used after dilution with organic solvents or oils are called oil suspension concentrates (Oil miscible flowable concentrate, oil flowable concentrate, oil miscible suspension), abbreviated as OF.

[0045] In order to achieve the above-mentioned purpose of another aspect of the present invention, the present invention adopts the following technical solutions:

[0046] A pyraclostrobin and captan composite suspension concentrate, comprising but not limited to pyraclostrobin, captan, a wetting and dispersing agent, and a composite stabilizer;

[0047] The compound suspending agent contains a compound stabilizer, including but not limited to an organic acid or its derivatives, and also including but not limited to an ascorbic acid fatty acid ester of formula (I) or its derivatives,

[0048] The mass ratio of the organic acid or its derivative to the ascorbic acid fatty acid ester of formula (I) or its derivative is (0.5-5):1;

[0049] In the compound suspending concentrate, the mass ratio of pyraclostrobin to captan is 1:(0.5-10).

[0050] Preferably, in the compound suspending agent, the mass ratio of the organic acid or its derivative to the ascorbic acid fatty acid ester of formula (I) or its derivative is (1-4):1.

[0051] Preferably, in the compound suspending agent, the mass ratio of the organic acid or its derivative to the ascorbic acid fatty acid ester of formula (I) or its derivative is (2-3):1.

[0052] Preferably, in the compound suspending concentrate, the mass ratio of pyraclostrobin to captan is 1:(2-8).

[0053] Furthermore, in the compound suspending concentrate, the mass ratio of pyraclostrobin to captan is 1:(4-7).

[0054] Preferably, the wetting and dispersing agent includes at least one of polymeric carboxylates, sulfonates, EOPO polyethers, and phosphates.

[0055] Among them, phosphate esters include but are not limited to tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and castor oil polyoxyethylene ether phosphate.

[0056] Preferably, the compound suspending agent further comprises a thickener, and the thickener comprises at least one of an organic thickener and an inorganic thickener;

[0057] Among them, organic thickeners include but are not limited to xanthan gum, and inorganic thickeners include but are not limited to magnesium aluminum silicate.

[0058] Preferably, the compound suspending agent further comprises a defoaming agent, and the defoaming agent includes but is not limited to an organosilicon defoaming agent.

[0059] Preferably, the compound suspension further comprises a preservative, which includes but is not limited to kasone.

[0060] Preferably, the compounded suspending agent further comprises an antifreeze agent, which includes but is not limited to ethylene glycol, propylene glycol, and glycerol.

[0061] In order to achieve the above-mentioned purpose of another aspect of the present invention, the present invention adopts the following technical solutions:

[0062] A method for preparing a composite suspension concentrate of pyraclostrobin and captan comprises the following steps:

[0063] S1: Weigh the target amount of pyraclostrobin and captan and set aside.

[0064] Weigh the target mass of wetting and dispersing agent and composite stabilizer and set aside.

[0065] Weigh the components of the composite stabilizer of the target mass separately and set aside.

[0066] Add the composite stabilizer and wetting dispersant into water and stir to disperse evenly to obtain an additive dispersion;

[0067] S2: adding pyraclostrobin and captan to the auxiliary agent dispersion, stirring and dispersing them uniformly, and then grinding them under a grinding medium. After grinding the particles of pyraclostrobin and captan to reach the target particle size, filtering to obtain a grinding liquid, thereby obtaining a composite suspension of pyraclostrobin and captan;

[0068] Among them, the composite stabilizer includes but is not limited to an organic acid or its derivative, and also includes but is not limited to an ascorbic acid fatty acid ester of formula (I) or its derivative, wherein the organic acid is selected from one or a combination of several of acetic acid, lactic acid, and citric acid, and the ascorbic acid fatty acid ester of formula (I) is selected from one or a combination of two of L-ascorbic acid palmitate and L-ascorbic acid stearate.

[0069] Preferably, in step S1, the ascorbic acid fatty acid ester of formula (I) or its derivative component of the composite stabilizer is first dispersed in a dispersant, then uniformly mixed with the organic acid or its derivative component of the composite stabilizer and a wetting dispersant, and then added to water and stirred to disperse uniformly;

[0070] The dispersant is selected from one or a combination of ethanol, ethylene glycol, propylene glycol and glycerol.

[0071] Preferably, the auxiliary agent dispersion in step S1 is further added with a defoaming agent in a targeted amount by mass;

[0072] And / or during the grinding process of step S2, a defoaming agent in a targeted amount by mass is added to perform defoaming treatment.

[0073] Preferably, the preparation method further comprises step S3,

[0074] S3: Weigh antifreeze, preservative, and thickener for later use; stir and disperse the antifreeze and thickener evenly, then add them to water, then add the preservative, stir and disperse evenly, to obtain a thickened dispersion;

[0075] The grinding liquid obtained in step S2 is mixed with the thickened dispersion liquid, and after stirring and dispersing evenly, a composite suspension concentrate of pyraclostrobin and captan is obtained.

[0076] Preferably, the particle size D of the grinding liquid 90 Less than 5 microns.

[0077] Preferably, the particle size D of the grinding liquid 95 Less than 8 microns.

[0078] In order to achieve the above-mentioned purpose of another aspect of the present invention, the present invention adopts the following technical solutions:

[0079] A seed treatment suspension containing a stable safener, wherein the liquid preparation contains at least a first coating active ingredient, and the first coating active ingredient is pyraclostrobin;

[0080] The stabilizing safener includes at least but is not limited to ascorbic acid fatty acid esters of formula (I) or derivatives thereof, and the ascorbic acid fatty acid esters of formula (I) include but are not limited to ascorbic acid laurate, ascorbic acid olivate, ascorbic acid palmitate, and ascorbic acid stearate;

[0081] And / or ascorbic acid fatty acid ester derivatives of formula (I) include but are not limited to lauroyl ascorbate, olivetyl ascorbate, palmitoyl ascorbate, stearoyl ascorbate.

[0082] Preferably, the liquid preparation further contains a second coating active ingredient, which includes but is not limited to captan.

[0083] Preferably, the liquid preparation further contains a third active ingredient of the coating, which is an insecticide, including but not limited to imidacloprid, acetamiprid, thiamethoxam, and clothianidin.

[0084] Furthermore, the liquid preparation also contains a fourth coating active ingredient, which includes but is not limited to fludioxonil.

[0085] Preferably, in the seed treatment suspension concentrate, the mass ratio of pyraclostrobin to the stabilizing safener is 100:(0.1-100).

[0086] Preferably, in the seed treatment suspension concentrate, the mass ratio of pyraclostrobin to the stabilizing safener is 100:(1-80).

[0087] Preferably, in the seed treatment suspension concentrate, the mass ratio of pyraclostrobin to the stabilizing safener is 100:(5-50).

[0088] Preferably, the stabilizing and safening agent further comprises an organic acid, including but not limited to fulvic acid, humic acid, amino acids, salicylic acid, lecithin, and malic acid. The purpose of adding stress-resistant organic acids to the seed treatment suspension of the present invention is to increase the vitamin C content and soluble solids content in the crop body, as well as the crop's stress resistance.

[0089] Preferably, the seed treatment suspending agent further comprises a film-forming agent, which includes but is not limited to any one of acrylic emulsion, polyethylene glycol, and polyvinyl alcohol, and the content of the film-forming agent is 0.5 wt % to 5 wt %.

[0090] Preferably, the seed treatment suspending agent further comprises a warning color dye, the content of which is 2.5 to 5.5 wt%.

[0091] Preferably, the viscosity of the seed treatment suspension at 20° C. is 170 to 200 mPa·s, and the viscosity at 40° C. is 120 to 150 mPa·s.

[0092] Preferably, the pH value of the seed treatment suspension is 4.5 to 6.5.

[0093] Preferably, the pH value of the seed treatment suspension is 5.0-6.0.

[0094] In order to achieve the above-mentioned purpose of another aspect of the present invention, the present invention adopts the following technical solutions:

[0095] A seed treatment suspension concentrate containing pyraclostrobin, fludioxonil and clothianidin,

[0096] The active ingredients of the seed treatment suspension agent include pyraclostrobin, fludioxonil and clothianidin, and the mass ratio of pyraclostrobin, fludioxonil and clothianidin is (1-5):(1-2):(10-100). In the seed treatment suspension agent, the amount of the active ingredients is 4-40wt%,

[0097] The seed treatment suspension contains a stabilizing and safening agent, which is ascorbyl palmitate or its derivatives.

[0098] Among them, the derivatives of ascorbyl palmitate include but are not limited to ascorbyl dipalmitate, ascorbyl tetrapalmitate, ascorbyl tetraisopalmitate, ascorbyl tetraisopalmitate, palmitoyl ascorbate, dipalmitoyl ascorbate, tetrapalmitoyl ascorbate, and tetraisopalmitoyl ascorbate.

[0099] Preferably, the amount of the active ingredient is 5 to 25 wt%.

[0100] Furthermore, the dosage of the active ingredient is 7 wt%.

[0101] The beneficial technical effects of the present invention are:

[0102] (1) To ensure that the liquid preparation containing captan is qualified, those skilled in the art control the degradation of captan within the qualified range, generally with a degradation rate of ≤5%, and need to maintain the liquid preparation at a pH of 2 to 3. The present invention reduces the degradation rate of captan to a minimum of 0.5% by adding a composite stabilizer to the liquid preparation, and also maintains the liquid preparation at a pH of 4 to 6. At the same time, during long-term storage, the degradation rate of the pesticide active ingredient captan can be ensured to be below 5%, thereby avoiding degradation of the active component captan caused by pH changes during storage and transportation of the pesticide liquid preparation product. Since the liquid preparation is prevented from being in a highly acidic environment, the physical stability of the liquid preparation is easier to maintain, and abnormal phenomena such as the formation of a paste, the growth of microparticle crystals, and water separation and stratification are avoided.

[0103] (2) The technical solution of the present invention can reduce the degradation of the active ingredients of the fungicide compounded with captan, so that the other active ingredients in the liquid preparation except captan can also be stable, such as pyraclostrobin can be kept stable, and the degradation rate of the active ingredients compounded with the pesticide active ingredient captan can be guaranteed to be below 5% during long-term storage. The pH of the liquid preparation is maintained between 4 and 6, avoiding the maintenance of the liquid preparation under high acidic conditions, which will cause the physical stability of the liquid preparation to deteriorate, and avoid the occurrence of abnormal phenomena such as the formation of a paste, the growth of microparticle crystals, and the separation of water.

[0104] (3) The raw materials used in this application are easy to add to the liquid preparation, and the operation is simple and easy to implement, thus avoiding the problem of difficult to control product quality due to complex process and the problem of excessive degradation rate of the active ingredients of the product, so that the degradation rate of the pesticide active ingredients can be guaranteed to be below 5% during long-term storage;

[0105] (4) The inventors of the present application unexpectedly discovered that the composite stabilizer of the present invention can also stabilize the active ingredient clothianidin that is stable in weak alkaline conditions, with a degradation rate as low as 0.5%. The inventors also unexpectedly discovered that the composite stabilizer of the present invention has the effect of reducing the risk of phytotoxicity of captan and its compound liquid preparations, especially when using fungicides during the seedling stage of crops, when crops are growing vigorously and fungicides are used in high temperature periods (above 37°C) and high humidity conditions. When the ascorbic acid fatty acid ester or its derivatives of the composite stabilizer component formula (I) are used in seed treatment suspensions, a safer seed treatment suspension product containing fungicides is obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0106] Figure 1 This is the sample after hot storage of the control sample CK3 of Example 2 of the present invention. After the hot storage, the bottom of the sample after removing the upper liquid is viscous, making sampling difficult.

[0107] Figure 2 The experimental samples 6 to 9 of Example 2 of the present invention and the control samples CK3 to CK4 were mixed after hot storage, and 1 ml was diluted 250 times for suspension rate test. After standing for 1 hour, 25 ml of the dilution solution was left at the bottom. It can be seen that CK3 and CK4 have obvious precipitation, while samples 6 to 9 have almost no precipitation.

[0108] Figure 3 This is the sample after hot storage of the control experiment example CK3 of Example 2 of the present invention, in which a clear water separation layer can be seen;

[0109] Figure 4 This is the sample after hot storage of the control experimental example CK4 of Example 2 of the present invention. It can be seen that there is an obvious water separation layer, but it is less than that of CK3;

[0110] Figure 5 These are the samples after hot storage of experimental example samples 6 to 10 of Example 2 of the present invention. It can be seen that there is no obvious water separation layer.

[0111] Figure 6 This is a comparison chart of the effects of corn coated with the experimental samples of the 20% pyraclostrobin·captan seed treatment suspension concentrate of Example 3 of the present invention. It can be seen that compared with CK5, samples 11 and 13 have more uniform coating, more uniform film formation, and higher brightness.

[0112] Figure 7This is a comparison chart of the effects of corn coating with the experimental samples of 20% pyraclostrobin·captan seed treatment suspension concentrate of Example 3 of the present invention. It can be seen that sample 14 is more evenly coated than CK6.

[0113] Figure 8 This is a comparison chart of the effects of corn coated with the experimental samples of the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate of Example 4 of the present invention. It can be seen that compared with CK7, samples 16 and 17 have more uniform coating, more uniform film formation, and higher brightness.

[0114] Figure 9 This is a comparison chart of the effects of corn coated with the experimental sample of 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate of Example 4 of the present invention. It can be seen that compared with CK8, sample 20 has more uniform coating, more uniform film formation, and higher brightness.

[0115] Figure 10 This is a picture of the effect of corn coating with Sample 18 of the experimental example of 7% pyraclostrobin, fludioxonil, and clothianidin seed treatment suspension concentrate of Example 4 of the present invention. It can be seen that Sample 18 forms a uniform film with high brightness, good surface appearance, good smoothness, and no seed adhesion. DETAILED DESCRIPTION

[0116] The present invention will be further described below in conjunction with the accompanying drawings. The following description of the embodiments will further help the public understand the present invention. However, the specific embodiments given by the applicant cannot and should not be regarded as limitations on the technical solution of the present invention. Any changes to the definition of local technical features or formal rather than substantive changes to the overall structure should be regarded as the scope of protection defined by the technical solution of the present invention.

[0117] like Figures 1-10 As shown, the content of the original drug and other agents in the examples are calculated based on the percentage.

[0118] Test method and steps: Add the composite stabilizer to the liquid preparation in a certain proportion and stir to obtain a sample. The sample is divided into three samples: before hot storage, hot storage (54±2°C) and room temperature storage.

[0119] After the samples are prepared, they are immediately stored at room temperature and the active ingredient content of the pre-storage samples is measured. The hot storage samples are placed in an oven set at 54±2°C. After 14 days, the content is tested. The relative decomposition rate is calculated using the pre-storage content as a reference. A hot storage decomposition rate of ≤5% is considered qualified. After passing the hot storage test, samples stored at room temperature for two years are sampled and analyzed for the active ingredient decomposition rate at 12 and 24 months to determine whether the stability over time is qualified. For samples whose decomposition rate after 14 days of hot storage fails, the room temperature samples are no longer subject to the 12-month and 24-month stability tests.

[0120] The decomposition rate is calculated using the content measured before storage as a reference. A decomposition rate of ≤5% after heat storage or room temperature storage is considered acceptable. The formula for calculating the decomposition rate is: Decomposition rate (%) = (content before storage - content after heat storage or room temperature storage) / content before storage × 100%.

[0121] The reagents and drugs used in the examples are all commercially available products, and the raw materials used are measured according to the 100% conversion.

[0122] Experimental Example 1: The purpose of this experiment is to detect whether different proportions of composite stabilizers can reduce the degradation of the active ingredient captan in an oily medium. A 35% captan dispersible oil suspension (oil-based susoension concentrate, oil dispersion, abbreviated OD) was selected for the corresponding experiment. However, this does not mean that other liquid preparations, such as emulsifiable concentrates, oils, and low-volume liquids cannot achieve the same purpose. Those skilled in the art select a suitable dispersion medium, wherein the dispersion medium of the oil is selected from any one or more of methyl oleate, toluene, xylene, trimethylbenzene, and solvent oil, and the dispersion medium of the low-volume liquid is selected from any one or more of toluene, xylene, trimethylbenzene, and solvent oil, and the captan liquid preparation with the target content can be configured.

[0123] 35% Captan Dispersible Oil Suspension

[0124] Weigh 350g of captan, 200g of emulsifier, an appropriate amount of composite stabilizer, 20g of suspension thixotropic agent, and make up the dispersion medium to 1000g.

[0125] The emulsifier selected in this experiment needs to be selected according to the original drug of captan, dispersion medium, etc. In this experimental example, the emulsifier selected is specifically 100g of nonylphenol polyoxyethylene ether, 80g of castor oil polyoxyethylene ether, and 20g of magnesium dodecylbenzenesulfonate; but this does not mean that technical personnel in this field cannot select other suitable emulsifiers, select suitable commercially available emulsifiers, and can obtain the target content of captan dispersible oil suspension.

[0126] The dispersion medium used in this experiment is selected from any one or more of soybean oil, methyl oleate, and rapeseed oil, specifically methyl oleate, but this does not mean that technical personnel in this field cannot select other suitable dispersion media, such as soybean oil, solvent oil, rapeseed oil, and select suitable emulsifiers to obtain a dispersible oil suspension of captan with the desired content.

[0127] The suspension thixotropic agent selected in this experiment is magnesium aluminum silicate. Those skilled in the art can also select other suitable suspension thixotropic agents to prepare a liquid preparation of captan with the desired content.

[0128] The composite stabilizer, nonylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, and magnesium dodecylbenzenesulfonate were added to methyl oleate and stirred and dispersed evenly. Then, captan was stirred and dispersed evenly again and then placed in a grinding mortar with a grinding medium for grinding. After the particle size of captan reached the target particle size, it was filtered to obtain a captan dispersible oil suspension. In this experimental example, the particle size D of the grinding liquid was 90 Less than 5 microns, the particle size D of the grinding fluid 95 Less than 8 microns.

[0129] The amount of compound stabilizer added can also be any value of 0.6 to 60 g, and other samples can be prepared according to the process of preparing 35% captan dispersible oil suspension as mentioned above. Due to the purpose of the experiment, this experimental example selected 5 groups of compound stabilizers, among which the organic acids selected were acetic acid, lactic acid, glutamic acid, adipic acid, and citric acid. However, this does not mean that those skilled in the art cannot achieve the purpose of the present invention by selecting other suitable organic acids. In fact, the inventors of this application have found through a large number of experiments that the organic acid selected for addition in the liquid preparation containing captan can be selected as long as its acidity coefficient (25°C) 2≤pKa≤5. If the acidity coefficient is lower than 2, the organic acid has a large polarity and is not easy to stabilize the liquid preparation containing captan. If the acidity coefficient is higher than 5, it is not easy to have a suitable concentration of H in the liquid preparation containing captan. + ions, making it difficult to stabilize the liquid preparation containing captan.

[0130] The ascorbic acid fatty acid ester of formula (I) is selected from ascorbic acid laurate, ascorbic acid olivate, ascorbic acid palmitate, and ascorbic acid stearate, and the ascorbic acid fatty acid ester derivative of formula (I) is selected from palmitoyl ascorbic acid magnesium salt. However, this does not mean that those skilled in the art cannot achieve the purpose of the present invention by selecting other suitable ascorbic acid fatty acid esters or their derivatives. In fact, through a large number of experiments, the inventors of the present application have found that when R in formula (I) is independently a monovalent hydrocarbon group having 9 to 21 carbon atoms, the purpose of the present invention can be achieved.

[0131] The ascorbic acid fatty acid ester or its derivative component of formula (I) of the composite stabilizer is first dispersed in a dispersant, then uniformly mixed with the organic acid or its derivative component of the composite stabilizer and a wetting dispersant, and then added into water and stirred to disperse uniformly; wherein the dispersant is selected from one or a combination of ethanol, ethylene glycol, propylene glycol, and glycerin.

[0132] The above samples were simultaneously subjected to pre-storage content determination, room temperature stability testing, and hot storage testing. The hot storage samples were placed in an oven at a set temperature of 54±2°C for 14 days, and the room temperature samples were stored for 12 and 24 months, respectively. The content of captan in the pre-storage samples, hot storage samples, and samples stored at different times at room temperature was determined by high-performance liquid chromatography, and the decomposition rate was calculated. The results are shown in Table 1. The test data in the table are the average of more than three test results.

[0133] Comparative Example 1: The formulation and preparation method of the 35% captan dispersible oil suspension prepared in Comparative Example 1 are substantially the same as those in Example 1, except that acetic acid is used in place of the composite stabilizer in Example 1 in an amount of 1.5 wt %.

[0134] Comparative Example 2: Figure 4 and Figure 5 As shown, the formula and preparation method of the 35% captan dispersible oil suspension prepared in Control Example 2 are substantially the same as those in Example 1. The difference between Control Example 2 and Example 1 is that ascorbic acid laurate is used to replace the composite stabilizer in Example 1 in an amount of 1.5 wt %.

[0135] Table 135% Captan dispersible oil suspension stability test results

[0136]

[0137] In the table, the relative decomposition rate of the sample after hot storage is higher than 5%, which is unqualified. The room temperature storage test is not carried out. The "-" in the table indicates that there is no test data. Component A is an organic acid, and component B is an ascorbic acid fatty acid ester of formula (I) or its derivative; A:B is the mass ratio of component A to component B. If A:B is 6:2.5, then component A (acetic acid) is 5g and component B (ascorbic laurate) is 2.5g. If A:B is 7:5, then component A (lactic acid) is 7g and component B (ascorbic olivetate) is 5g, and so on.

[0138] In Table 1, A1 is acetic acid, A2 is lactic acid, A3 is glutamic acid, A4 is adipic acid, and A5 is citric acid; B1 is ascorbyl laurate, B2 is ascorbyl olivate, B3 is ascorbyl palmitate, B4 is ascorbyl stearate, and B5 is magnesium palmitoyl ascorbate. In Table 1, CK1 is Comparative Example 1, and CK2 is Comparative Example 2.

[0139] As can be seen from the test result of Table 1, owing to need to be added with 20% emulsifying agent in the 35% captan dispersible oil suspension formula, so that use makes dispersible oil suspension have hydrophilic component.In 35% captan dispersible oil suspension, add composite stabilizer of the present invention, can keep effective ingredient captan stable in storage process, 1~No. 5 sample degradation rates of the embodiment of the present invention 1 are all lower than control example 1 (CK1) and control example 1 (CK2), also find that storage 12 months degradation rate is generally lower than half the storage 24 months degradation rate, reason may be that in the normal temperature storage process, formulation system may absorb water from environment.

[0140] Example 2: The purpose of this experiment is to detect different proportions of composite stabilizers that can reduce the degradation of the active ingredient captan in a dispersion medium of water. A 40% pyraclostrobin captan suspension was selected for configuration to carry out the corresponding experiment, but this does not mean or be interpreted as captan cannot be compounded with other active ingredients to achieve the same purpose. Those skilled in the art select suitable other active ingredients, such as difenoconazole, tebuconazole, trifloxystrobin, picoxystrobin, polyoxin, bromothionil and other active ingredients, and select suitable wetting dispersants to obtain a liquid preparation of captan compounded with other active ingredients of the purpose content.

[0141] 40% pyraclostrobin·captan suspension concentrate

[0142] Weigh 350 g of captan, 50 g of pyraclostrobin, 80 g of wetting and dispersing agent, an appropriate amount of composite stabilizer, 30 g of antifreeze, 2 g of preservative, 20 g of thickener, 2 g of defoaming agent, and make up the dispersion medium to 1000 g with water.

[0143] In this experimental example, the wetting and dispersing agent is specifically 40g of a polycarboxylate wetting and dispersing agent and 40g of a non-ionic hydroxy polyethylene oxide block copolymer wetting and dispersing agent. However, technical personnel in this field can select other suitable wetting and dispersing agents. The wetting and dispersing agents that can be selected by technical personnel in this field include at least one of polycarboxylates, sulfonates, EOPO polyethers, and phosphates, among which phosphates include but are not limited to tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and castor oil polyoxyethylene ether phosphate, and the liquid preparation of the compound of the target content of captan and other active ingredients is prepared, including 40% pyraclostrobin·captan suspension.

[0144] In this experimental example, the inventors of the present application selected suitable antifreeze agents, including but not limited to ethylene glycol, propylene glycol, and glycerin. In this experimental example, ethylene glycol was specifically selected as the antifreeze agent.

[0145] In this experimental example, the inventors of the present application selected suitable preservatives, including but not limited to preservatives including but not limited to kason, sodium benzoate, etc. The antifreeze agent in this experimental example is specifically kason, which is a mixture of 2-methyl-4-isothiazolin-3-one (MI) and 2-methyl-5-chloro-4-isothiazolin-3-one (CMI) and an inorganic salt stabilizer, usually CMI:MI=3:1.

[0146] In this experimental example, the inventors of the present application selected suitable thickeners, including organic thickeners and inorganic thickeners, wherein the organic thickeners include but are not limited to xanthan gum, and the inorganic thickeners include but are not limited to magnesium aluminum silicate. More specifically, in this experimental example, a combination of 3g of xanthan gum and 17g of magnesium aluminum silicate was selected.

[0147] In this experimental example, the inventors of the present application selected a suitable defoaming agent, including but not limited to an organosilicon defoaming agent and n-octanol. More specifically, the defoaming agent selected in this experimental example is an organosilicon defoaming agent.

[0148] In this experimental example, the dispersion medium selected is water, more specifically, the dispersion medium selected is deionized water; deionized water is a colorless, clear liquid, odorless, and tasteless, with a resistivity greater than 0.5 MΩ·cm (megaohm·centimeter), and the maximum resistivity can reach 18 MΩ·cm.

[0149] The amount of composite stabilizer added can also be any numerical value of 0.6 to 60 g, and other samples are prepared according to the process of preparing 40% pyraclostrobin·captan suspension concentrate. Due to the purpose of facilitating experimental comparison, this experimental example selected 5 groups of composite stabilizers. More specifically, the types of organic acids selected are shown in Table 2, and the types of ascorbic acid fatty acid esters or their derivatives are also shown in Table 2. However, this does not mean that those skilled in the art cannot achieve the purpose of the present invention by selecting other suitable organic acids and ascorbic acid fatty acid esters or their derivatives. In fact, the inventors of the present application have found through a large number of experiments that as long as the organic acid has an acidity coefficient (25°C) 2≤pKa≤5 and R in formula (I) is independently a monovalent hydrocarbon group having 9 to 21 carbon atoms, the purpose of the present invention can be achieved.

[0150] The composite stabilizer and the wetting dispersant are added to water and stirred and dispersed evenly to obtain an additive dispersion liquid; pyraclostrobin and captan are added to the additive dispersion liquid and stirred and dispersed evenly, and then placed under a grinding medium for grinding. After the particle size of pyraclostrobin and captan reaches the target particle size, the grinding liquid is filtered to obtain a grinding liquid; in this experimental example, the particle size D of the grinding liquid is 90 Less than 5 microns, the particle size D of the grinding fluid 95The antifreeze agent and thickener are stirred and dispersed uniformly, then added to water, and then the preservative is added and stirred and dispersed uniformly to obtain a thickened dispersion. The grinding liquid is mixed with the thickened dispersion and stirred and dispersed uniformly to obtain a 40% pyraclostrobin-captan suspension.

[0151] The above samples were simultaneously subjected to pre-storage content determination, room temperature stability testing, and hot storage testing. The hot storage samples were placed in an oven at a set temperature of 54±2°C for 14 days, and the room temperature samples were stored for 12 and 24 months, respectively. The content of captan in the pre-storage samples, hot storage samples, and samples stored at different times at room temperature was determined by high-performance liquid chromatography, and the decomposition rate was calculated. The results are shown in Table 1. The test data in the table are the average of more than three test results.

[0152] Comparative Example 3: The formula and preparation method of the 40% pyraclostrobin·captan suspension concentrate configured in Comparative Example 3 are basically the same as those in Example 2, except that Comparative Example 3 uses acetic acid instead of the composite stabilizer in Example 2 in an amount of 1.5wt%.

[0153] Comparative Example 4: The formula and preparation method of the 40% pyraclostrobin·captan suspension concentrate configured in Comparative Example 4 are basically the same as those in Example 2, and are different from Example 2 and Comparative Example 3 in that Comparative Example 4 uses ascorbyl palmitate instead of the composite stabilizer in Example 2 in an amount of 1.5wt%.

[0154] The inventors of this application found that the change rate of Example Samples 6 to 10 and Comparative Example Samples 3 to 4 was about 0.2% after 14 days of hot storage and 24 months of storage at room temperature; among the samples after storage, Example Samples 6 to 10 performed normally, as shown in Figure 3.

[0155] Comparative Example Samples 3 to 4 have obvious abnormalities. Taking Comparative Example Sample 4 as an example, Figure 1 After 14 days of heat storage, the sample of the comparative example 4 becomes very viscous and difficult to sample. Figure 2 As shown in FIG. 4 , the pourability of the comparative example sample 4 also deteriorated, so that it could not be tested. Figure 3 As shown, after the control example sample 4 was hot stored for 14 days, when it was diluted with water for suspension rate test, it can be seen that obvious sediment appeared in the 25mL sample state of the dilution at the bottom of the graduated cylinder.

[0156] The inventors of the present application also found that the control example sample 4 had obvious bottoming after 24 months of hot storage and room temperature. After pouring out the upper layer of the hot storage sample, the active ingredient captan was detected to be 20.88wt% and pyraclostrobin was 6.01wt%. However, after shaking the hot storage sample and then testing it, the active ingredient captan was detected to be 36.24wt% and pyraclostrobin was 5.86%.

[0157] Table 2 Storage stability test results of 40% pyraclostrobin·captan suspension concentrate

[0158]

[0159] In Tables 2 and 3, the relative decomposition rate of the sample in Example 1 after hot storage was higher than 5%, which was unqualified, and the room temperature storage test was not carried out. In the table, "-" indicates that there is no test data. Component A is an organic acid, and component B is an ascorbic acid fatty acid ester of formula (I) or its derivative; A:B is the mass ratio of component A to component B. For example, if component A6 (propionic acid) is 5g and component B6 (ascorbic dipalmitate) is 25g, then A:B is 5:25; if component A7 (glycolic acid) is 2.5g and component B7 (ascorbic acid tetraisopalmitate) is 50g, then A:B is 2.5:50, and so on.

[0160] In Tables 2 and 3, A6 is propionic acid, A7 is glycolic acid, A8 is citric acid, A9 is glutaric acid, and A10 is adipic acid; B6 is ascorbyl dipalmitate, B7 is ascorbyl tetraisopalmitate, B8 is ascorbyl palmitate, B9 is ascorbyl tetrapalmitate, and B10 is trisodium ascorbyl palmitate phosphate.

[0161] In Table 2 and Table 3, CK3 is Control Example 3, and CK4 is Control Example 4.

[0162] As can be seen from the results in Table 2, the degradation rates of samples 6 to 10 of the present invention are significantly lower than those of control samples CK3 to CK4. No organic acid is added to CK4. Even though 2 wt % ascorbyl palmitate is added as a stabilizer, the degradation rate of captan is as high as 14.3% after 14 days of hot storage and as high as 16.9% at room temperature, indicating poor stability. Only organic acid is added to CK3. Although the degradation rate of captan reaches the qualified level of 4.3%, the degradation rate of pyraclostrobin rises to 6.9%, which is an unqualified level.

[0163] The inventor further detected the changes in the pH values ​​of the samples before and after heat storage, and found that the pH values ​​of samples 6 to 10 of this embodiment 2 were 4.10 to 5.93 before heat storage and 3.91 to 5.65 after heat storage, the pH value of the CK3 sample was 3.09 before heat storage and 2.82 after heat storage, and the pH value of the CK4 sample was 5.90 before heat storage and 4.18 after heat storage; the pH values ​​of the samples changed before and after room temperature storage, and found that the pH values ​​of samples 6 to 10 of Example 1 were 4.10 to 5.93 before room temperature storage and 3.59 to 5.56 after room temperature storage, and found that the pH value of the CK3 sample at room temperature storage was 3.09 and 2.82 at room temperature storage, and the pH value of the CK4 sample at room temperature storage was 3.09 before and 2.63 after room temperature storage. Based on the above data, the inventor of the present application speculates that the degradation of captan may lead to acidification of the system.

[0164] Table 3 Physical stability test results of 40% pyraclostrobin·captan suspension concentrate

[0165]

[0166] As can be seen from the result of Table 3, the apparent stability of samples 6 to 10 of the present invention is all obviously better than control samples CK3 to CK4. CK3 only adds organic acid citric acid. Since the wetting and dispersing agent reduces the wetting and dispersing performance under acidic conditions, the sample water separation rate is increased to 18%, resulting in unqualified apparent stability. In CK4, captan is not added with organic acid. Even if 2wt% ascorbyl palmitate is added as a stabilizer, because of captan degradation, the CK4 sample water separation rate is increased to a certain extent. Although lower than CK3, it is much higher than samples 6 to 10 of the present invention. Boiling phenomenon also occurs, and the particle size is also enlarged to a certain extent.

[0167] The inventors also found through experiments that controlling the particle size of the 40% pyraclostrobin·captan suspension grinding liquid can also solve the bottoming problem of CK3 and CK4 to a certain extent. 90 Less than 5 microns, especially for further grinding liquid particle size D 95 The problem of particle size growth of CK3 and CK4 is solved to a certain extent. Although the particle size of the microparticles also grows, the problem of particle size growth is better solved after adding the composite stabilizer of the present invention. The inventors of this application have developed 20% pyraclostrobin·captan seed treatment suspension and 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension and found that by controlling the particle size D 90 and D 95 , under the same conditions, it can also solve the bottoming problem to a certain extent.

[0168] The above test results show that adding the composite stabilizer of the present invention to the 40% pyraclostrobin·captan suspension concentrate can keep the active ingredient pyraclostrobin stable during storage.

[0169] Example 3: The purpose of this experiment is to configure different proportions of composite stabilizers to reduce the degradation of the active ingredient captan in water as a dispersion medium, as well as the stability of the liquid formulation system after adding a film-forming agent. 20% pyraclostrobin captan seed treatment suspension was selected for configuration to carry out corresponding experiments, but this does not mean or be interpreted as captan cannot be compounded with other active ingredients to achieve the same purpose. Those skilled in the art select suitable other active ingredients, such as difenoconazole, tebuconazole, trifloxystrobin, picoxystrobin, polyoxin, bromothionil and other active ingredients, and select suitable wetting dispersants to obtain the purpose content of captan and the seed treatment suspension compounded with other active ingredients.

[0170] 20% pyraclostrobin·captan seed treatment suspension concentrate

[0171] Weigh 150g of captan, 50g of pyraclostrobin, 60g of wetting and dispersing agent, an appropriate amount of composite stabilizer, 30g of antifreeze agent, 2g of preservative, 10g of thickener, 2g of defoamer, 30g of film-forming agent, 30g of warning color dye, and make up the dispersion medium to 1000g with water.

[0172] In this experimental example, the wetting and dispersing agent is specifically 30g of a polycarboxylate wetting and dispersing agent and 30g of a non-ionic hydroxy polyethylene oxide block copolymer wetting and dispersing agent. However, technical personnel in this field can select other suitable wetting and dispersing agents. The wetting and dispersing agents that can be selected by technical personnel in this field include at least one of polycarboxylates, sulfonates, EOPO polyethers, and phosphates, among which phosphates include but are not limited to tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and castor oil polyoxyethylene ether phosphate, and the liquid preparation of the compound of the target content of captan and other active ingredients is prepared, including 20% ​​pyraclostrobin·captan treated suspension.

[0173] In this experimental example, the inventors of the present application selected suitable antifreeze agents, including but not limited to ethylene glycol, propylene glycol, and glycerin. In this experimental example, ethylene glycol was specifically selected as the antifreeze agent.

[0174] In this experimental example, the inventors of the present application selected suitable preservatives, including but not limited to preservatives including but not limited to kason, sodium benzoate, etc. The antifreeze agent in this experimental example is specifically kason, which is a mixture of 2-methyl-4-isothiazolin-3-one (MI) and 2-methyl-5-chloro-4-isothiazolin-3-one (CMI) and an inorganic salt stabilizer, usually CMI:MI=3:1.

[0175] In this experimental example, the inventors of the present application selected suitable thickeners, including organic thickeners and inorganic thickeners, wherein the organic thickeners include but are not limited to xanthan gum, and the inorganic thickeners include but are not limited to magnesium aluminum silicate. More specifically, in this experimental example, a combination of 1g of xanthan gum and 9g of magnesium aluminum silicate was selected.

[0176] In this experimental example, the inventors of the present application selected a suitable film-forming agent, which includes but is not limited to acrylic emulsion, polyethylene glycol, and polyvinyl alcohol. The content of the film-forming agent is 0.5wt% to 5wt%. More specifically, the film-forming agent selected in this experimental example is acrylic emulsion.

[0177] One purpose of the inventors of this application in selecting thickeners and film-forming agents is to adjust the viscosity of the seed treatment suspension at 20°C to 170-200 mPa·s and the viscosity at 40°C to 120-150 mPa·s. Those skilled in the art can achieve the purpose of the present invention by adjusting the dosage and selecting the corresponding types of raw materials.

[0178] In this experimental example, the warning color dye is selected from one or more of Dekma, alkaline rose essence, water-based rose red, and acid scarlet, and the amount used is 2.5-5.5wt%; more specifically, acid scarlet is selected as the warning color dye.

[0179] In this experimental example, the inventors of the present application selected a suitable defoaming agent, including but not limited to silicone defoaming agent, n-octanol, and lauryl alcohol. More specifically, the defoaming agent selected in this experimental example is silicone defoaming agent.

[0180] In this experimental example, the dispersion medium selected is water, more specifically, the dispersion medium selected is deionized water; deionized water is a colorless, clear liquid, odorless, and tasteless, with a resistivity greater than 0.5 MΩ·cm (megaohm·centimeter), and the maximum resistivity can reach 18 MΩ·cm.

[0181] The amount of composite stabilizer added can also be any numerical value of 0.3 to 31.5 g, and other samples are prepared according to the process of preparing 20% ​​pyraclostrobin captan suspension concentrate with the above-mentioned formula. Due to the purpose of facilitating experimental comparison, this experimental example selected 5 groups of composite stabilizers. More specifically, the types of organic acids are shown in Table 4, and the types of ascorbic acid fatty acid esters or their derivatives are also shown in Table 4. However, this does not mean that those skilled in the art cannot achieve the purpose of the present invention by selecting other suitable organic acids and ascorbic acid fatty acid esters or their derivatives. In fact, the inventors of the present application have found through a large number of experiments that the organic acid can achieve the purpose of the present invention as long as its acidity coefficient (25°C) 2≤pKa≤5 and R in formula (I) is independently a monovalent hydrocarbon group with 9 to 21 carbon atoms.

[0182] The composite stabilizer and the wetting dispersant are added to water and stirred and dispersed evenly to obtain an additive dispersion liquid; pyraclostrobin and captan are added to the additive dispersion liquid and stirred and dispersed evenly, and then placed under a grinding medium for grinding. After the particle size of pyraclostrobin and captan reaches the target particle size, the grinding liquid is filtered to obtain a grinding liquid; in this experimental example, the particle size D of the grinding liquid is 90 Less than 5 microns, the particle size D of the grinding fluid 95 Less than 8 microns. The antifreeze agent and thickener are stirred and dispersed uniformly, then added to water. The preservative is then added and stirred and dispersed uniformly to obtain a thickened dispersion. The grinding fluid is mixed with the thickened dispersion, film-forming agent, and warning color dye, and stirred and dispersed uniformly to obtain a 20% pyraclostrobin-captan seed treatment suspension concentrate.

[0183] The above samples were simultaneously subjected to pre-storage content determination, room temperature stability testing, and hot storage testing. The hot storage samples were placed in an oven at a set temperature of 54±2°C for 14 days, and the room temperature samples were stored for 12 and 24 months, respectively. The content of captan in the pre-storage samples, hot storage samples, and samples stored at different times at room temperature was determined by high-performance liquid chromatography, and the decomposition rate was calculated. The results are shown in Table 1. The test data in the table are the average of more than three test results.

[0184] Comparative Example 5: The formula and preparation method of the 20% pyraclostrobin·captan seed treatment suspension concentrate configured in Comparative Example 5 are basically the same as those in Example 3. The difference from Example 3 is that Comparative Example 5 uses acetic acid instead of the composite stabilizer in Example 3 in an amount of 0.5wt%.

[0185] Comparative Example 6: The formula and preparation method of the 20% pyraclostrobin·captan seed treatment suspension concentrate configured in Comparative Example 6 are basically the same as those in Example 3, except that Comparative Example 6 uses acetic acid to replace the composite stabilizer in Example 3, and is different from Comparative Example 5 in that the amount of acetic acid used in Comparative Example 6 is 2wt%.

[0186] Table 4 Storage stability test results of 20% pyraclostrobin·captan seed treatment suspension concentrate

[0187]

[0188] In Table 4 and Table 5, the relative decomposition rate of the sample in Example 3 after hot storage is higher than 5%, which is unqualified and does not undergo the normal temperature storage test. In the table, "-" indicates that there is no test data. Component A is an organic acid, and component B is an ascorbic acid fatty acid ester of formula (I) or its derivative; A:B is the mass ratio of component A to component B. If component A11 (acetic acid) is 5g and component B11 (ascorbic laurate) is 20g, then A:B is 5:20; if component A12 (butenedioic acid) is 4g and component B12 (ascorbic olivetate) is 15g, then A:B is 4:15, and so on.

[0189] In Tables 4 and 5, A11 is acetic acid, A12 is butenedioic acid, A13 is adipic acid, A14 is dodecylbenzenesulfonic acid, and A15 is methylbenzenesulfonic acid; B11 is ascorbyl laurate, B12 is ascorbyl olivate, B13 is ascorbyl palmitate, B14 is ascorbyl stearate, and B15 is palmitoyl ascorbate magnesium salt.

[0190] In Tables 4 and 5, CK5 is Control Example 5, and CK6 is Control Example 6.

[0191] As can be seen from the results in Table 4, the degradation rates of samples 11 to 15 of the 20% pyraclostrobin·captan seed treatment suspension concentrate of the present invention were significantly lower than those of the control samples CK5 to CK6. No organic acid was added to CK6, and even with the addition of 2 wt % ascorbic acid laurate as a stabilizer, the degradation rate of captan was as high as 8.36% after 14 days of hot storage, and as high as 10.18% when stored at room temperature, indicating poor stability.

[0192] The inventors further detected the changes in the pH values ​​of the samples before and after heat storage, and found that the pH values ​​of samples 11 to 15 of Example 3 were 4.50 to 5.96 before heat storage and 4.36 to 5.72 after heat storage, the pH value of the CK5 sample was 3.02 before heat storage and 2.76 after heat storage, the pH value of the CK6 sample was 6.49 before heat storage and 4.27 after heat storage; therefore, the pH value of the samples of the present invention in Example 3 changed less; the pH values ​​of the samples changed before and after room temperature storage, and found that the pH values ​​of samples 6 to 10 of Example 1 were 4.50 to 5.96 before room temperature storage and 4.34 to 5.62 after room temperature storage, the pH value of the CK5 sample was 3.02 before room temperature storage and 2.65 after room temperature storage, and the pH value of the CK6 sample was 6.49 before room temperature storage and 4.03 after room temperature storage. The degradation of captan may lead to acidification of the system, thereby increasing the degradation rate of pyraclostrobin.

[0193] CK5 only added organic acid acetic acid. Although the degradation rate of captan reached the qualified level of 3.74%, the degradation rate of pyraclostrobin increased to 7.74%, which was an unqualified level. The reason was that pyraclostrobin was unstable under acidic conditions, resulting in an increased degradation rate.

[0194] Table 5 Physical stability test results of 20% pyraclostrobin·captan seed treatment suspension concentrate

[0195]

[0196] As can be seen from the results in Table 5, the apparent stability of samples 11 to 15 of the present invention is significantly better than that of control samples CK5 to CK6. CK5 only contains acetic acid, an organic acid. Due to the reduced wetting and dispersing properties of the wetting and dispersing agent under acidic conditions, the sample water separation rate increases to 10%, resulting in unqualified apparent stability. CK6 does not contain an organic acid. Even with the addition of 2 wt % ascorbyl laurate as a stabilizer, the degradation of captan causes the CK6 sample to have a certain water separation rate, which is lower than that of CK5 but higher than that of samples 6 to 10 of the present invention. CK5 to CK6 also experience a bottoming phenomenon, and the particle size also increases to a certain extent.

[0197] The above test results show that adding the composite stabilizer of the present invention to the 20% pyraclostrobin·captan seed treatment suspension concentrate can keep the active ingredients pyraclostrobin and captan stable during storage.

[0198] The inventors of the present invention also used the samples of this experimental example and CK5 and CK6 for seed coating, see Figure 6 and Figure 7 The experimental samples have certain surface activity and lipophilicity due to the addition of ascorbic acid fatty acid esters and their derivatives, so that the seeds after coating have good film-forming agents and uniform film formation, and also show high brightness, good appearance, and good smoothness, so that the seeds do not stick together, and the seeds are planted evenly, without affecting sowing and causing missing seedlings and broken ridges; and because ascorbic acid fatty acid esters and their derivatives have antioxidant ability, they can prevent pigments and effective ingredients from being oxidized, so the seeds after coating are bright in color and have good appearance. Ascorbic acid fatty acid esters and their derivatives have stress resistance, are safe for seeds, and do not affect the germination rate.

[0199] Example 4: The purpose of this experiment is to configure different proportions of composite stabilizers to reduce the degradation of the active ingredient pyraclostrobin in water as a dispersion medium, as well as the stability of the liquid formulation system after the addition of a film-forming agent. A 7% pyraclostrobin·fludioxonil·thiamethoxam seed treatment suspension was selected for corresponding experiments, but this does not mean or be interpreted as pyraclostrobin cannot be compounded with other active ingredients to achieve the same purpose. Technicians in this field select suitable other active ingredients, such as difenoconazole, tebuconazole, trifloxystrobin, picoxystrobin, polyoxin, bromothionil and other active ingredients, and select suitable wetting and dispersing agents to obtain a seed treatment suspension of the target content of captan compounded with other active ingredients.

[0200] Pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate

[0201] Weigh an appropriate amount of pesticide active ingredient, 60g of wetting and dispersing agent, an appropriate amount of stabilizing and safening agent, 30g of antifreeze agent, 2g of preservative, 20g of thickener, 2g of defoaming agent, 30g of film-forming agent, 30g of warning color dye, and make up the dispersion medium to 1000g with water.

[0202] In this experimental example, the inventors of the present application selected the active ingredients of the pesticide as pyraclostrobin, fludioxonil, and clothianidin. The mass ratio of pyraclostrobin, fludioxonil, and clothianidin is (1-5):1:(10-100), and the dosage is 4-40wt%. Preferably, the dosage is 5-25wt%. More preferably, the active ingredient of the pesticide in this experimental example is 7wt%.

[0203] In this experimental example, the wetting and dispersing agent is specifically 30g of a polycarboxylate wetting and dispersing agent and 30g of a non-ionic hydroxy polyethylene oxide block copolymer wetting and dispersing agent. However, technical personnel in this field can select other suitable wetting and dispersing agents. The wetting and dispersing agents that can be selected by technical personnel in this field include at least one of polycarboxylates, sulfonates, EOPO polyethers, and phosphates, among which phosphates include but are not limited to tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and castor oil polyoxyethylene ether phosphate, and the liquid preparation of compound of captan and other active ingredients with the target content is prepared, including 7% pyraclostrobin·fluanid·thiamethoxam seed treatment suspension.

[0204] In this experimental example, the inventors of the present application selected suitable antifreeze agents, including but not limited to ethylene glycol, propylene glycol, and glycerin. In this experimental example, ethylene glycol was specifically selected as the antifreeze agent.

[0205] In this experimental example, the inventors of the present application selected suitable preservatives, including but not limited to preservatives including but not limited to kason, sodium benzoate, etc. The antifreeze agent in this experimental example is specifically kason, which is a mixture of 2-methyl-4-isothiazolin-3-one (MI) and 2-methyl-5-chloro-4-isothiazolin-3-one (CMI) and an inorganic salt stabilizer, usually CMI:MI=3:1.

[0206] In this experimental example, the inventors of the present application selected suitable thickeners, including organic thickeners and inorganic thickeners, wherein the organic thickeners include but are not limited to xanthan gum, and the inorganic thickeners include but are not limited to magnesium aluminum silicate. More specifically, in this experimental example, a combination of 2g of xanthan gum and 18g of magnesium aluminum silicate was selected.

[0207] In this experimental example, the inventors of the present application selected a suitable film-forming agent, which includes but is not limited to acrylic emulsion, polyethylene glycol, and polyvinyl alcohol. The content of the film-forming agent is 0.5wt% to 5wt%. More specifically, the film-forming agent selected in this experimental example is acrylic emulsion.

[0208] One purpose of the inventors of this application in selecting thickeners and film-forming agents is to adjust the viscosity of the seed treatment suspension at 20°C to 170-200 mPa·s and the viscosity at 40°C to 120-150 mPa·s. Those skilled in the art can achieve the purpose of the present invention by adjusting the dosage and selecting the corresponding types of raw materials.

[0209] In this experimental example, the warning color dye is selected from one or more of Dekma, alkaline rose essence, water-based rose red, and acid scarlet, and the amount used is 2.5-5.5wt%; more specifically, water-based rose red is selected as the warning color dye.

[0210] In this experimental example, the inventors of the present application selected a suitable defoaming agent, including but not limited to silicone defoaming agent, n-octanol, and lauryl alcohol. More specifically, the defoaming agent selected in this experimental example is silicone defoaming agent.

[0211] In this experimental example, the dispersion medium selected is water, more specifically, the dispersion medium selected is deionized water; deionized water is a colorless, clear liquid, odorless, and tasteless, with a resistivity greater than 0.5 MΩ·cm (megaohm·centimeter), and the maximum resistivity can reach 18 MΩ·cm.

[0212] The amount of the stabilizer added can also be any value between 0.6 and 60 g. Other samples can be prepared according to the process for preparing 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate with the above formula. For the purpose of facilitating experimental comparison, this experimental example selected 5 groups of stabilizers and safeners. More specifically, the types of organic acids selected are shown in Table 6. Similarly, the types of ascorbic acid fatty acid esters or their derivatives are shown in Table 6. However, this does not mean that those skilled in the art cannot achieve the purpose of the present invention by selecting other suitable organic acids and ascorbic acid fatty acid esters or their derivatives. In fact, through a large number of experiments, the inventors of the present application found that as long as the organic acid has an acidity coefficient (25°C)2≤pKa≤5 and R in formula (I) is independently a monovalent hydrocarbon group having 9 to 21 carbon atoms, the purpose of the present invention can be achieved. More importantly, the purpose of adding organic acid to the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate is somewhat different from that of Experimental Example 1. The purpose of adding stress-resistant organic acid to the seed treatment suspension concentrate of the present invention is to increase the vitamin C content and soluble solids content in the crop body, as well as the stress resistance of the crop. The pH value of the seed treatment suspension concentrate can also be adjusted to the target range by adding organic acid. Therefore, when the pH value of the seed treatment suspension concentrate is already within the target pH range, the organic acid can also be omitted.

[0213] The stabilizer and the wetting dispersant are added to water and stirred and dispersed evenly to obtain an additive dispersion; pyraclostrobin, fludioxonil and clothianidin are added to the additive dispersion and stirred and dispersed evenly, and then placed under a grinding medium for grinding. After the particle size of pyraclostrobin, fludioxonil and clothianidin reaches the target particle size, the grinding liquid is filtered to obtain the grinding liquid; in this experimental example, the particle size D of the grinding liquid is 90 Less than 5 microns, the particle size D of the grinding fluid 95 Less than 8 microns. The antifreeze agent and thickener are stirred and dispersed uniformly, then added to water. The preservative is then added and stirred and dispersed uniformly to obtain a thickened dispersion. The grinding fluid is mixed with the thickened dispersion, film-forming agent, and warning color dye, and stirred and dispersed uniformly to obtain a 7% pyraclostrobin, fludioxonil, and clothianidin seed treatment suspension concentrate.

[0214] The above samples were simultaneously subjected to pre-storage content determination, room temperature stability testing, and hot storage testing. The hot storage samples were placed in an oven at a set temperature of 54±2°C for 14 days, and the room temperature samples were stored for 12 and 24 months, respectively. The content of captan in the pre-storage samples, hot storage samples, and samples stored at different times at room temperature was determined by high-performance liquid chromatography, and the decomposition rate was calculated. The results are shown in Table 1. The test data in the table are the average of more than three test results.

[0215] Comparative Example 7: The formulation and preparation method of the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate configured in Comparative Example 7 are substantially the same as those in Example 4, except that Comparative Example 7 uses acetic acid instead of the composite stabilizer in Example 4 in an amount of 1.5 wt%.

[0216] Comparative Example 8: The formula and preparation method of the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate configured in Comparative Example 8 are basically the same as those in Example 4. The difference from Example 4 and Comparative Example 7 is that Comparative Example 8 uses triethanolamine instead of the composite stabilizer in Example 4 in an amount of 1.5wt%.

[0217] Table 6 Storage stability test results of 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate

[0218]

[0219]

[0220] In table 6 and table 7, sample relative decomposition rate after hot storage is higher than 5% in embodiment 4, is unqualified, then does not carry out normal temperature storage test, and "-" represents that there is no test data in the table. Component A is an organic acid, and component B is ascorbic acid fatty acid ester of formula (I) or its derivative; A:B is the mass ratio of component A and component B, and if component A (fulvic acid) is 10g, and component B (ascorbic laurate) is 2.5g, then A:B is 10:2.5, if component A is zero, and component B (ascorbic acid tetraisopalmitate) is 5g, then A:B is 0:5, and so on.

[0221] In Tables 6 and 7, A16 is blank and no organic acid is added, A17 is fulvic acid, A18 is malic acid, A19 is glycine, and A20 is citric acid; B16 is ascorbyl dipalmitate, B17 is ascorbyl tetraisopalmitate, B18 is ascorbyl palmitate, B19 is ascorbyl tetrapalmitate, and B20 is trisodium ascorbyl palmitate phosphate; and B21 is triethanolamine.

[0222] In Tables 6 and 7, CK7 is Control Example 7, and CK8 is Control Example 8.

[0223] As can be seen from the results in Table 6, the stabilizer of the present invention was used in a 7% pyraclostrobin, fludioxonil, and clothianidin seed treatment suspension concentrate. The degradation rates of experimental samples 16 to 20 were significantly lower than those of control samples CK7 to CK8. Addition of the organic acid glycine to CK7 resulted in an unsatisfactory 14.38% degradation rate of clothianidin after 14 days of hot storage. Because the entire system was in acidic conditions, the pyraclostrobin degradation rate reached 6.26%, while the degradation rate reached 6.67% when stored at room temperature. The degradation rate of fludioxonil reached 5.95%, reaching 6.03% when stored at room temperature, indicating poor stability. When triethanolamine, an organic base, was added to CK8, the degradation rate of clothianidin was qualified at 4.94% after 14 days of hot storage. However, the entire system was placed under alkaline conditions. The degradation rate of pyraclostrobin was as high as 6.73% after 14 days of hot storage, and as high as 6.90% when stored at room temperature. The degradation rate of fludioxonil was 6.19% and 6.30% when stored at room temperature, indicating poor stability.

[0224] Therefore, the inventors of the present application have discovered that the ascorbic acid fatty acid ester or its derivative and the composite stabilizer of the present invention can also stabilize the active ingredient clothianidin which is stable in a weak alkaline solution.

[0225] Table 7 Physical stability test results of 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate

[0226]

[0227] The results in Table 7 show that the apparent stability of samples 16-20 from Example 4 of the present invention is significantly superior to that of control samples CK7-CK8. CK7, which only incorporates the organic acid glycine, suffers from a water extraction rate of 12% due to the reduced wetting and dispersing properties of the wetting and dispersing agent under acidic conditions, resulting in a failure in apparent stability. CK8, which lacks the organic base triethanolamine, exhibits a water extraction rate comparable to that of samples 16-20. Furthermore, CK7 exhibits bottoming and a somewhat enlarged particle size.

[0228] The above test results show that adding the stabilizing safener of the present invention to the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate can keep the active ingredients pyraclostrobin, fludioxonil and clothianidin stable during storage.

[0229] The inventors of the present invention also used the samples of this experimental example and CK7 and CK8 to coat corn seeds, see Figure 8 and Figure 9Because ascorbic acid fatty acid esters and their derivatives are added to the samples of this experimental example, they have certain surface activity and lipophilicity, so that the seeds after coating have good film-forming agents and uniform film formation, and also show high brightness, good appearance, and good smoothness, so that the seeds do not stick together, and the seeds are planted evenly, without affecting sowing and causing missing seedlings and broken ridges; and because ascorbic acid fatty acid esters and their derivatives have antioxidant ability, they can prevent pigments and effective ingredients from being oxidized, so the seeds after coating are bright in color and have good appearance. Ascorbic acid fatty acid esters and their derivatives have stress resistance, are safe for seeds, and do not affect the germination rate.

[0230] Biological activity test example 1:

[0231] The purpose of this biological activity experiment is to test the effect of adding the composite stabilizer 40% pyraclostrobin·captan suspension concentrate of the present invention in reducing phytotoxicity.

[0232] 1. Materials and Methods

[0233] 1.1. Test materials

[0234] The test agents were samples prepared in Example 2, namely Sample 6 (sample number 6), Sample 7 (sample number 7), and Sample 8 (sample number 8), and the control sample was Control Example 3 (CK3). The test corn varieties were three conventional varieties commonly grown in Shandong Province: Zhengdan 958, Nonghua 101, and Nongda 108.

[0235] 1.2. Test methods

[0236] The experiment was conducted in Heze City, Shandong Province in 2021. Three corn varieties were tested, Zhengdan 958, Nonghua 101, and Nongda 108. Seedlings were raised and transplanted on May 8, 2021. The farmland was flat, with a medium water level and medium to high soil fertility. Planting was done in raised beds with a plant spacing of 30 cm and a row spacing of 50 cm. Every 667m 2 There are about 3,000 plants, and the fertilizer and water management and pest control measures during the corn seedling stage are at a medium level in the local area.

[0237] There were three test agents for 40% pyraclostrobin·caprolactone suspension concentrate. Each test agent had six treatments of 3000, 2000, 1000, 750, 500 and 250 times. The corresponding control sample CK3 test also had six treatments of 3000, 2000, 1000, 750, 500 and 250 times, as well as a water treatment. Each treatment had two replicates, each replicate had one plot, for a total of 50 plots, randomly arranged in blocks. About 20 corn plants were tested in each plot. The pesticide was applied in the afternoon on a cloudy day. The application tool was a hand-crank sprayer, and the whole plant was sprayed every 667m 2The application rate was approximately 150 L. During the trial, the pesticide was sprayed once on the afternoon of June 7 (cloudy day, 24-26°C). The growth stages of the varieties were: Zhengdan 958, Nonghua 101, and Nongda 108 were all at the 5-leaf stage.

[0238] 1.3. Survey Methodology

[0239] During the experiment, two surveys were conducted, one on 4 days and one on 11 days after the first application of pesticides. The specific survey times were June 11 (when the test corn was at the 6-7 leaf stage) and June 18 (when the test corn was at the 9-10 leaf stage).

[0240] The survey involves visually inspecting the effects of the pesticide on the crop: observing the effects of each test concentration on the heart and leaves of corn seedlings, any signs of pesticide damage, and observing changes in leaf color. If any pesticide damage is present, record the type and extent of the damage, as well as any beneficial effects on the crop (e.g., growth stimulation, accelerated maturity, etc.).

[0241] According to the pesticide damage grading method, record the pesticide damage situation of each plot, which is expressed as -, +, ++, +++, and ++++. The pesticide damage grading is:

[0242] -: No pesticide damage; +: Slight pesticide damage, which has a slight impact on the growth of corn seedlings and does not affect the normal growth of crops; ++: Mild pesticide damage, which can be recovered and has a slight impact on the growth of corn seedlings and will not cause crop yield reduction; +++: Obvious pesticide damage, which affects the normal growth of corn seedlings and causes a certain degree of loss to crop yield and quality; ++++: Severe pesticide damage, which hinders the growth of corn seedlings and causes serious losses in crop yield and quality.

[0243] 2. Results and Analysis

[0244] Four days after the first application, treatments with 3000x, 2000x, 1000x, and 750x of Sample 6 at the seedling stage showed no damage to the heart leaves of three corn varieties, demonstrating normal growth. Treatments with 500x and 250x of Sample 6 at the seedling stage showed no damage to the heart leaves and leaves of the three corn varieties, demonstrating normal growth. However, some minor damage occurred at the base of some young leaves, resulting in yellowing and chlorosis. This may be due to the liquid on the leaves flowing down to the base of the young leaves.

[0245] Table 8 Survey results of safety test on corn seedlings of sample 6

[0246]

[0247] Eleven days after the first application, treatments with Sample 6 at six test concentrations—3000x, 2000x, 1000x, 750x, 500x, and 250x—showed no damage to the heart leaves of the three corn varieties at the seedling stage, demonstrating normal growth. This indicates that the damage caused by Sample 6 was limited to the bases of individual young leaves. Over time, the damage gradually subsided, and normal vegetative growth, flowering, and fruiting in the middle and later stages of the corn crop were not affected.

[0248] Treatments with 3000x, 2000x, 1000x, and 750x concentrations of Sample 7 showed no damage to the heart leaves of the three corn varieties at the seedling stage, with normal growth. Treatment with 500x concentration of Sample 7 showed no damage to the heart leaves and leaves of Zhengdan 958 at the seedling stage, with normal growth, but caused slight damage to the bases of some young leaves, with symptoms of yellowing and chlorosis. However, treatments with 250x concentration of Sample 7 showed no damage to the heart leaves of the three corn varieties at the seedling stage, with normal growth, but caused slight damage to the bases of some young leaves, with symptoms of yellowing and chlorosis.

[0249] Table 9 Survey results of safety test on corn seedlings of sample 7

[0250]

[0251]

[0252] Eleven days after the first application, six test concentrations of Sample 7 (3000x, 2000x, 1000x, 750x, 500x, and 250x) showed no phytotoxicity to the heart leaves of three corn varieties at the seedling stage, demonstrating normal growth. Therefore, the phytotoxicity caused by Sample 7 was limited to the bases of individual young leaves. Over time, the damage gradually subsided, and normal vegetative growth, flowering, and fruiting in the middle and later stages of the corn crop were not affected.

[0253] When treated with 3000 times, 2000 times, 1000 times, 750 times and 500 times the test concentration of sample 8, there was no phytotoxicity on the heart leaves of the three varieties of corn at the seedling stage and the leaves grew normally; when treated with 250 times the test concentration of sample 8, there was no phytotoxicity on the heart leaves and leaves of the three varieties of corn at the seedling stage and the leaves grew normally, but there was slight phytotoxicity on the base of some tender leaves of corn, which showed yellow and chlorosis symptoms.

[0254] Table 10 Survey results of safety test on corn seedlings of sample 8

[0255]

[0256] Eleven days after the first application of the pesticide, the six test concentrations of sample 8 (3000 times, 2000 times, 1000 times, 750 times, 500 times, and 250 times) had no effect on the heart leaves of the three varieties of corn in the seedling stage, and the leaves grew normally. Therefore, the damage caused by sample 8 was limited to the base of individual young leaves of the corn. With the passage of time, the damage to the corn was gradually alleviated, and the normal nutritional growth, flowering and fruiting of the corn in the middle and late stages were not affected.

[0257] Treatments with 3000x, 2000x, and 1000x the control sample CK3 at three test concentrations showed no damage to the heart leaves of the three corn varieties at the seedling stage, and the leaves grew normally. Treatments with 750x and 500x the control sample CK3 at the seedling stage showed no damage to the heart leaves and leaves of the three corn varieties at the seedling stage, and the leaves grew normally, but caused slight damage to the bases of some young leaves, with symptoms of yellow chlorosis. Treatments with 250x the control sample CK3 also showed no damage to the heart leaves of the three corn varieties at the seedling stage, and the leaves grew normally, but caused slight damage to the bases of some young leaves, with symptoms of yellow chlorosis, manifested as yellow translucent stripes. The main reason for this may be that the pesticide solution on the leaves flows down to the base of the young leaves.

[0258] Table 11 Investigation results of safety test of control sample CK3 on corn seedlings

[0259]

[0260] Eleven days after the first application, treatments with the four test concentrations of 3000, 2000, 1000, and 750 times the control sample CK3 showed no damage to the heart leaves of the three maize varieties at the seedling stage, and growth remained normal. Treatment with a 500-fold concentration of the control sample CK3 still caused slight damage to Zhengdan 958, with visible chlorosis. However, the slight damage to the base of the young leaves of Nonghua 101 and Nongda 108 was alleviated, with virtually no visible symptoms, and normal growth in the middle and late stages of the maize was not affected. Treatment with a 250-fold concentration of the control sample CK3 still caused slight damage to the three varieties, with visible chlorosis. Therefore, the damage caused by the control sample CK3 was limited to the base of individual young leaves of the maize. Over time, the damage to the maize was gradually alleviated. However, at the higher concentration, slight damage was still present in all maize varieties 11 days after application.

[0261] 3. Conclusion

[0262] During the corn seedling stage, application of the composite stabilizer 40% pyraclostrobin-captan suspension concentrate of the present invention can significantly reduce the risk of phytotoxicity. Even if phytotoxicity occurs to the corn, the affected parts of the corn can be gradually alleviated without affecting the normal nutritional growth, flowering and fruiting of the corn in the middle and late stages.

[0263] Biological activity test example 2:

[0264] The purpose of this biological activity experiment is to test the effect of 7% pyraclostrobin, fludioxonil, and clothianidin seed treatment suspension added with the stable safener of the present invention in reducing phytotoxicity, and to conduct a wheat safety test. The safety of the agent to the current crop wheat was determined by using seed coating.

[0265] 1 Test conditions

[0266] 1.1 Test targets

[0267] The wheat varieties tested in the safety test are Lumai 21, Luyuan 502 and Jimai 22.

[0268] 1.2 Culture conditions

[0269] The experiment was conducted in a solar greenhouse. Plastic pots with a diameter of 35 cm were used as cultivation containers. An appropriate amount of moist sterilized loam was added to the pot surface, leaving a 25 cm diameter. The temperature was maintained at 28-30°C, with a humidity of 80% and natural light. The culture medium consisted of sieved, air-dried sandy loam with an organic matter content of 1.26% and a pH of 6.9. The test soil was filled to 4 / 5 of the pot's surface and watered from the top to completely moisten the soil.

[0270] 1.3 Instruments and Equipment

[0271] 1.3.1 Solar Greenhouse

[0272] 1.3.2 Small coating machine

[0273] 1.3.3 Electronic balance (sensitivity 0.1 mg)

[0274] 1.3.4 Plastic basin with a diameter of 35 cm

[0275] 1.3.5 Graduated cylinder

[0276] 1.3.6 Beaker, rubber gloves, etc.

[0277] 2 Experimental design

[0278] 2.1 Test Agents

[0279] The test agent was the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate sample prepared in Example 4, which was sample 18 (sample number 18), and the control sample was control example 7 (CK7).

[0280] 2.2 Dose setting and repetition

[0281] The maximum dosage of the 7% pyraclostrobin, fludioxonil, and clothianidin seed treatment suspension concentrate was 2000 ml / 100 kg of seeds. Sample 18 was treated with four dosages: 2000 ml / 100 kg, 3000 ml / 100 kg, 4000 ml / 100 kg, and 5000 ml / 100 kg. Each treatment was replicated four times. The dosage of the control sample CK8 was set accordingly. A blank control was also included, consisting of water without the agent.

[0282] 2.3 Treatment Methods

[0283] 2.3.1 Test time

[0284] The trial time is March 1, 2021.

[0285] 2.3.2 Method of use

[0286] The test used a seed coating method. After coating according to the above dosage, wheat seeds of uniform size were sown in 35cm-diameter plastic pots and covered with 2cm of soil. A blank control was used with water containing no pesticide.

[0287] Pretreated wheat seeds were evenly sown on the soil surface, 15 seeds per pot, and covered with 2 cm of soil. After sowing, the seeds were transplanted into a greenhouse for cultivation. After emergence, 10 plants were planted per pot. Separately, plastic pots of the same size were prepared, each with 25 wheat seeds. Four pots were used per treatment, for a total of 100 seeds. Germination was observed.

[0288] 3 Data Survey and Statistical Methods

[0289] After seedling emergence, surveys were conducted daily to observe wheat seedling emergence, plant growth, and leaf discoloration, necrosis, wilting, and deformities. Seven days after sowing, the number of wheat seedlings emerging from each treatment was recorded, and the emergence rate for each treatment was calculated. Twenty-one days after sowing, five plants were randomly selected from each treatment, and plant height and root length were measured and recorded. Changes in plant morphology and color were also observed. Raw data for all replicates of each treatment were recorded. The experimental results were processed, and the emergence rate, average plant height, and root length for each dose treatment were calculated and tested for significance.

[0290] 4 Results Analysis and Discussion

[0291] 4.1 Test results

[0292] 4.1.1 Through experimental observation, wheat seeds were coated with 7% pyraclostrobin-isothiazolin-clothianidin seed treatment suspension at 1, 1.5, 2, and 2.5 times the recommended maximum dosage. The emergence and plant growth of the three varieties of wheat were normal, and there were no symptoms such as leaf discoloration, necrosis, wilting, and deformity.

[0293] 4.1.2 Survey Results

[0294] Sample 18 formulation was applied to three wheat varieties at dosages of 2000 ml / 100 kg, 3000 ml / 100 kg, 4000 ml / 100 kg, and 5000 ml / 100 kg, respectively. The seedling emergence rate, plant height, and root length of each treatment were significantly different from those of the blank control, as shown in Tables 12, 13, and 14. The seedling emergence rate, plant height, and root length of the three wheat varieties were all higher than those of the plain water control, indicating that the test agent, at the test dosage, was safe for wheat seedling emergence and growth and promoted both.

[0295] Table 12. Effects of seed dressing treatment of sample 18 on the growth and development of wheat seedlings (variety: Lumai 21)

[0296]

[0297] The safety of Sample 18 on the seeds and plants of the test wheat crop Lumai 21 was determined through seed coating. The test results, detailed in Table 12, indicate that wheat seeds coated with Sample 18 exhibited good safety. At twice the recommended dose (2000 ml / 100 kg seed and 4000 ml / 100 kg seed), the wheat seedling emergence rate increased, and the leaves showed no discoloration, necrosis, wilting, or deformities. This not only maintained normal plant growth but also promoted wheat seedling emergence and growth. Sample 18 demonstrates good safety.

[0298] Table 13. Effects of Seed Dressing Treatment with Sample 18 on Seedling Growth and Development of Wheat Seedlings (Variety: Luyuan 502)

[0299]

[0300] The safety of Sample 18 on the seeds and plants of the test wheat crop, Luyuan 502, was determined by seed coating. The test results, detailed in Table 13, demonstrate that Sample 18 exhibits good safety when used as seed coating for wheat seeds. At twice the recommended dosage (2000 ml / 100 kg seed and 4000 ml / 100 kg seed), wheat seedling emergence increased significantly, with no discoloration, necrosis, wilting, or deformity of leaves. This not only does not affect the normal growth of the plants but also promotes wheat seedling emergence and growth to a certain extent. Sample 18 demonstrates good safety.

[0301] Table 14. Effects of seed dressing treatment of sample 18 on the growth and development of wheat seedlings (variety: Jimai 22)

[0302]

[0303] The safety of Sample 18 on the seeds and plants of the test wheat crop, Jimai 22, was tested through seed coating. The test results showed that wheat seeds coated with Sample 18 had good safety. At twice the recommended dosage (2000 ml / 100 kg seed and 4000 ml / 100 kg seed), the emergence rate of wheat seedlings increased to a certain extent, and the leaves of the plants showed no discoloration, necrosis, wilting, or deformity. Not only did it not affect the normal growth of the plants, but it also promoted growth to a certain extent. Sample 18 has good safety.

[0304] The control sample CK7 formulation was used to coat three wheat varieties at dosages of 2000 ml / 100 kg, 3000 ml / 100 kg, 4000 ml / 100 kg, and 5000 ml / 100 kg, respectively. The differences in seedling emergence rate, plant height, and root length between each treatment and the blank control are detailed in Tables 15, 16, and 17. The seedling emergence rate, plant height, and root length of the three wheat varieties were not significantly higher than those of the plain water control, and plant morphology was normal. This indicates that the control sample CK7 exhibited a certain degree of safety for wheat seedling emergence and growth at the tested doses, but did have a certain degree of inhibitory effect on these two conditions.

[0305] Table 15. Effects of wheat seed dressing with control sample CK7 on seedling growth and development (variety: Lumai 21)

[0306]

[0307] The safety of the control sample CK7 on the seeds and plants of the test wheat crop Lumai 21 was determined through seed coating. The test results showed that wheat seed coating with the control sample CK7 had a certain degree of safety. At twice the recommended dose (4000 ml / 100 kg of seeds), wheat seedling emergence was slightly affected, and plant leaves showed no discoloration, necrosis, wilting, or deformity. Plant morphology was normal, and normal plant growth was not affected. Therefore, the control sample CK7 had a certain degree of safety for the wheat Lumai 21, and also had a certain degree of inhibitory effect on seedling emergence and growth.

[0308] Table 16. Effects of wheat seed dressing with control sample CK7 on seedling growth and development (variety: Luyuan 502)

[0309]

[0310] The safety of the control sample CK7 on wheat seeds and plants was determined through seed coating. The results showed that the control sample CK7 was somewhat safe for wheat seeds. At twice the recommended dose (4000 ml / 100 kg of seeds), wheat seedling emergence was somewhat affected, but plant leaves showed no discoloration, necrosis, wilting, or deformities, and plant growth remained normal. Therefore, the control sample CK7 was somewhat safe for the wheat variety Luyuan 502, while also having a limited inhibitory effect on seedling emergence and growth.

[0311] Table 17. Effects of wheat seed dressing with control sample CK7 on seedling growth and development (variety: Jimai 22)

[0312]

[0313]

[0314] The safety of the control sample CK7 on the seeds and plants of the test wheat Jimai 22 was determined through seed coating. The results showed that wheat seed coating with the control sample CK7 exhibited a certain degree of safety. At twice the recommended dose (4000 ml / 100 kg of seeds), wheat seedling emergence was not affected, but plant leaves showed no discoloration, necrosis, wilting, or deformity, and plant growth remained normal. Therefore, the control sample CK7 exhibited a certain degree of safety for wheat Jimai 22, while also exhibiting a certain degree of inhibitory effect on seedling emergence and growth.

[0315] 5. Conclusion

[0316] The safety of sample 18 and control sample CK7 on wheat seeds and plants of the test crop was determined by seed coating. The test results showed that wheat seeds coated with sample 18 had better safety than control sample CK7. Both showed no symptoms such as discoloration, necrosis, wilting, and deformity of plant leaves, and the plants grew normally, both with good safety. However, at the recommended dose and double the dosage (preparation dosage of 2000 ml / 100 kg of seeds and 4000 ml / 100 kg of seeds), sample 18 was higher than control sample CK7 in wheat seedling emergence rate, plant height, and root length. Therefore, sample 18, which has been added with the stabilizing safener of the present invention, has higher safety.

[0317] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims attached to the present invention.

Claims

1. A composite suspension concentrate of pyraclostrobin and captan, comprising pyraclostrobin, captan, a wetting and dispersing agent and a composite stabilizer; characterized in that: The compound suspending agent contains a compound stabilizer, including an organic acid, and also includes an ascorbic acid fatty acid ester of formula (I) or its derivatives. Formula (I) wherein R is independently a monovalent hydrocarbon group having 9 to 21 carbon atoms; wherein the mass ratio of the organic acid to the ascorbic acid fatty acid ester of formula (I) or its derivative is (1-4):1, the acidity coefficient of the organic acid at 25° C. is 2≤pKa≤5, and the organic acid is any one of acetic acid, citric acid, propionic acid, glycolic acid, glutaric acid, adipic acid, butenedioic acid, dodecylbenzenesulfonic acid, or methylbenzenesulfonic acid; In the compound suspension concentrate, the mass ratio of pyraclostrobin to captan is 1:(2-8); The ascorbic acid fatty acid ester of formula (I) is selected from ascorbyl laurate, ascorbyl olivate, ascorbyl palmitate, ascorbyl stearate; and / or the ascorbic acid fatty acid ester derivative of formula (I) is palmitoyl ascorbate.

2. The composite suspending agent according to claim 1, wherein In the compound suspending agent, the mass ratio of the organic acid to the ascorbic acid fatty acid ester of formula (I) or its derivative is (2-3):

1.

3. The composite suspending agent according to claim 1, wherein In the compound suspension concentrate, the mass ratio of pyraclostrobin to captan is 1:(4-7).

4. The composite suspending agent according to claim 1, wherein The wetting and dispersing agent is selected from at least one of polymeric carboxylates, sulfonates, EOPO polyethers, and phosphates. Wherein, the phosphate ester is selected from tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and castor oil polyoxyethylene ether phosphate.

5. The composite suspending agent according to claim 1, wherein The compound suspending agent further comprises a thickener, wherein the thickener is selected from at least one of an organic thickener and an inorganic thickener. Wherein, the organic thickener is selected from xanthan gum, and the inorganic thickener is selected from magnesium aluminum silicate; and / or the compound suspending agent further comprises a defoaming agent, wherein the defoaming agent is selected from an organosilicon defoaming agent; and / or the compound suspension further comprises a preservative, and the preservative is selected from kason; And / or the composite suspending agent further comprises an antifreeze agent, and the antifreeze agent is selected from ethylene glycol, propylene glycol, and glycerol.

6. A method for preparing the composite suspension concentrate of pyraclostrobin and captan as claimed in claim 1, comprising the steps of: S1: Weigh pyraclostrobin and captan and set aside. Weigh the wetting and dispersing agent and set aside. Weigh the components of the composite stabilizer separately and set aside. Add the composite stabilizer and wetting dispersant into water and stir to disperse evenly to obtain an additive dispersion; S2: adding pyraclostrobin and captan to the auxiliary agent dispersion, stirring and dispersing them uniformly, and then grinding them under a grinding medium. After grinding the particles of pyraclostrobin and captan to reach the target particle size, filtering to obtain a grinding liquid, thereby obtaining a composite suspension of pyraclostrobin and captan.

7. The preparation method according to claim 6, characterized in that In step S1, the ascorbic acid fatty acid ester or its derivative component of formula (I) of the composite stabilizer is first dispersed in a dispersant, then mixed with the organic acid component of the composite stabilizer and a wetting dispersant, and then added into water and stirred for uniform dispersion; The dispersant is selected from one or a combination of ethylene glycol, propylene glycol and glycerol.

8. The preparation method according to claim 6, characterized in that The additive dispersion in step S1 is further added with a defoaming agent; And / or during the grinding process of step S2, a defoaming agent is added to perform defoaming treatment.

9. The preparation method according to claim 6, characterized in that The preparation method further comprises step S3, S3: Weigh antifreeze, preservative, and thickener for later use; stir and disperse the antifreeze and thickener evenly, then add them to water, then add the preservative, stir and disperse evenly, to obtain a thickened dispersion; The grinding liquid obtained in step S2 is mixed with the thickened dispersion liquid, and after stirring and dispersing evenly, a composite suspension concentrate of pyraclostrobin and captan is obtained.

10. The preparation method according to claim 6, characterized in that The particle size D of the polishing liquid 90 Less than 5 microns; and / or the particle size D of the polishing liquid 95 Less than 8 microns.

Images