A seed treatment suspension concentrate containing a stabilised safener

Abstract

The application discloses a seed treatment suspension agent containing a stable security agent, and the effective component of the seed treatment suspension agent contains pyraclostrobin, fludioxonil and thiamethoxam, the mass ratio of pyraclostrobin, fludioxonil and thiamethoxam is (1-5):(1-2):(10-100), the effective component is used in an amount of 4-40 wt%, and the stable security agent at least includes ascorbic acid fatty acid ester or its derivative of formula (I), the ascorbic acid fatty acid ester of formula (I) is selected from ascorbic acid laurate, ascorbic acid olivate and ascorbic acid stearate; in the seed treatment suspension agent, the mass ratio of pyraclostrobin and the stable security agent is 100:(0.1-100). The application maintains the seed treatment suspension agent between pH 4 and 9 by adding the stable security agent in the seed treatment suspension agent, reduces the degradation rate of the effective component, reduces the risk of pesticide damage, and has safety to crop seeds.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of pesticide formulations, in particular to a seed treatment suspension concentrate containing a stable safener. BACKGROUND

[0002] Captan, also known as Gepdan, chemical name is N-(trichloromethylthio)-cyclohex-4-ene-1,2-dicarboxamide, is a kind of organic sulfur broad-spectrum low-toxic fungicide, mainly protective effect, with certain therapeutic effect, safe to use, has good preventive effect on many kinds of fungal diseases on many crops, especially suitable for crops sensitive to copper fungicide. The drug can penetrate the cell membrane of the pathogen, both can interfere with the respiration process, and can interfere with cell division, has multiple fungicidal sites, continuous multiple use is difficult to induce the pathogen to produce drug resistance, continuous spraying disease prevention effect is more obvious. It is mainly used for spraying, also can be used for seed treatment, after harvest, dip the product, before sowing or planting soil treatment.

[0003] Pyraclostrobin, also known as pyraclostrobin, chemical name is methyl (N)-[[[1-(4-chlorophenyl) pyrazol-3-yl)-oxy]-O-methoxy]-N-methoxy carbamate, is a broad-spectrum fungicide of methoxy acrylate developed by BASF in Germany in 1993, which was listed in 2002. The mechanism is mitochondrial respiration inhibitor, which makes mitochondria unable to produce and provide energy required for normal cell metabolism, and eventually leads to cell death. Pyraclostrobin has a wide fungicidal spectrum and is widely used in rice, soybean, cucumber and other crops, which can control most diseases of ascomycetes, basidiomycetes, deuteromycetes and oomycetes. It has strong inhibition effect on spore germination and leaf mycelium growth, and has protective and therapeutic activity, as well as penetration and local systemic activity, with a long lasting period. Under the condition of 25℃ and pH 5-7, the stability of pyraclostrobin is more than 30 days. The skilled person in the art urgently needs to solve the problem of the stability of the effective ingredient captan in the formulation system, including chemical stability and physical stability. In terms of chemical stability, the captan degradation rate (2 years) needs to be controlled within 5%, and in terms of physical stability, no abnormal phenomenon occurs within 2 years. If the formulation is a homogeneous system, the formulation does not appear crystallization. If the formulation is a non-homogeneous system, the particle size of the micro-particles in the formulation remains stable, no obvious crystal growth, no bottoming, no layering, and the water or oil separation rate is controlled within the qualified range.

[0004] Thiamethoxam is a new neonicotinoid insecticide, which has contact, stomach and systemic activity by acting on nicotinyl acetylcholine receptors. Thiamethoxam is relatively stable (50℃) under weak acid conditions (pH 5-7) and degrades slowly, and is stable under weak alkaline conditions (pH 7-9) and has a long half-life (DT 501401 days (pH 9, 20°C) (European Union Rev. Rep.).

[0005] Chlorantraniliprole is relatively stable under acidic conditions and degrades slowly. Under alkaline conditions, chlorantraniliprole degrades rapidly. At 20°C, the half-life DT50 of chlorantraniliprole is 32.4 hours at pH 5, 8.3 hours at pH 7, and less than 2 minutes at pH 10. 50 Chlorantraniliprole is relatively stable under acidic conditions and degrades slowly. Under alkaline conditions, chlorantraniliprole degrades rapidly. At 20°C, the half-life DT50 of chlorantraniliprole is 32.4 hours at pH 5, 8.3 hours at pH 7, and less than 2 minutes at pH 10. 50 Chlorantraniliprole is relatively stable under acidic conditions and degrades slowly. Under alkaline conditions, chlorantraniliprole degrades rapidly. At 20°C, the half-life DT50 of chlorantraniliprole is 32.4 hours at pH 5, 8.3 hours at pH 7, and less than 2 minutes at pH 10. 50 Chlorantraniliprole is relatively stable under acidic conditions and degrades slowly. Under alkaline conditions, chlorantraniliprole degrades rapidly. At 20°C, the half-life DT50 of chlorantraniliprole is 32.4 hours at pH 5, 8.3 hours at pH 7, and less than 2 minutes at pH 10. 50 Chlorantraniliprole is relatively stable under acidic conditions and degrades slowly. Under alkaline conditions, chlorantraniliprole degrades rapidly. At 20°C, the half-life DT50 of chlorantraniliprole is 32.4 hours at pH 5, 8.3 hours at pH 7, and less than 2 minutes at pH 10.

[0006] However, the solution to the chemical stability of chlorantraniliprole by fine-tuning the acidification treatment parameters often leads to the chemical stability of other active ingredients in the formulation system being unqualified. For example, if there are other active ingredients in the formulation system, such as pyraclostrobin, adjusting the pH to 3 or even 1-2 will cause the degradation rate (2 years) of pyraclostrobin in the pesticide formulation to exceed 5%, and the degradation rate can even be as high as 40% or more. If the degradation rate of pyraclostrobin in the pesticide formulation needs to be controlled within 5%, the pH of the formulation needs to be adjusted to 4 or more, i.e., 4-6.

[0007] The solution to the chemical stability of chlorantraniliprole by fine-tuning the acidification treatment parameters also easily leads to the physical stability of the formulation system being unqualified. If the chlorantraniliprole formulation is a heterogeneous system, such as a suspension concentrate system or a dispersible oil suspension concentrate system, the partial loss of dispersing ability of the dispersant in the weakly acidic system leads to the chlorantraniliprole particles sinking to the bottom, the chlorantraniliprole particle crystals growing, and the formulation separating into layers. Moreover, if the pesticide formulation is a complex system, such as chlorantraniliprole and pyraclostrobin.

[0008] Pyraclostrobin has four crystal forms, and the melting point span is relatively large, between 40-67℃; the physical properties of each crystal form are not exactly the same, which causes great difficulty in the sanding process of suspension concentrate, especially the stability of the compound preparation. After heat storage and melting, the low melting point pyraclostrobin in the four crystal forms is in a molten state, and is not constrained by the existing dispersant, and continues to agglomerate and fuse to grow, quickly settles, and adheres or adsorbs with other component particles during the settling process, so that the suspension concentrate will precipitate together with the other components after subsequent heat storage and transfer to room temperature.

[0009] The skilled in the art can effectively solve the problem of the stability of pyraclostrobin suspension concentrate with a content of less than 30% by selecting suitable wetting dispersants, such as polycarboxylate high-efficiency wetting dispersants and sulfonate wetting dispersants, and dispersing pyraclostrobin particles through the multi-anchor point of the dispersant. However, its compound preparation still has no good solution, especially when it is compounded with captan. The difficulty lies in that, on the one hand, the commercial pyraclostrobin has a low melting point (pure product 63.7-65.2℃), and when it is compounded with other components, the melting point of the mixed components is reduced, which makes it more difficult to control the sanding temperature and select high-efficiency wetting dispersants. At present, pyraclostrobin compound products in the pesticide preparation industry are difficult to ensure not to crystallize within two months after heat storage and transfer to room temperature, and the stability of the preparation products over time is not guaranteed, and there is a risk of crystallization and return after circulating in the market. On the other hand, polycarboxylate high-efficiency wetting dispersants and sulfonate wetting dispersants have good wetting and dispersing properties at pH 5-7, but when the pH is lower than 3, the wetting and dispersing properties of the wetting dispersants are significantly reduced, and when the pH is lower than 2, the dispersing properties of the wetting dispersants are basically reduced to zero. Adjusting the pH to below 3 will directly affect the stability of pyraclostrobin, and in terms of affecting the physical stability of pyraclostrobin, it will cause pyraclostrobin particles to settle at the bottom, and the particle crystals to grow, resulting in stratification and other phenomena in pesticide preparations.

[0010] The Chinese patent contains the fungicidal composition of myclobutanil and captan and application (patent application number: CN201410495968.6) is to prevent the degradation of the active ingredient, the selected stabilizer is sodium citrate, resorcinol, but resorcinol is in the list of 3 carcinogens, the chemical properties of resorcinol are similar to those of diacid, and it reacts with sodium hydroxide, ammonia and other substances to form salt, sodium citrate has the effect of adjusting the acid-base, this patent mainly adjusts the pH to prevent the degradation of the active ingredient, the actual effect is not good, and the composition is not a general component. The Chinese patent contains the fungicide composition with synergistic effect of captan (patent application number: CN200710013632.1) is to prevent the degradation of the active ingredient, the selected stabilizer is ethanolamine, diethanolamine, tributyl phosphate, epichlorohydrin, triphenyl phosphite, ethanolamine and diethanolamine have the effect of adjusting the acid-base, tributyl phosphate is a colorless and odorless liquid, which can be mixed with many organic solvents, nitrocellulose, cellulose acetate, chlorinated rubber and polyvinyl chloride plasticizer, paint, ink and adhesive solvent, used in water-based liquid preparation, on the one hand, it is easy to make the physical system unstable, on the other hand, it is difficult to prevent the degradation of the active ingredient, triphenyl phosphite is a reducing agent, but it is too active, the package must be sealed during storage, do not get wet, should be stored separately from oxidizing agents, acids, bases, and food chemicals, on the other hand, it is an oily substance, insoluble in water, soluble in alcohol, ether, benzene and acetone and other organic solvents, easy to make water-based liquid preparation unstable, epichlorohydrin is a stabilizer containing oxygen, but it is a colorless liquid, with a chloroform-like odor, volatile, unstable, secondly, epichlorohydrin is in the list of 2A carcinogens. The Chinese patent contains the fungicide composition of zinc thiazole (patent application number: CN201010282092.9) is to prevent the degradation of the active ingredient, the selected stabilizer is epoxidized soybean oil, epichlorohydrin, triphenyl phosphite, glycidyl ether and / or pentaerythritol, epoxidized soybean oil has strong lipophilicity, is difficult to be emulsified, and has poor affinity with other active ingredients, resulting in poor stability effect, glycidyl ether and / or pentaerythritol is a polyether polyol with certain dispersing performance, but the stability effect is not good. The Chinese patent a pesticide fungicide composition and its application (patent application number: CN202210411587.X) is to prevent the degradation of the active ingredient, the selected stabilizer is epoxidized soybean oil, epichlorohydrin, BHT and triphenyl phosphate, BHT is a chemical name of 2,6-di-tert-butyl-4-methyl phenol, which is used as an antioxidant in food processing, on the one hand, BHT is mainly used in the field of food oil, to increase the shelf life of oil, it is a good antioxidant additive for petroleum products, the working temperature of antioxidant BHT is best at 100 degrees, many brands have prohibited the use of industrial-grade BHT in their product packaging, on the other hand, in terms of room temperature antioxidant, BHT has strong lipophilicity, and the stability of the active ingredients in water-based liquid preparation, especially the hydrophilic active ingredients, is not good.In summary, the stabilizers of procymidone selected by the prior art have obvious defects, that is, the stabilizing effect is poor, and there are defects such as being not conducive to the stability of liquid preparation or being a carcinogen.

[0011] In terms of crop application of fungicides, the pyraclostrobin suspension product has a risk of phytotoxicity in the crop seedling nursery period, when the crops grow vigorously and the temperature is high (above 37℃) and the humidity is high. If the concentration of pyraclostrobin is too high, leaf burning of the crops may occur. Taking bananas as an example, under the condition that the 25% suspension and the emulsifiable concentrate are both sprayed at a dilution concentration of 375 times and the above growth conditions are maintained, each treatment shows a more serious leaf burning phenomenon. After the crops produce phytotoxicity, the physiological process of the crops will change complexly, such as the decrease of water absorption capacity, the water deficiency in the body, the destruction of the structure of protoplast membrane, the decrease of active transport capacity, the increase of permeability, the exosmosis of intracellular substances, and the massive hydrolysis of carbohydrates and proteins. Among them, the production of reactive oxygen species (ROS) is considered to be an important reason for these processes. Under normal conditions, plants can timely remove toxic reactive oxygen species (ROS) to keep it at a low level. After the occurrence of phytotoxicity, the generation of reactive oxygen species is accelerated, which accumulates in the body and causes oxidative damage. In order to prevent the toxic effect of ROS, there is a system for removing ROS in the plant body. The ascorbic acid-glutathione (ASA-GSH) cycle system is an important way to remove ROS free radicals in the plant body, which is responsible for removing H:O·, and can regulate the oxidation-reduction potential in the body to make the signal transduction system in the direction conducive to plant growth. However, ascorbic acid has strong reducing property and is easily oxidized to dehydroascorbic acid, but the reaction is reversible, and ascorbic acid and dehydroascorbic acid have the same physiological function, but if dehydroascorbic acid is further hydrolyzed to diketogulonic acid, the reaction is irreversible and completely loses physiological efficiency, so it is difficult to use ascorbic acid in pesticide formulations.

[0012] In summary, those skilled in the art urgently need a stabilizer for a liquid preparation containing the active ingredient procymidone to solve the chemical stability and physical stability problems existing in the preparation system, and to solve the problem of fungicide phytotoxicity and reduce the risk of phytotoxicity caused by the use of fungicides. SUMMARY

[0013] The purpose of the present application is to solve the problems in the prior art, and to provide a seed treatment suspension containing a stable safener, so as to stabilize the active ingredient of the pesticide in the liquid preparation, especially in the water-based liquid preparation with water as the main dispersion medium, to reduce the decomposition of the active ingredient, and also to avoid the decomposition of the active ingredient of the compounded pesticide, such as pyraclostrobin, caused by low pH and the decrease of pesticide activity.

[0014] To achieve the above-mentioned purpose of one aspect of the present application, the present application adopts the following technical solutions:

[0015] A composite stabilizer for a liquid preparation containing at least a first active ingredient, the first active ingredient being captan;

[0016] 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 or its derivative of formula (I);

[0017]

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

[0019] In the liquid preparation, the acidity coefficient (25℃) of the organic acid 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, an alkyl benzene sulfonic acid or its derivative.

[0020] The present inventors have also found that the organic acid can reach a sufficient concentration of free H+ in the pesticide preparation. + A concentration range of 0.00001-0.01 mol / L ensures the stability of the active ingredient captan, but the larger the ionization constant of the organic acid, the better the stability. When pKa<5, a large difference in pH before and after heat storage (52±2℃, 14 days) is easily caused, and when pKa>5, it cannot ensure that the free H+ reaches a sufficient concentration in the pesticide preparation.

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

[0022] and / or the mass ratio of the ascorbic acid fatty acid ester or its derivative of formula (I) to the first active ingredient in the liquid preparation 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 derivative of the alkyl acid includes but is not limited to glycolic acid and lactic acid.

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

[0026] and / or the derivative of the alkyl diacid includes but is not limited to glutamic acid.

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

[0028] and / or the derivatives of the alkyl sulfonic acid include but are not limited to nitrobenzoic acid.

[0029] Preferably, the alkyl sulfonic acid includes but is not limited to benzene sulfonic acid, methyl benzene sulfonic acid, dodecyl benzene sulfonic acid,

[0030] and / or the derivatives of the alkyl sulfonic 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 an ammonium salt, a sodium salt, a potassium salt, a magnesium salt.

[0033] Further, the ascorbic acid fatty acid ester of formula (I) includes but is not limited to ascorbic acid laurate, ascorbic acid olivate, ascorbic acid palmitate, ascorbic acid stearate;

[0034] and / or the ascorbic acid fatty acid ester derivative of formula (I) includes but is not limited to lauroyl ascorbate, olivoyl ascorbate, palmitoyl ascorbate, stearoyl ascorbate.

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

[0036] Preferably, the liquid preparation includes but is not limited to an aqueous emulsion, a suspension concentrate, a seed treatment suspension concentrate, a dispersible oil suspension concentrate, an oil suspension concentrate, an oil agent, a low volume liquid agent;

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

[0038] the dispersion medium of the suspension concentrate is water,

[0039] the dispersion medium of the seed treatment suspension concentrate is water,

[0040] the dispersion medium of the dispersible oil suspension concentrate is selected from any one or several of soybean oil, methyl oleate, rapeseed oil,

[0041] the dispersion medium of the oil suspension concentrate is selected from any one or several of soybean oil, methyl oleate, rapeseed oil,

[0042] the dispersion medium of the oil agent is selected from any one or several of methyl oleate, toluene, xylene, trimethylbenzene, solvent oil,

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

[0044] An oil dispersion is a liquid formulation in which the active ingredient is stably suspended in a water-immiscible liquid, and is used after dilution with water. An oil flowable concentrate is a liquid formulation in which the active ingredient is stably suspended or partially dissolved in a water-immiscible liquid, and is used after dilution with an organic solvent or oil.

[0045] To achieve the above-mentioned purpose of another aspect of the present application, the present application adopts the following technical solutions:

[0046] A pyraclostrobin and captan compound suspension agent, including but not limited to pyraclostrobin, captan, wet dispersant and composite stabilizer;

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

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

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

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

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

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

[0053] Further, in the compound suspension agent, the mass ratio of pyraclostrobin to captan is 1:(4-7).

[0054] Preferably, the wet dispersant includes at least one of a polymeric carboxylate, a sulfonate, an EOPO polyether, and a phosphate ester.

[0055] The phosphate ester includes but is not limited to triphenyl ethenyl phenol polyoxyethylene ether phosphate ester, fatty alcohol polyoxyethylene ether phosphate ester, castor oil polyoxyethylene ether phosphate ester.

[0056] Preferably, the compound suspension agent further comprises a thickening agent, and the thickening agent includes at least one of an organic thickening agent and an inorganic thickening agent.

[0057] The organic thickening agent includes but is not limited to xanthan gum, and the inorganic thickening agent includes but is not limited to magnesium aluminum silicate.

[0058] Preferably, the compound suspension agent further comprises an antifoaming agent, and the antifoaming agent includes but is not limited to silicone antifoaming agent.

[0059] Preferably, the compound suspension agent further comprises a preservative, and the preservative includes but is not limited to carboxin.

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

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

[0062] A preparation method of a pyraclostrobin and captan compound suspension agent, comprising the following steps:

[0063] S1: weighing pyraclostrobin and captan of a target mass, and reserving,

[0064] weighing wetting dispersant and composite stabilizer of a target mass, and reserving,

[0065] weighing components of the composite stabilizer of a target mass, and reserving,

[0066] adding the composite stabilizer and the wetting dispersant into water, stirring and dispersing uniformly, and obtaining an auxiliary dispersing liquid;

[0067] S2: adding pyraclostrobin and captan into the auxiliary dispersing liquid, stirring and dispersing uniformly, and then placing under a grinding medium to grind, and after the particle size of pyraclostrobin and captan reaches a target particle size, filtering to obtain a grinding liquid, so as to obtain a pyraclostrobin and captan compound suspension agent;

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

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

[0070] Preferably, the co-dispersant is selected from one or a combination of several of ethanol, ethylene glycol, propylene glycol, and glycerol.

[0071] Preferably, the co-dispersant is selected from one or a combination of several of ethanol, ethylene glycol, propylene glycol, and glycerol.

[0072] Preferably, the co-dispersant is selected from one or a combination of several of ethanol, ethylene glycol, propylene glycol, and glycerol.

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

[0074] S3: Weigh the antifreeze, preservative, and thickening agent, and prepare for use; mix the antifreeze and thickening agent, stir to disperse uniformly, then add water, and then add the preservative, stir to disperse uniformly, and obtain a thickening dispersion liquid;

[0075] Mix the grinding liquid obtained in step S2 with the thickening dispersion liquid, stir to disperse uniformly, and obtain a pyraclostrobin and captan compound suspension concentrate.

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

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

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

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

[0080] The stable safener at least includes but is not limited to ascorbyl fatty acid ester or its derivative of formula (I), and the ascorbyl fatty acid ester of formula (I) includes but is not limited to ascorbyl laurate, ascorbyl olivate, ascorbyl palmitate, and ascorbyl stearate.

[0081] And / or the ascorbyl fatty acid ester derivative of formula (I) includes but is not limited to lauroyl ascorbate, olivoyl ascorbate, palmitoyl ascorbate, and stearoyl ascorbate.

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

[0083] Preferably, the liquid preparation further contains a third coating effective component, and the third coating effective component is a pesticide, including but not limited to imidacloprid, acetamiprid, thiamethoxam, clothianidin.

[0084] Further, the liquid preparation further contains a fourth coating effective component, and the fourth coating effective component includes but is not limited to fludioxonil.

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

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

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

[0088] Preferably, the stabilizing safener further includes an organic acid, and the organic acid includes but is not limited to fulvic acid, humic acid, amino acid, salicylic acid, leucine, malic acid. The purpose of adding the stress resistance organic acid in the seed treatment suspension agent of the present application is to increase the content of vitamin C and soluble solids in the crop body, and the stress resistance of the crop.

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

[0090] Preferably, the seed treatment suspension agent further includes an alarm color dye, and the content is 2.5-5.5wt%.

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

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

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

[0094] In order to realize the above-mentioned purpose of the further aspect of the present application, the present application adopts the following technical scheme:

[0095] A seed treatment suspension agent containing pyraclostrobin, fludioxonil and thiamethoxam,

[0096] The effective component of the seed treatment suspension agent contains pyraclostrobin, fludioxonil and clothianidin, and the mass ratio of pyraclostrobin, fludioxonil and clothianidin is (1-5):(1-2):(10-100), and the effective component is used in an amount of 4-40wt% in the seed treatment suspension agent,

[0097] The seed treatment suspension agent contains a stable safener, and the stable safener is ascorbyl palmitate or its derivative,

[0098] The derivative of ascorbyl palmitate includes but is not limited to ascorbyl dipalmitate, ascorbyl tetrapalmitate, ascorbyl tetraisopalmitate, ascorbyl tetraisopalmitate, palmitoyl ascorbate, dipalmitoyl ascorbate, tetrapalmitoyl ascorbate and tetraisopalmitoyl ascorbate.

[0099] Preferably, the effective component is used in an amount of 5-25wt%.

[0100] Further, the effective component is used in an amount of 7wt%.

[0101] The present application has the beneficial technical effects of:

[0102] (1) The raw materials used in the present application are easy to add to liquid preparations, and the operation is simple and easy to implement, avoiding the problem that the product quality is difficult to control due to complex process, and avoiding the problem that the degradation rate of the effective component of the product is large, so that the degradation rate of the pesticide active ingredient can be ensured to be below 5% during long-term storage;

[0103] (2) The inventors of the present application accidentally found that the composite stabilizer of the present application can also stabilize the effective component clothianidin which is stable in weak alkaline, and the degradation rate is as low as 0.5%; the inventors also accidentally found that the composite stabilizer of the present application can reduce the risk of phytotoxicity of captan and its compounded liquid preparation, especially when the fungicide is used in the condition of high temperature (above 37℃) and high humidity during the vigorous growth period of crops, the ascorbyl fatty acid ester or its derivative of the composition formula (I) is used in the seed treatment suspension agent, and a more safe seed treatment suspension agent containing fungicide is obtained. BRIEF DESCRIPTION OF DRAWINGS

[0104] Figure 1 The sample after heat storage of the control sample CK3 of Example 2 of the present application is removed from the bottom of the liquid, and it can be seen that the bottom shows viscous and sampling is difficult;

[0105] Figure 2The 1ml sample of the sample 6-9 of the embodiment 2 of the present application and the control sample CK3-CK4 after heat storage is diluted 250 times, and the suspension rate is tested. After 1 hour, 25ml of the bottom diluent is left, and it can be seen that the CK3 and CK4 have obvious precipitates, and the sample 6-9 has no obvious precipitate;

[0106] Figure 3 The sample of the control sample CK3 of the embodiment 2 of the present application after heat storage can be seen to have obvious water separation layer;

[0107] Figure 4 The sample of the control sample CK4 of the embodiment 2 of the present application after heat storage can be seen to have obvious water separation layer, but less than CK3.

[0108] Figure 5 The sample of the sample 6-10 of the embodiment 2 of the present application after heat storage can be seen to have no obvious water separation layer.

[0109] Figure 6 The effect control diagram of the sample 11 and the sample 13 of the 20% pyraclostrobin·climb seed treatment suspension agent of the embodiment 3 of the present application after coating corn can be seen, and compared with CK5, the coating is more uniform, the film forming is more uniform, and the brightness is higher.

[0110] Figure 7 The effect control diagram of the sample 14 and the sample 13 of the 20% pyraclostrobin·climb seed treatment suspension agent of the embodiment 3 of the present application after coating corn can be seen, and compared with CK6, the coating is more uniform.

[0111] Figure 8 The effect control diagram of the sample 16 and the sample 17 of the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension agent of the embodiment 4 of the present application after coating corn can be seen, and compared with CK7, the coating is more uniform, the film forming is more uniform, and the brightness is higher.

[0112] Figure 9 The effect control diagram of the sample 20 and the sample 17 of the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension agent of the embodiment 4 of the present application after coating corn can be seen, and compared with CK8, the coating is more uniform, the film forming is more uniform, and the brightness is higher.

[0113] Figure 10 The effect diagram of the sample 18 of the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension agent of the embodiment 4 of the present application after coating corn can be seen, and the sample 18 has uniform film forming, high brightness, good appearance, good smoothness, and no seed adhesion. DETAILED DESCRIPTION

[0114] The application will be further described below with reference to the accompanying drawings. The application will be further understood from the following description of the embodiments. However, the specific embodiments given by the applicant should not be regarded as limiting the technical solutions of the application. Any change to the defined local technical features or formal but not substantial change to the overall structure should be regarded as falling within the protection scope of the technical solutions defined by the application.

[0115] As shown in Figures 1-10 The content of the original drug and other medicaments in the embodiments is calculated as a percentage.

[0116] Test method and procedure: the composite stabilizer is added to the liquid preparation in a certain proportion, stirred and mixed to obtain a sample, and the sample is divided into three samples before heat storage, heat storage (54±2℃) and normal temperature storage.

[0117] After the sample is prepared, normal temperature storage and determination of the content of the active ingredient before storage are immediately performed; the heat storage sample is placed in an oven, and the temperature is set to 54±2℃; after 14 days, the content is detected. The content determined before storage is used as a control to calculate the relative decomposition rate, and the heat storage decomposition rate ≤5% is qualified. After the heat storage test is qualified, the sample placed at normal temperature is observed for 2 years, and the samples are taken for analysis of the decomposition rate of the active ingredient at 12 months and 24 months, respectively, to determine whether the stability over time is qualified. For the sample with an unqualified heat storage decomposition rate of 14 days, the sample at normal temperature is not subjected to the stability test over time for 12 months and 24 months.

[0118] The content determined before storage is used as a control to calculate the decomposition rate, and the decomposition rate after heat storage and normal temperature storage over time ≤5% is qualified. The decomposition rate calculation formula is: decomposition rate % = (content before storage-content after heat storage or normal temperature storage over time) / content before storage × 100%.

[0119] The reagents and drugs used in the embodiments are commercially available products, and the original drugs are measured according to the percentage.

[0120] Experimental Example 1: The purpose of this experiment is to detect whether different proportions of the composite stabilizer can reduce the degradation of the active ingredient captan in the oil medium. The 35% captan oil-based suspension concentrates (oil dispersion, abbreviated as OD) is selected for the corresponding experiment, but this does not mean that other liquid preparations, such as emulsifiable concentrates, oil agents and low-volume liquid agents, cannot achieve the same purpose. The person skilled in the art can select a suitable dispersion medium, wherein the dispersion medium of the oil agent is selected from any one or several of methyl oleate, toluene, xylene, trimethylbenzene and solvent oil, and the dispersion medium of the low-volume liquid agent is selected from any one or several of toluene, xylene, trimethylbenzene and solvent oil, and the liquid preparation with the desired content of captan can be prepared.

[0121] 35% Captan dispersible oil suspension

[0122] Captan 350 g, emulsifier 200 g, composite stabilizer in proper amount, suspension thixotropic agent 20 g, dispersion medium to 1000 g.

[0123] The emulsifier selected in the experiment needs to be selected according to the Captan technical material, dispersion medium, etc. In the experimental example, the emulsifier selected is nonylphenol polyoxyethylene ether 100 g, castor oil polyoxyethylene ether 80 g, and magnesium dodecylbenzenesulfonate 20 g. However, this does not mean that those skilled in the art cannot select other suitable emulsifiers to obtain the desired content of Captan dispersible oil suspension by selecting suitable commercially available emulsifiers.

[0124] The dispersion medium selected in the experiment is selected from any one or several of soybean oil, methyl oleate, and rapeseed oil, and is specifically methyl oleate. However, this does not mean that those skilled in the art cannot select other suitable dispersion media, such as soybean oil, solvent oil, and rapeseed oil, to obtain the desired content of Captan dispersible oil suspension by selecting suitable emulsifiers.

[0125] The suspension thixotropic agent selected in the experiment is magnesium aluminum silicate. Those skilled in the art can also select other suitable suspension thixotropic agents to obtain the desired content of Captan liquid preparation.

[0126] The composite stabilizer, nonylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, and magnesium dodecylbenzenesulfonate are added to the methyl oleate and stirred to disperse uniformly. Then Captan is added and stirred again to disperse uniformly. After that, the mixture is ground in a grinding bowl containing a grinding medium until the particle size of Captan reaches the desired particle size. The Captan dispersible oil suspension is obtained by filtering the ground mixture. In the experimental example, the particle size D 90 of the ground mixture is less than 5 microns, and the particle size D 95 of the ground mixture is less than 8 microns.

[0127] The amount of composite stabilizer added can also be any value between 0.6 and 60 g. Other samples are prepared according to the process described above for preparing 35% Captan dispersible oil suspension. For experimental purposes, five groups of composite stabilizers are selected in the experimental example, with organic acids selected from acetic acid, lactic acid, glutamic acid, adipic acid, and citric acid. However, this does not mean that those skilled in the art cannot select other suitable organic acids to achieve the purpose of the present application. In fact, through extensive experiments, the present inventors have found that the organic acid added to the Captan-containing liquid preparation can be selected as long as its acidity coefficient (25°C) satisfies 2 ≤ pKa ≤ 5. If the acidity coefficient is less than 2, the organic acid has high polarity and is not easy to stabilize the Captan-containing liquid preparation. If the acidity coefficient is higher than 5, it is not easy to have a suitable concentration of H+ The ion is not easy to make the liquid formulation containing captan stable.

[0128] The ascorbic acid fatty acid ester of formula (I) is selected from ascorbyl laurate, ascorbyl olivate, ascorbyl palmitate, ascorbyl stearate, and the ascorbic acid fatty acid ester derivative of formula (I) is selected from magnesium palmitoyl ascorbate, but this does not mean that the person skilled in the art cannot select other suitable ascorbic acid fatty acid esters or their derivatives to achieve the purpose of the present application. In fact, the present inventors have found through a large number of experiments that when R in formula (I) is independently a monovalent hydrocarbon group having 9 to 21 carbon atoms, the purpose of the present application can be achieved.

[0129] The ascorbic acid fatty acid ester of formula (I) or its derivative component of the composite stabilizer is first dispersed in a dispersing aid, then mixed uniformly with the organic acid or its derivative component of the composite stabilizer and the wet dispersing agent, and then added to water and stirred to disperse uniformly; wherein the dispersing aid is selected from one or a combination of several of ethanol, ethylene glycol, propylene glycol, and glycerol.

[0130] The above samples are simultaneously subjected to pre-storage content determination, room temperature time stability test and heat storage test. The heat storage samples are placed in an oven at a temperature of 54±2℃ for 14 days, and the room temperature samples are placed for 12 and 24 months, respectively. The content of captan in the pre-storage samples, heat storage samples and room temperature storage samples at different time periods is determined by high performance liquid chromatography, and the decomposition rate is calculated. The determination results are shown in Table 1, and the test data in the table are the average values of more than 3 test results.

[0131] Comparative Example 1: The 35% captan dispersible oil suspension formulation and preparation method of Comparative Example 1 are basically the same as those of Example 1, except that acetic acid is used instead of the composite stabilizer in Example 1, and the amount is 1.5wt%.

[0132] Comparative Example 2: As shown in Figure 4 and Figure 5 The 35% captan dispersible oil suspension formulation and preparation method of Comparative Example 2 are basically the same as those of Example 1, except that ascorbyl laurate is used instead of the composite stabilizer in Example 1, and the amount is 1.5wt%.

[0133] Table 1 Stability test results of 35% captan dispersible oil suspension

[0134]

[0135]

[0136] The sample in Example 1 in the table has a relative decomposition rate higher than 5% after heat storage, which is unqualified, so no normal temperature storage test is conducted, and "-" in the table indicates no test data. Component A is an organic acid, component B is ascorbic acid fatty acid ester or its derivative of formula (I); A:B is the mass ratio of component A to component B, for example, A:B is 6:2.5, component A (acetic acid) is 5 g, and component B (ascorbic acid laurate) is 2.5 g, for example, A:B is 7:5, component A (lactic acid) is 7 g, and component B (ascorbic acid olivate) is 5 g, and so on.

[0137] 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 ascorbic acid laurate, B2 is ascorbic acid olivate, B3 is ascorbic acid palmitate, B4 is ascorbic acid stearate, and B5 is palmitoyl magnesium ascorbate. In Table 1, CK1 is Control Example 1, and CK2 is Control Example 2.

[0138] As can be seen from the test results in Table 1, because 20% of an emulsifier needs to be added in the 35% captan dispersible oil suspension formulation for use, the dispersible oil suspension has a hydrophilic component. The addition of the composite stabilizer of the present application in the 35% captan dispersible oil suspension can keep the effective component captan stable during storage, and the degradation rates of samples 1-5 in Example 1 of the present application are all lower than those of Control Example 1 (CK1) and Control Example 2 (CK2), and it is also found that the degradation rate after 12 months of storage is generally less than half of the degradation rate after 24 months of storage, which may be due to the fact that the formulation system may absorb water from the environment during normal temperature storage.

[0139] Example 2: The purpose of this experiment is to detect the degradation of the effective component captan in a dispersing medium of water by using different proportions of the composite stabilizer, and a 40% pyraclostrobin·captan suspension is selected for the corresponding experiment, but this does not mean or be interpreted as captan cannot be compounded with other effective components to achieve the same purpose. Those skilled in the art can select other effective components such as difenoconazole, tebuconazole, trifloxystrobin, picoxystrobin, polyoxin, bromoxynil, and other effective components, and select a suitable wetting dispersant to prepare a liquid formulation of captan and other effective components with a desired content.

[0140] 40% pyraclostrobin·captan suspension

[0141] Captan 350 g, pyraclostrobin 50 g, wetting dispersant 80 g, composite stabilizer in an appropriate amount, antifreeze 30 g, preservative 2 g, thickening agent 20 g, and defoaming agent 2 g are weighed, and the dispersing medium water is supplemented to 1000 g.

[0142] In the experimental example, the wetting dispersant is specifically polycarboxylate wetting dispersant 40 g, non-ionic hydroxyl polyethylene oxide block copolymer wetting dispersant 40 g, but the skilled person in the art can select other suitable wetting dispersants, which include at least one of polymeric carboxylate, sulfonate, EOPO polyether, and phosphate, wherein the phosphate includes but is not limited to triphenyl ethenyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and castor oil polyoxyethylene ether phosphate. The desired content of captan and other active ingredient complex liquid preparation is obtained, including 40% pyraclostrobin captan suspension concentrate.

[0143] In the experimental example, the present inventors select a suitable antifreeze agent, including but not limited to ethylene glycol, propylene glycol, and glycerol. In the experimental example, the antifreeze agent is specifically selected as ethylene glycol.

[0144] In the experimental example, the present inventors select a suitable preservative, including but not limited to carboxin, sodium benzoate, etc. In the experimental example, the antifreeze agent is specifically selected as carboxin, which is a mixture of 2-methyl-4-isothiazolin-3-one (MI) and 2-methyl-5-chloro-4-isothiazolin-3-one (CMI) and inorganic salt stabilizer, usually CMI:MI = 3:1.

[0145] In the experimental example, the present inventors select a suitable thickening agent, including organic thickening agent and inorganic thickening agent, wherein the organic thickening agent includes but is not limited to xanthan gum, and the inorganic thickening agent includes but is not limited to magnesium aluminum silicate. More specifically, xanthan gum 3 g and magnesium aluminum silicate 17 g are selected in the experimental example.

[0146] In the experimental example, the present inventors select a suitable antifoaming agent, including but not limited to silicone antifoaming agent and n-octanol. More specifically, the antifoaming agent is selected as silicone antifoaming agent in the experimental example.

[0147] In the experimental example, the selected dispersing medium is water, and more specifically, the selected dispersing medium is deionized water. The deionized water is a colorless and clear liquid, odorless and tasteless, with a resistivity of more than 0.5 MΩ·cm (megaohm·centimeter), and the highest resistivity can reach 18 MΩ·cm.

[0148] The amount of the composite stabilizer can also be any value between 0.6 and 60 g. Other samples were prepared according to the process for preparing the above-mentioned 40% pyraclostrobin · clorothanol suspension agent. For the purpose of convenient comparison, 5 groups of composite stabilizers were selected in this experimental example, and more specifically, the types of organic acids are shown in Table 2, and the types of ascorbic acid fatty acid esters or their derivatives are shown in Table 2. However, this does not mean that those skilled in the art cannot achieve the purpose of the present application by selecting other suitable organic acids and ascorbic acid fatty acid esters or their derivatives. In fact, the present inventors have found through a large number of experiments that when the acidity coefficient (25°C) of the organic acid is 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 application can be achieved.

[0149] The composite stabilizer and the wetting dispersant were added to water and stirred to disperse uniformly to obtain an auxiliary dispersing liquid; pyraclostrobin and clorothanol were added to the auxiliary dispersing liquid and stirred to disperse uniformly, and then placed under a grinding medium to grind. The particle size of pyraclostrobin and clorothanol reached the desired particle size, and then the grinding liquid was filtered to obtain a grinding liquid. In this experimental example, the particle size D 90 of the grinding liquid was less than 5 microns, and the particle size D 95 of the grinding liquid was less than 8 microns. The antifreeze agent and the thickening agent were stirred and dispersed uniformly, then added to water, and then the preservative was added. After stirring and dispersing uniformly, a thickening dispersing liquid was obtained. The grinding liquid and the thickening dispersing liquid were mixed and stirred to disperse uniformly to obtain a 40% pyraclostrobin · clorothanol suspension agent.

[0150] The above samples were simultaneously subjected to pre-storage content determination, room temperature time stability test and heat storage test. The heat storage samples were placed in an oven set at a temperature of 54±2°C for 14 days, and the room temperature samples were placed for 12 and 24 months, respectively. The content of clorothanol in the pre-storage samples, heat storage samples and room temperature storage samples at different time periods was determined by high performance liquid chromatography, and the decomposition rate was calculated. The test results are shown in Table 1, and the test data in the table are the average values of more than 3 test results.

[0151] Comparative Example 3: The formulation and preparation method of the 40% pyraclostrobin · clorothanol suspension agent prepared in Comparative Example 3 are basically the same as those in Example 2, and the difference between them is that acetic acid is used instead of the composite stabilizer in Example 2, and the amount is 1.5 wt%.

[0152] Comparative Example 4: The formulation and preparation method of the 40% pyraclostrobin · clorothanol suspension agent prepared in Comparative Example 4 are basically the same as those in Example 2, and the difference between them is that ascorbic acid palmitate is used instead of the composite stabilizer in Example 2, and the amount is 1.5 wt%.

[0153] The inventors of this application found that, after 14 days of heat storage and 24 months of storage at room temperature, the change rate of Samples 6 to 10 of Examples and Samples 3 to 4 of Control Examples was approximately 0.2%. Among the samples after storage, Samples 6 to 10 of Examples showed normal performance, as detailed in the figure.

[0154] Significant abnormalities were observed in samples 3 through 4 of the control examples. Taking sample 4 of the control example as an example, for instance... Figure 1 The sample shown, after 14 days of heat storage, became very viscous, making sampling difficult, as indicated by the control example sample 4. Figure 2 As shown, the pourability of control example sample 4 also deteriorated, making the test impossible. Figure 3 As shown, when the control example sample 4 was heat-stored for 14 days and then diluted with water for suspension testing, the diluted solution was at the bottom of the graduated cylinder with 25 mL of sample. It can be seen that there is obvious precipitate.

[0155] The inventors of this application also discovered that, after 24 months of heat storage and at room temperature, the control sample 4 showed obvious sedimentation. After pouring out the upper layer of liquid from the heat-stored sample, the effective components were found to be 20.88 wt% captan and 6.01 wt% pyraclostrobin. However, after shaking the heat-stored sample and testing it again, the effective components were found to be 36.24 wt% captan and 5.86% pyraclostrobin.

[0156] Table 2. Storage stability test results of 40% pyraclostrobin·captan suspension concentrate

[0157]

[0158] In Tables 2 and 3, the samples in Example 1 showed a relative decomposition rate higher than 5% after heat storage, which is unqualified. Therefore, no room temperature storage test was conducted. "-" in the table indicates 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 acid 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.

[0159] In Tables 2 and 3, A6 is propionic acid, A7 is glycolic acid, A8 is citric acid, A9 is glutaric acid, and A10 is triglyceride; B6 is ascorbate dipalmitate, B7 is ascorbate tetraisopalmitate, B8 is ascorbate palmitate, B9 is ascorbate tetrapalmitate, and B10 is ascorbate palmitate trisodium phosphate.

[0160] In Tables 2 and 3, CK3 is the control example 3 and CK4 is the control example 4.

[0161] From the results of Table 2, it can be seen that the degradation rates of samples 6-10 of the present application are significantly lower than those of control samples CK3-CK4. In CK4, no organic acid is added, even if 2wt% ascorbic acid palmitate is added as a stabilizer, the degradation rate of captan is as high as 14.3% after 14 days of heat storage, and the degradation rate is as high as 16.9% at room temperature, and the stability is also poor. CK3 only adds organic acid, although the degradation rate of captan reaches the qualified level of 4.3%, but the degradation rate of pyraclostrobin is as high as 6.9%, which is unqualified.

[0162] The inventors further detected the pH value changes of the samples before and after heat storage, and found that the pH values of samples 6-10 of Example 2 before heat storage were 4.10-5.93, and the pH values after heat storage were 3.91-5.65. The pH value of CK3 sample before heat storage was 3.09, and the pH value after heat storage was 2.82. The pH value of CK4 sample before heat storage was 5.90, and the pH value after heat storage was 4.18. The pH value changes of the samples before and after storage at room temperature were found, and it was found that the pH values of samples 6-10 of Example 1 before storage at room temperature were 4.10-5.93, and the pH values after storage at room temperature were 3.59-5.56. It was found that the pH value of CK3 sample before storage at room temperature was 3.09, and the pH value after storage at room temperature was 2.82. The pH value of CK4 before storage at room temperature was 3.09, and the pH value after storage at room temperature was 2.63. Based on the above data, the inventors of the present application speculate that the degradation of captan may cause acidification of the system.

[0163] Table 3 Physical stability test results of 40% pyraclostrobin·captan suspension concentrate

[0164]

[0165]

[0166] From the results of Table 3, it can be seen that the apparent stability of samples 6-10 of the present application is significantly better than that of control samples CK3-CK4. CK3 only adds organic acid citric acid, due to the decrease of wetting and dispersing performance of the wetting and dispersing agent under acidic conditions, the water separation rate of the sample increases to 18%, resulting in unqualified apparent stability. In CK4, captan is not added with organic acid, even if 2wt% ascorbic acid palmitate is added as a stabilizer, due to the degradation of captan, the water separation rate of CK4 sample increases to a certain extent, although it is lower than that of CK3, but it is much higher than that of samples 6-10 of the present application, and the bottoming phenomenon occurs, and the particle size also expands to a certain extent.

[0167] The inventors also found through experiments that controlling the particle size of the 40% pyraclostrobin·captan suspension concentrate grinding liquid can also solve the bottoming problem of CK3 and CK4 to a certain extent. The particle size D 90less than 5 microns, especially further grinding the microparticle size D of the liquid 95 less than 8 microns, the particle size of CK3 and CK4 is solved to a certain extent, although the microparticle size is also increased, but after adding the composite stabilizer of the application, the microparticle size is also increased to a certain extent. The inventors of the present application found that by controlling the above microparticle size D 90 and D 95 , to a certain extent, the problem of caking is also solved under the same conditions.

[0168] The above test results show that the addition of the composite stabilizer of the application in the 40% pyraclostrobin·clorimazole suspension can keep the active ingredient pyraclostrobin stable during storage.

[0169] Example 3: The purpose of this experiment is to configure different proportions of composite stabilizer to reduce the degradation of active ingredient clorimazole in water as the dispersion medium, and the stability of the liquid preparation system after adding the film forming agent. 20% pyraclostrobin·clorimazole seed treatment suspension is selected for corresponding experiments, but this does not mean or be interpreted as clorimazole cannot be compounded with other active ingredients to achieve the same purpose. The skilled person in the art can select suitable other active ingredients such as difenoconazole, tebuconazole, trifloxystrobin, enoxastrobin, polyoxin, bromoxynil, etc. and suitable wetting dispersants to configure clorimazole with other active ingredients to obtain the desired content of seed treatment suspension.

[0170] 20% pyraclostrobin·clorimazole seed treatment suspension

[0171] Take clorimazole 150g, pyraclostrobin 50g, wetting dispersant 60g, composite stabilizer appropriate amount, antifreeze 30g, preservative 2g, thickening agent 10g, defoaming agent 2g, film forming agent 30g, warning color dye 30g, dispersion medium water to 1000g.

[0172] In this experimental example, the wetting dispersant is specifically polycarboxylate wetting dispersant 30g, non-ionic hydroxyl polyethylene oxide block copolymer wetting dispersant 30g, but the skilled person in the art can select suitable other wetting dispersants. The wetting dispersants that can be selected by the skilled person in the art include at least one of polymeric carboxylate, sulfonate, EOPO polyether, phosphate, wherein the phosphate includes but is not limited to triphenyl ethenyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, castor oil polyoxyethylene ether phosphate. The wetting dispersant is configured to obtain the desired content of clorimazole and other active ingredient liquid preparation, including 20% pyraclostrobin·clorimazole treatment suspension.

[0173] In the present experimental example, the present inventors selected a suitable antifreezing agent, including but not limited to ethylene glycol, propylene glycol, glycerol, and in the present experimental example, ethylene glycol was specifically selected as the antifreezing agent.

[0174] In the present experimental example, the present inventors selected a suitable antifreezing agent, including but not limited to ethylene glycol, propylene glycol, glycerol, and in the present experimental example, ethylene glycol was specifically selected as the antifreezing agent.

[0175] In the present experimental example, the present inventors selected a suitable thickening agent, including an organic thickening agent and an inorganic thickening agent, wherein the organic thickening agent includes but is not limited to xanthan gum, and the inorganic thickening agent includes but is not limited to magnesium aluminum silicate, and more specifically, 1 g of xanthan gum and 9 g of magnesium aluminum silicate were selected in the present experimental example.

[0176] In the present experimental example, the present inventors selected a suitable film-forming agent, including but not limited to acrylic emulsion, polyethylene glycol, and polyvinyl alcohol, and the content of the film-forming agent was 0.5 wt% to 5 wt%, and more specifically, acrylic emulsion was selected as the film-forming agent in the present experimental example.

[0177] The present inventors selected a thickening agent and a film-forming agent for the purpose of achieving a viscosity of 170 to 200 mPa·s at 20°C and a viscosity of 120 to 150 mPa·s at 40°C for the seed treatment suspension, and those skilled in the art can achieve the purpose of the present application by adjusting the amount and selecting the corresponding type of raw material.

[0178] In the present experimental example, the warning color dye was selected from one or more than two of DeKema, basic roseine, water-based magenta, and acid scarlet, and the amount was 2.5 to 5.5 wt%, and more specifically, acid scarlet was selected as the warning color dye.

[0179] In the present experimental example, the present inventors selected a suitable antifreezing agent, including but not limited to ethylene glycol, propylene glycol, glycerol, and in the present experimental example, ethylene glycol was specifically selected as the antifreezing agent.

[0180] In the present experimental example, the selected dispersion medium was water, and more specifically, deionized water was selected as the dispersion medium; the deionized water was a colorless and clear liquid, odorless, tasteless, and had a resistivity of greater than 0.5 MΩ·cm (megaohm·centimeter), and the maximum resistivity could reach 18 MΩ·cm.

[0181] The amount of the composite stabilizer can also be any value between 0.3 and 31.5 g. Other samples were prepared according to the process for preparing 20% pyraclostrobin · clorimazone suspending agent with the above-mentioned formula. For the purpose of convenient comparison, 5 groups of composite stabilizers were selected in this experimental example, and more specifically, the types of organic acids were selected as shown in Table 4, and the types of ascorbic acid fatty acid ester or its derivatives were also selected as shown in Table 4. However, this does not mean that those skilled in the art cannot achieve the purpose of the present application by selecting other suitable organic acids and ascorbic acid fatty acid ester or its derivatives. In fact, the present inventors have found through a large number of experiments that when the acidity coefficient (25℃) of the organic acid is 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 application can be achieved.

[0182] The composite stabilizer and the wetting dispersant were added to water and stirred to disperse uniformly to obtain an auxiliary dispersing liquid; pyraclostrobin and clorimazone were added to the auxiliary dispersing liquid and stirred to disperse uniformly, and then ground under a grinding medium. The particle size of pyraclostrobin and clorimazone reached the desired particle size, and then the grinding liquid was filtered to obtain a grinding liquid. In this experimental example, the particle size D 90 of the grinding liquid was less than 5 microns, and the particle size D 95 of the grinding liquid was less than 8 microns. The antifreeze agent and the thickening agent were stirred and dispersed uniformly, and then added to water. The preservative was then added, stirred and dispersed uniformly to obtain a thickening dispersing liquid. The grinding liquid was mixed with the thickening dispersing liquid, the film-forming agent and the warning color dye, stirred and dispersed uniformly to obtain 20% pyraclostrobin · clorimazone seed treatment suspending agent.

[0183] The above samples were simultaneously subjected to pre-storage content determination, room temperature time stability test and heat storage test. The heat storage samples were placed in an oven at a temperature of 54±2℃ for 14 days, and the room temperature samples were placed for 12 and 24 months, respectively. The content of clorimazone in the pre-storage samples, heat storage samples and room temperature time storage samples at different time periods was determined by high performance liquid chromatography, and the decomposition rate was calculated. The test results are shown in Table 1, and the test data in the table are the average values of more than 3 test results.

[0184] Comparative Example 5: The formula and preparation method of 20% pyraclostrobin · clorimazone seed treatment suspending agent prepared in Comparative Example 5 were basically the same as those in Example 3, except that acetic acid was used instead of the composite stabilizer in Example 3, and the amount was 0.5 wt%.

[0185] Comparative Example 6: The formula and preparation method of 20% pyraclostrobin · clorimazone seed treatment suspending agent prepared in Comparative Example 6 were basically the same as those in Example 3, except that acetic acid was used instead of the composite stabilizer in Example 3, and the amount was 2 wt%.

[0186] Table 4 Storage stability test results of 20% pyraclostrobin · clorimazone seed treatment suspensions

[0187]

[0188] The relative decomposition rates of the samples in Example 3 in Table 4 and Table 5 after heat storage were higher than 5%, which were unqualified, so no normal temperature storage test was conducted, and "-" in the table indicates no test data. Component A is an organic acid, component B is ascorbyl fatty acid ester or its derivative of formula (I); A:B is the mass ratio of component A to component B, for example, component Al l (acetic acid) is 5 g, component Bl l (ascorbyl laurate) is 20 g, then A:B is 5:20, for example, component A12 (butenedioic acid) is 4 g, component B12 (ascorbyl olivate) is 15 g, then A:B is 4:15, and so on.

[0189] In Table 4 and Table 5, Al l is acetic acid, A12 is butenedioic acid, A13 is hexanetricarboxylic acid, A14 is dodecylbenzenesulfonic acid, and A15 is methylbenzenesulfonic acid; Bl l is ascorbyl laurate, B12 is ascorbyl olivate, B13 is ascorbyl palmitate, B14 is ascorbyl stearate, and B15 is palmitoyl magnesium ascorbate.

[0190] In Table 4 and Table 5, CK5 is control example 5, and CK6 is control example 6.

[0191] From the results in Table 4, it can be seen that the degradation rates of the 20% pyraclostrobin · clorimazone seed treatment suspension samples 11-15 of the present application were significantly lower than those of the control samples CK5-CK6. In CK6, no organic acid was added, even if 2 wt% of ascorbyl laurate was added as a stabilizer, the degradation rate of clorimazone was as high as 8.36% after 14 days of heat storage, the normal temperature storage degradation rate was as high as 10.18%, and the stability was also poor.

[0192] The inventors further detected the pH value change of the samples before and after heat storage, and found that the pH value of the samples 11-15 of Example 3 was 4.50-5.96 before heat storage and 4.36-5.72 after heat storage, the pH value of the CK5 sample was 3.02 before heat storage and 2.76 after heat storage, and the pH value of the CK6 sample was 6.49 before heat storage and 4.27 after heat storage; thus, the pH value change of the samples of the present application in Example 3 was small; the pH value change of the samples before and after normal temperature storage was found, and the pH value of the samples 6-10 of Example 1 was 4.50-5.96 before normal temperature storage and 4.34-5.62 after normal temperature storage, the pH value of the CK5 sample was 3.02 before normal temperature storage and 2.65 after normal temperature storage, and the pH value of the CK6 sample was 6.49 before normal temperature storage and 4.03 after normal temperature storage; the degradation of the chlorothalonil can cause the acidification of the system, thus leading to the increase of the degradation rate of the pyraclostrobin.

[0193] The CK5 only added the organic acid acetic acid, although the degradation rate of the chlorothalonil reached the qualified level of 3.74%, but the degradation rate of the pyraclostrobin rose to 7.74%, which was an unqualified level; the reason was that the pyraclostrobin was unstable under acidic conditions, and the increase of the degradation rate led to the increase.

[0194] Table 5 Physical stability test results of 20% pyraclostrobin-chlorothalonil seed treatment suspensions

[0195]

[0196]

[0197] From the results in Table 5, it can be seen that the apparent stability of the samples 11-15 of the present application was obviously superior to the control samples CK5-CK6; the CK5 only added the organic acid acetic acid, and due to the decrease of the wetting and dispersing performance of the wetting and dispersing agent under acidic conditions, the water separation rate of the sample rose to 10%, leading to the unqualified apparent stability. The CK6 did not add the organic acid, even though 2wt% of ascorbic acid laurate was added as a stabilizer, due to the degradation of the chlorothalonil, the CK6 sample had a certain water separation rate, which was lower than that of the CK5, but higher than that of the samples 6-10 of the present application; the CK5-CK6 also had the phenomenon of bottoming and the particle size was also expanded to a certain extent.

[0198] The above test results show that the addition of the composite stabilizer of the present application in the 20% pyraclostrobin-chlorothalonil seed treatment suspensions can keep the effective components pyraclostrobin and chlorothalonil stable during the storage process.

[0199] The inventors of the present application also used the samples of the present experimental example and the CK5 and CK6 for seed coating, which will be described in detail in Figure 6 and Figure 7The experimental sample has certain surface activity and lipophilicity due to the addition of ascorbic acid fatty acid ester and its derivatives, so that the seed coating film forming agent is good and the film forming is uniform. It also shows high brightness, good appearance and smoothness, so that the seeds are not sticky, the seeds are evenly sown, the sowing is not affected, and the seedling rate is not affected.

[0200] Example 4: The purpose of this experiment is to configure different proportions of composite stabilizers to reduce the degradation of the effective ingredient pyraclostrobin in a water dispersion medium, and to investigate the stability of the liquid preparation system after the addition of a film forming agent. A 7% pyraclostrobin·fludioxonil·thiamethoxam seed treatment suspension concentrate was selected for the corresponding experiment, but this does not mean or be interpreted as pyraclostrobin cannot be compounded with other effective ingredients to achieve the same purpose. Skilled persons in the art can select appropriate other effective ingredients, such as difenoconazole, tebuconazole, trifloxystrobin, enoxastrobin, polyoxin, bromoxynil, etc. and select appropriate wetting dispersants to configure a seed treatment suspension concentrate of dithianon and other effective ingredients with the desired content.

[0201] Pyraclostrobin·fludioxonil·thiamethoxam seed treatment suspension concentrate

[0202] An appropriate amount of pesticide active ingredient, 60g of wetting dispersant, an appropriate amount of stabilizing and safety agent, 30g of antifreeze, 2g of preservative, 20g of thickening agent, 2g of defoaming agent, 30g of film forming agent, 30g of warning color dye, and water to make up to 1000g.

[0203] In this experimental example, the inventors selected pyraclostrobin, fludioxonil and thiamethoxam as the pesticide active ingredient, and the mass ratio of pyraclostrobin, fludioxonil and thiamethoxam was (1-5):1:(10-100). The dosage was 4-40wt%, preferably 5-25wt%, and more preferably, the pesticide active ingredient in this experimental example was 7wt%.

[0204] In the experimental example, the wetting dispersant is specifically 30 g of polycarboxylate wetting dispersant and 30 g of non-ionic hydroxyl polyethylene oxide block copolymer wetting dispersant, but the person skilled in the art can select other wetting dispersants, and the wetting dispersants that the person skilled in the art can select include at least one of polymeric carboxylate, sulfonate, EOPO polyether, and phosphate, wherein the phosphate includes but is not limited to triphenylethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, and castor oil polyoxyethylene ether phosphate. The purpose content of the captan and other effective ingredient complex liquid preparation is configured to obtain 7% pyraclostrobin · fludioxonil · thiamethoxam seed treatment suspension concentrate.

[0205] In the experimental example, the present inventors select a suitable antifreeze agent, including but not limited to ethylene glycol, propylene glycol, and glycerol. In the experimental example, the antifreeze agent is specifically selected to be ethylene glycol.

[0206] In the experimental example, the present inventors select a suitable preservative, including but not limited to Kathon, sodium benzoate, and the like. In the experimental example, the antifreeze agent is specifically selected to be Kathon, which is a mixture of 2-methyl-4-isothiazolin-3-one (MI) and 2-methyl-5-chloro-4-isothiazolin-3-one (CMI) and inorganic salt stabilizer, and generally CMI:MI = 3:1.

[0207] In the experimental example, the present inventors select a suitable thickening agent, including an organic thickening agent and an inorganic thickening agent, wherein the organic thickening agent includes but is not limited to xanthan gum, and the inorganic thickening agent includes but is not limited to magnesium aluminum silicate. More specifically, the combination of 2 g of xanthan gum and 18 g of magnesium aluminum silicate is selected in the experimental example.

[0208] In the experimental example, the present inventors select a suitable film-forming agent, including but not limited to acrylic emulsion, polyethylene glycol, and polyvinyl alcohol. The content of the film-forming agent is 0.5 wt% to 5 wt%. More specifically, the film-forming agent selected in the experimental example is acrylic emulsion.

[0209] The purpose of selecting the thickening agent and the film-forming agent in one aspect is to make the viscosity of the seed treatment suspension concentrate be 170 mPa·s to 200 mPa·s at 20°C and be 120 mPa·s to 150 mPa·s at 40°C. The person skilled in the art can achieve the purpose of the present application by adjusting the amount and selecting the corresponding type of raw material.

[0210] In the experimental example, the warning color dye is selected from one or more than two of DeKema, basic roseine, water-based rose, and acid scarlet. The amount is 2.5 wt% to 5.5 wt%. More specifically, water-based rose is selected as the warning color dye.

[0211] In the present experimental example, the present inventors selected suitable antifoaming agents, including but not limited to silicone antifoaming agents, n-octanol, lauryl alcohol, and more specifically, the present inventors selected silicone antifoaming agents as the antifoaming agents.

[0212] In the present experimental example, the dispersing medium selected is water, and more specifically, the dispersing medium selected is deionized water; the deionized water is a colorless and clear liquid, odorless, tasteless, and has a resistivity of greater than 0.5 MΩ·cm (megaohm·centimeter), and the highest resistivity can reach 18 MΩ·cm.

[0213] The amount of the stabilizing and safening agent can also be any value within the range of 0.6-60 g, and other samples were prepared according to the process of preparing 7% fluazinam·fludioxonil·clothianidin seed treatment suspension concentrate with the above-mentioned formulation. Since the purpose of the present experimental example is to facilitate comparison, the present inventors selected 5 groups of stabilizing and safening agents, and more specifically, the types of organic acids are shown in Table 6, and the types of ascorbic acid fatty acid esters or their derivatives are also shown in Table 6, but this does not mean that those skilled in the art cannot achieve the purpose of the present application by selecting other suitable organic acids and ascorbic acid fatty acid esters or their derivatives. In fact, through a large number of experiments, the present inventors found that when the acidity coefficient (25℃) of the organic acid is 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 application can be achieved. It is particularly important that the purpose of adding the organic acid to the 7% fluazinam·fludioxonil·clothianidin seed treatment suspension concentrate is different from that of experimental example 1. The purpose of adding the stress-resistant organic acid to the seed treatment suspension concentrate of the present application is to increase the content of vitamin C and soluble solids in the plant body and the stress resistance of the plant. The pH value of the seed treatment suspension concentrate can also be adjusted to the desired range by adding the organic acid. Therefore, when the pH value of the seed treatment suspension concentrate is already within the desired range, the organic acid can also not be added.

[0214] The stabilizing and safening agent and the wetting and dispersing agent were added to water and stirred to disperse uniformly to obtain an auxiliary dispersing liquid; the fluazinam, fludioxonil, and clothianidin were added to the auxiliary dispersing liquid and stirred to disperse uniformly, and then the mixture was subjected to grinding under a grinding medium. The particle size of the ground fluazinam, fludioxonil, and clothianidin reached the desired particle size, and then the mixture was filtered to obtain a ground liquid. In the present experimental example, the particle size D 90 of the ground liquid was less than 5 microns, and the particle size D 95 of the ground liquid was less than 8 microns. The antifreeze agent and the thickening agent were stirred and dispersed uniformly, and then added to water. The preservative was then added, and the mixture was stirred and dispersed uniformly to obtain a thickening dispersing liquid. The ground liquid was mixed with the thickening dispersing liquid, the film-forming agent, and the warning color dye, and the mixture was stirred and dispersed uniformly to obtain the 7% fluazinam·fludioxonil·clothianidin seed treatment suspension concentrate.

[0215] The above samples were subjected to pre-storage content determination, room temperature stability test and heat storage test at the same time. The heat storage samples were placed in an oven at a temperature of 54±2℃ for 14 days, and the room temperature samples were placed for 12 and 24 months, respectively. The content of captan in the pre-storage samples, heat storage samples and room temperature storage samples at different time periods was determined by high performance liquid chromatography, and the decomposition rate was calculated. The determination results are shown in Table 1. The test data in the table are the average values of more than 3 test results.

[0216] Comparative Example 7: The preparation method of the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate formula configured in Comparative Example 7 is basically the same as that in Example 4, and the difference between Comparative Example 7 and Example 4 is that acetic acid is used instead of the composite stabilizer in Example 4, and the amount is 1.5wt%.

[0217] Comparative Example 8: The preparation method of the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension concentrate formula configured in Comparative Example 8 is basically the same as that in Example 4, and the difference between Comparative Example 8 and Example 4 and Comparative Example 7 is that triethanolamine is used instead of the composite stabilizer in Example 4, and the amount is 1.5wt%.

[0218] Table 6 and Table 7, CK7 is Comparative Example 7, and CK8 is Comparative Example 8.

[0219]

[0220] The relative decomposition rate of the sample in Example 4 in Table 6 and Table 7 after heat storage is higher than 5%, which is unqualified, so no room temperature storage test is performed. In the table, “-” indicates no test data. Component A is an organic acid, component B is ascorbyl fatty acid ester or its derivative of formula (I); A:B is the mass ratio of component A to component B. For example, if component A (fulvic acid) is 10g and component B (ascorbyl laurate) is 2.5g, then A:B is 10:2.5. If component A is zero and component B (ascorbyl tetraisopalmitate) is 5g, then A:B is 0:5. Similarly, A:B is calculated in the same way.

[0221] In Table 6 and Table 7, A16 is blank, 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 ascorbyl palmitate phosphate trisodium; and B21 is triethanolamine.

[0222] In Table 6 and Table 7, CK7 is Comparative Example 7, and CK8 is Comparative Example 8.

[0223] From the results of Table 6, it can be seen that the stabilizer of the present application is used for 7% fluoxastrobin·flumetover·clothianidin seed treatment suspension concentrate, the degradation rates of the experimental example samples 16-20 are all significantly lower than those of the control samples CK7-CK8. In CK7, organic acid glycine is added, after 14 days of heat storage, the degradation rate of clothianidin is unqualified, which is 14.38%, due to the whole system being in an acidic condition, the degradation rate of fluoxastrobin is also 6.26%, the degradation rate at room temperature storage is as high as 6.67%, the degradation rate of flumetover is 5.95%, the degradation rate at room temperature storage is as high as 6.03%, and the stability is also poor. In CK8, organic base triethanolamine is added, although the degradation rate of clothianidin is qualified, which is 4.94% after 14 days of heat storage, but it also makes the whole system in an alkaline condition, the degradation rate of fluoxastrobin is as high as 6.73% after 14 days of heat storage, the degradation rate at room temperature storage is as high as 6.90%, the degradation rate of flumetover is 6.19%, the degradation rate at room temperature storage is as high as 6.30%, and the stability is also poor.

[0224] Therefore, the inventors of the present application found that the ascorbic acid fatty acid ester or its derivative of the present application, and the complex stabilizer can also stabilize the effective component clothianidin which is stable in weak alkaline.

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

[0226]

[0227] From the results of Table 7, it can be seen that the apparent stability of the samples 16-20 of Example 4 of the present application is significantly better than that of the control samples CK7-CK8, CK7 only adds organic acid glycine, due to the decrease of wetting and dispersing performance of the wetting and dispersing agent under acidic conditions, the water separation rate of the sample increases to 12%, resulting in unqualified apparent stability. CK8 does not add organic base triethanolamine, and the water separation rate and the sample 16-20 are equivalent, in addition, CK7 also produces bottoming phenomenon, and the particle size is also expanded to a certain extent.

[0228] The above test results show that the addition of the stabilizing and safening agent of the present application in 7% fluoxastrobin·flumetover·clothianidin seed treatment suspension concentrate can keep the effective components fluoxastrobin, flumetover and clothianidin stable during storage.

[0229] The inventors of the present application also use the experimental example samples and CK7, CK8 for corn seed coating, which is described in detail in Figure 8 and Figure 9The sample of the present experimental example has certain surface activity and lipophilicity due to the addition of ascorbic acid fatty acid ester and its derivatives, so that the seed coating film forming agent is good and the film is uniform after coating. It also shows high brightness, good appearance and smoothness, so that the seeds are not sticky, the seeds are evenly sown, the sowing is not affected, and the seedling rate is not affected. Because ascorbic acid fatty acid ester and its derivatives have antioxidant capacity, they can avoid the oxidation of pigments and active ingredients, so the color of the coated seeds is bright and the appearance is good. Ascorbic acid fatty acid ester and its derivatives have stress resistance and are safe to seeds, and do not affect the seedling rate.

[0230] Biological activity experiment example 1

[0231] The present biological activity experiment is to test the effect of the composite stabilizer 40% pyraclostrobin · captan suspension concentrate of the present application on reducing phytotoxicity.

[0232] 1. Materials and methods

[0233] 1.1. Test materials

[0234] The test agents are samples prepared in Example 2, namely sample 6 (sample number 6), sample 7 (sample number 7), and sample 8 (sample number 8). The control sample is control example 3 (CK3). The test corn varieties are three conventional varieties commonly planted in Shandong Province, namely Zhengdan 958, Nonghua 101, and Nongda 108.

[0235] 1.2. Test method

[0236] The test was conducted in Heze City, Shandong Province in 2021. The three test corn varieties, Zhengdan 958, Nonghua 101, and Nongda 108, were transplanted on May 8, 2021. The farmland was flat, with medium water level and medium to high soil fertility. The plants were planted in ridges with a plant spacing of 30 cm and a row spacing of 50 cm. There were about 3000 plants per 667m 2 The water management and pest control measures during the corn seedling stage were at the local medium level.

[0237] The 40% pyraclostrobin · captan suspension concentrate test agent has a total of three, and each test agent test is set to 3000, 2000, 1000, 750, 500 and 250 times 6 treatments. The corresponding control sample CK3 test is also set to 3000, 2000, 1000, 750, 500 and 250 times 6 treatments, as well as a water treatment. Each treatment has 2 replicates, each replicate has 1 plot, a total of 50 plots, and a random block arrangement. Each plot has about 20 test corn plants. The pesticide is applied in the afternoon on a cloudy day, and the spraying tool is a hand sprayer. The whole plant is sprayed, and each 667m 2The application amount was about 150L. The test was sprayed once, and the specific application time was the afternoon of June 7 (overcast, 24-26°C), and the growth stages of each variety were as follows: Zhengdan 958, Nonghua 101, and Nongda 108 were at the 5-leaf stage.

[0238] 1.3. Investigation method

[0239] The test was investigated twice during the test, once 4 days and 11 days after the first application, and the specific investigation time was June 11 (6-7 leaf stage of the test corn) and June 18 (9-10 leaf stage of the test corn).

[0240] The investigation content was to visually observe the influence of the agent on the crop: to observe the influence of each test concentration of the agent on the corn heart leaf and leaf at the seedling stage or whether there was phytotoxicity phenomenon, and to observe the color change of the corn leaf at the seedling stage. If there was phytotoxicity, the type and degree of phytotoxicity were recorded, and the beneficial influence on the crop (such as stimulating growth, promoting maturity, etc.) was also recorded.

[0241] According to the phytotoxicity classification method, the phytotoxicity of each plot was recorded, and -, +, ++, +++, and ++++ were used to represent. The phytotoxicity classification was as follows:

[0242] -: no phytotoxicity; +: slight phytotoxicity, which slightly affected the growth of corn at the seedling stage and did not affect the normal growth of the crop; ++: mild phytotoxicity, which could be recovered, slightly affected the growth of corn at the seedling stage, and would not cause yield reduction of the crop; +++: obvious phytotoxicity, which affected the normal growth of corn at the seedling stage, caused a certain degree of loss of yield and quality of the crop; ++++: high phytotoxicity, which hindered the growth of corn at the seedling stage, and caused serious loss of yield and quality of the crop.

[0243] 2. Results and analysis

[0244] 4 days after the first application, the 3000-fold, 2000-fold, 1000-fold, and 750-fold test concentration treatments of sample 6 did not cause phytotoxicity to the heart leaf and leaf of the three varieties of corn at the seedling stage, and the growth was normal; the 500-fold and 250-fold test concentration treatments of sample 6 did not cause phytotoxicity to the heart leaf and leaf of the three varieties of corn at the seedling stage, and the growth was normal, but slight phytotoxicity was caused to the base of individual tender leaves of corn, which showed yellow chlorosis. The main reason may be that the pesticide solution on the leaves converged to the base of the tender leaves.

[0245] Table 8 Investigation results of sample 6 on the safety of corn at the seedling stage

[0246]

[0247]

[0248] After 11 days of 1-time application, the 3000-fold, 2000-fold, 1000-fold, 750-fold, 500-fold and 250-fold test concentrations of sample 6 did not cause phytotoxicity to the heart leaves of the three corn varieties at the seedling stage, and the leaves grew normally. Therefore, it can be seen that the phytotoxicity caused by sample 6 is limited to the base of individual tender leaves of corn, and with the passage of time, the phytotoxicity site of corn is gradually relieved, which does not affect the normal vegetative growth and flowering of corn at the middle and late stages.

[0249] The 3000-fold, 2000-fold, 1000-fold and 750-fold test concentrations of sample 7 did not cause phytotoxicity to the heart leaves of the three corn varieties at the seedling stage, and the leaves grew normally; the 500-fold test concentration of sample 7 did not cause phytotoxicity to the heart leaves of Zhengdan 958 corn at the seedling stage, and the leaves grew normally, but caused slight phytotoxicity to the base of individual tender leaves of corn, showing yellow chlorosis; however, the 500-fold test concentration of sample 7 did not cause phytotoxicity to the heart leaves of Nonghua 101 and Nongda 108 corn at the seedling stage, and the leaves grew normally. After treatment with the 250-fold test concentration of sample 7, the heart leaves of the three corn varieties at the seedling stage did not cause phytotoxicity, and the leaves grew normally, but caused slight phytotoxicity to the base of individual tender leaves of corn, showing yellow chlorosis.

[0250] Table 9 Investigation results of sample 7 on corn seedling safety test

[0251]

[0252] After 11 days of 1-time application, the 3000-fold, 2000-fold, 1000-fold, 750-fold, 500-fold and 250-fold test concentrations of sample 6 did not cause phytotoxicity to the heart leaves of the three corn varieties at the seedling stage, and the leaves grew normally. Therefore, it can be seen that the phytotoxicity caused by sample 6 is limited to the base of individual tender leaves of corn, and with the passage of time, the phytotoxicity site of corn is gradually relieved, which does not affect the normal vegetative growth and flowering of corn at the middle and late stages.

[0253] The 3000-fold, 2000-fold, 1000-fold, 750-fold and 500-fold test concentrations of sample 8 did not cause phytotoxicity to the heart leaves of the three corn varieties at the seedling stage, and the leaves grew normally; the 250-fold test concentration of sample 8 did not cause phytotoxicity to the heart leaves of the three corn varieties at the seedling stage, and the leaves grew normally, but caused slight phytotoxicity to the base of individual tender leaves of corn, showing yellow chlorosis.

[0254] Table 10 Investigation results of sample 8 on corn seedling safety test

[0255]

[0256] Eleven days after one application, six tested concentrations (3000x, 2000x, 1000x, 750x, 500x, and 250x) of sample 8 were applied to the central leaves of three corn varieties during the seedling stage. No phytotoxicity was observed in the leaves, and the growth was normal. Therefore, the phytotoxicity caused by sample 8 was limited to the base of individual tender leaves of corn. Over time, the phytotoxicity gradually subsided and did not affect the normal vegetative growth, flowering, and fruiting of corn in the middle and late stages.

[0257] Treatment with the control sample CK3 at concentrations of 3000, 2000, and 1000 times showed no phytotoxicity to the whorls and leaves of the three maize seedlings, and the seedlings grew normally. Treatment with the control sample CK3 at concentrations of 750 and 500 times showed no phytotoxicity to the whorls and leaves of the three maize seedlings, and the seedlings grew normally, but some young leaves showed slight phytotoxicity at the base, exhibiting yellowing and chlorosis. Treatment with the control sample CK3 at a concentration of 250 times showed no phytotoxicity to the whorls and leaves of the three maize seedlings, and the seedlings grew normally, but some young leaves showed slight phytotoxicity at the base, exhibiting yellowing and chlorosis, manifested as yellow translucent streaks. The main reason for this is likely that the pesticide solution on the leaves flowed downstream and accumulated at the base of the young leaves.

[0258] Table 11 Results of the safety test of control sample CK3 on maize seedlings

[0259]

[0260]

[0261] Eleven days after a single application, treatments with four tested concentrations of CK3 (3000, 2000, 1000, and 750 times dilution) showed no phytotoxicity in the central leaves of the three maize seedlings, and growth was normal. Treatment with CK3 at a concentration of 500 times dilution still caused slight phytotoxicity in Zhengdan 958, with visible chlorotic spots. However, the slight phytotoxicity at the base of the young leaves of Nonghua 101 and Nongda 108 was alleviated, with symptoms barely visible to the naked eye, and did not affect the normal growth of maize in the later stages. Treatment with CK3 at a concentration of 250 times dilution still caused slight phytotoxicity in all three varieties, with visible chlorotic spots. Therefore, the phytotoxicity caused by CK3 was limited to the base of individual young leaves of maize, and the affected areas gradually improved over time. However, even at high concentrations, slight phytotoxicity remained 11 days after application.

[0262] 3. Conclusion

[0263] During the corn seedling stage, applying 40% pyraclostrobin·captan suspension containing the compound stabilizer of this invention significantly reduces the risk of phytotoxicity. Even if phytotoxicity occurs in corn, the affected parts can be gradually alleviated without affecting the normal vegetative growth, flowering, and fruiting of corn in the later stages.

[0264] Bioactivity Experiment Example 2

[0265] The present bioactivity experiment aims to test the case of 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension agent added with the stabilizing safener of the present application in reducing phytotoxicity, conduct a wheat safety test, and determine the safety to wheat, the succeeding crop, by using seed coating with the agent.

[0266] 1 Test Conditions

[0267] 1.1 Test Target

[0268] The test wheat varieties for the safety test were three wheat varieties, Luma 21, Luyuan 502, and Jimai 22.

[0269] 1.2 Cultivation Conditions

[0270] The test was conducted in a sunlight greenhouse, and plastic pots with a diameter of 35 cm were used on the cultivation container, and an appropriate amount of moistened sterilized soil was added to make the soil surface have a diameter of 25 cm, the temperature was 28-30°C, the humidity was 80%, the natural light was used, the culture medium soil was sieved and dried sandy soil, the organic matter content was 1.26%, and the pH was 6.9. The test soil was quantitatively loaded to 4 / 5 of the pot body, and water was poured from the top to completely wet the soil.

[0271] 1.3 Instruments and Equipment

[0272] 1.3.1 Sunlight Greenhouse

[0273] 1.3.2 Small Coating Machine

[0274] 1.3.3 Electronic Balance (sensitivity 0.1 mg)

[0275] 1.3.4 Plastic Pots with a Diameter of 35 cm

[0276] 1.3.5 Measuring Cylinder

[0277] 1.3.6 Beaker, Rubber Gloves, etc.

[0278] 2 Test Design

[0279] 2.1 Test Agent

[0280] The test agent was the 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension agent sample prepared in Example 4, which was sample 18 (sample number 18), and the control sample was Control Example 7 (CK7).

[0281] 2.2 Dose Setting and Repetition

[0282] The test formulation of 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension agent has a maximum use amount of 2000 ml / 100 kg of seeds; the test sample 18 is coated with seeds at four dosages of 2000 ml / 100 kg of seeds, 3000 ml / 100 kg of seeds, 4000 ml / 100 kg of seeds, and 5000 ml / 100 kg of seeds. Each treatment is repeated 4 times. The dosage of the control sample CK8 is set accordingly. The test also sets a blank control of water without the drug.

[0283] 2.3 Treatment method

[0284] 2.3.1 Test time

[0285] The test time is March 1, 2021.

[0286] 2.3.2 Drug administration method

[0287] The test uses seed coating. After coating according to the above dosage, small wheat seeds of uniform size are selected and sown in a 35 cm diameter plastic pot, and the soil is covered with 2 cm. The test sets a blank control of water without the drug.

[0288] The pre-treated wheat seeds are evenly sown on the soil surface, 15 seeds per pot, covered with 2 cm of soil, and then moved to a sunlight greenhouse for cultivation. After germination, 10 plants per pot are selected. In addition, the same size plastic pots are prepared, 25 wheat seeds are sown in each pot, 4 pots per treatment, a total of 100 seeds, and the germination is observed.

[0289] 3 Data investigation and statistical method

[0290] After germination, the wheat seedling situation and the growth of wheat plants are observed every day, and whether the leaves have discoloration, necrosis, wilting, deformity, etc. The number of wheat seedlings is recorded 7 days after sowing, and the germination rate of each treatment is calculated. 21 days after sowing, 5 plants are randomly selected from each treatment, and the height and root length of the wheat plants are measured and recorded, and the plant morphology and color are observed for any changes. The original data of all repeats of each treatment are recorded. The test results are processed to calculate the germination rate and the average height and root length of each dosage treatment and perform significance test.

[0291] 4 Results analysis and discussion

[0292] 4.1 Test results

[0293] 4.1.1 After the test observation, the use of 7% pyraclostrobin·fludioxonil·clothianidin seed treatment suspension agent for seed coating treatment of wheat is recommended at 1 times, 1.5 times, 2 times, and 2.5 times the maximum dosage. The germination and plant growth of the three varieties of wheat are normal, and the leaves have no discoloration, necrosis, wilting, deformity, etc.

[0294] 4.1.2 Investigation results

[0295] Sample 18 was used for seed coating of three wheat varieties, with the dosage of 2000 ml / 100 kg seeds, 3000 ml / 100 kg seeds, 4000 ml / 100 kg seeds, and 5000 ml / 100 kg seeds, respectively. The seedling emergence rate, plant height, and root length of the treated wheat seeds were significantly different from the blank control, but see Tables 12, 13, and 14. The seedling emergence rate, plant height, and root length of the three wheat varieties were higher than the water control, indicating that the test agent was safe to the wheat emergence and growth at the test dosage, and had a promoting effect on the wheat emergence and growth.

[0296] Table 12, Effect of seed treatment with sample 18 on the growth and development of wheat seedlings (variety: Lumaizi 21)

[0297]

[0298]

[0299] The safety of sample 18 to the wheat Lumaizi 21 seeds and plants was determined by seed coating. The test results are shown in Table 12, indicating that the seed coating of sample 18 on wheat seeds has good safety. At the recommended dosage and double the amount (the dosage of 2000 ml / 100 kg seeds and 4000 ml / 100 kg seeds), the wheat emergence rate increases, and the plant leaves have no discoloration, necrosis, wilting, deformity, and other symptoms. Not only the normal growth of the plants, but also the wheat emergence and growth are promoted, indicating that sample 18 has good safety.

[0300] Table 13, Effect of seed treatment with sample 18 on the growth and development of wheat seedlings (variety: Luyuan 502)

[0301]

[0302] The safety of sample 18 to the wheat Luyuan 502 seeds and plants was determined by seed coating. The test results are shown in Table 13, indicating that the seed coating of sample 18 on wheat seeds has good safety. At the recommended dosage and double the amount (the dosage of 2000 ml / 100 kg seeds and 4000 ml / 100 kg seeds), the wheat emergence rate increases to a certain extent, and the plant leaves have no discoloration, necrosis, wilting, deformity, and other symptoms. Not only the normal growth of the plants, but also the wheat emergence and growth are promoted to a certain extent, indicating that sample 18 has good safety.

[0303] Table 14, Effect of seed treatment with sample 18 on the growth and development of wheat seedlings (variety: Jimai 22)

[0304]

[0305] The safety of sample 18 to the seeds and plants of the test crop, wheat Jimai 22, was determined by seed coating. The test results showed that the seed coating of sample 18 to wheat seeds had good safety. At the recommended dosage and 2 times the recommended dosage (formulation dosage 2000 ml / 100 kg seeds, 4000 ml / 100 kg seeds), the emergence rate of wheat increased to a certain extent, the leaves of the plants had no discoloration, necrosis, wilting, deformity and other symptoms, and not only did not affect the normal growth of the plants, but also promoted the growth to a certain extent. Sample 18 had good safety.

[0306] The formulation of control sample CK7 at 2000 ml / 100 kg seeds, 3000 ml / 100 kg seeds, 4000 ml / 100 kg seeds and 5000 ml / 100 kg seeds was used for seed coating of three varieties of wheat seeds, and the differences in the emergence rate, plant height and root length of the treated wheat seeds from the blank control were shown in Tables 15, 16 and 17. The emergence rate, plant height and root length of the three varieties of wheat seeds were not significantly higher than those of the water control, and the plant morphology was normal, indicating that the control sample CK7 had a certain safety to the emergence and growth of wheat at the test dosage, but had a certain degree of inhibition to the emergence and growth of wheat.

[0307] Table 15, Effect of seed treatment with control sample CK7 on the growth and development of seedlings (variety: Luma 21)

[0308]

[0309] The safety of control sample CK7 to the seeds and plants of the test crop, wheat Luma 21, was determined by seed coating. The test results showed that the seed coating of control sample CK7 to wheat seeds had a certain degree of safety. At 2 times the recommended dosage (4000 ml / 100 kg seeds), the emergence of wheat was slightly affected, the leaves of the plants had no discoloration, necrosis, wilting, deformity and other symptoms, the plant morphology was normal, and the normal growth of the plants was not affected. Therefore, control sample CK7 had a certain degree of safety to wheat Luma 21, and also had a certain degree of inhibition to the emergence and growth of wheat.

[0310] Table 16, Effect of seed treatment with control sample CK7 on the growth and development of seedlings (variety: Luyuan 502)

[0311]

[0312] The safety of the control sample CK7 to the test crop wheat seeds and plants was determined by seed coating. The test results showed that the wheat seeds coated with the control sample CK7 had a certain degree of safety, and under the recommended dosage of 2 times (4000 ml / 100 kg of seeds), the wheat seedling emergence was affected to a certain extent, the plant leaves had no discoloration, necrosis, wilting, deformity and other symptoms, and the plant growth was normal; therefore, the control sample CK7 had a certain degree of safety to the wheat Lu yuan 502, and also had a certain degree of inhibition on the seedling emergence and growth.

[0313] Table 17, Effect of seed dressing treatment of wheat seeds with the control sample CK7 on the growth and development of seedlings (variety: Jimai 22)

[0314]

[0315] The safety of the control sample CK7 to the test crop wheat seeds and plants was determined by seed coating. The test results showed that the wheat seeds coated with the control sample CK7 had a certain degree of safety, and under the recommended dosage of 2 times (4000 ml / 100 kg of seeds), the wheat seedling emergence was affected to a certain extent, the plant leaves had no discoloration, necrosis, wilting, deformity and other symptoms, and the plant growth was normal; therefore, the control sample CK7 had a certain degree of safety to the wheat Lu yuan 502, and also had a certain degree of inhibition on the seedling emergence and growth.

[0316] 5. Conclusion

[0317] The safety of the control sample CK7 to the test crop wheat seeds and plants was determined by seed coating. The test results showed that the wheat seeds coated with the control sample CK7 had a certain degree of safety, and under the recommended dosage of 2 times (4000 ml / 100 kg of seeds), the wheat seedling emergence was affected to a certain extent, the plant leaves had no discoloration, necrosis, wilting, deformity and other symptoms, and the plant growth was normal; therefore, the control sample CK7 had a certain degree of safety to the wheat Lu yuan 502, and also had a certain degree of inhibition on the seedling emergence and growth.

[0318] Of course, the present application can have other various embodiments, and those skilled in the art can make various corresponding changes and modifications to the present application without departing from the spirit and essence of the present application, but these corresponding changes and modifications should all belong to the protection scope of the claims attached to the present application.

Claims

1. A seed treatment suspension concentrate containing a stabilised safener, characterised in that, The effective component of the seed treatment suspension agent contains pyraclostrobin, fludioxonil and clothianidin, and the mass ratio of pyraclostrobin, fludioxonil and clothianidin is (1-5):(1-2):(10-100), and the effective component is used in an amount of 4-40wt% in the seed treatment suspension agent, The stable safener is a derivative of ascorbyl palmitate, The derivative of ascorbyl palmitate is selected from ascorbyl dipalmitate, ascorbyl tetrapalmitate, ascorbyl tetraisopalmitate, palmitoyl ascorbate, bis-palmitoyl ascorbate, tetrapalmitoyl ascorbate and tetraisopalmitoyl ascorbate. The mass ratio of pyraclostrobin to the stable safener in the seed treatment suspension agent is 100:(0.1-100). The stable safener further comprises an organic acid selected from fulvic acid, humic acid and amino acid.

2. The seed treatment suspension concentrate according to claim 1, characterized in that, The effective component is used in an amount of 5-25wt% in the seed treatment suspension agent. Or the effective component is used in an amount of 7wt%.

3. The seed treatment suspension concentrate according to claim 1, characterized in that, The mass ratio of pyraclostrobin to the stable safener in the seed treatment suspension agent is 100:(1-80).

4. The seed treatment suspension concentrate according to claim 1, characterized in that, The mass ratio of pyraclostrobin to the stable safener in the seed treatment suspension agent is 100:(5-50).

5. The seed treatment suspension concentrate according to claim 1, characterized in that, The seed treatment suspension agent further comprises a film forming agent selected from acrylic emulsion, polyethylene glycol and polyvinyl alcohol, and the content of the film forming agent is 0.5wt%-5wt%.

6. The seed treatment suspension concentrate according to claim 1, characterized in that, The seed treatment suspension agent further comprises an alarm color dye in an amount of 2.5-5.5wt%.

7. The seed treatment suspension concentrate according to claim 1, characterized in that, The viscosity of the seed treatment suspension agent at 20℃ is 170-200mPa·s, and the viscosity at 40℃ is 120-150mPa·s.

8. The seed treatment suspension concentrate according to claim 1, characterized in that, The pH value of the seed treatment suspension agent is 4.5-6.

5.

9. The seed treatment suspension concentrate according to claim 1, characterized in that, The pH value of the seed treatment suspension agent is 5.0-6.0.

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