CN116210690A

CN116210690A - Seed treatment suspending agent containing stable safener

Info

Publication number: CN116210690A
Application number: CN202310263614.8A
Authority: CN
Inventors: 高祥文; 赵圣英; 赵克思; 周中义; 庞允舜
Original assignee: Shandong Shibang Agrochemical Co ltd
Current assignee: Shandong Shibang Agrochemical Co ltd
Priority date: 2022-07-25
Filing date: 2022-07-25
Publication date: 2023-06-06
Also published as: CN115152754A; CN116210689A; CN115152754B

Abstract

The invention discloses a seed treatment suspending agent containing a stable safener, wherein the active ingredients of the seed treatment suspending agent comprise pyraclostrobin, fludioxonil and clothianidin, the mass ratio of the pyraclostrobin to the fludioxonil to the clothianidin is (1-5): 1-2): 10-100, the dosage of the active ingredients is 4-40 wt%, the stable safener at least comprises an ascorbic acid fatty acid ester of the formula (I) or a derivative thereof, and the ascorbic acid fatty acid ester of the formula (I) is selected from ascorbyl laurate, ascorbyl olivate and ascorbyl stearate; in the seed treatment suspending agent, the mass ratio of the pyraclostrobin to the stable safener is 100 (0.1-100). According to the invention, the stabilizing safety agent is added into the seed treatment suspending agent, so that the seed treatment suspending agent is maintained to be between pH4 and 9, the degradation rate of active ingredients is reduced, the hazard risk of the medicament is reduced, and the seed treatment suspending agent has safety to crop seeds.

Description

Seed treatment suspending agent containing stable safener

Technical Field

The invention relates to the field of pesticide preparations, in particular to a seed treatment suspending agent containing a stable safener.

Background

The captan, also called as captan, has the chemical name of N- (trichloromethylthio) -cyclohex-4-ene-1, 2-dicarboximide, is an organic sulfur broad-spectrum low-toxicity bactericide, has a certain treatment effect based on a protection effect, is safer to use, has good prevention effect on a plurality of fungal diseases on various crops, and is particularly suitable for crops sensitive to copper preparation pesticides. The medicine can permeate to the cell membrane of the germ, not only can interfere the respiration process of the germ, but also can interfere the cell division of the germ, has a plurality of sterilization sites, is extremely difficult to induce the germ to generate drug resistance after being used for a plurality of times, and has more obvious disease prevention effect after being continuously sprayed. It is mainly used for spraying application, also can be used for seed treatment, and can be used for dipping product after harvesting, and can be used for soil treatment before sowing or planting.

Pyraclostrobin, also known as pyraclostrobin, has the chemical name methyl (N) - [ [ [1- (4-chlorophenyl) pyrazol-3-yl) -oxy ] -O-methoxy ] -N-methoxycarbamate, is a broad-spectrum fungicide of methoxy acrylic esters developed by Pasteur company in 1993, and is marketed in 2002 as a mitochondrial respiration inhibitor, and the action mechanism is that mitochondria cannot generate and provide energy required by normal metabolism of cells, and finally leads to cell death. The pyraclostrobin has wide bactericidal spectrum, is widely used for crops such as rice, soybean, cucumber and the like, and can control most diseases such as ascomycetes, basidiomycetes, semi-known fungi, oomycetes and the like. Has strong inhibiting effect on spore germination and in-leaf mycelium growth, and has protective and therapeutic activity, permeability and local systemic activity, and lasting period. Under the conditions of 25 ℃ and pH5-7, the stability of pyraclostrobin is more than 30 days. The man skilled in the art is urgent to solve the problem of the stability of the captan in the preparation system, including chemical stability and physical stability, in terms of chemical stability, the degradation rate (2 years) of captan needs to be controlled within 5%, in terms of physical stability, no abnormal phenomenon occurs within 2 years, if the preparation is a uniform system, no crystallization occurs in the preparation, if the preparation is a heterogeneous system, the particle size of particles in the preparation remains stable, no obvious crystallization growth occurs, no bottoming, no layering, and the water or oil separation rate is controlled within a qualified range.

Clothianidin is a neonicotinoid insecticide, acts similarly to the nicotinic acetylcholine receptor, and has contact killing, stomach poisoning and systemic activity. Clothianidin is stable in pH 5-7 (50 ℃) under weak acidic condition, slow in degradation, stable in pH 7-9 under weak alkaline condition, DT ₅₀ Is 1401 days (pH 9,20 ℃) (European Union Rev. Rep.).

The captan is stable under the acidic condition, the degradation is slow, the degradation is rapid under the alkaline condition, and the half-life DT of the captan is when the pH is 5 under the condition of 20 DEG C ₅₀ 32.4 hours; half-life DT of captan at pH7 ₅₀ Half-life DT of captan at 8.3 hours and pH 10 ₅₀ Is less than 2 minutes. The captan has better heat-resistant stability, and the half-life DT of the captan at 80 DEG C ₅₀ Greater than 4 years. When captan is prepared into a pesticide preparation, the inventor also finds that a stabilizer must be added to control the degradation rate (2 years) of captan to be within 5%. The current general treatment method is acidification, i.e. straightThe inventor of the present application found that, on the one hand, the degradation rate (2 years) can be controlled within 5% when the pH is adjusted to 3 or even 1-2 during the acidification treatment. In the process of storing and transporting the pesticide liquid preparation product, the pH value of the liquid preparation is maintained to be 3 or below, namely under stronger acidic conditions, the components of the liquid preparation are easy to generate various phenomena such as oxidation-reduction reaction, molecular ionization, hydrolysis, reaction with a packaging material and the like, so that the pH value of the liquid preparation shifts to a neutral environment, and the degradation of captan is easy to cause.

However, the solution of solving the chemical stability of captan by fine adjustment of the acidification treatment parameters often leads to unqualified chemical stability of other active ingredients in the preparation system. If other effective components such as pyraclostrobin are also contained in the preparation system, the degradation rate (2 years) of the pyraclostrobin in the pesticide preparation can be more than 5% when the pH is adjusted to 3 or even the pH is adjusted to 1-2, and the degradation rate is even more than 40%. If the degradation rate of pyraclostrobin in the pesticide preparation is controlled within 5%, the pH of the preparation is adjusted to be more than 4, namely 4-6.

The solution of solving the chemical stability of captan by fine adjustment of the acidification treatment parameters also easily leads to unqualified physical stability of the preparation system. If the captan preparation is a heterogeneous system, such as a suspending agent system and a dispersible oil suspending agent system, the dispersing ability of the dispersing agent in the weak acid system is partially lost, so that captan particles are sunk, captan particles grow up, and layering and other phenomena appear in the preparation. And if the pesticide preparation is a compound system, such as captan and pyraclostrobin compound.

The pyraclostrobin has four crystal forms in total, the melting point span is relatively large, and the temperature is between 40 and 67 ℃; the physical properties are not exactly the same among the individual crystal forms, which presents great difficulties in the suspension sanding process, especially in the stability of the formulations. After the pyraclostrobin compound preparation is subjected to heat storage and melting, the pyraclostrobin parts with low melting points in the four crystal forms are in a molten state, are not constrained by the existing dispersing agent, are continuously agglomerated, fused and grown up, are quickly settled, and adhere or adsorb with other component particles in the settling process, so that the two components can be separated out together after the suspension agent is subjected to subsequent heat storage and conversion to normal temperature.

By selecting proper wetting dispersant, such as polycarboxylate high-efficiency wetting dispersant and sulfonate wetting dispersant for compounding, and dispersing pyraclostrobin particles through multiple anchor points of the dispersant, the problem that a single pyraclostrobin suspending agent with a content of less than 30% is stable in formula, crystallization-free and layering-free is effectively solved, and a compounding preparation of the pyraclostrobin suspending agent still has no better solution, particularly when the pyraclostrobin suspending agent is compounded with captan, the difficulty is that on one hand, the commercial pyraclostrobin raw material has a low melting point (pure product 63.7-65.2 ℃), and when the commercial pyraclostrobin raw material is compounded with other components, the melting point of a mixed component is reduced, so that the control of sanding temperature and the selection of the high-efficiency wetting dispersant have higher requirements. At present, the pyraclostrobin compound product in the pesticide preparation industry is difficult to ensure that crystallization is not performed within two months after being stored and transferred at normal temperature, the stability of the preparation product is not ensured over time, and crystallization and return risks exist after the preparation product is circulated in the market. On the other hand, because the polycarboxylate high-efficiency wetting dispersant and the sulfonate type wetting dispersant have better wetting and dispersing performance at the pH of 5-7, when the pH is lower than 3, the wetting and dispersing performance of the wetting dispersant is obviously reduced, the pH is lower than 2, and the dispersing performance of the wetting dispersant is basically reduced to zero. The pH is adjusted to be less than 3, so that the stability of the pyraclostrobin is directly influenced, and the physical stability of the pyraclostrobin is influenced, so that pyraclostrobin particles are sunk, the particles grow up, and layering and other phenomena of the pesticide preparation occur.

The sterilizing composition containing penconazole and captan and the application thereof (patent application number: CN 201410495968.6) are characterized in that the stabilizer is sodium citrate and resorcinol, but resorcinol in a 3-class carcinogen list has chemical properties similar to dibasic acid, and reacts with sodium hydroxide, ammonia water and the like to generate salt, and the sodium citrate has the function of adjusting acid and base. The sterilizing composition (patent application number: CN 200710013632.1) with synergistic effect, which contains captan, is characterized in that the stabilizer selected from ethanolamine, diethanolamine, tributyl phosphate, epichlorohydrin and triphenyl phosphite is ethanolamine, the ethanolamine and diethanolamine have the effect of regulating acid and alkali, tributyl phosphate is colorless and odorless liquid, and can be mixed with various organic solvents, the plasticizer of cellulose nitrate, cellulose acetate, chlorinated rubber and polyvinyl chloride, the solvent of paint, ink and adhesive is used in water-based liquid preparation, on the one hand, the physical system is easily unstable, on the other hand, the stabilizer is difficult to prevent the degradation of the effective component, triphenyl phosphite is a reducing agent, but has strong activity, the package must be sealed when being stored in normal times, and is not wetted, the stabilizer should be stored separately from oxidants, acids, alkalis and edible chemicals, on the other hand, the stabilizer is oily substance, is insoluble in water, is dissolved in organic solvents such as alcohol, ether, benzene and acetone, is easy to make the water-based liquid preparation unstable, the epichlorohydrin is the stabilizer of oxygen-containing substance, is colorless liquid, is easy to be volatile, and the chloroform is not as well as the carcinogenic substance is volatile in chloroform, and is not volatile in chloroform, and the chloroform is similar to the odor of the liquid is stable in the chloroform, and is not shown in the table A2. The sterilizing composition containing zinc thiazole in China patent (patent application number: CN 201010282092.9) is used for preventing the degradation of active ingredients, the selected stabilizer is epoxidized soybean oil, epichlorohydrin, triphenyl phosphite, glycidyl ether and/or pentaerythritol, the epoxidized soybean oil has stronger lipophilicity and is difficult to emulsify, the compatibility with other active ingredients is poor, the stabilizing effect is poor, the glycidyl ether and/or the pentaerythritol are polyether polyols, and the sterilizing composition has certain dispersion performance but poor stabilizing effect. A Chinese patent pesticide sterilization composition and application thereof (patent application number: CN202210419587. X) are used for preventing degradation of active ingredients, the selected stabilizer is epoxidized soybean oil, epichlorohydrin, BHT and triphenyl phosphate, the chemical name of the BHT is 2, 6-di-tert-butyl-4-methylphenol, the BHT is mainly used as an antioxidant in the field of grease of food to increase the shelf life of the grease, the BHT is an excellent antioxidant additive of petroleum products, the antioxidant BHT has optimal antioxidant effect when the working temperature is 100 ℃, and a plurality of brands of the BHT have prohibited product packaging bags from containing industrial BHT substances. In summary, the stabilizers of captan selected in the prior art have obvious defects of poor stabilizing effect and defects such as adverse stability of liquid preparation or carcinogen.

In the aspect of phytotoxicity caused by applying bactericides to crops, pyraclostrobin suspending agent products are in vigorous growth and high-humidity conditions in a high-temperature period (more than 37 ℃) in a seedling nursery period of the crops, and if the pyraclostrobin is used at too high concentration, phytotoxicity risks can occur, and the phenomenon of leaf burning of the crops is likely to occur. Also taking banana as an example, under the condition that 25% of suspending agent and emulsifiable concentrate are sprayed by 375 times of dilution concentration and the growth conditions are maintained, each treatment shows serious leaf burning phenomenon. After the crop generates phytotoxicity, the physiological process of the crop can be changed in a complex way, such as reduced water absorption capacity and internal water deficiency; the structure of the plasma membrane is destroyed, the active transport capacity is reduced, the permeability is increased, and the intracellular substances are extravasated; carbohydrate and protein hydrolysis in large amounts, etc., wherein the production of Reactive Oxygen Species (ROS) is believed to be a significant cause of these processes. Under normal conditions, plants can timely remove toxic Reactive Oxygen Species (ROS) to keep the ROS at a low level. After the injury occurs, the generation of active oxygen is accelerated, so that the active oxygen is accumulated in the body to cause oxidative injury. In order to protect against the deleterious effects of ROS, systems exist in plants that scavenge ROS. The ascorbic acid-glutathione (ASA-GSH) circulatory system is an important path for scavenging ROS free radicals in plants, is responsible for scavenging H.O.and can regulate the oxidation-reduction potential in the body so that the signal transduction system is carried out in a direction favorable for plant growth. However, ascorbic acid has strong reducibility and is easily oxidized into dehydrovitamin C, but the reaction is reversible, and the ascorbic acid and dehydroascorbic acid have the same physiological functions, but if dehydroascorbic acid is further hydrolyzed to generate diketone gulonic acid, the reaction is irreversible and the physiological efficacy is completely lost, so that it is difficult to use ascorbic acid in pesticide preparations.

In view of the above, a need exists in the art for a stabilizer for a liquid formulation containing captan as an active ingredient to solve the problems of chemical stability and physical stability of the formulation system, and to solve the problem of phytotoxicity of the bactericide, thereby reducing the risk of phytotoxicity possibly caused by using the bactericide.

Disclosure of Invention

The invention aims to solve the defects in the prior art, and provides a seed treatment suspending agent containing a stabilizing safener, so that the pesticide active ingredient gram is stable in a liquid preparation, especially in a water-based liquid preparation taking water as a main dispersion medium, the decomposition of active ingredients is reduced, and meanwhile, the phenomenon that the compound pesticide active ingredient such as pyraclostrobin is decomposed due to low pH and the pesticide activity is reduced is avoided.

In order to achieve the above object of one aspect of the present invention, the present invention adopts the following technical solutions:

a compound stabilizer for a liquid formulation, the liquid formulation containing at least a first active ingredient, the first active ingredient being captan;

the complex stabilizer includes, but is not limited to, an organic acid or its derivative, and also includes, but is not limited to, an ascorbyl fatty acid ester of formula (I) or its derivative;

Wherein R is independently a monovalent hydrocarbon group having 9 to 21 carbon atoms;

in the liquid preparation, the acidity coefficient (25 ℃) of the organic acid is 2-pKa-5, and the organic acid or the derivative thereof is any one of alkyl acid or the derivative thereof, alkyl diacid or the derivative thereof, alkyl triacid or the derivative thereof, and alkyl benzene sulfonic acid or the derivative thereof.

The inventors of the present application have also found that organic acids free H in pesticide formulations ⁺ The concentration range is 0.00001-0.01 mol/L to ensure the stability of the active ingredient captan, but the larger the ionization constant of the organic acid is, the better the stability is, when the pKa is less than 5, the larger the difference of pH values before and after heat storage (52+/-2 ℃ for 14 days) is easily caused, and the pKa is large> 5, there is no guarantee that a sufficient concentration of free H+ is reached in the pesticide formulation.

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

and/or the mass ratio of the ascorbyl fatty acid ester of formula (I) or a derivative thereof to the first active ingredient in the liquid formulation is (0.05-5): 35.

Preferably, the alkyl acid includes, but is not limited to, any of formic acid, acetic acid, propionic acid, hexenoic acid,

and/or derivatives of the alkyl acids include, but are not limited to, glycolic acid, lactic acid.

Preferably, the alkyl diacids include, but are not limited to, butenedioic acid, glutaric acid, adipic acid,

and/or derivatives of the alkyl diacids include, but are not limited to, glutamic acid.

Preferably, the alkyl triacids include, but are not limited to, hexanetrioic acid,

and/or derivatives of the alkyl tri-acids include, but are not limited to, citric acid.

Preferably, the alkylbenzene sulfonic acid includes, but is not limited to, benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid,

and/or derivatives of the alkylbenzenesulfonic acids include, but are not limited to, nitrobenzoic acid.

Preferably, the ascorbyl fatty acid ester of formula (I) contains an ascorbyl group, and the ascorbyl group is an L-ascorbyl group;

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 an ascorbic acid fatty acid ester of formula (I), including but not limited to ammonium, sodium, potassium, magnesium salts.

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

And/or ascorbyl fatty acid ester derivatives of formula (I) include, but are not limited to, lauroyl ascorbate, olivoyl ascorbate, palmitoyl ascorbate, stearoyl ascorbate.

Preferably, the liquid formulation contains at least a second pesticide active ingredient, including but not limited to pyraclostrobin.

Preferably, the liquid formulation includes, but is not limited to, aqueous emulsions, suspensions, seed treatment suspensions, dispersible oil suspensions, oils, low volume liquids;

wherein the dispersion medium of the aqueous emulsion is water,

the dispersion medium of the suspending agent is water,

the dispersion medium of the seed treatment suspending agent is water,

the dispersion medium of the dispersible oil suspending agent is selected from one or more of soybean oil, methyl oleate and rapeseed oil,

the dispersion medium of the oil suspending agent is selected from one or more of soybean oil, methyl oleate and rapeseed oil,

the dispersion medium of the oiling agent is selected from any one or more of methyl oleate, toluene, xylene, trimethylbenzene and solvent oil,

the dispersion medium of the low volume liquid is selected from one or more of toluene, xylene, trimethylbenzene and solvent oil.

The Oil suspending agent used after dilution with water is referred to as Oil suspending agent (Oil-basedsusoension concentrates, oil dispersion) abbreviated as OD, and the liquid preparation in which the active ingredient is suspended or partially dissolved in water-immiscible liquid is referred to as Oil suspending agent (oilmiscible flowable concentrate, oil flowableconcentrate, oil miscible suspension) used after dilution with organic solvent or Oil abbreviated as OF.

In order to achieve the above object of the further aspect of the present invention, the present invention adopts the following technical solutions:

pyraclostrobin and captan compound suspending agent, including but not limited to pyraclostrobin, captan, wetting dispersant and compound stabilizer;

the compound suspending agent contains a compound stabilizer, including but not limited to organic acid or derivatives thereof, and also including but not limited to ascorbyl fatty acid ester of formula (I) or derivatives thereof,

wherein the mass ratio of the organic acid or the derivative thereof to the ascorbyl fatty acid ester of the formula (I) or the derivative thereof is (0.5-5): 1;

in the compound suspending agent, the mass ratio of the pyraclostrobin to the captan is 1 (0.5-10).

Preferably, in the compound suspending agent, the mass ratio of the organic acid or the derivative thereof to the ascorbyl fatty acid ester of the formula (I) or the derivative thereof is (1-4): 1.

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

Preferably, in the compound suspending agent, the mass ratio of pyraclostrobin to captan is 1 (2-8).

Further, in the compound suspending agent, the mass ratio of pyraclostrobin to captan is 1 (4-7).

Preferably, the wetting dispersant comprises at least one of polymeric carboxylate, sulfonate, EOPO polyether, phosphate,

among them, the phosphate esters include, but are not limited to, tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, castor oil polyoxyethylene ether phosphate.

Preferably, the compound suspending agent further comprises a thickening agent, wherein the thickening agent comprises at least one of an organic thickening agent and an inorganic thickening agent;

wherein the organic thickener includes but is not limited to xanthan gum and the inorganic thickener includes but is not limited to magnesium aluminum silicate.

Preferably, the compounded suspending agent further comprises an antifoaming agent, including but not limited to silicone antifoaming agents.

Preferably, the compounded suspending agent further comprises a preservative, including but not limited to pinocembrane.

Preferably, the compounded suspending agent further comprises an antifreezing agent, wherein the antifreezing agent comprises, but is not limited to, ethylene glycol, propylene glycol and glycerin.

a preparation method of pyraclostrobin and captan compound suspending agent comprises the following steps:

s1: weighing pyraclostrobin and captan with target mass for later use,

weighing wetting dispersant and composite stabilizer with target quality for standby,

the components of the composite stabilizer with the target quality are respectively weighed for standby,

adding the composite stabilizer and the wetting dispersant into water, and stirring and dispersing uniformly to obtain an auxiliary agent dispersion liquid;

s2, adding pyraclostrobin and captan into the auxiliary agent dispersion liquid, stirring and dispersing uniformly, then placing the mixture under a grinding medium for grinding, and filtering the mixture after the particle size of the ground pyraclostrobin and captan reaches the target particle size to obtain a grinding liquid, thereby obtaining a pyraclostrobin and captan compound suspending agent;

wherein the compound stabilizer comprises, but is not limited to, organic acid or its derivative, and also comprises, but is not limited to, ascorbic acid fatty acid ester of formula (I) or its derivative, wherein the organic acid is selected from one or a combination of several of acetic acid, lactic acid and citric acid, and the ascorbic acid fatty acid ester of formula (I) is selected from one or a combination of two of L-ascorbyl palmitate and L-ascorbyl stearate.

Preferably, in step S1, the ascorbic acid fatty acid ester of formula (I) or its derivative component of the compound stabilizer is dispersed in the auxiliary dispersant, then mixed with the organic acid or its derivative component of the compound stabilizer and the wetting dispersant uniformly, and then added into water to be stirred and dispersed uniformly;

wherein the dispersion aid agent is selected from one or a combination of a plurality of ethanol, ethylene glycol, propylene glycol and glycerin.

Preferably, the auxiliary agent dispersion liquid in the step S1 is further added with a defoaming agent with the aim mass part;

and/or adding a defoaming agent with a target mass part to perform defoaming treatment in the grinding process of the step S2.

Preferably, the preparation method further comprises a step S3,

s3, weighing an antifreezing agent, a preservative and a thickening agent for standby; stirring and dispersing the antifreezing agent and the thickening agent uniformly, adding the antifreezing agent and the thickening agent into water, adding the preservative, and stirring and dispersing uniformly to obtain a thickening dispersion liquid;

and (3) mixing the grinding liquid obtained in the step (S2) with the thickening dispersion liquid, and stirring and dispersing uniformly to obtain the pyraclostrobin and captan compound suspending agent.

Preferably, the polishing liquid has a particle size D ₉₀ Less than 5 microns.

Preferably, the polishing liquid has a particle size D ₉₅ Less than 8 microns.

a seed treatment suspending agent containing a stable safener, wherein the liquid preparation contains at least a first seed coating active ingredient, and the first seed coating active ingredient is pyraclostrobin;

the stabilizing safener at least comprises but is not limited to an ascorbyl fatty acid ester of formula (I) or a derivative thereof, wherein the ascorbyl fatty acid ester of formula (I) comprises but is not limited to ascorbyl laurate, ascorbyl olivate, ascorbyl palmitate, ascorbyl stearate;

Preferably, the liquid formulation further comprises a second seed coating active ingredient, including but not limited to captan.

Preferably, the liquid formulation further comprises a third seed coating active ingredient, the third seed coating active ingredient being an insecticide, including but not limited to imidacloprid, acetamiprid, thiamethoxam, clothianidin.

Further, the liquid formulation also contains a fourth seed coating active ingredient, including but not limited to fludioxonil.

Preferably, in the seed treatment suspending agent, the mass ratio of pyraclostrobin to the stable safener is 100 (0.1-100).

Preferably, in the seed treatment suspending agent, the mass ratio of pyraclostrobin to the stable safener is 100 (1-80).

Preferably, in the seed treatment suspending agent, the mass ratio of pyraclostrobin to the stable safener is 100 (5-50).

Preferably, the stabilizing safener further comprises an organic acid including, but not limited to, fulvic acid, humic acid, amino acid, salicylic acid, legume She An acid, malic acid. The invention relates to a seed treatment suspending agent, which is added with stress-resistant organic acid for improving the vitamin C content and the soluble solid content in the crop organism and the stress resistance of crops.

Preferably, the seed treatment suspending agent further comprises a film forming agent, wherein the film forming agent comprises any one of acrylic emulsion, polyethylene glycol and polyvinyl alcohol, and the content of the film forming agent is 0.5-5 wt%.

Preferably, the seed treatment suspending agent also comprises warning color dye, and the content of the warning color dye is 2.5-5.5 wt%.

Preferably, the seed treatment suspending agent has a viscosity of 170 to 200 mPas at 20℃and a viscosity of 120 to 150 mPas at 40 ℃.

Preferably, the pH value of the seed treatment suspending agent is 4.5-6.5.

Preferably, the pH value of the seed treatment suspending agent is 5.0-6.0.

a seed treatment suspending agent containing pyraclostrobin, fludioxonil and clothianidin,

the seed treatment suspending agent comprises the active ingredients of pyraclostrobin, fludioxonil and clothianidin in a mass ratio of (1-5): 1-2): 10-100, wherein the dosage of the active ingredients in the seed treatment suspending agent is 4-40 wt%,

the seed treatment suspending agent contains a stabilizing safener which is ascorbyl palmitate or a derivative thereof,

among these, ascorbyl palmitate derivatives include, but are not limited to, ascorbyl dipalmitate, ascorbyl tetrapalmitate, ascorbyl tetraisopalmitate, palmitoyl ascorbate, dipalmitoyl ascorbate, tetrapalmitoyl ascorbate, tetraisopalmitoyl ascorbate.

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

Further, the amount of the active ingredient is 7wt%.

The invention has the beneficial technical effects that:

(1) The raw materials adopted by the method are easy to add into the liquid preparation, the operation is simple and convenient, the realization is easy, the problem that the quality of the product is difficult to control due to complex technology is avoided, and the degradation rate of the effective components of the product is large is avoided, so that the degradation rate of the pesticide active components can be ensured to be below 5% in the long-term storage process;

(2) The inventor of the application unexpectedly finds that the compound stabilizer of the invention can also stabilize the clothianidin which is an effective component and is stable in weak alkalinity, and the degradation rate is 0.5% at the minimum; the inventor also surprisingly found that the compound stabilizer provided by the invention has the advantages of reducing the hazard risk of captan and the compound liquid preparation thereof, especially when the bactericide is used in the condition of vigorous crop growth and high temperature time (more than 37 ℃) and high humidity in the seedling stage of crops, and the ascorbyl fatty acid ester or the derivative thereof in the component formula (I) of the compound stabilizer is used for the seed treatment suspending agent, so that a safer seed treatment suspending agent product containing the bactericide is obtained.

Drawings

FIG. 1 is a sample after heat storage of a comparative sample CK3 of example 2 of the present invention, and the sample after heat storage is removed from the bottom left by the upper liquid, and the bottom is seen to be sticky and difficult to sample;

FIG. 2 shows that the experimental samples 6 to 9 of the embodiment 2 and the samples CK3 to CK4 of the comparison example are uniformly mixed after being subjected to heat storage, 1mL of the mixture is diluted 250 times for suspension rate test, 25mL of diluent is left at the bottom after standing for 1 hour, obvious precipitate generation of CK3 and CK4 can be seen, and the samples 6 to 9 are basically free of precipitate;

FIG. 3 is a sample after heat storage of the control experimental sample CK3 of example 2 of the present invention, and a significant water separation layer can be seen;

FIG. 4 shows the sample after heat storage of the control sample CK4 of example 2 of the present invention, which shows a remarkable water-separating layer but less than CK 3;

FIG. 5 shows the heat-stored samples of the test example samples 6 to 10 of example 2 according to the present invention, and it can be seen that there is no significant water precipitation layer.

Fig. 6 is a graph showing the effect of the 20% pyraclostrobin-captan seed treatment suspension of example 3 of the present invention after coating corn, and it can be seen that sample 11 and sample 13 are more uniform in coating, more uniform in film formation and higher in brightness than sample CK 5.

Fig. 7 is a graph showing the effect of the 20% pyraclostrobin-captan seed treatment suspension of example 3 of the present invention after coating corn, and it can be seen that sample 14 was coated more uniformly than CK 6.

Fig. 8 is a graph showing the effect of the 7% pyraclostrobin fludioxonil clothianidin seed treatment suspension of example 4 of the present invention after coating corn, and it can be seen that sample 16 and sample 17 are more uniform in coating, more uniform in film formation and higher in brightness than CK 7.

Fig. 9 is a graph showing the effect of the 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent of example 4 of the present invention after coating corn, and it can be seen that sample 20 is more uniform in coating, more uniform in film formation and higher in brightness than CK 8.

FIG. 10 is a graph showing the effect of 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent according to example 4 of the present invention after coating corn on sample 18, and it can be seen that sample 18 has a uniform film formation, high brightness, good appearance, good smoothness, and no seed sticking.

Detailed Description

The present invention will be further described with reference to the following examples, which are given to assist the public in understanding the invention, but the applicant should not be construed to limit the technical scope of the invention in any way, and any modification to the definition of the local technical features or the form of the whole structure without substantial change should be construed as the scope of protection defined by the technical scheme of the invention.

As shown in fig. 1-10, the content of the original drug and the content of other drugs in the examples are calculated according to the weight percentage.

The test method comprises the following steps: the composite stabilizer is added into the liquid preparation according to a certain proportion, stirred and mixed to obtain samples, and the samples are divided into three samples before heat storage, heat storage (54+/-2 ℃) and normal temperature storage.

After the sample is prepared, immediately storing at normal temperature and measuring the content of the effective components of the sample before storage; placing the heat storage sample into an oven, and setting the temperature to be 54+/-2 ℃; after standing for 14 days, the content was measured. And (3) calculating the relative decomposition rate by taking the content measured before storage as a control, wherein the thermal storage decomposition rate is less than or equal to 5 percent and is qualified, and after the thermal storage detection is qualified, sampling and analyzing the conditions of the decomposition rate of the effective components by taking samples for 12 months and 24 months respectively after the samples are placed at normal temperature for 2 years, so as to judge whether the stability over time is qualified. Whereas the normal temperature samples were no longer tested for 12 months and 24 menses stability against 14 days of failure in thermal storage dissolution.

The decomposition rate is calculated by taking the content measured before storage as a control, and the decomposition rate after heat storage and normal temperature stability storage is less than or equal to 5 percent and is qualified. The decomposition rate calculation formula: decomposition rate = (pre-storage content-heat storage or normal temperature post-storage content)/pre-storage content×100%.

The reagents and medicines used in the examples are all commercial products, and the raw medicines are measured according to the weight percent.

Experimental example 1: the experiment aims to detect the degradation condition of the captan serving as an effective component in an oily medium by using a compound stabilizer with different proportions, and adopts 35% captan dispersible oil suspension (OD) for corresponding experiments, but does not mean that other liquid preparations such as emulsifiable concentrates, oiling agents and low-volume liquid preparations cannot achieve the same purpose, and a person skilled in the art adopts a proper dispersing medium, wherein the dispersing medium of the oiling agents is selected from any one or more of methyl oleate, toluene, xylene, trimethylbenzene and solvent oil, the dispersing medium of the low-volume liquid preparation is selected from any one or more of toluene, xylene, trimethylbenzene and solvent oil, and the captan liquid preparation with the target content can be prepared.

35% captan dispersible oil suspending agent

350g of captan, 200g of emulsifier, a proper amount of composite stabilizer, 20g of suspension thixotropic agent and 1000g of dispersion medium are weighed.

The emulsifier selected in the experiment is selected according to captan raw medicine, a dispersion medium and the like, and the emulsifier selected in the experiment is specifically 100g of nonylphenol polyoxyethylene ether, 80g of castor oil polyoxyethylene ether and 20g of magnesium dodecyl benzene sulfonate; however, this does not mean that the skilled person cannot prepare the intended content of captan dispersible oil suspension by selecting other suitable emulsifiers, commercially available suitable emulsifiers.

The dispersing medium selected in the experiment is selected from any one or more of soybean oil, methyl oleate and rapeseed oil, and is specifically methyl oleate, but the dispersing medium does not mean that a person skilled in the art cannot prepare the captan dispersible oil suspending agent with the target content by selecting other suitable dispersing mediums, such as soybean oil, solvent oil and rapeseed oil and selecting a suitable emulsifying agent.

The suspension thixotropic agent selected in the experiment is magnesium aluminum silicate, and a person skilled in the art can also prepare the captan liquid preparation with the target content by selecting other suitable suspension thixotropic agents.

Adding the composite stabilizer, the nonylphenol polyoxyethylene ether, the castor oil polyoxyethylene ether and the magnesium dodecyl benzene sulfonate into methyl oleate, stirring and dispersing uniformly, and then adding gram bacteriaThe pellets are stirred and dispersed again uniformly and then are put into a grinding pot with grinding media for grinding, the particle size of the ground captan reaches the target particle size, and then the captan dispersible oil suspending agent is obtained by filtering, in the experimental example, the particle size D of the grinding fluid ₉₀ Particle size D of the grinding fluid smaller than 5 microns ₉₅ Less than 8 microns.

The addition amount of the compound stabilizer can be any value of 0.6-60 g, and other samples are prepared according to the process for preparing 35% captan dispersible oil suspending agent. Because 5 groups of composite stabilizers are selected for experimental purposes, wherein the organic acid is selected from acetic acid, lactic acid, glutamic acid, adipic acid and citric acid, but the method does not mean that a person skilled in the art cannot achieve the aim of the invention by selecting other suitable organic acids, in fact, through a large number of experiments, the inventor finds that the organic acid which is selected to be added into the liquid preparation containing captan can be selected as long as the acidity coefficient (25 ℃) 2 is less than or equal to 5, the acidity coefficient is lower than 2, the polarity of the organic acid is large, the liquid preparation containing captan is not easy to stabilize, the acidity coefficient is higher than 5, and the liquid preparation containing captan is not easy to have H with a proper concentration ⁺ The ion is not easy to stabilize the liquid preparation containing the captan.

The ascorbyl fatty acid ester of formula (I) is selected from ascorbyl laurate, ascorbyl olivate, ascorbyl palmitate, ascorbyl stearate, and the ascorbyl fatty acid ester derivative of formula (I) is selected from palmitoyl magnesium ascorbate, but this does not mean that the skilled person cannot achieve the object of the present invention by selecting other suitable ascorbyl fatty acid esters or derivatives thereof, and in fact, the inventors of the present invention have achieved the object of the present invention through a number of experiments when R in formula (I) is independently a monovalent hydrocarbon group having 9 to 21 carbon atoms.

The ascorbic acid fatty acid ester or derivative component thereof in the formula (I) of the composite stabilizer is firstly dispersed in a dispersion aid agent, then is uniformly mixed with the organic acid or derivative component thereof of the composite stabilizer and a wetting dispersing agent, and then is added into water to be uniformly stirred and dispersed; wherein the dispersion aid agent is selected from one or a combination of a plurality of ethanol, ethylene glycol, propylene glycol and glycerin.

The above samples were subjected to content measurement before storage, normal temperature time stability test and heat storage test simultaneously, the heat storage samples were placed in an oven at a set temperature of 54.+ -. 2 ℃ for 14 days, and the normal temperature samples were placed for 12 and 24 months, respectively. The high performance liquid chromatography is adopted to measure the content of captan in the pre-storage sample, the thermal storage sample and the normal temperature time storage sample in different time periods, and the decomposition rate is calculated, the measurement results are shown in the table 1, and the test data in the table are all average values of the test results of more than 3 times.

Comparative example 1: the 35% captan dispersible oil suspension formulation and method of preparation of comparative example 1 was substantially the same as example 1, except that acetic acid was used in comparative example 1 instead of the complex stabilizer of example 1 in an amount of 1.5wt%.

Comparative example 2: as shown in fig. 4 and 5, the 35% captan dispersible oil suspension formulation and the preparation method of comparative example 2 were substantially the same as example 1, except that comparative example 2 used ascorbyl laurate instead of the complex stabilizer of example 1 in an amount of 1.5wt% as in example 1 and comparative example 1.

Table 135% results of stability test of captan dispersible oil suspension

In the table, the samples of example 1 had a relative decomposition rate after heat storage of more than 5%, and if they failed, no room temperature storage test was performed, and "-" in the table indicates no test data. The component A is organic acid, and the component B is ascorbic acid fatty acid ester of the formula (I) or a derivative thereof; a: B is the mass ratio of component A to component B, if A: B is 6:2.5, then component A (acetic acid) is 5g, component B (ascorbyl laurate) is 2.5g, if A: B is 7:5, then component A (lactic acid) is 7g, component B (ascorbyl olivate) is 5g, and so on.

In table 1, A1 is acetic acid, A2 is lactic acid, A3 is glutamic acid, A4 is adipic acid, and A5 is citric acid; b1 is ascorbyl laurate, B2 is ascorbyl olivate, B3 is ascorbyl palmitate, B4 is ascorbyl stearate, and B5 is palmitoyl magnesium ascorbate. In table 1, CK1 is comparative example 1, and CK2 is comparative example 2.

From the test results in Table 1, it can be seen that the dispersible oil suspension has a hydrophilic component due to the addition of 20% of the emulsifier to the 35% captan dispersible oil suspension formulation for use. The compound stabilizer of the invention is added into 35% captan dispersible oil suspending agent, so that the stability of the effective component captan in the storage process can be maintained, the degradation rate of samples No. 1-5 of the invention in the embodiment 1 is lower than that of the samples in the comparison embodiment 1 (CK 1) and the comparison embodiment 1 (CK 2), and the degradation rate of the product in the storage for 12 months is generally lower than half of that in the storage for 24 months, because the preparation system can absorb water from the environment in the normal-temperature storage process.

Example 2: the experiment aims to detect the degradation condition of the captan serving as an active ingredient in water of a composite stabilizer with different proportions, and select 40% pyraclostrobin and captan suspending agent for corresponding experiments, but the experiment does not mean or read that the captan cannot be compounded with other active ingredients so as to achieve the same purpose, and a person skilled in the art selects other suitable active ingredients, such as difenoconazole, tebuconazole, trifloxystrobin, picoxystrobin, polyoxin, bromothalonil and other active ingredients, selects a suitable wetting dispersant, and can prepare a captan and other active ingredient compound liquid preparation with the target content.

40% pyraclostrobin-captan suspending agent

350g of captan, 50g of pyraclostrobin, 80g of wetting dispersant, a proper amount of composite stabilizer, 30g of antifreezing agent, 2g of preservative, 20g of thickener, 2g of defoamer and 1000g of dispersion medium water are weighed.

In the experimental example, the wetting dispersant is specifically 40g of polycarboxylate wetting dispersant and 40g of nonionic hydroxyl polyethylene oxide segmented copolymer wetting dispersant, but a person skilled in the art selects other suitable wetting dispersants, and the wetting dispersant which can be selected by the person skilled in the art comprises at least one of polymeric carboxylate, sulfonate, EOPO polyether and phosphate, wherein the phosphate comprises but is not limited to tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and castor oil polyoxyethylene ether phosphate, and the liquid preparation of the captan with the target content and other effective components is prepared and comprises 40% pyraclostrobin and captan suspending agent.

In this experimental example, the inventor selects a proper antifreezing agent, including but not limited to ethylene glycol, propylene glycol and glycerin, and in this experimental example, the antifreezing agent specifically selects ethylene glycol.

In this experimental example, the inventors selected suitable preservatives, including but not limited to preservatives including but not limited to, carbopine, sodium benzoate, etc., and in this experimental example, carbopine, which is a mixture of 2-methyl-4-isothiazolin-3-one (MI) and 2-methyl-5-chloro-4-isothiazolin-3-one (CMI) and an inorganic salt stabilizer, was specifically selected, CMI: mi=3:1.

In this experimental example, the inventors selected suitable thickeners, including organic thickeners, including but not limited to xanthan gum, and inorganic thickeners, including but not limited to magnesium aluminum silicate, more specifically, in this experimental example, a combination of 3g of xanthan gum and 17g of magnesium aluminum silicate.

In this experimental example, the inventor selects a suitable defoamer, including but not limited to an organosilicon defoamer and n-octanol, and more specifically, selects the defoamer as the organosilicon defoamer in this experimental example.

In the experimental example, the dispersion medium is water, more specifically deionized water; deionized water is colorless clear liquid, odorless and tasteless, the resistivity is more than 0.5MΩ & cm (megaohm & cm), and the highest resistivity can reach 18MΩ & cm.

The addition amount of the compound stabilizer can be any value of 0.6-60 g, and other samples are prepared according to the process of preparing 40% pyraclostrobin and captan suspending agent. Since 5 groups of compound stabilizers are selected for the purpose of experimental comparison, more specifically, the types of organic acids are shown in table 2, and the same types of ascorbic acid fatty acid esters or derivatives thereof are shown in table 2, but this does not mean that the person skilled in the art cannot achieve the purpose of the invention by selecting other suitable organic acids and ascorbic acid fatty acid esters or derivatives thereof, in fact, the inventors of the present application can achieve the purpose of the invention through a great deal of experiments as long as the acidity coefficient (25 ℃) of the organic acid is 2.ltoreq.pKa.ltoreq.5, and R in formula (I) is independently a monovalent hydrocarbon group having 9 to 21 carbon atoms.

Adding the composite stabilizer and the wetting dispersant into water, and stirring and dispersing uniformly to obtain an auxiliary agent dispersion liquid; adding pyraclostrobin and captan into the auxiliary agent dispersion liquid, stirring and dispersing uniformly, then placing the mixture under a grinding medium for grinding, and filtering the mixture after the particle sizes of the pyraclostrobin and captan reach the target particle sizes; in this experimental example, the polishing liquid had a particle diameter D ₉₀ Particle size D of the grinding fluid smaller than 5 microns ₉₅ Less than 8 microns. Stirring and dispersing the antifreezing agent and the thickening agent uniformly, adding the antifreezing agent and the thickening agent into water, adding the preservative, stirring and dispersing uniformly to obtain a thickening dispersion liquid, mixing the grinding liquid and the thickening dispersion liquid, and stirring and dispersing uniformly to obtain the 40% pyraclostrobin-captan suspending agent.

Comparative example 3: the formulation and preparation method of the 40% pyraclostrobin-captan suspension prepared in comparative example 3 were substantially the same as in example 2, except that acetic acid was used in the comparative example 3 instead of the complex stabilizer in example 2 in an amount of 1.5wt%.

Comparative example 4: the formulation and preparation method of 40% pyraclostrobin-captan suspension prepared in comparative example 4 were substantially the same as in example 2, except that ascorbyl palmitate was used in comparative example 4 instead of the complex stabilizer in example 2 in an amount of 1.5wt% as in example 2 and comparative example 3.

The inventors of the present application found that the rate of change was about 0.2% after 14 days of heat storage and 24 months of storage at room temperature for example samples 6 to 10 and comparative example samples 3 to 4; in the stored samples, examples 6 to 10 are shown in the detailed figures

Control sample 3 to control sample 4 were significantly abnormal, and as the control sample 4 was taken as an example, the sample after 14 days of heat storage as shown in fig. 1, the control sample 4 became so viscous and difficult to sample, and as shown in fig. 2, the control sample 4 was too pourable to test, and as shown in fig. 3, the dilution was diluted with water for 14 days after heat storage of the control sample 4 to perform a suspension rate test, and as a result, a significant precipitate was observed in the state of 25mL of the dilution at the bottom of the measuring cylinder.

The inventor also found that the heat storage and normal temperature of the sample 4 of the comparative example have obvious bottom after 24 months, the heat storage sample pours out the upper liquid medicine, the effective component of captan is detected to be 20.88wt%, the pyraclostrobin is detected to be 6.01wt%, but the heat storage sample is detected after being shaken uniformly, the effective component of captan is detected to be 36.24wt%, and the pyraclostrobin is detected to be 5.86%.

Table 240% storage stability test results of pyraclostrobin-captan suspension

In tables 2 and 3, the samples of example 1 had a relative decomposition rate of more than 5% after heat storage, and were failed to undergo no room temperature storage test, and "-" in the tables indicates no test data. The component A is organic acid, and the component B is ascorbic acid fatty acid ester of the formula (I) or a derivative thereof; a: B is the mass ratio of component A to component B, e.g., component A6 (propionic acid) is 5g, component B6 (ascorbyl dipalmitate) is 25g, then A: B is 5:25, e.g., component A7 (glycolic acid) is 2.5g, component B7 (ascorbyl tetraisopalmitate) is 50g, then A: B is 2.5:50, and so on.

In tables 2 and 3, A6 is propionic acid, A7 is glycolic acid, A8 is citric acid, A9 is glutaric acid, and a10 is hexanetrioic acid; b6 is ascorbyl dipalmitate, B7 is ascorbyl tetraisopalmitate, B8 is ascorbyl palmitate, B9 is ascorbyl tetrapalmitate, and B10 is ascorbyl palmitate phosphate trisodium.

In tables 2 and 3, CK3 is comparative example 3 and CK4 is comparative example 4.

As can be seen from the results in Table 2, the degradation rates of the samples 6 to 10 of the invention are all obviously lower than those of the control samples CK3 to CK4, no organic acid is added in CK4, and even if 2wt% of ascorbyl palmitate is added as a stabilizer, the degradation rate of captan is as high as 14.3% after 14 days of heat storage, the storage degradation rate at normal temperature is as high as 16.9%, and the stability is poor; the CK3 is only added with organic acid, and the degradation rate of captan reaches the qualified level and is 4.3 percent, but the degradation rate of pyraclostrobin is increased to 6.9 percent and is the unqualified level.

The inventors further examined the pH change of the samples before and after heat storage, and found that the samples 6 to 10 of this example 2 had a pH of 4.10 to 5.93 before heat storage, a pH of 3.91 to 5.65 after heat storage, a pH of 3.09 before heat storage of the CK3 sample, a pH of 2.82 after heat storage, a pH of 5.90 before heat storage of the CK4 sample, and a pH of 4.18 after heat storage; the pH values of the samples before and after the normal temperature storage were changed, the pH values of the samples 6 to 10 in example 1 were found to be 4.10 to 5.93 before the normal temperature storage, the pH value after the normal temperature storage was found to be 3.59 to 5.56, the pH value of the CK3 sample was found to be 3.09 after the normal temperature storage, the pH value of the sample was found to be 2.82 after the normal temperature storage, the pH value of the sample before the normal temperature storage was found to be 3.09 after the normal temperature storage, and the pH value after the normal temperature storage was found to be 2.63. Based on the above data, the inventors speculate that degradation of captan may result in acidification of the system.

Table 340% physical stability test results of pyraclostrobin and captan suspension

As can be seen from the results in Table 3, the apparent stability of the samples 6 to 10 of the invention is obviously better than that of the control samples CK3 to CK4, and the sample water separation rate is increased to 18% due to the reduced wetting and dispersing performance of the wetting and dispersing agent under the acidic condition by only adding the organic acid citric acid into the sample CK3, so that the apparent stability is unqualified. The captan in CK4 is not added with organic acid, even if the ascorbyl palmitate of 2wt% is added as a stabilizer, the water separation rate of the CK4 sample is increased to a certain extent due to the degradation of the captan, and the captan is far higher than that of samples 6-10 of the invention although the captan is lower than that of CK3, the phenomenon of bottom formation is generated, and the particle size of particles is also enlarged to a certain extent.

The inventor also found through experiments that the problem of the bottom of CK3 and CK4 can be solved to a certain extent by controlling the particle size of the particles of the 40% pyraclostrobin and captan suspending agent grinding fluid, and the particle size D of the grinding fluid ₉₀ Particle size D of less than 5 μm, in particular of the further grinding fluid ₉₅ The problem of particle size growth of CK3 and CK4 particles smaller than 8 microns is solved to a certain extent, and although the particle sizes of the particles are also large, the particle sizes of the particles are also large after the composite stabilizer is added, so that the problem of particle size growth of the particles is solved better. The inventors of the present application have found that by controlling the particle diameter D of the above-mentioned fine particles, a 20% pyraclostrobin-captan seed treatment suspension and a 7% pyraclostrobin-fludioxonil-clothianidin seed treatment suspension were developed ₉₀ And D ₉₅ Under the same conditions, the problem of bottom formation can be solved to a certain extent.

The test results show that the compound stabilizer can keep the stability of the active ingredient pyraclostrobin in the storage process when the compound stabilizer is added into 40% pyraclostrobin-captan suspending agent.

Example 3: the experiment aims to reduce the degradation condition of the captan serving as an active ingredient in water by preparing the composite stabilizer with different proportions, and the stability condition of a liquid preparation system after adding the film forming agent, and select 20% pyraclostrobin and captan seed treatment suspending agent for corresponding experiments, but the experiment does not mean or is read that the captan cannot be compounded with other active ingredients so as to achieve the same purpose, and a person skilled in the art selects other suitable active ingredients, such as difenoconazole, tebuconazole, trifloxystrobin, picoxystrobin, polyoxin, bromothalonil and the like, selects a suitable wetting dispersing agent, and can prepare the seed treatment suspending agent compounded with the captan with the other active ingredients with target content.

20% pyraclostrobin and captan seed treatment suspending agent

150g of captan, 50g of pyraclostrobin, 60g of wetting dispersant, a proper amount of composite stabilizer, 30g of antifreezing agent, 2g of preservative, 10g of thickening agent, 2g of defoamer, 30g of film forming agent, 30g of warning color dye and 1000g of dispersion medium water are weighed.

In the experimental example, the wetting dispersant is specifically a polycarboxylate wetting dispersant 30g and a nonionic hydroxyl polyethylene oxide block copolymer wetting dispersant 30g, but a person skilled in the art selects other suitable wetting dispersants, and the wetting dispersant which can be selected by the person skilled in the art comprises at least one of polymeric carboxylate, sulfonate, EOPO polyether and phosphate, wherein the phosphate comprises but is not limited to tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and castor oil polyoxyethylene ether phosphate, and the liquid preparation of the captan with the target content and other effective components is prepared, and comprises 20% pyraclostrobin and captan treatment suspending agent.

In this experimental example, the inventors selected suitable thickeners, including organic thickeners, including but not limited to xanthan gum, and inorganic thickeners, including but not limited to magnesium aluminum silicate, more specifically, in this experimental example, a combination of 1g of xanthan gum and 9g of magnesium aluminum silicate.

In this experimental example, the inventor selects a proper film forming agent, wherein the film forming agent comprises, but is not limited to, acrylic emulsion, polyethylene glycol and polyvinyl alcohol, the content of the film forming agent is 0.5-5wt%, and more specifically, the film forming agent is acrylic emulsion in this experimental example.

The inventor selects one aspect of the thickening agent and the film forming agent, and aims to achieve the aim of the invention by adjusting the dosage and selecting corresponding raw materials by a person skilled in the art, wherein the viscosity of the seed treatment suspending agent is 170-200 mPa.s at 20 ℃ and 120-150 mPa.s at 40 ℃.

In the experimental example, the warning color dye is one or more than two of Dekkera, alkaline rose essence, aqueous rose and acid scarlet, and the dosage is 2.5-5.5 wt%; more specifically, acid scarlet is selected as the warning color dye.

In this experimental example, the inventor selects a suitable defoamer, including but not limited to an organosilicon defoamer, n-octanol and lauryl alcohol, and more specifically, selects the defoamer as the organosilicon defoamer in this experimental example.

The addition amount of the compound stabilizer can be any value of 0.3-31.5 g, and other samples are prepared according to the process of preparing 20% pyraclostrobin and captan suspending agent with the formula. Since 5 sets of compound stabilizers are selected for the purpose of experimental comparison, more specifically, the types of organic acids are shown in table 4, and the same types of ascorbic acid fatty acid esters or derivatives thereof are shown in table 4, but this does not mean that the person skilled in the art cannot achieve the object of the present invention by selecting other suitable organic acids and ascorbic acid fatty acid esters or derivatives thereof, in fact, the inventors of the present invention can achieve the object of the present invention through a great number of experiments as long as the acidity coefficient (25 ℃) 2 pKa is less than or equal to 5, and R in formula (I) is independently a monovalent hydrocarbon group having 9 to 21 carbon atoms.

Adding the composite stabilizer and the wetting dispersant into water, and stirring and dispersing uniformly to obtain an auxiliary agent dispersion liquid; adding pyraclostrobin and captan into the auxiliary agent dispersion liquid, stirring and dispersing uniformly, then placing the mixture under a grinding medium for grinding, and filtering the mixture after the particle sizes of the pyraclostrobin and captan reach the target particle sizes; in this experimental example, the polishing liquid had a particle diameter D ₉₀ Particle size D of the grinding fluid smaller than 5 microns ₉₅ Less than 8 microns. Stirring and dispersing an antifreezing agent and a thickening agent uniformly, adding the antifreezing agent and the thickening agent into water, adding a preservative, stirring and dispersing uniformly to obtain a thickening dispersion liquid, mixing the grinding liquid with the thickening dispersion liquid, a film forming agent and a warning color dye, and stirring and dispersing uniformly to obtain the 20% pyraclostrobin and captan seed treatment suspending agent.

Comparative example 5: the formulation and preparation method of the 20% pyraclostrobin-captan seed treatment suspending agent configured in comparative example 5 were substantially the same as in example 3, except that acetic acid was used in the comparative example 5 instead of the complex stabilizer in example 3 in an amount of 0.5wt%.

Comparative example 6: the formulation and preparation method of the 20% pyraclostrobin-captan seed treatment suspending agent configured in comparative example 6 were substantially the same as in example 3, except that acetic acid was used in comparative example 6 instead of the complex stabilizer in example 3, and that the amount of acetic acid used in comparative example 6 was 2wt% as in comparative example 5.

Table 420% storage stability test results of pyraclostrobin and captan seed treatment suspension

In tables 4 and 5, the samples of example 3 had a relative decomposition rate of more than 5% after heat storage, and were failed to undergo no room temperature storage test, and "-" in the tables indicates no test data. The component A is organic acid, and the component B is ascorbic acid fatty acid ester of the formula (I) or a derivative thereof; a is the mass ratio of component A to component B, for example, component A11 (acetic acid) is 5g, component B11 (ascorbyl laurate) is 20g, A is 5:20, for example, component A12 (butenedioic acid) is 4g, component B12 (ascorbyl olivate) is 15g, A is 4:15, and so on.

In tables 4 and 5, a11 is acetic acid, a12 is butenedioic acid, a13 is hexanetrioic acid, a14 is dodecylbenzenesulfonic acid, and a15 is methylbenzenesulfonic acid; b11 is ascorbyl laurate, B12 is ascorbyl olivate, B13 is ascorbyl palmitate, B14 is ascorbyl stearate, and B15 is magnesium ascorbyl palmitate.

In tables 4 and 5, CK5 is comparative example 5, and CK6 is comparative example 6.

As can be seen from the results in Table 4, the degradation rate of 20% pyraclostrobin and captan seed treatment suspending agent samples 11-15 of the invention is obviously lower than that of control samples CK 5-CK 6, organic acid is not added in CK6, even if 2wt% of ascorbyl laurate is added as a stabilizer, the degradation rate of captan is as high as 8.36% after 14 days of heat storage, the degradation rate of captan is as high as 10.18% after normal-temperature storage, and the stability is poor.

The inventors further examined the pH change of the samples before and after heat storage, and found that the samples 11 to 15 of example 3 had a pH of 4.50 to 5.96 before heat storage, a pH of 4.36 to 5.72 after heat storage, a pH of 3.02 before heat storage of the CK5 sample, a pH of 2.76 after heat storage, a pH of 6.49 before heat storage of the CK6 sample, and a pH of 4.27 after heat storage; thus, the sample of the invention of example 3 has less pH change; the pH values of the samples before and after normal temperature storage are changed, the pH value of the sample in the embodiment 1 is found to be 4.50-5.96, the pH value of the sample after normal temperature storage is 4.34-5.62, the pH value of the sample CK5 before normal temperature storage is 3.02, the pH value of the sample after normal temperature storage is 2.65, the pH value of the sample CK6 before normal temperature storage is found to be 6.49, the pH value after normal temperature storage is found to be 4.03, and the degradation of captan possibly leads to acidification of the system, so that the degradation rate of pyraclostrobin is increased.

The CK5 is only added with organic acid acetic acid, and the degradation rate of captan reaches the qualified level and is 3.74%, but the degradation rate of pyraclostrobin rises to 7.74%, and the degradation rate is the unqualified level, because pyraclostrobin is unstable under the acidic condition and the degradation rate rises.

Table 520% physical stability test results of pyraclostrobin and captan seed treatment suspending agent

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As can be seen from the results of Table 5, the apparent stability of the samples 11 to 15 of the present invention is significantly better than that of the control samples CK5 to CK6, and the sample water separation rate is increased to 10% due to the decrease of the wetting and dispersing performance of the wetting and dispersing agent under the acidic condition by only adding the organic acid acetic acid to CK5, so that the apparent stability is not qualified. No organic acid is added into CK6, even if 2wt% of ascorbyl laurate is added as a stabilizer, the CK6 sample has a certain water separation rate due to degradation of captan, and the CK6 sample is lower than CK5 but higher than samples 6-10 of the invention, the CK 5-CK 6 also has the phenomenon of bottom formation, and the particle size of the particles is also enlarged to a certain extent.

The test results show that the compound stabilizer can keep the stability of the active ingredients pyraclostrobin and captan in the storage process when the compound stabilizer is added into 20% pyraclostrobin and captan seed treatment suspending agent.

The inventor of the invention also uses the sample of the experimental example and CK5 and CK6 to coat seeds, and the detailed description is shown in fig. 6 and 7, and the sample of the experimental example has certain surface activity and lipophilicity due to the addition of the ascorbic acid fatty acid ester and the derivatives thereof, so that the coated seeds have good film forming agent and uniform film forming, and the coated seeds also have high brightness, good appearance and good smoothness, so that the seeds are not adhered, are uniformly planted, do not influence sowing and do not cause seedling missing and ridge breaking; and because the ascorbyl fatty acid ester and the derivative thereof have antioxidant capacity, the oxidation of pigments, active ingredients and the like can be avoided, so that the wrapped seeds have bright color and good appearance, and the ascorbyl fatty acid ester and the derivative thereof have stress resistance, are safe to the seeds and do not influence the emergence rate.

Example 4: the experiment aims to reduce the degradation condition of the active ingredient pyraclostrobin in water by preparing composite stabilizers with different proportions and the stability condition of a liquid preparation system after adding a film forming agent, and the corresponding experiment is carried out by selecting and preparing 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent, but the experiment does not mean or is interpreted that pyraclostrobin cannot be compounded with other active ingredients so as to obtain the seed treatment suspending agent for realizing the same purpose, and a person skilled in the art can select suitable other active ingredients, such as difenoconazole, tebuconazole, trifloxystrobin, picoxystrobin, polyoxin, bromothalonil and the like, select suitable wetting dispersing agent and obtain the seed treatment suspending agent with the target content of captan and other active ingredients.

Pyraclostrobin fludioxonil clothianidin seed treatment suspending agent

Weighing a proper amount of pesticide active ingredients, 60g of wetting dispersant, a proper amount of stabilizing safener, 30g of antifreezing agent, 2g of preservative, 20g of thickener, 2g of defoamer, 30g of film forming agent, 30g of warning color dye and 1000g of dispersion medium water.

In the experimental example, the inventor selects pesticide active ingredients of pyraclostrobin, fludioxonil and clothianidin, wherein the mass ratio of the pyraclostrobin to the fludioxonil to the clothianidin is (1-5): 1, the dosage is 4-40 wt%, the preferred dosage is 5-25 wt%, and the more preferred dosage is 7wt% of the pesticide active ingredients in the experimental example.

In the experimental example, the wetting dispersant is specifically a polycarboxylate wetting dispersant 30g and a nonionic hydroxyl polyethylene oxide block copolymer wetting dispersant 30g, but a person skilled in the art selects other suitable wetting dispersants, and the wetting dispersant which can be selected by the person skilled in the art comprises at least one of polymeric carboxylate, sulfonate, EOPO polyether and phosphate, wherein the phosphate comprises but is not limited to tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and castor oil polyoxyethylene ether phosphate, and the preparation comprises a captan and other effective components compound liquid preparation with target content, and comprises 7% pyraclostrobin fludioxonil thiamethoxam seed treatment suspending agent.

In this experimental example, the inventors selected suitable thickeners, including organic thickeners, including but not limited to xanthan gum, and inorganic thickeners, including but not limited to magnesium aluminum silicate, more specifically, in this experimental example, a combination of 2g of xanthan gum and 18g of magnesium aluminum silicate.

In the experimental example, the warning color dye is one or more than two of Dekkera, alkaline rose essence, aqueous rose and acid scarlet, and the dosage is 2.5-5.5 wt%; more specifically, water-based rose is selected as the warning dye.

The addition amount of the stabilizing safener can be any value of 0.6-60 g, and other samples are prepared according to the process of preparing the 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent with the formula. Since 5 groups of stable safeners are selected for the purpose of experimental comparison, more specifically, the types of organic acids are shown in table 6, and the same types of ascorbic acid fatty acid esters or derivatives thereof are shown in table 6, but this does not mean that the person skilled in the art cannot achieve the purpose of the invention by selecting other suitable organic acids and ascorbic acid fatty acid esters or derivatives thereof, in fact, the inventors of the present application can achieve the purpose of the invention by a large number of experiments as long as the acidity coefficient (25 ℃) 2 is less than or equal to 5, when R in formula (I) is independently monovalent hydrocarbon groups with 9 to 21 carbon atoms, and particularly, the purpose of adding 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent is a certain difference from that of experiment example 1, the purpose of adding the organic acids in the seed treatment suspending agent of the invention is to improve the vitamin C content and the soluble solid content in the crop bodies, and the stress resistance of the crop seeds can also be adjusted by adding the organic acids to the suspending agent to the purpose of the pH value range, so that the suspending agent can not be added to the pH value of the organic acid.

Adding the stable safety agent and the wetting dispersant into water, and stirring and dispersing uniformly to obtain an auxiliary agent dispersion; adding pyraclostrobin, fludioxonil and clothianidin into the auxiliary agent dispersion liquid, uniformly stirring and dispersing, then placing the mixture under a grinding medium for grinding, and filtering the mixture after the particle size of the ground pyraclostrobin, fludioxonil and clothianidin reaches the target particle size to obtain grinding liquid; in this experimental example, the polishing liquid had a particle diameter D ₉₀ Particle size D of the grinding fluid smaller than 5 microns ₉₅ Less than 8 microns. Stirring and dispersing an antifreezing agent and a thickening agent uniformly, adding the antifreezing agent and the thickening agent into water, adding a preservative, stirring and dispersing uniformly to obtain a thickening dispersion liquid, mixing the grinding liquid with the thickening dispersion liquid, a film forming agent and a warning color dye, and stirring and dispersing uniformly to obtain the 7% pyraclostrobin fludioxonil thiamethoxam seed treatment suspending agent.

Comparative example 7: the formulation and preparation method of the 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent configured in comparative example 7 are basically the same as those in example 4, except that acetic acid was used in the comparative example 7 instead of the complex stabilizer in example 4 in an amount of 1.5wt%.

Comparative example 8: the formulation and preparation method of the 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent configured in comparative example 8 were substantially the same as in example 4, except that triethanolamine was used in the comparative example 8 instead of the complex stabilizer in example 4 in an amount of 1.5wt% as in example 4 and comparative example 7.

Table 67% pyraclostrobin fludioxonil clothianidin seed treatment suspension storage stability test results

In tables 6 and 7, the samples of example 4 had a relative decomposition rate of more than 5% after heat storage, and were failed to undergo no room temperature storage test, and "-" in the tables indicates no test data. The component A is organic acid, and the component B is ascorbic acid fatty acid ester of the formula (I) or a derivative thereof; a: B is the mass ratio of component A to component B, if component A (fulvic acid) is 10g, component B (ascorbyl laurate) is 2.5g, A: B is 10:2.5, if component A is zero, component B (ascorbyl tetraisopalmitate) is 5g, A: B is 0:5, and so on.

In tables 6 and 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; b21 is triethanolamine.

In tables 6 and 7, CK7 is comparative example 7, and CK8 is comparative example 8.

As can be seen from the results in Table 6, the stabilizer of the invention is used for 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent, and the degradation rate of each of samples 16 to 20 of the experimental example is obviously lower than that of the control samples CK7 to CK8. After the CK7 is added with organic acid glycine and is thermally stored for 14 days, the degradation rate of clothianidin is disqualified and is 14.38%, and because the whole system is in an acid condition, the degradation rate of pyraclostrobin is 6.26%, the degradation rate of fludioxonil is 6.67% in normal-temperature storage, the degradation rate of fludioxonil is 5.95%, the degradation rate of fludioxonil is 6.03% in normal-temperature storage, and the stability is poor. After the CK8 is heated and stored for 14 days, although the degradation rate of clothianidin is qualified and is 4.94%, the degradation rate of pyraclostrobin is 6.73% after the whole system is heated and stored for 14 days, the degradation rate of fludioxonil is 6.90% after normal temperature storage, the degradation rate of fludioxonil is 6.19% after normal temperature storage, and the stability is poor.

Accordingly, the inventors of the present application found that the ascorbyl fatty acid ester or its derivative of the present invention, and the complex stabilizer can also stabilize clothianidin, an active ingredient that is stable in weak alkalinity.

Table 77% physical stability test results of pyraclostrobin fludioxonil clothianidin seed treatment suspension

As can be seen from the results of Table 7, the apparent stability of samples 16 to 20 of example 4 of the present invention is significantly better than that of the control samples CK7 to CK8, and CK7 is only added with glycine as an organic acid, so that the water separation rate of the samples is increased to 12% due to the reduced wetting and dispersing properties of the wetting and dispersing agent under acidic conditions, resulting in unacceptable apparent stability. The CK8 is not added with organic alkali triethanolamine, the water separation rate is equivalent to that of samples 16-20, in addition, the CK7 is subjected to bottom formation, and the particle size of the particles is expanded to a certain extent.

The test results show that the stable and safe agent disclosed by the invention is added into the 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent, so that the active ingredients pyraclostrobin, fludioxonil and clothianidin can be kept stable in the storage process.

The inventor of the invention also uses the sample of the experimental example and CK7 and CK8 to coat corn seeds, and the detailed description is shown in fig. 8 and 9, and the sample of the experimental example has certain surface activity and lipophilicity due to the addition of the ascorbic acid fatty acid ester and the derivatives thereof, so that the coated seed film forming agent is good, the film forming is uniform, the brightness is high, the appearance is good, the smoothness is good, the seeds are not adhered, the sowing is uniform, the seeding is not influenced, and the ridge breaking caused by the lack of seedlings is avoided; and because the ascorbyl fatty acid ester and the derivative thereof have antioxidant capacity, the oxidation of pigments, active ingredients and the like can be avoided, so that the wrapped seeds have bright color and good appearance, and the ascorbyl fatty acid ester and the derivative thereof have stress resistance, are safe to the seeds and do not influence the emergence rate.

Biological Activity Experimental example 1:

the biological activity experiment is to test the condition of adding 40% pyraclostrobin and captan suspending agent serving as the composite stabilizer in the invention in the aspect of reducing phytotoxicity.

1. Materials and methods

1.1. Test materials

The test agents were samples prepared in example 2, sample 6 (sample No. 6), sample 7 (sample No. 7), sample 8 (sample No. 8), and the control sample was control example 3 (CK 3). The corn varieties to be tested are 3 conventional varieties of Zhengdan 958, nonghua 101 and nonghua 108 which are commonly planted in Shandong provinces.

1.2. Test method

The test was performed in the city of lotus in the eastern Shandong province in 2021. 3 varieties of tested corn, zhengdan 958, nonghua 101 and Nongda 108 are transplanted in 2021, 5 month 8 seedlings, the farmland is flat, the water level is medium, the soil fertility is medium, the plant spacing is 30cm, the row spacing is 50cm, and each 667m ² About 3000 plants, fertilizer and water management and pest control measures in the seedling stage of corn belong to local medium level.

The 40% pyraclostrobin and chlorothalonil suspending agent is used as three test agents, each test agent is subjected to 3000, 2000, 1000, 750, 500 and 250 times 6 treatments, the corresponding control sample CK3 is subjected to 3000, 2000, 1000, 750, 500 and 250 times 6 treatments, and one clear water treatment is carried out, each treatment is repeated for 2 times, each treatment is carried out Repeat 1 cell, total 50 cells, random block arrangement. About 20 plants per cell of corn tested. Selecting in the afternoon of cloudy day, spraying the pesticide by hand sprayer, and spraying the pesticide every 667m ² The dosage was about 150L. The drug is sprayed for 1 time in the test period, the specific drug application time is 6 months and 7 days afternoon (overcast days, 24-26 ℃), and the growth period of each variety is respectively: zhengdan 958, nonghua 101 and nonghua 108 are all in the 5-leaf stage.

1.3. Investigation method

The test period was investigated 2 times in total, and 1 time was investigated for each of 4d and 11d after the 1 st application, respectively, and the specific investigation time was 6 months 11 days (6 to 7 leaf period of test corn) and 6 months 18 days (9 to 10 leaf period of test corn).

The investigation content is to observe the influence of the chemical on crops by visual inspection, namely observing the influence of each test concentration of the chemical on the corn seedling stage heart leaves and leaves or the occurrence of phytotoxicity, observing the color change of the corn seedling stage leaves and the like. If the plant is harmful, the type and extent of the plant is recorded, and beneficial effects on crops (such as stimulating growth, promoting maturation, etc.) are also recorded.

Recording the phytotoxicity condition of each district according to a phytotoxicity grading method, in the form of-, +, ++, ++ + + and and (3) representing. The classification of the phytotoxicity is as follows:

no phytotoxicity; slight phytotoxicity, slight influence on the growth of corn in seedling stage, and no influence on the normal growth of crops; the low-grade phytotoxicity is recoverable, the effect on the growth of corns in the seedling stage is slight, and the crop yield reduction is not caused; obvious phytotoxicity, influence the normal growth of the maize seedling stage, and cause a certain loss to the yield and quality of crops; high phytotoxicity, blocked growth in maize seedling stage and serious crop yield and quality loss.

2. Results and analysis

4d after 1 time of application, the corn seedling stage heart leaves of 3 varieties are treated by four tested concentrations of 3000 times, 2000 times, 1000 times and 750 times of sample 6, and the leaves are not damaged and grow normally; the 500-time and 250-time 2-time tested concentration treatments of the sample 6 have no phytotoxicity to the leaves and leaves of 3 varieties in the seedling stage of corn, and grow normally, but have slight phytotoxicity to the bases of individual young leaves of corn, and are yellow and green-losing. The main reason for this is probably that the liquid medicine on the leaves is gathered to the base of the tender leaves along the flow.

Table 8 sample 6 results of the test for corn seedling safety

After 11d of 1 time of application, 6 tested concentrations of 3000 times, 2000 times, 1000 times, 750 times, 500 times and 250 times of sample 6 are treated on corn seedling stage heart leaves of 3 varieties, and the leaves are not harmful and grow normally. Therefore, the part of the phytotoxicity caused by the sample 6 is limited to the base of the individual young leaves of the corn, and the part of the corn which is subjected to the phytotoxicity is gradually relieved along with the time, so that the normal nutrition growth and flowering and fruiting in the middle and later stages of the corn are not affected.

4 tested concentrations of 3000 times, 2000 times, 1000 times and 750 times of sample 7 are treated on corn seedling stage heart leaves of 3 varieties, and the leaves are not subjected to phytotoxicity and grow normally; sample 7 is treated at 500 times of the tested concentration, so that the corn leaves and leaves of Zhengdan 958 in the seedling stage have no phytotoxicity, and grow normally, but the base parts of individual tender leaves of the corn have slight phytotoxicity, and the corn leaves are yellow and green; but the leaves of the seedling stage heart leaves of the maize of the Nonghua 101 and the Nongda 108 are not damaged by the drugs and grow normally. The tested concentration of the sample 7 is 250 times that of the corn seedling stage heart leaves of 3 varieties, the leaves are not subjected to phytotoxicity, and the leaves grow normally, but slightly subjected to phytotoxicity on the bases of individual young leaves of corn, and the corn seedling stage heart leaves are yellow and green-losing.

Table 9 sample 7 results of the test for corn seedling safety

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After 11d of 1 time of application, 6 tested concentrations of 3000 times, 2000 times, 1000 times, 750 times, 500 times and 250 times of sample 7 are treated on corn seedling stage heart leaves of 3 varieties, and the leaves are not harmful and grow normally. Therefore, the part of the phytotoxicity caused by the sample 7 is only limited to the base part of the individual young leaves of the corn, and the part of the corn which is subjected to the phytotoxicity is gradually relieved along with the time, so that the normal nutrition growth, flowering and fruiting in the middle and later stages of the corn are not affected.

The treatment of 4 tested concentrations of 3000 times, 2000 times, 1000 times, 750 times and 500 times of sample 8 is carried out on the corn seedling stage heart leaves of 3 varieties, and the leaves are not damaged and grow normally; the 250 times test concentration treatment of the sample 8 has no phytotoxicity to the heart leaves and leaves of 3 varieties in the seedling stage of the corn, and the corn grows normally, but has slight phytotoxicity to the base parts of individual young leaves of the corn, and is yellow and green-losing.

Table 10 sample 8 results of the corn seedling safety test

After 11d of 1 time of application, 6 tested concentrations of 3000 times, 2000 times, 1000 times, 750 times, 500 times and 250 times of sample 8 are treated on corn seedling stage heart leaves of 3 varieties, and the leaves are not damaged and grow normally, so that the damage caused by sample 8 is only limited to the base parts of individual young leaves of corn, and the damage parts of the corn are gradually relieved along with the time, so that the normal nutrition growth, flowering and fruiting in the middle and later stages of the corn are not influenced.

The corn seedling stage heart leaves of 3 varieties are treated by 3 tested concentrations of 3000 times, 2000 times and 1000 times of the control sample CK3, and the leaves are not damaged and grow normally; the treatment of the control sample CK3 with the concentration of 750 times and 500 times of 2 tested samples has no phytotoxicity to the leaves and the leaves of 3 varieties in the seedling stage of corn, and has normal growth, but has slight phytotoxicity to the bases of individual young leaves of corn, and is yellow and green-losing; the leaves of the corn seedling stage heart leaves of 3 varieties after 250 times treatment of the control sample CK3 are not subjected to phytotoxicity, and grow normally, but the base parts of individual young leaves of corn are subjected to slight phytotoxicity, and the corn seedling stage heart leaves are yellow and green-losing symptoms and are in yellow semitransparent strip-shaped spots. The main reason for this is probably that the liquid medicine on the leaves is gathered to the base of the tender leaves along the flow.

Table 11 investigation results of control sample CK3 for corn seedling safety test

11d after 1 time of application, 4 tested concentrations of 3000, 2000, 1000 times and 750 times of the control sample CK3 are treated on corn seedling stage heart leaves of 3 varieties, and the leaves are not damaged and grow normally; the treatment of the Zhengdan 958 by 500 times of the tested concentration of the control sample CK3 still has slight phytotoxicity, green spots can be seen by naked eyes, but the slight phytotoxicity generated by the tender leaf bases of the agricultural bloom 101 and the agricultural bloom 108 is relieved, and symptoms of the phytotoxicity can not be seen by naked eyes basically, so that the normal growth of the middle and later stages of corns is not influenced; the 250-fold treatment of the control sample CK3 still had slight phytotoxicity to the three varieties, and the green spots were still visible to the naked eye. Therefore, the part of the phytotoxicity caused by the control sample CK3 is limited to the basal part of the individual young leaves of the corn, and the part of the corn which is subjected to the phytotoxicity is gradually relieved along with the time, but the part of the corn which is subjected to the phytotoxicity still has slight phytotoxicity after 11 days of administration at high concentration.

3. Conclusion(s)

In the seedling stage of corn, the 40% pyraclostrobin-captan suspending agent added with the compound stabilizer of the invention obviously reduces the risk of phytotoxicity, and even if the corn produces phytotoxicity, the phytotoxicity-bearing part of the corn can be gradually relieved, and normal nutrition growth and flowering and fruiting in the middle and later stages of the corn are not affected.

Biological Activity Experimental example 2:

the biological activity experiment is to test the condition of the 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent added with the stable safener in the aspect of reducing the phytotoxicity, carry out a wheat safety experiment, and adopt a medicament seed coating to determine the safety of wheat for crops.

1 test conditions

1.1 test targets

The test wheat varieties of the safety test are three wheat varieties of the lupulus 21, the Lu Yuan 502 and the jimai 22 to participate in the test.

1.2 culture conditions

The test is carried out in a sunlight greenhouse, a plastic basin with the caliber of 35cm is arranged on a cultivation container, a proper amount of moist sterilized loam is added, the soil surface diameter is 25cm, the temperature is 28-30 ℃, the humidity is 80%, natural illumination is carried out, the culture substrate soil is sieved air-dried sandy loam, the organic matter content is 1.26%, and the pH is 6.9. The test soil was quantitatively loaded at 4/5 of the pot, and watered from the top to completely wet the soil.

1.3 instrumentation

1.3.1 sunlight greenhouse

1.3.2 Small-sized coating machine

1.3.3 electronic balance (sensitivity 0.1 mg)

1.3.4 caliber 35cm plastic basin

1.3.5 measuring cylinder

1.3.6 beaker, rubber glove, etc

2 test design

2.1 test Agents

The test agent was 7% pyraclostrobin fludioxonil clothianidin seed-treated suspension prepared in example 4, sample 18 (sample number 18), and control sample was control example 7 (CK 7).

2.2 dose setting and repetition

The highest dosage of the test preparation of the 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent is 2000 ml/100 kg seed; test setup sample 18 was treated with four doses of seed coating 2000 ml/100 kg seed, 3000 ml/100 kg seed, 4000 ml/100 kg seed, 5000 ml/100 kg seed. Each treatment was repeated 4 times. The amount of the control sample CK8 was set accordingly. The test was also provided with a clear water treatment without the agent as a blank.

2.3 modes of treatment

2.3.1 test time

The test time was 2021, 3 months and 1 day.

2.3.2 methods of administration

The test used a seed coating method. After coating according to the dosage, selecting wheat seeds with the same size, sowing the wheat seeds into a plastic basin with the caliber of 35cm, and covering soil for 2cm. The test was run with a clear water treatment without the agent as a blank.

Uniformly sowing the pretreated wheat seeds on the soil surface, sowing 15 seeds in each pot, covering soil for 2cm, transferring the wheat seeds into a sunlight greenhouse for culture after sowing, and setting 10 plants in each pot after seedling emergence. In addition, plastic pots with the same size are prepared, 25 wheat seeds are sown in each pot, and 100 pots are treated in each pot, and the germination condition is observed.

3 data investigation and statistics method

And (3) 1 time per day after emergence, observing the emergence condition of wheat, the growth condition of wheat plants, and judging whether the leaves have symptoms of color change, necrosis, wilting, deformity and the like. And 7d after sowing, respectively recording the emergence number of each wheat treated, and calculating the emergence rate of each wheat treated. After sowing, 5 plants are randomly pulled out after each treatment 21d, the plant height and root length of the wheat are measured and recorded respectively, and meanwhile, the shape, the color and the like of the plants are observed. Record all duplicate raw data for each process. And (5) processing the test results, calculating the emergence rate and the average plant height and root length of each dose of treatment, and carrying out difference significance test.

4 results analysis and discussion

4.1 test results

4.1.1 experiments show that wheat is subjected to seed coating treatment by using a 7% pyraclostrobin fludioxonil clothianidin seed treatment suspending agent, and the three varieties of wheat seedlings and plants grow normally without symptoms such as discoloration, necrosis, wilting, deformity and the like under the recommended maximum dosage of 1 times, 1.5 times, 2 times and 2.5 times.

4.1.2 survey results

Sample 18 preparation dosage is 2000 ml/100 kg seed, 3000 ml/100 kg seed, 4000 ml/100 kg seed, 5000 ml/100 kg seed are respectively coated on three varieties of wheat seeds, and the emergence rate, plant height, root length and blank control of each treated wheat seed are obviously different, however, see tables 12, 13 and 14. The emergence rate, plant height and root length of the three wheat seeds are higher than those of the clear water control, so that the test agent is safe for wheat emergence and growth under the test dosage, and has a promoting effect on wheat emergence and growth.

TABLE 12 influence of sample 18 seed dressing treatment on seedling growth (variety: lu wheat 21)

Sample 18 was tested for safety against the seeds and plants of the test crop wheat Lu Mai by seed coating. The test results are shown in Table 12 in detail, and show that the wheat seeds are coated with sample 18 seeds, the safety is better, the emergence rate of the wheat is increased under the recommended dosage and 2 times (the dosage of the preparation is 2000 ml/100 kg seeds and 4000 ml/100 kg seeds), the plant leaves are free from the symptoms of discoloration, necrosis, wilting, deformity and the like, the normal growth of the plants is realized, the promotion effect on the emergence and the growth of the wheat is realized, and the sample 18 has better safety.

TABLE 13 influence of sample 18 seed dressing treatment on seedling growth (variety: lu Yuan 502)

Sample 18 was tested for seed and plant safety for the test crop wheat Lu Yuan 502 by seed coating. The test results are shown in Table 13 in detail, and show that the wheat seeds are coated with the sample 18 seeds, the safety is better, the emergence rate of wheat seedlings is increased to a certain extent under the recommended dosage and 2 times (the dosage of the preparation is 2000 ml/100 kg seeds and 4000 ml/100 kg seeds), the plant leaves are free from symptoms such as discoloration, necrosis, wilting and deformity, the normal growth of the plants is not influenced, the emergence and growth of the wheat are promoted to a certain extent, and the sample 18 has better safety.

TABLE 14 influence of sample 18 seed dressing treatment on seedling growth (variety: jimai 22)

The safety of sample 18 was determined by seed coating on seeds and plants of the test crop wheat 22. The test result shows that the wheat seeds are coated with the sample 18 seeds, the safety is better, the emergence rate of wheat seedlings is increased to a certain extent under the recommended dose and the dosage of 2 times (the dosage of the preparation is 2000 ml/100 kg seeds and 4000 ml/100 kg seeds), the plant leaves are free from the symptoms such as discoloration, necrosis, wilting, deformity and the like, the normal growth of the plants is not influenced, the promotion effect is also to a certain extent, and the sample 18 has better safety.

The CK7 preparation of the control sample is coated with 2000 ml/100 kg seed, 3000 ml/100 kg seed, 4000 ml/100 kg seed and 5000 ml/100 kg seed of three varieties of wheat seeds respectively, and the emergence rate, plant height, root length and blank control differences of the treated wheat seeds are shown in table 15, table 16 and table 17. The emergence rate, plant height and root length of the three wheat seeds are not obviously higher than those of the clear water control, and the plant forms are normal, so that the control sample CK7 has certain safety on the emergence and growth of the wheat at the test dosage, but has a certain inhibition effect on the emergence and growth of the wheat.

TABLE 15 influence of seed dressing treatment of control sample CK7 wheat seeds on seedling growth (variety: lu wheat 21)

The safety of the control sample CK7 on the seeds and plants of the test crop wheat Lu Mai was determined by seed coating. The test result shows that the wheat seeds are coated with the CK7 seeds serving as a control sample, the safety is high to a certain extent, the wheat seedlings are slightly affected when the recommended dose is 2 times (4000 ml/100 kg seeds), the plant leaves are free of symptoms such as discoloration, necrosis, wilting and deformity, the plant morphology is normal, and the normal growth of the plant is not affected; therefore, the control sample CK7 had a certain degree of safety against wheat Lu Mai 21 and also had a certain degree of inhibition in emergence and growth.

TABLE 16 influence of control sample CK7 seed dressing treatment on seedling growth (variety: lu Yuan 502)

The safety of the control sample CK7 on the test crop wheat seeds and plants was determined by seed coating. The test result shows that the wheat seeds are coated with the CK7 seeds serving as a control sample, the safety is high to a certain extent, the wheat seedlings are affected to a certain extent under the recommended dose of 2 times (4000 ml/100 kg seeds), the plant leaves are free from symptoms such as discoloration, necrosis, wilting and deformity, and the plant grows normally; therefore, the control sample CK7 had a certain degree of safety against wheat Lu Yuan 502 and also had a certain degree of inhibition in emergence and growth.

TABLE 17 influence of seed dressing treatment of control sample CK7 wheat seeds on seedling growth (variety: jimai 22)

The safety of the control sample CK7 on the seeds and plants of the test crop wheat ji wheat 22 was determined by seed coating. The test result shows that the wheat seeds are coated with the CK7 seeds serving as a control sample, the safety is high to a certain extent, the wheat seedlings are affected when the recommended dose is 2 times (4000 ml/100 kg seeds), the plant leaves are free from symptoms such as discoloration, necrosis, wilting and deformity, and the plant grows normally; therefore, the control sample CK7 has a certain degree of safety on the wheat malt 22 and also has a certain degree of inhibition on emergence and growth.

5. Conclusion(s)

The safety of sample 18 and control sample CK7 to the test crop wheat seeds and plants was determined by seed coating. The test result shows that the wheat seeds are coated with the sample 18 seeds, and the wheat seeds have better safety than the control sample CK7, and the wheat seeds and the sample 18 seeds have no symptoms of discoloration, necrosis, wilting, deformity and the like of plant leaves, and the normal growth of the plants, but have better safety at recommended dosage and 2 times (the dosage of the preparation is 2000 ml/100 kg seeds and 4000 ml/100 kg seeds), and the sample 18 has higher safety in three aspects of wheat emergence rate, plant height and root length than the control sample CK7, so the sample 18 added with the stabilizing safener of the invention.

The present invention is, of course, capable of other and further embodiments and of modification in accordance with the invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention, but these modifications and variations are intended to be within the scope of the appended claims.

Claims

1. The seed treatment suspending agent containing the stable safener is characterized in that the active ingredients of the seed treatment suspending agent contain pyraclostrobin, fludioxonil and clothianidin, the mass ratio of the pyraclostrobin to the fludioxonil to the clothianidin is (1-5): (1-2): (10-100), the dosage of the active ingredients in the seed treatment suspending agent is 4-40 wt%,

The stabilizing safener comprises at least an ascorbic acid fatty acid ester of formula (I) or a derivative thereof, wherein the ascorbic acid fatty acid ester of formula (I) is selected from the group consisting of ascorbyl laurate, ascorbyl olivate, ascorbyl stearate,

and/or the ascorbyl fatty acid ester derivative of formula (I) is selected from lauroyl ascorbate, olivoyl ascorbate, stearoyl ascorbate;

and/or the stabilizing safener is ascorbyl palmitate or a derivative thereof,

wherein the ascorbyl palmitate derivatives are selected from the group consisting of ascorbyl dipalmitate, ascorbyl tetrapalmitate, ascorbyl tetraisopalmitate, palmitoyl ascorbate, dipalmitoyl ascorbate, tetrapalmitoyl ascorbate, and tetraisopalmitoyl ascorbate;

in the seed treatment suspending agent, the mass ratio of the pyraclostrobin to the stable safety agent is 100 (0.1-100).

2. The seed treatment suspension of claim 1, wherein in the seed treatment suspension the active ingredient is present in an amount of 5 to 25wt%;

and/or the amount of the active ingredient is 7wt%.

3. The seed treatment suspension according to claim 1, wherein the mass ratio of pyraclostrobin to the stabilizing safener in the seed treatment suspension is 100 (1-80).

4. The seed treatment suspension according to claim 1, wherein the mass ratio of pyraclostrobin to the stabilizing safener in the seed treatment suspension is 100 (5-50).

5. The seed treatment suspension of claim 1, wherein the stabilizing safener further comprises an organic acid selected from the group consisting of fulvic acid, humic acid, amino acid, salicylic acid, legume She An acid, malic acid.

6. The seed treatment suspension of claim 1, further comprising a film former in the seed treatment suspension, wherein the film former is selected from the group consisting of acrylic emulsion, polyethylene glycol, polyvinyl alcohol, and wherein the film former is present in an amount of 0.5wt% to 5wt%.

7. The seed treatment suspension of claim 1, further comprising a warning color dye in an amount of 2.5 to 5.5wt% in the seed treatment suspension.

8. The seed treatment suspension of claim 1, wherein the seed treatment suspension has a viscosity of 170 to 200 mPa-s at 20 ℃ and 120 to 150 mPa-s at 40 ℃.

9. The seed treatment suspension of claim 1, wherein the pH of the seed treatment suspension is from 4.5 to 6.5.

10. The seed treatment suspension of claim 1, wherein the pH of the seed treatment suspension is from 5.0 to 6.0.