A solid preparation containing a stabilizer and its application

Abstract

The present invention relates to pesticide preparations, specifically a solid preparation containing a stabilizer and its application. The solid preparation uses compound A as an active ingredient, and is equipped with at least one auxiliary agent and at least one carrier filler to prepare water-dispersible granules, wherein the weight percentage of the active ingredient compound A in the solid preparation is 10-70%, and the auxiliary agent contains stabilizer B, and the stabilizer B accounts for more than or equal to 0.2% of the weight percentage of the solid preparation. The present invention can effectively solve the problem of flocculation of the dilution liquid and the long wetting time of the solid preparation under the conditions of low-temperature hard water and low dilution multiples (325-1500ppm, 0-15℃ hard water, 5-40 times dilution) by adding a specific proportion of stabilizer to the solid preparation under the conditions of selecting and matching a suitable auxiliary agent system. The solid preparation can also be applied to flying spray medicine under the above-mentioned special conditions.

Description

Technical Field

[0001] The invention relates to a pesticide preparation, in particular to a solid preparation containing a stabilizer and its application. Background Art

[0002] As a major agricultural country, China has 1.8 billion mu of basic farmland, a vast territory from east to west and north to south, and diverse planting conditions, which requires a large amount of agricultural plant protection operations every year. Plant protection drones can be remotely controlled from a distance, avoiding the risk of pesticide poisoning for spraying workers and ensuring the safety of spraying operations.

[0003] In 2020, the number of agricultural drones in China has exceeded 110,000, and the annual operation has exceeded 1 billion mu. Drones have become an indispensable key tool in China's farmland management. At present, many aerial spraying projects are facing a difficulty in the process of advancement, that is, there are few special pesticides on the market, and the granules and stability of many existing pesticide preparations are not suitable for aerial spraying.

[0004] Currently, the solid preparations available for spraying on the market are mainly wettable powders and water-dispersible granules. When these traditional solid preparations are used for aerial spraying, they are prone to problems such as stratification, flocculation, and nozzle clogging due to their low dilution multiples, and do not meet the requirements of ultra-low volume spraying.

[0005] Water dispersible granules (code name, WG) are usually made by superfine grinding or air flow grinding of each component of the formula into powder, which is then granulated by extrusion or fluidized bed granulation under the action of water and then dried. The particle size of the product is generally in the millimeter level, and the particle size of the diluent is generally between 20-50μm. The formula usually contains a binder and a disintegrant.

[0006] In recent years, with the further improvement of the performance of pesticide formulations, water-dispersible granules prepared by spray drying process have attracted much attention due to the fact that the particle size of the diluted liquid is generally between 1-15μm, and it has the characteristics of good dispersibility, high suspension rate, good stability, and easy use. Spray drying process water-dispersible granules are a preparation process in which the components of the formula and a certain amount of water are wet-grinded and crushed into a suspension according to a proportion, and then dehydrated by a high-temperature spray drying device to prepare a granular or powdered product.

[0007] Although the water-dispersible granules prepared by the spray drying process are new solid preparations, generally speaking, they have the characteristics of small average particle size, good dispersion stability, and high suspension rate (suspension rate>90%). However, the water-dispersible granule products prepared by the spray drying process in China are still managed in accordance with the relevant regulations on water-dispersible granule dosage forms, "GB / T 19378-2017 Pesticide Formulation Names and Codes". However, when it comes to specific varieties, under the conditions of low temperature hard water and low dilution multiples (325-1500ppm, 0-15℃ hard water, 5-40 times dilution), there will still be problems of flocculation of the dilution liquid and long wetting time, which will make it impossible to wet and disperse the preparation well, thus affecting the use of water-dispersible granules for aerial spraying, and the efficacy cannot be guaranteed. When encountering this problem, the solution usually adopted is to replace the adjuvant or adjuvant system. However, when compound A described in this patent is prepared into spray-dried water-dispersible granules, the problems of rapid flocculation and long wetting time of the dilution liquid with low-temperature hard water and low dilution multiple (325-1500ppm, 0-15℃ hard water, 5-40 times dilution conditions) cannot be solved by replacing the auxiliary agent and auxiliary agent system.

[0008] Chinese patent CN 103329925 B discloses a water-dispersible granule of a compound pesticide of thiamethoxam and pymetrozine. It has strong systemic and contact effects, destroys the normal nervous system of insects, has a fast insecticidal knockdown speed, a long lasting effect, and has a good effect on controlling rice planthoppers. At the test dose, it is safe for flowers, no pesticide damage occurs, and has little effect on beneficial organisms such as natural enemies.

[0009] Chinese patent CN 103329925 B discloses a sustained-release thiamethoxam water-dispersible granule and a preparation method thereof, and relates to the technical field of water-dispersible granule pesticides. The problem of short residual effect period of the original thiamethoxam water-dispersible granule is overcome, the drug effect period is long, the preparation method can adopt a forming method such as extrusion granulation, the process is simple and controllable, and the production cost is low.

[0010] Chinese patent CN 101422157 B discloses an insecticidal composition containing pymetrozine, specifically a compound composition of pymetrozine, cypermethrin and carbaryl, which is highly effective against wheat, cotton, vegetable aphids and rice planthoppers. The main characteristics of the composition are: the weight percentage of pymetrozine to cypermethrin is 1:80-80:1, and the weight percentage of pymetrozine to carbaryl is 1:80-80:1. The main dosage forms are wettable powder, water dispersible granules, etc.

[0011] However, the above documents do not specify the problem that the dilution liquid of these water-dispersible granules quickly flocculates and has a long wetting time under low-temperature hard water and low dilution multiples (325-1500ppm, 0-15°C hard water, 5-40 times dilution conditions). It is recorded in the subsequent specific implementation methods that the water-dispersible granules in the above documents quickly flocculate and have a long wetting time under low-temperature hard water and low dilution multiples.

[0012] There are no reports on the application of flavonoids in the field of pesticide spray granulation water dispersible granules to solve the flocculation of dilution liquid and shorten the wetting time. Summary of the invention

[0013] The purpose of the invention is to disclose a solid preparation containing a stabilizer and an application thereof.

[0014] To achieve the above purpose, the present invention adopts the following technical solution:

[0015] A solid preparation containing a stabilizer, which uses compound A as an active component, is prepared with at least one auxiliary agent and at least one carrier filler to prepare water-dispersible granules, wherein the weight percentage of the active component compound A in the solid preparation is 10-70%, the auxiliary agent contains stabilizer B, and the weight percentage of stabilizer B in the solid preparation is greater than or equal to 0.2%.

[0016] The stabilizer B is selected from baicalin (B1), dihydrochalcone (B2) or aurone (B3).

[0017] Preferably, the stabilizer B accounts for 0.2-50% by weight of the solid preparation, and more preferably 0.2-30% by weight.

[0018] The compound A is selected from one or more of pymetrozine (A1), imidacloprid (A2), thiamethoxam (A3), clothianidin (A4) or thiacloprid (A5).

[0019] The auxiliary agents in the solid preparation are wetting agent, dispersant, pH regulator and defoamer, and the weight percentage of each component in the solid preparation is 1-40% of wetting agent, 1-40% of dispersant, 0.01-2% of pH regulator and 0.1-5% of defoamer.

[0020] The wetting agent is selected from one or a combination of alkylbenzene sulfonate, α-olefin sulfonate and succinate sulfonate;

[0021] Preferably, the wetting agent is selected from sodium dodecylbenzene sulfonate, calcium dodecylbenzene sulfonate, sodium α-olefin sulfonate, sodium diisooctyl sulfosuccinate, sodium fatty alcohol polyoxyethylene ether succinate sulfonate, sodium alkylphenol polyoxyethylene ether succinate sulfonate, or a combination thereof;

[0022] The dispersant is selected from one or a combination of naphthalenesulfonate dispersants and polycarboxylate dispersants;

[0023] Preferably, the dispersant is selected from the group consisting of naphthalenesulfonic acid formaldehyde condensate sodium salt PD, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF, methylene bis-naphthalenesulfonate sodium salt, methylnaphthalenesulfonic acid formaldehyde condensate sodium salt MF, naphthalenesulfonic acid formaldehyde condensate sodium salt, benzylnaphthalenesulfonic acid formaldehyde condensate, methylnaphthalenesulfonic acid formaldehyde condensate, phenol derivative sulfonate formaldehyde condensate, β-naphthol cresol formaldehyde condensate sulfonate, β-naphthalenesulfonic acid formaldehyde condensate sodium salt, fatty alcohol polyoxyethylene ether carboxylate, alkylphenol polyoxyethylene ether carboxylate, dodecanol polyoxyethylene ether carboxylate, nonylphenol polyoxyethylene ether carboxylate, or a combination of the two.

[0024] The pH regulator is selected from one or a combination of organic weak acids.

[0025] Preferably, the pH adjuster is selected from one or a combination of metaphosphoric acid, sorbic acid, citric acid, salicylic acid, tartaric acid, malic acid and taurine.

[0026] The carrier filler is selected from one of ammonium sulfate, sodium sulfate, potassium chloride, diatomaceous earth, kaolin, calcined kaolin, bentonite, and light calcium carbonate, or a combination of the two or more, and accounts for 0.1-80% of the weight percentage of the solid preparation.

[0027] A method for preparing a solid preparation containing a stabilizer comprises preparing water-dispersible granules with compound A as an active component by a spray drying process according to the components and dosage ratio.

[0028] The invention discloses an application of a solid preparation containing a stabilizer, wherein the preparation is used as an agricultural insecticide (aerial insecticide).

[0029] The preparation is applied to the pests to be controlled or the medium where they grow at 10-500 g of active ingredient per hectare.

[0030] The advantages of the present invention are:

[0031] In the actual application of water dispersible granules in aerial spraying, it is very likely that unpurified cold well water (with a high hardness of 325-1500ppm) will be used directly to disperse the water dispersible granules at a relatively low temperature (0-15°C). Under this condition, combined with a relatively low dilution factor, it is difficult for the water dispersible granules to disperse quickly, resulting in a long wetting time and flocculation of the dilution liquid.

[0032] The present invention uses compound A, stabilizer B and other additives to prepare water-dispersible granules by spray drying, solves the problems of dilution flocculation and long wetting time of water-dispersible granules under low-temperature hard water and low dilution multiple conditions (325-1500ppm, 0-15°C hard water, 5-40 times dilution conditions), and makes it more suitable for actual production according to a more reasonable material ratio.

[0033] Good wettability and diluent stability play an important role in the efficacy of the preparation.

[0034] Due to the above advantages, the spray-dried water dispersible granules containing stabilizer described in the present invention can be applied to aerial spraying. DETAILED DESCRIPTION

[0035] The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to these examples. It is well known to those skilled in the art that the present invention encompasses all alternatives, improvements and equivalents that may be included within the scope of the claims. The original drug and the remaining materials in the examples are all commercially available.

[0036] Experimental method: Each example and control example is prepared according to the formula ratio, and then deionized water is added to the solid content of 30%-40%. After rough grinding and slurrying by a high shearing machine, the slurry is sanded by a sand mill to a particle size of D90 between 2-15μm for discharge. The slurry is dried by a pressure spray drying tower at an inlet air temperature of 100-130℃, and the dilution stability and wetting time under low temperature hard water and low dilution multiple conditions are tested.

[0037] Determination of dilution stability: Pour out the entire bottle of product and mix well. Weigh an appropriate amount of sample, accurate to 0.0002g. Place it in a measuring cylinder containing 100mL hard water at a temperature of ±2℃, and dilute it to the scale with the hard water. Cover the stopper, and turn the measuring cylinder upside down 30 times within 1 minute with the middle of the measuring cylinder as the axis. Open the stopper and place it vertically in a vibration-free constant temperature water bath (the water bath temperature is the same as the hard water temperature), avoid direct sunlight, and place it for 30 minutes to observe whether the dilution flocculates.

[0038] Determination of wetting time: Take 100mL±1mL of specific hard water and pour it into a 250mL beaker. Place the beaker in a constant temperature water bath at hard water temperature so that the liquid surface is flush with the horizontal surface of the water bath. After the temperature is balanced, weigh the corresponding mass of the sample (the sample should be a representative uniform powder, and it is not allowed to form a mass or agglomerate), place it on a watch glass, and pour all the samples from the position flush with the beaker mouth onto the liquid surface of the beaker at one time, but do not disturb the liquid surface excessively. When adding the sample, immediately use a stopwatch to record the time until the sample is completely wetted (the fine powder film left on the liquid surface can be ignored). Record the wetting time (accurate to seconds). Repeat this 5 times and take the average value as the wetting time of the sample. Observe whether there is a problem of long wetting time.

[0039] The wetting time of spray-dried water-dispersible granules shall refer to the wetting time standard of water-dispersible granules, and it is usually considered unqualified if it exceeds 60 seconds.

[0040] The percentages in the formulations in all the examples are all weight percentages.

[0041] In the following examples and comparative examples, water dispersible granules were prepared according to the spray drying process, and the process was as follows:

[0042] 1Accurately weigh each material according to the feeding table, add appropriate amount of water to disperse, and use a high-speed shearing machine to disperse and mix evenly to obtain slurry;

[0043] 2. Use a horizontal sand mill to grind the slurry. When the particle size of the material meets the requirements, the material is discharged to obtain a suspension;

[0044] 3 Use a spray dryer to spray dry the obtained suspension at a certain temperature to obtain spray-dried water-dispersible granules.

[0045] Preparation formula example

[0046] Comparative Example 1-1

[0047] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0048] Pymetrozine (Compound A1) 10%, sodium α-olefin sulfonate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0049] Comparative Example 1-2

[0050] 30% pymetrozine (compound A1) spray-dried water dispersible granules

[0051] Pymetrozine (Compound A1) 30%, sodium α-olefin sulfonate 5%, methylnaphthalenesulfonic acid formaldehyde condensate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0052] Comparative Examples 1-3

[0053] 50% pymetrozine (compound A1) spray-dried water dispersible granules

[0054] Pymetrozine (Compound A1) 50%, sodium dodecylbenzenesulfonate 5%, β-naphthalenesulfonic acid formaldehyde condensate sodium salt 15%, lauryl alcohol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0055] Comparative Examples 1-4

[0056] 70% pymetrozine (compound A1) spray-dried water dispersible granules

[0057] Pymetrozine (Compound A1) 70%, sodium dodecylbenzenesulfonate 3%, sodium methylenebisnaphthalenesulfonate 3%, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF 3%, polysiloxane defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0058] Example 1-1

[0059] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0060] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 50%, α-olefin sulfonic acid 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0061] Example 1-2

[0062] 30% pymetrozine (compound A1) spray-dried water dispersible granules

[0063] Pymetrozine (compound A1) 30%, baicalin (stabilizer B1) 3%, sodium dodecylbenzenesulfonate 5%, methylnaphthalenesulfonic acid formaldehyde condensate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with kaolin to 100%.

[0064] Examples 1-3

[0065] 70% pymetrozine (compound A1) spray-dried water dispersible granules

[0066] Pymetrozine (compound A1) 70%, baicalin (stabilizer B1) 1.4%, sodium α-olefin sulfonate 3%, sodium methylene bisnaphthalene sulfonate 3%, sodium salt of naphthalenesulfonic acid formaldehyde condensate 3%, polysilicone defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0067] Examples 1-4

[0068] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0069] Pymetrozine (compound A1) 10%, dihydrochalcone (stabilizer B2) 50%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0070] Examples 1-5

[0071] 30% pymetrozine (compound A1) spray-dried water dispersible granules

[0072] Pymetrozine (compound A1) 30%, dihydrochalcone (stabilizer B2) 3%, sodium dodecylbenzenesulfonate 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt 15%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD5%, polysilicone defoamer 0.5%, and the rest is made up to 100% with kaolin.

[0073] Examples 1-6

[0074] 70% pymetrozine (compound A1) spray-dried water dispersible granules

[0075] Pymetrozine (compound A1) 70%, dihydrochalcone (stabilizer B2) 1.4%, sodium α-olefin sulfonate 3%, sodium methylene bisnaphthalene sulfonate 3%, fatty alcohol polyoxyethylene ether carboxylate 3%, polysilicone defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0076] Examples 1-7

[0077] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0078] Pymetrozine (compound A1) 10%, aurone (stabilizer B3) 50%, calcium dodecylbenzenesulfonate 5%, β-naphthalenesulfonic acid formaldehyde condensate sodium salt 15%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0079] Examples 1-8

[0080] 30% pymetrozine (compound A1) spray-dried water dispersible granules

[0081] Pymetrozine (compound A1) 30%, aurone (stabilizer B3) 3%, calcium dodecylbenzenesulfonate 5%, sodium methylenebisnaphthalenesulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with kaolin to 100%.

[0082] Examples 1-9

[0083] 70% pymetrozine (compound A1) spray-dried water dispersible granules

[0084] Pymetrozine (compound A1) 70%, aurone (stabilizer B3) 1.4%, sodium dodecylbenzene sulfonate 3%, sodium methylene bisnaphthalene sulfonate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, nonylphenol polyoxyethylene ether carboxylate 0.5%, polysiloxane defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0085] Examples 1-10

[0086] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0087] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 50%, calcium dodecylbenzenesulfonate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF 15%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD 5%, polysilicone defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0088] Embodiment 1-11

[0089] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0090] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 40%, sodium α-olefin sulfonate 5%, methylnaphthalenesulfonic acid formaldehyde condensate sodium salt MF 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysilicone defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0091] Examples 1-12

[0092] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0093] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 30%, calcium dodecylbenzenesulfonate 5%, sodium methylenebisnaphthalenesulfonate 15%, methylnaphthalenesulfonic acid formaldehyde condensate sodium salt MF5%, polysiloxane defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0094] Examples 1-13

[0095] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0096] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 20%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is made up to 100% with bentonite.

[0097] Examples 1-14

[0098] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0099] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 10%, calcium dodecylbenzenesulfonate 5%, β-naphthalenesulfonic acid formaldehyde condensate sodium salt 15%, methylnaphthalenesulfonic acid formaldehyde condensate sodium salt MF5%, polysiloxane defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0100] Examples 1-15

[0101] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0102] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 5%, calcium dodecylbenzenesulfonate 5%, sodium methylenebisnaphthalenesulfonate 15%, methylnaphthalenesulfonic acid formaldehyde condensate sodium salt MF5%, polysiloxane defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0103] Examples 1-16

[0104] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0105] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 3.33%, α-olefin sodium sulfonate 5%, β-naphthalenesulfonic acid formaldehyde condensate sodium salt 15%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD5%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0106] Examples 1-17

[0107] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0108] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 2.5%, sodium α-olefin sulfonate 5%, methylnaphthalenesulfonic acid formaldehyde condensate sodium salt MF 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0109] Examples 1-18

[0110] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0111] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 2%, calcium dodecylbenzenesulfonate 5%, sodium methylenebisnaphthalenesulfonate 15%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD5%, polysiloxane defoamer 0.5%, and the rest is supplemented with kaolin to 100%.

[0112] Examples 1-19

[0113] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0114] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 1%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, fatty alcohol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0115] Examples 1-20

[0116] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0117] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 0.5%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is made up to 100% with bentonite.

[0118] Embodiment 1-21

[0119] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0120] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 0.33%, sodium α-olefin sulfonate 5%, phenol derivative sulfonate formaldehyde condensate 15%, fatty alcohol polyoxyethylene ether carboxylate 5%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0121] Examples 1-22

[0122] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0123] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 0.25%, alkylphenol polyoxyethylene ether succinate sodium sulfonate 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0124] Examples 1-23

[0125] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0126] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 0.2%, α-olefin sodium sulfonate 5%, β-naphthol cresol formaldehyde condensate sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0127] Examples 1-24

[0128] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0129] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 0.16%, α-olefin sodium sulfonate 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt 15%, β-naphthol cresol formaldehyde condensate sulfonate 5%, polysilicone defoamer 0.5%, and the rest is made up to 100% with bentonite.

[0130] Examples 1-25

[0131] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0132] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 0.14%, sodium alkylphenol polyoxyethylene ether succinate sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF5%, polysilicone defoamer 0.5%, and the rest is supplemented with sodium sulfate to 100%.

[0133] Examples 1-26

[0134] 10% pymetrozine (Compound A1) spray-dried water dispersible granules

[0135] Pymetrozine (compound A1) 10%, baicalin (stabilizer B1) 50%, sodium α-olefin sulfonate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysilicone defoamer 0.5%, and the rest is supplemented with light calcium carbonate to 100%.

[0136] Examples 1-27

[0137] 20% pymetrozine (compound A1) spray-dried water dispersible granules

[0138] Pymetrozine (compound A1) 20%, baicalin (stabilizer B1) 40%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysilicone defoamer 0.5%, and the rest is supplemented with light calcium carbonate to 100%.

[0139] Examples 1-28

[0140] 30% pymetrozine (compound A1) spray-dried water dispersible granules

[0141] Pymetrozine (compound A1) 30%, baicalin (stabilizer B1) 3%, calcium dodecylbenzenesulfonate 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with kaolin to 100%.

[0142] Examples 1-29

[0143] 40% pymetrozine (compound A1) spray-dried water dispersible granules

[0144] Pymetrozine (compound A1) 40%, baicalin (stabilizer B1) 2%, alkylphenol polyoxyethylene ether succinate sodium sulfonate 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD15%, dodecanol polyoxyethylene ether carboxylate 5%, polysiloxane defoamer 0.5%, and the rest is supplemented with light calcium carbonate to 100%.

[0145] Examples 1-30

[0146] 50% pymetrozine (compound A1) spray-dried water dispersible granules

[0147] Pymetrozine (compound A1) 50%, baicalin (stabilizer B1) 1%, sodium fatty alcohol polyoxyethylene ether succinate sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, polysilicone defoamer 0.5%, and the rest is supplemented with light calcium carbonate to 100%.

[0148] Example 1-31

[0149] 60% pymetrozine (Compound A1) spray-dried water dispersible granules

[0150] Pymetrozine (compound A1) 60%, baicalin (stabilizer B1) 1.2%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 5%, alkylphenol polyoxyethylene ether carboxylate 5%, polysilicone defoamer 0.5%, and the rest is supplemented with light calcium carbonate to 100%.

[0151] Example 1-32

[0152] 70% pymetrozine (compound A1) spray-dried water dispersible granules

[0153] Pymetrozine (compound A1) 70%, baicalin (stabilizer B1) 1.4%, sodium fatty alcohol polyoxyethylene ether succinate sulfonate 2%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD2%, alkylphenol polyoxyethylene ether carboxylate 2%, polysilicone defoamer 0.5%, and the rest is supplemented with light calcium carbonate to 100%.

[0154] Examples 1-33

[0155] 70% pymetrozine (compound A1) spray-dried water dispersible granules

[0156] Pymetrozine (compound A1) 70%, baicalin (stabilizer B1) 1.16%, calcium dodecylbenzenesulfonate 2%, sodium methylenebisnaphthalenesulfonate 2%, alkylphenol polyoxyethylene ether carboxylate 2%, polysiloxane defoamer 0.5%, and the rest is supplemented with diatomaceous earth to 100%.

[0157] Examples 1-34

[0158] 70% pymetrozine (compound A1) spray-dried water dispersible granules

[0159] Pymetrozine (compound A1) 70%, baicalin (stabilizer B1) 1%, sodium α-olefin sulfonate 2%, sodium methylene bisnaphthalene sulfonate 2%, alkylphenol polyoxyethylene ether carboxylate 2%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0160] Table 1. Wetting time of spray-dried water dispersible granules of pymetrozine (Compound A1) and flocculation of dilution

[0161]

[0162]

[0163] As can be seen from Table 1, the spray-dried water-dispersible granules prepared with pymetrozine (Compound A1) as the active ingredient, the four control examples without adding stabilizers, the wetting time under the conditions of low temperature hard water and low dilution multiples are all greater than 60s, and the dilution liquid under the conditions of low temperature hard water and low dilution multiples has flocculation phenomenon. Example 1-1, Example 1-2, and Example 1-3 show that within the scope of the patent, adding baicalin (stabilizer B1) as a stabilizer, the wetting time under the conditions of low temperature hard water and low dilution multiples is short and the dilution liquid has no flocculation phenomenon. Example 1-4, Example 1-5, and Example 1-6 show that within the scope of the patent, adding dihydrochalcone (stabilizer B2) as a stabilizer, the wetting time under the conditions of low temperature hard water and low dilution multiples is short and the dilution liquid has no flocculation phenomenon. Example 1-7, Example 1-8, and Example 1-9 show that within the scope of the patent, adding orange ketone (stabilizer B3) as a stabilizer, the wetting time under the conditions of low temperature hard water and low dilution multiples is short and the dilution liquid has no flocculation phenomenon.

[0164] Table 2. Wetting time of spray-dried water dispersible granules of pymetrozine (Compound A1) and flocculation of dilution

[0165]

[0166]

[0167] As can be seen from Table 2, for the spray-dried water dispersible granules prepared with the same content of pymetrozine (compound A1) as the active ingredient, taking baicalin (stabilizer B1) as an example: when the amount of baicalin added is within the range specified in this patent, the wetting time is short under the conditions of low temperature hard water and low dilution multiple, and the dilution liquid has no flocculation phenomenon; when the amount of pymetrozine added is outside the range specified in this patent, the wetting time is long and the dilution liquid has flocculation phenomenon.

[0168] Table 3. Wetting time of spray-dried water dispersible granules of pymetrozine (Compound A1) and flocculation of dilution

[0169]

[0170] As can be seen from Table 3, the spray-dried water dispersible granules prepared with different contents of pymetrozine (compound A1) as the active ingredient, and the stabilizer added with different proportions of baicalin (stabilizer B1): the amount of baicalin added is within the range specified in this patent, and the wetting time is short under the conditions of low temperature hard water and low dilution multiple, and the diluted solution has no flocculation phenomenon.

[0171] Comparative Example 2-1

[0172] 10% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0173] Imidacloprid (Compound A2) 10%, diisooctyl sodium sulfosuccinate 5%, diisooctyl sodium sulfosuccinate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0174] Comparative Example 2-2

[0175] 30% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0176] Imidacloprid (compound A2) 30%, sodium α-olefin sulfonate 5%, sodium diisooctyl sulfosuccinate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 6%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0177] Comparative Example 2-3

[0178] 50% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0179] Imidacloprid (Compound A2) 50%, sodium fatty alcohol polyoxyethylene ether succinate sulfonate 5%, sodium diisooctyl succinate sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 10%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0180] Comparative Example 2-4

[0181] 70% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0182] Imidacloprid (Compound A2) 70%, naphthalenesulfonic acid formaldehyde condensate sodium salt 3%, α-olefin sodium sulfonate 3%, diisooctyl sodium succinate sulfonate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, tar-based naphthalenesulfonic acid formaldehyde condensate 14%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0183] Example 2-1

[0184] 10% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0185] Imidacloprid (compound A2) 10%, baicalin (stabilizer B1) 50%, sodium fatty alcohol polyoxyethylene ether succinate sulfonate 5%, sodium diisooctyl succinate sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0186] Example 2-2

[0187] 70% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0188] Imidacloprid (compound A2) 70%, baicalin (stabilizer B1) 1.4%, naphthalenesulfonic acid formaldehyde condensate sodium salt 3%, sodium α-olefin sulfonate 3%, sodium diisooctyl succinate sulfonate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, tar-based naphthalenesulfonic acid formaldehyde condensate 14%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0189] Example 2-3

[0190] 10% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0191] Imidacloprid (compound A2) 10%, dihydrochalcone (stabilizer B2) 50%, calcium dodecylbenzenesulfonate 5%, sodium diisooctyl sulfosuccinate 15%, sodium methylenebisnaphthalenesulfonate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0192] Embodiment 2-4

[0193] 70% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0194] Imidacloprid (compound A2) 70%, dihydrochalcone (stabilizer B2) 1.4%, naphthalenesulfonic acid formaldehyde condensate sodium salt 3%, calcium dodecylbenzenesulfonate 3%, sodium diisooctyl sulfosuccinate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, tar-based naphthalenesulfonic acid formaldehyde condensate 14%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0195] Embodiment 2-5

[0196] 10% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0197] Imidacloprid (compound A2) 10%, aurone (stabilizer B3) 50%, calcium dodecylbenzenesulfonate 5%, sodium diisooctyl sulfosuccinate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, sodium methylene bisnaphthalene sulfonate 2%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0198] Embodiment 2-6

[0199] 70% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0200] Imidacloprid (compound A2) 70%, aurone (stabilizer B3) 1.4%, naphthalenesulfonic acid formaldehyde condensate sodium salt 3%, sodium α-olefin sulfonate 3%, sodium diisooctyl succinate sulfonate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, tar-based naphthalenesulfonic acid formaldehyde condensate 14%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0201] Embodiment 2-7

[0202] 10% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0203] Imidacloprid (compound A2) 10%, baicalin (stabilizer B1) 40%, sodium dodecylbenzenesulfonate 5%, sodium diisooctyl sulfosuccinate 15%, sodium methylenebisnaphthalenesulfonate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0204] Embodiment 2-8

[0205] 10% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0206] Imidacloprid (compound A2) 10%, dihydrochalcone (stabilizer B2) 1%, sodium dodecylbenzenesulfonate 5%, sodium diisooctyl sulfosuccinate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0207] Embodiment 2-9

[0208] 10% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0209] Imidacloprid (compound A2) 10%, aurone (stabilizer B3) 0.2%, sodium α-olefin sulfonate 5%, sodium diisooctyl sulfosuccinate 15%, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF5%, tar-based naphthalenesulfonic acid formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0210] Embodiment 2-10

[0211] 10% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0212] Imidacloprid (compound A2) 10%, baicalin (stabilizer B1) 0.16%, sodium dodecylbenzenesulfonate 5%, sodium diisooctyl sulfosuccinate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0213] Example 2-11

[0214] 12% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0215] Imidacloprid (compound A2) 12%, baicalin (stabilizer B1) 60%, sodium α-olefin sulfonate 5%, sodium diisooctyl sulfosuccinate 5%, alkylphenol polyoxyethylene ether carboxylate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0216] Example 2-12

[0217] 40% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0218] Imidacloprid (compound A2) 40%, dihydrochalcone (stabilizer B2) 0.8%, sodium alkylphenol polyoxyethylene ether succinate sulfonate 5%, sodium diisooctyl succinate sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0219] Example 2-13

[0220] 60% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0221] Imidacloprid (compound A2) 60%, aurone (stabilizer B3) 1.2%, sodium alkylphenol polyoxyethylene ether succinate sulfonate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF15%, alkylphenol polyoxyethylene ether carboxylate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 4%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0222] Embodiment 2-14

[0223] 70% Imidacloprid (Compound A2) spray-dried water dispersible granules

[0224] Imidacloprid (compound A2) 70%, dihydrochalcone (stabilizer B2) 1.16%, naphthalenesulfonic acid formaldehyde condensate sodium salt 3%, sodium α-olefin sulfonate 4%, sodium diisooctyl succinate sulfonate 3%, alkylphenol polyoxyethylene ether carboxylate 5%, tar-based naphthalenesulfonic acid formaldehyde condensate 6%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0225] Table 4. Wetting time of spray-dried water dispersible granules of imidacloprid (Compound A2) and flocculation of dilution

[0226]

[0227] As can be seen from Table 4, the spray-dried water-dispersible granules prepared with imidacloprid (Compound A2) as the active ingredient, the 4 control examples without adding stabilizers, the wetting time under low-temperature hard water and low dilution conditions is greater than 60s, and the dilution has flocculation. Example 2-1 and Example 2-2 show that within the scope of the patent, adding baicalin (stabilizer B1) as a stabilizer, the wetting time under low-temperature hard water and low dilution conditions is short and the dilution has no flocculation. Example 2-3 and Example 2-4 show that within the scope of the patent, adding dihydrochalcone (stabilizer B2) as a stabilizer, the wetting time under low-temperature hard water and low dilution conditions is short and the dilution has no flocculation. Example 2-5 and Example 2-6 show that within the scope of the patent, adding orange ketone (stabilizer B3) as a stabilizer, the wetting time under low-temperature hard water and low dilution conditions is short and the dilution has no flocculation.

[0228] Table 5. Wetting time of spray-dried water dispersible granules of imidacloprid (Compound A2) and flocculation of dilution

[0229]

[0230] As can be seen from Table 5, the spray-dried water-dispersible granules prepared with imidacloprid (Compound A2) as the active ingredient are added with stabilizers of different types and amounts: if the amount of stabilizer added is within the range specified in this patent, the wetting time is short under the conditions of low temperature hard water and low dilution multiple, and the dilution liquid has no flocculation phenomenon; if the amount of stabilizer added is outside the range specified in this patent, the wetting time is long under the conditions of low temperature hard water and low dilution multiple, and the dilution liquid has flocculation phenomenon.

[0231] Comparative Example 3-1

[0232] 10% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0233] Thiamethoxam (Compound A3) 10%, sodium diisooctyl sulfosuccinate 5%, sodium methylene bisnaphthalene sulfonate 15%, nonylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl sulfosuccinate 2%, polysilicone defoamer 0.5%, metaphosphoric acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0234] Comparative Example 3-2

[0235] 30% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0236] Thiamethoxam (compound A3) 30%, sodium dodecylbenzene sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, nonylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 6%, polysilicone defoamer 0.5%, metaphosphoric acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0237] Comparative Example 3-3

[0238] 50% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0239] Thiamethoxam (Compound A3) 50%, sodium diisooctyl sulfosuccinate 5%, sodium methylene bisnaphthalene sulfonate 15%, nonylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl sulfosuccinate 10%, polysilicone defoamer 0.5%, metaphosphoric acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0240] Comparative Example 3-4

[0241] 70% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0242] Thiamethoxam (Compound A3) 70%, sodium dodecylbenzene sulfonate 3%, sodium methylene bisnaphthalene sulfonate 3%, nonylphenol polyoxyethylene ether carboxylate 3%, sodium diisooctyl succinate sulfonate 14%, polysilicone defoamer 0.5%, sorbic acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0243] Example 3-1

[0244] 10% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0245] Thiamethoxam (compound A3) 10%, baicalin (stabilizer B1) 50%, sodium dodecylbenzene sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, nonylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, sorbic acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0246] Example 3-2

[0247] 70% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0248] Thiamethoxam (compound A3) 70%, baicalin (stabilizer B1) 1.4%, sodium dodecylbenzenesulfonate 3%, sodium methylenebisnaphthalenesulfonate 3%, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF 3%, sodium diisooctyl succinate sulfonate 14%, polysilicone defoamer 0.5%, sorbic acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0249] Example 3-3

[0250] 10% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0251] Thiamethoxam (compound A3) 10%, dihydrochalcone (stabilizer B2) 50%, sodium dodecylbenzene sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, nonylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, citric acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0252] Embodiment 3-4

[0253] 70% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0254] Thiamethoxam (compound A3) 70%, dihydrochalcone (stabilizer B2) 1.4%, sodium diisooctyl sulfosuccinate 3%, sodium methylene bisnaphthalene sulfonate 3%, sodium salt of tar-based naphthalenesulfonic acid formaldehyde condensate MF3%, sodium diisooctyl sulfosuccinate 14%, polysilicone defoamer 0.5%, citric acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0255] Embodiment 3-5

[0256] 10% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0257] Thiamethoxam (compound A3) 10%, aurone (stabilizer B3) 50%, sodium dodecylbenzene sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, nonylphenol polyoxyethylene ether carboxylate 5%, dodecanol polyoxyethylene ether carboxylate 2%, polysilicone defoamer 0.5%, citric acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0258] Embodiment 3-6

[0259] 70% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0260] Thiamethoxam (compound A3) 70%, aurone (stabilizer B3) 1.4%, sodium dodecylbenzene sulfonate 3%, sodium methylene bisnaphthalene sulfonate 3%, polyoxyethylene lauryl ether carboxylate 3%, sodium diisooctyl succinate sulfonate 14%, polysilicone defoamer 0.5%, salicylic acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0261] Embodiment 3-7

[0262] 10% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0263] Thiamethoxam (compound A3) 10%, baicalin (stabilizer B1) 40%, sodium dodecylbenzene sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, nonylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, salicylic acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0264] Embodiment 3-8

[0265] 10% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0266] Thiamethoxam (compound A3) 10%, dihydrochalcone (stabilizer B2) 1%, sodium dodecylbenzene sulfonate 5%, lauryl alcohol polyoxyethylene ether carboxylate, nonylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, salicylic acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0267] Embodiment 3-9

[0268] 10% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0269] Thiamethoxam (compound A3) 10%, aurone (stabilizer B3) 0.2%, sodium dodecylbenzene sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, nonylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, tartaric acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0270] Embodiment 3-10

[0271] 10% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0272] Thiamethoxam (compound A3) 10%, baicalin (stabilizer B1) 0.16%, sodium dodecylbenzenesulfonate 5%, sodium methylenebisnaphthalenesulfonate 15%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, tartaric acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0273] Example 3-11

[0274] 12% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0275] Thiamethoxam (compound A3) 12%, baicalin (stabilizer B1) 60%, sodium dodecylbenzenesulfonate 5%, sodium methylene bisnaphthalenesulfonate 5%, nonylphenol polyoxyethylene ether carboxylate 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD2%, polysilicone defoamer 0.5%, tartaric acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0276] Example 3-12

[0277] 40% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0278] Thiamethoxam (compound A3) 40%, dihydrochalcone (stabilizer B2) 0.8%, sodium dodecylbenzenesulfonate 5%, methylnaphthalenesulfonic acid formaldehyde condensate 15%, nonylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, malic acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0279] Example 3-13

[0280] 60% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0281] Thiamethoxam (compound A3) 60%, aurone (stabilizer B3) 1.2%, sodium dodecylbenzene sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, nonylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 4%, polysilicone defoamer 0.5%, malic acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0282] Embodiment 3-14

[0283] 70% Thiamethoxam (Compound A3) spray-dried water dispersible granules

[0284] Thiamethoxam (compound A3) 70%, dihydrochalcone (stabilizer B2) 1.16%, sodium dodecylbenzenesulfonate 4%, sodium methylenebisnaphthalenesulfonate 3%, methylnaphthalenesulfonic acid formaldehyde condensate 5%, sodium diisooctyl succinate sulfonate 6%, polysilicone defoamer 0.5%, malic acid 0.1%, and the rest is made up to 100% with ammonium sulfate.

[0285] Table 6. Wetting time of spray-dried water dispersible granules of thiamethoxam (Compound A3) and flocculation of dilution

[0286]

[0287] As can be seen from Table 6, the spray-dried water-dispersible granules prepared with thiamethoxam (compound A3) as the active ingredient, the four control examples without adding stabilizers, the wetting time under low-temperature hard water and low dilution conditions are all greater than 60s, and the dilution has flocculation. Example 3-1 and Example 3-2 show that within the scope of the patent, adding baicalin (stabilizer B1) as a stabilizer, the wetting time under low-temperature hard water and low dilution conditions is short and the dilution has no flocculation. Example 3-3 and Example 3-4 show that within the scope of the patent, adding dihydrochalcone (stabilizer B2) as a stabilizer, the wetting time under low-temperature hard water and low dilution conditions is short and the dilution has no flocculation. Example 3-5 and Example 3-6 show that within the scope of the patent, adding aurone (stabilizer B3) as a stabilizer, the wetting time under low-temperature hard water and low dilution conditions is short and the dilution has no flocculation.

[0288] Table 7. Wetting time of spray-dried water dispersible granules of thiamethoxam (Compound A3) and flocculation of dilution

[0289]

[0290] As can be seen from Table 7, the spray-dried water-dispersible granules prepared with thiamethoxam (Compound A3) as the active ingredient are added with stabilizers of different types and amounts: if the amount of stabilizer added is within the range specified in this patent, the wetting time is short under the conditions of low temperature hard water and low dilution multiple, and the dilution liquid has no flocculation phenomenon; if the amount of stabilizer added is outside the range specified in this patent, the wetting time is long under the conditions of low temperature hard water and low dilution multiple, and the dilution liquid has flocculation phenomenon.

[0291] Comparative Example 4-1

[0292] 10% Clothianidin (Compound A4) spray-dried water dispersible granules

[0293] Clothianidin (Compound A4) 10%, naphthalenesulfonic acid formaldehyde condensate sodium salt 5%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, fatty alcohol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with diatomaceous earth.

[0294] Comparative Example 4-2

[0295] 30% Clothianidin (Compound A4) spray-dried water dispersible granules

[0296] Thiamphenicol (Compound A4) 30%, β-naphthol cresol formaldehyde condensate sulfonate 5%, α-olefin sodium sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 6%, polysilicone defoamer 0.5%, and the rest is made up to 100% with diatomaceous earth.

[0297] Comparative Example 4-3

[0298] 50% Clothianidin (Compound A4) spray-dried water dispersible granules

[0299] Clothianidin (Compound A4) 50%, naphthalenesulfonic acid formaldehyde condensate sodium salt 5%, α-olefin sodium sulfonate 5%, methylene bis-naphthalene sodium sulfonate 15%, fatty alcohol polyoxyethylene ether carboxylate 5%, lauryl alcohol polyoxyethylene ether carboxylate 10%, polysilicone defoamer 0.5%, and the rest is made up to 100% with diatomaceous earth.

[0300] Comparative Example 4-4

[0301] 70% Clothianidin (Compound A4) spray-dried water dispersible granules

[0302] Clothianidin (Compound A4) 70%, β-naphthol cresol formaldehyde condensate sulfonate 3%, α-olefin sodium sulfonate 3%, sodium methylene bisnaphthalene sulfonate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, sodium diisooctyl succinate sulfonate 14%, polysilicone defoamer 0.5%, and the rest is made up to 100% with diatomaceous earth.

[0303] Example 4-1

[0304] 10% Clothianidin (Compound A4) spray-dried water dispersible granules

[0305] Clothianidin (compound A4) 10%, baicalin (stabilizer B1) 50%, benzylnaphthalenesulfonic acid formaldehyde condensate 5%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with diatomaceous earth.

[0306] Example 4-2

[0307] 70% Clothianidin (Compound A4) spray-dried water dispersible granules

[0308] Clothianidin (compound A4) 70%, baicalin (stabilizer B1) 1.4%, β-naphthol cresol formaldehyde condensate sulfonate 3%, sodium α-olefin sulfonate 3%, sodium methylene bisnaphthalene sulfonate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, lauryl alcohol polyoxyethylene ether carboxylate 14%, polysilicone defoamer 0.5%, and the rest is made up to 100% with diatomaceous earth.

[0309] Example 4-3

[0310] 10% Clothianidin (Compound A4) spray-dried water dispersible granules

[0311] Clothianidin (compound A4) 10%, dihydrochalcone (stabilizer B2) 50%, benzylnaphthalenesulfonic acid formaldehyde condensate 5%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0312] Example 4-4

[0313] 70% Clothianidin (Compound A4) spray-dried water dispersible granules

[0314] Clothianidin (compound A4) 70%, dihydrochalcone (stabilizer B2) 1.4%, β-naphthol cresol formaldehyde condensate sulfonate 3%, α-olefin sodium sulfonate 3%, methyl naphthalene sulfonic acid formaldehyde condensate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, fatty alcohol polyoxyethylene ether carboxylate 14%, polysilicone defoamer 0.5%, and the rest is made up with kaolin to 100%.

[0315] Embodiment 4-5

[0316] 10% Clothianidin (Compound A4) spray-dried water dispersible granules

[0317] Clothianidin (compound A4) 10%, aurone (stabilizer B3) 50%, β-naphthol cresol formaldehyde condensate sulfonate 5%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, sodium methylene bisnaphthalene sulfonate 2%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0318] Embodiment 4-6

[0319] 70% Clothianidin (Compound A4) spray-dried water dispersible granules

[0320] Clothianidin (compound A4) 70%, aurone (stabilizer B3) 1.4%, β-naphthol cresol formaldehyde condensate sulfonate 3%, α-olefin sodium sulfonate 3%, methylene bis-naphthalene sodium sulfonate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, methylnaphthalene sulfonic acid formaldehyde condensate 14%, polysilicone defoamer 0.5%, and the rest is made up to 100% with diatomaceous earth.

[0321] Embodiment 4-7

[0322] 10% Clothianidin (Compound A4) spray-dried water dispersible granules

[0323] Clothianidin (compound A4) 10%, baicalin (stabilizer B1) 40%, β-naphthol cresol formaldehyde condensate sulfonate 5%, α-olefin sodium sulfonate 5%, methylene bis-naphthalene sodium sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, methylnaphthalene sulfonic acid formaldehyde condensate sodium salt 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with diatomaceous earth.

[0324] Embodiment 4-8

[0325] 10% Clothianidin (Compound A4) spray-dried water dispersible granules

[0326] Clothianidin (compound A4) 10%, dihydrochalcone (stabilizer B2) 1%, β-naphthol cresol formaldehyde condensate sulfonate 5%, α-olefin sodium sulfonate 5%, methylene bis-naphthalene sodium sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, methylnaphthalene sulfonic acid formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0327] Embodiment 4-9

[0328] 10% Clothianidin (Compound A4) spray-dried water dispersible granules

[0329] Clothianidin (compound A4) 10%, aurone (stabilizer B3) 0.2%, β-naphthol cresol formaldehyde condensate sulfonate 5%, α-olefin sodium sulfonate 5%, methylene bis-naphthalene sodium sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, methyl naphthalene sulfonic acid formaldehyde condensate sodium salt 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with bentonite.

[0330] Embodiment 4-10

[0331] 10% Clothianidin (Compound A4) spray-dried water dispersible granules

[0332] Clothianidin (compound A4) 10%, baicalin (stabilizer B1) 0.16%, lauryl alcohol polyoxyethylene ether carboxylate 5%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with bentonite.

[0333] Embodiment 4-11

[0334] 12% Clothianidin (Compound A4) spray-dried water dispersible granules

[0335] Clothianidin (compound A4) 12%, baicalin (stabilizer B1) 60%, lauryl alcohol polyoxyethylene ether carboxylate 5%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 5%, alkylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0336] Embodiment 4-12

[0337] 40% Clothianidin (Compound A4) spray-dried water dispersible granules

[0338] Clothianidin (compound A4) 40%, dihydrochalcone (stabilizer B2) 0.8%, sodium fatty alcohol polyoxyethylene ether succinate sulfonate 5%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0339] Embodiment 4-13

[0340] 60% Clothianidin (Compound A4) spray-dried water dispersible granules

[0341] Clothianidin (compound A4) 60%, aurone (stabilizer B3) 1.2%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD 5%, sodium α-olefin sulfonate 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 4%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0342] Embodiment 4-14

[0343] 70% Clothianidin (Compound A4) spray-dried water dispersible granules

[0344] Clothianidin (compound A4) 70%, dihydrochalcone (stabilizer B2) 1.16%, sodium fatty alcohol polyoxyethylene ether succinate sulfonate 3%, sodium α-olefin sulfonate 4%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD3%, alkylphenol polyoxyethylene ether carboxylate 5%, sodium diisooctyl succinate sulfonate 6%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0345] Table 8. Wetting time of spray-dried water dispersible granules of clothianidin (Compound A4) and flocculation of dilution

[0346]

[0347] As can be seen from Table 8, the spray-dried water-dispersible granules prepared with thiamethoxam (compound A4) as the active ingredient, the four control examples without adding stabilizers, the wetting agent under low-temperature hard water and low dilution conditions is greater than 60s, and the released liquid has flocculation phenomenon. Example 4-1 and Example 4-2 show that within the scope of the patent, adding baicalin (stabilizer B1) as a stabilizer, the wetting time under low-temperature hard water and low dilution conditions is short and the dilution has no flocculation phenomenon. Example 4-3 and Example 4-4 show that within the scope of the patent, adding dihydrochalcone (stabilizer B2) as a stabilizer, the wetting time under low-temperature hard water and low dilution conditions is short and the dilution has no flocculation phenomenon. Example 4-5 and Example 4-6 show that within the scope of the patent, adding aurone (stabilizer B3) as a stabilizer, the wetting time under low-temperature hard water and low dilution conditions is short and the dilution has no flocculation phenomenon.

[0348] Table 9. Wetting time of spray-dried water dispersible granules of clothianidin (Compound A4) and flocculation of dilution

[0349]

[0350] As can be seen from Table 9, the spray-dried water-dispersible granules prepared with clothianidin (Compound A4) as the active ingredient are added with stabilizers of different types and amounts: if the amount of stabilizer added is within the range specified in this patent, the wetting time under low-temperature hard water and low dilution multiple conditions is short and the diluted liquid has no flocculation phenomenon; if the amount of stabilizer added is outside the range specified in this patent, the wetting time under low-temperature hard water and low dilution multiple conditions is long and the diluted liquid has flocculation phenomenon.

[0351] Comparative Example 5-1

[0352] 10% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0353] Thiacloprid (Compound A5) 10%, alkylphenol polyoxyethylene ether succinic acid 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, alkylphenol polyoxyethylene ether sodium succinate sulfonate 2%, polysilicone defoamer 0.5%, and the rest is made up with sodium sulfate to 100%.

[0354] Comparative Example 5-2

[0355] 30% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0356] Thiacloprid (Compound A5) 30%, alkylphenol polyoxyethylene ether succinic acid 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, alkylphenol polyoxyethylene ether sodium succinate sulfonate 6%, polysilicone defoamer 0.5%, and the rest is made up with sodium sulfate to 100%.

[0357] Comparative Example 5-3

[0358] 50% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0359] Thiacloprid (Compound A5) 50%, alkylphenol polyoxyethylene ether succinic acid 5%, methylene bis-naphthalene sulfonate sodium 15%, alkylphenol polyoxyethylene ether carboxylate 5%, β-naphthalenesulfonic acid formaldehyde condensate sodium salt 10%, polysilicone defoamer 0.5%, and the rest is made up with sodium sulfate to 100%.

[0360] Comparative Example 5-4

[0361] 70% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0362] Thiacloprid (Compound A5) 70%, alkylphenol polyoxyethylene ether succinic acid 3%, methylene bis-naphthalene sulfonate sodium 3%, alkylphenol polyoxyethylene ether carboxylate 3%, naphthalenesulfonic acid formaldehyde condensate sodium salt 14%, polysilicone defoamer 0.5%, and the rest is supplemented with potassium chloride to 100%.

[0363] Example 5-1

[0364] 10% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0365] Thiacloprid (compound A5) 10%, baicalin (stabilizer B1) 50%, alkylphenol polyoxyethylene ether succinic acid 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, nonylphenol polyoxyethylene ether carboxylate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0366] Example 5-2

[0367] 70% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0368] Thiacloprid (compound A5) 70%, baicalin (stabilizer B1) 1.4%, alkylphenol polyoxyethylene ether succinic acid 3%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD 3%, alkylphenol polyoxyethylene ether carboxylate 3%, nonylphenol polyoxyethylene ether carboxylate 14%, polysilicone defoamer 0.5%, and the rest is made up with sodium sulfate to 100%.

[0369] Example 5-3

[0370] 10% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0371] Thiacloprid (compound A5) 10%, dihydrochalcone (stabilizer B2) 50%, alkylphenol polyoxyethylene ether succinic acid 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0372] Example 5-4

[0373] 70% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0374] Thiacloprid (compound A5) 70%, dihydrochalcone (stabilizer B2) 1.4%, alkylphenol polyoxyethylene ether succinic acid 3%, sodium methylene bisnaphthalene sulfonate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, naphthalenesulfonic acid formaldehyde condensate sodium salt 14%, polysilicone defoamer 0.5%, and the rest is made up with sodium sulfate to 100%.

[0375] Example 5-5

[0376] 10% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0377] Thiacloprid (compound A5) 10%, aurone (stabilizer B3) 50%, alkylphenol polyoxyethylene ether succinic acid 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0378] Embodiment 5-6

[0379] 70% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0380] Thiacloprid (compound A5) 70%, aurone (stabilizer B3) 1.4%, calcium dodecylbenzenesulfonate 3%, sodium methylene bisnaphthalenesulfonate 3%, alkylphenol polyoxyethylene ether carboxylate 3%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD 14%, polysilicone defoamer 0.5%, and the rest is made up to 100% with calcined kaolin.

[0381] Embodiment 5-7

[0382] 10% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0383] Thiacloprid (compound A5) 10%, baicalin (stabilizer B1) 40%, alkylphenol polyoxyethylene ether succinic acid 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, β-naphthol cresol formaldehyde condensate sulfonate 2%, polysilicone defoamer 0.5%, and the rest is made up with sodium sulfate to 100%.

[0384] Embodiment 5-8

[0385] 10% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0386] Thiacloprid (compound A5) 10%, dihydrochalcone (stabilizer B2) 1%, alkylphenol polyoxyethylene ether succinic acid 5%, phenol derivative sulfonate formaldehyde condensate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, β-naphthol cresol formaldehyde condensate sulfonate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with potassium chloride.

[0387] Embodiment 5-9

[0388] 10% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0389] Thiacloprid (compound A5) 10%, aurone (stabilizer B3) 0.2%, alkylphenol polyoxyethylene ether succinic acid 5%, sodium methylene bisnaphthalene sulfonate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, phenol derivative sulfonate formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0390] Embodiment 5-10

[0391] 10% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0392] Thiacloprid (compound A5) 10%, baicalin (stabilizer B1) 0.16%, alkylphenol polyoxyethylene ether succinic acid 5%, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF 15%, alkylphenol polyoxyethylene ether carboxylate 5%, phenol derivative sulfonate formaldehyde condensate 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0393] Example 5-11

[0394] 12% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0395] Thiacloprid (compound A5) 12%, baicalin (stabilizer B1) 60%, alkylphenol polyoxyethylene ether succinic acid 5%, sodium methylene bisnaphthalene sulfonate 5%, alkylphenol polyoxyethylene ether carboxylate 5%, methylnaphthalene sulfonic acid formaldehyde condensate sodium salt MF 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0396] Example 5-12

[0397] 40% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0398] Thiacloprid (compound A5) 40%, dihydrochalcone (stabilizer B2) 0.8%, alkylphenol polyoxyethylene ether succinic acid 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD15%, alkylphenol polyoxyethylene ether carboxylate 5%, methylnaphthalenesulfonic acid formaldehyde condensate sodium salt MF 2%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0399] Example 5-13

[0400] 60% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0401] Thiacloprid (compound A5) 60%, aurone (stabilizer B3) 1.2%, alkylphenol polyoxyethylene ether succinic acid 5%, phenol derivative sulfonate formaldehyde condensate 15%, alkylphenol polyoxyethylene ether carboxylate 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD4%, polysilicone defoamer 0.5%, and the rest is made up to 100% with sodium sulfate.

[0402] Embodiment 5-14

[0403] 70% Thiacloprid (Compound A5) spray-dried water dispersible granules

[0404] Thiacloprid (compound A5) 70%, dihydrochalcone (stabilizer B2) 1.16%, alkylphenol polyoxyethylene ether succinic acid 4%, sodium methylene bisnaphthalene sulfonate 4%, alkylphenol polyoxyethylene ether carboxylate 5%, naphthalenesulfonic acid formaldehyde condensate sodium salt PD6%, polysilicone defoamer 0.5%, and the rest is made up with sodium sulfate to 100%.

[0405] Table 10. Wetting time of spray-dried water dispersible granules of thiacloprid (Compound A5) and flocculation of dilution

[0406]

[0407] As can be seen from Table 10, for the spray-dried water-dispersible granules prepared with thiacloprid (Compound A5) as the active ingredient, the four control examples without adding stabilizers, the wetting time of the wetting agent under the conditions of low temperature hard water and low dilution multiples is greater than 60s, and the dilution has flocculation phenomenon. Example 5-1 and Example 5-2 show that within the scope of the patent, adding baicalin (stabilizer B1) as a stabilizer, the wetting time under the conditions of low temperature hard water and low dilution multiples is short and the dilution has no flocculation phenomenon. Example 5-3 and Example 5-4 show that within the scope of the patent, adding dihydrochalcone (stabilizer B2) as a stabilizer, the wetting time under the conditions of low temperature hard water and low dilution multiples is short and the dilution has no flocculation phenomenon. Example 5-5 and Example 5-6 show that within the scope of the patent, adding aurone (stabilizer B3) as a stabilizer, the wetting time under the conditions of low temperature hard water and low dilution multiples is short and the dilution has no flocculation phenomenon.

[0408] Table 11. Wetting time of spray-dried water dispersible granules of thiacloprid (Compound A5) and flocculation of dilution

[0409]

[0410] As can be seen from Table 11, the spray-dried water-dispersible granules prepared with thiacloprid (compound A5) as the active ingredient are added with stabilizers of different types and amounts: if the amount of stabilizer added is within the range specified in this patent, the wetting time is short under the conditions of low temperature hard water and low dilution multiple, and the diluted liquid has no flocculation phenomenon; if the amount of stabilizer added is outside the range specified in this patent, the wetting time is long under the conditions of low temperature hard water and low dilution multiple, and the diluted liquid has flocculation phenomenon.

[0411] Table 12. Wetting time and dilution flocculation of different compounds (Compound A1 / A2 / A3 / A4 / A5) spray-dried water dispersible granules at different temperatures, hard water hardness and dilution multiples

[0412]

[0413]

[0414] It can be seen from the control examples 1-1 / 1-2 / 1-3 / 1-4 in Table 12 that when the hardness of hard water is lower than 325 ppm, no stabilizer is added and the wetting is longer than 60 seconds, but the diluted liquid will not show flocculation.

[0415] It can be seen from control example 2-1 / 2-2 / 2-3 / 2-4 that when the dilution ratio is greater than 40 times, the wetting time is greater than 60s without adding stabilizer, but the diluted solution will not show flocculation.

[0416] It can be seen from control examples 3-1 / 3-2 / 3-3 / 3-4 that when the hard water temperature is greater than 15°C, the wetting time is greater than 60s without adding stabilizer, but the diluted solution will not show flocculation.

[0417] It can be seen from the control example 4-1 / 4-2 / 4-3 / 4-4 that when the dilution ratio is less than 5 times, no stabilizer or wetting agent is added for more than 60s, and flocculation will occur in the diluted solution.

[0418] It can be seen from Example 1-3 / 2-2 that when the hardness of hard water is greater than 1500ppm, the wetting time after adding the stabilizer is greater than 60s, and flocculation will occur.

[0419] It can be seen from Example 3-2 / 4-1 that when the hard water temperature is greater than 15°C, the wetting time after adding the stabilizer is very short and the dilution does not flocculate. In combination with Comparative Examples 3-1 / 3-2 / 3-2 / 3-4, the temperature is higher than the temperature range specified by the present invention, and no flocculation occurs with or without the addition of the stabilizer, but the wetting time is different.

[0420] It can be seen from Examples 5-1 / 5-2 / 5-3 that when the dilution ratio is less than 5, the sample with the stabilizer added also has the problem of long wetting time and flocculation of the dilution liquid. Combined with the control examples 4-1 / 4-2 / 4-3 / 4-4, when the dilution ratio is lower than the specified range of the present invention, the flocculation problem will occur with or without the addition of the stabilizer, and the wetting time is also long.

[0421] From the above embodiments, it can be seen that the water dispersible granules obtained by the present invention are significantly stable when a specific stabilizer and auxiliary agent are matched: the dilution liquid does not flocculate under low temperature hard water and low dilution multiple (325-1500ppm, 0-15℃ hard water, 5-40 times dilution conditions); and the wetting time is short.

[0422] Biologically active examples

[0423] In order to verify the effect of adding stabilizer B and other adjuvants to compound A and preparing water dispersible granules using spray drying process on the efficacy, the following biological activity test was carried out: the biological activities of Example 1-1, Example 1-4 and Control Example 1-1 against rice brown planthopper were compared in the test.

[0424] Bioactivity test on rice brown planthopper

[0425] Test conditions: greenhouse conditions, temperature 25-30℃, light (L / D) 14h / 10h.

[0426] Preparation of drug solution: Use an electronic analytical balance to accurately weigh the test drug, directly add water to the preparation to make the stock solution of the required concentration, and then dilute it with water to form a series of drug solutions with a certain concentration gradient according to the designed experimental dosage.

[0427] Test method: Live seedling spray method was used. The germinated rice seeds were sown directly in plastic pots (upper diameter of 10 cm, height of 10 cm), 12 seeds per pot, and numbered for use when the rice seedlings grew to the three-leaf and one-heart stage. The prepared liquid was sprayed on the whole plant with an airbrush manual sprayer in the order of the experimental design dose from low to high. After the rice seedlings were naturally dried in the shade, they were covered with glass covers (diameter of 9 cm, height of 12 cm), and the third-instar nymphs of brown planthoppers were inoculated. 20 nymphs were inoculated in each pot. The test was repeated 3 times, and a clean water treatment was set as a blank control.

[0428] Table 13. Results of indoor activity test of pymetrozine (compound A) samples against brown planthopper

[0429]

[0430] As can be seen from Table 13, the LC50 of Example 1-1 and Example 1-4 are lower than that of Control Example 1-1. It can be judged that the biological activity of compound A prepared by spray drying process after adding stabilizer B and other additives is not affected, but is better than the sample without adding stabilizer (Control Example 1-1) to a certain extent.

[0431] It can be inferred that this kind of solid preparation containing stabilizers can be used for aerial spraying under low temperature hard water and low dilution conditions (325-1500ppm, 0-15℃ hard water, 5-40 times dilution) while ensuring that all indicators meet the relevant regulations of water-dispersible granules "GB / T 19378-2017 Names and Codes of Pesticide Formulations". The dilution liquid has no flocculation and short wetting time. This solid preparation product can well solve the problems of dilution liquid flocculation and long wetting time that often occur when traditional water-dispersible granules are used for aerial spraying without reducing the efficacy.

[0432] The solid preparation prepared in this patent has a crop control range far beyond the rice brown planthopper mentioned in the above examples.

Claims

1. A solid preparation containing a stabilizer, wherein compound A is used as an active ingredient, and is prepared into water dispersible granules in combination with at least one auxiliary agent and at least one carrier filler, characterized in that: The weight percentage of the active ingredient compound A in the solid preparation is 10-70%, and the auxiliary agent contains a stabilizer B, and the weight percentage of the stabilizer B in the solid preparation is greater than or equal to 0.2%; The stabilizer B is selected from Baicalin (B1); The compound A is selected from one or more of pymetrozine (A1), imidacloprid (A2), thiamethoxam (A3), clothianidin (A4) or thiacloprid (A5).

2. The solid preparation containing a stabilizer according to claim 1, characterized in that: The stabilizer B accounts for 0.2-50% by weight of the solid preparation.

3. The solid preparation containing a stabilizer according to any one of claims 1 to 2, characterized in that: The auxiliary agents in the solid preparation include a wetting agent, a dispersant, a pH regulator and a defoamer, and the weight percentage of each component in the solid preparation is 1-40% of the wetting agent, 1-40% of the dispersant, 0.01-2% of the pH regulator and 0.1-5% of the defoamer.

4. The solid preparation containing a stabilizer according to claim 3, characterized in that: The wetting agent is selected from one or a combination of alkylbenzene sulfonate, α-olefin sulfonate and succinate sulfonate; The dispersant is selected from one or a combination of naphthalenesulfonate dispersants and polycarboxylate dispersants; The pH regulator is selected from one or a combination of organic weak acids.

5. The solid preparation containing a stabilizer according to claim 4, characterized in that: The wetting agent is selected from sodium dodecylbenzene sulfonate, calcium dodecylbenzene sulfonate, sodium α-olefin sulfonate, sodium diisooctyl sulfosuccinate, sodium fatty alcohol polyoxyethylene ether succinate sulfonate, sodium alkylphenol polyoxyethylene ether succinate sulfonate, or a combination thereof; The dispersant is selected from the group consisting of naphthalenesulfonic acid formaldehyde condensate sodium salt PD, tar-based naphthalenesulfonic acid formaldehyde condensate sodium salt MF, methylene bis-naphthalenesulfonate sodium salt, methylnaphthalenesulfonic acid formaldehyde condensate sodium salt MF, naphthalenesulfonic acid formaldehyde condensate sodium salt, benzylnaphthalenesulfonic acid formaldehyde condensate, methylnaphthalenesulfonic acid formaldehyde condensate, phenol derivative sulfonate formaldehyde condensate, β-naphthol cresol formaldehyde condensate sulfonate, β-naphthalenesulfonic acid formaldehyde condensate sodium salt, fatty alcohol polyoxyethylene ether carboxylate, alkylphenol polyoxyethylene ether carboxylate, lauryl alcohol polyoxyethylene ether carboxylate, and nonylphenol polyoxyethylene ether carboxylate, or a combination of the two; The pH regulator is selected from one or a combination of metaphosphoric acid, sorbic acid, citric acid, salicylic acid, tartaric acid, malic acid and taurine.

6. The solid preparation containing a stabilizer according to claim 1, characterized in that: The carrier filler is selected from one of ammonium sulfate, sodium sulfate, potassium chloride, diatomaceous earth, kaolin, calcined kaolin, bentonite, and light calcium carbonate, or a combination of the two or more, and accounts for 0.1-80% of the weight percentage of the solid preparation.

7. A method for preparing a solid preparation containing a stabilizer according to claim 1, characterized in that: According to the ingredients and dosage ratios described in claim 1, water-dispersible granules with compound A as the active ingredient are prepared by spray drying.

8. Use of the solid preparation containing a stabilizer according to claim 1, characterized in that: The preparation is used as an agricultural insecticide.

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