Soluble concentrate containing flubendiamide and preparation method thereof

Abstract

The invention discloses a soluble concentrate containing flubendiamide and a preparation method of the soluble concentrate, and belongs to the technical field of pesticides. The soluble concentrate comprises the following components in percentage by mass: 1%-10% of flubendiamide, 1%-10% of an active component B, 25%-45% of an amide solvent, 5%-15% of an alcohol solvent, 5%-15% of a phosphate emulsifier, 0%-1% of a stabilizer and the balance of water. The preparation is safe and environment-friendly in raw material, simple in formula process and good in storage stability, the active ingredients are in a molecular or ionic state after being diluted with water, the preparation has the characteristics of good pesticide effect, small dosage and the like when being used for pest control, the pesticide dosage can be effectively reduced, and the purposes of reduction and synergism are achieved.

Description

Technical Field

[0001] The invention relates to the technical field of pesticides, and in particular to a soluble agent containing brofenoxamide and a preparation method thereof. Background Art

[0002] Bromitriptyline belongs to the diamide insecticide class and is an allosteric modulator of GABA-gated chloride channels (also known as ionotropic GABA receptors). It mainly acts on a unique binding site on the ion channel, inhibiting the transmission of chloride ions into the cell, causing insects to become overexcited or spasmodic, thereby showing rapid insecticidal activity. IRAC classifies this type of compound as Group 30. Bromitriptyline has good insecticidal activity against Lepidoptera and Coleoptera insects, especially against Lepidoptera pests, showing high larvicidal activity.

[0003] Although bromofenac has a unique mechanism of action, its resistance problem has become increasingly prominent with its large-scale promotion and application. At present, the use of different types of insecticides to delay or reduce the occurrence of pest resistance is one of the most effective ways to solve the above problems. In addition, due to the high cost and long cycle of developing new insecticides, the development and research of high-efficiency, low-toxicity, and low-residue compound insecticide combinations have low investment and short development cycle, and have attracted attention at home and abroad. Various companies have increased their research and development efforts.

[0004] At present, there are many compound varieties of brofenac, and the formulation development is mainly focused on water dispersible granules, suspension concentrates, dispersible oil suspension concentrates, wettable powders, emulsifiable concentrates, suspoemulsions, water emulsions or microemulsions. For example, patent publication number CN110959615A discloses an insecticide composition containing brofenac, in which the weight ratio of brofenac to emamectin benzoate or abamectin is 1:20. 20:1, the dosage form is wettable powder, water dispersible granules and suspension; the patent with publication number CN110199995A discloses a pesticide composition containing brofenoxamide and lufenuron, the active ingredients of which are brofenoxamide and lufenuron, and the dosage form is emulsifiable concentrate, suspension concentrate, wettable powder, water dispersible granules, water emulsion or microemulsion; the patent with publication number CN110063331A discloses a synergistic pesticide composition of brofenoxamide and neonicotinoid insecticide, the active ingredients of which are brofenoxamide and neonicotinoid insecticide, and the dosage form is water dispersible granules, wettable powder, suspension concentrate, emulsifiable concentrate, microemulsion or water emulsion; The patent with publication number CN109258651A discloses an insecticidal composition containing brofenac and chlorfenapyr, wherein the active ingredients are brofenac and chlorfenapyr, and the dosage form is wettable powder, granules, water-dispersible granules, suspension or emulsifiable concentrate; the patent with publication number CN109221127A discloses an insecticidal composition containing brofenac and neonicotinoids, wherein the active ingredient A is brofenac, and the active ingredient B is any one of thiamethoxam, imidacloprid, acetamiprid, nitenpyram, dinotefuran, clothianidin, and the dosage form can be wettable powder, water-dispersible granules, suspension, suspoemulsion, emulsion in water or microemulsion. Patent publication number CN108077264A discloses an insecticide composition containing spinetoram and bromofenac, the formulation of which is a wettable powder, water dispersible granules, suspension, suspoemulsion, emulsion in water or microemulsion. None of the above patents involve soluble solutions.

[0005] The emulsifiable concentrate formulations involved in the above patents require a large amount of aromatic organic solvents such as toluene and xylene during the processing process. The use of aromatic solvents increases the residue of toxic substances in crops and reduces the quality of agricultural products. Microemulsions have certain advantages for liquid technical drugs, but the development of formulations for medium-to-high content or poorly soluble solid drugs still requires a large amount of harmful solvents such as N,N-dimethylformamide, N-methylpyrrolidone, cyclohexanone, methanol, etc., which have high reproductive toxicity to humans and animals and are easy to pollute the environment. Water emulsions and suspensions are environmentally friendly pesticides based on water, but their storage physical stability is poor and their efficacy is relatively poor, which increases the amount of active ingredients of pesticides, is not conducive to environmental protection, and may increase pest resistance. In addition, after the formulations involved in the above patents are diluted with water, the particle size of the suspension or emulsion formed is relatively large, the spreading and penetration performance is poor, and the efficacy is generally not high. It is well known that for the same type of pesticide technical drugs, the efficacy of pesticide preparations depends on its formulation type and the dispersion state and size of pesticide particles. Scientific common sense tells us that, under the same conditions, the smaller the particle size of the pesticide original, the larger its surface area, the wider the contact area with plant leaves and pests, the more effective the pesticide will be, and the amount of pesticide used will be reduced accordingly. It can be seen that it is very necessary to develop new dosage forms to improve the efficacy of bromofenac. Summary of the invention

[0006] The invention provides a bromofenac-containing soluble preparation and a preparation method thereof. The bromofenac-containing soluble preparation of the invention uses a phosphate surfactant as an emulsifier, overcomes the defects of a traditional dosage form, and improves the physical and chemical properties and application properties of the preparation. After being diluted with water, the active ingredient is in a molecular or ionic state, which makes it easier to spread and penetrate on the surface of a plant, is conducive to giving full play to the efficacy of the drug, and can reduce the amount of pesticide used, thereby achieving the purpose of reducing the amount and increasing the efficiency.

[0007] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0008] A soluble agent containing brofenac, which is composed of the following components in percentage by mass: 1% to 10% brofenac, 1% to 10% active component B, 25% to 45% amide solvent, 5% to 15% alcohol solvent, 5% to 15% phosphate emulsifier, 0% to 1% stabilizer and the balance of water.

[0009] In the above-mentioned soluble agent, the active component B is selected from at least one of the following: emamectin benzoate, abamectin, high-efficiency chlorflucythrinate, thiamethoxam, acetamiprid, lufenuron, tolfenpyrad and cypermethrin.

[0010] In the above-mentioned soluble agent, the amide solvent is selected from at least one of N,N-diethylformamide, N,N-dimethyllactamide, N,N-dimethyloctanamide and N,N-dimethyldecylamide.

[0011] In the above-mentioned soluble solution, the amide solvent is selected from any one of the following:

[0012] 1) N,N-diethylformamide and N,N-dimethyloctanamide;

[0013] 2) N,N-dimethyl lactamide and N,N-dimethyl decylamide;

[0014] 3) N,N-dimethyl lactamide and N,N-dimethyl octanamide.

[0015] Specifically, the amide solvent can be selected from any one of the following:

[0016] 1) N,N-diethylformamide and N,N-dimethyloctanamide in a mass ratio of 1:0.5 to 0.8; specifically, N,N-diethylformamide and N,N-dimethyloctanamide in a mass ratio of 1:0.6, 1:0.5, 1:0.75 or 1:0.8;

[0017] 2) N,N-dimethyl lactamide and N,N-dimethyl decanamide in a mass ratio of 1:0.125 to 0.25; specifically, N,N-dimethyl lactamide and N,N-dimethyl decanamide in a mass ratio of 1:0.125 or 1:0.25;

[0018] 3) N,N-dimethyl lactamide and N,N-dimethyl octanamide in a mass ratio of 1:0.6-1; specifically, N,N-dimethyl lactamide and N,N-dimethyl octanamide in a mass ratio of 1:1.

[0019] In the above-mentioned soluble agent, the alcohol solvent is selected from at least one of tetrahydrofurfuryl alcohol, diacetone alcohol, 3-methoxy-3-methyl-1-butanol and isohexanediol.

[0020] In the above-mentioned soluble agent, the phosphate emulsifier is at least one selected from tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, polyethylene glycol 400 monooleate phosphate, oleyl alcohol polyoxyethylene ether phosphate and alkoxylated phosphate.

[0021] In the above soluble solution, the stabilizer is selected from at least one of octanoic acid, 2,6-di-tert-butyl-p-methylphenol (BHT) and 2-hydroxy-4-n-octyloxybenzophenone (UV-531).

[0022] Furthermore, the present invention provides a method for preparing the above-mentioned soluble solution, comprising the following steps:

[0023] (1) Mix an amide solvent, an alcohol solvent, bromofenac, an active ingredient B and a stabilizer, and stir until the mixture is transparent and uniform;

[0024] (2) adding a phosphate emulsifier to the solution in (1) and stirring until the solution becomes transparent and uniform;

[0025] (3) Add water to the solution in (2) and stir until the solution becomes transparent and uniform.

[0026] In the above-mentioned preparation method, in step (1), the stirring time is 5 to 15 minutes;

[0027] In steps (2) and (3), the stirring time is 5 to 10 minutes.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) The present invention creatively disperses and dissolves the originally water-insoluble solid active ingredient in water in a stable manner, forming a true solution state, thereby improving the efficacy and maintaining the normal physical and chemical stability of the preparation;

[0030] (2) Phosphate surfactants are used as emulsifiers in the formula. They have both wetting and synergistic functions, making it easier for the diluted solution to spread and penetrate the target, reducing the amount of pesticide used and complying with national industrial policies. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is the appearance of 5% bromofenac + 4% emamectin benzoate diluted 20 times. Note: 1st on the left is SC, 2nd on the left is EC, 3rd on the left is ME, and 4th on the left is SL.

[0032] Figure 2 The wetting and spreading of 5% bromofenac + 4% emamectin benzoate in different dosage forms after dilution 1500 times on the canvas. Note: The sampling volume is 0.05mL, 1 on the left is SC, 2 on the left is EC, 3 on the left is ME, and 4 on the left is SL. DETAILED DESCRIPTION

[0033] The present invention is further described in detail below in conjunction with specific embodiments. The given examples are only for illustrating the present invention, but not for limiting the scope of the present invention.

[0034] The experimental methods in the following examples are all conventional methods unless otherwise specified.

[0035] The quantitative tests in the following examples were all repeated three times, and the results were averaged.

[0036] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0037] Unless otherwise specified, the percentages in the following embodiments are by mass.

[0038] The quality technical index testing method of the soluble preparation containing bromofenac in the following examples is as follows:

[0039] 1. Mass fraction of active ingredients: Bromofenac is determined by high performance liquid chromatography; active component B is determined by high performance liquid chromatography;

[0040] 2. pH range: measured according to CIPAC MT 75.3 method;

[0041] 3. Solution stability: Determine according to the method of CIPAC MT 41.1; dilute 20 times with standard hard water and let stand at 20°C for 18 hours.

[0042] 4. Persistent foaming: measured in accordance with CIPAC MT 47.3;

[0043] 5. Thermal storage stability: measured according to CIPAC MT 46.4, standing at 54°C for 14 days;

[0044] 6. Low temperature stability: Measured in accordance with CIPAC MT 39.3, standing at 0°C for 7 days.

[0045] Example 1, 5% bromofenac + 4% emamectin benzoate soluble solution

[0046] 1. The content of each component is as follows:

[0047] Brofenac (active ingredient, Mitsui Chemicals, Ltd.) 5%

[0048] Emamectin benzoate (active ingredient, Shandong Jingbo Agrochemical Technology Co., Ltd.) 4%

[0049] N,N-Dimethyl lactamide AGNIQUE AMD 3L (amide solvent, BASF) 25%

[0050] Tetrahydrofurfuryl alcohol (alcohol solvent, Luxi Chemical Group Co., Ltd.) 10%

[0051] N,N-Dimethyloctanamide (amide solvent, Nantong Zhongkai Chemical Co., Ltd.) 15%

[0052] Dispersogen LFH (phosphate emulsifier, Clariant) 15%

[0053] BHT (stabilizer, Jiangsu Maida New Materials Co., Ltd.) 1%

[0054] Water top up 100%

[0055] 2. The preparation process according to the above formula is as follows:

[0056] (1) Prepare various raw materials according to the formula quality ratio;

[0057] (2) Add the measured AGNIQUE AMD 3L, tetrahydrofurfuryl alcohol and N,N-dimethyloctanamide into the kettle, then add bromofenac, emamectin benzoate and BHT, and stir well for about 10 minutes until the mixture is transparent and uniform;

[0058] (3) Add Dispersogen LFH to the solution in (2) above and stir for 10 min until the solution becomes transparent and uniform;

[0059] (4) Add the remaining amount of water to the solution in (3) above, stir for 5 minutes until transparent and uniform, let stand, and filter to obtain the product.

[0060] The quality and technical indicators of the 9% bromofenac·emamectin benzoate soluble solution prepared in this example are shown in Table 1.

[0061] Table 1 Quality specifications of 9% bromofenac·emamectin benzoate soluble solution

[0062]

[0063] The appearance of 5% bromofenac + 4% emamectin benzoate diluted 20 times is shown in Figure 1 , left 4SL is the sample prepared in this embodiment.

[0064] The wetting and spreading of 5% bromofenac + 4% emamectin benzoate in different dosage forms after dilution 1500 times on the canvas are shown in the figure. Figure 2 , left 4SL is the sample prepared in this embodiment.

[0065] Figure 1 and Figure 2 In the figure, the preparation method of the suspension concentrate (SC) on the left is as follows:

[0066] In terms of mass percentage, 5% bromofenac, 4% emamectin benzoate, 3% dispersant Supragil MNS / 90 (alkyl naphthalene formaldehyde condensate sulfonate, Solvay), 1% wetting agent TERGITOL W-600 (isomeric alcohol polyoxyethylene ether, DOW), 5% 1,2-propylene glycol (antifreeze, Shandong Guohua Chemical Co., Ltd.), 0.5% stabilizer BHT (Jiangsu Maida New Materials Co., Ltd.), 0.1% xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% kason (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% SAG 1522 (organic silicon defoamer, Maitu High-tech Materials Group), and deionized water (self-made) are added to 100%. The above raw materials are mixed, sand-milled to a particle size of less than 5 μm, and filtered to obtain a 5% bromofenac + 4% emamectin benzoate suspension.

[0067] The preparation method of left 2 emulsifiable concentrate (EC) is as follows:

[0068] In terms of mass percentage, weigh 5% bromofenac, 4% emamectin benzoate, 7% emulsifier EL-40 (castor oil polyoxyethylene ether, Nantong Deyi Chemical Co., Ltd.), 3% emulsifier 505# (calcium dodecylbenzene sulfonate, Nantong Deyi Chemical Co., Ltd.), 15% solvent N,N-dimethylacetamide (Nantong Zhongkai Chemical Co., Ltd.), 0.5% stabilizer BHT (Jiangsu Maida New Materials Co., Ltd.), and solvent oil S-150 (Jiangsu Hualun Chemical Co., Ltd.) to make up to 100%. The above raw materials are mixed and stirred until transparent, and filtered to obtain 5% bromofenac + 4% emamectin benzoate emulsifiable concentrate.

[0069] The preparation method of left 3 microemulsion (ME) is as follows:

[0070] In terms of mass percentage, weigh 5% bromofenac, 4% emamectin benzoate, 20% emulsifier 602 (tristyrylphenol polyoxyethylene ether, Nantong Deyi Chemical Co., Ltd.), 20% dimethyl sulfoxide (Hubei Xingfa Chemical Group Co., Ltd.), 30% cyclohexanone (China Petroleum Liaoyang Petrochemical Fiber Company), 0.5% stabilizer BHT (Jiangsu Maida New Materials Co., Ltd.), and water (self-made) to make up to 100%. Dissolve the above bromofenac technical and emamectin benzoate technical in an organic solvent, add the emulsifier and stir until transparent, finally add water and stir until transparent, and filter to obtain a 5% bromofenac + 4% emamectin benzoate microemulsion.

[0071] With the same mass, the area of ​​contact between the liquid medicine and the pest will be larger. It can cover the surface of plant leaves or the body of the pest more widely, and it is easier to enter the body of the pest and play a toxic and killing role. Figure 1As shown in the figure, the suspension concentrate (SC) is a suspension in a diluted state, with a particle size between 1-10 microns; the emulsifiable concentrate (EC) is an emulsion in a diluted state, with a particle size between 1-5 microns; the microemulsion (ME) is a translucent emulsion in a diluted state, with a particle size between 0.01-0.1 microns; the soluble concentrate (SL) is a true solution in a diluted state, with a particle size generally less than 1 nanometer. It can be seen that from the perspective of particle size, the active ingredients in the soluble concentrate (SL) are usually evenly dispersed in the solvent in a molecular or ionic state, with an extremely small particle size, which can efficiently contact and exert its effect on the target, so the drug efficacy is excellent. The droplet size of the microemulsion (ME) is also relatively small, and it has certain advantages in dispersion and penetration, and its drug efficacy is second. The particle size of the emulsifiable concentrate (EC) is larger than the first two, and it is slightly inferior in terms of drug dispersion uniformity and contact efficiency with the target. Suspension concentrate (SC) is a dispersed system formed by solid particles dispersed in liquid. Its particle size is relatively larger, and its efficiency in deposition, attachment and entry into the target organism is relatively low, so its efficacy is relatively poor.

[0072] 3. Comparison of biological efficacy

[0073] In order to clarify the difference in control effect between 9% brofenoxamide·emamectin benzoate soluble concentrate and 9% brofenoxamide·emamectin benzoate suspension and microemulsion against cabbage diamondback moth, a field plot efficacy test was carried out.

[0074] The experimental method is as follows:

[0075] This experiment was conducted in accordance with GB / T 17980.13-2000 Pesticide Field Efficacy Test Guidelines (I) Pesticides for Control of Lepidoptera Larvae on Cruciferous Vegetables. The experimental agents, control agents, and blank control were randomly arranged in plots with a plot area of ​​50 m2. 2 3WBD-20 backpack electric sprayer is used for uniform spraying. Each agent is treated at 667m 2 30 kg of water was evenly sprayed on each plot. No other pesticides were used during the test, and each treatment was repeated 4 times.

[0076] Survey and statistical methods: Samples were taken at 5 diagonal points in each plot before spraying, and 10 plants were selected at each point to investigate the base number of diamondback moths. The number of live diamondback moths was investigated on the 3rd, 7th and 14th days after spraying. The population reduction rate and control effect of cabbage diamondback moth were calculated according to the following formulas:

[0077] Insect population reduction rate (%) = {(number of insects before application - number of insects after application) / number of insects before application} × 100;

[0078] Control effect (%) = {(pest reduction rate in the pesticide treatment area - pest reduction rate in the blank control area) / (100 - pest reduction rate in the blank control area)} × 100

[0079] Safety investigation and effects on other organisms: On the first day and several days after each spraying, observe the effects of each treatment on cabbage growth and other organisms.

[0080] The preparation method of the 9% bromofenac·emamectin benzoate suspension concentrate used is as follows:

[0081] In terms of mass percentage, 5% of bromofenac, 4% of emamectin benzoate, 3% of dispersant Soprophor SC (phosphate triethanolamine salt, Solvay), 2% of wetting agent YUS-EP60P (sodium sulfonyl succinate, TAKEMOTO), 5% of 1,2-propylene glycol (antifreeze, Shandong Guohua Chemical Co., Ltd.), 0.1% of xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% of kason (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% of SAG 1522 (organic silicon defoamer, Maitu High-tech Materials Group), 0.5% of BHT (stabilizer, Jiangsu Maida New Materials Co., Ltd.), and 100% of deionized water (self-made) were added. The above raw materials were mixed, sand-milled to a particle size of less than 5 μm, and filtered to obtain a 9% bromofenac·emamectin benzoate suspension.

[0082] The preparation method of 9% bromofenac·emamectin benzoate microemulsion is as follows:

[0083] In terms of mass percentage, weigh 5% bromofenac, 4% emamectin benzoate, 15% N,N-dimethylformamide (solvent, Changzhou Jufeng Chemical Co., Ltd.), 15% cyclohexanone (solvent, Hunan Dongwei Chemical New Materials Co., Ltd.), 5% methanol (solvent, Qilu Petrochemical Company), 20% 602# (emulsifier, Nanjing Taihua Chemical Co., Ltd.), 0.5% BHT (stabilizer, Jiangsu Maida New Materials Co., Ltd.), and make up to 100% with deionized water (self-made). Dissolve bromofenac, emamectin benzoate and stabilizer in an organic solvent, add emulsifier and stir evenly, and finally add water and stir evenly to obtain 9% bromofenac·emamectin benzoate microemulsion.

[0084] Agent 1: 9% bromofenac·emamectin benzoate soluble solution diluted 1500 times with water;

[0085] Agent 2: 9% bromofenac·emamectin benzoate soluble solution diluted 2000 times with water;

[0086] Agent 3: 9% bromofenac·emamectin benzoate suspension diluted 1500 times with water;

[0087] Agent 4: 9% bromofenac·emamectin benzoate microemulsion diluted 1500 times with water;

[0088] Table 2 Efficacy test data of bromofenac·emamectin benzoate mixture

[0089]

[0090] As shown in Table 2, at the same dilution multiple, the control effect of bromofenac·emamectin benzoate soluble concentrate on cabbage diamondback moth is significantly higher than other formulations with the same content, and has obvious advantages in reducing dosage and increasing efficiency. No phytotoxicity was found during the application period, and it is safe for cabbage growth.

[0091] Example 2, 8% bromofenac + 2% avermectin soluble solution

[0092] 1. The content of each component is as follows:

[0093]

[0094] 2. The preparation process according to the above formula is as follows:

[0095] (1) Prepare various raw materials according to the weight ratio of the formula;

[0096] (2) Add the measured AGNIQUE AMD 3L, 3-methoxy-3-methyl-1-butanol and N,N-dimethyldecylamide into the kettle, then add bromofenac, avermectin and octyl decanoic acid, and stir well for about 10 minutes until the mixture is transparent and uniform;

[0097] (3) Add the phosphate emulsifier MOA-9P to the solution of (2) above and stir for 5 minutes until the solution becomes transparent and uniform;

[0098] (4) Add the remaining amount of water to the solution in (3) above, stir for 5 minutes until transparent and uniform, let stand, and filter to obtain the product.

[0099] The quality and technical indicators of the 10% bromofenac·avermectin soluble solution prepared in this example are shown in Table 3.

[0100] Table 3 Quality specifications of 10% bromofenac·avermectin soluble solution

[0101]

[0102] After the sample of this embodiment was diluted 20 times with standard hard water, it showed a true solution state, and its appearance was similar to that of the attached Figure 1 Similar to that shown in 4 on the left, it is easier to wet, spread and penetrate and absorb on the target surface, thereby improving drug efficacy.

[0103] 3. Comparison of biological efficacy

[0104] In order to clarify the difference in control effect between 10% bromofenac·avermectin soluble concentrate and 10% bromofenac·avermectin suspension and microemulsion against rice stem borer, a field plot efficacy test was carried out.

[0105] The experimental method is as follows:

[0106] This experiment was conducted in accordance with GB / T 17980.1-2000 Pesticide Field Efficacy Test Guidelines (I) Pesticides for Control of Rice Lepidoptera Boring Pests. The experimental agents, control agents, and blank control were randomly arranged in plots with a plot area of ​​50 m2. 2 3WBD-20 backpack electric sprayer is used for uniform spraying. Each agent is treated at 667m 2 30 kg of water was evenly sprayed on each plot. No other pesticides were used during the test, and each treatment was repeated 4 times.

[0107] Survey and statistical methods: Parallel jump sampling, survey 50 rice clumps in each plot, count the dead heart rate or white ear number, and survey the dead heart rate and mortality rate on the 5th, 14th and 27th day after spraying. The dead heart (white ear) rate and control effect are calculated according to the following formulas:

[0108] Dead heart (white ear) rate (%) = {(number of dead heart and white ears surveyed) / total number of ears surveyed} × 100;

[0109] Control effect (%) = {(blank control withered heart (white ear) rate after drug application - drug treatment area withered heart (white ear) rate after drug application) / blank control withered heart (white ear) rate after drug application} × 100

[0110] Safety investigation and effects on other organisms: On the first day and several days after each spraying, observe the effects of each treatment on rice growth and other organisms.

[0111] The preparation method of the 10% bromofenac·avermectin suspension used is as follows:

[0112] In terms of mass percentage, 8% of bromofenac, 2% of avermectin, 3% of dispersant Morwet D-425 (alkyl naphthalene sulfonate, Nouryon), 2% of wetting agent YUS-EP60P (sodium sulfonyl succinate, TAKEMOTO), 5% of 1,2-propylene glycol (antifreeze, Shandong Guohua Chemical Co., Ltd.), 0.1% of xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% of kason (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% of SAG 1522 (organic silicon defoamer, Maitu High-tech Materials Group), 0.5% of BHT (stabilizer, Jiangsu Maida New Materials Co., Ltd.), and 100% of deionized water (self-made) were added. The above raw materials were mixed, sand-milled to a particle size of less than 5 μm, and filtered to obtain a 10% bromofenac·avermectin suspension.

[0113] The preparation method of 10% bromofenac·avermectin microemulsion is as follows:

[0114] In terms of mass percentage, weigh 8% of brofenac, 2% of avermectin, 20% of N,N-dimethylformamide (solvent, Changzhou Jufeng Chemical Co., Ltd.), 17% of cyclohexanone (solvent, Hunan Dongwei Chemical New Materials Co., Ltd.), 5% of methanol (solvent, Qilu Petrochemical Company), 20% of 602# (emulsifier, Nanjing Taihua Chemical Co., Ltd.), 0.5% of BHT (stabilizer, Jiangsu Maida New Materials Co., Ltd.), and make up to 100% with deionized water (self-made). Dissolve brofenac, avermectin and stabilizer in organic solvent, add emulsifier and stir evenly, and finally add water and stir evenly to obtain 10% brofenac·avermectin microemulsion.

[0115] Agent 1: 10% bromofenac·avermectin soluble solution diluted 1500 times with water;

[0116] Agent 2: 10% bromofenac·avermectin soluble solution diluted 2000 times with water;

[0117] Agent 3: 10% bromofenac·avermectin suspension diluted 1500 times with water;

[0118] Agent 4: 10% bromofenac·avermectin microemulsion diluted 1500 times with water;

[0119] Table 4 Efficacy test data of bromofenac·avermectin mixture

[0120]

[0121] As shown in Table 4, at the same dilution multiple, the control effect of bromofenac·avermectin soluble concentrate on rice stem borer is significantly higher than other formulations with the same content, and has obvious advantages in reducing dosage and increasing efficiency. No phytotoxicity was found during the application period, and it is safe for rice growth.

[0122] Example 3: 6% bromofenac + 4% highly effective cyhalothrin soluble solution

[0123] 1. The content of each component is as follows:

[0124]

[0125] 2. The preparation process according to the above formula is as follows:

[0126] (1) Prepare various raw materials according to the weight ratio of the formula;

[0127] (2) Add the measured N,N-diethylformamide, tetrahydrofurfuryl alcohol and N,N-dimethyloctanamide into the kettle, then add bromofenac and high-efficiency chlorfenapyr, and stir well for about 10 minutes until the mixture is transparent and uniform;

[0128] (3) Add the phosphate emulsifier polyethylene glycol 400 monooleate phosphate to the solution of (2) above and stir for 10 minutes until the solution becomes transparent and uniform;

[0129] (4) Add the remaining amount of water to the solution in (3) above, stir for 5 minutes until transparent and uniform, let stand, and filter to obtain the product.

[0130] The quality and technical indicators of the 10% bromofenac·lambda-cyhalothrin soluble solution prepared in this example are shown in Table 5.

[0131] Table 5 Quality and technical indicators of 10% bromofenac·lambda-cyhalothrin soluble solution

[0132]

[0133] After the sample of this embodiment was diluted 20 times with standard hard water, it showed a true solution state, and its appearance was similar to that of the attached Figure 1 Similar to that shown in 4 on the left, it is easier to wet, spread and penetrate and absorb on the target surface, thereby improving drug efficacy.

[0134] 3. Comparison of biological efficacy

[0135] In order to clarify the difference in control effect between 10% brofenac·highly effective chlorfenac cypermethrin soluble concentrate and 10% brofenac·highly effective chlorfenac cypermethrin suspension and microemulsion against Spodoptera exigua, a field plot efficacy test was conducted.

[0136] The experimental method is as follows:

[0137] This experiment was conducted in accordance with GB / T 23392.4-2009 Technical Specifications for Cruciferous Vegetable Pests and Diseases Monitoring and Forecasting Part 4: Beet Armyworm. The experimental pesticide, control pesticide and blank control were randomly arranged in plots with a plot area of ​​50 m 2 3WBD-20 backpack electric sprayer is used for uniform spraying. Each agent is treated at 667m 2 30 kg of water was evenly sprayed on each plot. No other pesticides were used during the test, and each treatment was repeated 4 times.

[0138] Survey and statistical methods: Select 5 large areas, survey 2 fields in each area, and conduct the survey during the peak egg period. Use the 5-point sampling method before and 1d, 3d, and 7d after application of pesticides, with 2 plants at each point, and observe the number of live larvae on the leaves of the whole plant. Use the DPS data processing system for data statistics and analysis, and use the Duncan new multiple range method for variance analysis. The reduction rate and control effect of beet armyworm on lettuce are calculated according to the following formulas:

[0139] Insect population reduction rate (%) = {(number of insects before application - number of insects after application) / number of insects before application} × 100;

[0140] Control effect (%) = {(pest reduction rate in the pesticide treatment area - pest reduction rate in the blank control area) / (100 - pest reduction rate in the blank control area)} × 100

[0141] Safety investigation and effects on other organisms: On the first day and several days after each spraying, observe the effects of each treatment on the growth of lettuce and other organisms.

[0142] The preparation method of the 10% bromofenac·high-efficiency cyhalothrin suspension used is as follows:

[0143] In terms of mass percentage, 6% of bromofenac, 4% of high-efficiency cyhalothrin, 3% of dispersant ATLOX4913 (polyacrylate, CRODA), 2% of wetting agent Genapol X 080 (isomeric alcohol polyoxyethylene ether, Clariant), 5% of 1,2-propylene glycol (antifreeze, Shandong Guohua Chemical Co., Ltd.), 0.1% of xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% of kason (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% of SAG 1522 (organic silicon defoamer, Maitu High-tech Materials Group), and deionized water (self-made) are added to 100%. The above raw materials are mixed, sand-milled with a sand mill to a particle size of less than 5 μm, and filtered to obtain a 10% bromofenac·high-efficiency cyhalothrin suspension.

[0144] The preparation method of 10% bromofenac·high-efficiency cyhalothrin microemulsion is as follows:

[0145] In terms of mass percentage, weigh 6% of brofenac, 4% of high-efficiency cyhalothrin, 15% of N,N-dimethylformamide (solvent, Changzhou Jufeng Chemical Co., Ltd.), 17% of cyclohexanone (solvent, Hunan Dongwei Chemical New Materials Co., Ltd.), 5% of methanol (solvent, Qilu Petrochemical Company), 20% of 602# (emulsifier, Nanjing Taihua Chemical Co., Ltd.), and make up to 100% with deionized water (self-made). Dissolve brofenac and high-efficiency cyhalothrin in an organic solvent, add the emulsifier and stir evenly, and finally add water and stir evenly to obtain a 10% brofenac·high-efficiency cyhalothrin microemulsion.

[0146] Agent 1: 10% bromofenac·highly effective chlorfenapyr soluble solution diluted 1500 times with water;

[0147] Agent 2: 10% bromofenac·highly effective chlorfenapyr soluble solution diluted 2000 times with water;

[0148] Agent 3: 10% bromofenac·high-efficiency chlorfenapyr suspension diluted 1500 times with water;

[0149] Agent 4: 10% bromofenac·highly effective chlorfenapyr microemulsion diluted 1500 times with water;

[0150] Table 6 Efficacy test data of bromofenac·high-efficiency cyhalothrin mixture

[0151]

[0152] As shown in Table 6, at the same dilution multiple, the control effect of brofenac·high-efficiency cyhalothrin soluble solution on lettuce beet armyworm was significantly higher than that of other formulations with the same content, and it has obvious advantages in reducing dosage and increasing efficiency. No phytotoxicity was found during the application period, and it was safe for lettuce growth.

[0153] Example 4: 5% bromofenac + 5% thiamethoxam soluble solution

[0154] 1. The content of each component is as follows:

[0155]

[0156] 2. The preparation process according to the above formula is as follows:

[0157] (1) Prepare various raw materials according to the weight ratio of the formula;

[0158] (2) Add the measured N,N-diethylformamide, diacetone alcohol and N,N-dimethyloctanamide into the kettle, then add bromofenac and thiamethoxam, and stir well for about 10 minutes until the mixture is transparent and uniform;

[0159] (3) Add the phosphate emulsifier O-5P to the solution of (2) above and stir for 10 minutes until the solution becomes transparent and uniform;

[0160] (4) Add the remaining amount of water to the solution in (3) above, stir for 5 minutes until transparent and uniform, let stand, and filter to obtain the product.

[0161] The quality and technical indicators of the 10% bromofenac·thiamethoxam soluble solution prepared in this example are shown in Table 7.

[0162] Table 7 Quality and technical indicators of 10% bromofenac·thiamethoxam soluble solution

[0163]

[0164] After the sample of this embodiment was diluted 20 times with standard hard water, it showed a true solution state, and its appearance was similar to that of the attached Figure 1 Similar to that shown in 4 on the left, it is easier to wet, spread and penetrate and absorb on the target surface, thereby improving drug efficacy.

[0165] 3. Comparison of biological efficacy

[0166] In order to clarify the difference in the control effect of 10% brofenoxamide·thiamethoxam soluble concentrate and 10% brofenoxamide·thiamethoxam suspension and microemulsion on pepper western flower thrips, a field plot efficacy test was carried out.

[0167] The experimental method is as follows:

[0168] This test was conducted in accordance with the NY / T 1464.6-2007 Guidelines for Field Efficacy Tests of Pesticides Part 6: Pesticides for Control of Vegetable Thrips. The experimental agents, control agents, and blank controls were randomly arranged in plots with a plot area of ​​40 m2. 2 3WBD-20 backpack electric sprayer is used for uniform spraying. Each agent is treated at 667m 2 30 kg of water was evenly sprayed on each plot. No other pesticides were used during the test, and each treatment was repeated 4 times.

[0169] Survey and statistical methods: 30 leaves were fixedly selected from the middle and upper parts of peppers in each plot to investigate the number of live nymphs. The base number of insects was investigated before application (the number of live nymphs before application), and the number of residual insects was investigated on the 1st, 3rd, 7th and 10th day after application (the number of live nymphs after application). The control effect was calculated according to the following formula, and the biostatistical method (DMRT method) was used for statistical analysis.

[0170] Control effect (%) = {1-(number of live nymphs in the blank control area before application × number of live nymphs in the treatment area after application) / number of live nymphs in the blank control area after application × number of live nymphs in the treatment area before application)} × 100

[0171] Safety investigation and effects on other organisms: On the first day and several days after each spraying, observe the effects of each treatment on pepper growth and other organisms.

[0172] The preparation method of the 10% bromofenac·thiamethoxam suspension used is as follows:

[0173] In terms of mass percentage, 5% of bromofenac, 5% of thiamethoxam, 3% of dispersant SuparexKpowder (naphthaldehyde condensate sulfonate dispersant, Argo Chemicals, Switzerland), 2% of wetting agent TERGITOL W-600 (isomeric alcohol polyoxyethylene ether, DOW), 5% of 1,2-propylene glycol (antifreeze agent, Shandong Guohua Chemical Co., Ltd.), 0.1% of xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% of kason (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% of SAG 1522 (organic silicon defoamer, Maitu High-tech Materials Group), and deionized water (self-made) are added to 100%. The above raw materials are mixed, sand-milled to a particle size of less than 5 μm, and filtered to obtain a 10% bromofenac·thiamethoxam suspension.

[0174] The preparation method of 10% bromofenac·thiamethoxam microemulsion is as follows:

[0175] In terms of mass percentage, weigh 5% bromofenac, 5% thiamethoxam, 15% N-methylpyrrolidone (solvent, Xinmaiqi Material Co., Ltd.), 15% cyclohexanone (solvent, Hunan Dongwei Chemical New Materials Co., Ltd.), 5% methanol (solvent, Qilu Petrochemical Company), 20% 602# (emulsifier, Nanjing Taihua Chemical Co., Ltd.), and make up to 100% with deionized water (self-made). Dissolve bromofenac and thiamethoxam in an organic solvent, add the emulsifier and stir evenly, and finally add water and stir evenly to obtain a 10% bromofenac·thiamethoxam microemulsion.

[0176] Agent 1: 10% bromofenac·thiamethoxam soluble solution diluted 1000 times with water;

[0177] Agent 2: 10% bromofenac·thiamethoxam soluble solution diluted 1500 times with water;

[0178] Agent 3: 10% bromofenac·thiamethoxam suspension diluted 1000 times with water;

[0179] Agent 4: 10% bromofenac·thiamethoxam microemulsion diluted 1000 times with water;

[0180] Table 8 Efficacy test data of bromofenac·thiamethoxam mixture

[0181]

[0182] As shown in Table 8, at the same dilution multiple, the control effect of bromofenac·thiamethoxam solution on pepper western flower thrips was significantly higher than other formulations with the same content, and it has obvious advantages in reducing dosage and increasing efficiency. No phytotoxicity was found during the application period, and it is safe for pepper growth.

[0183] Example 5: 2% bromofenac + 8% acetamiprid soluble solution

[0184] 1. The content of each component is as follows:

[0185]

[0186] 2. The preparation process according to the above formula is as follows:

[0187] (1) Prepare various raw materials according to the weight ratio of the formula;

[0188] (2) Add the measured AGNIQUE AMD 3L, isohexanediol and N,N-dimethyldecylamide into the kettle, then add bromofenac and acetamiprid, and stir well for about 10 minutes until the mixture is transparent and uniform;

[0189] (3) Add the phosphate emulsifier E1310P to the solution of (2) above and stir for 10 min until the solution becomes transparent and uniform;

[0190] (3) Add the remaining amount of water to the solution in (3) above, stir for 5 minutes until transparent and uniform, let stand, and filter to obtain the product.

[0191] The quality and technical indicators of the 10% bromofenac·acetamiprid soluble solution prepared in this example are shown in Table 9.

[0192] Table 9 Quality and technical indicators of 10% bromofenac·acetamiprid soluble solution

[0193]

[0194] After the sample of this embodiment was diluted 20 times with standard hard water, it showed a true solution state, and its appearance was similar to that of the attached Figure 1 Similar to that shown in 4 on the left, it is easier to wet, spread and penetrate and absorb on the target surface, thereby improving drug efficacy.

[0195] 3. Comparison of biological efficacy

[0196] In order to clarify the difference in control effect between 10% brofenac·acetamiprid soluble concentrate and 10% brofenac·acetamiprid suspension and microemulsion against cabbage yellow flea beetle, a field plot efficacy test was carried out.

[0197] The experimental method is as follows:

[0198] This experiment was conducted in accordance with GB / T 17980.18-2000 Pesticide Field Efficacy Test Guidelines (I) Pesticide Control of Yellow Striped Flea Beetle on Cruciferous Vegetables. The experimental agent, control agent, and blank control were randomly arranged in plots with a plot area of ​​40 m 2 3WBD-20 backpack electric sprayer is used for uniform spraying. Each agent is treated at 667m 2 30 kg of water was evenly sprayed on each plot. No other pesticides were used during the test, and each treatment was repeated 4 times.

[0199] Survey and statistical methods:

[0200] Adult survey: At least 20 cabbages were randomly selected from each plot to investigate the number of live adults.

[0201] Larvae survey: During the last survey after application of pesticides, at least three points were fixed in each plot, and two plants were surveyed at each point. The roots of the plants and the surrounding soil were dug out and rinsed with clean water, and the number of live larvae in the soil was investigated.

[0202] Conduct a base survey before applying the pesticide. Conduct a second survey: 2 days after applying the pesticide. Conduct a third survey: 7 days after applying the pesticide.

[0203] Insect population reduction rate (%) = {(number of insects before application - number of insects after application) / number of insects before application} × 100;

[0204] Adult control effect (%) = {(insect population reduction rate in the pesticide treatment area - insect population reduction rate in the blank control area) / (100 - insect population reduction rate in the blank control area)} × 100;

[0205] Larva control effect (%) = {(number of larvae in the blank control area - number of larvae in the drug treatment area) / number of larvae in the blank control area} × 100

[0206] Safety investigation and effects on other organisms: On the first day and several days after each spraying, observe the effects of each treatment on cabbage growth and other organisms.

[0207] The preparation method of the 10% bromofenac·acetamiprid suspension used is as follows:

[0208] In terms of mass percentage, 2% of bromofenac, 8% of acetamiprid, 3% of dispersant Dispersogen LFS (alkylphenol polyoxyethylene phosphate, Solvay), 2% of wetting agent TERGITOL W-600 (isomeric alcohol polyoxyethylene ether, DOW), 5% of 1,2-propylene glycol (antifreeze, Shandong Guohua Chemical Co., Ltd.), 0.1% of xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% of kason (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% of SAG 1522 (organic silicon defoamer, Maitu High-tech Materials Group), and deionized water (self-made) are added to 100%. The above raw materials are mixed, sand-milled with a sand mill to a particle size of less than 5 μm, and filtered to obtain a 10% bromofenac·acetamiprid suspension.

[0209] The preparation method of 10% bromofenac·acetamiprid microemulsion is as follows:

[0210] In terms of mass percentage, weigh 2% of bromofenac, 8% of acetamiprid, 12% of N-methylpyrrolidone (solvent, Xinmaiqi Materials Co., Ltd.), 10% of cyclohexanone (solvent, Hunan Dongwei Chemical New Materials Co., Ltd.), 5% of methanol (solvent, Qilu Petrochemical Company), 20% of 602# (emulsifier, Nanjing Taihua Chemical Co., Ltd.), and make up to 100% with deionized water (self-made). Dissolve bromofenac and acetamiprid in an organic solvent, add the emulsifier and stir evenly, and finally add water and stir evenly to obtain a 10% bromofenac·acetamiprid microemulsion.

[0211] Agent 1: 10% bromofenac·acetamiprid soluble solution diluted 1500 times with water;

[0212] Agent 2: 10% bromofenac·acetamiprid soluble solution diluted 2000 times with water;

[0213] Agent 3: 10% bromofenac·acetamiprid suspension diluted 1500 times with water;

[0214] Agent 4: 10% bromofenac·acetamiprid microemulsion diluted 1500 times with water;

[0215] Table 10 Efficacy test data of bromofenac·acetamiprid mixture

[0216]

[0217] As shown in Table 10, at the same dilution multiple, the control effect of bromofenac·acetamiprid soluble agent on cabbage yellow flea beetle was significantly higher than that of other formulations with the same content, and it had obvious advantages in reducing dosage and increasing efficiency. No phytotoxicity was found during the application period, and it was safe for cabbage growth.

[0218] Example 6: 8% bromofenac + 8% lufenuron soluble solution

[0219] 1. The content of each component is as follows:

[0220]

[0221] 2. The preparation process according to the above formula is as follows:

[0222] (1) Prepare various raw materials according to the weight ratio of the formula;

[0223] (2) Add the measured N,N-diethylformamide, tetrahydrofurfuryl alcohol and N,N-dimethyloctanamide into the kettle, then add bromofenac and lufenuron, and stir well for about 10 minutes until the mixture becomes transparent and uniform;

[0224] (3) Add phosphate emulsifier 601P to the solution in (2) above and stir for 10 min until the solution becomes transparent and uniform;

[0225] (4) Add the remaining amount of water to the solution in (3) above, stir for 5 minutes until transparent and uniform, let stand, and filter to obtain the product.

[0226] The quality and technical indicators of the 16% bromofenac·acetamiprid soluble solution prepared in this example are shown in Table 11.

[0227] Table 11 Quality and technical specifications of 16% bromofenac·lufenuron soluble solution

[0228]

[0229] After the sample of this embodiment was diluted 20 times with standard hard water, it showed a true solution state, and its appearance was similar to that of the attached Figure 1 Similar to that shown in 4 on the left, it is easier to wet, spread and penetrate and absorb on the target surface, thereby improving drug efficacy.

[0230] 3. Comparison of biological efficacy

[0231] In order to clarify the difference in control effect between 16% brofenoxamide·lufenuron soluble concentrate and 16% brofenoxamide·lufenuron suspension and microemulsion against cabbage beet armyworm, a field plot efficacy test was carried out.

[0232] The experimental method is as follows:

[0233] This experiment was conducted in accordance with GB / T 23392.4-2009 Technical Specifications for Cruciferous Vegetable Pests and Diseases Monitoring and Forecasting Part 4: Beet Armyworm. The experimental pesticide, control pesticide and blank control were randomly arranged in plots with a plot area of ​​50 m 23WBD-20 backpack electric sprayer is used for uniform spraying. Each agent is treated at 667m 2 30 kg of water was evenly sprayed on each plot. No other pesticides were used during the test, and each treatment was repeated 4 times.

[0234] Survey and statistical methods: Select 5 large areas, survey 2 fields in each area, and conduct the survey during the peak egg period. Use the 5-point sampling method before and 1d, 3d, and 7d after application of pesticides, with 2 plants at each point, and observe the number of live larvae on the leaves of the whole plant. Use the DPS data processing system for data statistics and analysis, and use the Duncan new multiple range method for variance analysis. The reduction rate and control effect of cabbage beet armyworm were calculated according to the following formulas:

[0235] Insect population reduction rate (%) = {(number of insects before application - number of insects after application) / number of insects before application} × 100;

[0236] Control effect (%) = {(pest reduction rate in the pesticide treatment area - pest reduction rate in the blank control area) / (100 - pest reduction rate in the blank control area)} × 100

[0237] Safety investigation and effects on other organisms: On the first day and several days after each spraying, observe the effects of each treatment on cabbage growth and other organisms.

[0238] The preparation method of the 16% bromofenac·lufenuron suspension used is as follows:

[0239] In terms of mass percentage, 8% bromofenac, 8% lufenuron, 3% dispersant Supragil MNS / 90 (alkyl naphthalene formaldehyde condensate sulfonate, Solvay), 2% dispersogen LFS (alkylphenol polyoxyethylene phosphate, Solvay), 5% 1,2-propylene glycol (antifreeze, Shandong Guohua Chemical Co., Ltd.), 0.1% xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% kason (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% SAG1522 (organic silicon defoamer, Maitu High-tech Materials Group), and deionized water (self-made) are added to make up 100%. The above raw materials are mixed, sand-milled to a particle size of less than 5 μm, and filtered to obtain a 16% bromofenac·lufenuron suspension.

[0240] The preparation method of 16% bromofenac·lufenuron microemulsion is as follows:

[0241] In terms of mass percentage, weigh 8% bromofenac, 8% lufenuron, 25% N-methylpyrrolidone (solvent, Xinmaiqi Material Co., Ltd.), 15% cyclohexanone (solvent, Hunan Dongwei Chemical New Materials Co., Ltd.), 5% methanol (solvent, Qilu Petrochemical Company), 15% 602# (emulsifier, Nanjing Taihua Chemical Co., Ltd.), and make up to 100% with deionized water (self-made). Dissolve bromofenac and lufenuron in an organic solvent, add the emulsifier and stir evenly, and finally add water and stir evenly to obtain a 16% bromofenac·lufenuron microemulsion.

[0242] Agent 1: 16% bromofenac·lufenuron soluble solution diluted 3000 times with water;

[0243] Agent 2: 16% bromofenac·lufenuron soluble solution diluted 4500 times with water;

[0244] Agent 3: 16% bromofenac·lufenuron suspension diluted 3000 times with water;

[0245] Agent 4: 16% bromofenac·lufenuron microemulsion diluted 3000 times with water;

[0246] Table 12 Efficacy test data of bromofenac·lufenuron mixture

[0247]

[0248] As shown in Table 12, at the same dilution multiple, the control effect of bromofenac·lufenuron soluble agent on cabbage beet armyworm was significantly higher than that of other formulations with the same content, and it had obvious advantages in reducing dosage and increasing efficiency. No phytotoxicity was found during the application period, and it was safe for cabbage growth.

[0249] Example 7: 5% bromofenac + 5% tolfenpyrad soluble solution

[0250] 1. The content of each component is as follows:

[0251]

[0252] 2. The preparation process according to the above formula is as follows:

[0253] (1) Prepare various raw materials according to the weight ratio of the formula;

[0254] (2) Add the measured N,N-dimethyl lactamide, 3-methoxy-3-methyl-1-butanol and N,N-dimethyl octanamide into the kettle, then add bromofenac and tolfenpyrad, and stir well for about 10 minutes until the mixture is transparent and uniform;

[0255] (3) Add the phosphate emulsifier OEP-70 to the solution of (2) above and stir for 10 minutes until the solution becomes transparent and uniform;

[0256] (4) Add the remaining amount of water to the solution in (3) above, stir for 5 minutes until transparent and uniform, let stand, and filter to obtain the product.

[0257] The quality and technical indicators of the 10% bromofenac·tofenapyr soluble concentrate prepared in this example are shown in Table 13.

[0258] Table 13 Quality and technical indicators of 10% bromofenac·tofenac soluble concentrate

[0259]

[0260] After the sample of this embodiment was diluted 20 times with standard hard water, it showed a true solution state, and its appearance was similar to that of the attached Figure 1 Similar to that shown in 4 on the left, it is easier to wet, spread and penetrate and absorb on the target surface, thereby improving drug efficacy.

[0261] 3. Comparison of biological efficacy

[0262] In order to clarify the difference in control effect between 10% bromofenac·tofenapyr soluble concentrate and 10% bromofenac·tofenapyr suspension and microemulsion against rice leaf folder, a field plot efficacy test was conducted.

[0263] The experimental method is as follows:

[0264] This test was conducted in accordance with GB / T 17980.2-2000 Pesticide Field Efficacy Test Guidelines (I) Pesticide Control of Rice Leaf Folder. The experimental agent, control agent and blank control were randomly arranged in plots with a plot area of ​​50 m 2 3WBD-20 backpack electric sprayer is used for uniform spraying. Each agent is treated at 667m 2 30 kg of water was evenly sprayed on each plot. No other pesticides were used during the test, and each treatment was repeated 4 times.

[0265] Survey and statistical methods: Take samples from five points in each plot and check a total of 25 rice clumps, count the leaf curling rate, compare it with the leaf curling rate in the control area, calculate the relative control effect, and investigate the insect rate in the curled leaves. Count the total number of leaves on the plants before applying the pesticide, and investigate the number of curled leaves on the plants 1d, 3d, and 7d after applying the pesticide. The control effect of rice leaf roller is calculated according to the following formula:

[0266] Leaf curling rate (%) = (number of curled leaves surveyed) / total number of leaves surveyed) × 100;

[0267] Control effect (%) = {(blank control area leaf curling rate after drug application - drug treatment area leaf curling rate after drug application) / blank control area leaf curling rate after drug application} × 100

[0268] Safety investigation and effects on other organisms: On the first day and several days after each spraying, observe the effects of each treatment on rice growth and other organisms.

[0269] The preparation method of the 10% bromofenac·toluamide suspension concentrate used is as follows:

[0270] In terms of mass percentage, 5% bromofenac, 5% tolfenpyrad, 3% dispersant ATLOX 4913 (polyacrylate, CRODA), 2% dispersogen LFS (alkylphenol polyoxyethylene phosphate, Solvay), 5% 1,2-propylene glycol (antifreeze, Shandong Guohua Chemical Co., Ltd.), 0.1% xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% kason (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% SAG 1522 (organic silicon defoamer, Maitu High-tech Materials Group), and deionized water (self-made) are added to 100%. The above raw materials are mixed, sand-milled to a particle size of less than 5 μm, and filtered to obtain a 10% bromofenac·tolfenpyrad suspension.

[0271] The preparation method of 10% bromofenac·toluamide microemulsion is as follows:

[0272] Calculated by mass percentage, weigh 5% bromofenac, 5% tolfenpyrad, 20% N,N-dimethylformamide (solvent, Changzhou Jufeng Chemical Co., Ltd.), 15% cyclohexanone (solvent, Hunan Dongwei Chemical New Materials Co., Ltd.), 5% methanol (solvent, Qilu Petrochemical Company), 15% 602# (emulsifier, Nanjing Taihua Chemical Co., Ltd.), and make up to 100% with deionized water (self-made). Dissolve bromofenac and tolfenpyrad in an organic solvent, add the emulsifier and stir evenly, and finally add water and stir evenly to obtain a 10% bromofenac·tolfenpyrad microemulsion.

[0273] Agent 1: 10% bromofenac·tofenac soluble solution diluted 1500 times with water;

[0274] Agent 2: 10% bromofenac·tofenac soluble solution diluted 2000 times with water;

[0275] Agent 3: 10% bromofenac·tofenac suspension diluted 1500 times with water;

[0276] Agent 4: 10% bromofenac·tofenac microemulsion diluted 1500 times with water;

[0277] Table 14 Efficacy test data of bromofenac·tofenac mixture

[0278]

[0279] As shown in Table 14, at the same dilution multiple, the control effect of bromofenac·toluamide soluble agent on rice leaf roller is significantly higher than other formulations with the same content, and has obvious advantages in reducing dosage and increasing efficiency. No phytotoxicity was found during the application period, and it is safe for rice growth.

[0280] Example 8: 10% bromofenac + 10% chlorfenapyr soluble solution

[0281] 1. The content of each component is as follows:

[0282]

[0283] 2. The preparation process according to the above formula is as follows:

[0284] (1) Prepare various raw materials according to the weight ratio of the formula;

[0285] (2) Add the measured N,N-diethylformamide, diacetone alcohol and N,N-dimethyloctanamide into the kettle, then add bromofenac and chlorfenapyr, and stir well for about 10 minutes until the mixture is transparent and uniform;

[0286] (3) Add phosphate emulsifier 601P to the solution in (2) above and stir for 10 min until the solution becomes transparent and uniform;

[0287] (4) Add the remaining amount of water to the solution in (3) above, stir for 5 minutes until transparent and uniform, let stand, and filter to obtain the product.

[0288] The quality technical indicators of the 20% bromofenac·chlorfenapyr soluble solution prepared in this example are shown in Table 15.

[0289] Table 15 Quality and technical indicators of 20% bromofenac·chlorfenapyr soluble solution

[0290]

[0291] After the sample of this embodiment was diluted 20 times with standard hard water, it showed a true solution state, and its appearance was similar to that of the attached Figure 1 Similar to that shown in 4 on the left, it is easier to wet, spread and penetrate and absorb on the target surface, thereby improving drug efficacy.

[0292] 3. Comparison of biological efficacy

[0293] In order to clarify the difference in control effect between 20% brofenac·chlorfenapyr soluble concentrate and 20% brofenac·chlorfenapyr suspension and microemulsion against Spodoptera exigua, a field plot efficacy test was conducted.

[0294] The experimental method is as follows:

[0295] This experiment was conducted in accordance with GB / T 23392.4-2009 Technical Specifications for Cruciferous Vegetable Pests and Diseases Monitoring and Forecasting Part 4: Beet Armyworm. The experimental pesticide, control pesticide and blank control were randomly arranged in plots with a plot area of ​​50 m 2 3WBD-20 backpack electric sprayer is used for uniform spraying. Each agent is treated at 667m 2 30 kg of water was evenly sprayed on each plot. No other pesticides were used during the test, and each treatment was repeated 4 times.

[0296] Survey and statistical methods: Select 5 large areas, survey 2 fields in each area, and conduct the survey during the peak egg period. Use the 5-point sampling method before and 1d, 3d, and 7d after application of pesticides, with 2 plants at each point, and observe the number of live larvae on the leaves of the whole plant. Use the DPS data processing system for data statistics and analysis, and use the Duncan new multiple range method for variance analysis. The reduction rate and control effect of the cabbage beet armyworm population were calculated according to the following formulas:

[0297] Insect population reduction rate (%) = {(number of insects before application - number of insects after application) / number of insects before application} × 100;

[0298] Control effect (%) = {(pest reduction rate in the pesticide treatment area - pest reduction rate in the blank control area) / (100 - pest reduction rate in the blank control area)} × 100

[0299] Safety investigation and effects on other organisms: On the first day and several days after each spraying, observe the effects of each treatment on the growth of Chinese cabbage and other organisms.

[0300] The preparation method of the 20% bromofenac·chlorfenapyr suspension used is as follows:

[0301] In terms of mass percentage, 10% of bromofenac, 10% of chlorfenapyr, 4% of dispersant ATLOX 4913 (polyacrylate, CRODA), 3% of wetting agent TERGITOL W-600 (isomeric alcohol polyoxyethylene ether, DOW), 5% of 1,2-propylene glycol (antifreeze, Shandong Guohua Chemical Co., Ltd.), 0.1% of xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% of kason (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% of SAG 1522 (organic silicon defoamer, Maitu High-tech Materials Group), and deionized water (self-made) were added to make up 100%. The above raw materials were mixed, sand-milled to a particle size of less than 5 μm, and filtered to obtain a 20% bromofenac·toluamide suspension.

[0302] The preparation method of 20% bromofenac·chlorfenapyr microemulsion is as follows:

[0303] In terms of mass percentage, weigh 10% bromofenac, 10% chlorfenapyr, 30% N,N-dimethylformamide (solvent, Changzhou Jufeng Chemical Co., Ltd.), 10% cyclohexanone (solvent, Hunan Dongwei Chemical New Materials Co., Ltd.), 5% methanol (solvent, Qilu Petrochemical Company), 15% 602# (emulsifier, Nanjing Taihua Chemical Co., Ltd.), and make up to 100% with deionized water (self-made). Dissolve bromofenac and chlorfenapyr in an organic solvent, add the emulsifier and stir evenly, and finally add water and stir evenly to obtain a 20% bromofenac·chlorfenapyr microemulsion.

[0304] Agent 1: 20% bromofenac·chlorfenapyr soluble solution diluted 3000 times with water;

[0305] Agent 2: 20% bromofenac·chlorfenapyr soluble solution diluted 4500 times with water;

[0306] Agent 3: 20% bromofenac·chlorfenapyr suspension diluted 3000 times with water;

[0307] Agent 4: 20% bromofenac·chlorfenapyr microemulsion diluted 3000 times with water;

[0308] Table 16 Efficacy test data of bromofenac·chlorfenapyr mixture

[0309]

[0310] As shown in Table 16, at the same dilution multiple, the control effect of brofenac·chlorfenapyr soluble solution on cabbage beet armyworm was significantly higher than that of other formulations with the same content, and it has obvious advantages in reducing dosage and increasing efficiency. No phytotoxicity was found during the application period, and it was safe for the growth of cabbage.

[0311] In summary, the soluble agent containing bromofenac and the preparation method thereof provided by the present invention can achieve the following beneficial effects:

[0312] The invention is beneficial to protecting the agricultural ecological environment, the raw materials used are safe and environmentally friendly, and the pollution to the environment is reduced;

[0313] The preparation method provided by the present invention can obtain a formulation product that meets the nanometer scale, and can effectively reduce the amount of pesticide used, thereby achieving the purpose of reducing the amount and increasing the efficiency.

[0314] The raw materials used in the invention are all convenient and easily available, and have significant market competitiveness for industrial promotion and application.

Claims

1. A soluble agent containing brofenac, which is composed of the following components by mass percentage: brofenac 1% to 10%, active component B 1% to 10%, amide solvent 25% to 45%, alcohol solvent 5% to 15%, phosphate emulsifier 5% to 15%, stabilizer 0% to 1% and the balance of water.

2. The soluble solution according to claim 1, characterized in that: The active component B is selected from at least one of the following: emamectin benzoate, abamectin, high-efficiency chlorflucythrinate, thiamethoxam, acetamiprid, lufenuron, tolfenpyrad and cypermethrin.

3. The soluble solution according to claim 1 or 2, characterized in that: The amide solvent is selected from at least one of N,N-diethylformamide, N,N-dimethyllactamide, N,N-dimethyloctanamide and N,N-dimethyldecylamide.

4. The soluble solution according to claim 3, characterized in that: The amide solvent is selected from any one of the following: 1) N,N-diethylformamide and N,N-dimethyloctanamide; 2) N,N-dimethyl lactamide and N,N-dimethyl decylamide; 3) N,N-dimethyl lactamide and N,N-dimethyl octanamide.

5. The soluble solution according to claim 4, characterized in that: The amide solvent is selected from any one of the following: 1) N,N-diethylformamide and N,N-dimethyloctanamide in a mass ratio of 1:0.5 to 0.8; 2) N,N-dimethyl lactamide and N,N-dimethyl decylamide in a mass ratio of 1:0.125 to 0.25; 3) N,N-dimethyl lactamide and N,N-dimethyl octanamide in a mass ratio of 1:0.6-1.

6. The soluble solution according to any one of claims 1 to 5, characterized in that: The alcohol solvent is selected from at least one of tetrahydrofurfuryl alcohol, diacetone alcohol, 3-methoxy-3-methyl-1-butanol and isohexanediol.

7. The soluble solution according to any one of claims 1 to 6, characterized in that: The phosphate emulsifier is selected from at least one of tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, polyethylene glycol 400 monooleate phosphate, oleyl alcohol polyoxyethylene ether phosphate and alkoxylated phosphate.

8. The soluble solution according to any one of claims 1 to 7, characterized in that: The stabilizer is selected from at least one of octanoic acid, 2,6-di-tert-butyl-p-methylphenol and 2-hydroxy-4-n-octyloxybenzophenone.

9. A method for preparing a soluble solution according to any one of claims 1 to 8, comprising the steps of: (1) Mix an amide solvent, an alcohol solvent, bromofenac, an active ingredient B and a stabilizer, and stir until the mixture is transparent and uniform; (2) adding a phosphate emulsifier to the solution in (1) and stirring until the solution becomes transparent and uniform; (3) Add water to the solution in (2) and stir until the solution becomes transparent and uniform.

10. The preparation method according to claim 9, characterized in that: In step (1), the stirring time is 5 to 15 minutes; In steps (2) and (3), the stirring time is 5 to 10 minutes.

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