A pesticide composition containing bifenazate and its use

Abstract

A pesticide composition containing bifenthiophanate-methyl and its application are disclosed. The pesticide composition comprises active ingredient A and active ingredient B, wherein the mass ratio of active ingredient A to active ingredient B is 1:30 to 30:1. Active ingredient A is bifenthiophanate-methyl, and active ingredient B is either fludioxonil or ethirimol sulfonate. The pesticide composition of this invention improves the control efficacy against pathogens, reduces the amount of active ingredient required, lowers the risk of resistance, and extends the lifespan of the pesticide.

Description

[0001] This invention application is a divisional application of application number CN202210357686.4, filed on April 7, 2022, entitled "A pesticide composition containing bifenthiophanate-methyl and its application". Technical Field

[0002] This invention belongs to the field of pesticide fungicide technology, specifically relating to a pesticide composition containing bifenthiophanate-methyl and its application. Background Technology

[0003] Bixafen, internationally known as N-(3',4'-dichloro-5-fluoro[1,1'-biphenyl]-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, CAS Registry Number: 581809-46-3, is a pyrazole amide succinate dehydrogenase inhibitor developed by Bayer. Bixafen inhibits mitochondrial function by interfering with succinate dehydrogenase on complex II of the mitochondrial respiratory electron transport chain in pathogens, preventing energy production, inhibiting pathogen growth, and ultimately leading to pathogen death. Bixafen is a systemic fungicide with a broad fungicidal spectrum and is specifically designed for foliar spraying.

[0004] Ethirimate, internationally known as bupirimate, CAS Registry Number: 41483-43-6, is a new generation of systemic fungicide. Belonging to the class of adenine nucleoside deaminase inhibitors, it possesses both protective and curative effects. It is rapidly absorbed by roots, stems, and leaves, and translocates throughout the plant, providing both protective and curative benefits. It is highly effective against powdery mildew in crops and is used for the control of powdery mildew in fruits, vegetables, flowers, ornamental plants, and field crops. Ethirimate belongs to the acetylene family of compounds and is an upgraded alternative to acetylene. This agent is characterized by high efficiency, low toxicity, and good environmental compatibility.

[0005] Fludioxonil, internationally known as fludioxonil, CAS Registry Number: 131341-86-1, chemical name: 4-(2,2-difluoro-1,3-benzodioxo-4-yl)pyrrolo-3-onitrile. Fludioxonil is a fungicide developed and manufactured by Novartis. Its mechanism of action is to inhibit the protein-activating enzyme PK-III (kinase PK-III), which plays a signaling role in osmotic sensing transport, leading to an increase in the concentration of non-phosphorylated regulatory proteins. This, in turn, disrupts the secretion of osmotically sensitive cell-mitotic activating proteases, ultimately resulting in pathogen death. Due to its unique mechanism of action, it exhibits no cross-resistance with existing fungicides and is a promising pyrrole fungicide. It is used for seed treatment to prevent seed-borne pathogens and cross-resistance with other fungicides, and is classified as a contact fungicide.

[0006] Pathogens readily develop resistance to single-target fungicides, while drug combination can delay resistance development. To improve the efficacy against pathogens, two active ingredients with different mechanisms of action are combined to target multiple sites on the pathogenic microorganisms, achieving a disease prevention effect. This reduces the amount of active ingredient required, lowers the risk of resistance, and extends the lifespan of the drug. Summary of the Invention

[0007] Based on the above, the purpose of this invention is to provide a pesticide composition containing bifenthiophanate-methyl, which is effective against a variety of target pathogens. This composition can significantly enhance the efficacy, reduce the amount of active ingredient used, reduce the risk of resistance, and extend the service life of the pesticide, especially showing significant effects against powdery mildew, gray mold, and white mold.

[0008] To achieve the above objectives, the present invention adopts the following technical solution: a pesticide composition containing bifenpyraclostrobin and its application, comprising active ingredient A and active ingredient B, wherein the mass ratio of active ingredient A to active ingredient B is 1:30 to 30:1;

[0009] Furthermore, the active ingredient A is bifenthiophanate-methyl, and the active ingredient B is either fludioxonil or ethirimol sulfonate.

[0010] Furthermore, the active ingredient B is ethirimol sulfonate, and the mass ratio of active ingredient A to active ingredient B is 1:10 to 15:1;

[0011] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:10 to 10:1;

[0012] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:10, 1:5, 1:1, 5:1, or 10:1;

[0013] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:5 to 10:1;

[0014] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:5, 1:1, 5:1, or 10:1;

[0015] Furthermore, the active ingredient B is fludioxonil, and the mass ratio of active ingredient A to active ingredient B is 1:10 to 30:1;

[0016] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:3 to 30:1;

[0017] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:3, 1:1, 3:1, 5:1, 6:1, 9:1, 10:1, 13:1, 16:1, 20:1, or 30:1.

[0018] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:1 to 20:1;

[0019] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:1, 3:1, 5:1, 6:1, 9:1, 10:1, 13:1, 16:1, or 20:1.

[0020] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:1 to 13:1;

[0021] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:1, 3:1, 5:1, 6:1, 9:1, 10:1, or 13:1;

[0022] Furthermore, based on the total weight of the pesticide composition being 100 wt%, the sum of the contents of active ingredient A and active ingredient B in the pesticide composition is 0.5% to 80%;

[0023] Furthermore, based on a total weight of 100 wt% of the pesticide composition, the sum of the contents of active ingredient A and active ingredient B in the pesticide composition is 1% to 60%.

[0024] Furthermore, the pesticide composition further includes auxiliary components, wherein the auxiliary agents are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, stabilizers, penetrants, and carriers;

[0025] Furthermore, the wetting agent is selected from one or more of the following: sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, pull-opening powder BX, wetting and penetrating agent F, soapberry powder, silkworm excrement, or soapberry powder;

[0026] Furthermore, the dispersant is selected from one or more of the following: polycarboxylate, lignin sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, calcium alkylbenzene sulfonate, sodium naphthalene sulfonate formaldehyde condensate, alkylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, fatty acid polyoxyethylene ether, or glycerol fatty acid ester polyoxyethylene ether.

[0027] Furthermore, the emulsifier is selected from one or a mixture of multiple of the following: calcium alkylbenzene sulfonate, OP series phosphate esters (nonylphenol polyoxyethylene ether phosphate ester), phenylphenol polyoxyethylene ether phosphate ester, styrene polyoxyethylene ether ammonium sulfate, alkyl biphenyl ether magnesium disulfonate, triethanolamine salt, benzyl dimethylphenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol polyoxyethylene polypropylene ether, ethylene oxide-propylene oxide block copolymer, OP series (nonylphenol polyoxyethylene ether), castor oil polyoxyethylene ether, alkyl aryl polyoxyethylene polyoxypropylene ether, sorbitan monostearate, dehydrated sorbitan fatty acid ester polyoxyethylene ether, or fatty alcohol polyoxyethylene ether.

[0028] Furthermore, the thickener is selected from one or more of xanthan gum, polyvinyl alcohol, bentonite, carboxymethyl cellulose, or magnesium aluminum silicate;

[0029] Furthermore, the disintegrant is selected from one or more of the following: bentonite, urea, ammonium sulfate, aluminum chloride, low-substituted hydroxypropyl cellulose, lactose, citric acid, succinic acid, or sodium bicarbonate;

[0030] Furthermore, the antifreeze is selected from one or more of ethylene glycol, propylene glycol, glycerol, or urea, or a mixture thereof;

[0031] Furthermore, the defoamer is selected from silicone oil, silicone compounds, and C. 10 ~C 20 Saturated fatty acid compounds or C8-C 10 A mixture of one or more fatty alcohol compounds;

[0032] Further, the solvent is selected from one or more of the following: N,N-dimethylformamide, cyclohexanone, butyl ether, xylene, dimethyl sulfoxide, methanol, ethylene glycol, ethanol, propanol, butanol, trimethylcyclohexanone, N-octylpyrrolidone, toluene, ethanolamine, triethanolamine, isopropylamine, N-methylpyrrolidone, diethylene glycol, ethylene glycol methyl ether, ethyl acetate, or acetonitrile.

[0033] Furthermore, the stabilizer is selected from one or more of the following: epoxidized soybean oil, epichlorohydrin, BHT, ethyl acetate, and triphenyl phosphate;

[0034] Furthermore, the penetrant is selected from one or more of penetrant JFC, penetrant T, azone, or organosilicon;

[0035] Furthermore, the carrier is one, two, or three of the solvent or filler, and the water is preferably deionized water;

[0036] Furthermore, the filler is selected from one or more of the following: kaolin, diatomaceous earth, bentonite, attapulgite, silica, starch, or light calcium carbonate.

[0037] All of the above substances are commercially available;

[0038] This pesticide composition can be prepared into any agriculturally permissible formulation as needed;

[0039] Furthermore, the formulation is a solid dosage form, a liquid dosage form, and / or a seed treatment dosage form;

[0040] Furthermore, the solid dosage form is a direct-use solid dosage form, a dispersible solid dosage form, or a soluble solid dosage form;

[0041] Furthermore, the directly usable solid dosage form is a powder, granule, ball, tablet, or strip;

[0042] The dispersible solid dosage form is a wettable powder, an oil-dispersible powder, an emulsion powder, a water-dispersible granule, an emulsion granule, or a water-dispersible tablet;

[0043] The soluble solid dosage form is a soluble powder, soluble tablet, or soluble granule;

[0044] Furthermore, the liquid formulation is a solution formulation, a dispersed liquid formulation, an emulsion formulation, a suspension formulation, or a multiphase formulation;

[0045] Furthermore, the solution formulation is a soluble agent, a soluble gel, an oil, or a film-spreading oil;

[0046] The dispersed liquid formulation is an emulsifiable concentrate, latex, dispersible liquid, or ointment;

[0047] The emulsion formulation is an aqueous emulsion, an oil emulsion, a microemulsion, or a lipid formulation;

[0048] The suspension formulation is a suspension agent, microcapsule suspension agent, oil suspension agent, or dispersible oil suspension agent;

[0049] The multiphase formulation is a suspension emulsion, a microcapsule suspension-suspension, a microcapsule suspension-water emulsion, or a microcapsule suspension-suspension emulsion;

[0050] Furthermore, the seed treatment formulation includes a solid seed treatment formulation or a liquid seed treatment formulation;

[0051] Furthermore, the seed treatment solid formulation is a seed treatment dry powder or a seed treatment dispersible powder;

[0052] The seed treatment liquid formulation is a seed treatment liquid, a seed treatment emulsion, or a seed treatment suspension;

[0053] Furthermore, the solid formulation is a water-dispersible granule, and the liquid formulation is a suspension concentrate, emulsifiable concentrate, and / or water emulsion.

[0054] The present invention also discloses the application of the pesticide composition containing bifenthiophanate-methyl as described above in the prevention and control of plant diseases.

[0055] Furthermore, the plants mentioned are economic crops and food crops;

[0056] Furthermore, the plant diseases are white mold, rust, gray mold, and powdery mildew; preferably, the plant diseases are white mold, gray mold, and powdery mildew.

[0057] The present invention has the following advantages over the prior art:

[0058] 1) The pesticide composition of the present invention uses two active ingredients with different mechanisms of action to combine and act on pathogenic microorganisms at multiple target sites to achieve the effect of disease prevention and control, thereby reducing the amount of active ingredient used;

[0059] 2) The pesticide composition of the present invention can prolong the duration of action of the agent, reduce the number of applications, reduce the risk of resistance, and extend the service life of the agent. Detailed Implementation

[0060] To make the technical solution, objectives and advantages of the present invention clearer, the present invention is described with reference to the following specific embodiments. However, the present invention can be implemented in various forms and should not be limited to the embodiments described herein.

[0061] Preparation Example

[0062] Preparation Example 1: 30% Bifenthrin·Ethylpyrimethanil sulfonate water emulsion (1:5)

[0063] By weight percentage: 5% bifenthrin, 25% ethirimol sulfonate, 2% fatty alcohol polyoxyethylene ether, 4% alkylphenol polyoxyethylene ether phosphate, 2% styrene-phenol polyoxyethylene ether, 22% cyclohexanone, 0.2% xanthan gum, 3% glycerol, 0.1% sodium benzoate, 0.1% silicone defoamer, deionized water to make up the balance.

[0064] Preparation method: According to the formulation ratio in the example, the surfactant, antifreeze and water are mixed to form an aqueous phase. Then, bifenthiophanate and ethirimol sulfonate are dissolved in solvent and added to the aqueous phase under stirring. After stirring evenly, thickener and preservative are added and shearing is continued for 10 minutes. Then, defoamer is added and stirred evenly to form an O / W type water emulsion.

[0065] Preparation Example 2: 10% Bifenthrin·Ethylpyrimethanil sulfonate water emulsion (1:1)

[0066] By weight percentage, 5% bifenthrin, 5% ethirimol sulfonate, 6% EO-PO block copolymer, 22% cyclohexanone, 0.15% xanthan gum, 4% propylene glycol, 0.5% sodium benzoate, 0.1% silicone defoamer, and deionized water to make up the balance.

[0067] Preparation method: Same as in Preparation Example 1

[0068] Preparation Example 3: 30% Bifenthrin·Ethylpyrimethanil Sulfonate Emulsifiable Concentrate (5:1)

[0069] By weight percentage, 25% bifenthrin, 5% ethirimol sulfonate, 14% styrene-phenol polyoxyethylene ether, 20% N-methylpyrrolidone, 3% calcium dodecylbenzenesulfonate, 20% propylene carbonate, and xylene to make up the balance.

[0070] Preparation method: According to the formulation ratio in the example, the metered bifenthrin, ethirimol sulfonate, solvent, and co-solvent are added to the mixing tank and stirred until dissolved. Then, the emulsifier is added, and the remaining solvent is used to make up the balance. The mixture is stirred evenly in the mixing tank and filtered to obtain the emulsifiable oil required by the present invention.

[0071] Preparation Example 4: 22% Bifenthrin·Ethylpyrimethanil Sulfonate Emulsifiable Concentrate (10:1)

[0072] By weight percentage, 20% bifenthrin, 2% ethirimol sulfonate, 10% alkylphenol polyoxyethylene ether, 20% N-methylpyrrolidone, 4% calcium dodecylbenzenesulfonate, 12% acetophenone, and trimethylbenzene to make up the balance.

[0073] Preparation method: Same as in preparation example 3.

[0074] Preparation Example 5: 20% Bifenthrin·Fluordioxonil Suspension (3:1)

[0075] By weight percentage, 15% bifenthrin, 5% fludioxonil, 2% isomeric alcohol polyoxyethylene ether, 4% alkylphenol polyoxyethylene ether phosphate, 1% sodium polycarboxylate, 0.25% xanthan gum, 5% glycerol, 0.1% sodium benzoate, 0.5% silicone oil, with deionized water to make up the balance.

[0076] Preparation method: According to the formulation ratio in the example, the metered bifenthiophanate, fludioxonil, surfactant and other functional additives are placed in a reaction vessel in sequence, water is added and mixed evenly, and then subjected to high-speed shearing, wet sand milling and finally homogenization filtration to obtain the suspension product.

[0077] Preparation Example 6: 21% Bifenthrin·Fluordioxonil Suspension (6:1)

[0078] By weight percentage, 18% bifenthrin, 3% fludioxonil, 2% isomeric alcohol polyoxyethylene ether, 2% alkyl aryl polyoxyethylene ether polyoxypropylene ether, 1% lignin sulfonate, 4% styrene-phenol polyoxyethylene ether phosphate, 1% magnesium aluminum silicate, 0.1% carboxyethyl cellulose, 1% sodium sorbate, 5% ethylene glycol, 0.5% silicone oil, and deionized water to make up the balance.

[0079] Preparation method: Same as in preparation example 5.

[0080] Preparation Example 7: 33% Bifenthrin·Fluordiamide Water Dispersible Granules (10:1)

[0081] By weight percentage, 30% bifenthrin, 3% fludioxonil, 12% lignin sulfonate, 5% sodium dodecylbenzene sulfonate, 2% naphthalene sulfonate formaldehyde condensate, 30% starch, and kaolin to make up the balance.

[0082] Preparation method: According to the formulation ratio in the example, add the active ingredients bifenthiophanate and fludioxonil to the carrier, and add surfactants and other functional additives to it. Mix, and after air jet milling, add 10-25% water. Then knead, granulate, dry and sieve to obtain water-dispersible granules; or spray water, granulate and dry the pulverized powder in a fluidized bed granulator, and then sieve to obtain the product.

[0083] Preparation Example 8: 21% Bifenthrin·Fluordiamide Water Dispersible Granules (20:1)

[0084] By weight percentage, 20% bifenthrin, 1% fludioxonil, 10% naphthalene sulfonate formaldehyde condensate, 3% sodium polycarboxylate, 3% bleaching powder BX, and kaolin to make up the balance.

[0085] Preparation method: Same as in preparation example 7.

[0086] Indoor activity test:

[0087] Example 1: Indoor combined effect test of bifenthrin and ethirimol sulfonate on cucumber powdery mildew.

[0088] Experimental basis: The experiment refers to NY / T 1156.11-2006 "Agricultural Industry Standard of the People's Republic of China: Indoor Bioassay Test Guidelines for Pesticides - Fungicides Part 11: Pot Test Method for Controlling Powdery Mildew of Cucumber"; NY / T 1156.6-2006 "Agricultural Industry Standard of the People's Republic of China: Indoor Bioassay Test Guidelines for Pesticides - Fungicides Part 6: Determination of Combined Effects of Mixtures".

[0089] Test reagents: 98% bifenthrin technical grade and 97% ethirimol sulfonate technical grade, provided by the R&D Center of Hailier Pharmaceutical Group.

[0090] Experimental target: Cucumber powdery mildew (Erysiphe cichoracearum);

[0091] Test material preparation: Select diseased cucumber variety (Xintai Mici) potted plants and wait for the seedlings to grow to the stage of 2-4 true leaves for use.

[0092] Preparation of spore suspension: Fresh spores from cucumber leaves infested with powdery mildew were washed with purified water containing a small amount of Tween 80 solution, filtered through double-layered gauze, and prepared to a spore concentration of 1*10⁻⁶. 5 One spore / mL suspension is available for use.

[0093] Preparation of reagents: Dissolve the two raw materials separately in acetone, dilute with 0.1% Tween 80 aqueous solution, and set them to the required series of mass concentrations.

[0094] Chemical treatment: Spray the prepared cucumber seedlings evenly with a spray until the leaves are completely wet. Allow the solution to air dry naturally before use. A blank control group without the chemical treatment was included in the experiment.

[0095] Inoculation and culture: Inoculation was carried out 24 hours after the treatment with the fungicide. The suspension of cucumber powdery mildew spores was sprayed onto the cucumber seedlings using an inoculator. After 12 hours of high humidity culture, the seedlings were then placed in a culture environment with a temperature of 20–24℃, humidity of 65–75%, and a light ratio of L:D = 12:12h. Each treatment consisted of 3 pots, with 4 replicates.

[0096] Data survey: When the diseased leaf rate in the blank control reaches over 80%, the disease incidence of each treatment is investigated by grade, with at least 30 leaves investigated for each treatment. The grading method is as follows:

[0097] Grade 0: No lesions;

[0098] Grade 1: The area of ​​lesions accounts for less than 5% of the total leaf area;

[0099] Grade 3: The lesion area accounts for 5% to 15% of the total leaf area;

[0100] Level 5: The lesion area accounts for 15% to 25% of the total leaf area;

[0101] Level 7: The lesion area accounts for 25% to 50% of the total leaf area;

[0102] Level 9: The lesion area accounts for 50% to 75% of the total leaf area;

[0103] Level 11: The lesion area accounts for more than 75% of the total leaf area.

[0104] Data statistics and analysis:

[0105] Based on the survey data, the disease index and prevention and control effects of each treatment were calculated.

[0106] The disease index is calculated using formula (1):

[0107] X=[∑(Ni×i) / (N×11)]×100........................(1)

[0108] In the formula:

[0109] X—Disease index;

[0110] N i —Number of diseased leaves at each level;

[0111] i — relative numerical value;

[0112] N—Total number of leaves surveyed.

[0113] The prevention and control effect is calculated according to formula (2):

[0114]

[0115] In the formula:

[0116] P – Prevention and control effect, expressed as a percentage (%);

[0117] CK – Blank control disease index;

[0118] PT – Disease index dictated by medication treatment.

[0119] Sun Yunpei's method: The synergistic effect of drug mixtures is evaluated based on the co-toxicity coefficient (CTC). A CTC ≥ 120 indicates a synergistic effect; a CTC ≤ 80 indicates an antagonistic effect; and 80 < CTC < 120 indicates an additive effect. The CTC value of the mixture is calculated according to formulas (3), (4), and (5):

[0120]

[0121] In the formula:

[0122] ATI – Actual Measured Toxicity Index of Mixtures;

[0123] S – EC of standard bactericides 50 The unit is milligrams per liter (mg / L);

[0124] M – EC of the mixture 50 The unit is milligrams per liter (mg / L).

[0125] TTI = TI A *P A +TI B *P B ······(4)

[0126] In the formula:

[0127] TTI – Theoretical Toxicity Index of Mixtures;

[0128] TI A —A. Toxicity index of drug A;

[0129] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0130] TI B —Toxicity index of drug B;

[0131] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0132]

[0133] In the formula:

[0134] CTC – Cotoxicity Coefficient;

[0135] ATI – Actual Measured Toxicity Index of Mixtures;

[0136] TTI – Theoretical Toxicity Index of Mixtures.

[0137] The experimental results were calculated using DPS data processing software, and the toxicity regression equations, R, and EC were obtained for single-dose and mixtures of different formulations of the test agent. 50 The 95% confidence limit was used to calculate the co-toxicity coefficient (CTC) of the two agents in different ratios, and the optimal ratio of the test agents was screened.

[0138] The test results are shown in the table below:

[0139] Table 1. Indoor activity test of bifenpyroximate mixed with ethirimol sulfonate against cucumber powdery mildew.

[0140]

[0141] Indoor activity tests showed (see Table 1) that bifenthrin and ethirimol sulfonate alone were effective against cucumber powdery mildew EC. 50The concentrations of bifenthrin and ethirimol sulfonate were 4.6892 mg / L and 5.6765 mg / L, respectively, indicating that cucumber powdery mildew is relatively sensitive to bifenthrin. The co-toxicity coefficients of bifenthrin and ethirimol sulfonate mixed at a ratio of 1:30 to 30:1 were all greater than 120, showing a synergistic effect in controlling cucumber powdery mildew. Among these, when the mass ratio of bifenthrin to ethirimol sulfonate was 1:10 to 10:1, the co-toxicity coefficient was greater than 140, demonstrating a significant synergistic effect. The highest co-toxicity coefficient against cucumber powdery mildew was 178.179 when the mass ratio of bifenthrin to ethirimol sulfonate was 1:1.

[0142] Example 2: Indoor combined effect test of bifenopyram and fludioxonil on cucumber gray mold.

[0143] Test basis: The test references NY / T 1156.2-2006 "Agricultural Industry Standard of the People's Republic of China: Indoor Bioassay Test Guidelines for Pesticides - Part 2: Test on Inhibition of Mycelial Growth of Pathogenic Fungi - Plate Method" and NY / T 1156.6-2006 "Agricultural Industry Standard of the People's Republic of China: Indoor Bioassay Test Guidelines for Pesticides - Part 6: Determination of Combined Effects of Mixtures".

[0144] Test reagents: 98% bifenthrin technical grade and 97% fludioxonil technical grade. Both reagents were provided by the R&D Center of Hailier Pharmaceutical Group.

[0145] Test pathogen: Botrytis cinerea, the causal agent of cucumber gray mold;

[0146] Reagent preparation: Dissolve the test drug in acetone first, then dilute with 0.1% Tween 80 aqueous solution. Prepare single-dose stock solutions separately, and set the required series of mass concentrations according to the purpose of mixing and the drug activity.

[0147] After melting the PDA medium in a microwave oven, cool it to about 50°C. Following the principle of starting from low concentration and gradually increasing the concentration, take 1 mL of the prepared test solution and 9 mL of PDA medium and add them to a 9 cm diameter petri dish. Mix well to prepare a drug-containing plate of the corresponding concentration.

[0148] Under aseptic conditions, the activated pathogenic fungi were punched into fungal cakes using a 5mm diameter punch. After the drug-containing culture medium solidified, the fungal cakes were placed in the center of the culture medium. Finally, the culture dish was sealed with sealing film and placed in an incubator at 27°C for incubation. A blank solution without the drug was set up as a blank control. Each treatment was repeated four times.

[0149] After 7 days of incubation, the diameter of the colonies was measured with calipers in millimeters (mm). The diameter of each colony was measured vertically once using the cross-sectional method, and the average value was taken.

[0150] Calculate the mycelial growth inhibition rate using the following formula, expressed as a percentage (%), and retain the result to two decimal places.

[0151] D=D1-D2·············(1)

[0152] D – Colony growth diameter;

[0153] D1—colony diameter;

[0154] D2 – Diameter of the mushroom cake.

[0155] I = (D0 - D) t ) / D0*100·············(2)

[0156] In the formula:

[0157] I – Mycelial growth inhibition rate;

[0158] D0—Correlation diameter of the blank control group;

[0159] D t — Diameter of colonies grown after chemical treatment.

[0160] Sun Yunpei's method: The synergistic effect of drug mixtures is evaluated based on the co-toxicity coefficient (CTC). A CTC ≥ 120 indicates a synergistic effect; a CTC ≤ 80 indicates an antagonistic effect; and 80 < CTC < 120 indicates an additive effect. The CTC value of the mixture is calculated according to formulas (3), (4), and (5):

[0161]

[0162] In the formula:

[0163] ATI – Actual Measured Toxicity Index of Mixtures;

[0164] S – EC of standard bactericides 50 The unit is milligrams per liter (mg / L);

[0165] M – EC of the mixture 50 The unit is milligrams per liter (mg / L).

[0166] TTI = TI A *P A +TI B *P B ······(4)

[0167] In the formula:

[0168] TTI – Theoretical Toxicity Index of Mixtures;

[0169] TI A —A. Toxicity index of drug A;

[0170] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0171] TI B —Toxicity index of drug B;

[0172] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0173]

[0174] In the formula:

[0175] CTC – Cotoxicity Coefficient;

[0176] ATI – Actual Measured Toxicity Index of Mixtures;

[0177] TTI – Theoretical Toxicity Index of Mixtures.

[0178] The experimental results were calculated using DPS data processing software, and the toxicity regression equations, R, and EC were obtained for single-dose and mixtures of different formulations of the test agent. 50 The 95% confidence limit was used to calculate the co-toxicity coefficient (CTC) of the two agents in different ratios, and the optimal ratio of the test agents was screened.

[0179] The test results are shown in the table below:

[0180] Table 2. Indoor activity test of bifenpyroxime and fludioxonil mixture against cucumber gray mold.

[0181]

[0182]

[0183] Indoor activity tests showed (see Table 2) that bifenthiophanate-methyl and fludioxonil alone were effective against EC50 in cucumber gray mold. 50 The concentrations were 4.9421 mg / L and 0.0403 mg / L, respectively, indicating that cucumber gray mold is relatively sensitive to fludioxonil. The co-toxicity coefficients of bifenpyroxime and fludioxonil mixed at a ratio of 1:10 to 30:1 were all greater than 120, showing a synergistic effect in the control of cucumber gray mold. Among them, when the mass ratio of bifenpyroxime and fludioxonil was 1:3 to 20:1, the co-toxicity coefficient after mixing was greater than 140, showing a significant synergistic effect.

[0184] Example 3: Indoor combined effect test of bifenopyram and fludioxonil on peanut white mold disease

[0185] Test basis: The test references NY / T 1156.2-2006 "Agricultural Industry Standard of the People's Republic of China: Test Guidelines for Indoor Bioassay of Pesticides - Fungicides Part 2: Test for Inhibition of Mycelial Growth of Pathogenic Fungi - Plate Method" and NY / T 1156.6-2006 "Agricultural Industry Standard of the People's Republic of China: Test Guidelines for Indoor Bioassay of Pesticides - Fungicides Part 6: Determination of Combined Effects of Mixtures".

[0186] Test reagents: 98% bifenthrin technical grade and 97% fludioxonil technical grade. Both reagents were provided by the R&D Center of Hailier Pharmaceutical Group.

[0187] Tested pathogen: Sclerotium rolfsii Sacc. (the causal agent of white mold in peanuts);

[0188] Reagent preparation: Dissolve the test drug in acetone first, then dilute with 0.1% Tween 80 aqueous solution. Prepare single-agent stock solutions separately, and set the required series of mass concentrations according to the purpose of mixing and the drug activity.

[0189] After melting the PDA culture medium in a microwave oven, cool it to about 50°C. Under aseptic conditions, following the principle of starting from low concentration and gradually increasing concentration, take 1 mL of the prepared test solution and 9 mL of PDA culture medium and add them to a 9 cm diameter petri dish. Mix well to prepare a plate containing the drug at the corresponding concentration.

[0190] Under aseptic conditions, the activated pathogenic fungi were punched into fungal cakes using a 5mm diameter punch. After the drug-containing culture medium solidified, the fungal cakes were placed in the center of the culture medium. Finally, the culture dish was sealed with sealing film and placed in an incubator at (26±0.5℃) for cultivation. A blank solution without the drug was set up as a blank control. Each treatment was repeated four times.

[0191] Data statistics and analysis:

[0192] The growth of pathogenic mycelia was investigated based on the growth of bacteria in the blank control culture dishes. Colony diameter was measured using calipers, in millimeters (mm). The diameter of each colony was measured vertically once using the cross-sectional method, and the average value was taken.

[0193] Calculate the mycelial growth inhibition rate using the following formula, expressed as a percentage (%), and retain the result to two decimal places.

[0194] D=D1-D2·············(1)

[0195] D – Colony growth diameter;

[0196] D1—colony diameter;

[0197] D2 – Diameter of the mushroom cake.

[0198] I = (D0 - D) t ) / D0*100·············(2)

[0199] In the formula:

[0200] I – Mycelial growth inhibition rate;

[0201] D0—Correlation diameter of the blank control group;

[0202] D t — Diameter of colonies grown after chemical treatment.

[0203] Sun Yunpei's method: The synergistic effect of drug mixtures is evaluated based on the co-toxicity coefficient (CTC). A CTC ≥ 120 indicates a synergistic effect; a CTC ≤ 80 indicates an antagonistic effect; and 80 < CTC < 120 indicates an additive effect. The CTC value of the mixture is calculated according to formulas (3), (4), and (5):

[0204]

[0205] In the formula:

[0206] ATI – Actual Measured Toxicity Index of Mixtures;

[0207] S – EC of standard bactericides 50 The unit is milligrams per liter (mg / L);

[0208] M – EC of the mixture 50 The unit is milligrams per liter (mg / L).

[0209] TTI = TI A *P A +TI B *P B ······(4)

[0210] In the formula:

[0211] TTI – Theoretical Toxicity Index of Mixtures;

[0212] TI A —A. Toxicity index of drug A;

[0213] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0214] TI B —Toxicity index of drug B;

[0215] P B—Percentage content of agent B in the mixture, expressed as percentage (%).

[0216]

[0217] In the formula:

[0218] CTC – Cotoxicity Coefficient;

[0219] ATI – Actual Measured Toxicity Index of Mixtures;

[0220] TTI – Theoretical Toxicity Index of Mixtures.

[0221] The experimental results were calculated using DPS data processing software, and the toxicity regression equations, R, and EC were obtained for single-dose and mixtures of different formulations of the test agent. 50 The 95% confidence limit was used to calculate the co-toxicity coefficient (CTC) of the two agents in different ratios, and the optimal ratio of the test agents was screened.

[0222] The test results are shown in the table below:

[0223] Table 3. Results of the indoor combined effect test of bifenpyroximate and fludioxonil on peanut white mold disease.

[0224] Test reagents Regression equation (Y = a + bx) R <![CDATA[EC 50 (mg / L) 95% confidence limit Cotoxicity coefficient (CTC) Bifenpyroximate (A) y = 3.8029 + 1.2214x 0.9993 9.5518(9.1536-9.9673) - Fludioxonil (B) y = 5.8543 + 1.2019x 0.9999 0.1946(0.1918-0.1975) - A:B (1:3) y = 5.8378 + 1.2203x 0.9989 0.2058(0.1951-0.2170) 125.227 A:B (1:1) y = 5.6309 + 1.1001x 0.9994 0.2670(0.2569-0.2775) 142.857 A:B (3:1) y = 5.3658 + 1.2362x 0.9996 0.5060(0.4900-0.5224) 144.973 A:B (6:1) y = 5.2122 + 1.2060x 0.9999 0.6669(0.6585-0.6754) 182.010 A:B (9:1) y = 4.9956 + 1.2846x 0.9997 1.0079(0.9831-1.0334) 163.158 A: B (13:1) y = 4.7800 + 1.2112x 0.9999 1.5194(1.4923-1.5470) 141.762 A:B (16:1) y = 4.6614 + 1.2226x 0.9994 1.8920(1.8179-1.9692) 131.867

[0225] Indoor activity tests (see Table 3) showed that the mixture of bifenthiophanate-methyl and fludioxonil exhibited good activity against peanut white mold, with fludioxonil alone showing higher toxicity against the disease (EC). 50 The concentration was 0.1946 mg / L. Peanut white mold is relatively sensitive to fludioxonil. The co-toxicity coefficient of bifenthiophanate-methyl and fludioxonil mixed at ratios of 1:3 to 16:1 was greater than 120, showing a synergistic effect in controlling peanut white mold. Among these, when the mass ratio of bifenthiophanate-methyl to fludioxonil was 1:1 to 13:1, the co-toxicity coefficient was greater than 140, indicating a significant synergistic effect. The highest co-toxicity coefficient (182.010) was observed at a mass ratio of 6:1, resulting in the best control effect.

[0226] Field efficacy trials

[0227] Example 4: Field efficacy trial of a mixture of bifenthrin and ethirimol sulfonate for controlling cucumber powdery mildew.

[0228] Experimental basis: The experiment was conducted in accordance with GB / T 17980.30-2000 "Guidelines for Field Efficacy Tests of Pesticides (I) Part 30: Control of Powdery Mildew by Fungicides in Cucumber".

[0229] Experiment location: Greenhouse in Nanpan Village, Shouguang City, Shandong Province; application time: mid-March 2021.

[0230] Experimental target: Cucumber powdery mildew.

[0231] Experimental crop and variety: Cucumber (Xintai Dense Thorn).

[0232] Test reagents: The test reagents and dosages are shown in the table below.

[0233] Experimental design: The treatment plots were randomly distributed in a block design, with a protection row around each plot. Each treatment was replicated four times, with each plot measuring 20 m. 2 The conventional spraying method was used, employing a Gongnong-16 manual sprayer to evenly spray the pesticide solution onto both sides of the leaves, ensuring that the leaves are wet but not dripping.

[0234] Application timing: The first spray was applied at the initial stage of cucumber powdery mildew infection, followed by a second spray 7 days later, for a total of two applications. No rainfall occurred within 24 hours of application, and there were no particularly severe weather conditions during the experiment. Routine field management was implemented.

[0235] Investigation methods: Before the first application of the pesticide, a baseline survey of the disease was conducted. The incidence of powdery mildew was investigated 7 days after the first application and 11 days after the second application. Four points were randomly selected from each plot for investigation, with two plants investigated at each point. All leaves of each plant were investigated, and each leaf was graded according to the percentage of leaf area covered by lesions. The disease index and control effect were calculated.

[0236] Statistics and Analysis:

[0237] The grading method (based on the number of blades) is as follows:

[0238] Grade 0: No lesions;

[0239] Grade 1: The lesion area accounts for less than 5% of the total leaf area;

[0240] Grade 3: Lesions cover 6-10% of the total leaf area;

[0241] Level 5: Lesions cover 11-20% of the total leaf area;

[0242] Level 7: Lesions cover 21-40% of the total leaf area;

[0243] Level 9: The lesion area accounts for more than 40% of the total leaf area.

[0244] The efficacy of the drug is calculated using the following formula:

[0245]

[0246]

[0247] The test results are shown in the table below:

[0248] Table 4. Field efficacy trial results of bifenpyroximate and ethirimol sulfonate mixture for controlling cucumber powdery mildew.

[0249]

[0250]

[0251] Field efficacy data (see Table 4) showed that the overall control efficacy of different treatments against cucumber powdery mildew ranged from 69.61% to 84.88% seven days after the first application. The control efficacy of spraying with 30% bifenthrin·ethirimol sulfonate emulsion (1:5), 10% bifenthrin·ethirimol sulfonate emulsion (1:1), 30% bifenthrin·ethirimol sulfonate emulsifiable concentrate (5:1), and 22% bifenthrin·ethirimol sulfonate emulsifiable concentrate (10:1) against cucumber powdery mildew differed, with efficacy rates of 80.24%, 84.88%, 83.16%, and 81.21%, respectively. These were superior to single agents (125 g / L bifenthrin emulsifiable concentrate and 25% ethirimol sulfonate microemulsion), with the 10% bifenthrin·ethirimol sulfonate emulsion (1:1) showing the best control efficacy.

[0252] Eleven days after the second application, the overall field efficacy of each treatment ranged from 70.36% to 85.98%. The control efficacy of 30% bifenthrin·ethirimol sulfonate emulsifiable concentrate (1:5), 10% bifenthrin·ethirimol sulfonate emulsifiable concentrate (1:1), 30% bifenthrin·ethirimol sulfonate emulsifiable concentrate (5:1), and 22% bifenthrin·ethirimol sulfonate emulsifiable concentrate (10:1) against cucumber powdery mildew was 81.65%, 85.98%, 83.88%, and 82.27%, respectively, all of which were superior to single-agent treatments.

[0253] Throughout the experiment, all agents were safe for the target crops and other organisms at the tested concentrations, with no phytotoxicity.

[0254] Example 5: Field efficacy trial of bifenpyroxime and fludioxonil mixture for controlling cucumber gray mold

[0255] Experimental basis: The experiment was conducted in accordance with GB / T 17980.28-2000 "Guidelines for Field Efficacy Tests of Pesticides (I)" Part 28: Control of Gray Mold in Vegetables by Fungicides.

[0256] Experiment location: Laixi City, Qingdao, Shandong Province; application time: mid-June 2020.

[0257] Experimental target: gray mold of cucumber.

[0258] Experimental crop and variety: Cucumber (Xintai Dense Thorn).

[0259] Test reagents: The test reagents and dosages are shown in the table below.

[0260] Experimental method: A randomized block design was used, with a plot size of 25m². 2 Repeated 4 times.

[0261] Application method and frequency: In the early stage of gray mold in cucumbers, apply the pesticide using the conventional spraying method, and apply it again 8 days after the first application, for a total of 2 applications;

[0262] Investigation methods: A baseline survey of disease incidence was conducted before the first application of pesticide, and a survey of control efficacy was conducted 11 days after the last application. Five sampling points were randomly selected from each plot, with two plants sampled at each point. All leaves and fruits of each plant were investigated, and the data were recorded according to the following methods for classification.

[0263] Classification method for leaf damage (by leaf):

[0264] Grade 0: No lesions;

[0265] Grade 1: Three lesions on a single leaf;

[0266] Grade 3: 4-6 lesions on a single leaf;

[0267] Grade 5: 7-10 lesions on a single leaf;

[0268] Grade 7: 11-20 lesions on a single leaf, some of which are densely clustered together;

[0269] Level 9: Dense lesions on a single leaf covering more than a quarter of the leaf area.

[0270] Fruit damage grading method (by fruit):

[0271] Grade 0: No lesions;

[0272] Level 1: Disease occurs in residual flowers;

[0273] Grade 3: Disease develops at the fruit's navel;

[0274] Level 5: The affected area accounts for less than 10% of the total length of the melon;

[0275] Level 7: The length of the diseased fruit accounts for less than 11% to 25% of the total length of the fruit;

[0276] Level 9: The length of the diseased fruit accounts for more than 26% of the total length of the fruit.

[0277] The efficacy of the drug is calculated using the following formula:

[0278]

[0279]

[0280] The test results are shown in the table below:

[0281] Table 5. Field efficacy (leaf) of bifenpyroxime and fludioxonil mixture in controlling cucumber gray mold.

[0282]

[0283] Table 6. Field efficacy (fruit) of bifenpyroxime and fludioxonil mixture in controlling cucumber gray mold.

[0284]

[0285]

[0286] Field efficacy results (see Table 5) showed that, 11 days after the last application, the overall control efficacy of different treatments against gray mold on cucumber leaves ranged from 68.75% to 85.14%. The control efficacy against gray mold on cucumber leaves after spraying with 20% bifenthrin·fludioxonil suspension (3:1), 21% bifenthrin·fludioxonil suspension (6:1), 33% bifenthrin·fludioxonil water-dispersible granules (10:1), and 21% bifenthrin·fludioxonil wettable powder (20:1) was 81.55%, 83.64%, 85.14%, and 82.36%, respectively, which were superior to single agents (20% bifenthrin suspension and 20% fludioxonil suspension). Among these, 33% bifenthrin·fludioxonil water-dispersible granules (10:1) showed the best control efficacy.

[0287] Field efficacy results (see Table 6) showed that, 11 days after the last application, the overall control efficacy of different treatments against gray mold on cucumber fruits ranged from 69.08% to 84.11%. The control efficacy against gray mold on cucumber leaves after spraying with 20% bifenthrin·fludioxonil suspension (3:1), 21% bifenthrin·fludioxonil suspension (6:1), 33% bifenthrin·fludioxonil water-dispersible granules (10:1), and 21% bifenthrin·fludioxonil wettable powder (20:1) was 80.46%, 81.82%, 84.11%, and 79.79%, respectively, which were superior to single agents (20% bifenthrin suspension and 20% fludioxonil suspension). Among these, 33% bifenthrin·fludioxonil water-dispersible granules (10:1) showed the best control efficacy.

[0288] Throughout the experiment, all agents were safe for the target crops and other organisms at the tested concentrations, with no phytotoxicity.

[0289] Example 6: Field efficacy trial of bifenthrin and fludioxonil mixture for controlling peanut white mold disease

[0290] Experimental site: Peanut experimental field in Laixi City, Qingdao City, Shandong Province. The experimental site has been continuously cropped with peanuts for many years, and the white mold disease of peanuts is relatively serious. The experimental site has sandy loam soil with medium fertility.

[0291] Experimental target: Peanut white mold pathogen (Sclerotium rolfsii Sacc.);

[0292] Experimental crop: Peanut (Luhua 14).

[0293] Test reagents: The test reagents and dosages are shown in the table below.

[0294] Experimental design: The treatment plots were randomly distributed in a block design, with a protection row around each plot. Each treatment was replicated four times, with each plot measuring 30 m. 2 The pesticide was applied by spraying water onto the roots.

[0295] Application timing: The first application of pesticide was carried out at the initial stage of peanut white mold disease, followed by a second application 15 days later, for a total of two applications. There were no particularly severe weather conditions during the trial period, and routine field management was implemented.

[0296] Investigation methods: Before the first application of the pesticide, a baseline survey of the disease was conducted. Fifteen days after the last application, the incidence of peanut white mold disease in each plot was investigated. Five random sampling points were taken from each plot, with 20 adjacent plants at each point, and 100 plants were investigated in each plot. The number of peanut plants with each level of disease was recorded.

[0297] The disease grading standards were based on the disease grading standards in the article "Greenhouse Inoculation Techniques and Resistance Identification of Peanut White Mold Disease" by Dong Weibao et al. The grading standards are as follows:

[0298] Level 0: The plant shows no symptoms;

[0299] Grade 1: Lesions only appear at the base of the stem;

[0300] Grade 2: The stem base shows constriction symptoms, and less than one-third of the whole plant shows systemic symptoms (wilt, death, wilting, etc.);

[0301] Grade 3: Less than two-thirds of the entire plant exhibit systemic symptoms;

[0302] Level 4: More than two-thirds of the entire plant exhibit systemic symptoms.

[0303] The efficacy of the drug is calculated using the following formula:

[0304]

[0305]

[0306] The test results are shown in the table below:

[0307] Table 7. Field efficacy trial results of bifenpyroxime and fludioxonil mixture for controlling peanut white mold.

[0308]

[0309] Field efficacy results (see Table 7) showed that the overall control efficacy of different treatments against peanut white mold ranged from 78.01% to 83.40% 15 days after the last application. With reduced dosage, the control efficacy of 21% bifenthrin·fludioxonil suspension (6:1) against peanut white mold was 83.40%, which was better than that of single agents (20% bifenthrin suspension and 20% fludioxonil suspension).

[0310] In summary, through indoor toxicity testing and field efficacy trials, it can be seen that the pesticide composition of bifenpyraclostrobin of the present invention has a good control effect on plant pathogens, is safe for target crops, and has significant control efficacy. It is superior to single agents in delaying the development of resistance and prolonging the duration of action, and can effectively reduce costs and pesticide residues.

[0311] Although the present invention has been described in detail above with general description and specific embodiments, some modifications or improvements can be made to it based on the present invention, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention are within the scope of protection claimed by the present invention.

Claims

1. An application of a pesticide composition containing bifenthiophanate-methyl for the control of plant diseases, characterized in that, The pesticide composition comprises active ingredient A and active ingredient B, wherein active ingredient A is bifenthiophanate-methyl and active ingredient B is fludioxonil; the plant disease is cucumber gray mold or peanut white mold; when the pesticide composition is used to control cucumber gray mold, the mass ratio of active ingredient A to active ingredient B is 1:10 to 30:1; when the pesticide composition is used to control peanut white mold, the mass ratio of active ingredient A to active ingredient B is 1:3 to 16:

1.

2. The application according to claim 1, characterized in that, When the pesticide composition is used to control gray mold in cucumbers, the mass ratio of active ingredient A to active ingredient B is 1:10, 1:5, 1:3, 1:1, 3:1, 5:1, 10:1, 20:1, or 30:

1.

3. The application according to claim 1, characterized in that, When the pesticide composition is used to control peanut white mold disease, the mass ratio of active ingredient A to active ingredient B is 1:3, 1:1, 6:1, 9:1, 13:1, or 16:

1.

4. The application according to claim 1, characterized in that, Based on a total weight of 100 wt% of the pesticide composition, the sum of the contents of active ingredient A and active ingredient B in the pesticide composition is 0.5% to 80%.

5. The application according to claim 4, characterized in that, Based on a total weight of 100 wt% of the pesticide composition, the sum of the contents of active ingredient A and active ingredient B in the pesticide composition is 1% to 60%.

6. The application according to claim 1, characterized in that, The pesticide composition further includes auxiliary components selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, stabilizers, penetrants, and carriers.

7. The application according to claim 1, characterized in that, The pesticide composition is prepared into any agriculturally permissible formulation.

8. The application according to claim 7, characterized in that, The dosage forms mentioned are solid dosage forms and liquid dosage forms.

9. The application according to claim 8, characterized in that, The solid formulation is a water-dispersible granule, and the liquid formulation is a suspension, emulsifiable concentrate, or water emulsion.

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