A bactericidal composition containing bronopol and its use

Abstract

The present invention belongs to the technical field of pesticides, and discloses a bactericidal composition containing bronopol and its use. The bactericidal composition comprises active ingredient A and active ingredient B. The active ingredient A is bronopol, and the active ingredient B is selected from any one of fluxapyroxad, isopyrazam or penflufen. The mass ratio of the active ingredient A to the active ingredient B is 1:35 to 35:1. The bactericidal composition of the present invention has high activity against diseases on various crops, has a significant synergistic effect, is superior to single agents in terms of quick-acting property and long-lasting property, reduces the usage amount of pesticides in agricultural production, reduces the pesticide residues in agricultural products, delays the generation of drug resistance of pathogenic bacteria, and is beneficial to the comprehensive management of agricultural diseases.

Description

[0001] This divisional application is a divisional application of the application with the application number CN202210548727.8, the application date of May 20, 2022, and the invention title of "A bactericidal composition containing bronopol and its uses". Technical Field

[0002] The present invention relates to the technical field of pesticidal bactericidal compositions and their applications, and particularly relates to a bactericidal composition containing bronopol and its uses. Background Art

[0003] Bronopol, chemical name: 2-bromo-2-nitro-1,3-propanediol, also known as bromonitropropane diol, bronopol, etc. Bronopol is a broad-spectrum bactericide of bromonitro alcohol type. Bronopol has good control effects on plant fungal and bacterial diseases, especially on bakanae disease of rice, and also has certain control effects on angular leaf spot of cotton and scab of wheat.

[0004] Pydiflumetofen, ISO common name: pydiflumetofen, chemical name: 3-(difluoromethyl)-N-methoxy-1-methyl-N-[(RS)-1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide, CAS registration number: 1228284-64-7. Pydiflumetofen is a pyridine amide bactericide developed by Syngenta that acts on succinate dehydrogenase. It mainly affects the respiratory chain electron conduction system of pathogenic bacteria. By acting on succinate dehydrogenase, the hub connecting oxidative phosphorylation and electron transfer in pathogenic bacteria, it causes disorders in the tricarboxylic acid cycle, hinders their energy metabolism, and then inhibits the growth of pathogenic bacteria, leading to their death, thereby achieving the purpose of controlling diseases. Pydiflumetofen has the characteristics of broad spectrum and high efficiency, and is applicable to many crops, such as corn, small grain cereals, soybeans, peanuts, rapeseed, quinoa, etc.

[0005] Isopyrazam, ISO common name: isopyrazam, CAS registration number: 881685-58-1. Isopyrazam is a succinate dehydrogenase inhibitor

[0006] (SDHI), with both preventive and therapeutic effects, mainly controls cereal foliar diseases, and can control powdery mildew and eyespot, etc. In addition to containing the common pyrazole ring in SDHI bactericides, isopyrazam also contains a unique benzobridge ring. These two ring structures enable isopyrazam to strongly bind to the binding site on the mitochondrial membrane SDHI enzyme and the wax layer on the leaf surface, making isopyrazam have higher activity, ensuring its high-efficiency disease control effect and long-lasting effect in the field. In addition, isopyrazam has a significant effect of maintaining crop health, which not only greatly improves the photosynthesis of crops, increases the yield, but also can significantly extend the harvest time of crops.

[0007] Penflufen, ISO common name: penflufen, chemical name: N-[2-(1,3-dimethylbutyl)phenyl]-5-(1,3-dimethyl-1H-pyrazol-4-yl)formamide, CAS registry number: 494793-67-8. Penflufen is a pyrazole carboxamide fungicide developed by Bayer. It has good activity against a variety of phytopathogenic fungi. This fungicide is a succinate dehydrogenase inhibitor, mainly acting on respiratory chain electron transfer complex II to block energy metabolism. Penflufen has both systemic, preventive and therapeutic effects and a long residual period. It is mainly used as a fungicidal seed treatment agent. After seed treatment, the agent penetrates into the germinating seeds and is conducted through the xylem of the young plants to the whole plant, thus protecting the growing seedlings.

[0008] Succinate dehydrogenase inhibitor (SDHI) fungicides act on the succinate dehydrogenase of the respiratory chain of pathogenic fungi, blocking electron transfer and interfering with fungal energy metabolism to play a fungicidal role. Due to their single site of action and broad fungicidal spectrum, SDHI fungicides have good control effects against a variety of phytopathogenic fungi. However, due to extensive and frequent use in the field, resistant strains have emerged, resulting in the generation of widespread resistance and a reduction in field efficacy. Due to the single site of action, FRAC classifies SDHI fungicides as medium to high resistance risk agents. With the extensive development and frequent use of such products, problems such as resistance development and efficacy reduction are inevitable. In order to delay the occurrence and development of resistance and improve the control effect, effective resistance management measures must be taken in agricultural production. Therefore, the inventors found through a large number of experimental studies that the compounding of bronopol with an SDHI fungicide (any one of fluxapyroxad, isopyrazam or penflufen) can improve the control effect, expand the control spectrum and delay the generation of pathogen resistance while.

[0009] Summary of the Invention In view of the above situation, the object of the present invention is to provide a bactericidal composition containing bronopol, which is effective against plant pathogenic bacteria, can significantly enhance the drug efficacy, is superior to the single agent in terms of quick-acting and long-lasting effects, reduces the amount of the agent used in agricultural production, slows down the development of pathogen resistance, reduces the drug residue in agricultural products, and is beneficial to the comprehensive management of agricultural diseases.

[0010] To achieve the above object, the present invention adopts the following technical solution: a bactericidal composition containing bronopol, the bactericidal composition contains active ingredient A and active ingredient B, the active ingredient A is bronopol, the active ingredient B is selected from any one of fluxapyroxad, isopyrazam or penflufen, and the mass ratio of the active ingredient A to the active ingredient B is 1:35 to 35:1;

[0011] ​

[0012] Furthermore, the active ingredient B is fluxapyroxad, and the mass ratio of the active ingredient A to the active ingredient B is 1:30 to 30:1;

[0013] More preferably, the mass ratio of the active ingredient A to the active ingredient B is 1:15 to 20:1;

[0014] Furthermore, the active ingredient B is isopyrazam, and the mass ratio of the active ingredient A to the active ingredient B is 1:30 to 30:1;

[0015] More preferably, the mass ratio of the active ingredient A to the active ingredient B is 1:20 to 30:1;

[0016] Furthermore, the active ingredient B is fluxametamide, and the mass ratio of the active ingredient A to the active ingredient B is 1:25 to 25:1;

[0017] More preferably, the mass ratio of the active ingredient A to the active ingredient B is 1:15 to 25:1.

[0018] Furthermore, based on 100 wt% of the total weight of the bactericidal composition, the total weight of the active ingredient A and the active ingredient B accounts for 1% to 80% of the total weight of the bactericidal composition;

[0019] Furthermore, the bactericidal composition further comprises other auxiliary ingredients in addition to the active ingredients, and the auxiliary ingredients are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreezing agents, defoaming agents, solvents, preservatives, stabilizers, warning colors, film-forming agents, synergists and carriers;

[0020] The wetting agent is selected from one or more of alkyl benzene sulfonates, alkyl naphthalene sulfonates, lignin sulfonates, sodium dodecyl sulfate, sodium dioctyl sulfosuccinate, α-olefin sulfonates, alkylphenol polyoxyethylene ethers, castor oil polyoxyethylene ethers, alkylphenol ethoxylates, fatty alcohol ethoxylates, sodium fatty alcohol polyoxyethylene ether sulfate, silkworm excrement, sophora powder, sapindus powder, SOPA, detergent, emulsifier 2000 series and wetting penetrant F; and / or

[0021] The dispersant is selected from one or more of lignin sulfonates, alkyl naphthalene sulfonate formaldehyde condensates, naphthalene sulfonates, triphenylvinylphenol ethoxylate phosphates, fatty alcohol ethoxylates, alkylphenol polyoxyethylene ethers, alkylphenol polyoxyethylene ether methyl ether condensate sulfates, fatty amine polyoxyethylene ethers, glycerol fatty acid ester polyoxyethylene ethers, polycarboxylates, polyacrylic acids, phosphates, EO-PO block copolymers and EO-PO graft copolymers; and / or

[0022] The emulsifier is selected from one or more of calcium dodecylbenzenesulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styrylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, and alkylphenol ether phosphate; and / or

[0023] The thickener is selected from one or more of xanthan gum, organic bentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose, and silica white; and / or

[0024] The disintegrant is selected from one or more of sodium sulfate, ammonium sulfate, aluminum chloride, sodium chloride, ammonium chloride, bentonite, glucose, sucrose, starch, cellulose, urea, sodium carbonate, sodium bicarbonate, citric acid, and tartaric acid; and / or

[0025] The antifreeze is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons, and inorganic salts; and / or

[0026] The defoamer is selected from one or more of C 10 -C 20 saturated fatty acid compounds, silicone oil, silicone compounds, C8-C 10 fatty alcohols; and / or

[0027] The solvent is selected from one or more of benzene, toluene, xylene, durene, methanol, ethanol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, cyclohexanone, alkylene carbonate, diesel oil, solvent naphtha, vegetable oil, vegetable oil derivatives, and water; and / or

[0028] The preservative is selected from one or more of propionic acid, sodium propionate, sorbic acid, sodium sorbate, potassium sorbate, benzoic acid, sodium benzoate, sodium p-hydroxybenzoate, methyl p-hydroxybenzoate, Kathon, and 1,2-benzisothiazolin-3-one; and / or

[0029] The stabilizer is selected from one or more of disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2,6-di-tert-butyl-p-cresol, triethanolamine oleate, epoxidized vegetable oil, kaolin, bentonite, attapulgite, silica white, talc powder, montmorillonite, and starch; and / or

[0030] The warning color is selected from any one or more of blue, green, red, and purple and their adjusted colors; and / or

[0031] The film-forming agent is selected from one or more of sodium carboxymethyl starch, cellulose derivatives (sodium carboxymethyl cellulose, sodium alginate, polyvinyl alcohol), and polyacrylic acid; and / or

[0032] The synergist is selected from synergistic phosphorus and synergistic ether; and / or

[0033] The carrier is selected from one or more of ammonium salts, ground natural minerals, ground artificial minerals, silicates, resins, waxes, solid fertilizers, water, organic solvents, mineral oils, vegetable oils, and vegetable oil derivatives;

[0034] Furthermore, the bactericidal composition can be prepared into any agriculturally acceptable preparation dosage form, and the preparation dosage form is a solid preparation, a liquid preparation, and / or a seed treatment preparation;

[0035] Furthermore, the solid preparation is a directly used solid preparation, a dispersible solid preparation, or a soluble solid preparation;

[0036] Even further, the directly used solid preparation is a powder, a granule, a pellet, a tablet, or a strip;

[0037] The dispersible solid preparation is a wettable powder, an oil-dispersible powder, an emulsion powder, a water-dispersible granule, an emulsion granule, or a water-dispersible tablet;

[0038] The soluble solid preparation is a soluble powder, a soluble tablet, or a soluble granule;

[0039] Furthermore, the liquid preparation is a solution preparation, a dispersion liquid preparation, an emulsion preparation, a suspension preparation, or a multiphase preparation;

[0040] Even further, the solution preparation is a soluble solution, a soluble sol, an oil agent, or a film-forming oil agent;

[0041] The dispersion liquid preparation is an emulsifiable concentrate, a latex, a dispersible liquid agent, or an ointment;

[0042] The emulsion preparation is an aqueous emulsion, an oil emulsion, a microemulsion, or a fat agent;

[0043] The suspension preparation is a suspending agent, a microcapsule suspension, an oil suspension, or a dispersible oil suspension;

[0044] The multiphase preparation is a suspension emulsion, a microcapsule suspension-suspending agent, a microcapsule suspension-aqueous emulsion, or a microcapsule suspension-suspension emulsion;

[0045] Furthermore, the seed treatment preparation includes a seed treatment solid preparation or a seed treatment liquid preparation;

[0046] Even further, the seed treatment solid preparation is a seed treatment dry powder or a seed treatment dispersible powder;

[0047] The seed treatment liquid preparation is a seed treatment liquid agent, a seed treatment emulsion, or a seed treatment suspending agent;

[0048] Further, the solid preparation is a water dispersible granule and / or a wettable powder, the liquid preparation is a suspension concentrate, and the seed treatment preparation is a seed treatment suspension concentrate.

[0049] The present invention also discloses the use of the bactericidal composition and / or its preparation as described above in preventing or controlling crop pathogenic bacteria.

[0050] Further, the crops are selected from food crops, cash crops, fruits and vegetables, and / or lawn and garden crops;

[0051] Further, the pathogenic bacteria are pathogenic bacteria of the genus Fusarium, and the pathogenic bacteria of the genus Fusarium include Fusarium oxysporum, Fusarium incarnatum, Fusarium proliferatum, Fusarium equiseti, Fusarium verticillicides, Fusarium graminearum, Fusarium moniliforme;

[0052] Furthermore, the pathogenic bacteria of the genus Fusarium are selected from Fusarium graminearum and Fusarium moniliforme.

[0053] The present invention also discloses a method for preventing and controlling crop pathogenic bacteria, and the bactericidal composition and / or its preparation are applied to plants, plant propagation materials and subsequently growing plant organs, cultivation media, materials or spaces by methods such as seed treatment, foliar application, stem application, soaking, drip irrigation, pouring, spraying, atomizing, dusting, spreading or smoking at an effective and substantially non-phytotoxic application rate.

[0054] Compared with the prior art, the advantages of the present invention are as follows:

[0055] 1) The reasonable compounding of bronopol with any one of fluxapyroxad, pyraclostrobin or fluxametamide has a significant synergistic effect and improves the control effect on pathogenic bacteria;

[0056] 2) The action mechanisms of bronopol and any one of fluxapyroxad, pyraclostrobin or fluxametamide are different from each other, which is conducive to delaying the development of pathogenic bacteria resistance;

[0057] 3) The usage amount of the medicament in agricultural production is reduced, the medicament residue in agricultural products is reduced, it is environmentally friendly, and it is conducive to the comprehensive management of agricultural diseases. Detailed implementation manners

[0058] To better understand the essence of the present invention, the content of the present invention will be further described below in conjunction with embodiments, but it should not be regarded as a limitation to the present invention. The content mentioned in the embodiments is not a limitation to the present invention. The selection of the material formula can be adjusted according to local conditions without substantial impact on the results.

[0059] Preparation Example of Preparation

[0060] Preparation Example 1: 30% Bronopol · Fluxapyroxad Seed Treatment Suspension Concentrate (1:1)

[0061] By weight percentage, 15% bronopol, 15% fluxapyroxad, 4% alkylphenol polyoxyethylene ether, 5% alkylphenol polyoxyethylene ether phosphate salt, 3% sodium lignosulfonate, 2% polyacrylic acid, 0.2% xanthan gum, 6% rose pigment, 5% ethylene glycol, 1% magnesium aluminum silicate, 0.5% silicone defoamer, 1% sodium benzoate, and deionized water to make up the balance.

[0062] Preparation method: According to the ratio, the active ingredient, auxiliary agent, and water are mixed and stirred evenly by high-shear shearing, and then sanded for 2.5 h by a sand mill to make the average particle size reach 1-5 microns. Finally, a thickener, preservative, and film-forming agent are added and sheared and stirred evenly to obtain the seed treatment suspension concentrate.

[0063] Preparation Example 2: 24% Bronopol · Fluxapyroxad Seed Treatment Suspension Concentrate (1:3)

[0064] By weight percentage, 6% bronopol, 18% fluxapyroxad, 4% triphenylvinylphenol polyoxyethylene ether polypropylene ether, 3% styrylphenol polyoxyethylene ether phosphate salt, 2% sodium polycarboxylate, 1% polyacrylic acid, 0.2% xanthan gum, 1% magnesium aluminum silicate, 5% glycerol, 5% rose pigment, 1% methyl p-hydroxybenzoate, 0.5% silicone defoamer, and deionized water to make up the balance.

[0065] Preparation method: The same as Preparation Example 1.

[0066] Preparation Example 3: 30% Bronopol · Fluxapyroxad Seed Treatment Suspension Concentrate (5:1)

[0067] By weight percentage, 25% bronopol, 5% fluxapyroxad, 4% fatty alcohol polyoxyethylene ether, 5% glycerol fatty acid ester polyoxyethylene ether phosphate, 2% sodium polycarboxylate, 0.2% xanthan gum, 5% rose pigment, 2% carboxymethyl starch sodium, 5% propylene glycol, 0.5% silicone defoamer, 2% sodium sorbate, and deionized water to make up the balance.

[0068] Preparation method: The same as Preparation Example 1.

[0069] Preparation Example 4: 28% Bronopol·Pydiflumetofen Seed Treatment Suspension Concentrate (3:1)

[0070] By weight percentage, 21% bronopol, 7% pydiflumetofen, 3% isomeric tridecanol polyoxyethylene ether, 3% alkylphenol polyoxyethylene ether phosphate, 2% sodium polycarboxylate, 1% polyacrylic acid, 0.2% xanthan gum, 4% rose pigment, 5% propylene glycol, 1% magnesium aluminum silicate, 3% sodium benzoate, 0.5% silicone defoamer, deionized water to make up the balance.

[0071] Preparation method: The same as Preparation Example 1.

[0072] Preparation Example 5: 30% Bronopol·Pydiflumetofen Seed Treatment Suspension Concentrate (1:1)

[0073] By weight percentage, 15% bronopol, 15% pydiflumetofen, 2% fatty alcohol polyoxyethylene ether, 3% alkylphenol polyoxyethylene ether phosphate, 3% naphthalene sulfonate formaldehyde condensate, 2% polyvinyl alcohol, 0.3% xanthan gum, 5% rose pigment, 4% ethylene glycol, 1.5% magnesium aluminum silicate, 0.5% silicone defoamer, 0.1% Kathon, deionized water to make up the balance.

[0074] Preparation method: The same as Preparation Example 1.

[0075] Preparation Example 6: 32% Bronopol·Pydiflumetofen Seed Treatment Suspension Concentrate (7:1)

[0076] By weight percentage, 28% bronopol, 4% pydiflumetofen, 4% isomeric tridecanol polyoxyethylene ether, 3% EO / PO block copolymer, 3% glycerol fatty acid ester polyoxyethylene ether phosphate, 3% sodium lignosulfonate, 2% sodium carboxymethyl cellulose, 5% glycerol, 0.3% xanthan gum, 1.5% magnesium aluminum silicate, 0.5% silicone defoamer, 6% rose pigment, 1% potassium benzoate, deionized water to make up the balance.

[0077] Preparation method: The same as Preparation Example 1.

[0078] Preparation Example 7: 20% Bronopol·Pydiflumetofen Suspension Concentrate (1:1)

[0079] By weight percentage, 10% bronopol, 10% pydiflumetofen, 2% sodium dodecyl sulfate, 1% alkylphenol polyoxyethylene ether, 3% styrylphenol polyoxyethylene ether phosphate, 0.2% xanthan gum, 1% magnesium aluminum silicate, 3% ethylene glycol, 1% sodium benzoate, 0.5% silicone oil, deionized water to make up the balance.

[0080] Preparation method: According to the formula ratio, the active ingredient, surfactant and other functional auxiliaries are successively placed in a reaction kettle, mixed evenly with water, subjected to high-speed shearing and wet grinding, and finally homogenized and filtered to obtain the suspension product.

[0081] Preparation Example 8: 36% Bronopol · fluxapyroxad water dispersible granule (3:1)

[0082] By weight percentage, 27% bronopol, 9% fluxapyroxad, 8% sodium lignosulfonate, 6% naphthalene sulfonate formaldehyde condensate, 3% Nekal BX, 5% white sugar, and kaolin to make up the balance.

[0083] Preparation method: According to the formula ratio of the example, the active ingredient is added to the carrier, and a surfactant and other functional auxiliaries are added thereto, mixed, 10 - 25% of water is added after air flow pulverization, and then the water dispersible granule product is obtained through kneading, granulation, drying and screening; or the pulverized powder is sprayed with water, granulated and dried in a fluidized bed granulator, and then screened to obtain the product.

[0084] Preparation Example 9: 48% Bronopol · fluxapyroxad wettable powder (1:5)

[0085] By weight percentage, 8% bronopol, 40% fluxapyroxad, 12% naphthalene sulfonate formaldehyde condensate, 3% calcium lignosulfonate, 2% sodium lignosulfonate, 2% sodium dodecyl sulfate, and kaolin to make up the balance.

[0086] Preparation method: According to the formula ratio, the active ingredient, dispersant, wetting agent and filler are mixed, stirred evenly in a stirring kettle, and pulverized and mixed evenly by an air flow pulverizer for multiple times to obtain the wettable powder of the composition of the present invention.

[0087] Preparation Example 10: 30% Bronopol · pyraclostrobin suspension (1:3)

[0088] By weight percentage, 7.5% bronopol, 22.5% pyraclostrobin, 2% fatty alcohol polyoxyethylene ether, 3% alkylphenol polyoxyethylene ether phosphate, 2% sodium lignosulfonate, 0.3% xanthan gum, 1.5% magnesium aluminum silicate, 5% propylene glycol, 0.5% silicone oil, 0.01% potassium benzisothiazolinone, and deionized water to make up the balance.

[0089] Preparation method: The same as that of Preparation Example 7.

[0090] Preparation Example 11: 32% Bronopol · pyraclostrobin water dispersible granule (1:1)

[0091] By weight percentage, 16% bronopol, 16% pyraclostrobin, 3% sodium dodecyl sulfate, 6% sodium lignosulfonate, 10% naphthalene sulfonate formaldehyde condensate, 10% ammonium sulfate, and starch to make up the balance.

[0092] Preparation method: the same as that of Preparation Example 8.

[0093] Preparation Example 12: 44% Bronopol·Pyraclostrobin wettable powder (1:10)

[0094] By weight percentage, 4% bronopol, 40% pyraclostrobin, 3% sodium polycarboxylate, 4% sodium lignosulfonate, 6% dispersant NNO, 3% sodium dodecyl sulfate, and kaolin to make up the balance.

[0095] Preparation method: the same as that of Preparation Example 9.

[0096] Indoor activity determination test:

[0097] Example 1: Indoor activity determination test on the compounding of bronopol with either fluxapyroxad or penflufen against bakanae disease of rice

[0098] Test basis: The test refers to the agricultural industry standard of the People's Republic of China NY / T 1156.2 - 2006 "Pesticide Bioassay Guidelines for Pesticide Registration - Fungicides - Part 2: Inhibiting Mycelial Growth of Pathogenic Fungi - Petri Dish Method".

[0099] Test strain: Fusarium moniliforme, provided by Shenyang Research Institute of Chemical Industry.

[0100] Instrument and equipment: High - pressure steam sterilizer, laminar flow hood, incubator, electro - thermal forced - air drying oven, ten - thousandth electronic balance, pipette, alcohol lamp, beaker (50 mL), volumetric flask, Erlenmeyer flask (100 mL), Petri dish (Φ9 cm), puncher (Φ0.6 cm), inoculator, ruler, etc.

[0101] Test target culture conditions: Transfer Fusarium moniliforme stored at 4°C in the refrigerator to potato dextrose agar medium, and place it in a 25°C incubator for dark culture for 5 days to activate it, and set aside for use.

[0102] Test agents: 95% bronopol technical, 98% fluxapyroxad technical, 95% penflufen technical, and the above agents are all provided by the R & D center of Hailir Pesticides & Chemicals Group Co., Ltd.

[0103] Other reagents: Acetone (analytical pure), Tween 80 (chemical pure).

[0104] Preparation of reagent mother liquor: Dissolve the above technical agents with acetone respectively to make high - concentration mother liquors, and then dilute them with 0.1% Tween 80 aqueous solution to prepare single - agent mother liquors respectively. According to the mixing purpose and the activity of the agents, design different ratios, and configure each single - agent and each group of mixed agents with the required series of mass concentrations.

[0105] Test repetition: For each concentration of the test agent, 4 Petri dishes were used, with 1 Petri dish for each repetition, and a total of 4 repetitions were carried out. An aqueous solution of 0.1% Tween 80 without the agent was used as the blank control.

[0106] Agent treatment: Under aseptic operation conditions, 5 mL of the liquid medicine with different concentrations was added to the pre-calibrated sterile Erlenmeyer flask using a pipette. Then, the medium melted and cooled to an appropriate temperature was added to the Erlenmeyer flask. After shaking well, it was poured equally into 4 Petri dishes to prepare the PDA plates containing the drug at the corresponding concentrations.

[0107] Inoculation: The pre-cultured Fusarium moniliforme was cut into a fungal cake at the edge of the colony under aseptic conditions using a sterilized borer. The fungal cake was inoculated in the center of the drug-containing plate using an inoculator, covered with the lid, and placed in a constant temperature incubator at 25 °C for dark culture.

[0108] Data investigation: The test was investigated when the colony in the control treatment grew to 2 / 3 - 4 / 5 of the diameter of the Petri dish. The diameter of the colony (cm) was measured with a ruler. The diameter of each colony was measured once using the cross method, and the average value was taken.

[0109] Data statistics and analysis: According to the investigation results, the mycelial growth inhibition rate of each treatment concentration on the test target fungus was calculated, and the unit was percentage (%). The calculation result was retained to two decimal places.

[0110] D = D1 - D2

[0111] In the formula:

[0112] D - - Colony growth diameter;

[0113] D1 - - Colony diameter;

[0114] D2 - - Fungal cake diameter.

[0115]

[0116] In the formula:

[0117] I - - Mycelial growth inhibition rate;

[0118] D0 - - Colony growth diameter of the blank control;

[0119] D T - - Colony growth diameter of the agent treatment.

[0120] The data was processed using the method of probit analysis. Analyzed with the IBM SPSS Statistics 20 statistical analysis system to obtain the toxicity regression line, EC 50 value and the correlation coefficient R 2 , and evaluate the activity of the test agent on the biological test materials.

[0121] Sun Yunpei method: The synergistic effect of mixed pesticides is evaluated according to the co-toxicity coefficient (CTC). When the co-toxicity coefficient CTC of the mixture is ≥ 120, it shows a synergistic effect; when CTC ≤ 80, it shows an antagonistic effect; when 80 < CTC < 120, it shows an additive effect.

[0122] Calculation of the co-toxicity coefficient (CTC value) of the mixture:

[0123]

[0124] Where:

[0125] ATI - Measured toxicity index of the mixture;

[0126] S - EC of the standard pesticide 50 , in milligrams per liter (mg / L);

[0127] M - EC of the mixture 50 , in milligrams per liter (mg / L).

[0128] TTI = TI A *P A +TI B *P B

[0129] Where:

[0130] TTI - Theoretical toxicity index of the mixture;

[0131] TI A - Toxicity index of pesticide A;

[0132] P A - Percentage content of pesticide A in the mixture, in percentage (%);

[0133] TI B - Toxicity index of pesticide B;

[0134] P B - Percentage content of pesticide B in the mixture, in percentage (%).

[0135]

[0136] Where:

[0137] CTC - Co-toxicity coefficient;

[0138] ATI - Measured toxicity index of the mixture;

[0139] TTI - Theoretical toxicity index of the mixture.

[0140] The test results are shown in the following table:

[0141] Table 1 Indoor Activity Test Results of the Compound of Bronopol and Fluxapyroxad against Bakanae Disease of Rice

[0142]

[0143] Table 2 Indoor Activity Test Results of the Compound of Bronopol and Penflufen against Bakanae Disease of Rice

[0144]

[0145] It can be seen from the indoor activity tests in Table 1 and Table 2 that the compound of bronopol with either penflufen or fluxapyroxad shows good control effects against bakanae disease of rice.

[0146] It can be seen from the test results in Table 1 that the tested agents bronopol and fluxapyroxad have good control effects on the pathogen of bakanae disease of rice, and their EC 50 are 4.628 mg / L and 5.344 mg / L respectively. When the mass ratio of bronopol to fluxapyroxad is in the range of 1:35 to 35:1, their co-toxicity coefficients are all greater than 120, showing a synergistic effect on bakanae disease of rice. Among them, when bronopol and fluxapyroxad are compounded at a mass ratio of 1:1, the co-toxicity coefficient is the largest and the synergistic effect is the most significant.

[0147] It can be seen from the test results in Table 2 that the tested agent penflufen has high toxicity to the pathogen of bakanae disease of rice, and its EC 50 is 0.053 mg / L. When bronopol and penflufen are compounded, and the mass ratio is in the range of 1:35 to 35:1, the co-toxicity coefficients are all greater than 80, showing different additive or synergistic effects on bakanae disease of rice. When the mass ratio of bronopol to penflufen is in the range of 1:15 to 25:1, the co-toxicity coefficient is greater than 120, showing a synergistic effect on bakanae disease of rice.

[0148] Example 2: Indoor Activity Determination Test of the Compound of Bronopol with Either Penflufen or Isopyrazam against Fusarium Head Blight of Wheat

[0149] Test Basis: The test refers to the Agricultural Industry Standard of the People's Republic of China NY / T 1156.2 - 2006 "Pesticide Bioassay Guidelines for Pesticide Registration - Fungicides - Part 2: Inhibiting Mycelial Growth of Pathogens - Petri Dish Method".

[0150] Test Target: Fusarium graminearum, collected from diseased plants in the wheat experimental field of Shandong Agricultural University, isolated, identified and preserved by the laboratory of Shandong Agricultural University.

[0151] Instruments and equipment: autoclave, laminar flow hood, constant temperature light incubator, electrothermal blast drying oven, one ten-thousandth electronic balance, pipette, alcohol lamp, small beaker, volumetric flask, Erlenmeyer flask, Petri dish (Φ9 cm), borer, inoculator (Φ0.6 cm), ruler, etc.

[0152] Culture conditions of the test target: Transfer the Fusarium graminearum preserved at 4°C in the refrigerator to the potato dextrose agar medium, place it in a 26°C incubator and incubate it in the dark for 4 days to activate it for standby.

[0153] Test agents: 95% bronopol technical, 98% fluxapyroxad technical, 92% pyraclostrobin technical. All the above agents are provided by the R & D center of Hailir Pharmaceutical Group.

[0154] Other reagents: solvent acetone (analytical pure), emulsifier Tween 80 (chemical pure).

[0155] Preparation of mother liquor of agents: Dissolve the above technical agents with acetone respectively to make high-concentration mother liquor, and then dilute them with 0.1% Tween 80 aqueous solution. Prepare single-agent mother liquor respectively, and design different ratios according to the purpose of mixing and the activity of agents. Each single agent and each mixture of ratios are configured into the required series of mass concentrations.

[0156] Experiment repetition: For each concentration of the test agents, 4 Petri dishes are used, 1 Petri dish for each repetition, with a total of 4 repetitions. Use 0.1% Tween 80 aqueous solution without agents as the blank control.

[0157] Agent treatment: Under aseptic operation conditions, quantitatively add the pre-melted and sterilized PDA medium into a sterile conical flask according to the test treatment. Sequentially and quantitatively pipette 10 mL of the prepared treatment solutions of each concentration from low to high concentration, and add them into the above conical flask respectively. Shake well, and then pour an equal amount into 4 Petri dishes with a diameter of 9 cm to make drug-containing plates with corresponding concentrations. Set 0.1% Tween 80 aqueous solution without adding agents as the blank control, with 4 repetitions for each treatment.

[0158] Inoculation: Cut the fungal cake from the edge of the colony of the pre-cultured Fusarium graminearum under aseptic conditions with a sterilized borer, and inoculate the fungal cake in the center of the drug-containing plate with an inoculator. Cover the lid and place it in a 26°C constant temperature light incubator and incubate it in the dark.

[0159] Data investigation: Investigate the growth of the pathogenic fungus mycelium according to the growth of the mycelium in the blank control Petri dish. Measure the colony diameter with a ruler, with the unit of centimeter (cm). Measure the diameter of each colony once with the cross method, take the average value, and record the original data of all repetitions of each treatment.

[0160] Data statistics and analysis: According to the survey results, calculate the mycelial growth inhibition rate of each treatment concentration on the tested target bacteria, with the unit of percentage (%). The calculation result is reserved to two decimal places after the decimal point.

[0161] D = D1 - D2

[0162] Where:

[0163] D - Colony growth diameter;

[0164] D1 - Colony diameter;

[0165] D2 - Mycelial disc diameter.

[0166]

[0167] Where:

[0168] I - Mycelial growth inhibition rate;

[0169] D0 - Colony growth diameter of blank control;

[0170] D T - Colony growth diameter of medicament treatment.

[0171] Use the method of probit analysis to process the data. Analyze with the IBM SPSS Statistics 20 statistical analysis system to obtain the toxicity regression line, EC 50 value and correlation coefficient R 2 , and evaluate the activity of the tested medicaments on the biological test materials.

[0172] Sun Yunpei method: Evaluate the synergistic effect of medicament mixture according to the co-toxicity coefficient (CTC). When the co-toxicity coefficient CTC of the mixture ≥ 120, it shows a synergistic effect; when CTC ≤ 80, it shows an antagonistic effect; when 80 < CTC < 120, it shows an additive effect.

[0173] Calculation of the co-toxicity coefficient (CTC value) of the mixture:

[0174]

[0175] Where:

[0176] ATI - Measured toxicity index of the mixture;

[0177] S - EC of the standard medicament 50 , with the unit of milligram per liter (mg / L);

[0178] M - EC of the mixture 50 , with the unit of milligram per liter (mg / L).

[0179] TTI = TI A *PA +TI B *P B

[0180] In the formula:

[0181] TTI——Theoretical toxicity index of the mixture;

[0182] TI A ——Toxicity index of agent A;

[0183] P A ——Percentage content of agent A in the mixture, in percentage (%)

[0184] TI B ——Toxicity index of agent B;

[0185] P B ——Percentage content of agent B in the mixture, in percentage (%).

[0186]

[0187] In the formula:

[0188] CTC——Coefficient of co-toxicity;

[0189] ATI——Actual toxicity index of the mixture;

[0190] TTI——Theoretical toxicity index of the mixture.

[0191] The test results are shown in the following table:

[0192] Table 3 Indoor activity test results of the combination of bronopol and fluxapyroxad against Gibberella zeae

[0193]

[0194] Table 4 Indoor activity test results of the combination of bronopol and isopyrazam against Gibberella zeae

[0195]

[0196] It can be seen from the indoor activity tests in Table 3 and Table 4 that the combination of bronopol with either fluxapyroxad or isopyrazam shows good control effects against Gibberella zeae.

[0197] It can be seen from the test results in Table 3 that the tested agent fluxapyroxad has good control effects on Gibberella zeae, and its EC 50It is 0.079 mg / L. When the mass ratio of bronopol to fluxapyroxad is within the range of 1:35 to 35:1, the co-toxicity coefficient is greater than 120, showing a synergistic effect on Gibberella zeae of wheat. Among them, when bronopol and fluxapyroxad are compounded according to the mass ratio of 1:1, the co-toxicity coefficient is the largest and the synergistic effect is the most significant.

[0198] As can be seen from the test results in Table 4, the tested agents bronopol and pyraclostrobin have good control effects on Gibberella zeae of wheat, and the EC 50 are 6.572 mg / L and 4.221 mg / L respectively. When bronopol and pyraclostrobin are compounded, within the range of the mass ratio of 1:30 to 30:1, the co-toxicity coefficient is greater than 120, showing a synergistic effect on Gibberella zeae of wheat.

[0199] Field efficacy test:

[0200] Example 3: Field efficacy test of compound preparation against bakanae disease of rice

[0201] Test basis: The test refers to GB / T 17980.104-2004 "Pesticide field efficacy test guidelines (part 2) - Part 104: Fungicides for controlling bakanae disease of rice".

[0202] Test target: Bakanae disease of rice.

[0203] Test crop: Rice (Ewan 17).

[0204] Test site: Bailianhe Village, Bailianhe Township, Luotian County, Huanggang City, Hubei Province. Bakanae disease of rice is a common disease in the rice production in this area, and it occurred mildly in the test field in 2018. The soil of the test field is gleyed paddy soil, with a pH value of 5.5, an organic matter content of 1.5%, and medium soil fertility.

[0205] Water and fertilizer management in the test field: 50 kg of 30% (15-7-8) compound fertilizer of Ezhong was applied per mu as base fertilizer before rice transplanting (on May 8), 12 kg of 46.4% urea was applied per mu as top dressing on May 17, and 6 kg of 46.4% urea was applied per mu as the second top dressing on July 1.

[0206] Meteorological data: The weather on March 31, 2019, when the medicine was applied, was cloudy, with an air temperature of 5 - 19 °C, and there was no bad weather affecting the test results during the test period.

[0207] Plot arrangement: The plot treatments of the test agent, the control agent and the blank control were arranged in a randomized block design.

[0208] Plot area: The area of each test plot is 24 m 2 , and there are protective rows between plots, with 4 replicates for each treatment.

[0209] Dosage of medicament: The tested medicaments and dosages are shown in the following table:

[0210] Table 4 Tested medicaments and dosages for field efficacy test of bakanae disease of rice

[0211] Number Name of medicament Dosage of active ingredient (g / 100 kg seeds) 1 30% Bronopol·Fluxapyroxad Seed Treatment Suspension Concentrate (1:1) 50 2 32% Bronopol·Pydiflumetofen Seed Treatment Suspension Concentrate (7:1) 50 3 28% Bronopol·Pydiflumetofen Seed Treatment Suspension Concentrate (3:1) 50 4 24% Bronopol·Fluxapyroxad Seed Treatment Suspension Concentrate (1:3) 50 5 200 g / L Pydiflumetofen Suspension Concentrate 100 6 22.4% Fluxapyroxad Seed Treatment Suspension Concentrate 60 7 20% Bronopol Wettable Powder 85 8 Blank control -

[0212] Application method: Coating is carried out before sowing rice. Weigh the seeds for each treatment according to the seeding rate per mu, put them into sealed plastic bags for standby. According to the test plan, fully stir the liquid medicine of each treatment with the seeds until the liquid medicine is evenly distributed on the surface of the seeds, and then sow after drying.

[0213] Sowing: Sow 4 trays (55cm * 25cm) per plot in the seedbed, place them in different directions of the plot, and the number of seeds sown per tray is about 3,900, which is used for the investigation of emergence rate.

[0214] Application time and number of applications: Seed coating was carried out on March 31, 2019, with a total of 1 application.

[0215] Test investigation: A total of 3 investigations are carried out. The first is to investigate the emergence time and emergence rate when the seedlings emerge in the seedbed. For each plot, 4 trays of rice sown at fixed points are investigated, and 1 / 2 tray is investigated for each tray; the second investigation is to investigate the diseased plant rate before transplanting the rice seedlings. Five points are sampled in each plot, and 100 plants are investigated at each point to investigate the number of diseased plants and the total number of plants in each treatment, and calculate the control effect; the third investigation is to investigate the disease occurrence before the rice heading stage. Five points are sampled in each plot, and 20 clusters are sampled at each point to investigate the number of diseased plants and the total number of plants in each treatment, and calculate the control effect.

[0216] Safety investigation: Field observation is carried out after the test. The rice in each medicament treatment area grows normally, which is basically the same as that in the blank control area. No phytotoxicity such as growth inhibition, chlorosis, and malformation and adverse effects occur to the rice for all the tested medicaments. Compared with the blank control, no effects on other target organisms are found for each treatment medicament.

[0217] Calculation method of efficacy:

[0218]

[0219]

[0220] The test results are shown in the following table:

[0221] Table 5 Results of field efficacy test of compound preparation against bakanae disease of rice

[0222]

[0223] Analysis of the efficacy of field trials: The compound preparation of the present invention was used for coating treatment of rice seeds. According to the results of the emergence rate investigation, the emergence rates of each treatment with the tested agents were basically the same as or even better than that of the control treatment. Before transplanting rice seedlings, the disease incidence of rice plants was investigated. The average disease incidence of the blank control treatment reached 8.50%, and the control effect of the compound preparation was higher than 84.12%. The results of the control effect investigation before the rice heading stage showed that the control effect of the compound preparation on bakanae disease of rice was between 84.71% and 94.76%, all of which were better than the single-agent control.

[0224] Example 4: Field efficacy trial of compound preparation against Fusarium head blight of wheat

[0225] Test basis: The test was carried out with reference to NY / T 1464.15-2007 "Guidelines for field efficacy trials of pesticides - Part 15: Fungicides against Fusarium head blight of wheat".

[0226] Test target: Fusarium head blight of wheat.

[0227] Test crop: Wheat (Jimai 22).

[0228] Test site: In a large field in Sanlitun Village, Zhanghuang Town, Yutai County, Jining City, Shandong Province, where rice-wheat rotation has been carried out for many years. The incidence of Fusarium head blight of wheat has been serious over the years. The seeding rate per mu is 20 kg. The soil of the test plot is clay loam with medium soil fertility. The cultivation conditions of all test plots are the same and meet the local good agricultural practices.

[0229] Arrangement of test plots: The plot treatments of the test agents, control agents, and blank control were arranged in a randomized block design. The area of each plot was 20 m 2 , and each treatment was replicated 4 times.

[0230] Dosage of agents: The tested agents and their dosages are shown in the following table:

[0231] Table 6 Tested agents and dosages for field efficacy trial of Fusarium head blight of wheat

[0232]

[0233]

[0234] Application time: The test was carried out with one application during the flowering stage of wheat. A Lino HD-400 type knapsack sprayer was used for full-plant spraying to make the droplet distribution uniform and thorough. The liquid volume applied per mu was 35 kg.

[0235] Investigation method and time: The control effect was investigated once 15 days after application (during the milk ripening stage of wheat). During the investigation, 5 sampling points were taken along the diagonal of each plot, and 100 ears were investigated at each point. The disease ears were classified according to the percentage of the area of withered ears in the total ear area, and the number of disease ears and the total number of ears at each level were recorded.

[0236] Classification standard for Fusarium head blight of wheat:

[0237] Grade 0: The whole ear is disease-free;

[0238] Grade 1: The area of withered ear accounts for less than 1 / 4 of the whole ear area;

[0239] Grade 3: The area of withered ear accounts for 1 / 4 - 1 / 2 of the whole ear area;

[0240] Grade 5: The area of withered ear accounts for 1 / 2 - 3 / 4 of the whole ear area;

[0241] Grade 7: The area of withered ear accounts for more than 3 / 4 of the whole ear area.

[0242] Calculation method of drug efficacy:

[0243]

[0244]

[0245] The test results are shown in the following table:

[0246] Table 5 Field efficacy test results of compound preparations against Fusarium head blight of wheat

[0247]

[0248]

[0249] The field efficacy results show that the compounding of bronopol with either fluxapyroxad or isopyrazam shows good control effects against Fusarium head blight of wheat. The overall control effects of each compound preparation treatment are above 86.25%, all better than the blank control treatment group of the control single agent.

[0250] It can be seen from the indoor toxicity test and field efficacy test that the bactericidal composition containing bronopol of the present invention shows good control effects against pathogenic bacteria of the genus Fusarium, is safe for crops, delays the generation of drug resistance of pathogenic bacteria, reduces the dosage of the drug while reducing the drug residues in agricultural products.

[0251] Although the present invention has been described in detail above with general descriptions and specific embodiments, based on the present invention, some modifications or improvements can be made, which are obvious to those skilled in the art. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection required by the present invention.

Claims

1. A bactericidal composition containing bronopol, characterized in that, The bactericidal composition comprises an active ingredient A and an active ingredient B, wherein the active ingredient A is bronopol, the active ingredient B is pyraclostrobin, and the mass ratio of the active ingredient A to the active ingredient B is 1:30 to 30:

1.

2. The bactericidal composition according to claim 1, wherein The active ingredient B is pyraclostrobin, and the mass ratio of the active ingredient A to the active ingredient B is 1:20-30:

1.

3. The bactericidal composition according to claim 1, wherein The total weight of the bactericidal composition is calculated as 100 wt %, and the total weight of the active ingredient A and the active ingredient B accounts for 1% to 80% of the total weight of the bactericidal composition.

4. The bactericidal composition according to claim 1, characterized in that, In addition to the active ingredients, the bactericidal composition also includes other auxiliary ingredients, and the auxiliary ingredients are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoaming agents, solvents, preservatives, stabilizers, warning colors, film formers, synergists and carriers.

5. The bactericidal composition according to claim 1, characterized in that, The bactericidal composition can be prepared into any formulation acceptable in agriculture, the formulation being a solid formulation or a liquid formulation; the solid formulation being a water-dispersible granule and / or a wettable powder, and the liquid formulation being a suspension or a seed treatment suspension.

6. Use of the bactericidal composition according to any one of claims 1-5 for preventing or controlling crop pathogenic bacteria, characterized in that, The pathogenic bacterium is Fusarium graminearum ( Fusarium graminearum ).

7. The use according to claim 6, characterized in that, The fungicidal composition is applied to plants, plant propagation materials and subsequently grown plant organs, cultivation media, materials or spaces by seed treatment, foliar application, stem application, drenching, dripping, pouring, spraying, atomizing, dusting, spreading or fumigating.

Images