Bactericidal composition containing bronopol and application thereof

Abstract

The invention belongs to the technical field of pesticides, and discloses a bronopol-containing bactericidal composition and application thereof.The bactericidal composition comprises an active ingredient A and an active ingredient B. The active ingredient A is bronopol, and the active ingredient B is selected from any one of pydiflumetofen, isopyrazam or penflufen. The mass ratio of the active component A to the active component B is (1: 35)-(35: 1). The bactericidal composition disclosed by the invention has relatively high activity on diseases of various crops, is remarkable in synergistic effect, is superior to a single agent in fast-acting property and persistent effect, reduces the dosage of agents in agricultural production, reduces pesticide residues of agricultural products, delays the generation of drug resistance of pathogenic bacteria, and is beneficial to comprehensive treatment of agricultural diseases.

Description

[0001] This divisional application of the present invention has an application number of CN202311812433.2, a filing date of May 20, 2022, and an 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 specifically 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 bromonitro alcohol fungicide. Bronopol has good control effects on plant fungal and bacterial diseases, especially on bakanae disease of rice. At the same time, it 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 fungicide 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, which is 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, thus 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 (SDHI) with both preventive and therapeutic effects. It mainly controls foliar diseases of cereals and can control powdery mildew and eyespot, etc. In addition to the pyrazole ring common to SDHI fungicides, isopyrazam also contains a unique benzobridge ring. These two ring structures enable isopyrazam to strongly bind to the binding site on the SDHI enzyme of the mitochondrial membrane and the cuticular wax layer on the leaf surface, making isopyrazam have higher activity, ensuring its high-efficiency disease control effect and long residual period 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.

[0006] Penflufen, ISO common name: penflufen, chemical name: N-[2-(1,3-dimethylbutyl)phenyl]-5-(1,3-dimethyl-1H-pyrazol-4-yl)carboxamide, CAS registry number: 494793-67-8. Penflufen is a pyrazole carboxamide fungicide developed by Bayer, which 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-lasting efficacy. 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.

[0007] 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 achieve a fungicidal effect. 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 emergence 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, through a large number of experimental studies, the inventors found 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 improving the control effect. Summary of the Invention

[0008] Based on 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 efficacy, is superior to single agents in terms of quick-acting and long-lasting effects, reduces the dosage of agents in agricultural production, slows down the development of pathogen resistance, reduces the residue of agents in agricultural products, and is conducive to the comprehensive management of agricultural diseases.

[0009] In order to achieve the above object, the present invention adopts the following technical scheme: 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;

[0010] Further, 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;

[0011] Furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1:15 to 20:1;

[0012] Further, 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;

[0013] Furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1:20 to 30:1;

[0014] Further, 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;

[0015] Furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1:15 to 25:1.

[0016] Further, 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;

[0017] Further, 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;

[0018] The wetting agent is selected from one or more of alkylbenzene sulfonates, alkylnaphthalene sulfonates, lignin sulfonates, sodium dodecyl sulfate, sodium dioctyl sulfosuccinate, α-olefin sulfonates, alkylphenol polyoxyethylene ethers, castor oil polyoxyethylene ethers, alkylphenol ethoxylates, fatty alcohol ethoxylates, fatty alcohol polyoxyethylene ether sulfates, silkworm excrement, sophora powder, sapindus powder, SOPA, detergents, emulsifier 2000 series and wetting penetrant F; and / or

[0019] The dispersant is selected from one or more of lignin sulfonates, alkylnaphthalene 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, polyacrylates, phosphates, EO-PO block copolymers and EO-PO graft copolymers; and / or

[0020] The emulsifier is selected from one or more of calcium dodecylbenzenesulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol polyoxyethylene polypropylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styrylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, and alkylphenol ether phosphate; and / or

[0021] The thickener is selected from one or more of xanthan gum, organobentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose, and white carbon black; and / or

[0022] 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

[0023] The antifreeze is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons, and inorganic salts; and / or

[0024] The defoamer is selected from one or more of C 10 -C 20 saturated fatty acid compounds, silicone oils, silicone compounds, C8-C 10 fatty alcohols; and / or

[0025] 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 oil, vegetable oil, vegetable oil derivatives, and water; and / or

[0026] 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

[0027] 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, white carbon black, talc, montmorillonite, and starch; and / or

[0028] The warning color is selected from any one or more of blue, green, red, and purple and their adjusted colors; and / or

[0029] 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

[0030] The synergist is selected from synergistic phosphorus and synergistic ether; and / or

[0031] 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;

[0032] Furthermore, the bactericidal composition can be prepared into any preparation dosage form acceptable in agriculture, and the preparation dosage form is a solid preparation, a liquid preparation, and / or a seed treatment preparation;

[0033] Furthermore, the solid preparation is a directly used solid preparation, a dispersible solid preparation, or a soluble solid preparation;

[0034] Even further, the directly used solid preparation is a powder, a granule, a ball, a tablet, or a strip;

[0035] 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;

[0036] The soluble solid preparation is a soluble powder, a soluble tablet, or a soluble granule;

[0037] Furthermore, the liquid preparation is a solution preparation, a dispersion liquid preparation, an emulsion preparation, a suspension preparation, or a multiphase preparation;

[0038] Even further, the solution preparation is a soluble solution, a soluble sol, an oil agent, or a film-forming oil agent;

[0039] The dispersion liquid preparation is an emulsifiable concentrate, a latex, a dispersible liquid agent, or an ointment;

[0040] The emulsion preparation is an aqueous emulsion, an oil emulsion, a microemulsion, or a fat agent;

[0041] The suspension preparation is a suspending agent, a microcapsule suspension agent, an oil suspension agent, or a dispersible oil suspension agent;

[0042] The multiphase preparation is a suspension emulsion, a microcapsule suspension-suspending agent, a microcapsule suspension-aqueous emulsion, or a microcapsule suspension-suspension emulsion;

[0043] Furthermore, the seed treatment preparation includes a seed treatment solid preparation or a seed treatment liquid preparation;

[0044] Even further, the seed treatment solid preparation is a seed treatment dry powder or a seed treatment dispersible powder;

[0045] The seed treatment liquid preparation is a seed treatment liquid agent, a seed treatment emulsion, or a seed treatment suspending agent;

[0046] Further, the solid preparation is a water dispersible granule and / or a wettable powder, the liquid preparation is a suspending agent, and the seed treatment preparation is a seed treatment suspending agent.

[0047] 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.

[0048] Further, the crops are selected from food crops, cash crops, fruits and vegetables, and / or lawn and garden crops;

[0049] Further, the pathogenic bacteria are Fusarium pathogenic bacteria, and the Fusarium pathogenic bacteria include Fusarium oxysporum, Fusarium incarnatum, Fusarium proliferatum, Fusarium equiseti, Fusarium verticillicides, Fusarium graminearum, and Fusarium moniliforme;

[0050] Still further, the Fusarium pathogenic bacteria are selected from Fusarium graminearum and Fusarium moniliforme.

[0051] The present invention also discloses a method for preventing and controlling crop pathogenic bacteria, and applying the bactericidal composition and / or its preparation in an effective and substantially non-phytotoxic amount to plants, plant propagation materials, and subsequently grown 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 fumigating.

[0052] Compared with the prior art, the advantages of the present invention are as follows:

[0053] 1) Reasonable compounding of bronopol with any one of fluxapyroxad, pyraclostrobin, or fluxametamide has a significant synergistic effect, improving the control effect on pathogenic bacteria;

[0054] 2) The action mechanisms of bronopol and any one of fluxapyroxad, pyraclostrobin, or fluxametamide are different from each other, which is beneficial to delaying the development of pathogenic bacteria resistance;

[0055] 3) Reduces the usage amount of pesticides in agricultural production, reduces pesticide residues in agricultural products, is environmentally friendly, and is beneficial to the comprehensive management of agricultural diseases. Detailed implementation manners

[0057] To better understand the essence of the present invention, the content of the present invention will be further described below in conjunction with embodiments. However, 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.

[0058] Preparation Example of Preparation:

[0059] Preparation Example 1: 30% Bronopol·Fluxapyroxad Seed Treatment Suspension (1:1)

[0060] 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% organosilicon defoamer, 1% sodium benzoate, and deionized water to make up the balance.

[0061] Preparation Method: According to the ratio, the active ingredient, auxiliaries, and water are mixed and stirred evenly by high-shear mixing, 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 stirred evenly by shearing to obtain the seed treatment suspension.

[0062] Preparation Example 2: 24% Bronopol·Fluxapyroxad Seed Treatment Suspension (1:3)

[0063] 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% organosilicon defoamer, and deionized water to make up the balance.

[0064] Preparation Method: The same as Preparation Example 1.

[0065] Preparation Example 3: 30% Bronopol·Fluxapyroxad Seed Treatment Suspension (5:1)

[0066] 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% organosilicon defoamer, 2% sodium sorbate, and deionized water to make up the balance.

[0067] Preparation Method: The same as Preparation Example 1.

[0068] Preparation Example 4: 28% Bronopol · fluxapyroxad Seed Treatment Suspension Concentrate (3:1)

[0069] By weight percentage, 21% bronopol, 7% fluxapyroxad, 3% isomeric tridecyl alcohol 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.

[0070] Preparation method: The same as Preparation Example 1.

[0071] Preparation Example 5: 30% Bronopol · fluxapyroxad Seed Treatment Suspension Concentrate (1:1)

[0072] By weight percentage, 15% bronopol, 15% fluxapyroxad, 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.

[0073] Preparation method: The same as Preparation Example 1.

[0074] Preparation Example 6: 32% Bronopol · fluxapyroxad Seed Treatment Suspension Concentrate (7:1)

[0075] By weight percentage, 28% bronopol, 4% fluxapyroxad, 4% isomeric tridecyl alcohol 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.

[0076] Preparation method: The same as Preparation Example 1.

[0077] Preparation Example 7: 20% Bronopol · fluxapyroxad Suspension Concentrate (1:1)

[0078] By weight percentage, 10% bronopol, 10% fluxapyroxad, 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.

[0079] Preparation method: According to the formula ratio, the active ingredient, surfactant and other functional auxiliaries are sequentially 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.

[0080] Preparation Example 8: 36% Bronopol · fluxapyroxad water dispersible granule (3:1)

[0081] 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.

[0082] 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.

[0083] Preparation Example 9: 48% Bronopol · fluxapyroxad wettable powder (1:5)

[0084] 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.

[0085] Preparation method: According to the formula ratio, the active ingredient, dispersant, wetting agent and filler are mixed, evenly stirred 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.

[0086] Preparation Example 10: 30% Bronopol · isopyrazam suspension (1:3)

[0087] By weight percentage, 7.5% bronopol, 22.5% isopyrazam, 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.

[0088] Preparation method: The same as Preparation Example 7.

[0089] Preparation Example 11: 32% Bronopol · isopyrazam water dispersible granule (1:1)

[0090] By weight percentage, 16% bronopol, 16% isopyrazam, 3% sodium dodecyl sulfate, 6% sodium lignosulfonate, 10% naphthalene sulfonate formaldehyde condensate, 10% ammonium sulfate, and starch to make up the balance.

[0091] Preparation method: the same as Preparation Example 8.

[0092] Preparation Example 12: 44% Bronopol·isopyrazam wettable powder (1:10)

[0093] By weight percentage, 4% bronopol, 40% isopyrazam, 3% sodium polycarboxylate, 4% sodium lignosulfonate, 6% dispersant NNO, 3% sodium dodecyl sulfate, and kaolin to make up the balance.

[0094] Preparation method: the same as Preparation Example 9.

[0095] Indoor activity determination test:

[0096] Example 1: Indoor activity determination test of the compounding of bronopol with any one of fluxapyroxad or penflufen against bakanae disease of rice

[0097] 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".

[0098] Test strain: Fusarium moniliforme, provided by Shenyang Research Institute of Chemical Industry.

[0099] Instrument and equipment: High - pressure steam sterilizer, laminar flow hood, incubator, electro - thermal blast drying oven, ten - thousandth electronic balance, pipette, alcohol lamp, beaker (50 mL), volumetric flask, Erlenmeyer flask (100 mL), petri dish (Φ9 cm), punch (Φ0.6 cm), inoculator, ruler, etc.

[0100] Test target culture conditions: Transfer the Fusarium moniliforme stored at 4°C in the refrigerator to potato dextrose agar medium, and place it in a 25°C incubator for dark cultivation for 5 days to activate it, and set aside for use.

[0101] 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.

[0102] Other reagents: Acetone (analytical pure), Tween 80 (chemical pure).

[0103] Preparation of reagent mother liquor: Dissolve the above technicals 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, different ratios are designed, and each single agent and the mixed agents of each group ratio are configured into the required series of mass concentrations.

[0104] 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.

[0105] Agent treatment: Under aseptic operation conditions, 5 mL of the liquid medicine with different concentrations was added to the pre-calibrated sterilized Erlenmeyer flask using a pipette, and then the medium melted and cooled to an appropriate temperature was added to the Erlenmeyer flask. After shaking well, it was poured into 4 petri dishes in equal amounts to prepare the corresponding concentration of PDA plates containing the agent.

[0106] Inoculation: The pre-cultured Fusarium moniliforme was cut into a fungal cake from the edge of the colony under aseptic conditions using a sterilized borer, and the fungal cake was inoculated in the center of the plate containing the agent using an inoculator. The lid was covered, and it was placed in a constant temperature incubator at 25 °C for dark cultivation.

[0107] 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, and the diameter of each colony was measured once using the cross method, and the average value was taken.

[0108] 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.

[0109] D = D1 - D2

[0110] In the formula:

[0111] D - - Colony growth diameter;

[0112] D1 - - Colony diameter;

[0113] D2 - - Fungal cake diameter.

[0114]

[0115] In the formula:

[0116] I - - Mycelial growth inhibition rate;

[0117] D0 - - Colony growth diameter of the blank control;

[0118] D T - - Colony growth diameter of the agent treatment.

[0119] The data was processed using the method of probit analysis. Analyzed with the IBM SPSS Statistics 20 statistical analysis system to obtain the virulence regression line, EC 50 value and the correlation coefficient R 2 , and evaluate the activity of the test agent on the biological test material.

[0120] Sun Yunpei's method: The synergistic effect of mixed pesticides is evaluated according to the co-toxicity coefficient (CTC). When the 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.

[0121] Calculation of the co-toxicity coefficient (CTC value) of the mixture:

[0122]

[0123] Where:

[0124] ATI - The actual toxicity index of the mixture;

[0125] S - The EC of the standard pesticide 50 , with the unit of milligrams per liter (mg / L);

[0126] M - The EC of the mixture 50 , with the unit of milligrams per liter (mg / L).

[0127] TTI = TI A *P A +TI B *P B

[0128] Where:

[0129] TTI - The theoretical toxicity index of the mixture;

[0130] TI A - The toxicity index of pesticide A;

[0131] P A - The percentage content of pesticide A in the mixture, with the unit of percentage (%).

[0132] TI B - The toxicity index of pesticide B;

[0133] P B - The percentage content of pesticide B in the mixture, with the unit of percentage (%).

[0134]

[0135] Where:

[0136] CTC - Co-toxicity coefficient;

[0137] ATI - The actual toxicity index of the mixture;

[0138] TTI - The theoretical toxicity index of the mixture.

[0139] The test results are shown in the following table:

[0140] Table 1 Indoor Activity Test Results of the Compound of Bronopol and Fluxapyroxad against Bakanae Disease of Rice

[0141]

[0142] Table 2 Indoor Activity Test Results of the Compound of Bronopol and Fluxapyroxad-ethyl against Bakanae Disease of Rice

[0143]

[0144] It can be seen from the indoor activity tests in Table 1 and Table 2 that the compound of bronopol with either fluxapyroxad-ethyl or fluxapyroxad shows good control effects against bakanae disease of rice.

[0145] 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, the co-toxicity coefficient is greater than 120, showing a synergistic effect on bakanae disease of rice. Among them, when the mass ratio of bronopol to fluxapyroxad is 1:1, the co-toxicity coefficient is the largest and the synergistic effect is the most significant.

[0146] It can be seen from the test results in Table 2 that the tested agent fluxapyroxad-ethyl has high toxicity to the bakanae disease of rice, and its EC 50 is 0.053 mg / L. When bronopol is compounded with fluxapyroxad-ethyl, and the mass ratio is in the range of 1:35 to 35:1, the co-toxicity coefficient is greater than 80, showing different additive or synergistic effects on bakanae disease of rice. When the mass ratio of bronopol to fluxapyroxad-ethyl 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.

[0147] Example 2: Indoor Activity Determination Test of the Compound of Bronopol with Either Fluxapyroxad-ethyl or Pyraclostrobin against Fusarium Head Blight of Wheat

[0148] 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".

[0149] 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.

[0150] Instruments and equipment: autoclave, laminar flow hood, constant temperature light incubator, electrothermal 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.

[0151] Culture conditions of the test target: Transfer the Fusarium graminearum preserved at 4°C in the refrigerator to the potato dextrose agar medium, and place it in the incubator at 26°C for dark culture for 4 days to activate it, and set aside for use.

[0152] Test agents: 95% bronopol technical, 98% fluxapyroxad technical, 92% pyraclostrobin technical. The above agents are all provided by the R & D center of Hailir Pharmaceutical Group.

[0153] Other reagents: Solvent acetone (analytical pure), emulsifier Tween 80 (chemical pure).

[0154] Preparation of mother liquor of the agent: Dissolve the above technical agents with acetone respectively to prepare 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 the agent. Each single agent and each group of mixed agents are configured into the required series of mass concentrations.

[0155] Experiment repetition: For each concentration of the test agent, 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 the agent as the blank control.

[0156] 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, 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 the agent as the blank control, with 4 repetitions for each treatment.

[0157] 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 the constant temperature light incubator at 26°C for dark culture.

[0158] Data investigation: Investigate the growth of the pathogenic fungus hyphae according to the growth of the hyphae 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.

[0159] Data statistics and analysis: According to the survey results, calculate the mycelial growth inhibition rate of each treatment concentration on the target test bacteria, with the unit of percentage (%). The calculation result is reserved to two decimal places.

[0160] D = D1 - D2

[0161] Where:

[0162] D - Colony growth diameter;

[0163] D1 - Colony diameter;

[0164] D2 - Disc diameter.

[0165]

[0166] Where:

[0167] I - Mycelial growth inhibition rate;

[0168] D0 - Colony growth diameter of blank control;

[0169] D T - Colony growth diameter of medicament treatment.

[0170] 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 test medicaments on the biological test materials.

[0171] 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 is ≥ 120, it shows a synergistic effect; when CTC ≤ 80, it shows an antagonistic effect; when 80 < CTC < 120, it shows an additive effect.

[0172] Calculation of co-toxicity coefficient (CTC value) of the mixture:

[0173]

[0174] Where:

[0175] ATI - Measured toxicity index of the mixture;

[0176] S - EC 50 , with the unit of milligram per liter (mg / L);

[0177] M - EC 50 , with the unit of milligram per liter (mg / L).

[0178] TTI = TI A *PA +TI B *P B

[0179] In the formula:

[0180] TTI——The theoretical toxicity index of the mixture;

[0181] TI A ——The toxicity index of agent A;

[0182] P A ——The percentage content of agent A in the mixture, in percentage (%)

[0183] TI B ——The toxicity index of agent B;

[0184] P B ——The percentage content of agent B in the mixture, in percentage (%).

[0185]

[0186] In the formula:

[0187] CTC——The co-toxicity coefficient;

[0188] ATI——The measured toxicity index of the mixture;

[0189] TTI——The theoretical toxicity index of the mixture.

[0190] The test results are shown in the following table:

[0191] Table 3 Indoor activity test results of the mixture of bronopol and fluxapyroxad against Gibberella zeae

[0192]

[0193] Table 4 Indoor activity test results of the mixture of bronopol and pyraclostrobin against Gibberella zeae

[0194]

[0195] It can be seen from the indoor activity tests in Table 3 and Table 4 that the mixture of bronopol and either fluxapyroxad or pyraclostrobin shows good control effects against Gibberella zeae.

[0196] 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 at a mass ratio of 1:1, the co-toxicity coefficient is the largest and the synergistic effect is the most significant.

[0197] As can be seen from the test results in Table 4, the tested agents bronopol and pyraclostrobin both 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, and the mass ratio is within the range of 1:30 to 30:1, the co-toxicity coefficient is greater than 120, showing a synergistic effect on Gibberella zeae of wheat.

[0198] Field efficacy test:

[0199] Example 3: Field efficacy test of compound preparation against bakanae disease of rice

[0200] 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".

[0201] Test target: Bakanae disease of rice.

[0202] Test crop: Rice (Ewan 17).

[0203] Test site: Bailianhe Village, Bailianhe Township, Luotian County, Huanggang City, Hubei Province. Bakanae disease of rice is a common disease in rice production in this area, and it occurred slightly in the test field in 2018. The soil of the test field is gley paddy soil, with a pH value of 5.5, an organic matter content of 1.5%, and medium soil fertility.

[0204] Water and fertilizer management in the test field: Before transplanting rice (on May 8), 50 kg of 30% (15-7-8) Ezhong compound fertilizer was applied per mu as base fertilizer. On May 17, 12 kg of 46.4% urea was applied per mu as top dressing. On July 1, 6 kg of 46.4% urea was applied per mu as the second top dressing.

[0205] 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.

[0206] Plot arrangement: The plot treatments of the test agents, control agents and blank control were arranged in a randomized block design.

[0207] 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.

[0208] Dosage of the agent: The tested agents and their dosages are shown in the following table:

[0209] Table 4 Tested agents and dosages for the field efficacy test of rice bakanae disease

[0210] 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·Pyraoxystrobin Seed Treatment Suspension Concentrate (7:1) 50 3 28% Bronopol·Pyraoxystrobin Seed Treatment Suspension Concentrate (3:1) 50 4 24% Bronopol·Fluxapyroxad Seed Treatment Suspension Concentrate (1:3) 50 5 200 g / L Pyraoxystrobin Suspension Concentrate 100 6 22.4% Fluxapyroxad Seed Treatment Suspension Concentrate 60 7 20% Bronopol Wettable Powder 85 8 Blank control -

[0211] 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 bags for standby. According to the test scheme, 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.

[0212] Sowing: Sow 4 trays (55cm * 25cm) in each plot of the seedbed, place them in different directions of the plot. The number of seeds sown in each tray is about 3900, which is used for the investigation of the emergence rate.

[0213] Application time and number of applications: Seed coating was carried out on March 31, 2019, with a total of 1 application.

[0214] Test investigation: A total of 3 investigations are carried out. The first investigation is to investigate the emergence time and emergence rate when the seedlings emerge in the seedbed. In each plot, 4 trays of rice sown at fixed points are investigated, and 1 / 2 tray is investigated in each tray; the second investigation is to investigate the disease 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 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.

[0215] Safety investigation: Field observation is carried out after the test. The rice in each agent treatment area grows normally, which is basically the same as that in the blank control area. No phytotoxicity such as growth inhibition, chlorosis, and deformity and adverse effects occur to the rice for all the tested agents. Compared with the blank control, no effects on other target organisms are found for each treatment agent.

[0216] Method for calculating the efficacy:

[0217]

[0218]

[0219]

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

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

[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 survey, the emergence rates of each treatment with the test agents were basically the same as or even better than that of the control treatment. Before transplanting rice seedlings, the disease plant rate of rice was investigated. The average disease plant rate 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 survey 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 better than that of 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 occurrence 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 test agents and their dosages are shown in the following table:

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

[0232]

[0233]

[0234] Application time: The test was applied once during the flowering stage of wheat using a Linuong HD-400 type knapsack sprayer for whole-plant spraying to make the droplets evenly distributed. The liquid volume 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 whole 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 withered ear area accounts for less than 1 / 4 of the whole ear area;

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

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

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

[0242] Method for calculating 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 residue in agricultural products.

[0251] Although the present invention has been described in detail above with general descriptions and specific implementation examples, 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 described bactericidal composition contains active ingredient A and active ingredient B. Active ingredient A is bronopol, and active ingredient B is fluxapyroxad. The mass ratio of active ingredient A to active ingredient B is 1:35 to 35:

1.

2. The bactericidal composition according to claim 1, characterized in that, The mass ratio of active ingredient A to active ingredient B is 1:25 to 25:

1.

3. The bactericidal composition according to claim 2, characterized in that, The mass ratio of active ingredient A to active ingredient B is 1:15 to 25:

1.

4. The bactericidal composition according to claim 1, characterized in that, Based on 100 wt% of the total weight of the described bactericidal composition, the total weight of active ingredient A and active ingredient B accounts for 1% to 80% of the total weight of the bactericidal composition.

5. The bactericidal composition according to claim 1, characterized in that, The described bactericidal composition includes other auxiliary ingredients in addition to the active ingredients. 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-forming agents, synergists, and carriers.

6. The bactericidal composition according to claim 1, characterized in that, The described bactericidal composition can be prepared into any agriculturally acceptable preparation dosage form. The preparation dosage form is a solid preparation, a liquid preparation, and / or a seed treatment preparation. The solid preparations include powders, granules, balls, tablets, strips, wettable powders, oil-dispersible powders, milk powders, water-dispersible granules, milk granules, water-dispersible tablets, soluble powders, soluble tablets, or soluble granules. The liquid preparations include soluble solutions, soluble sols, oils, film-forming oils, emulsifiable concentrates, latexes, dispersible liquids, pastes, emulsions, oil emulsions, microemulsions, lipid suspensions, microcapsule suspensions, oil suspensions, dispersible oil suspensions, suspension emulsions, microcapsule suspension-suspensions, microcapsule suspension-emulsions, or microcapsule suspension-suspension emulsions. The seed treatment preparations include seed treatment dry powders, seed treatment dispersible powders, seed treatment liquids, seed treatment emulsions, or seed treatment suspensions.

7. The bactericidal composition according to claim 6, characterized in that, The solid preparation is a water-dispersible granule and / or a wettable powder. The liquid preparation is a suspension. The seed treatment preparation is a seed treatment suspension.

8. Use of the bactericidal composition according to any one of claims 1-7 and / or its preparation for preventing or controlling pathogenic bacteria of crops.

9. The use according to claim 8, characterized in that, The crops are selected from food crops, cash crops, fruits and vegetables, and / or lawn and garden crops. The pathogenic bacteria are pathogenic bacteria of the genus Fusarium. The pathogenic bacteria of the genus Fusarium include Fusarium oxysporum, Fusarium incarnatum, Fusarium proliferatum, Fusarium equiseti, Fusarium verticillicides, Fusarium graminearum, and Fusarium moniliforme. Preferably, the pathogenic bacteria of the genus Fusarium are selected from Fusarium graminearum and Fusarium moniliforme.

10. A method for preventing and controlling pathogenic bacteria of crops, characterized in that, The effective and substantially phytotoxicity-free application rate of the described bactericidal composition and / or its preparation is applied to plants, plant propagation materials, and subsequently grown plant organs, cultivation media, materials, or spaces by methods such as seed treatment, foliar application, stem application, soaking, drip irrigation, pouring, spraying, atomizing, dusting, scattering, or fumigating.

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