CN114766483A - Sterilization composition containing bronopol and application thereof - Google Patents

Sterilization composition containing bronopol and application thereof Download PDF

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Publication number
CN114766483A
CN114766483A CN202210548727.8A CN202210548727A CN114766483A CN 114766483 A CN114766483 A CN 114766483A CN 202210548727 A CN202210548727 A CN 202210548727A CN 114766483 A CN114766483 A CN 114766483A
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active ingredient
agent
fusarium
percent
preparation
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CN114766483B (en
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葛家成
杨志鹏
刘金玲
刘桂娟
隋书婷
王玉
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Qingdao Hailier Biotechnology Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18Nitro compounds
    • A01N33/20Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00Protecting plants
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles

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  • Environmental Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention belongs to the technical field of pesticides, and discloses a bactericidal composition containing bronopol and an application thereof, wherein the bactericidal composition contains an active ingredient A and an active ingredient B, the active ingredient A is bronopol, the active ingredient B is selected from one of fluconazole hydroxylamine, isopyrazam or fluconazole aniline, and the mass ratio of the active ingredient A to the active ingredient B is 1: 35-35: 1. The bactericidal composition has higher activity on various diseases of crops, has obvious synergistic effect, is better than a single agent in quick-acting property and persistent effect, reduces the using amount of medicaments in agricultural production, reduces medicament residues of agricultural products, delays the generation of medicament resistance of pathogenic bacteria, and is favorable for comprehensive treatment of agricultural diseases.

Description

Sterilization composition containing bronopol and application thereof
Technical Field
The invention relates to the technical field of pesticide sterilization compositions and application thereof, in particular to a sterilization composition containing bronopol and application thereof.
Background
Bronopol, chemical name: 2-bromo-2-nitro-1, 3-propanediol, also known as bronopol, and the like. Bronopol is a broad-spectrum bactericide of bromonitroalcohol. The bronopol has good control effects on plant fungal and bacterial diseases, particularly on rice bakanae disease, and also has certain control effects on cotton angular leaf spot and wheat scab.
Fluxapyroxad, 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 accession No.: 1228284-64-7. The fluxapyroxad is a pyridine amide bactericide which is developed by the Jundana company and acts on succinate dehydrogenase, and mainly acts on the pivotal succinate dehydrogenase which is used for connecting oxidative phosphorylation and electron transfer in pathogenic bacteria by influencing a respiratory chain electron conduction system of the pathogenic bacteria, so that tricarboxylic acid cycle disorder is caused, the energy metabolism of the pathogenic bacteria is hindered, the growth of the pathogenic bacteria is inhibited, and the pathogenic bacteria is killed, so that the purpose of preventing and treating diseases is achieved. The fluxapyroxad has the characteristics of broad spectrum and high efficiency, and is suitable for many crops, such as corn, small-grain corn, soybean, peanut, rapeseed, quinoa and the like.
Isopyrazam, ISO common name: isopyrazam, CAS accession No.: 881685-58-1. The isopyrazam is a succinate dehydrogenase inhibitor (SDHI), has prevention and treatment effects, is mainly used for preventing and treating grain foliar diseases, and can be used for preventing and treating powdery mildew, eye spot disease and the like. The isopyrazam contains a unique benzobridge ring besides a common pyrazole ring shared by SDHI bactericides, and the two cyclic structures enable the isopyrazam to be strongly combined with a binding site on mitochondrial membrane SDHI enzyme and a wax layer on the surface of a leaf, so that the isopyrazam has higher activity, and the isopyrazam has high-efficiency disease control effect and longer duration in the field. In addition, the isopyrazam has the obvious effect of keeping the health of crops, so that the photosynthesis of the crops is greatly improved, the yield is improved, and the harvesting time of the crops can be obviously prolonged.
Penflufen, ISO common name: penflufen, chemical name: n- [2- (1, 3-dimethylbutyl) phenyl ] -5-1, 3-dimethyl-1H-pyrazole-4-carboxamide, CAS accession No.: 494793-67-8. The penflufen is a pyrazole amide bactericide developed by Bayer and has good activity on various plant pathogenic fungi, and the bactericide is a succinate dehydrogenase inhibitor and mainly acts on a respiratory chain electron transfer complex II to block energy metabolism. The penflufen has the functions of systemic absorption, prevention and treatment and has long lasting period. It is mainly used as a bactericidal seed treatment agent, after the seed treatment, the agent can be permeated into the germinated seed, and can be transferred into whole plant by means of xylem of young plant so as to protect the grown seedling.
The succinate dehydrogenase inhibitor (SDHI) bactericide acts on succinate dehydrogenase of respiratory chain of pathogenic fungi, blocks electron transfer to interfere energy metabolism of fungi, and has bactericidal effect. The SDHI fungicide has single action site and wide bactericidal spectrum, and has good control effect on various plant pathogenic fungi. However, due to extensive high frequency use, drug resistant strains have emerged in the field, resulting in the development of a wide range of drug resistance and a reduction in field efficacy. Due to the single action site, FRAC classifies the SDHI bactericide as a medium-to-high-resistance risk medicament, and with the wide development and frequent use of the product, the problems of resistance development, drug effect reduction and the like 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 inventor finds that the combination of the bronopol and the SDHI bactericide (any one of the fluxapyroxad, the isopyrazam or the fluxapyroxad) can improve the control effect, expand the control spectrum and delay the generation of pathogenic bacteria resistance through a great amount of experimental research.
Disclosure of Invention
Based on the situation, the invention aims to provide the bactericidal composition containing the bronopol, the bactericidal composition is effective to plant pathogenic bacteria, can obviously enhance the pesticide effect, is superior to a single agent in quick acting property and lasting effect, reduces the using amount of the pesticide in agricultural production, slows down the development of the drug resistance of pathogenic bacteria, reduces the pesticide residue of agricultural products, and is beneficial to the comprehensive treatment of agricultural diseases.
In order to achieve the purpose, the invention adopts the following technical scheme: the bactericidal composition contains an active ingredient A and an active ingredient B, wherein the active ingredient A is bronopol, the active ingredient B is selected from one of fluxapyroxad, isopyrazam or fluxapyroxad, and the mass ratio of the active ingredient A to the active ingredient B is 1: 35-35: 1;
further, the active ingredient B is penflufen-ethyl, and the mass ratio of the active ingredient A to the active ingredient B is 1: 30-30: 1;
furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1: 15-20: 1;
further, the active ingredient B is isopyrazam, and the mass ratio of the active ingredient A to the active ingredient B is 1: 30-30: 1;
furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1: 20-30: 1;
further, the active ingredient B is penflufen, and the mass ratio of the active ingredient A to the active ingredient B is 1: 25-25: 1;
furthermore, the mass ratio of the active component A to the active component B is 1: 15-25: 1.
Further, the total weight of the bactericidal composition is calculated according to 100 wt%, and the total weight of the active ingredient A and the active ingredient B accounts for 1-80% of the total weight of the bactericidal composition;
further, the bactericidal composition comprises other auxiliary components besides the active component, wherein the auxiliary components are selected from one or more of wetting agents, dispersing agents, emulsifying agents, thickening agents, disintegrating agents, antifreezing agents, antifoaming agents, solvents, preservatives, stabilizing agents, warning colors, film forming agents, synergistic agents and carriers;
the wetting agent is selected from one or more of alkyl benzene sulfonate, alkyl naphthalene sulfonate, lignosulfonate, sodium dodecyl sulfate, dioctyl sodium sulfosuccinate, alpha-olefin sulfonate, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, alkylphenol ethoxylate, fatty alcohol ethoxylate, sodium fatty alcohol polyoxyethylene ether sulfate, silkworm excrement, Chinese honeylocust fruit powder, soapberry powder, SOPA, detergent, emulsifier 2000 series and wetting penetrant F; and/or
The dispersing agent is selected from one or more of lignosulfonate, alkyl naphthalene sulfonate formaldehyde condensate, naphthalene sulfonate, tristyrylphenol ethoxylate phosphate, fatty alcohol ethoxylate, alkylphenol polyoxyethylene ether methyl ether condensate sulfate, fatty amine polyoxyethylene ether, glycerol fatty acid ester polyoxyethylene ether, polycarboxylate, polyacrylic acid, phosphate, EO-PO block copolymer and EO-PO graft copolymer; and/or
The emulsifier is selected from one or more of calcium dodecylbenzene sulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenethyl phenol polyoxyethylene polyoxypropylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styryl phenol polyoxyethylene ether, castor oil polyoxyethylene ether and alkylphenol ether phosphate; and/or
The thickener is one or more selected from xanthan gum, organic bentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose and white carbon black; and/or
The disintegrating agent 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
The antifreezing agent is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons and inorganic salts; and/or
The antifoaming agent is selected from the group consisting of C10-C20Saturated fatty acid compound, silicone oil, silicone compound, and C8-C10One or more of fatty alcohols; and/or
The solvent is one or more selected from benzene, toluene, xylene, durene, methanol, ethanol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, cyclohexanone, alkylene carbonate, diesel oil, solvent oil, vegetable oil derivative and water; and/or
The preservative is selected from one or more of propionic acid, propionic acid sodium salt, sorbic acid sodium salt, sorbic acid potassium salt, benzoic acid sodium salt, p-hydroxybenzoic acid methyl ester, carbazone and 1, 2-benzisothiazoline 3-one; and/or
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, talcum powder, montmorillonite and starch; and/or
The warning color is selected from any one or more of blue, green, red and purple; and/or
The film forming agent is selected from one or more of carboxymethyl starch sodium, cellulose derivatives (carboxymethyl cellulose sodium, sodium alginate, polyvinyl alcohol), and polyacrylic acid; and/or
The synergist is selected from synergistic phosphorus and synergistic ether; and/or
The carrier is selected from one or more of ammonium salt, ground natural mineral, ground artificial mineral, silicate, resin, wax, solid fertilizer, water, organic solvent, mineral oil, vegetable oil and vegetable oil derivative;
furthermore, the bactericidal composition can be prepared into any agriculturally acceptable preparation form, and the preparation form is a solid preparation, a liquid preparation and/or a seed treatment preparation;
further, the solid preparation is a direct-use solid preparation, a dispersible solid preparation or a soluble solid preparation;
further, the directly used solid preparation is powder, granules, pellets, tablets or bars;
the dispersible solid preparation is wettable powder, oil dispersible powder, emulsion powder, water dispersible granules, emulsion granules or water dispersible tablets;
the soluble solid preparation is soluble powder, soluble tablets or soluble granules;
further, the liquid preparation is a solution preparation, a dispersion liquid preparation, an emulsion preparation, a suspension preparation or a multi-phase preparation;
further, the solution preparation is soluble agent, soluble colloid, oil agent or spreading oil agent;
the dispersion liquid preparation is missible oil, latex, dispersible agent or paste;
the emulsion preparation is an aqueous emulsion, an oil emulsion, a microemulsion or a fatliquor;
the suspension preparation is a suspending agent, a microcapsule suspending agent, an oil suspending agent or a dispersible oil suspending agent;
the multi-phase preparation is a suspending emulsion, a microcapsule suspension-suspending agent, a microcapsule suspension-water emulsion or a microcapsule suspension-suspending emulsion;
further, the seed treatment preparation comprises a seed treatment solid preparation or a seed treatment liquid preparation;
further, the seed treatment solid preparation is seed treatment dry powder or seed treatment dispersible powder;
the seed treatment liquid preparation is a seed treatment liquid agent, a seed treatment emulsion or a seed treatment suspending agent;
furthermore, the solid preparation is water dispersible granules and/or wettable powder, the liquid preparation is a suspending agent, and the seed treatment preparation is a seed treatment suspending agent.
The invention also discloses the application of the bactericidal composition and/or the preparation thereof in preventing or controlling crop pathogenic bacteria.
Further, the crops are selected from grain crops, economic crops, fruits and vegetables and/or lawn garden crops;
further, the pathogenic bacteria are Fusarium (Fusarium) pathogenic bacteria, and the Fusarium pathogenic bacteria include Fusarium oxysporum (Fusarium oxysporum), Fusarium semitectum (Fusarium incarnatum), Fusarium proliferatum (Fusarium proliferatum), Fusarium equiseti (Fusarium equiseti), Fusarium verticillium (Fusarium verticillioides), Fusarium graminearum (Fusarium graminearum), Fusarium moniliforme (Fusarium moniliforme);
further, the Fusarium pathogenic bacteria are selected from Fusarium graminearum (Fusarium graminearum), Fusarium moniliforme (Fusarium moniliforme).
Also disclosed is a method of preventing and controlling crop pathogens by applying the fungicidal composition and/or formulation thereof in an effective and substantially non-phytotoxic application rate to plants, plant propagation material and subsequently emerging plant organs, cultivation media, materials or spaces by seed treatment, foliar application, stem application, drenching, instillation, pouring, spraying, dusting, scattering or fuming.
Compared with the prior art, the invention has the advantages that:
1) the reasonable compounding of the bronopol and any one of the triflumizole hydroxylamine, the isopyrazam or the triflumizole aniline has obvious synergistic effect, and the prevention and treatment effect on pathogenic bacteria is improved;
2) the action mechanisms of the bronopol and one of the fluxapyroxad, the isopyrazam or the fluxapyroxad are different, which is beneficial to delaying the development of the drug resistance of pathogenic bacteria;
3) the use amount of the pesticide in agricultural production is reduced, pesticide residue of agricultural products is reduced, and the method is environment-friendly and is beneficial to comprehensive treatment of agricultural diseases.
Detailed Description
In order to better understand the essence of the present invention, the following examples are further described, but should not be construed as limiting the present invention, the contents mentioned in the examples are not limiting the present invention, and the material formulation can be selected according to local conditions without substantial influence on the result.
Preparation example of the formulation:
preparation example 1: 30% bronopol-fluxapyroxad aniline seed treatment suspending agent (1:1)
According to the weight percentage, 15 percent of bronopol, 15 percent of fluxapyroxad, 4 percent of alkylphenol polyoxyethylene, 5 percent of alkylphenol polyoxyethylene phosphate, 3 percent of sodium lignosulfonate, 2 percent of polyacrylic acid, 0.2 percent of xanthan gum, 6 percent of rose bengal pigment, 5 percent of glycol, 1 percent of magnesium aluminum silicate, 0.5 percent of organic silicon defoamer, 1 percent of sodium benzoate and deionized water are used for supplementing the rest.
The preparation method comprises the following steps: the active ingredients, the auxiliary agents and the water are subjected to high-shear shearing, mixing and stirring uniformly according to the proportion, then are subjected to sanding for 2.5 hours by a sanding machine to enable the average particle size to reach 1-5 microns, and finally the thickening agent and the preservative film-forming agent are added to continue to be sheared and stirred uniformly, so that the seed treatment suspending agent can be obtained.
Preparation example 2: 24% bronopol-penflufen seed treatment suspending agent (1:3)
According to the weight percentage, 6 percent of bronopol, 18 percent of penflufen, 4 percent of tristyrylphenol polyoxyethylene ether polyoxypropylene ether, 3 percent of styrylphenol polyoxyethylene ether phosphate ester salt, 2 percent of sodium polycarboxylate, 1 percent of polyacrylic acid, 0.2 percent of xanthan gum, 1 percent of magnesium aluminum silicate, 5 percent of glycerol, 5 percent of rose bengal pigment, 1 percent of methyl p-hydroxybenzoate, 0.5 percent of organosilicon defoamer and deionized water are added for the rest.
The preparation method comprises the following steps: the same as in preparation example 1.
Preparation example 3: 30% bronopol-fluxapyroxad aniline seed treatment suspending agent (5:1)
According to the weight percentage, 25 percent of bronopol, 5 percent of penflufen, 4 percent of fatty alcohol-polyoxyethylene ether, 5 percent of glycerin fatty acid ester polyoxyethylene ether phosphate, 2 percent of sodium polycarboxylate, 0.2 percent of xanthan gum, 5 percent of rose bengal pigment, 2 percent of sodium carboxymethyl starch, 5 percent of propylene glycol, 0.5 percent of organic silicon defoaming agent, 2 percent of sodium sorbate and deionized water are added for the rest.
The preparation method comprises the following steps: the same as in preparation example 1.
Preparation example 4: 28% Denitritol-Fluxapyroxad seed treatment suspending agent (3:1)
According to the weight percentage, 21 percent of bronopol, 7 percent of fluxapyroxad, 3 percent of isomeric tridecanol polyoxyethylene ether, 3 percent of alkylphenol polyoxyethylene ether phosphate, 2 percent of sodium polycarboxylate, 1 percent of polyacrylic acid, 0.2 percent of xanthan gum, 4 percent of rose bengal pigment, 5 percent of propylene glycol, 1 percent of magnesium aluminum silicate, 3 percent of sodium benzoate, 0.5 percent of organic silicon defoamer and deionized water are added for the rest.
The preparation method comprises the following steps: the same as in preparation example 1.
Preparation example 5: 30% seed treatment suspending agent of bronopol-fluxapyroxad (1:1)
According to the weight percentage, 15 percent of bronopol, 15 percent of fluxapyroxad, 2 percent of fatty alcohol-polyoxyethylene ether, 3 percent of alkylphenol polyoxyethylene phosphate, 3 percent of naphthalenesulfonate formaldehyde condensate, 2 percent of polyvinyl alcohol, 0.3 percent of xanthan gum, 5 percent of rose bengal pigment, 4 percent of glycol, 1.5 percent of magnesium aluminum silicate, 0.5 percent of organosilicon antifoaming agent, 0.1 percent of karson and deionized water are added for the rest.
The preparation method comprises the following steps: the same as in preparation example 1.
Preparation example 6: 32% Denitritol-Fluxapyroxad seed treatment suspending agent (7:1)
According to the weight percentage, 28 percent of bronopol, 4 percent of fluxapyroxad, 4 percent of isomeric tridecanol polyoxyethylene ether, 3 percent of EO/PO block copolymer, 3 percent of glycerin fatty acid ester polyoxyethylene ether phosphate, 3 percent of sodium lignosulfonate, 2 percent of sodium carboxymethylcellulose, 5 percent of glycerol, 0.3 percent of xanthan gum, 1.5 percent of magnesium aluminum silicate, 0.5 percent of organosilicon defoamer, 6 percent of rose pigment, 1 percent of potassium benzoate and the balance of deionized water.
The preparation method comprises the following steps: the same as in preparation example 1.
Preparation example 7: 20% bronopol-fluxapyroxad suspension (1:1)
According to the weight percentage, the balance of the composition is 10 percent of bronopol, 10 percent of fluxapyroxad hydroxylamine, 2 percent of sodium dodecyl sulfate, 1 percent of alkylphenol polyoxyethylene, 3 percent of styrol polyoxyethylene ether phosphate, 0.2 percent of xanthan gum, 1 percent of magnesium aluminum silicate, 3 percent of ethylene glycol, 1 percent of sodium benzoate, 0.5 percent of silicone oil and deionized water.
The preparation method comprises the following steps: according to the formula proportion, the active ingredients, the surfactant and other functional additives are sequentially placed in a reaction kettle, water is added for uniform mixing, and the suspending agent product is obtained through high-speed shearing, wet sanding and finally homogeneous filtration.
Preparation example 8: 36% bronopol-fluxapyroxad water dispersible granule (3:1)
27 percent of bronopol, 9 percent of fluxapyroxad, 8 percent of sodium lignosulfonate, 6 percent of naphthalenesulfonate formaldehyde condensate, 3 percent of nekal BX, 5 percent of white sugar and kaolin which are calculated according to the weight percentage and make up the rest.
The preparation method comprises the following steps: adding an active ingredient into a carrier according to the formula proportion of an embodiment, adding a surfactant and other functional auxiliaries, mixing, performing jet milling, adding 10-25% of water, kneading, granulating, drying and screening to obtain a water dispersible granule product; or spraying water to the pulverized powder in a boiling granulator, granulating, drying, and sieving to obtain the final product.
Preparation example 9: wettable powder of 48% bronopol-fluxapyroxad (1:5)
According to the weight percentage, 8 percent of bronopol, 40 percent of fluxapyroxad, 12 percent of naphthalenesulfonate formaldehyde condensate, 3 percent of calcium lignosulfonate, 2 percent of sodium dodecyl sulfate and kaolin are used for supplementing the rest.
The preparation method comprises the following steps: according to the formula proportion, the active ingredients, the dispersing agent, the wetting agent and the filler are mixed, evenly stirred in a stirring kettle, and are smashed and evenly mixed for many times by a jet mill, so that the wettable powder of the composition can be prepared.
Preparation example 10: 30% bronopol-isopyrazam suspending agent (1:3)
According to the weight percentage, 7.5 percent of bronopol, 22.5 percent of pyrazolonaphthalein, 2 percent of fatty alcohol-polyoxyethylene ether, 3 percent of alkylphenol polyoxyethylene phosphate, 2 percent of sodium lignosulfonate, 0.3 percent of xanthan gum, 1.5 percent of magnesium aluminum silicate, 5 percent of propylene glycol, 0.5 percent of silicone oil, 0.01 percent of benzisothiazolinone potassium and deionized water are added for the rest.
The preparation method comprises the following steps: the same as in preparation example 7.
Preparation example 11: 32% bronopol-isopyrazam water dispersible granule (1:1)
The composition comprises, by weight, 16% of bronopol, 16% of isopyrazam, 3% of sodium dodecyl sulfate, 6% of sodium lignin sulfonate, 10% of naphthalene sulfonate formaldehyde condensate, 10% of ammonium sulfate and starch, and the balance of the composition.
The preparation method comprises the following steps: the same as in preparation example 8.
Preparation example 12: 44% bronopol-isopyrazam wettable powder (1:10)
The balance of the components are 4 percent of bronopol, 40 percent of isopyrazam, 3 percent of sodium polycarboxylate, 4 percent of sodium lignosulfonate, 6 percent of dispersant NNO, 3 percent of sodium dodecyl sulfate and kaolin in percentage by weight.
The preparation method comprises the following steps: the same as in preparation example 9.
Indoor activity measurement test:
example 1: indoor activity determination test of combination of bronopol and fluconazole hydroxylamine or fluconazole aniline on rice bakanae disease
The test basis is as follows: the test refers to NY/T1156.2-2006 agricultural industry Standard "pesticide indoor bioassay test criteria fungicide part 2 of the national agricultural standards of the people's republic of China: the plate method of the experiment for inhibiting the growth of pathogenic bacteria hypha.
Test strains: fusarium moniliforme (Fusarium moniliforme) was supplied by Shenyang chemical research institute.
An instrument device: the device comprises an autoclave, a superclean bench, an incubator, an electric heating blowing drying box, a ten-thousandth electronic balance, a pipettor, an alcohol lamp, a beaker (50mL), a volumetric flask, a triangular flask (100mL), a culture dish (phi 9cm), a puncher (phi 0.6cm), an inoculator, a ruler and the like.
Test target culture conditions: transferring Fusarium moniliforme stored in an indoor refrigerator at 4 ℃ onto a potato glucose agar culture medium, placing the Fusarium moniliforme in an incubator at 25 ℃ for dark culture for 5 days, and activating the Fusarium moniliforme for later use.
Reagent to be tested: 95 percent of bronopol technical, 98 percent of fluxapyroxad technical and 95 percent of fluxafen technical, which are provided by the research and development center of the Heliel pharmaceutical industry group.
Other reagents: acetone (analytical grade), tween 80 (chemical grade).
Preparing a medicament mother solution: dissolving the raw materials with acetone to obtain high-concentration mother liquor, diluting with 0.1% Tween 80 aqueous solution, preparing single mother liquor, and mixing to obtain required serial mass concentrations.
The test was repeated: the test agent was tested in 4 dishes per concentration, 1 dish per replicate, 4 replicates, and a blank of 0.1% tween 80 in water without agent.
Medicament treatment: under the aseptic operation condition, 5mL of liquid medicine with different concentrations is respectively added into a sterilized triangular flask which is calibrated accurately in advance by a liquid transfer device, then a culture medium which is melted and cooled to the appropriate temperature is added into the triangular flask, the mixture is fully shaken up and poured into 4 culture dishes in equal amount, and the PDA plate containing the medicine with the corresponding concentration is prepared.
Inoculation: cutting off cake from the edge of bacterial colony by a sterilized perforator under aseptic condition, inoculating the cake to the center of the medicated plate by an inoculator, covering with a pileus, and culturing in dark at 25 deg.C in a constant temperature incubator.
Data investigation: according to the control treatment, when the colony grows to 2/3-4/5 of the diameter of the culture dish, the experimental investigation is carried out. The colony diameters (cm) were measured with a ruler, and the diameter was measured once for each colony by the cross method, and the average was taken.
Data statistics and analysis: according to the investigation result, the hypha growth inhibition rate of each treatment concentration on the test target bacteria is calculated, and the two decimal places are reserved in the unit of percentage (%) calculation result.
D=D1-D2
In the formula:
d-colony growing diameter;
D1-colony diameter;
D2-cake diameter.
Figure BDA0003653515890000081
In the formula:
i-hypha growth inhibition rate;
D0-growing the diameter of the blank colony;
DTmedicament-treated colonies grow in diameter.
And processing the data by adopting a method of analyzing a few rate value. Statistical analysis system using IBM SPSS Statistics 20Systematic analysis to obtain virulence regression line and EC50Value and correlation coefficient R2The activity of the test agent on the biological sample is evaluated.
Sun Yupei method: evaluating the synergistic effect of the mixed medicament according to the co-toxicity coefficient (CTC), wherein the compounded co-toxicity coefficient (CTC) is more than or equal to 120 and shows the synergistic effect; CTC is less than or equal to 80 and shows antagonism; 80 < CTC < 120 showed additive effects.
Co-toxicity coefficient (CTC value) calculation of the blend:
Figure BDA0003653515890000082
in the formula:
ATI-actually measured toxicity index of mixed agent;
S-EC of Standard drug50In milligrams per liter (mg/L);
EC of M-mixtures50In milligrams per liter (mg/L).
TTI=TIA*PA+TIB*PB
In the formula:
TTI-mixture theory virulence index;
TIA-agent virulence index a;
PA-the percentage of agent a in the mixture in percent (%);
TIB-agent B virulence index;
PB-the percentage of the agent B in the mixture in percent (%).
Figure BDA0003653515890000083
In the formula:
CTC-co-toxicity coefficient;
ATI-measured virulence index of the mixture;
TTI-mixture theory virulence index.
The results of the tests are given in the following table:
TABLE 1 indoor Activity test results of combination of bronopol and penflufen for Rice bakanae disease
Figure BDA0003653515890000091
TABLE 2 indoor activity test results of combination of bronopol and fluxapyroxad for rice bakanae disease
Figure BDA0003653515890000092
As can be seen from the indoor activity tests in tables 1 and 2, the combination of the bronopol and either the fluconazole hydroxylamine or the fluconazole aniline shows good prevention and treatment effects on the bakanae disease of rice.
As can be seen from the test results in Table 1, the test agents bronopol and penflufen have good control effect on rice bakanae disease bacteria, and the EC thereof50The synergistic agent is respectively 4.628mg/L and 5.344mg/L, the mass ratio of the bronopol to the penflufen is 1: 35-35: 1, the cotoxicity coefficient is more than 120, and the synergistic agent has a synergistic effect on the rice bakanae disease, wherein the cotoxicity coefficient is the largest when the bronopol and the penflufen are compounded according to the mass ratio of 1:1, and the synergistic effect is the most remarkable.
As can be seen from the test results in Table 2, the test agent, fluxapyroxad, has high toxicity to rice bakanae disease, EC500.053mg/L, compounding the bronopol and the fluxapyroxad in a mass ratio of 1: 35-35: 1, wherein the cotoxicity coefficient is more than 80, the bronopol and the fluxapyroxad have different additive or synergistic effects on the rice bakanae disease, the mass ratio of the bronopol to the fluxad is 1: 15-25: 1, the cotoxicity coefficient is more than 120, and the synergistic effect on the rice bakanae disease is shown.
Example 2: indoor activity determination test for wheat scab by compounding of bronopol and fluxapyroxad or isopyrazam
The test basis is as follows: the test refers to NY/T1156.2-2006 agricultural industry Standard "pesticide indoor bioassay test criteria fungicide part 2 of the national agricultural standards of the people's republic of China: experiment plate method for inhibiting the growth of hypha of pathogenic bacteria.
Test targets: fusarium graminearum (Fusarium graminearum), harvested from wheat test field disease plants at Shandong university of agriculture, was isolated, identified and stored by the laboratory at Shandong university of agriculture.
The instrument equipment comprises: a moist heat sterilization pot, an ultra-clean workbench, a constant-temperature illumination incubator, an electric heating drum windproof drying box, a one-ten-thousandth electronic balance, a liquid-transferring gun, an alcohol lamp, a small beaker, a volumetric flask, a triangular flask, a culture dish (phi 9cm), a puncher, an inoculator (phi 0.6cm), a ruler and the like.
Test target culture conditions: fusarium graminearum stored at 4 ℃ in an indoor refrigerator is transferred onto a potato glucose agar culture medium, and is activated after being placed in an incubator at 26 ℃ for dark culture for 4 days for later use.
Reagent to be tested: 95 percent of bronopol technical, 98 percent of fluxapyroxad technical and 92 percent of isopyrazam technical, which are provided by the research and development center of the Heliel pharmaceutical industry group.
Other reagents: acetone (analytical grade), emulsifier Tween 80 (chemical grade).
Preparing a medicament mother solution: dissolving the raw materials with acetone to obtain high-concentration mother liquor, diluting with 0.1% Tween 80 aqueous solution, preparing single mother liquor, and mixing to obtain required serial mass concentrations.
The test was repeated: the test agent was applied to 4 dishes at each concentration, 1 dish for each replicate, 4 replicates, and a blank of 0.1% aqueous tween 80 without agent.
Treating a medicament: under the aseptic operation condition, quantitatively adding the pre-melted and sterilized PDA culture medium into an aseptic conical flask according to the test treatment, sequentially and quantitatively sucking 10mL of each prepared treatment liquid medicine from low concentration to high concentration, respectively adding into the conical flasks, fully shaking up, and then pouring into 4 culture dishes with the diameter of 9cm in equal amount to prepare the medicine-containing flat plates with corresponding concentrations. The test setup was blank with 0.1% tween 80 in water without addition of agent, 4 replicates per treatment.
Inoculation: cutting off the bacterial cake from the edge of bacterial colony by a sterilization puncher under aseptic condition, inoculating the bacterial cake to the center of a medicine-containing flat plate by an inoculator, covering with a pileus, and placing in a constant-temperature light incubator at 26 ℃ for dark culture.
Data investigation: and (5) investigating the growth condition of the hyphae of the pathogenic bacteria according to the growth condition of the hyphae in a blank control culture dish. The colony diameters were measured in centimeters (cm) with a ruler, the diameter was measured once for each colony using the cross method, the average was taken, and the raw data for all replicates of each treatment was recorded.
Data statistics and analysis: according to the investigation result, the hypha growth inhibition rate of each treatment concentration on the test target bacteria is calculated, and the two decimal places are reserved in the unit of percentage (%) calculation result.
D=D1-D2
In the formula:
d-colony growth diameter;
D1-colony diameter;
D2-cake diameter.
Figure BDA0003653515890000111
In the formula:
i-hypha growth inhibition rate;
D0-growing the diameter of the blank colony;
DTmedicament-treated colonies grow in diameter.
And processing the data by adopting a method of analyzing a few values. Analyzing by IBM SPSS Statistics 20 statistical analysis system to obtain virulence regression line and EC50Value and correlation coefficient R2The activity of the test agent on the biological sample is evaluated.
Sun Yunpei law: evaluating the synergistic action of the mixed medicament according to the co-toxicity coefficient (CTC), wherein the compounded co-toxicity coefficient (CTC) is more than or equal to 120, and the synergistic action is shown; CTC is less than or equal to 80 and shows antagonism; 80 < CTC < 120 shows additive effects.
Co-toxicity coefficient (CTC value) calculation of the blend:
Figure BDA0003653515890000112
in the formula:
ATI-measured virulence index of the mixture;
S-EC of Standard drug50In milligrams per liter (mg/L);
EC of M-mixtures50Units are milligrams per liter (mg/L).
TTI=TIA*PA+TIB*PB
In the formula:
TTI-mixture theory virulence index;
TIA-agent virulence index a;
PA-the percentage of agent a in the mixture in units of percentage (%);
TIB-agent B virulence index;
PB-the percentage of the agent B in the mixture is given in percentage (%).
Figure BDA0003653515890000121
In the formula:
CTC-co-toxicity coefficient;
ATI-measured virulence index of the mixture;
TTI-mixture theory virulence index.
The results of the tests are given in the following table:
TABLE 3 indoor activity test results of the compound pairing of bronopol and fluxapyroxad for wheat scab
Figure BDA0003653515890000122
TABLE 4 indoor activity test results of combination of bronopol and isopyrazam for wheat scab
Figure BDA0003653515890000131
As can be seen from the indoor activity tests in tables 3 and 4, the combination of the bronopol and either the pyraclostrobin or the isopyrazam has good control effect on the wheat scab.
As can be seen from the test results in Table 3, the tested agent, fluxapyroxad, has a good control effect on wheat scab germs and its EC50The mass ratio of the bronopol to the fluxapyroxad is 0.079mg/L, the cotoxicity coefficient of the bronopol to the fluxapyroxad is more than 120 within the range of 1: 35-35: 1, and the synergistic effect on wheat scab is achieved, wherein the cotoxicity coefficient is the largest when the bronopol and the fluxapyroxad are compounded according to the mass ratio of 1:1, and the synergistic effect is the most remarkable.
As can be seen from the test results in Table 4, the bronopol and isopyrazam as the test agents have good control effect on wheat scab, and EC506.572mg/L and 4.221mg/L respectively, the bronopol and the isopyrazam are compounded, the mass ratio is within the range of 1: 30-30: 1, the cotoxicity coefficient is more than 120, and the bactericidal composition has a synergistic effect on wheat scab.
And (3) field efficacy test:
example 3: field efficacy test of compound preparation for preventing and treating rice bakanae disease
The test basis is as follows: the test refers to GB/T17980.104-2004' pesticide field efficacy test criteria (second) part 104: the bactericide can be used for preventing and treating rice bakanae disease.
Test targets: bakanae disease of rice.
Test crops: rice (Hubei No. 17).
Test site: bailian river county of Luo Tian city of Huanggang, Hubei province. The rice bakanae disease is a disease frequently occurring in the rice production in the area, and the rice bakanae disease in the test field in 2018 slightly occurs. The soil of the test field is submerged rice soil, the pH value is 5.5, the content of organic matters is 1.5 percent, and the soil fertility is medium.
And (3) water and fertilizer management of a test field: before transplanting rice (5 months and 8 days), 50kg of 30 percent (15-7-8) of compound fertilizer in each area is applied as base fertilizer, 12kg of 46.4 percent urea is applied as additional fertilizer in each area in 5 months and 17 days, and 6kg of 46.4 percent urea is applied in each area in 7 months and 1 day as second additional fertilizer.
Weather data: the weather of 3 months and 31 days of 2019 years is cloudy, the temperature is 5-19 ℃, and severe weather influencing the test result does not appear in the test period.
Cell arrangement: the treatment of the test, control and blank cells was performed in a randomized block array.
Area of the cell: area of each test cell is 24m2Guard rows are set between cells, and each process is repeated 4 times.
The dosage of the medicament is as follows: the test agents and the dosages are shown in the following table:
TABLE 4 field test of pesticide for bakanae disease of rice and its dosage
Number of Name of medicament The dosage of effective components (g/100kg seed)
1 30% bronopol-fluxapyroxad aniline seed treatment suspending agent (1:1) 50
2 32% seed treatment suspending agent of bronopol-fluxapyroxad (7:1) 50
3 28% seed treatment suspending agent of bronopol-fluxapyroxad (3:1) 50
4 24% bronopol-penflufen seed treatment suspending agent (1:3) 50
5 200 g/l of fluxapyroxad suspension 100
6 22.4% penflufen seed treatment suspending agent 60
7 20% bronopol wettable powder 85
8 Blank control -
The application method comprises the following steps: coating is carried out before the rice is sowed. Weighing each treated seed according to the mu seed amount, filling the seed into a sealing bag for later use, fully stirring each treated liquid medicine and the seed according to a test scheme until the liquid medicine is uniformly distributed on the surface of the seed, and sowing the seeds after drying.
Sowing: 4 disks (55cm by 25cm) are sowed in each plot of the seedbed, the seedbed is placed in different directions of the plot, and about 3900 seeds are sowed in each disk for the investigation of the emergence rate.
The application time and the application frequency are as follows: seed coating was carried out 3 months and 31 days in 2019, and the application was 1 time in total.
And (3) test investigation: totally performing 3 times of investigation, investigating seedling emergence time and seedling emergence rate when seedling emergence is carried out on a seedbed for the first time, investigating 4 disks of rice sowed at fixed points in each cell, and investigating 1/2 disks in each disk; investigating the disease rate before transplanting rice seedlings for the second time, sampling at 5 points in each cell, investigating 100 plants at each point, investigating the number of diseased plants and the total number of plants treated each time, and calculating the control effect; the third survey is to survey the disease occurrence before rice heading, 5 points are sampled in each cell, 20 clumps are measured in each point, the number of the disease occurrence plants and the total number of the plants in each treatment are surveyed, and the control effect is calculated.
Safety investigation: after the test, field observation is carried out, the rice in each reagent treatment area grows normally and basically consistent with that in the blank control area, and all the test reagents have no phytotoxicity conditions and adverse effects on the rice, such as growth blockage, green loss, deformity and the like. Compared with the blank control, no effect of each treatment agent on other target organisms was observed.
The drug effect calculation method comprises the following steps:
Figure BDA0003653515890000141
Figure BDA0003653515890000151
Figure BDA0003653515890000152
the results of the tests are given in the following table:
table 5 results of field efficacy test of compound preparation for preventing and treating bakanae disease of rice
Figure BDA0003653515890000153
The drug effect of the field test is analyzed: the rice seeds are coated by the compound preparation, and the emergence rate of each treatment of the test agent is basically consistent with that of a contrast treatment or even superior to that of the contrast treatment according to the emergence rate survey result. Before transplanting rice seedlings, investigating the disease rate of rice, wherein the average disease rate of blank control treatment reaches 8.50%, and the control effect of the compound preparation is higher than 84.12%; the investigation result of the control effect before the heading of rice shows that the control effect of the compound preparation on the bakanae disease of rice is between 84.71 and 94.76 percent and is superior to that of a single-dose control.
Example 4: compound preparation field efficacy test for preventing and treating wheat scab
The test basis is as follows: the test refers to NY/T1464.15-2007 part 15 of the pesticide field efficacy test guidelines: the bactericide can be used for preventing and treating wheat scab.
Test targets: wheat scab.
And (3) test crops: wheat (jimai 22).
Test site: in a field where rice and wheat rotation is carried out for years in Shandong Jining City, Fish platform county, Zhang Huang Zhen Tountun village, the rice and wheat scab is serious all the year round, the seed consumption per mu is 20kg, the soil of a test field is clay loam, the soil fertility is medium, the cultivation conditions of all test districts are consistent, and the good agricultural standard of the local area is met.
Arrangement of test cells: the treatment of the test, control and blank cells was performed in a random block arrangement with a cell area of 20m2Each treatment was repeated 4 times.
The dosage of the medicament: the test agents and dosages are shown in the following table:
TABLE 6 wheat scab field test reagent and dosage
Figure BDA0003653515890000154
Figure BDA0003653515890000161
The application time is as follows: the test is that the pesticide is applied for 1 time in the wheat flowering phase, and the whole plant is sprayed by a Linong HD-400 type knapsack sprayer, so that the fog drops are uniformly distributed. The amount of the liquid medicine applied per mu is 35 kg.
Investigation method and investigation time: and performing control effect investigation once 15 days after application (at the wheat milk stage), sampling 5 points of each cell diagonal line during investigation, investigating 100 spikes at each point, grading by percentage of the area of the withered spikes to the whole spike area, and recording the number of diseased spikes and the total number of spikes at each level.
Wheat scab grading standard:
level 0: the whole ear is disease-free;
stage 1: the withered spike area accounts for less than 1/4 of the whole spike area;
and 3, level: the withered spike area accounts for 1/4-1/2 of the whole spike area;
and 5, stage: the withered spike area accounts for 1/2-3/4 of the whole spike area;
and 7, stage: the area of the withered spike accounts for more than 3/4 of the area of the whole spike.
The drug effect calculation method comprises the following steps:
Figure BDA0003653515890000162
Figure BDA0003653515890000163
the results of the tests are given in the following table:
table 5 field efficacy test results of the compounded preparation against wheat scab
Figure BDA0003653515890000164
Figure BDA0003653515890000171
The field efficacy results show that the combination of the bronopol and the fluxapyroxad or the isopyrazam has better control effect on the wheat scab, the total control effect of each compound preparation treatment is over 86.25 percent, and the control effect is superior to that of a blank control treatment group with a single control agent.
As can be seen from indoor toxicity tests and field efficacy tests, the bactericidal composition containing the bronopol has good control effect on fusarium pathogenic bacteria, is safe to crops, delays the generation of drug resistance of the pathogenic bacteria, reduces the dosage of the pesticide and reduces the pesticide residue of agricultural products.
Although the invention has been described in detail with respect to the general description and the specific embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto without departing from the spirit of the invention.

Claims (10)

1. The bactericidal composition containing the bronopol is characterized by comprising an active ingredient A and an active ingredient B, wherein the active ingredient A is the bronopol, the active ingredient B is selected from any one of the fluxapyroxad, the isopyrazam or the fluxapyroxad, and the mass ratio of the active ingredient A to the active ingredient B is 1: 35-35: 1.
2. The bactericidal composition according to claim 1, wherein the active ingredient B is penflufen, and the mass ratio of the active ingredient A to the active ingredient B is 1: 30-30: 1, preferably 1: 15-20: 1.
3. The bactericidal composition according to claim 1, wherein the active ingredient B is isopyrazam, and the mass ratio of the active ingredient A to the active ingredient B is 1: 30-30: 1, preferably 1: 20-30: 1.
4. The bactericidal composition according to claim 1, wherein the active ingredient B is penflufen, and the mass ratio of the active ingredient A to the active ingredient B is 1: 25-25: 1, preferably 1: 15-25: 1.
5. The bactericidal composition of claim 1, wherein the total weight of the bactericidal composition is 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.
6. The bactericidal composition of claim 1, wherein the bactericidal composition further comprises other auxiliary ingredients in addition to the active ingredient, and the auxiliary ingredients are selected from one or more of a wetting agent, a dispersing agent, an emulsifier, a thickener, a disintegrant, an antifreeze, an antifoaming agent, a solvent, a preservative, a stabilizer, a warning color, a film forming agent, a synergist and a carrier.
7. The bactericidal composition according to claim 1, wherein the bactericidal composition can be prepared into any agriculturally acceptable preparation form, and the preparation form is a solid preparation, a liquid preparation and/or a seed treatment preparation;
the solid preparation comprises powder, granules, pellets, tablets, bars, wettable powder, oil dispersible powder, emulsion powder, water dispersible granules, emulsion granules, water dispersible tablets, soluble powder, soluble tablets or soluble granules;
the liquid preparation comprises a soluble agent, a soluble colloid agent, an oil agent, a spreading oil agent, missible oil, latex, a dispersible agent, an ointment, an aqueous emulsion, an oil emulsion, a microemulsion, a fatliquor suspending agent, a microcapsule suspending agent, an oil suspending agent, a dispersible oil suspending agent, a suspoemulsion, a microcapsule suspension-suspending agent, a microcapsule suspension-aqueous emulsion or a microcapsule suspension-suspoemulsion;
the seed treatment preparation comprises a seed treatment dry powder agent, a seed treatment dispersible powder agent, a seed treatment liquid agent, a seed treatment emulsion or a seed treatment suspending agent;
preferably, the solid preparation is water dispersible granules and/or wettable powder, the liquid preparation is a suspending agent, and the seed treatment preparation is a seed treatment suspending agent.
8. Use of the fungicidal composition according to any one of claims 1 to 7 and/or its preparation for the prevention or control of crop pathogens.
9. Use according to claim 8, wherein the crop is selected from food crops, cash crops, fruits and vegetables and/or lawn garden crops;
the pathogenic bacteria are Fusarium (Fusarium) pathogenic bacteria, and the Fusarium pathogenic bacteria comprise Fusarium oxysporum, Fusarium semicarpium, Fusarium proliferatum, Fusarium equiseti, Fusarium verticillium, Fusarium graminearum and Fusarium moniliforme;
preferably, the Fusarium pathogenic bacteria are selected from Fusarium graminearum (Fusarium graminearum) and Fusarium moniliforme (Fusarium moniliforme).
10. A method of preventing and controlling pathogenic bacteria in crops, characterised in that an effective and substantially non-phytotoxic application rate of the fungicidal composition and/or formulation thereof is applied to the plant, plant propagation material and plant organs, cultivation media, materials or spaces that grow at a time by seed treatment, foliar application, stem application, drenching, dripping, pouring, spraying, dusting, scattering or fuming.
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CN108112593A (en) * 2016-11-28 2018-06-05 陕西美邦农药有限公司 A kind of bactericidal composition containing bronopol
CN113163762A (en) * 2018-09-27 2021-07-23 0903608Bc有限公司 Synergistic pesticidal compositions for delivery of pesticidal active ingredients and methods thereof
CN114391538A (en) * 2022-03-11 2022-04-26 顺毅股份有限公司 Bactericidal composition containing bronopol

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102781233A (en) * 2010-03-04 2012-11-14 巴斯夫欧洲公司 Synergistic fungicidal mixtures
CN108112593A (en) * 2016-11-28 2018-06-05 陕西美邦农药有限公司 A kind of bactericidal composition containing bronopol
CN107494568A (en) * 2017-08-14 2017-12-22 河北省农林科学院植物保护研究所 Prevent and treat compound synergistic bactericidal composition and its application of tomato and pear tree Major Diseases
CN107926958A (en) * 2017-12-13 2018-04-20 江西中迅农化有限公司 Sterilization group composition
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