CN114766492A - Pesticide composition containing bixafen and application thereof - Google Patents

Pesticide composition containing bixafen and application thereof Download PDF

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Publication number
CN114766492A
CN114766492A CN202210357686.4A CN202210357686A CN114766492A CN 114766492 A CN114766492 A CN 114766492A CN 202210357686 A CN202210357686 A CN 202210357686A CN 114766492 A CN114766492 A CN 114766492A
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active ingredient
bixafen
pesticide composition
test
mass ratio
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CN114766492B (en
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葛家成
隋书婷
杨志鹏
张永芳
王玉
张凯莉
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Qingdao Hengning Biotechnology Co ltd
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Qingdao Hengning 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
    • 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
    • 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
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • 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
    • A01N43/541,3-Diazines; Hydrogenated 1,3-diazines
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The pesticide composition comprises an active ingredient A and an active ingredient B, the mass ratio of the active ingredient A to the active ingredient B is 1: 30-30: 1, the active ingredient A is Bixafen, and the active ingredient B is any one of fludioxonil or bupirimate. The pesticide composition improves the control efficiency on pathogenic bacteria, reduces the dosage of effective components, reduces the resistance risk and prolongs the service life of the pesticide.

Description

Pesticide composition containing bixafen and application thereof
Technical Field
The invention belongs to the technical field of pesticide sterilization, and particularly relates to a pesticide composition containing bixafen and application thereof.
Background
Bixafen, international common name: bixafen, chemical name: n- (3 ', 4 ' -dichloro-5-fluoro [1,1 ' -biphenyl ] -2-yl) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, CAS accession No.: 581809-46-3. Bixafen is a pyrazole amide succinate dehydrogenase inhibitor developed by Bayer company, inhibits the functions of mitochondria, prevents the generation of energy, inhibits the growth of pathogenic bacteria and finally causes the death of the mitochondria by interfering succinate dehydrogenase on a complex II in a respiratory electron transfer chain of the pathogenic bacteria mitochondria. Bixafen is a systemic fungicide, has a wide bactericidal spectrum and is specially used for foliar spray.
Bupirimate, international common name: bupirimate, CAS accession number: 41483-43-6. Bupirimate is a new generation systemic fungicide, belongs to an adenine nucleoside deaminase inhibitor, has the functions of protection and treatment, can be quickly absorbed by roots, stems and leaves, can be transported to each part in plants, has the functions of protection and treatment, has special effect on powdery mildew of crops, and is used for preventing and treating powdery mildew of ornamental plants such as fruits, vegetables and flowers and field crops. Bupirimate belongs to bupirimate compounds, is an upgraded substitute of bupirimate, and has the characteristics of high efficiency, low toxicity, good environmental compatibility and the like.
Fludioxonil, international common name: fludioxonil, CAS accession No.: 131341-86-1, chemical name: 4- (2, 2-difluoro-1, 3-benzodioxo-4-yl) pyrrole-3-carbonitrile. Fludioxonil is a bactericide developed and produced by Nowa company, and has the action mechanism of inhibiting protein kinase PK-III (kinase PK-III) with a signal effect in an osmotic induction transmission process, so that the concentration of non-phosphorylation regulating protein is increased, further, the secretion of activated protease of an osmotic sensitive cell splitting agent is abnormal, and finally, germs die. Because of the unique action mechanism, the compound has no cross resistance with the existing bactericide, and is a pyrrole bactericide with great development prospect. It is used in seed treatment, can prevent and control seed bacteria and produce cross resistance with other bactericide, and belongs to the field of contact bactericide.
Pathogenic bacteria easily generate drug resistance to bactericides with single site, and the drug resistance can be delayed by compounding the bactericide. In order to improve the killing effect on pathogenic bacteria, two effective components with different action mechanisms are compounded, and multiple target sites act on pathogenic microorganisms to achieve the effect of preventing diseases, so that the dosage of the effective components is reduced, the resistance risk is reduced, and the service life of the medicament is prolonged.
Disclosure of Invention
Based on the situation, the invention aims to provide a pesticide composition containing bixafen, which is effective on various target pathogenic bacteria, can obviously enhance the pesticide effect, reduce the dosage of effective components, reduce the resistance risk and prolong the service life of a pesticide, and particularly has obvious effect on powdery mildew, gray mold and southern blight.
In order to achieve the purpose, the invention adopts the following technical scheme: a pesticide composition containing bixafen and application thereof comprise an active ingredient A and an active ingredient B, wherein the mass ratio of the active ingredient A to the active ingredient B is 1: 30-30: 1;
further, the active ingredient A is bixafen, and the active ingredient B is any one of fludioxonil or bupirimate;
further, the active ingredient B is bupirimate, and the mass ratio of the active ingredient A to the active ingredient B is 1: 10-15: 1;
further, the mass ratio of the active ingredient A to the active ingredient B is 1: 10-10: 1;
further, the mass ratio of the active ingredient A to the active ingredient B is 1:10, 1:5, 1:1, 5:1 and 10: 1;
further, the mass ratio of the active ingredient A to the active ingredient B is 1: 5-10: 1;
further, the mass ratio of the active component A to the active component B is 1:5, 1:1, 5:1 and 10: 1;
further, the active ingredient B is fludioxonil, and the mass ratio of the active ingredient A to the active ingredient B is 1: 10-30: 1;
further, the mass ratio of the active ingredient A to the active ingredient B is 1: 3-30: 1;
further, the mass ratio of the active component A to the active component B is 1:3, 1:1, 3:1, 5:1, 6:1, 9:1, 10:1, 13:1, 16:1, 20:1, 30: 1;
further, the mass ratio of the active ingredient A to the active ingredient B is 1: 1-20: 1;
further, the mass ratio of the active component A to the active component B is 1:1, 3:1, 5:1, 6:1, 9:1, 10:1, 13:1, 16:1 and 20: 1;
further, the mass ratio of the active ingredient A to the active ingredient B is 1: 1-13: 1;
further, the mass ratio of the active ingredient A to the active ingredient B is 1:1, 3:1, 5:1, 6:1, 9:1, 10:1 and 13: 1;
further, the sum of the content of the active ingredient A and the active ingredient B in the pesticide composition is 0.5-80 percent based on the total weight of the pesticide composition as 100 percent by weight;
further, the sum of the content of the active ingredient A and the content of the active ingredient B in the pesticide composition is 1 to 60 percent, wherein the total weight of the pesticide composition is 100 percent by weight;
further, the pesticide composition also comprises auxiliary ingredients, wherein the auxiliary ingredients are selected from one or more of wetting agents, dispersing agents, emulsifying agents, thickening agents, disintegrating agents, antifreezing agents, antifoaming agents, solvents, stabilizing agents, penetrating agents and carriers;
further, the wetting agent is selected from one or a mixture of more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, nekal BX, wetting penetrant F, Chinese honeylocust fruit powder, silkworm excrement or soapberry powder;
further, the dispersing agent is selected from one or a mixture of a plurality of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, calcium alkylbenzene sulfonate, naphthalene sulfonic acid formaldehyde condensate sodium salt, alkylphenol polyoxyethylene, fatty amine polyoxyethylene, fatty acid polyoxyethylene or glycerol fatty acid ester polyoxyethylene;
further, the emulsifier is selected from one or a mixture of a plurality of calcium alkyl benzene sulfonate, OP series phosphate (nonylphenol polyoxyethylene ether phosphate), phenylphenol polyoxyethylene ether phosphate, styrene polyoxyethylene ether ammonium sulfate, magnesium salts of alkyl diphenyl ether disulfonate, triethanolamine salts, benzyl dimethyl phenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol polyoxyethylene polypropylene ether, ethylene oxide-propylene oxide block copolymer, OP series (nonylphenol polyoxyethylene ether), castor oil polyoxyethylene ether, alkylaryl polyoxyethylene polyoxypropylene ether, sorbitan monostearate, sorbitan polyoxyethylene ether or fatty alcohol polyoxyethylene ether;
further, the thickening agent is selected from one or more of xanthan gum, polyvinyl alcohol, bentonite, carboxymethyl cellulose or magnesium aluminum silicate;
further, the disintegrating agent is selected from one or more of bentonite, urea, ammonium sulfate, aluminum chloride, low-substituted hydroxypropyl cellulose, lactose, citric acid, succinic acid or sodium bicarbonate;
further, the antifreezing agent is a mixture consisting of one or more of ethylene glycol, propylene glycol, glycerol or urea;
further, the defoaming agent is selected from silicone oil, silicone compounds and C10~C20Saturated fatty acids or C8~C10One or more of fatty alcohol compounds;
further, the solvent is selected from one or a mixture of more of N, N-dimethylformamide, cyclohexanone, butyl ether, xylene, dimethyl sulfoxide, methanol, ethylene glycol, ethanol, propanol, butanol, trimethyl cyclohexanone, N-octyl pyrrolidone, toluene, ethanolamine, triethanolamine, isopropylamine, N-methyl pyrrolidone, diethylene glycol, ethylene glycol methyl ether, ethyl acetate or acetonitrile;
further, the stabilizing agent is selected from one or more of epoxidized soybean oil, epichlorohydrin, BHT, ethyl acetate and triphenyl phosphate;
further, the penetrating agent is selected from one or more of penetrating agent JFC, penetrating agent T, azone or organic silicon;
further, the carrier is one, two or three of a solvent or a filler, and water is preferably deionized water;
further, the filler is selected from one or a mixture of more of kaolin, diatomite, bentonite, attapulgite, white carbon black, starch or light calcium carbonate;
the above substances can be obtained commercially;
the pesticide composition can be prepared into any agriculturally allowable preparation formulation according to the requirement;
further, the preparation dosage 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 fat agent;
the suspension preparation is a suspending agent, a microcapsule suspending agent, an oil suspending agent or a dispersible oil suspending agent;
the multiphase preparation is a suspoemulsion, a microcapsule suspension-suspending agent, a microcapsule suspension-water emulsion or a microcapsule suspension-suspoemulsion;
further, the seed treatment preparation comprises a seed treatment solid preparation or a seed treatment liquid preparation;
furthermore, the seed treatment solid preparation is a seed treatment dry powder agent or a seed treatment dispersible powder agent;
the seed treatment liquid preparation is a seed treatment liquid agent, a seed treatment emulsion or a seed treatment suspending agent;
further, the solid preparation is water dispersible granules, and the liquid preparation is a suspending agent, missible oil and/or an aqueous emulsion.
The invention also discloses application of the pesticide composition containing bixafen in preventing and treating plant diseases.
Further, the plants are economic crops and food crops;
further, the plant diseases comprise southern blight, rust disease, gray mold and powdery mildew, and preferably, the plant diseases comprise southern blight, gray mold and powdery mildew.
Compared with the prior art, the invention has the following advantages:
1) the pesticide composition is compounded by adopting two active ingredients with different action mechanisms, and multiple target sites act on pathogenic microorganisms, so that the disease prevention effect is achieved, the prevention and control effect is enhanced, and the dosage of the active ingredients is reduced;
2) the pesticide composition can prolong the lasting period of the pesticide, reduce the frequency of pesticide application, reduce the resistance risk and prolong the service life of the pesticide.
Detailed Description
To make the technical solutions, objects, and advantages of the present invention more apparent, the present invention is described with the following specific examples, but the present invention may be implemented in various forms and should not be limited by the embodiments set forth herein.
Preparation examples
Preparation example 1: 30% Bixafen-bupirimate emulsion in water (1:5)
According to the weight percentage, 5% of bixafen, 25% of bupirimate, 2% of fatty alcohol-polyoxyethylene ether, 4% of alkylphenol polyoxyethylene phosphate, 2% of styryl phenol polyoxyethylene ether, 22% of cyclohexanone, 0.2% of xanthan gum, 3% of glycerol, 0.1% of sodium benzoate, 0.1% of an organic silicon defoamer and deionized water are used for supplementing the balance.
The preparation method comprises the following steps: according to the formula proportion of the embodiment, a surfactant, an antifreezing agent and water are mixed into a water phase, bixafen and bupirimate are dissolved by a solvent and then added into the water phase under stirring, after uniform stirring, a thickening agent and a preservative are added and continuously sheared for 10min, and then a defoaming agent is added and uniformly stirred to form the O/W type aqueous emulsion.
Preparation example 2: 10% Bixafen-bupirimate emulsion in water (1:1)
According to the weight percentage, 5% of bixafen, 5% of bupirimate, 6% of EO-PO block copolymer, 22% of cyclohexanone, 0.15% of xanthan gum, 4% of propylene glycol, 0.5% of sodium benzoate, 0.1% of organic silicon defoamer and deionized water are added for the balance.
The preparation method comprises the following steps: same as in preparation example 1
Preparation example 3: 30% Bixafen-bupirimate emulsifiable concentrate (5:1)
According to the weight percentage, 25 percent of bixafen, 5 percent of bupirimate, 14 percent of styrylphenol polyoxyethylene ether, 20 percent of N-methyl pyrrolidone, 3 percent of calcium dodecyl benzene sulfonate, 20 percent of propylene carbonate and xylene are added for the rest.
The preparation method comprises the following steps: according to the formula proportion of the embodiment, the measured bixafen, bupirimate, the solvent and the cosolvent are added into a blending kettle to be stirred and dissolved, then the emulsifier is added, the rest solvent is used for complementing the balance, the mixture is stirred uniformly in a stirring kettle, and the missible oil required by the invention is obtained after filtration.
Preparation example 4: 22% Bixafen-bupirimate emulsifiable concentrate (10:1)
According to the weight percentage, 20 percent of bixafen, 2 percent of bupirimate, 10 percent of alkylphenol polyoxyethylene, 20 percent of N-methylpyrrolidone, 4 percent of calcium dodecyl benzene sulfonate, 12 percent of acetophenone and trimethylbenzene are added for the rest.
The preparation method comprises the following steps: the same as in preparation example 3.
Preparation example 5: 20% Bixafen-fludioxonil suspension (3:1)
According to the weight percentage, 15 percent of bixafen, 5 percent of fludioxonil, 2 percent of isomeric alcohol polyoxyethylene ether, 4 percent of alkylphenol polyoxyethylene ether phosphate, 1 percent of sodium polycarboxylate, 0.25 percent of xanthan gum, 5 percent of glycerol, 0.1 percent of sodium benzoate, 0.5 percent of silicone oil and deionized water are added for the rest.
The preparation method comprises the following steps: according to the formula proportion of the embodiment, the measured bixafen, fludioxonil, 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 filtering.
Preparation example 6: 21% Bixafen-fludioxonil suspension (6:1)
According to the weight percentage, 18% of Bixafen, 3% of fludioxonil, 2% of isomeric alcohol polyoxyethylene ether, 2% of alkylaryl polyoxyethylene ether polyoxypropylene ether, 1% of lignosulfonate, 4% of styrol polyoxyethylene ether phosphate, 1% of magnesium aluminum silicate, 0.1% of carboxyethyl cellulose, 1% of sodium sorbate, 5% of ethylene glycol, 0.5% of silicone oil and deionized water are used for making up the balance.
The preparation method comprises the following steps: the same as in preparation example 5.
Preparation example 7: 33% Bixafen-fludioxonil water dispersible granule (10:1)
According to the weight percentage, 30 percent of bixafen, 3 percent of fludioxonil, 12 percent of lignosulfonate, 5 percent of sodium dodecyl benzene sulfonate, 2 percent of naphthalenesulfonate formaldehyde condensate, 30 percent of starch and the balance of kaolin are complemented.
The preparation method comprises the following steps: according to the formula proportion of an embodiment, adding active ingredients of Bixafen and fludioxonil into a carrier, adding a surfactant and other functional auxiliaries, mixing, adding 10-25% of water after airflow crushing, 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 8: 21% Bixafen-fludioxonil water dispersible granule (20:1)
According to the weight percentage, 20 percent of bixafen, 1 percent of fludioxonil, 10 percent of naphthalenesulfonate formaldehyde condensate, 3 percent of sodium polycarboxylate, 3 percent of nekal BX and the balance of kaolin are complemented.
The preparation method comprises the following steps: the same as in preparation example 7.
Indoor activity test:
example 1: indoor combined action test of Bixafen and bupirimate mixed on cucumber powdery mildew
The test basis is as follows: the test refers to NY/T1156.11-2006 part 11 of agricultural chemical indoor bioassay test standard bactericide of the agricultural industry Standard of the people's republic of China: test pot culture method for preventing and treating powdery mildew of cucumber; NY/T1156.6-2006 part 6 of indoor bioassay pesticide test standard of agricultural industry Standard of the people's republic of China bactericide: combined action assay of blending.
Reagent to be tested: 98 percent of Bixafen technical, 97 percent of bupirimate technical, which are provided by the Helil pharmaceutical industry group research and development center.
Test targets: cucumber powdery mildew (Erysiphe cichoracearum);
preparing a test material: and (3) selecting a susceptible cucumber variety (Xintai Mici) for potting, and keeping the seedling growing to 2-4 true leaves for later use.
Spore suspension preparation: washing fresh spores of cucumber leaves with purified water containing small amount of Tween 80 aqueous solution, filtering with double-layer gauze to obtain spores with concentration of 1 x 105spores/mL of suspension were kept ready.
Preparation of the medicament: dissolving the two raw materials with acetone, diluting with 0.1% Tween 80 water solution, and setting to required mass concentration.
Treating a medicament: the agent is uniformly sprayed on the cucumber seedlings for standby by a spraying method until the leaves are completely wetted, and the liquid medicine is naturally dried for standby. The test is blanked with treatment without agent.
Inoculation and culture: inoculating for 24 hours after medicament treatment, spraying the cucumber powdery mildew spore suspension on cucumber seedlings by using an inoculator, culturing for 12 hours under high humidity, and then culturing under the conditions that the temperature is 20-24 ℃, the humidity is 65-75%, and the illumination ratio L: D is 12:12 hours. Each treatment was 3 pots and repeated 4 times.
Data survey: when the blank control disease leaf rate reaches more than 80%, the disease occurrence condition of each treatment is investigated in a grading way, and at least 30 leaves are investigated in each treatment. The following classification method was used:
stage 0: no lesion spots;
level 1: the lesion area accounts for less than 5% of the whole leaf area;
and 3, level: the area of the lesion spots accounts for 5 to 15 percent of the area of the whole leaf;
stage 5: the area of the lesion spots accounts for 15 to 25 percent of the area of the whole leaf;
and 7, stage: the area of the lesion spots accounts for 25 to 50 percent of the area of the whole leaf;
and 9, stage: the area of the lesion spots accounts for 50 to 75 percent of the area of the whole leaf;
stage 11: the area of the lesion spots accounts for more than 75 percent of the area of the whole leaf.
Data statistics and analysis:
and calculating disease indexes and prevention and treatment effects of the treatments according to the survey data.
The disease index is calculated according to the formula (1):
X=[∑(Ni×i)/(N×11)]×100...........................(1)
in the formula:
x-disease index;
Ni-number of leaves of each grade;
i-relative grade value;
n-survey total leaf number.
The prevention and treatment effect is calculated according to the formula (2):
Figure BDA0003583617520000071
in the formula:
p-control effect, unit is percentage%;
CK-blank disease index;
PT-index of disease treated by drug.
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 showed additive effects. The co-toxicity coefficient (CTC value) of the mixture is calculated according to the formulas (3), (4) and (5):
Figure BDA0003583617520000072
in the formula:
ATI-measured virulence index of the mixture;
S-EC of Standard Fungicide50In milligrams per liter (mg/L);
EC of M-mixtures50In milligrams per liter (mg/L).
TTI=TIA*PA+TIB*PB·······(4)
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 BDA0003583617520000081
In the formula:
CTC-co-toxicity coefficient;
ATI-actually measured toxicity index of mixed agent;
TTI-mixture theory virulence index.
DPS data processing software is adopted to calculate test results, and toxicity regression equations and R, EC of single test agent and mixed agents with different proportions are respectively obtained50And 95% confidence limit, and calculating co-toxicity coefficient (CTC) of the two medicaments in different proportions, and screening out the optimal proportion of the test medicament.
The results of the tests are given in the following table:
TABLE 1 indoor Activity test for Bixafen and bupirimate compounding against cucumber powdery mildew
Figure BDA0003583617520000082
As shown in the indoor activity test (see table 1), the single agents of bixafen and bupirimate have the effect of treating cucumber powdery mildew EC504.6892mg/L and 5.6765mg/L respectively, and cucumber powdery mildew is more sensitive to bixafen; the co-toxicity coefficients of bixafen and bupirimate are all larger than 120 after the bixafen and the bupirimate are mixed according to the proportion of 1: 30-30: 1, and the synergistic effect is shown for preventing and treating powdery mildew of cucumber; when the mass ratio of the bixafen to the bupirimate is 1: 10-10: 1, the co-toxicity coefficient after mixing is more than 140, and the synergistic effect is obvious; when the mass ratio of the bixafen to the bupirimate is 1:1, the co-toxicity coefficient of the mixed compound to cucumber powdery mildew is 178.179.
Example 2: indoor combined action test of blending of bixafen and fludioxonil on cucumber gray mold
The test basis is as follows: the test refers to NY/T1156.2-2006 part 2 of agricultural industry Standard pesticide indoor bioassay test Standard germicide of the people's republic of China: the plate method of pathogenic fungus hypha growth inhibition test; NY/T1156.6-2006 Combined action determination of bactericide part 6 of Standard agricultural chemical indoor bioassay test criteria of the people's republic of China.
Reagent to be tested: 98 percent of Bixafen technical and 97 percent of fludioxonil technical, which are provided by the Helil pharmaceutical industry group research and development center.
Pathogenic bacteria to be tested: botrytis cinerea (Botrytis cinerea);
preparing a medicament: the test drug was dissolved in acetone and diluted with 0.1% aqueous tween 80. Respectively preparing single-dose mother liquor, and setting the single-dose mother liquor into required series of mass concentrations according to the mixing purpose and the medicament activity.
Melting PDA culture medium with microwave oven, cooling to about 50 deg.C, adding 1mL of prepared liquid medicine to be tested and 9mL of PDA culture medium into a culture dish with diameter of 9cm according to principle from low concentration to high concentration, mixing, and making into flat plate containing medicine with corresponding concentration.
Beating the cultured pathogenic fungi into fungus cakes by using a puncher with the diameter of 5mm under the aseptic condition, placing the fungus cakes in the central position of a culture medium after the medicine-containing culture medium is solidified, sealing the culture dish by using a sealing film, culturing in an incubator at 27 ℃, setting a blank solution without a medicine as a blank control, and repeating the treatment for four times.
After incubation for 7d, the colony diameter was measured in millimeters (mm) with calipers. The diameter of each colony was measured perpendicularly by the cross method once and averaged.
The hypha growth inhibition rate is calculated according to the following formula, the unit is percentage (%), and the calculation result retains two decimal points.
D=D1-D2············(1)
D-colony growing diameter;
D1-colony diameter;
D2-cake diameter.
I=(D0-Dt)/D0*100············(2)
In the formula:
i-hypha growth inhibition rate;
D0-the diameter of the blank colony is increased;
Dtmedicament-treated colonies grow in diameter.
Sun Yupei method: 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 showed additive effects. The co-toxicity coefficient (CTC value) of the mixture is calculated according to the following formula (3), formula (4) and formula (5):
Figure BDA0003583617520000101
in the formula:
ATI-measured virulence index of the mixture;
S-EC of Standard Fungicide50In milligrams per liter (mg/L);
EC of M-mixtures50In milligrams per liter (mg/L).
TTI=TIA*PA+TIB*PB·······(4)
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 BDA0003583617520000102
In the formula:
CTC-co-toxicity coefficient;
ATI-measured virulence index of the mixture;
TTI-mixture theory virulence index.
DPS data processing software is adopted to calculate test results, and toxicity regression equations and R, EC of single test agent and mixed agents with different proportions are respectively obtained50And 95% confidence limit, and calculating co-toxicity coefficient (CTC) of the two medicaments in different proportions, and screening out the optimal proportion of the test medicament.
The results of the tests are given in the following table:
TABLE 2 indoor Activity test for cucumber Gray mold by Bixafen and fludioxonil blending
Figure BDA0003583617520000103
Figure BDA0003583617520000111
As shown in the indoor activity test (see table 2), the single agents of bixafen and fludioxonil have the effect of treating cucumber gray mold EC504.9421mg/L and 0.0403mg/L respectively, and the cucumber gray mold is more sensitive to fludioxonil; the co-toxicity coefficients of the bixafen and the fludioxonil are all larger than 120 after the bixafen and the fludioxonil are mixed according to the ratio of 1: 10-30: 1, and the synergistic effect is shown for preventing and treating cucumber gray mold; when the mass ratio of the bixafen to the fludioxonil is 1: 3-20: 1, the co-toxicity coefficient after mixing is larger than 140, and the synergistic effect is obvious.
Example 3: indoor combined action test of blending bifendamide and fludioxonil on peanut southern blight
The test basis is as follows: the test refers to NY/T1156.2-2006 part 2 of agricultural industry Standard pesticide indoor bioassay test Standard germicide of the people's republic of China: test plate method for inhibiting pathogenic fungi hypha growth; NY/T1156.6-2006 Combined action determination of part 6 of bactericide for indoor bioassay test criteria of agricultural chemicals standard in the people's republic of China.
Reagent to be tested: 98 percent of Bixafen technical and 97 percent of fludioxonil technical, which are provided by the Helil pharmaceutical industry group research and development center.
Pathogenic bacteria to be tested: sclerotium rolfsii Sacc, Sclerotium rolfsii, Sclerotium, um, Sclerotium, um, Sclerotium, um, Sclerotium, um, and the like;
preparing a medicament: the test drug is dissolved by acetone and then diluted by 0.1% tween 80 water solution. Respectively preparing single-dose mother liquor, and setting the required series mass concentration according to the mixing purpose and the medicament activity.
Melting PDA culture medium with microwave oven, cooling to about 50 deg.C, adding 1mL of prepared liquid medicine to be tested and 9mL of PDA culture medium into a culture dish with diameter of 9cm under aseptic condition according to principle from low concentration to high concentration, mixing, and making into flat plate containing medicine with corresponding concentration.
Beating the cultured pathogenic fungi into fungus cakes by using a puncher with the diameter of 5mm under the aseptic condition, placing the fungus cakes in the central position of a culture medium after the medicine-containing culture medium is solidified, sealing the culture dish by using a sealing film, then placing the culture dish in an incubator (26 +/-0.5 ℃) for culturing, simultaneously setting a blank solution without the medicine as a blank control, and repeating the treatment for four times each time.
Data statistics and analysis:
and (5) investigating the growth condition of the hyphae of the pathogenic bacteria according to the growth condition of the bacteria in the blank control culture dish. The colony diameter was measured in millimeters (mm) with calipers. The diameter of each colony was measured perpendicularly by the cross method once and averaged.
The inhibition rate of hypha growth is calculated according to the following formula, the unit is percentage (%), and the two digits after decimal point are reserved in the calculation result.
D=D1-D2············(1)
D-colony growth diameter;
D1-colony diameter;
D2-cake diameter.
I=(D0-Dt)/D0*100············(2)
In the formula:
i-hypha growth inhibition rate;
D0-growing the diameter of the blank colony;
Dtmedicament-treated colonies grow in diameter.
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 shows additive effects. The co-toxicity coefficient (CTC value) of the mixture is calculated according to the following formula (3), formula (4) and formula (5):
Figure BDA0003583617520000121
in the formula:
ATI-actually measured toxicity index of mixed agent;
S-EC of Standard Fungicide50In milligrams per liter (mg/L);
EC of M-mixtures50Units are milligrams per liter (mg/L).
TTI=TIA*PA+TIB*PB·······(4)
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 is given in percentage (%).
Figure BDA0003583617520000122
In the formula:
CTC-co-toxicity coefficient;
ATI-actually measured toxicity index of mixed agent;
TTI-mixture theory virulence index.
DPS data processing software is adopted to calculate test results, and toxicity regression equations and R, EC of single test agent and mixed agents with different proportions are respectively obtained50And 95% confidence limit, and calculating co-toxicity coefficient (CTC) of the two medicaments in different proportions, and screening out the optimal proportion of the test medicament.
The results of the tests are given in the following table:
TABLE 3 indoor combined action test results of Bixafen and fludioxonil blending for southern blight peanut
Reagent for testing Regression equation (Y ═ a + bx) R EC50(mg/L) 95% confidence limits Co-toxicity coefficient (CTC)
Bixafen (A) y=3.8029+1.2214x 0.9993 9.5518(9.1536-9.9673) -
Fludioxonil (B) y=5.8543+1.2019x 0.9999 0.1946(0.1918-0.1975) -
A:B(1:3) y=5.8378+1.2203x 0.9989 0.2058(0.1951-0.2170) 125.227
A:B(1:1) y=5.6309+1.1001x 0.9994 0.2670(0.2569-0.2775) 142.857
A:B(3:1) y=5.3658+1.2362x 0.9996 0.5060(0.4900-0.5224) 144.973
A:B(6:1) y=5.2122+1.2060x 0.9999 0.6669(0.6585-0.6754) 182.010
A:B(9:1) y=4.9956+1.2846x 0.9997 1.0079(0.9831-1.0334) 163.158
A:B(13:1) y=4.7800+1.2112x 0.9999 1.5194(1.4923-1.5470) 141.762
A:B(16:1) y=4.6614+1.2226x 0.9994 1.8920(1.8179-1.9692) 131.867
As can be seen from indoor activity tests (see Table 3), the Bifenapyr and fludioxonil mixed compound has good activity on peanut southern blight, wherein fludioxonil single agent has high toxicity on peanut southern blight, and EC500.1946mg/L, peanut southern blight is more sensitive to fludioxonil; the co-toxicity coefficients of the bixafen and the fludioxonil are all larger than 120 after the bixafen and the fludioxonil are mixed according to the proportion of 1: 3-16: 1, and the synergistic effect is shown on the prevention and treatment of the peanut southern blight. When the mass ratio of the fenpyrazamine to the fludioxonil is 1: 1-13: 1, the co-toxicity coefficient after mixing is more than 140, and the synergistic effect is obvious; when the mass ratio of the bixafen to the fludioxonil is 6:1, the cotoxicity coefficient is 182.010, and the prevention and treatment effect is the best.
Test of field drug effect
Example 4 field efficacy test of Bixafen and bupirimate mixture for controlling cucumber powdery mildew
The test basis is as follows: the test refers to GB/T17980.30-2000 part 30 of pesticide field efficacy test guidelines (I): the bactericide can be used for preventing and treating cucumber powdery mildew.
Test site: the application time of the greenhouse in Nanpan village, shouguang, Shandong province is 2021, 3 middle of the month.
Test targets: powdery mildew of cucumber.
Test crops and varieties: cucumber (Xintai honey thorn).
Test agents: the test agents and dosages are shown in the following table.
And (3) experimental design: the medicament-treated cells are distributed according to random block groups, and protective rows are arranged around the cells. 20m per cell per 4 replicates per treatment2. The conventional spraying method is adopted, and a worker-agriculture-16 type hand sprayer is used for spraying, and the liquid medicine is uniformly sprayed on the front and back surfaces of the leaves to be wet without dripping.
The application time is as follows: the experiment shows that the medicine is sprayed for the 1 st time at the early stage of powdery mildew of cucumber, and the medicine is sprayed for the 2 nd time at intervals of 7 days, wherein the medicine is sprayed for two times. The rainfall does not occur within 24 hours after the pesticide is applied, no special severe weather exists during the test period, and the field is regularly managed.
The investigation method comprises the following steps: the test is that disease condition base investigation is carried out before the 1 st application, powdery mildew attack conditions are respectively investigated 7d after the 1 st application and 11d after the 2 nd application, four points are randomly selected for investigation in each cell, two plants are investigated at each point, all leaves are investigated by each plant, and each leaf is graded according to the percentage of scabs to the leaf area, and disease condition index and prevention and treatment effect are calculated.
Statistics and analysis:
the classification method (in units of leaves) is as follows:
level 0: no lesion spots;
level 1: the lesion area accounts for less than 5% of the whole leaf area;
and 3, stage: the lesion area accounts for 6-10% of the whole leaf area;
and 5, stage: the lesion area accounts for 11-20% of the whole leaf area;
and 7, stage: the lesion area accounts for 21-40% of the whole leaf area;
and 9, stage: the lesion area accounts for more than 40% of the whole leaf area.
The efficacy is calculated as follows:
Figure BDA0003583617520000141
Figure BDA0003583617520000142
the results of the tests are given in the following table:
TABLE 4 field efficacy test results of Bixafen and bupirimate mixed control of cucumber powdery mildew
Figure BDA0003583617520000143
The field efficacy shows (see table 4), the overall control effect of the field effect of each treatment 7 days after the first application of different treatments for controlling cucumber powdery mildew is 69.61-84.88%, and the control effects of the treatments for the cucumber powdery mildew after spraying 30% of Bixafen-bupirimate emulsion in water (1:5), 10% of Bixafen-bupirimate emulsion in water (1:1), 30% of Bixafen-bupirimate missible oil (5:1) and 22% of Bixafen-bupirimate missible oil (10:1) are respectively 80.24%, 84.88%, 83.16% and 81.21%, and are superior to single agents (125 g/l of Bixafen-and 25% of bupirimate microemulsion), wherein the 10% of Bixafen-bupirimate emulsion in water (1:1) has the best control effect.
The overall control effect of each treatment in 11 days after the second pesticide application is 70.36-85.98%, the control effects of 30% of Bixafen-bupirimate emulsion in water (1:5), 10% of Bixafen-bupirimate emulsion in water (1:1), 30% of Bixafen-bupirimate missible oil (5:1) and 22% of Bixafen-bupirimate missible oil (10:1) on cucumber powdery mildew are 81.65%, 85.98%, 83.88% and 82.27% respectively, and the control effects are superior to those of a single agent.
In the whole test process, each medicament is safe to target crops and other organisms under the test concentration and has no phytotoxicity.
Example 5: bifenpyrad and fludioxonil mixed field pesticide effect test for preventing and treating cucumber gray mold
The test basis is as follows: the test refers to GB/T17980.28-2000 part 28 of pesticide field efficacy test criteria (I): the bactericide can be used for preventing and treating gray mold of vegetables.
Test site: the application time of the drug in Laxi City of Qingdao, Shandong province is 6 middle of the month in 2020.
Test targets: cucumber gray mold.
Test crops and varieties: cucumber (Xintai honey thorn).
Test agents: the test agents and dosages are shown in the following table.
The test method comprises the following steps: the cell area is 25m by random block arrangement24 repeats.
The application method and times are as follows: applying the pesticide once after 8 days after the pesticide application, wherein the pesticide application is performed for 2 times totally;
the investigation method comprises the following steps: the disease condition base is investigated before the first application, and the control effect is investigated 11 days after the last application. Five samples were randomly taken from each cell, 2 plants were examined at each point, and all leaves and fruits were investigated for each plant and recorded in grades according to the following method.
Leaf damage grading method (taking leaves as a unit):
level 0: no lesion spots;
level 1:3 scabs exist on a single leaf;
and 3, stage: 4-6 scabs exist on a single leaf;
stage 5: 7-10 scabs exist on a single leaf;
and 7, stage: the number of the disease spots on a single leaf is 11-20, and the parts are densely divided into pieces;
and 9, stage: the single leaf has more than one fourth of the area of the dense diseased spots.
Fruit damage grading method (taking fruit as unit):
stage 0: no lesion spots;
level 1: residual flowers are attacked;
and 3, level: onset of disease at the navel of the melon;
stage 5: the disease length accounts for less than 10% of the total length of the melon strips;
and 7, stage: the disease length accounts for less than 11-25% of the total length of the melon strips;
and 9, stage: the disease length accounts for more than 26 percent of the total length of the melon strips.
The drug effect was calculated as follows:
Figure BDA0003583617520000161
Figure BDA0003583617520000162
the results of the tests are given in the following table:
TABLE 5 Bixafen and fludioxonil mixed field efficacy (leaf) for controlling cucumber gray mold
Figure BDA0003583617520000163
TABLE 6 field efficacy (fruit) of Bixafen and fludioxonil mixed for controlling cucumber gray mold
Figure BDA0003583617520000164
The field efficacy shows (see table 5), the overall field effect of different treatments for preventing and treating the cucumber leaf gray mold in 11 days after the last application is 68.75% -85.14%, 20% of bispyribac-sodium and fludioxonil suspending agent (3:1), 21% of bispyribac-sodium and fludioxonil suspending agent (6:1), 33% of bispyribac-sodium and fludioxonil water dispersible granules (10:1) and 21% of bispyribac-sodium and fludioxonil wettable powder (20:1) are sprayed, and the prevention and treatment effects on the cucumber leaf gray mold after the treatments are respectively 81.55%, 83.64%, 85.14% and 82.36%, and are better than single agents (20% of bispyribac-sodium and 20% of fludioxonil suspending agent), wherein the prevention effect of 33% of bispyribac-sodium and fludioxonil water dispersible granules (10:1) is the best.
The field efficacy shows (see table 6), the overall field effect of different treatments for preventing and controlling the gray mold of cucumber fruits in 11 days after the last application is 69.08-84.11%, 20% of Bifenapyr, fludioxonil suspending agent (3:1), 21% of Bifenapyr, fludioxonil suspending agent (6:1), 33% of Bifenapyr, fludioxonil water dispersible granules (10:1) and 21% of Bifenapyr, fludioxonil wettable powder (20:1) are sprayed, and the prevention and control effects on the gray mold of cucumber leaves are respectively 80.46%, 81.82%, 84.11% and 79.79%, and are better than those of single agents (20% of Bifenapyr suspending agent and 20% of fludioxonil suspending agent), wherein the prevention effect of 33% of Bifenapyr and the fludioxonil water dispersible granules (10:1) is the best.
In the whole test process, each medicament is safe to target crops and other organisms under the test concentration and has no phytotoxicity.
Example 6: bixafen and fludioxonil mixed field efficacy test for preventing and treating peanut southern blight
Test site: in the peanut test field of Lexi, Qingdao, Shandong, the test field is multi-year peanut continuous cropping, the southern blight of the peanuts is serious, the test field is sandy loam, and the fertility is moderate.
Test targets: sclerotium rolfsii Sacc (Sclerotium rolfsii) Sclerotium rolfsii;
and (3) test crops: peanut (luhua No. 14).
Test agents: the test agents and dosages are shown in the following table.
And (3) experimental design: the medicament-treated cells are distributed according to random block groups, and protective rows are arranged around the cells. 30m per cell per treatment 4 replicates2. The spraying and root irrigating method is adopted for pesticide application.
The application time is as follows: the test is to apply the pesticide for the 1 st time in the initial stage of peanut southern blight and apply the pesticide for the 2 nd time at intervals of 15 days, and the pesticide application is carried out twice in total. No special severe weather exists during the test period, and the field is regularly managed.
The investigation method comprises the following steps: the test is carried out before the 1 st application, disease base investigation is carried out, the disease condition of peanut southern blight in each cell is respectively investigated 15 days after the last application, sampling is carried out at 5 points randomly in each cell, 20 plants are connected in each point investigation, 100 plants are investigated in each cell, and the number of each level of disease plants of peanuts is recorded.
The disease grading standard is classified according to the disease grading standard in Weiweibo et al greenhouse inoculation technology and resistance identification of peanut southern blight, and the investigation grading standard is as follows:
level 0: the plant is asymptomatic;
stage 1: lesions are produced only at the base of the stem;
stage 2: stem base produces a constriction symptom, and less than one third of the whole plant shows a systemic symptom (withering, death, wilting, etc.);
and 3, level: less than two thirds of the whole plant presents with systemic symptoms;
4, level: more than two thirds of the whole plant showed systemic symptoms.
The efficacy was calculated according to the following formula:
Figure BDA0003583617520000181
Figure BDA0003583617520000182
the results of the tests are given in the following table:
TABLE 7 field test results of pesticide effect of Bixafen and fludioxonil mixture for preventing and treating peanut southern blight
Figure BDA0003583617520000183
The field efficacy shows (see table 7), the field effect of different treatments for preventing and treating peanut southern blight is 78.01% -83.40% in whole, 21% of bispyribac-sodium is applied under the condition of reducing the dosage, and the prevention and treatment effect of fludioxonil suspending agent (6:1) on peanut southern blight is 83.40% and is better than that of single agent (20% of bispyribac-sodium suspending agent and 20% of fludioxonil suspending agent).
In conclusion, through indoor toxicity measurement and field efficacy tests, the pesticide composition of bixafen has good control effect on plant pathogenic bacteria, is safe to target crops, has obvious control effect, is superior to a single agent in the aspects of delaying the generation of drug resistance and prolonging the persistence, and can effectively reduce the cost and reduce the drug residue.
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 or improvements may be made thereto without departing from the spirit of the invention.

Claims (10)

1. The pesticide composition containing the Bixafen is characterized by comprising an active ingredient A and an active ingredient B, wherein the mass ratio of the active ingredient A to the active ingredient B is 1: 30-30: 1, the active ingredient A is the Bixafen, and the active ingredient B is any one of fludioxonil or bupirimate.
2. The pesticide composition as claimed in claim 1, wherein the active ingredient B is bupirimate, and the mass ratio of the active ingredient A to the active ingredient B is 1: 10-15: 1;
preferably, the mass ratio of the active ingredient A to the active ingredient B is 1: 10-10: 1;
more preferably, the mass ratio of the active component A to the active component B is 1: 5-10: 1.
3. The pesticide composition as set forth in claim 1, characterized in that the active ingredient B is fludioxonil, and the mass ratio of the active ingredient A to the active ingredient B is 1: 10-30: 1;
preferably, the mass ratio of the active ingredient A to the active ingredient B is 1: 3-30: 1;
more preferably, the mass ratio of the active ingredient A to the active ingredient B is 1: 1-20: 1.
4. The pesticide composition as set forth in claim 1, wherein the sum of the contents of the active ingredient A and the active ingredient B in the pesticide composition is 0.5-80%, preferably 1-60%, based on 100 wt% of the total weight of the pesticide composition.
5. The pesticidal composition of claim 1, further comprising an auxiliary ingredient 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 stabilizer, a penetrant, and a carrier.
6. The pesticide composition as set forth in claim 1, wherein the pesticide composition can be prepared into any agriculturally acceptable formulation.
7. The pesticide composition as set forth in claim 6, wherein the formulation is in the form of a solid formulation, a liquid formulation and/or a seed treatment formulation;
preferably, the solid preparation is water dispersible granules, and the liquid preparation is a suspending agent, missible oil and/or an aqueous emulsion.
8. Use of the pesticidal composition according to any one of claims 1 to 7 for controlling a plant disease.
9. The use according to claim 8, wherein the plant is a cash crop and/or a food crop.
10. The use according to claim 8, wherein the plant disease is southern blight, rust disease, gray mold and/or powdery mildew; preferably, the plant diseases are southern blight, gray mold and powdery mildew.
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