CN111264528A - Aminopyrofen-containing pesticide composition and application thereof - Google Patents

Aminopyrofen-containing pesticide composition and application thereof Download PDF

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CN111264528A
CN111264528A CN202010181189.4A CN202010181189A CN111264528A CN 111264528 A CN111264528 A CN 111264528A CN 202010181189 A CN202010181189 A CN 202010181189A CN 111264528 A CN111264528 A CN 111264528A
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bupirimate
aminopyrofen
pesticide
disease
agent
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李健
杨志鹏
张凯莉
隋书婷
李晶
王玉
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Qingdao Tengrunxiang Testing And Evaluation Co Ltd
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Qingdao Tengrunxiang Testing And Evaluation 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
    • A01N43/541,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

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  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention belongs to the field of pesticide bactericides and discloses a pesticide composition containing Aminopyrofen and application thereof; the active ingredients of the pesticide composition comprise an ingredient A and an active ingredient B; the active ingredient A is a compound shown as a formula (I), and the active ingredient B is bupirimate. The pesticide composition overcomes the defect of using a single pesticide, has a broad-spectrum sterilization effect, effectively reduces the using amount and the using cost of effective components, and delays the generation and development of resistance. The pesticide composition has higher control effect on various plant fungal diseases.

Description

Aminopyrofen-containing pesticide composition and application thereof
Technical Field
The invention relates to the field of pesticide bactericides, and in particular relates to a pesticide composition containing Aminopyrefen and bupirimate and application thereof. The pesticide composition or the preparation thereof can enhance the pesticide effect, reduce the dosage, simultaneously improve the quick action, prolong the persistence and delay the development of the pesticide resistance.
Background
Aminopyrefen is a broad-spectrum pyridine bactericide developed by the company Agro-kanesho, Japan, under the development code AKD-5195, IUPAC chemical name: 4-phenoxybenzyl 2-amino-6-methylnicotinate, CAS chemical name: (4-phenoxyphenyl) methyl 2-amino-6-methyl-3-pyridinecarboxylate. CAS accession number: 1531626-08-0. The agent has high prevention effect on powdery mildew and gray mold of various fruit and vegetable crops. The chemical structural formula is as follows:
Figure BDA0002412626550000011
bupirimate is a new generation systemic fungicide, belonging to an adenosine deaminase inhibitor. Can be rapidly absorbed by plant stem and leaf, and transported to various parts in plant body to inhibit pathogen sporulation. Has the functions of protection and treatment, has special effect on the powdery mildew of crops, can be used in the whole growth period of the crops, can comprehensively and effectively control each development stage of the powdery mildew germs, and has good functions of prevention, treatment and eradication. The chemical structural formula is as follows:
Figure BDA0002412626550000012
the melon powdery mildew (Sphaeotheca fuliginea) commonly occurs on various melon crops in various parts of China, is a disease which is widely distributed on the crops and seriously damaged, and is commonly called 'white lime coating'. Powdery mildew of melons can occur in the whole growth period of melon crops such as cucumbers, pumpkin, pumpkins, melons, wax gourds, watermelons and the like, and is seriously harmful in the middle and later periods. Mainly harmful leaves, stems and petioles, wherein in the initial generation stage, white small approximately circular pink spots are generated on two sides of the leaves, the disease spots gradually expand into larger white pink spots along with the development of disease conditions, the edges of the disease spots are unclear, most of the disease spots are connected and shaped like a layer of white powder which is scattered on the whole leaves, and when the disease spots are serious, the white powder is gradually changed into grey white or grey brown; in the later stage of growth, many small black particles can be scattered on some lesions. With the continuous expansion of the planting area of melon crops, the diseases are commonly generated, and serious economic loss is caused to farmers.
The cucumber powdery mildew is a leaf disease caused by cucumber powdery mildew, which has short incubation period, frequent re-infection and strong popularity, is commonly generated in various regions at home and seriously harmful, and is one of the main diseases in cucumber production. The disease is easy to occur under high humidity conditions, and mainly damages leaves, stems and vines. When the powdery mildew occurs at the beginning, the powdery mildew which is nearly round is firstly generated on the leaves and then is fused into powdery spots, and when the powdery mildew is serious, the powdery stains are fully distributed on the leaves, so that the leaves are withered or fall off. Causing serious economic loss to the normal growth of the cucumber.
Melon powdery mildew is a common disease of melons and can cause serious harm. The muskmelon growing period can be all started, white tiny powder spots appear on the front and back of the muskmelon at the initial stage, the white tiny powder spots gradually expand to form white round powder spots, and a plurality of disease spots are connected with each other, so that the surface of the muskmelon is full of white powder. With the development of diseases, the color of the powder spot gradually changes into grey white, and black dots are occasionally generated under the powder layer in the later period. Finally, the diseased leaves are withered and yellow and necrotic. The higher humidity is beneficial to spore germination and invasion, can occur at 10-25 ℃, and can be popular or not depending on the humidity and the growth vigor of hosts. Can germinate under low humidity, and the germination rate under high humidity is obviously improved. Therefore, the rain is dry or less rain, but the field humidity is high, and the epidemic speed of powdery mildew is accelerated. In the agricultural production process, chemical agents are the most effective means for controlling diseases. The long-term continuous high-dosage use of a single chemical agent easily causes a series of problems of drug resistance of harmful bacteria, environmental pollution and the like. The reasonable compounding or mixing of the chemical agents has the positive characteristics of expanding the bactericidal spectrum, improving the control effect, prolonging the application suitable period, reducing the dosage, reducing the phytotoxicity, reducing the residue, delaying the occurrence of the drug resistance and the drug resistance of harmful bacteria and the like. With the deeper and deeper understanding of the environmental protection concept by farmers, the inevitable trend of pesticide development is high efficiency, low toxicity, high activity and low residue. Therefore, with the increasing requirements on environment and food safety and the resistance problem of medicaments, how to scientifically apply the medicaments, reduce the dosage of chemical pesticides and improve the pesticide effect becomes a problem which needs to be solved urgently in the field of pesticides; in addition, no related report exists on the application of the pesticide composition of the Aminopyrofen and the bupirimate in the aspect.
Disclosure of Invention
Based on the situation, the invention aims to provide the pesticide composition containing the Aminopyrofen and the preparation thereof, which are mainly used for preventing and treating fungal diseases of fruit and vegetable crops.
In order to achieve the purpose, the pesticide composition containing the Aminopyrofen comprises an active ingredient A and an active ingredient B, wherein the active ingredient A is the Aminopyrofen and has the following structural formula:
Figure BDA0002412626550000031
the active component B is bupirimate.
Further, the mass ratio of Aminopyrefen to bupirimate is 50: 1-1: 50.
Further, the mass ratio of Aminopyrefen to bupirimate is 20: 1-1: 20.
Further, the sum of the contents of the active ingredient A and the active ingredient B in the pesticide composition is 1-95 wt%, preferably 5-80 wt%, and more preferably 10-60 wt%, based on 100 wt% of the total weight of the pesticide composition;
further, the pesticide composition also comprises an auxiliary agent, wherein the auxiliary agent is selected from one or more of a wetting agent, a dispersing agent, an emulsifying agent, a thickening agent, a disintegrating agent, an antifreezing agent, an antifoaming agent, a solvent, a preservative, a stabilizing agent, a synergist or a carrier.
Furthermore, the pesticide composition can be any one of missible oil, aqueous emulsion, microemulsion, suspending agent, wettable powder or water dispersible granules;
further, the preparation is in the form of microemulsion or aqueous emulsion.
Further, the pesticide composition is applied to the aspect of preventing and treating plant diseases.
Further, the plant disease is a plant disease caused by fungi or bacteria; preferably, the plant disease is a plant disease caused by a fungus; more preferably, the fungi are cucurbit monocystus shells (Sphaerotheca cucurbitae (Jacz) z.y.zhao) and cucurbit erysiphe necator (erysiphe cucurbitaceae Zheng & Chen) belonging to the genus ascomycota or erysiphe.
Preferably, the plant disease is a disease of a cucurbitaceae plant; more preferably, the cucurbitaceae plant is cucumber or melon.
Detailed description of the invention
The pesticide composition containing the Aminopyrofen comprises an active ingredient A and an active ingredient B, wherein the active ingredient A is the Aminopyrofen and has the following structural formula:
Figure BDA0002412626550000041
the active component B is bupirimate.
Further, the mass ratio of Aminopyrefen to bupirimate is 50:1, 20:1, 10:1, 5:1, 3:1, 1:3, 1:5, 1:10, 1:20 or 1: 50.
Further, the mass ratio of Aminopyrefen to bupirimate is 20: 1-1: 20.
Further, the sum of the contents of the active ingredient A and the active ingredient B in the pesticide composition is 1-95 wt%, preferably 5-80 wt%, and more preferably 10-60 wt%, based on 100 wt% of the total weight of the pesticide composition;
in an embodiment, the sum of the amounts of Aminopyrofen and bupirimate in the pesticidal composition is 10 to 60 wt%, for example, the sum of the amounts of Aminopyrofen and bupirimate is 20 wt%, 25 wt%, 30 wt% and 40 wt%.
The invention optimizes the content of the effective components in the pesticide composition, so that the toxicity and the residue of the pesticide composition are well balanced, the pesticide effect can be enhanced, the dosage can be reduced, and the cost can be reduced.
According to the pesticide composition containing Aminopyrefen, provided by the invention, the pesticide composition further comprises an auxiliary agent, wherein the auxiliary agent is selected from one or more of a wetting agent, a dispersing agent, an emulsifying agent, a thickening agent, a disintegrating agent, an antifreezing agent, an antifoaming agent, a solvent, a preservative, a stabilizer, a synergist or a carrier.
The wetting agent is selected from one or more of alkyl benzene sulfonate, alkyl naphthalene sulfonate, lignosulfonate, sodium dodecyl sulfate, dioctyl sodium sulfosuccinate, α olefin sulfonate, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, alkylphenol ethoxylate, fatty alcohol ethoxylate, sodium fatty alcohol polyoxyethylene ether sulfate, faeces Bombycis, fructus Gleditsiae Abnormalis powder, fructus Sapindi Mukouossi 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
Disintegrant the disintegrant is selected from one or more of sodium sulfate, ammonium sulfate, aluminum chloride, sodium chloride, ammonium chloride, bentonite, glucose, sucrose, starch, cellulose, urea, sodium carbonate, sodium bicarbonate, citric acid, and tartaric acid; and/or
The antifreezing agent is selected from one or more of alcohols, alcohol ethers, chlorohydrocarbons and inorganic salts; and/or
The defoaming agent is selected from C10-C20Saturated fatty acid compound, silicone oil, silicone compound, C8-C10One or more of fatty alcohols; and/or
The solvent is selected from one or more of benzene, toluene, xylene, durene, methanol, ethanol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, cyclohexanone, alkylene carbonate, diesel oil, solvent oil, vegetable oil derivative and water; and/or
The preservative is selected from one or more of propionic acid, sodium propionate, sorbic acid, sodium sorbate, potassium sorbate, benzoic acid, sodium benzoate, sodium parahydroxybenzoate, methyl parahydroxybenzoate, 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 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.
The invention provides a pesticide composition containing Aminopyrefen and application thereof, and further the dosage form of the pesticide composition is selected from missible oil, aqueous emulsion, microemulsion, suspending agent, wettable powder and water dispersible granules; preferably, the preparation is in a dosage form selected from microemulsion and aqueous emulsion.
The emulsifiable concentrate is a liquid prepared by dissolving high-concentration effective components into a solvent and adding an emulsifier. Emulsifiers are mostly used as mixtures of nonionic and anionic surface activity. The emulsifiable solution is simple and convenient to prepare, has higher biological effect, but has high raw material cost and overhigh preparation cost, and increases the preparation manufacturing cost.
The aqueous emulsion is a preparation prepared by dispersing a liquid pesticide raw pesticide prepared by mixing liquid or a solvent into water in small droplets of 0.5-1.5 microns, and the appearance of the aqueous emulsion is milky liquid. Besides the effective components and the solvent, the emulsion in water can also be added with auxiliary agents such as an emulsifier, a dispersant, an antifreeze agent and the like, so that the stability of the emulsifier is improved.
The microemulsion consists of liquid pesticide, dispersant, water, stabilizer and the like, wherein the pesticide particles are 0.01-0.1 micron, the water is used as a medium, and the microemulsion does not contain or contains little organic solvent, has small environmental pollution, strong permeability to target organisms and good adhesive force, and is an environment-friendly green pesticide preparation.
The suspending agent is prepared by mixing the composition with appropriate surfactant, water or organic solvent at a certain ratio, grinding with sand mill using glass beads to obtain D90(the grain diameter of 90 percent of particles) is less than 10 mu m to obtain crushed slurry, and then thickening agent, dispersing agent, anti-settling agent, defoaming agent, antifreezing agent, deionized water and the like are added into the crushed slurry to be mixed to obtain the product. The suspending agent is divided into an aqueous suspending agent and an oil suspending agent, and has small particle size, high biological activity, no dust flying problem, and no flammability and explosion.
The wettable powder is prepared by pre-crushing and uniformly mixing the raw pesticide of the composition with a dispersant, a wetting agent, a filler and the like according to a certain proportion, and crushing the mixture by using an airflow crusher until the fineness of the mixture meets the requirement that at least 98 wt% of the mixture passes through a 45-micron test sieve. Wettable powders are formulations which are uniformly dispersible in water and which contain, in addition to the active substance and inert substance, a certain amount of an anionic or nonionic surfactant. The wettable powder does not use solvent and emulsifier, is safe to plants, is not easy to generate phytotoxicity and is safe to the environment.
The water dispersible granule is obtained by re-granulating wettable powder or suspending agent into water dispersible granule, mixing the composition with appropriate surfactant and inert substance (kaolin, diatomite and pottery clay) powder according to a certain proportion to form a mixture, and then granulating by a fluidized bed granulation method, a spray granulation method or a disc granulation method. The raw materials are pulverized by airflow in the mixing process to ensure that the fineness of the powder particles meets the requirement, and the product is uniformly mixed by using a double-helix mixer and a coulter type mixer for multiple times. The preparation has good fluidity, convenient use, no dust flying, safety and reliability.
The invention provides a pesticide composition containing Aminopyrofen, and preferably relates to application of the pesticide composition in the aspect of controlling plant diseases. Preferably, the plant disease is a plant disease caused by a fungus or a bacterium; preferably, the plant disease is a plant disease caused by a fungus; further preferably, the fungi are cucurbit monocystus shells (Sphaerotheca cucurbitae (Jacz) z.y.zhao) and cucurbitaceae Erysiphe cucurbitaceae (Erysiphe cucurbitaceae Zheng & Chen) belonging to the genus ascomycota or Erysiphe; still more preferably, the plant disease is a disease of a cucurbitaceae plant; more preferably, the cucurbitaceae plant is cucumber or melon.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) through compounding Aminopyrefen and bupirimate, the bactericidal activity is increased, and the application range is expanded;
(2) the method is safe and environment-friendly, has wide development prospect, reduces the usage amount of pesticides and reduces the agricultural cost;
(3) the bactericidal composition has super-high efficiency and wide bactericidal spectrum, and can delay the generation of the drug resistance of harmful bacteria and prolong the drug duration.
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.
Reference is made to the criteria of the indoor bioassay test of pesticides, part 11, test potting method for controlling melon powdery mildew, NT/T1156.11-2008; section 7: the combined effect of compounding was determined for NT/T1154.7-2008.
Experimental apparatus equipment: electronic balance (sensing 0.01mg), climatic chamber, pipette gun, small atomizer, etc.
Example 1
Toxicity determination of Aminopyrofen and bupirimate on powdery mildew pathogen
Test crop and strain
Test work: and (3) planting the cucumber in a pot, and waiting for the seedling to grow to 2-4 true leaves for later use.
Pathogenic bacteria to be tested: powdery mildew (Sphaeotheca fuliginea) is collected from diseased leaves of cucumber (variety: Jinyou No. 1) in south village and town of Qingdao flatness, and the collected diseased leaves are washed with 4 ℃ distilled water to obtain leaf surface powdery mildew spores, which are prepared into suspension (the concentration is 1 x 10)5spores/mL) was placed in a refrigerator at 4 ℃ until use.
Preparing a medicament:
aminopyrofen raw drug and bupirimate raw drug are provided by research center of Helil pharmaceutical industry group, Inc.
Dissolving Aminopyrofen raw drug and bupirimate raw drug in DMF, and diluting with 0.1% Tween-80 aqueous solution. Preparing single-dose mother liquor respectively, designing 5 groups of proportioning according to the mixing purpose and the medicament activity, and preparing 5 series of mass concentrations of each single dose and each group of proportioning mixing agent according to an equal ratio method.
The application method comprises the following steps: the application apparatus is a small sprayer with the capacity of 250ml and the diameter of a spray hole of 1mm, the medicament is uniformly sprayed on the blades (preferably a layer of water film appears on the blades) by a spraying method, the blades are naturally dried, the treatment is repeated for not less than 4 times, 5 pots are treated for each time, 2 plants are treated for each pot, and the treatment without the medicament (containing all organic solvents and emulsifiers) is set as a blank control.
Data statistics and analysis:
spraying fresh spore suspension on inoculated leaves, spraying 24h after artificial inoculation, and culturing under appropriate conditions.
After the application, the disease incidence of each treatment is graded and investigated, the disease incidence grade is recorded in detail, and the disease incidence of each treatment is graded and investigated when the blank control disease leaf rate reaches more than 80%. The grading method comprises the following steps:
level 0: disease free
Level 1: only a few small disease spots are on the leaves, and the disease spots occupy less than 5% of the leaf area;
and 3, level: the disease spots on the leaves occupy 6 to 15 percent of the area of the leaves;
and 5, stage: the disease spots on the leaves occupy 16 to 25 percent of the area of the leaves;
and 7, stage: the disease spots on the leaves occupy 26-50% of the leaf area;
9, the disease spots on the leaves occupy 51 to 75 percent of the area of the leaves;
stage 11: the disease spots on the leaves account for more than 75 percent of the area of the leaves.
And calculating disease indexes and prevention and treatment effects of the treatments according to the survey data. Calculating according to the formulas (1) and (2), and reserving the calculation results to the last two decimal points:
Figure BDA0002412626550000081
x is disease index;
Ni-number of diseased leaves in each stage;
i-relative step number;
n-survey total leaf number.
Figure BDA0002412626550000082
P-control effect, in percent (%);
CK-placebo disease index;
PT-agent treatment disease index.
And processing the data by adopting a method of analyzing a few rate value. Can be analyzed by an IBM SPSS Statistics2.0 statistical analysis system to obtain the EC of a virulence regression line50The value and its 95% confidence limit and the correlation coefficient r, and the activity of the test agent on the biological test material.
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. The co-toxicity coefficient (CTC value) of the mixture is calculated according to the following formula (3), formula (4) and formula (5):
Figure BDA0002412626550000083
in the formula:
ATI-actually measured toxicity index of mixed agent;
S-EC of Standard Fungicide50In milligrams per liter (mg/L);
EC of M-mixtures50In milligrams per liter (mg/L).
TTITIA *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 BDA0002412626550000091
In the formula:
CTC-co-toxicity coefficient;
ATI-actually measured toxicity index of mixed agent;
TTI-mixture theory virulence index.
Results and analysis:
as can be seen from table 1: aminopyrifen and bupirimate single-agent and compound agent thereof have good bactericidal activity on powdery mildew, and Aminopyrifen single-agent EC50With a value of 12.378mg/L, bupirimate single dose EC50The value was 6.272 mg/L. EC of Aminopyrofen and bupirimate compound 1:550The minimum value was 5.851 mg/L.
TABLE 1 Combined virulence determination of Aminopyrofen and bupirimate in different ratios for powdery mildew
Figure BDA0002412626550000092
Figure BDA0002412626550000101
Figure BDA0002412626550000111
As can be seen from table 2: aminopyrefen and bupirimate single agents and compound agents thereof have additive or synergistic effects on powdery mildew, Aminopyrefen and bupirimate compound agents have synergistic effects in a ratio of 1: 10-20: 1, and Aminopyrefen and bupirimate compound agents 5:1 have the maximum co-toxicity coefficient value which is 153.36-120.
TABLE 2 Aminopyrefen and bupirimate different formulations for determining synergistic effect on powdery mildew
Reagent for testing EC50 Co-toxicity coefficient Synergistic action
Biopesticide (mg/L) (ATI) (TTI) (CTC)
Aminopyrifen 12.387 100 / / /
Bupirimate sulfonate 6.272 197.49 / / /
Aminopyrofen bupirimate ═ 1:50 7.700 160.87 195.58 82.25 Additive effect
Aminopyrofen bupirimate ═ 1:20 6.669 185.74 192.85 96.31 Additive effect
Aminopyrofen bupirimate ═ 1:10 6.258 197.94 188.63 104.93 Efficiency enhancementFunction of
Aminopyrofen bupirimate ═ 1:5 5.851 211.71 181.24 116.81 Synergistic action
Aminopyrofen bupirimate ═ 1:3 5.989 206.83 173.12 119.47 Synergistic action
Aminopyrofen bupirimate ═ 1:1 6.900 179.53 148.74 120.69 Synergistic action
Aminopyrofen bupirimate ═ 3:1 7.200 172.04 124.37 138.33 Synergistic action
Aminopyrofen: bupirimate ═ 5:1 6.948 178.28 116.24 153.36 Synergistic action
Aminopyrofen bupirimate ═ 10:1 7.914 156.52 108.86 143.78 Synergistic action
Aminopyrofen bupirimate ═ 20:1 8.753 141.52 104.64 135.24 Synergistic action
Aminopyrofen bupirimate ═ 50:1 10.586 117.01 101.91 114.82 Additive effect
Preparation example 1:20 wt% Aminopyrefen bupirimate aqueous emulsion
Dissolving 15g of Aminopyrefen raw drug and 5g of bupirimate raw drug in a compound solvent consisting of 10g of cyclohexanone and 15g of No. 150 solvent oil, and then fully and uniformly mixing with 3g of castor oil polyoxyethylene ether and 3g of EO-PO block copolymer to prepare an oil phase; 5g of ethylene glycol, 0.2g of organic silicon defoamer and 43.8g of water are uniformly mixed to prepare a water phase; and (3) dropwise adding the water phase into the oil phase under high-speed shearing (5000 r/min), and continuously shearing for 10min to obtain small droplets of 0.5-1.5 microns of oil phase particles, so as to obtain the Aminopyrefen bupirimate aqueous emulsion with the mass content of the effective component of 20 wt%.
Preparation example 2: 25 wt% Aminopyrofen bupirimate microemulsion
Dissolving 20g of Aminopyrofen raw drug and 5g of bupirimate raw drug in a compound solvent consisting of 10g of cyclohexanone and 15g of No. 150 solvent oil, and then fully and uniformly mixing with 3g of castor oil polyoxyethylene ether and 3g of EO-PO block copolymer to prepare an oil phase; 5g of ethylene glycol, 0.2g of organic silicon defoamer and 38.8g of water are uniformly mixed to prepare a water phase; and (3) dropwise adding the water phase into the oil phase under high-speed shearing (5000 revolutions per minute), and continuously shearing for 10 minutes until the particles of the oil phase are small droplets of 0.01-0.1 micrometer, so as to prepare the Aminopyrofen bupirimate microemulsion with the mass content of the effective component of 25 wt%.
Preparation example 3: 30 wt% Aminopyrefen bupirimate aqueous emulsion
Dissolving 15g of Aminopyrefen raw drug and 15g of bupirimate raw drug in a compound solvent consisting of 10g of cyclohexanone and 15g of No. 150 solvent oil, and then fully and uniformly mixing with 3g of castor oil polyoxyethylene ether and 3g of EO-PO block copolymer to prepare an oil phase; 5g of ethylene glycol, 0.2g of organic silicon defoamer and 33.8g of water are uniformly mixed to prepare a water phase; and (3) dropwise adding the water phase into the oil phase under high-speed shearing (5000 r/min), and continuously shearing for 10min to obtain small droplets of 0.5-1.5 microns of oil phase particles, so as to obtain the Aminopyrefen bupirimate aqueous emulsion with the mass content of the effective component of 30 wt%.
Preparation example 4: 40 wt% Aminopyrofen bupirimate microemulsion
Dissolving 30g of Aminopyrofen raw drug and 10g of bupirimate raw drug in a compound solvent consisting of 10g of cyclohexanone and 15g of No. 150 solvent oil, and then fully and uniformly mixing with 3g of castor oil polyoxyethylene ether and 3g of EO-PO block copolymer to prepare an oil phase; 5g of ethylene glycol, 0.2g of organic silicon defoamer and 23.8g of water are uniformly mixed to prepare a water phase; and (3) dropwise adding the water phase into the oil phase under high-speed shearing (5000 revolutions per minute), and continuously shearing for 10min to obtain the Aminopyrofen bupirimate microemulsion with the mass content of the effective component of 40 wt%, wherein the particle size of the oil phase is 0.01-0.1 micron.
Example 2
Field test for preventing and treating powdery mildew of cucumber
Test protocol
Test work: cucumber (Cucumis sativus L)
Test subjects: powdery mildew
The test is carried out in a southern village and town cucumber plantation in the flatness city of Shandong province, the cucumber variety is the small cucumber in the Netherlands, the soil fertility of the test cell is moderate, the terrain is smooth, the fertility is uniform, and the irrigation condition is good. All test plot cultivation conditions (soil type, fertilization, cultivation, row spacing, etc.) were uniform and consistent with local agricultural cultivation practices (GAP). The preparation treatment, control treatment and blank control are arranged in random blocks, and the cell area is 10m2(4 rows), the cells are arranged in random block groups, and the buffer rows are arranged between adjacent cells and repeated for 4 times.
The application time is 7 middle ten days and 8 early months, the application is continuously performed for 3 times at intervals of 1 time every 7 days in the early disease occurrence period, the weather is good in the test period, the daily average temperature is 25 ℃, the highest temperature is 32 ℃ and the lowest temperature is 21 ℃ on the first application day.
The pesticide application apparatus is a WS-16D guard electric sprayer, the spray head is a single fan-shaped fog spray head, the working pressure is 0.15-0.4Mpa, and the dosage is accurately measured according to the dosage requirement of the pesticide and the area of a cell. When dispensing, firstly adding clean water with one third of actual water consumption into the sprayer, adding a little water into the small measuring cup to uniformly stir the medicament, pouring the medicament into the sprayer, and finally adding the rest water and uniformly mixing. When the pesticide is applied, the control is sprayed firstly, and the spraying is carried out from low concentration to high concentration in sequence, and the constant spraying method is adopted, and the uniform spraying is carried out at a constant speed according to the calculated step speed. When different medicaments are replaced, the sprayer is cleaned for three times, and water in the spray rod is completely sprayed out.
The investigation method comprises the following steps: before drug application, the disease index of the cell is investigated at a fixed point, 20 plants are investigated randomly in each cell, 5 leaves are investigated from top to bottom in each cell, the disease progression is recorded respectively, and the disease leaf rate and the disease index are counted simultaneously. And (3) investigating the morbidity condition of each cell before pesticide application, 7 days after 1-time pesticide spraying, 7 days after 2-time pesticide spraying and 7 days after 3-time pesticide spraying, calculating the disease index and the control effect, and analyzing data.
By 9-stage classification
Level 0: no disease spots;
level 1: the lesion area accounts for less than 5% of the whole leaf area;
and 3, level: the lesion area accounts for 6 to 10 percent of the whole leaf area;
and 5, stage: the lesion area accounts for 11 to 20 percent of the whole leaf area;
and 7, stage: the lesion area accounts for 21 to 50 percent of the whole leaf area;
and 9, stage: the lesion area accounts for more than 50% of the whole leaf area.
The drug effect is calculated according to the formula (1) and the formula (2):
(1) disease index { (leaf number of each grade relative grade value)/total leaf number of survey 9 }. 100
(2) The preventing and treating effect (%) is {1- (pre-drug disease index in the blank control area after drug treatment area)/(post-drug disease index in the blank control area before drug treatment area) } 100
Or the prevention and treatment effect (no base before application)% (blank control area disease index-treatment area disease index)/blank control area disease index 100
Test results of each treatment medicament for preventing and treating cucumber powdery mildew
TABLE 3 field test results of different tested agents on cucumber powdery mildew
Figure BDA0002412626550000131
Note: the control (%) in the table above is the average of each repetition. Lower case letters represent 5% level difference and upper case letters represent 1% level difference.
As can be seen from Table 3, the powdery mildew of cucumber in the test plot is in the early stage of onset, and the disease index is 4.36-5.39. 7 days after the application for the 1 st time, the control effect of each compound medicament is more than 77.01%, the control effect of the 20% Aminopyrofen aqueous emulsion is 74.89%, the compound medicament shows better quick-acting performance, test data are processed by a Duncan method through IBM SPSS data processing software, and the variance analysis result shows that the difference between the 30% Aminopyrofen ethirimol sulfonate aqueous emulsion and the 40% Aminopyrofen ethirimol sulfonate microemulsion does not exist at the levels of 0.05 and 0.01. Test results show that the 30% Aminopyrefen bupirimate aqueous emulsion has high quick-acting performance and control effect of 79.15%, and each compound medicament has obvious difference with a control single agent. With the increase of the application time, the control effect of most medicaments of the 40% Aminopyrofen bupirimate microemulsion after 7d of the second application is increased, the maximum control effect is 84.06%, the control effects of the 25% Aminopyrofen bupirimate microemulsion, the 30% Aminopyrofen bupirimate aqueous emulsion and the 40% Aminopyrofen bupirimate microemulsion are 81.09%, 83.95% and 84.06% respectively, the control effect of the 25% bupirimate microemulsion is reduced to 60.96% with the increase of the application time, and the analysis of variance results show that the 25% bupirimate microemulsion is under the levels of 0.05 and 0.01, and the control effects of the 7d after the first application and the 7d after the second application are obviously different from other treatments. The highest 30 percent Aminopyrefen bupirimate emulsion in water is 91.43 percent 7 days after the 3 rd application. The control effect of four mixed medicaments, namely 20% of Aminopyrefen bupirimate aqueous emulsion, 25% of Aminopyrefen bupirimate microemulsion, 30% of Aminopyrefen bupirimate aqueous emulsion and 40% of Aminopyrefen bupirimate microemulsion, is more than 83.69%, and the two medicaments have no difference at the level of 0.05 and 0.01 and have obvious difference with a single medicament. Tests show that powdery mildew of cucumber is easy to attack under high humidity conditions, and mainly damages leaves, stems and vines. When the cucumber grows in early stage, powdery mildew which is nearly circular is firstly generated on leaves and then fused into powdery spots, and when the powdery mildew is serious, the powdery spots are fully distributed on the leaves, so that the leaves are withered or fall off, and serious economic loss is caused to the normal growth of the cucumber. The key point of preventing and controlling the powdery mildew of cucumber is to master the optimal prevention and control period, and continuously prevent and control for 2-3 times in the disease circulation period.
Example 3
Field test for preventing and treating powdery mildew of muskmelon
Test protocol
Test work: melon (Cucumis melo L)
Test subjects: powdery mildew
The experiment is carried out in the Weifang melon plantation in late ten days of 7 months, and the melon variety is greenGem No. 2, moderate soil fertility in the test field, smooth terrain, uniform fertility and good irrigation conditions. All test plot cultivation conditions (soil type, fertilization, cultivation, row spacing, etc.) were uniform and consistent with local agricultural cultivation practices (GAP). The preparation treatment, control treatment and blank control are arranged in random blocks, and the cell area is 20m2The cells are arranged in random block groups, and the buffer lines are arranged between adjacent cells and repeated for 4 times.
The application time is in late 7 months, the application is continuously performed for 3 times at intervals of 1 time every 7 days in the early disease occurrence period, the weather is good in the test period, the daily average temperature is 23 ℃, the maximum temperature is 31 ℃, and the minimum temperature is 19 ℃ on the first application day.
The pesticide application apparatus is a WS-16D guard electric sprayer, the spray head is a single fan-shaped fog spray head, the working pressure is 0.15-0.4Mpa, and the dosage is accurately measured according to the dosage requirement of the pesticide and the area of a cell. When dispensing, firstly adding clean water with one third of actual water consumption into the sprayer, adding a little water into the small measuring cup to uniformly stir the medicament, pouring the medicament into the sprayer, and finally adding the rest water and uniformly mixing. When the pesticide is applied, the control is sprayed firstly, and the spraying is carried out from low concentration to high concentration in sequence, and the constant spraying method is adopted, and the uniform spraying is carried out at a constant speed according to the calculated step speed. When different medicaments are replaced, the sprayer is cleaned for three times, and water in the spray rod is completely sprayed out.
The investigation method comprises the following steps: before drug application, the disease indexes of the cells are investigated at fixed points, 10 plants are investigated randomly in each cell, 5 leaves are investigated in each cell, the disease progression is recorded, and the disease leaf rate and the disease index are counted. Before pesticide application, the 1 st pesticide spraying 7d, the 2 nd pesticide spraying 7d and the 3 rd pesticide spraying 7d are used for investigating the disease incidence of each cell, calculating the disease index and the control effect and analyzing data.
By 9-stage classification
Level 0: no disease spots;
level 1: the lesion area accounts for less than 5% of the whole leaf area;
and 3, level: the lesion area accounts for 6 to 10 percent of the whole leaf area;
and 5, stage: the lesion area accounts for 11 to 20 percent of the whole leaf area;
and 7, stage: the lesion area accounts for 21 to 50 percent of the whole leaf area;
and 9, stage: the lesion area accounts for more than 50% of the whole leaf area.
The drug effect is calculated according to the formula (1) and the formula (2):
(1) disease index { (leaf number of each grade relative grade value)/total leaf number of survey 9 }. 100
(2) The preventing and treating effect (%) is {1- (pre-drug disease index in the blank control area after drug treatment area)/(post-drug disease index in the blank control area before drug treatment area) } 100
Or the prevention and treatment effect (no base before application)% (blank control area disease index-treatment area disease index)/blank control area disease index 100
Test results of various treatment medicaments for preventing and treating powdery mildew of melons
TABLE 4 field test results of different test agents on powdery mildew of melon
Figure BDA0002412626550000151
Figure BDA0002412626550000161
Note: the control (%) in the table above is the average of each repetition. Lower case letters represent 5% level difference and upper case letters represent 1% level difference.
The test results show that the powdery mildew of melons in the test plot is serious and is in the disease development stage, and the disease index is 8.61-10.17, as can be seen from table 4. The control effect of each compound medicament is more than 49.65 percent 7 days after the application of the 1 st time, the control effect of 20 percent Aminopyrofen aqueous emulsion is 49.73 percent, the control effect of 25 percent bupirimate microemulsion is 52.38 percent, the control effect is relatively poor, the control effect is increased along with the time advance, the control effect is increased 7 days after the application of the 2 nd time, the control effect of 30 percent Aminopyrofen and bupirimate aqueous emulsion is 64.77 percent, the control effect of 40 percent Aminopyrofen and bupirimate microemulsion is 64.50 percent, the control effect of 20 percent Aminopyrofen and bupirimate aqueous emulsion is 62.62 percent, the control effect of 30 percent Aminopyrofen and bupirimate aqueous emulsion is 62.41 percent, and the control effect of four compound medicaments is improved compared with the control effect of the 7 days after the application of the 1 st time. And the IBM SPSS data processing software is used for processing the test data by a Duncan new double offset (Duncan) method, and the analysis of variance results show that the four compound medicaments have no difference at the levels of 0.05 and 0.01. The highest 30 percent Aminopyrefen-bupirimate aqueous emulsion is 81.76 percent 7 days after the 3 rd application; the control effect of 20% Aminopyrefen bupirimate aqueous emulsion is 80.28%. The control effect of the 25 percent bupirimate microemulsion is 66.00 percent, the control effect of the 20 percent Aminopyrofen aqueous emulsion is 70.10 percent, and the control effect is obviously higher than that of the 25 percent bupirimate microemulsion. Melon powdery mildew is a common disease of melons and can cause serious harm. The muskmelon growing period can be all started, white tiny powder spots appear on the front and back of the muskmelon at the initial stage, the white tiny powder spots gradually expand to form white round powder spots, and a plurality of disease spots are connected with each other, so that the surface of the muskmelon is full of white powder. With the development of diseases, the color of the powder spot gradually changes into grey white, and black dots are occasionally generated under the powder layer in the later period. Finally, the diseased leaves are withered and yellow and necrotic. The higher humidity is beneficial to spore germination and invasion, can occur at 10-25 ℃, and can be popular or not depending on the humidity and the growth vigor of hosts. Can germinate under low humidity, and the germination rate under high humidity is obviously improved. Therefore, the rain is dry or less rain, but the field humidity is high, and the epidemic speed of powdery mildew is accelerated. Experiments show that the control of the powdery mildew of the melon should be carried out for 2-3 times at the early stage of disease incidence and in the disease circulation stage, and the control effect is better.
Through indoor toxicity measurement and field tests, the pesticide composition compounded by the Aminopyrefen and the bupirimate has good control effect on fungal diseases (cucumber powdery mildew and melon powdery mildew) of fruit and vegetable crops. The pesticide composition or the preparation thereof obtained by compounding has obvious control effect, and is superior to a single preparation in the aspects of delaying the generation of drug resistance and prolonging the drug-holding property. And no phytotoxicity of the compound pesticide on crops is found in tests, which shows that the production cost and the use cost can be reduced and the pesticide composition or the preparation is safe to the crops under the condition of improved sterilization synergy.
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 (9)

1. An agricultural chemical composition containing Aminopyrofen, which is characterized in that: the active ingredient A is Aminopyrofen, and the structural formula is as follows:
Figure FDA0002412626540000011
the active component B is bupirimate.
2. The pesticide composition as set forth in claim 1, wherein the mass ratio of Aminopyrefen to bupirimate is 50: 1-1: 50.
3. The pesticide composition as set forth in claim 1, wherein the mass ratio of Aminopyrefen to bupirimate is 20: 1-1: 20.
4. A pesticidal composition according to any one of claims 1 to 3, characterised in that the sum of the amounts of active ingredient a and active ingredient B in the pesticidal composition is from 1 to 95 wt%, preferably from 5 to 80 wt%, more preferably from 10 to 60 wt%, based on 100 wt% of the total weight of the pesticidal composition.
5. A pesticidal composition according to any one of claims 1 to 4, further comprising an adjuvant 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 stabiliser, a synergist or a carrier.
6. The pesticide composition as set forth in claim 5, wherein the pesticide composition is in the form of any one of emulsifiable concentrate, aqueous emulsion, microemulsion, suspending agent, wettable powder or water dispersible granule;
preferably, the preparation is in the form of microemulsion or aqueous emulsion.
7. Use of the pesticidal composition of any one of claims 1-6 for controlling plant diseases.
8. The use according to claim 7, characterized in that the plant diseases are plant diseases caused by fungi or bacteria; preferably, the plant disease is a plant disease caused by a fungus; more preferably, the fungi are cucurbit monocystus shells (Sphaerotheca cucurbitae (Jacz) z.y.zhao) and cucurbit Erysiphe cucurbitaceae powdery mildew (Erysiphe cucurbitaceae Zheng & Chen) belonging to the genus ascomycota or the genus Erysiphe.
9. Use according to any one of claims 7 to 8, characterized in that the plant diseases are those of the cucurbitaceae family;
preferably, the cucurbitaceae plant is cucumber or melon.
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