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CN114617129B - Sterilization composition and application thereof - Google Patents

Sterilization composition and application thereof Download PDF

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Publication number
CN114617129B
CN114617129B CN202210382871.9A CN202210382871A CN114617129B CN 114617129 B CN114617129 B CN 114617129B CN 202210382871 A CN202210382871 A CN 202210382871A CN 114617129 B CN114617129 B CN 114617129B
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benzovindiflupyr
test
zineb
bromothalonil
composition
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CN114617129A (en
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隋书婷
杨志鹏
王玉
葛家成
李晶
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Qingdao Hailier Biotechnology Co ltd
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Qingdao Hailier Biotechnology Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34Nitriles
    • 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
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14Di-thio analogues thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention belongs to the technical field of agricultural sterilization, and discloses a sterilization composition and application thereof, wherein the sterilization composition comprises a synergistically effective amount of benzovindiflupyr and a bactericide, the bactericide is any one of zineb or bromothalonil, the composition has a good control effect on various plant diseases, has a synergistic effect on the control of various fungal diseases, especially diseases caused by fungi of the phylum of the semi-known mycotina and fungi of the ascomycotina, can effectively control pathogenic microorganisms to generate drug resistance, reduces the use amount of medicaments, reduces the use cost of medicaments and is environment-friendly.

Description

Sterilization composition and application thereof
Technical Field
The invention belongs to the technical field of agricultural sterilization, and particularly relates to a sterilization composition and application thereof.
Background
Benzovindiflupyr, CAS number: 1072957-71-1, english name: benzovindiflupyr, chemical name: n- [9- (dichloromethyl) -1,2,3, 4-tetrahydro-1, 4-methylenenaphthalen-5-yl ] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide. Benzovindiflupyr is a novel pyrazole bactericide developed by Zhengda, belongs to a succinic dehydrogenase inhibitor, can act on a composite protein II on a respiratory electron transfer chain of pathogenic bacteria mitochondria, namely succinic dehydrogenase or succinic acid-ubiquinone reductase, and acts on target pathogenic bacteria by interfering the normal respiration process of fungal cells. Benzovindiflupyr is a broad-spectrum leaf fungicide, can be compounded with various types of fungicides and has no cross resistance.
Zineb, english name: zineb is an Ethylene-bis-thiocarbamate (EBDCs) protective bactericide, has good control effect on downy mildew, late blight and anthracnose, and can be used for controlling various diseases of crops such as fruits, vegetables and the like.
Bromothalonil, english name: bromothalonil, chemical name: 2-bromo-2-bromomethylglutaronitrile has low toxicity, broad spectrum and sterilization, mildew resistance and algae removal properties. Bromothalonil can inhibit the growth of bacteria, fungi and algae. The mechanism of action is related to the high-density electrophilic center contained in the molecular structure, and can be tightly assembled with nucleophilic groups in pathogenic microorganism cells, so that the cell metabolism is disturbed.
The prevention and control of the medicament is still a main method for preventing and controlling plant diseases, and the prevention and control effect is drastically reduced due to the obvious drug resistance of pathogenic bacteria caused by the long-term and large-scale use of a single medicament. How to effectively control pathogenic bacteria harm becomes one of the bottlenecks of high and stable yield of crops. Because of the great difficulty in creating new pesticides, the most effective method is to compound and apply the bactericide, the reasonable compounding can improve the control effect of single drug, delay the generation of resistance of pathogenic microorganisms, inhibit the pathogenic bacteria which have generated resistance, and reduce the dosage of the medicament to reduce the cost and toxicity.
Disclosure of Invention
Based on the above circumstances, an object of the present invention is to provide a fungicidal composition having a good control effect on various plant diseases, having a synergistic effect on the control of various fungal diseases, particularly diseases caused by fungi of the phylum of the half-known fungus and fungi of the phylum of the ascomycota, which can effectively control the generation of drug resistance by pathogenic microorganisms, reduce the amount of the agent used, reduce the cost of the agent used, and is environmentally friendly, and a preparation thereof
In order to achieve the above purpose, the present invention adopts the following technical scheme: a bactericidal composition and application thereof, wherein the bactericidal composition comprises active ingredient A benzovindiflupyr and active ingredient B with synergistic effective amounts, and the active ingredient B is any one of zineb or bromothalonil.
Further, the mass ratio of the benzovindiflupyr to the zineb or bromothalonil is 1:30-20:1;
further, the mass ratio of the benzovindiflupyr to the zineb is 1:30-10:1;
further, the mass ratio of the benzovindiflupyr to the zineb is 1:30, 1:20, 1:10, 1:5, 1:3, 1:1, 3:1, 5:1 and 10:1;
furthermore, the mass ratio of the benzovindiflupyr to the zineb is 1:30-1:1;
further, the mass ratio of the benzovindiflupyr to the zineb is 1:30, 1:20, 1:10, 1:5, 1:3 and 1:1;
further, the mass ratio of the benzovindiflupyr to the bromothalonil is 1:20-20:1;
further, the mass ratio of the benzovindiflupyr to the bromothalonil is 1:20, 1:15, 1:10, 1:5, 1:3, 1:1, 5:1, 10:1 and 20:1;
further, the mass ratio of the benzovindiflupyr to the bromothalonil is 1:15-15:1;
further, the mass ratio of the benzovindiflupyr to the bromothalonil is 1:15, 1:10, 1:5, 1:3, 1:1 and 5:1;
further, the total weight of the bactericidal composition is calculated by 100 weight percent, and the total weight of the active component A and the active component B accounts for 0.1 to 90 percent of the total weight of the bactericidal composition;
further, the total weight of the bactericidal composition is calculated by 100 weight percent, and the total weight of the active component A and the active component B accounts for 2-70 percent of the total weight of the bactericidal composition;
further, the bactericidal composition comprises an agriculturally acceptable auxiliary ingredient besides an active ingredient, wherein the auxiliary ingredient is selected from one or more of wetting agents, dispersing agents, thickening agents, disintegrating agents, emulsifying agents, defoaming agents, preservatives, stabilizers, synergists, carriers and solvents;
further, the wetting agent is selected from one or more of alkylbenzene sulfonate, alkyl naphthalene sulfonate, lignin sulfonate, sodium dodecyl sulfate, dioctyl sodium succinate, alpha-olefin sulfonate, alkylphenol ethoxylate, castor oil polyoxyethylene ether, alkylphenol ethoxylate, fatty alcohol polyoxyethylene ether sodium sulfate, silkworm excrement, chinese honeylocust fruit powder, soapberry powder, SOPA, detergent, emulsifier 2000 series and wetting penetrating agent 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, glycerin fatty acid ester polyoxyethylene ether, polycarboxylate, polyacrylic acid, phosphate, EO-PO block copolymer and EO-PO graft copolymer; and/or
The thickener is one or more selected from xanthan gum, polyvinyl alcohol, organic bentonite, magnesium aluminum silicate and carboxymethyl cellulose; and/or
The disintegrating agent is one or more selected from 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 emulsifier is one or more selected from fatty alcohol polyoxyethylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, phenethyl phenol polyoxyethylene polyoxypropylene ether, alkylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, alkylbenzene sulfonate, styrylphenol polyoxyethylene ether and fatty acid polyoxyethylene ester; and/or
The defoamer is selected from silicone oil and C 10 ~C 20 Saturated fatty acid compound, C 8 ~C 10 One or more of fatty alcohol compounds or silicone compounds; and/or
The preservative is one or more of sorbic acid, sodium sorbate, potassium sorbate, benzoic acid, sodium benzoate, sodium p-hydroxybenzoate and methyl p-hydroxybenzoate; and/or
The stabilizer is one or more selected from disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2, 6-di-tert-butyl-p-cresol and epoxidized vegetable oil; and/or
The synergistic agent is selected from synergistic phosphorus and synergistic ether; and/or
The carrier is one or more selected from kaolin, bentonite, attapulgite, light calcium carbonate, diatomite and white carbon black; and/or
The solvent is selected from one or more of benzene, toluene, xylene, methanol, ethanol, isopropanol, N-butanol, diesel oil, N-dimethylformamide, cyclohexanone, ethyl acetate, N-methylpyrrolidone, propanol, butanol, ethylene glycol, diethylene glycol, ethylene glycol methyl ether, butyl ether, solvent oil, vegetable oil derivatives and deionized water; and/or
Further, the pesticide composition can be prepared into any agriculturally acceptable formulation;
further, the preparation formulation is any one of a solid preparation, a liquid preparation 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, granule, sphere, tablet or strip;
the dispersible solid preparation is wettable powder, oil dispersion powder, emulsion powder, water dispersible granule, emulsion granule or water dispersible tablet;
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 multiphase preparation;
further, the solution preparation is a soluble agent, an oil agent or a film spreading oil agent;
the dispersion liquid preparation is emulsifiable concentrate, emulsion, dispersible agent or paste;
the emulsion preparation is aqueous emulsion, oil emulsion, microemulsion or fat agent;
the suspension preparation is suspending agent, microcapsule suspending agent, oil suspending agent or dispersible oil suspending agent;
the multiphase preparation is a suspension emulsion, a microcapsule suspension-suspending agent, a microcapsule suspension-water emulsion or a microcapsule suspension-suspending emulsion;
further, the seed treatment preparation comprises a seed treatment solid preparation or a seed treatment liquid preparation;
further, the seed treatment solid preparation is seed treatment dry powder or seed treatment dispersible powder;
the seed treatment liquid preparation is a seed treatment liquid, a seed treatment emulsion or a seed treatment suspending agent;
further, the solid preparation is water dispersible granule and/or wettable powder, and the liquid preparation is suspending agent and/or emulsifiable concentrate.
The invention also discloses an application of the bactericidal composition and/or the preparation thereof in preventing and treating plant diseases.
Further, the disease comprises a fungal disease and/or a bacterial disease;
further, when the bactericidal composition is used for preventing and treating fungal diseases, the fungal diseases are diseases caused by one or more of the following pathogenic bacteria: fungi of the phylum Deuteromycotina, fungi of the phylum Basidiomycotina, fungi of the phylum Ascomycotina and/or fungi of the phylum Trigonella;
further, the fungal diseases are diseases caused by the following pathogenic bacteria: fungi of the phylum Deuteromycotina and fungi of the phylum ascomycotina;
further, the fungi of the subdivision Deuteromycotina are melon anthracnose (Colletotrichum lagenarium (pass.) and/or ell.et halst) and/or tomato early blight (Alternaria solani), and the fungi of the subdivision Deuteromycotina are wheat powdery mildew (Blumeria graminis f.sp.tritici);
further, the bactericidal composition is applied to bacteria or a growth medium thereof to be controlled in an effective dose.
Compared with the prior art, the invention has the following advantages:
1) The bactericidal composition is compounded by two medicaments with different action mechanisms, and has synergistic effect while delaying the drug resistance of pathogenic bacteria;
2) The bactericidal composition can effectively reduce the dosage of the medicament, and is safe to crops and non-target organisms;
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention can be embodied in various forms and should not be construed as being limited to the embodiments set forth herein.
Preparation example of the formulation
Preparation example 1:63% benzovindiflupyr/zineb wettable powder (1:20)
3% of benzovindiflupyr, 60% of zineb, 12% of sodium lignin sulfonate, 2% of sodium dodecyl sulfate, 5% of naphthalene sulfonate formaldehyde condensate and the balance of kaolin;
the preparation method comprises the following steps: mixing the active ingredients, the dispersing agent, the wetting agent and the filler, uniformly stirring in a stirring kettle, and carrying out multiple crushing and uniform mixing by an airflow crusher to obtain the required wettable powder.
Preparation example 2:44% benzovindiflupyr/zineb wettable powder (1:10)
4 weight percent of benzovindiflupyr, 40 weight percent of zineb, 8 weight percent of sodium lignin sulfonate, 4 weight percent of polycarboxylate sodium salt, 3 weight percent of nekal BX and the balance of kaolin;
the preparation method comprises the following steps: the same as in preparation example 1.
Preparation example 3:30% benzovindiflupyr/zineb suspension (1:5)
According to the weight percentage, 5 percent of benzovindiflupyr, 25 percent of zineb, 2 percent of naphthalene sulfonate formaldehyde condensate, 3 percent of alkylphenol polyoxyethylene ether phosphate, 4 percent of EO-PO segmented copolymer, 0.2 percent of xanthan gum, 5 percent of glycol, 0.1 percent of sodium benzoate, 0.5 percent of silicone oil and the balance of deionized water;
the preparation method comprises the following steps: according to the formula proportion, the active ingredients, the surfactant and other functional auxiliary agents are sequentially placed in a reaction kettle, water is added and mixed uniformly, high-speed shearing and wet sanding are carried out, and finally, the suspending agent product is obtained through homogenizing and filtering.
Preparation example 4:40% benzovindiflupyr/zineb water dispersible granule (1:3)
According to the weight percentage, 10 percent of benzovindiflupyr, 30 percent of zineb, 3 percent of sodium lignin sulfonate, 10 percent of naphthalene sulfonate formaldehyde condensate, 3 percent of nekal BX, 10 percent of ammonium sulfate and the balance of kaolin are complemented;
the preparation method comprises the following steps: adding active ingredients into a carrier according to the formula proportion, adding a surfactant and other functional additives into the carrier, mixing, adding 10-25% of water after jet milling, and then kneading, granulating, drying and screening to obtain a water dispersible granule product; or spraying water, granulating, drying, and sieving to obtain the final product.
Preparation example 5:44% benzovindiflupyr bromothalonil wettable powder (1:10)
4 weight percent of benzovindiflupyr, 40 weight percent of bromothalonil, 10 weight percent of calcium lignosulfonate, 5 weight percent of sodium polycarboxylate, 4 weight percent of dispersant NNO and the balance of kaolin;
the preparation method comprises the following steps: the same as in preparation example 1.
Preparation example 6:30% benzovindiflupyr bromothalonil suspension (1:5)
According to the weight percentage, 5 percent of benzovindiflupyr, 25 percent of bromothalonil, 3 percent of alkylaryl polyoxyethylene ether polyoxypropylene ether, 3 percent of tristyrylphenol ethoxylate phosphate, 2 percent of sodium lignin sulfonate, 1 percent of alkylphenol polyoxyethylene ether, 0.25 percent of xanthan gum, 1 percent of magnesium aluminum silicate, 5 percent of glycerol, 0.3 percent of potassium benzoate, 0.5 percent of silicone oil and the balance of deionized water;
the preparation method comprises the following steps: the same as in preparation example 3.
Preparation example 7:24% benzovindiflupyr bromothalonil suspension (1:3)
6 weight percent of benzovindiflupyr, 18 weight percent of bromothalonil, 3 weight percent of alkylaryl polyoxyethylene ether polyoxypropylene ether, 3 weight percent of fatty alcohol polyoxyethylene ether phosphate, 1 weight percent of isomeric alcohol polyoxyethylene ether, 2 weight percent of lignin sulfonic acid, 0.25 weight percent of xanthan gum, 5 weight percent of glycerol, 1 weight percent of sodium sorbate, 0.5 weight percent of silicone oil and the balance of deionized water;
the preparation method comprises the following steps: the same as in preparation example 3.
Preparation example 8:20% benzovindiflupyr bromothalonil emulsifiable concentrate (1:1)
According to the weight percentage, 10 percent of benzovindiflupyr, 10 percent of bromothalonil, 30 percent of propylene carbonate, 10 percent of cyclohexanone, 12 percent of castor oil polyoxyethylene ether, 5 percent of isomeric tridecanol polyoxyethylene ether, 2 percent of calcium dodecyl benzene sulfonate and the balance of trimethylbenzene are complemented;
the preparation method comprises the following steps: adding the metered active ingredients, the solvent and the cosolvent into a blending kettle, stirring to dissolve the active ingredients, the solvent and the cosolvent, adding the emulsifier, supplementing the rest with the solvent, stirring uniformly in a stirrer, and filtering to obtain the required emulsifiable concentrate.
Indoor toxicity test
Example 1: benzenofloxacin and zineb or bromothalonil compounded indoor toxicity test for cucumber anthracnose
The test is based on: test reference NY/T1156.2-2006 section 2 of pesticide indoor bioassay test criteria section 2: test plate method for inhibiting growth of pathogenic fungi hyphae.
Test target: colletotrichum cucumerinum (Colletotrichum lagenarium (pass.) ell.et halst).
Experimental agent: 96% of benzovindiflupyr original drug and 95% of bromothalonil original drug are provided by the research and development center of the halier pharmaceutical industry, and 80% of zineb wettable powder is commercially available.
And (3) preparation of a medicament: dissolving benzovindiflupyr and bromothalonil for test by using acetone, diluting by using 0.1% Tween 80 aqueous solution, diluting the zineb wettable powder by using sterile water, and preparing mother solutions respectively. According to the purpose of mixing and the activity of the medicament, different proportions are designed, and each group of single agent and each group of mixed agent are prepared into a required series of mass concentrations according to an equal proportion method.
The proportion of the effective components of the mixed components is as follows:
benzovindiflupyr: zineb is 1:30, 1:20, 1:10, 1:5, 1:3, 1:1, 3:1, 5:1, 10:1;
benzovindiflupyr: bromothalonil is 1:20, 1:15, 1:10, 1:5, 1:3, 1:1, 5:1, 10:1, 20:1.
And (3) medicament treatment: under aseptic operation conditions, quantitatively adding pre-melted sterilized culture medium into an aseptic conical flask according to test treatment, quantitatively sucking liquid medicine from low concentration to high concentration, respectively adding into the conical flask, and shaking thoroughly. Then the mixture was poured into a petri dish with a diameter of 9cm in equal amounts to prepare a medicated plate with a corresponding concentration.
Inoculating: the cultured pathogenic bacteria are inoculated in the center of a medicine-containing flat plate by an inoculator by using a sterilization puncher with the diameter of 6mm from the edge of a bacterial colony, the mycelium surface faces upwards, a dish cover is covered, and the bacteria are placed in an incubator with proper temperature for culture.
The calculation method comprises the following steps:
the growth of pathogenic hyphae was investigated according to the growth of bacteria in a blank culture dish, and the colony diameter was measured with a caliper in millimeters (mm). The diameter of each colony was measured vertically by the cross-over method and the average value was taken.
The hypha growth inhibition rate of each treatment concentration on the test target bacteria was calculated according to the following formula based on the investigation result, and the unit is percentage (%).
D=D 1 -D 2
Wherein:
d-colony growth diameter;
D 1 colony diameter;
D 2 -diameter of the bacterial cake.
I, hypha growth inhibition rate;
D 0 -the control colony increased in diameter;
D t -the agent-treated colonies increased in diameter.
The co-toxicity coefficient (CTC value) of the blend was calculated as follows:
wherein:
ati—actual measured virulence index of the mixture;
S-EC of Standard bactericides 50 Milligrams per liter (mg/L);
M-EC of mixture 50 Units are milligrams per liter (mg/L).
TTI=TI A *P A +TI B *P B
Wherein:
TTI-the theoretical toxicity index of the mixture;
TI A -a medicament virulence index;
P A -the percentage of agent a in the mix, in percent (%);
TI B -B agent virulence index;
P B the percentage of the B medicament in the mixture is expressed as percentage (%).
Wherein:
ctc—co-toxicity coefficient;
ati—actual measured virulence index of the mixture;
TTI-the theoretical toxicity index of the mixture.
The compound co-toxicity coefficient CTC is more than or equal to 120 and shows synergistic effect; ctc.ltoreq.80 shows antagonism; 80< CTC <120 shows additive effect.
Calculating test results by adopting DPS data processing software, and respectively solving virulence regression equations, EC of single test medicament and mixed medicaments with different proportions 50 And 95% confidence limit, and solving co-toxicity coefficients (CTC) of the two medicaments in different proportions, and screening out the optimal proportion of the test medicaments. Record raw data for each process all repetitions.
The results of the indoor toxicity test are shown in the following table:
TABLE 1 Benzenefluoroazole and zineb combination pair cucumber anthracnose indoor virulence test results
Test agent Regression equation (y=a+bx) R EC 50 (mg/L) 95% confidence limit Co-toxicity coefficient (CTC)
Benzovindiflupyr (A) y=6.1741+1.1770x 0.9999 0.1006(0.0989-0.1022) -
Zineb (B) y=2.0989+1.2607x 0.9993 200.0831(192.0047-208.5015) -
A:B(1:30) y=4.6312+1.1586x 0.9992 2.0810(1.9911-2.1750) 147.634
A:B(1:20) y=4.8262+1.2326x 0.9995 1.3836(1.3374-1.4313) 151.169
A:B(1:10) y=5.1788+1.1609x 0.9988 0.7014(0.6646-0.7403) 156.981
A:B(1:5) y=5.4697+1.1715x 0.9989 0.3973(0.3775-0.4180) 151.545
A:B(1:3) y=5.6793+1.1818x 0.9999 0.2662(0.2612-0.2713) 150.937
A:B(1:1) y=5.9657+1.1704x 0.9989 0.1496(0.1420-0.1575) 134.424
A:B(3:1) y=6.1806+1.1855x 0.9997 0.1010(0.0984-0.1036) 132.783
A:B(5:1) y=6.2103+1.1863x 0.9994 0.0954(0.0919-0.0992) 126.528
A:B(10:1) y=6.3245+1.2620x 0.9994 0.0892(0.0858-0.0928) 124.052
As can be seen from the indoor toxicity test results in Table 1, the benzovindiflupyr has higher toxicity to cucumber anthracnose and EC thereof 50 0.1006mg/L, but zineb has poor effect of inhibiting the growth of cucumber anthracnose. After the benzovindiflupyr and the zineb are compounded, the compound shows good inhibition effect on cucumber anthracnose germs. Wherein the mass ratio of the benzovindiflupyr to the zineb is 1:30-10:1, the co-toxicity coefficient is more than 120, and the combined action is shown as synergy; the mass ratio of the benzovindiflupyr to the zineb is 1:20-1:3, the co-toxicity coefficient is more than 150, and the synergy is obvious.
TABLE 2 indoor toxicity test results of benzovindiflupyr and bromothalonil on cucumber anthracnose
Test agent Regression equation (y=a+bx) R EC 50 (mg/L) 95% confidence limit Co-toxicity coefficient (CTC)
Benzovindiflupyr (A) y=6.1741+1.1770x 0.9999 0.1006(0.0989-0.1022) -
Bromothalonil (B) y=4.6526+1.1536x 0.9998 2.0005(1.9612-2.0406) -
A:B(1:20) y=5.0794+1.0988x 0.9989 0.8467(0.8046-0.8910) 124.397
A:B(1:15) y=5.2137+1.2704x 0.9989 0.6789(0.6435-0.7163) 135.147
A:B(1:10) y=5.3376+1.1807x 0.9992 0.5177(0.4950-0.5415) 142.230
A:B(1:5) y=5.5918+1.1582x 0.9993 0.3083(0.2961-0.3211) 156.447
A:B(1:3) y=5.6930+1.1385x 0.9994 0.2462(0.2368-0.2560) 142.019
A:B(1:1) y=5.9852+1.1403x 0.9987 0.1368(0.1292-0.1449) 140.034
A:B(5:1) y=6.1860+1.1252x 0.9997 0.0883(0.0860-0.0907) 135.354
A:B(10:1) y=6.2606+1.1859x 0.9995 0.0865(0.0835-0.0896) 127.291
A:B(20:1) y=6.3490+1.2506x 0.9995 0.0834(0.0806-0.0864) 126.337
As can be seen from the indoor toxicity test results in Table 2, bromothalonil and benzovindiflupyr have good inhibition effect on the growth of cucumber anthracnose. The benzovindiflupyr and bromothalonil are mixed, the co-toxicity coefficients are all larger than 120 in the mass ratio range of 1:20-20:1, and the combined effect is shown as synergy; in the mass ratio of 1:15-5:1, the co-toxicity coefficient is more than 130, and the synergy is remarkable.
Example 2: indoor toxicity test of benzovindiflupyr and zineb on tomato early blight
The test is based on: test reference NY/T1156.2-2006 section 2 of pesticide indoor bioassay test criteria section 2: test plate method for inhibiting growth of pathogenic fungi hyphae.
Test target: tomato early blight germ (Alternaria solani).
Experimental agent: 96% benzovindiflupyr original drug is provided by the research and development center of the sea rill pharmaceutical industry group, and 80% zineb wettable powder is commercially available.
And (3) preparation of a medicament: dissolving the benzovindiflupyr crude drug for test with acetone, diluting with 0.1% Tween 80 aqueous solution, diluting the zineb wettable powder with sterile water, and preparing mother solutions respectively. According to the purpose of mixing and the activity of the medicament, different proportions are designed, and each group of single agent and each group of mixed agent are prepared into a required series of mass concentrations according to an equal proportion method.
The proportion of the effective components of the mixed components is as follows:
benzovindiflupyr: zineb is 1:30, 1:20, 1:10, 1:5, 1:3, 1:1.
And (3) medicament treatment: under aseptic operation conditions, quantitatively adding pre-melted sterilized culture medium into an aseptic conical flask according to test treatment, quantitatively sucking liquid medicine from low concentration to high concentration, respectively adding into the conical flask, and shaking thoroughly. Then the mixture was poured into a culture medium having a diameter of 9cm in equal amounts to prepare a drug-containing plate having a corresponding concentration.
Inoculating: the cultured pathogenic bacteria are inoculated in the center of a medicine-containing flat plate by an inoculator by using a sterilization puncher with the diameter of 6mm from the edge of a bacterial colony, the mycelium surface faces upwards, a dish cover is covered, and the bacteria are placed in an incubator with proper temperature for culture.
Data investigation:
the growth of pathogenic hyphae was investigated according to the growth of bacteria in a blank culture dish, and the colony diameter was measured with a caliper in millimeters (mm). The diameter of each colony was measured vertically by the cross-over method and the average value was taken.
The hypha growth inhibition rate of each treatment concentration on the test target bacteria was calculated according to the following formula based on the investigation result, and the unit is percentage (%).
D=D 1 -D 2
Wherein:
d-colony growth diameter;
D 1 colony diameter;
D 2 -diameter of the bacterial cake.
I, hypha growth inhibition rate;
D 0 -the control colony increased in diameter;
D t -the agent-treated colonies increased in diameter.
The co-toxicity coefficient (CTC value) of the blend was calculated as follows:
wherein:
ati—actual measured virulence index of the mixture;
S-EC of Standard bactericides 50 Milligrams per liter (mg/L);
M-EC of mixture 50 Units are milligrams per liter (mg/L).
TTI=TI A *P A +TI B *P B
Wherein:
TTI-the theoretical toxicity index of the mixture;
TI A -a medicament virulence index;
P A -the percentage of agent a in the mix, in percent (%);
TI B -B agent virulence index;
P B the percentage of the B medicament in the mixture is expressed as percentage (%).
Wherein:
ctc—co-toxicity coefficient;
ati—actual measured virulence index of the mixture;
TTI-the theoretical toxicity index of the mixture.
The compound co-toxicity coefficient CTC is more than or equal to 120 and shows synergistic effect; ctc.ltoreq.80 shows antagonism; 80< CTC <120 shows additive effect.
Calculating test results by adopting DPS data processing software, and respectively solving virulence regression equations, EC of single test medicament and mixed medicaments with different proportions 50 And 95% confidence limit, and solving co-toxicity coefficients (CTC) of the two medicaments in different proportions, and screening out the optimal proportion of the test medicaments. Record raw data for each process all repetitions.
The results of the indoor toxicity test are shown in the following table:
TABLE 3 results of indoor toxicity test of benzovindiflupyr and zineb on tomato early blight
Test agent Regression equation (y=a+bx) R EC 50 (mg/L) 95% confidence limit Co-toxicity coefficient (CTC)
Benzovindiflupyr (A) y=4.8283+1.2073x 0.9992 1.3875(1.3262-1.4517) -
Zineb (B) y=2.6156+1.1964x 0.9999 98.3981(96.7086-100.1172) -
A:B(1:30) y=3.4410+1.1653x 0.9998 21.7681(21.2433-22.3059) 138.855
A:B(1:20) y=3.5707+1.2082x 0.9997 15.2420(14.8338-15.6615) 149.113
A:B(1:10) y=3.8705+1.2339x 0.9991 8.2299(7.8568-8.6208) 162.533
A:B(1:5) y=4.1471+1.2082x 0.9997 5.0807(4.9446-5.2205) 153.064
A:B(1:3) y=4.3242+1.1615x 0.9999 3.8178(3.7700-3.8662) 139.472
A:B(1:1) y=4.6412+1.1803x 0.9997 2.0139(1.9599-2.0694) 135.876
As can be seen from the results of the indoor toxicity test in Table 3, the benzovindiflupyr has higher toxicity to the tomato early blight bacteria, and the EC thereof 50 1.3875mg/L. The benzovindiflupyr and the zineb are mixed to have a good inhibition effect on the growth of the tomato early blight bacteria. The mass ratio of the benzovindiflupyr to the zineb is 1:30-1:1, the co-toxicity coefficients of the benzovindiflupyr and the zineb are all greater than 130, and the synergism is remarkable.
Example 3: indoor toxicity test of benzovindiflupyr and bromothalonil on wheat powdery mildew
The test is based on: ny/T1156.4-2006 section 4 of pesticide, section 4 of biological assay test criteria in pesticide: experimental potting method for preventing and curing wheat powdery mildew.
Test target: powdery mildew (Blumeria graminis f.sp.tritici) is a strain from Shenyang-neutralization pesticide chemical research and development Co.
Test crop: selecting wheat variety Luyuan 502 pot culture with powdery mildew, numbering for standby after seedlings grow to 2-3 leaf period.
Experimental agent: 96% benzovindiflupyr original drug and 95% bromothalonil original drug are provided by the research and development center of the sea li pharmaceutical industry group.
And (3) preparation of a medicament: dissolving the benzovindiflupyr and bromothalonil crude drug in acetone, and diluting with 0.1% Tween 80 aqueous solution to prepare mother solutions respectively. According to the purpose of mixing and the activity of the medicament, different proportions are designed, and each group of single agent and each group of mixed agent are prepared into a required series of mass concentrations according to an equal proportion method.
The proportion of the effective components of the mixed components is as follows:
benzovindiflupyr: bromothalonil is 1:15, 1:10, 1:5, 1:3, 1:1, 5:1.
And (3) medicament treatment: spraying the preparation onto wheat seedling, and naturally air drying. The test was run with no drug-containing treatment as a blank. Each concentration treatment was repeated 4 times, 3 pots each, 10 plants each.
Inoculating and culturing: and uniformly shaking out fresh spores of powdery mildew generated in 24h on the diseased wheat leaves, and inoculating the fresh spores on the treated 2-3 leaf stage potted wheat seedlings. Then culturing under proper condition.
Data investigation: grading investigation is carried out according to the disease condition of the blank control. The following classification method is adopted:
level 0: no disease spots;
stage 1: the area of the disease spots accounts for less than 5% of the area of the whole leaf;
3 stages: the area of the disease spots accounts for 6-15% of the area of the whole leaf;
5 stages: the area of the disease spots accounts for 16-25% of the area of the whole leaf;
7 stages: the area of the disease spots accounts for 26-50% of the area of the whole leaf;
stage 9: the area of the disease spots accounts for more than 50% of the area of the whole leaf.
Data statistics and analysis:
the disease index is calculated as follows:
wherein:
x-disease index;
N i -leaf numbers at each stage;
i—relative grade value;
n-total leaf number was investigated.
The control effect is calculated according to the following formula:
wherein:
p, the prevention and treatment effect, the unit is;
CK-blank disease index;
PT-agent treatment index.
And evaluating the synergistic effect of the mixed medicament according to a grand cloud peak co-toxicity coefficient method (CTC), wherein CTC is less than or equal to 80 and is antagonistic, CTC is 80 and CTC is 120 and is additive, CTC is more than or equal to 120 and is synergistic, and the co-toxicity coefficient (CTC) is calculated according to the following formula.
Wherein:
ati—the measured virulence index of the mixture;
S-EC of Standard Agents 50 Milligrams per liter (mg/L);
M-EC of mixture 50 Units are milligrams per liter (mg/L).
TTI=TI A ×P A +TI B ×P B
Wherein:
TTI-theoretical toxicity index of the mixture;
TI A -a toxicity index of the agent;
P A -the percentage of agent a in the mix, in percent (%);
TI B -toxicity index of B agent;
P B the percentage of the B medicament in the mixture is expressed as percentage (%).
Wherein:
ctc—co-toxicity coefficient;
ati—actual measured virulence index of the mixture;
TTI-the theoretical toxicity index of the mixture.
Calculating test results by adopting DPS data processing software, and respectively solving virulence regression equations, EC of single test medicament and mixed medicaments with different proportions 50 And 95% confidence limit, and solving co-toxicity coefficients (CTC) of the two medicaments in different proportions, and screening out the optimal proportion of the test medicaments. Record raw data for each process all repetitions.
TABLE 4 indoor toxicity test of benzovindiflupyr and bromothalonil on wheat powdery mildew
As can be seen from the indoor toxicity test results of the wheat powdery mildew in Table 4, the benzovindiflupyr has higher toxicity to the wheat powdery mildew and EC thereof 50 1.5545mg/L.The mass ratio of the benzovindiflupyr to the bromothalonil is in the range of 1:15-5:1, the co-toxicity coefficient is more than 120, and the combined effect is shown in synergy. The mass ratio of benzovindiflupyr to bromothalonil is 1:5, the co-toxicity coefficient is 152.281, and the synergistic effect is most remarkable.
Field efficacy test
Example 4: benzovindiflupyr and zineb or bromothalonil compounded field efficacy test for cucumber anthracnose
The test is based on: the test is described in GB/T17980.112-2004 section 112 of pesticide field efficacy test criterion (two): the bactericide can prevent and treat cucumber anthracnose.
Test crop: cucumber (jin Chun No. 2).
Test site: the open-field cucumber field in North Chen area of Tianjin is cucumber, the previous crop in the test field is cucumber, the soil fertility is medium, and the field planting density is 5 ten thousand plants/hm 2 The plant grows uniformly.
And (3) test design: testing random group arrangement of each cell, cell area 30m 2 Each treatment was repeated 4 times.
Time of application: the cucumber plants are uniformly sprayed by adopting a industrial and agricultural 16-type knapsack sprayer, and the pesticide application liquid amount is 50 kg/mu. The test was performed for the first time in the last 8 th 2020, and 1 more time at 7-day intervals thereafter, for a total of two times.
Experimental investigation: disease number was investigated before the second application (i.e. 7d after the first application) and disease index was investigated after the second application and 11d after the second application and control effect was calculated for a total of 3 surveys.
The investigation method comprises the following steps: 5-point sampling method for each cell, 3 plants are investigated for each point, and 5-10 leaves are investigated for each plant from top to bottom.
The classification was performed according to the following classification method:
level 0: no disease spots;
stage 1: the area of the disease spots accounts for less than 5% of the whole leaf area;
3 stages: the area of the lesion accounts for 6-10% of the whole leaf area;
5 stages: the area of the lesion accounts for 11% -25% of the whole leaf area;
7 stages: the area of the lesion accounts for 26% -50% of the whole leaf area;
7 stages: the area of the disease spots accounts for more than 51% of the whole leaf area;
the drug effect calculation method comprises the following steps:
the cucumber growth in each treatment cell is observed to be good during the test period, and each treatment agent does not generate chemical injury to cucumber plants and other non-target organisms at the tested concentration.
The results of the field efficacy test are shown in the following table:
TABLE 5 field efficacy test results of benzovindiflupyr and zineb in cucumber anthracnose
The field efficacy test results of the cucumber anthracnose compounded by the benzovindiflupyr and the zineb in table 5 show that the benzovindiflupyr and the zineb show good control effects on the cucumber anthracnose. 7 days after the 1 st medicine, the control effect of each preparation on cucumber anthracnose is more than 81.67%, and the preparation has good quick-acting performance. 11 days after the 2 nd medicine, the control effects of 63% of benzovindiflupyr-zineb wettable powder (1:20), 35% of benzovindiflupyr-zineb suspending agent (1:10), 30% of benzovindiflupyr-zineb suspending agent (1:5) and 40% of benzovindiflupyr-zineb water dispersible granule (1:3) are 84.20%, 87.04%, 85.21% and 83.55% of cucumber anthracnose respectively.
Table 6 field efficacy test of benzovindiflupyr and bromothalonil for cucumber anthracnose
From the results of the field efficacy test in Table 6, the compound formulation of benzovindiflupyr and bromothalonil has good control effect on cucumber anthracnose. Compared with the single dosage, the mixed treatment has the advantages that the control effect is improved to different degrees under the condition of reduced dosage, wherein the control effect is best when the mass ratio of the benzovindiflupyr to the bromothalonil is 1:5.
Example 5: benzovindiflupyr and zineb compounded field efficacy test for early blight of tomato
The test is based on: the test is described in GB/T17980.31-2000 section 31 of pesticide field efficacy test criterion (one): the bactericide can be used for preventing and treating tomato early blight and late blight.
Test crop: tomato (Zhongza No. 2).
Test site: in Yang Lingou tomato sunlight greenhouse of Shaanxi province, the soil fertility of the test land is medium, the planting density is 30cm, the row spacing is 60cm, and the plant growth vigor is uniform.
And (3) test design: testing random group arrangement of each cell, cell area 20m 2 Each treatment was repeated 4 times.
Time of application: the stem and leaf spray was carried out by a industrial and agricultural 16-type knapsack sprayer, and the stem and leaf spray was carried out in 25 am on 2 months in 2020 at 7-day intervals for 1 time, and the total of two times of spray was carried out. The liquid medicine amount per application is 45kg/667m 2 The tomatoes are in flowering and fruit setting period during pesticide application, and are in early epidemic disease onset period, and the humidity in the greenhouse is low.
Experimental investigation: disease cardinality was investigated before administration, disease index was investigated 7d after the second administration and control effect was calculated for a total of 2 surveys.
The investigation method comprises the following steps: samples were taken at random 5 spots per cell, 2 plants were investigated per spot, and 10 leaves were investigated per plant, and the leaves were classified as a percentage of the lesion on each leaf to the total leaf area.
The classification was performed according to the following classification method:
level 0: no disease spots;
stage 1: the area of the disease spots accounts for less than 5% of the whole leaf area;
3 stages: the area of the lesion accounts for 6-10% of the whole leaf area;
5 stages: the area of the lesion accounts for 11% -25% of the whole leaf area;
7 stages: the area of the lesion accounts for 26% -50% of the whole leaf area;
7 stages: the area of the disease spots accounts for more than 51% of the whole leaf area;
the drug effect calculation method comprises the following steps:
during the test period, tomatoes in each treatment district are observed to grow well, and each treatment medicament does not generate chemical injury to tomato plants and other non-target organisms at the tested concentration.
The results of the field efficacy test are shown in the following table:
TABLE 7 results of field efficacy test of benzovindiflupyr and zineb on early blight of tomato
According to the field efficacy test, the benzovindiflupyr and the zineb are compounded to have good control effect on the early blight of tomatoes, and 7d and 44% of benzovindiflupyr after the second drug is used, wherein the control effect of the zineb wettable powder (1:10) is best when the dosage of the active ingredients is 120 g/hectare.
Example 6: field efficacy test of benzovindiflupyr and bromothalonil on wheat powdery mildew
The test is based on: the test is referred to GB/T17980.22-2000 pesticide field efficacy test criterion (one) Bactericide for controlling cereal powdery mildew;
experiment site: the wheat field in Huaian city of Jiangsu province has moderate soil fertility in the test field, and the wheat plants in each district grow uniformly and consistently, thereby conforming to the local scientific agricultural test;
test target: powdery mildew (Blumeria graminis f.sp.tritici);
test crops and varieties: wheat (Huai wheat 33);
test setup: the cells are arranged according to random group, 20m per cell 2 The periphery of the cell is provided with protection rows. Each treatment was repeated 4 times.
The application method comprises the following steps: conventional spraying is carried out by adopting a industrial and agricultural 16-type knapsack sprayer, the conventional spraying is uniformly carried out on the front and back sides of wheat blades, and the water consumption for test is 35kg/667m 2
Time of application and investigation time: the first application time is the last ten days of 4 months in 2020, wheat powdery mildew slightly occurs, the second application is carried out 7 days after the application, the disease index is investigated before the application, the disease index is investigated 10 days after the last application, and the control effect is calculated.
The investigation method comprises the following steps: five-point sampling is fixed on the diagonal of each cell, and each point is investigated by 0.25m 2 Plants, each after heading, were investigated for flag leaves and the first leaf under flag leaves.
Powdery mildew classification method (in leaf units):
level 0: no disease;
stage 1: the area of the disease spots accounts for less than 5% of the whole leaf area;
3 stages: the area of the lesion accounts for 6-15% of the whole leaf area;
5 stages: the area of the lesion accounts for 16% -25% of the whole leaf area;
7 stages: the area of the lesion accounts for 26% -50% of the whole leaf area;
stage 9: the area of the disease spots accounts for more than 50% of the whole leaf area.
Drug effect calculation method
The disease index and the control effect are calculated by the following method
During the test period, the wheat in each treatment cell is observed to grow well, and each treatment agent does not generate phytotoxicity to wheat plants and other non-target organisms at the tested concentration.
The results of the field efficacy test are shown in the following table:
table 8 results of field efficacy test of benzovindiflupyr and bromothalonil on wheat powdery mildew
From the results of the field efficacy test in Table 8, the benzovindiflupyr and bromothalonil compound has good control effect on wheat powdery mildew. Compared with a single-dose suspension, the 30% benzovindiflupyr-bromothalonil suspension (1:5) has obviously improved control effect under the condition of reduced dosage.
In conclusion, through indoor toxicity measurement and field efficacy tests, the bactericidal composition disclosed by the invention has a good control effect on plant diseases, especially plant fungal diseases, is safe to target crops, has remarkable control effect, is superior to a single dose in the aspects of delaying the generation of drug resistance and prolonging the lasting effect, and can effectively reduce the cost and reduce the medicament residues.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto, and it is therefore intended that the invention as defined in the appended claims be interpreted as broadly as possible without departing from the spirit of the invention.

Claims (11)

1. The bactericidal composition is characterized by comprising a synergistically effective amount of active ingredient A benzovindiflupyr and active ingredient B, wherein the active ingredient B is any one of zineb or bromothalonil; the mass ratio of the benzovindiflupyr to the zineb is 1:30-10:1; the mass ratio of the benzovindiflupyr to the bromothalonil is 1:20-20:1.
2. The bactericidal composition according to claim 1, wherein the mass ratio of the benzovindiflupyr to the zineb is 1:30-1:1.
3. The bactericidal composition according to claim 1, wherein the mass ratio of the benzovindiflupyr to the bromothalonil is 1:15-15:1.
4. The sterilizing composition according to claim 1, wherein the total weight of the sterilizing composition is 0.1-90% of the total weight of the sterilizing composition based on 100 wt%.
5. The sterilizing composition according to claim 4, wherein the total weight of the sterilizing composition is 2-70% of the total weight of the sterilizing composition based on 100 wt%.
6. The composition of claim 1, wherein the composition further comprises agriculturally acceptable auxiliary ingredients in addition to the active ingredient, wherein the auxiliary ingredients are selected from one or more of wetting agents, dispersing agents, thickening agents, disintegrants, emulsifying agents, antifoaming agents, preservatives, stabilizers, synergists, and carriers.
7. The sterilizing composition according to claim 1, wherein the sterilizing composition is in the form of a solid preparation or a liquid preparation.
8. The sterilization composition according to claim 7, wherein the solid preparation is water dispersible granule and/or wettable powder, and the liquid preparation is suspending agent and/or emulsifiable concentrate.
9. Use of the fungicidal composition according to any one of claims 1 to 8 for controlling plant diseases.
10. The use according to claim 9, wherein the disease comprises a fungal disease and/or a bacterial disease;
the fungal diseases are diseases caused by one or more of the following pathogenic bacteria: fungi of the phylum Deuteromycotina, fungi of the phylum Basidiomycotina, fungi of the phylum Ascomycotina and/or fungi of the phylum Trigonella.
11. The use according to claim 9, wherein the bactericidal composition is applied to the pathogenic bacteria or growth medium thereof in need of control in an effective dose.
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Publication number Priority date Publication date Assignee Title
CN101677558A (en) * 2007-04-25 2010-03-24 先正达参股股份有限公司 fungicidal compositions
CN109906034A (en) * 2016-11-04 2019-06-18 Upl有限公司 Fungicidal combinations
WO2020078797A1 (en) * 2018-10-19 2020-04-23 Basf Se Ternary mixtures containing fenpropimorph, succinate dehydrogenase inhibitors and one other compound
WO2022018767A1 (en) * 2020-07-24 2022-01-27 Rajdhani Petrochemicals Private Limited Agrochemical composition comprising sdhi fungicides.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101677558A (en) * 2007-04-25 2010-03-24 先正达参股股份有限公司 fungicidal compositions
CN109906034A (en) * 2016-11-04 2019-06-18 Upl有限公司 Fungicidal combinations
WO2020078797A1 (en) * 2018-10-19 2020-04-23 Basf Se Ternary mixtures containing fenpropimorph, succinate dehydrogenase inhibitors and one other compound
WO2022018767A1 (en) * 2020-07-24 2022-01-27 Rajdhani Petrochemicals Private Limited Agrochemical composition comprising sdhi fungicides.

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