CN117204425A

CN117204425A - Sterilization composition containing cyclopurifiuram and application thereof

Info

Publication number: CN117204425A
Application number: CN202311180045.7A
Authority: CN
Inventors: 郑志明; 戚德才; 李敏; 葛尧伦; 张芳; 杨志鹏; 吕文东
Original assignee: Qingdao Hailier Biotechnology Co ltd
Current assignee: Qingdao Hailier Biotechnology Co ltd
Priority date: 2023-09-13
Filing date: 2023-09-13
Publication date: 2023-12-12

Abstract

The application belongs to the technical field of pesticide sterilization, and discloses a bactericidal composition containing cyclob rifluram and application thereof, wherein the bactericidal composition comprises an active ingredient A and an active ingredient B, the active ingredient A is cyclob rifluram, and the active ingredient B is bronopol. The mass ratio of the active component A to the active component B is 1:25-35:1. The bactericidal composition has higher activity on various crop diseases, has remarkable synergistic effect, can delay the generation of pathogenic bacteria drug resistance, and is beneficial to the comprehensive treatment of agricultural diseases.

Description

Sterilization composition containing cyclopurifiuram and application thereof

Technical Field

The application belongs to the technical field of pesticide bactericides, and particularly relates to a bactericidal composition containing cycloprotrifluram and application thereof.

Background

Cyclobutrifluram is a new nicotinamide class of bactericidal nematicide developed by the company Zhengda. The plant pesticide composition has broad control spectrum, is safe and efficient, can effectively control various nematodes and main fungal diseases, and can effectively control nematodes such as root knots, beet cysts and corn short bodies on crops such as cucumber, tomato, corn and beet by direct application or seed treatment; can also effectively prevent and treat plant diseases, and has excellent preventing and treating effect on fusarium especially. Its CAS accession number: 1460292-16-3. The chemical structure is as follows:

bromonitroalcohol is a bromonitroalcohol broad-spectrum fungicide. The bronopol has good control effect on plant fungi and bacterial diseases, especially on bakanae disease of rice, and has certain control effect on angular leaf spot of cotton and scab of wheat.

Fusarium fungi are important pathogenic bacteria causing various soil-borne diseases of crops, can cause various plant diseases in agricultural production, such as wheat scab, wheat stem basal rot, rice bakanae disease and the like, and causes great economic loss to the agricultural production when the diseases occur seriously.

The inventor conducts intensive research on the cyclyl fluoride and the bromonitrol, discovers that the cyclyl fluoride and the bromonitrol are mixed, has obvious synergism on wheat scab, wheat stem basal rot and rice bakanae disease in a certain mixing proportion range, can effectively improve and prevent plant diseases, and completes the application through further research. The compounding of Cyclobutrifluram and bronopol for preventing and treating diseases caused by Fusarium fungi is not reported at present.

Disclosure of Invention

Based on the problems, the application provides a sterilization composition which can effectively control plant diseases, has obvious synergism on pathogenic bacteria prevention effects such as wheat scab, wheat stem basal rot, bakanae disease and the like, effectively reduces the dosage of pesticides, and is environment-friendly.

In order to achieve the above purpose, the present application adopts the following technical scheme: the bactericidal composition comprises an active ingredient A and an active ingredient B, wherein the active ingredient A is the cyclyl fluoride, and the active ingredient B is bromonitrol;

further, the mass ratio of the Cyclobutrifluram to the bronopol is 1:25-35:1;

further, the mass ratio of the cyclyl fluoride to the bromonitrol is 1:25, 1:24, 1:21, 1:15, 1:10, 1:5, 1:3, 2:5, 6:5, 10:4, 7:2, 5:1, 17:2, 12:1, 16:1, 24:1, 35:1;

further, the mass ratio of the Cyclobutrifluram to the bronopol is 1:24-24:1;

further, the mass ratio of the cyclyl fluoride to the bromonitroalcohol is 1:24, 1:21, 1:15, 1:10, 1:5, 1:3, 2:5, 6:5, 10:4, 7:2, 5:1, 17:2, 12:1, 16:1, 24:1;

further, the mass ratio of the Cyclobutrifluram to the bronopol is 1:21-24:1;

further, the mass ratio of the cyclyl fluoride to the bromonitrol is 1:21, 1:15, 1:10, 1:5, 1:3, 2:5, 6:5, 10:4, 7:2, 5:1, 17:2, 12:1, 16:1, 24:1;

further, the sum of the contents of the cyclyl fluoride and the bromonitrool in the sterilizing composition is 1-90 wt percent based on 100wt percent of the total weight of the sterilizing composition;

still further, the sum of the contents of the cyclyl fluoride and the bromonitrool in the bactericidal composition is 5 to 80 weight percent.

Further, the bactericidal composition comprises an agriculturally acceptable auxiliary ingredient in addition to the active ingredient, wherein the auxiliary ingredient is selected from one or more of wetting agents, dispersing agents, emulsifying agents, thickening agents, disintegrating agents, antifreezing agents, antifoaming agents, solvents, preservatives, stabilizers, synergists, binders or carriers;

the wetting agent is selected from one or more of alkylbenzene sulfonate, alkyl naphthalene sulfonate, lignin sulfonate, sodium dodecyl sulfate, dioctyl sodium sulfosuccinate, alpha-olefin sulfonate, alkylphenol ethoxylate, castor oil polyoxyethylene ether, alkylphenol ethoxylate, fatty alcohol polyoxyethylene ether sodium sulfate, silkworm excrement, spina gleditsiae 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 ethoxylate methyl ether condensate sulfate, fatty amine ethoxylate, glycerin fatty acid ester polyoxyethylene ether, polycarboxylate, polyacrylic acid, phosphate, EO-PO block copolymer and EO-PO graft copolymer; and/or

The emulsifier is one or more selected from calcium dodecyl benzene sulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenethyl phenol polyoxyethylene polyoxypropylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styrylphenol polyoxyethylene ether, castor oil polyoxyethylene ether and alkylphenol ether phosphate; and/or

The thickener is one or more selected from xanthan gum, organic bentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose and white carbon black; and/or

The disintegrating agent is 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 antifreezing agent is one or more selected from alcohols, alcohol ethers, chlorinated hydrocarbons and inorganic salts; and/or

The defoamer is selected from C ₁₀ -C ₂₀ Saturated fatty acid compound, silicone oil, silicone compound, C ₈ -C ₁₀ One or more of the 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 derivatives 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 p-hydroxybenzoate, methyl p-hydroxybenzoate, pinocembrane and 1, 2-benzisothiazolin-3-one; 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, triethanolamine oleate, epoxidized vegetable oil, kaolin, bentonite, attapulgite, white carbon black, talcum powder, montmorillonite and starch; and/or

The synergistic agent 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 application optimizes the content of the effective components and the auxiliary agent in the pesticide composition, so that the toxicity and the residue of the pesticide composition reach better balance, and the pesticide effect can be enhanced, the dosage can be reduced, and the cost can be reduced.

Further, the dosage form of the bactericidal composition is selected from a solid preparation and/or a liquid preparation and/or a seed treatment preparation;

the solid preparation comprises powder, granules, balls, tablets, strips, wettable powder, oil dispersion powder, emulsion powder, water dispersible granules, emulsion granules, water dispersible tablets, soluble powder, soluble tablets or soluble granules;

the liquid preparation comprises a soluble agent, an oil agent, a spreading oil agent, an emulsifiable concentrate, a latex, a dispersible agent, a paste, an aqueous emulsion, an oil emulsion, a microemulsion, a lipid agent, a suspending agent, a microcapsule suspending agent, an oil suspending agent, a dispersible oil suspending agent, a suspending emulsion, a microcapsule suspension-suspending agent, a microcapsule suspension-aqueous emulsion or a microcapsule suspension-suspending emulsion;

further, the powder is a free-flowing powder preparation which is suitable for spraying or spreading and contains an active ingredient;

further, the granule is a granular preparation with a certain particle size range and free flowing active ingredients;

further, the spherical agent is a spherical agent containing an active ingredient;

further, the tablet is a tablet formulation having a shape and size containing an active ingredient;

further, the strip agent is a strip or rod-shaped preparation containing active ingredients;

further, the wettable powder is a powdery preparation in which the active ingredients are dispersed into suspension in water;

further, the oil dispersion powder is a powder preparation in which an active ingredient is dispersed into a suspension in an organic solvent;

further, the emulsion powder is a powdery preparation of which the active ingredients are dissolved by an organic solvent and are wrapped in soluble or insoluble inert ingredients, and the active ingredients are dispersed in water to form oil-in-water emulsion;

further, the water dispersible granule is a granular preparation which disintegrates in water and the effective components are dispersed into suspension;

further, the emulsion granule is a granular preparation of which the active ingredient is dissolved by an organic solvent and is wrapped in soluble or insoluble inert ingredients, and the active ingredient is dispersed in water to form oil-in-water emulsion;

further, the water dispersible tablet is a tablet preparation which disintegrates in water and the active ingredient is dispersed into suspension;

further, the soluble powder is a powdery preparation of which the active ingredient forms a true solution in water, and can contain inert ingredients which are insoluble in water;

further, the soluble granule is a granular preparation of which the effective component forms a true solution in water, and can contain an inert component which is insoluble in water;

further, the soluble tablet is a tablet preparation in which the active ingredient forms a true solution in water, and may contain an inert ingredient which is insoluble in water;

further, the soluble agent is a liquid preparation which is diluted into transparent or semitransparent containing active ingredients by water, and can contain inert ingredients which are insoluble in water;

further, the soluble agent is a colloidal preparation which is diluted into true solution by water and contains active ingredients;

further, the oil is a liquid preparation which is diluted (or not diluted) by an organic solvent to be homogeneous and contains active ingredients;

further, the film spreading oiling agent is an oiling agent which automatically diffuses into an oil film on the water surface and contains active ingredients;

further, the emulsifiable concentrate is a homogeneous liquid preparation which is diluted and dispersed into emulsion by water and contains active ingredients;

further, the emulsion is a latex preparation which is diluted and dispersed into emulsion by water and contains active ingredients;

further, the dispersible agent is a homogeneous liquid preparation which is diluted and dispersed into suspension containing the active ingredients by water;

furthermore, the ointment is a water-based ointment preparation containing active ingredients and capable of forming a film, and is generally used directly;

further, the aqueous emulsion is an emulsion liquid preparation formed by the active ingredient (or organic solution thereof) in water;

further, the oil emulsion is an emulsion liquid preparation formed by the effective component (or aqueous solution thereof) in oil;

further, the microemulsion is a microemulsion liquid preparation with the active ingredient being transparent or semitransparent in water, and is used directly or after being diluted by water;

further, the fat agent is an oil or fat-based viscous preparation containing an active ingredient, and is generally used directly;

further, the suspending agent is a stable suspension liquid preparation prepared by dispersing the active ingredient in water in solid particles, and is generally diluted by water;

further, the microcapsule suspending agent is a stable suspension liquid preparation formed by dispersing microcapsules containing active ingredients in liquid;

further, the oil suspending agent is a stable suspension liquid preparation prepared by dispersing solid particles as an active ingredient in liquid, and is generally diluted by an organic solvent;

further, the dispersible oil suspending agent is a stable suspension liquid preparation prepared by dispersing solid particles of an active ingredient in a non-aqueous medium, and is generally diluted with water for use;

further, the suspoemulsion is a heterogeneous liquid preparation in which the active ingredients are stably dispersed in a continuous water phase in the form of solid particles and water-insoluble tiny liquid drops;

further, the microcapsule suspension-suspending agent is a stable suspension liquid preparation prepared by dispersing the effective components in water by using microcapsules and solid particles;

further, the microcapsule suspension-water emulsion is a heterogeneous liquid preparation which is formed by stably dispersing the effective component in a continuous water phase in a microcapsule and micro droplet form;

further, the microcapsule suspension-suspension emulsion is a heterogeneous liquid preparation with active ingredients stably dispersed in a continuous water phase in the forms of microcapsules, solid particles and tiny liquid drops;

further, the bactericidal composition can be prepared into a preparation formulation which is acceptable in pesticide, wherein the preparation formulation is microemulsion, aqueous emulsion, suspending agent, dispersible oil suspending agent, solution, emulsifiable concentrate, suspending agent, microcapsule suspending agent, water dispersible granule, wettable powder, granule, seed treatment suspending agent and seed treatment dry powder;

further, the preparation formulation is microemulsion, emulsifiable concentrate, suspending agent, aqueous emulsion, water dispersible granule and seed treatment suspending agent.

The application also discloses an application of the bactericidal composition containing the Cyclobutrifluram in preventing and treating plant diseases;

further, the plant disease is a fungal or bacterial caused plant disease;

further, the plant disease is a fungal-caused plant disease;

further, the plant disease caused by the fungus is wheat scab and rice bakanae disease.

The beneficial effects of the application are as follows:

1) The bactericidal composition has different action mechanisms of active ingredients and has obvious effect of delaying the development of pathogen resistance;

2) The bactericidal composition is safe and efficient, is safe to crops, non-target organisms, beneficial organisms and natural enemies, and has the functions of increasing yield and ensuring income.

Detailed Description

In order to make the objects, advantages and technical solutions of the present application more apparent, the technical solutions of the present application will be explained by using the following preparation examples and specific examples, but the scope of the present application should not be limited by the specific embodiments set forth herein.

Preparation example:

preparation example 1:

28% Cyclokutrifluram bronopol seed treatment suspending agent (8:20)

The formula comprises the following components: 8% of Cyclobutrifluram, 20% of bronitol, 2.5% of sodium lignin sulfonate, 2% of isomeric tridecanol polyoxyethylene ether, 2% of styrylphenol polyoxyethylene ether, 1% of polyacrylic emulsion, 0.2% of xanthan gum, 4.2% of rose pigment, 5% of ethylene glycol, 0.5% of magnesium aluminum silicate, 0.4% of organosilicon defoamer, 1.2% of sodium benzoate and the balance of deionized water;

the preparation method comprises the following steps: the active ingredients, the auxiliary agent and the water are uniformly mixed and stirred through high-cutting shearing according to the proportion, and then are sanded for 2.5 hours through a sand mill, so that the average particle size reaches 1-5 microns, and the seed treatment suspending agent can be obtained.

Preparation example 2:

20% Cyclokutrifluham-bronopol suspension (10:10)

The formula comprises the following components: 10% of Cyclobutrifluram, 10% of bronitol, 3% of dioctyl sodium sulfosuccinate, 1.2% of castor oil polyoxyethylene ether, 2% of EO-PO block copolymer, 3% of alkylphenol polyoxyethylene ether methyl ether condensate sodium sulfate, 1.5% of sodium polycarboxylate, 1% of organosilicon defoamer, 0.2% of xanthan gum, 1% of magnesium aluminum silicate, 4% of ethylene glycol, 1% of sodium benzoate 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 3:

44% Cyclobinifluram bronopol water dispersible granule (24:20)

The formula comprises the following components: 24% of Cyclobutriflura, 20% of bromonitro alcohol, 8% of sodium dodecyl sulfate, 8% of naphthalene sulfonate formaldehyde condensate, 2% of sodium polycarboxylate, 5% of organic swelling soil and the balance of kaolin;

the preparation method comprises the following steps: according to the formula proportion of the embodiment, adding the active ingredients into a carrier, 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 4:

10% Cyclokutrifluham-bronopol emulsion in water (5:5)

The formula comprises the following components: 5% of Cyclobutrifluram, 5% of bronidazole, 3% of glycerol fatty acid ester polyoxyethylene ether, 3% of polyoxyethylene sorbitan monooleate, 15% of cyclohexanone, 0.1% of xanthan gum, 5% of glycerol, 1.5% of urea, 0.2% of sodium sorbate, 0.5% of organosilicon defoamer and the balance of deionized water;

the preparation method comprises the following steps: according to the formula proportion of the embodiment, dissolving the active ingredients into a solvent, adding an emulsifier to dissolve the active ingredients into a uniform oil phase, and mixing deionized water, an antifreezing agent and the like together to form a uniform water phase; adding the water phase into the oil phase under high-speed shearing to form a well-dispersed aqueous emulsion product.

Indoor toxicity

Test agent: 90% of cyclobictricofluram crude drug and 95% of bronopol crude drug; other reagents: solvent acetone (analytically pure), emulsifier tween 80 (chemically pure); are provided by the group development center.

Example 1:

indoor activity test of wheat scab

The test is based on: test reference NY/T1156.2-2006 agricultural industry standard "pesticide indoor bioassay test criteria section 2 of the people's republic of China: test plate method for inhibiting growth of pathogenic bacterial hyphae.

Test target: fusarium pseudograminearum (Fusarium pseudograminearum).

Instrument apparatus: a wet heat sterilization pot, an ultra-clean workbench, a constant temperature illumination incubator, a drying box, an electronic balance, a pipetting gun, an alcohol lamp, a small beaker, a volumetric flask, a triangular flask, a culture dish (phi 9 cm), a puncher, an inoculator (phi 0.6 cm), a ruler and the like.

And (3) preparation of a medicament: the raw materials are respectively dissolved by acetone, diluted by 0.1% Tween 80 aqueous solution, and respectively prepared into single-dose mother solutions, and different proportions are designed according to the mixing purpose and the medicament activity, and each single dose and each group of proportion mixture are prepared into a required series of mass concentrations.

Test replicates: test agents were 4 dishes per concentration, 1 dish per replicate, 4 replicates total, with 0.1% tween 80 in water without agent as a blank.

And (3) medicament treatment: under the aseptic operation condition, the PDA culture medium which is melted and sterilized in advance is quantitatively added into an aseptic conical flask according to the test treatment, 10mL of each prepared treatment liquid medicine is quantitatively sucked from low concentration to high concentration in sequence, the prepared treatment liquid medicines are respectively added into the conical flask, fully and uniformly shaken, and then the mixture is poured into a culture dish in equal quantity to prepare a medicine-containing flat plate with corresponding concentration. The test set up was run with a blank of 0.1% tween 80 in water without the addition of the agent, and 4 replicates per treatment.

Inoculating: cutting bacterial cake from colony edge with sterilized Fusarium pseudograminearum under aseptic condition, inoculating bacterial cake in the center of medicated plate with inoculator, covering with bacterial cover, and culturing in dark in constant temperature illumination incubator at 26deg.C.

Data investigation: the growth of pathogenic hyphae was investigated according to the growth of hyphae in a blank culture dish. Colony diameters were measured in centimeters (cm) using a ruler, diameters were measured once per colony using the cross-over method, averages were taken, and raw data was recorded for each treatment in duplicate.

The hypha growth inhibition rate was calculated in percent (%) according to the following formula, and the calculated result remained two bits after the decimal point.

D＝D ₁ -D ₂

D-colony growth diameter;

D ₁ colony diameter;

D ₂ -diameter of the bacterial cake.

I＝(D ₀ -D _t )/D ₀ *100

Wherein:

i, hypha growth inhibition rate;

D ₀ -the control colony increased in diameter;

D _t -the agent-treated colonies increased in diameter.

Analyzing by DPS statistical analysis system to obtain virulence regression line and EC ₅₀ And evaluating the activity of the test agent on the biological test material.

Grand cloud Pei method: evaluating the synergistic effect of the mixed medicaments 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.ltoreq.80 shows antagonism; 80 < CTC < 120 shows additive effect.

The coefficients (CTC values) are 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 test results are shown in the following table:

indoor bioassay test results of Cyclokutrif and bronopol for preventing and treating wheat scab:

the results in Table 1 show that Cycloborifluram prevents wheat scab EC ₅₀ EC for controlling wheat scab with bronopol at 4.223mg/L ₅₀ The bactericidal composition of the Cycloborifluram and the bronopol shows good prevention effect in the range of 1:25-35:1, and the co-toxicity coefficient of the Cycloborifluram and the bronopol is more than 120 in the range of 1:21-24:1, and the synergistic effect is shown. Wherein, the maximum cotoxicity coefficient value of the Cyclobutrifluram and the bronopol=10:4 is 229.644, EC ₅₀ 2.071mg/L, the synergistic effect is obvious.

Table 1 results of measuring synergism of different proportions of Cyclobutrifluram and bronopol on wheat scab

Test agent	Regression equation	r ²	EC ₅₀			Co-toxicity coefficient	Action
								Biopesticide	B value.+ -. Standard error	/	(mg/L)	(ATI)	(TTI)	(CTC)	/
Cyclobutrifluram(A)	1.100±0.119	0.982	4.223(3.428～5.202)	100.000	/	/	/
								Bronopol (B)	1.861±0.152	0.990	6.948(5.887～8.200)	60.780	/	/	/
A:B＝1:25	1.876±0.255	0.973	6.559(5.001～8.604)	64.385	62.289	103.365	Additive effect
								A:B＝1:21	2.212±0.257	0.980	4.082(3.228～5.162)	103.454	62.563	165.361	Synergistic effect
A:B＝1:10	1.926±0.190	0.985	3.831(3.151～4.659)	110.232	64.346	171.313	Synergistic effect
								A:B＝1:5	2.094±0.223	0.983	3.587(2.913～4.418)	117.731	67.317	174.891	Synergistic effect
A:B＝2:5	1.978±0.132	0.993	3.121(2.743～3.552)	135.309	71.986	187.967	Synergistic effect
								A:B＝10:4	1.886±0.116	0.994	2.071(1.839～2.332)	203.911	88.794	229.644	Synergistic effect
A:B＝5:1	2.02±0.140	0.992	3.181(2.783～3.635)	132.757	93.463	142.042	Synergistic effect
								A:B＝12:1	2.008±0.138	0.993	3.337(2.922～3.811)	126.551	96.983	130.487	Synergistic effect
A:B＝24:1	1.926±0.158	0.990	3.518(2.996～4.130)	120.040	98.431	121.953	Synergistic effect
								A:B＝35:1	2.164±0.196	0.987	3.681(3.081～4.39)	114.724	98.911	115.988	Additive effect

Note that: the above data were analyzed using DPS statistical analysis software, with values remaining 3 bits after the decimal point, as in Table 2 below.

Example 2:

indoor activity test for bakanae disease of rice

Test strain: fusarium moniliforme (Fusarium moniliforme), offered by the Shenyang chemical institute.

Instrument apparatus: high pressure steam sterilizer, ultra clean bench, incubator, drying box, electronic balance, pipettor, alcohol lamp, beaker (50 mL), volumetric flask, triangular flask (100 mL), culture dish (Φ9 cm), puncher (Φ0.6 cm), inoculator, ruler, etc.

Test target culture conditions: fusarium moniliforme preserved at the temperature of 4 ℃ in an indoor refrigerator is transferred onto a culture medium, and is activated for standby after being placed in a 25 ℃ incubator for 5 days of dark culture.

And (3) preparation of a medicament: the raw materials are respectively dissolved by acetone to prepare high-concentration mother liquor, then the mother liquor is diluted by 0.1% Tween 80 aqueous solution to respectively prepare single-dose mother liquor, and different proportions are designed according to the mixing purpose and the medicament activity, and each single dose and each group of proportion are mixed to prepare the required series of mass concentrations.

And (3) medicament treatment: under the aseptic operation condition, 5mL of liquid medicine with different concentrations is respectively added into a sterilized triangular flask which is calibrated accurately in advance by a liquid transfer device, then a culture medium which is melted and cooled to a proper temperature is added into the triangular flask, and the culture medium is poured into 4 culture dishes with equal quantity after being fully and evenly shaken, so that a tablet of the PDA containing the medicine with corresponding concentration is prepared.

Inoculating: cutting bacterial cake from colony edge with sterilized puncher under aseptic condition, inoculating bacterial cake in the center of medicated plate with inoculator, covering bacterial cover, and culturing in dark in constant temperature incubator at 25deg.C.

Data investigation: the experimental investigation was performed according to the time when colonies grew to a size of 2/3 to 4/5 of the diameter of the dish in the control treatment. Colony diameters (cm) were measured with a ruler, and each colony was measured once by the cross method, and the average value was taken.

D＝D ₁ -D ₂

D-colony growth diameter;

D ₁ colony diameter;

D ₂ -diameter of the bacterial cake.

I＝(D ₀ -D _t )/D ₀ *100

Wherein:

i, hypha growth inhibition rate;

D ₀ -the control colony increased in diameter;

D _t -the agent-treated colonies increased in diameter.

The coefficients (CTC values) are 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;

Wherein:

ctc—co-toxicity coefficient;

ati—actual measured virulence index of the mixture;

TTI-the theoretical toxicity index of the mixture.

Results of in-vivo bioassay test of controlling rice bakanae disease by Cyclokutrifluram and bronopol:

the results in Table 2 show that Cycloborifluram prevents bakanae disease EC in rice ₅₀ EC for controlling bakanae disease of rice by bronopol at 7.453mg/L ₅₀ The bactericidal composition of the cycloprifluram and the bronopol shows good prevention effect in the proportion of 5.346mg/L, the co-toxicity coefficient is more than 120, and the bactericidal composition of the cycloprifluram and the bronopol shows synergistic effect in the proportion of 1:24-24:1. Wherein, the maximum cotoxicity coefficient value of the Cyclobutrifluram and the bronopol=6:5 is 270.229 > 120, and EC ₅₀ At 2.339mg/L, the synergistic effect is shown.

Table 2 results of measuring synergistic effects of different proportions of Cyclobutrifluram and bronopol on bakanae disease of rice

Test agent

Regression equation

r ²

EC ₅₀

Co-toxicity coefficient

Action

Biopesticide

B value.+ -. Standard error

/

(mg/L)

(ATI)

(TTI)

(CTC)

/

Cyclobutrifluram(A)

1.723±0.100

0.996

7.453(6.784～8.188)

100.000

/

Bronopol (B)

1.206±0.135

0.987

5.346(4.164～6.864)

139.413

/

A:B＝1:24

1.577±0.044

0.998

3.677(3.475～3.891)

202.692

137.836

147.053

Synergistic effect

A:B＝1:15

1.651±0.077

0.996

3.529(3.208～3.882)

211.193

136.949

154.212

Synergistic effect

A:B＝1:10

1.609±0.045

0.998

2.982(2.819～3.155)

249.933

135.830

184.005

Synergistic effect

A:B＝1:3

1.631±0.050

0.998

2.772(2.602～2.953)

268.867

129.559

207.524

Synergistic effect

A:B＝6:5

1.657±0.066

0.997

2.339(2.159～2.534)

318.640

117.915

270.229

Synergistic effect

A:B＝7:2

1.696±0.096

0.995

3.422(3.062～3.824)

217.797

108.758

200.257

Synergistic effect

A:B＝16:1

2.142±0.084

0.997

4.358(4.038～4.704)

171.019

102.318

167.144

Synergistic effect

A:B＝24:1

1.729±0.039

0.999

5.380(5.146～5.624)

138.532

101.577

136.382

Synergistic effect

A:B＝30:1

1.712±0.163

0.986

6.183(5.1435～7.432)

120.599

101.271

119.085

Additive effect

Example 3:

test for controlling bakanae disease of rice in field

The test is based on: the test is described in GB/T17980.104-2004 section 104 of pesticide field efficacy test criterion (II): bactericide for controlling bakanae disease of rice.

Test target: bakanae disease germ of rice.

Test crop: and (3) rice.

And (3) test design: cell treatments with test, control and blank control agents used a randomized block arrangement.

Table 3 test agents and dosage amounts

The test set 4 treatments for seed soaking with clear water as a blank. The treatment area of each seedbed was 10m ² Seedbed testNo repetition is set; the planting area of the field is 30m ² Each treatment was repeated 4 times for the field test.

The test was carried out by soaking seeds at 20 days 5 months of 2021, accelerating germination at 24 days 5 months and sowing at 27 days 5 months.

Preparing liquid medicine according to the test design concentration, fully stirring, pouring dry seeds, soaking seeds for 48 hours to accelerate germination, keeping the rice seeds not exposed to the water surface during seed soaking, and directly accelerating germination without cleaning the rice seeds after seed soaking.

And sowing in seedling trays after 3d, and strictly controlling the temperature and humidity of seedling beds in different leaf ages according to the technical specifications of rice. After seedling emergence, the seedling tray is moved to seedling bed, and the seedling age is moved to the field for 30 days.

Investigation items: the germination rate was investigated before sowing, and the disease index was investigated 1 time before transplanting (15 days of 6 months) and during the booting period of field rice (20 days of 8 months).

Checking germination rate before sowing, repeating each treatment for 4 times, randomly selecting 100 seeds, checking germination condition, and calculating germination rate;

before transplanting in seedling stage, sampling 5 points in each district in the seedling bed, investigating 200 seedlings at each point, investigating disease plant rate, and calculating control effect;

and 5 points are randomly sampled in each district during the booting period of the field, 20 clusters are surveyed at each point, the number of the sick plants is recorded, and the disease plant rate and the prevention and treatment effect of each treatment are calculated.

The drug effect calculation method comprises the following steps:

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the test results are shown below:

as can be seen from Table 4, the pesticide composition of the present application has obvious control effect on bakanae disease of rice, and compared with the treatment of a blank control medicament, the emergence rate is basically equivalent to that of the blank control, which indicates that the seed soaking treatment of rice seeds by each preparation example can not generate phytotoxicity on rice. Compared with single bactericides, the disease and plant rate of each compound preparation is reduced, and the compound bactericide has better control effect.

TABLE 4 test results of different treatments for controlling bakanae disease in rice

Example 4:

wheat scab field efficacy test

Test site: wheat scab in Hebei province is planted in places where wheat scab happens all year round

Test time: wheat first spike period of 5-10 days 2020

Test agent and dosage: the dosage is shown in Table 5.

Table 5 comparison of the amounts of the field trials

Treatment of	Medicament	Dosage g a.i/hm ²
			A1	20% Cyclokutrifluham-bronopol suspension (10:10)	40
A2	20% bronopol water dispersible granule	150
			A3	20% Cyclobulifluram suspension	50
A4	Clear water control	/

Test treatment: setting single dose and clear water contrast, and setting the application interval of 2 times for 10 days, wherein the spraying time is respectively the initial spike period and the flowering period of wheat. Cell test 667m per treatment area ² No duplication. Spraying by using a conventional electric sprayer.

The investigation method comprises the following steps: a 5-point sampling site-directed investigation was used. 1m per treatment per point investigation ² The total spike count and the number of diseased spikes were investigated 10d before harvest. The severity of the illness is divided by the illness state of wheat ears, and the illness state is divided into 5 grades:

grade 0, no disease;

1 grade, the number of diseased wheat ears is less than 1/4 of the total wheat ears;

2, the number of diseased wheat ears accounts for 1/4 to 1/2 of the total wheat ears;

grade 3, the number of diseased wheat ears accounts for 1/2-3/4 of the total wheat ears;

grade 4, the number of diseased wheat ears is more than 3/4 of the total wheat ears.

The calculation formula is as follows:

index of disease:

disease index = Σ (number of disease plants at each stage×number of disease stages)/(total number of investigation×maximum stage value)

Preventing effect:

control effect = (control disease index-treatment disease index)/control disease index

And calculate 1m per unit area ² Average spike number and disease spike rate; sampling during wheat harvest period, airing for 3d, and measuring 667m of each cell ² Yield was measured.

Data were processed with Microsoft Excel 2003 and statistically analyzed with DPS data and checked for difference significance (Duncan method). Results of field efficacy test of wheat scab

The results in Table 6 show that the effect of the 20% cyclob-riflur-bromonitro alcohol suspending agent (10:10) on controlling wheat scab is 96.12% by the field efficacy plot test, and compared with the control single agent 20% bromonitro alcohol water dispersible granule and the 24% cyclob-riflur suspending agent, the mixed preparation is obviously higher than the control single agent at the 0.01 level and the 0.05 level.

Table 6 different formulations and single dose for preventing and treating wheat scab

Note that: the above processing data are 1m calculated per unit area ² Average spike number and disease spike rate; the% control effect in the above table is the average of each repetition; lower case letters represent a significant 5% level difference and upper case letters represent a significant 1% level difference.

TABLE 7 influence of different agents for controlling wheat scab on wheat yield

Treatment of	Yield/kg/667 m ²	Differentiation of	Safety of
				20% Cyclokutrifluham-bronopol suspension (10:10)	485.26	a	Normal state
20% bronopol water dispersible granule	473.48	a	Normal state
				24% Cyclobulifluram suspension	467.29	a	Normal state
Clear water control	371.51	b	Normal state

Note that: the yields in the above table are the average of each replicate; lower case letters represent a significant difference in 5% levels.

The field efficacy plot test result shows that the combination of the cyclob rifluram and the bronopol not only reduces the head of a disease and the disease index in the wheat scab control process, but also has obvious control effect, can improve the yield of wheat and shows obvious yield increasing effect. In addition, according to observation after the medicine, the wheat growth in each treatment area is normal, and no phytotoxicity phenomenon occurs, which indicates that the wheat growth of each medicine is safe under the test dosage.

In conclusion, through indoor toxicity measurement and field efficacy tests, the pesticide composition provided by the application has a good control effect on wheat scab and rice bakanae disease, 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 drug residue.

Although the application has been described in detail with reference to certain embodiments by way of example, the disclosure of the application is capable of numerous modifications and alternatives. It should be understood, however, that the disclosure of the application is not intended to be limited to the particular forms disclosed. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the scope of the application as defined by the appended claims and their legal equivalents.

Claims

1. The bactericidal composition containing the cyclyl fluoride is characterized by comprising an active ingredient A and an active ingredient B, wherein the active ingredient A is cyclyl fluoride, and the active ingredient B is bromonitrol.

2. The bactericidal composition according to claim 1, wherein the mass ratio of the cyclyl fluoride to the bromonitrol is 1:25-35:1.

3. The bactericidal composition according to claim 1, wherein the mass ratio of the cyclyl fluoride to the bromonitroalcohol is 1:24-24:1;

preferably, the mass ratio of the cyclyl fluoride to the bromonitrol is 1:21-24:1.

4. The sterilizing composition according to claim 1, wherein the sum of the contents of the cyclyl fluoride and the bromonitrool in the sterilizing composition is 1 to 90wt%, based on 100wt% of the total weight of the sterilizing composition;

preferably, the sum of the contents of the cyclyl fluoride and the bromonitrool in the bactericidal composition is 5-80 wt%.

5. The composition of claim 1, wherein the composition further comprises agriculturally acceptable auxiliary ingredients in addition to the active ingredient, the auxiliary ingredients being selected from one or more of wetting agents, dispersing agents, emulsifying agents, thickening agents, disintegrating agents, freezing point depressants, antifoaming agents, solvents, preservatives, stabilizers, synergists, binders, or carriers.

6. The bactericidal composition of claim 5, wherein the dosage form of the bactericidal composition is selected from a solid formulation and/or a liquid formulation and/or a seed treatment formulation.

7. The bactericidal composition of claim 6, wherein the bactericidal composition is formulated into a pesticidally acceptable formulation, the formulation being a microemulsion, an aqueous emulsion, a suspension, a dispersible oil suspension, a solution, an emulsifiable concentrate, a suspoemulsion, a microencapsulated suspension, a water dispersible granule, a wettable powder, a granule, a seed treatment suspension, a seed treatment dry powder.

8. The bactericidal composition of claim 7, wherein the formulation is a microemulsion, a emulsifiable concentrate, a suspension, an aqueous emulsion, a water dispersible granule, a seed treatment suspension.

9. Use of the fungicidal composition as claimed in any one of claims 1 to 8 for controlling plant diseases.

10. The use according to claim 9, wherein the plant disease is a fungal or bacterial caused plant disease;

preferably, the plant disease is a fungal plant disease;

still more preferably, the plant disease caused by the fungus is wheat scab and rice bakanae disease.