CN104904721B - A kind of microbicide compositions and preparation and its application - Google Patents

Abstract

The invention relates to the field of agricultural fungicides, and discloses a fungicide composition and preparation as well as applications thereof, in particular to a fungicide composition and preparation for preventing and treating Botrytis cinerea and applications thereof. The composition is a bactericidal composition containing fludioxonil and pyrazole amide compounds, and the weight ratio of fludioxonil to pyrazole amide compounds is 1:1000-1000:1. The pesticide preparation processed from the composition can be used for preventing and treating Botrytis cinerea, has both therapeutic and protective effects, has good synergistic effect, good bactericidal effect, can reduce the frequency of application, is safe for crops and other performance advantages.

Description

A kind of bactericide composition and preparation and application thereof

technical field

The present invention relates to the field of agricultural fungicides, in particular to a fungicide composition and preparation and its application, in particular to a fungicide composition and preparation for preventing and treating Botrytis cinerea and its application.

Background technique

Botrytis cinerea is a common and difficult to control fungal disease of open field and protected crops. It is a low-temperature and high-humidity disease. period of high incidence of disease. Botrytis cinerea is caused by the infection of Botrytis cinerea, which is a fungal disease and can affect flowers, fruits, leaves and stems. Botrytis cinerea (Botrytiscinerea) is a broad-hosted gray mold disease that can cause more than 200 known plants (such as fruits, vegetables and flowers). It can not only infect field crops, but also affect the post-harvest stage cause huge losses.

Fludioxonil (fludioxonil), the chemical name is 4-(2,2-difluoro-1,3-benzodiox-4-yl)pyrrole-3-carbonitrile, a new type of pyrrole contact fungicide, and its mechanism of action It inhibits the transfer related to glucose phosphorylation and inhibits the growth of fungal mycelium, eventually leading to the death of pathogens. It has no cross-resistance with existing fungicides and is a non-systemic broad-spectrum fungicide. It can be used as a stem and leaf treatment agent or as a seed treatment agent. As a seed treatment agent, it is mainly used to prevent and control seed-borne and soil-borne pathogens such as Alternaria, Ascodiospora, Aspergillus, Fusarium, and Helminthias Genus, Rhizoctonia and Penicillium, etc., but a single use can easily cause pathogenic bacteria to develop resistance.

Pyrazole amide compounds are novel and innovative compound I and compound II with independent intellectual property rights developed by Central China Normal University (see the compounds shown in the following formula (I) and formula (II) for the structure). Preliminary studies have shown that the two The compound has a broad bactericidal spectrum and has certain systemic conductivity.

There is no report about the combination of pyrazole amide compound I and compound II with fludioxonil for the control of Botrytis cinerea.

Contents of the invention

The object of the present invention is to provide a fungicide composition with remarkable control effect on plant diseases, especially to provide a fungicide composition with remarkable control effect on Botrytis cinerea.

After in-depth research, the inventors of the present invention found that the combined use of pyrazole amide compounds with the following specific structures and fludioxonil not only did not offset the respective drug effects of pyrazole amide compounds and fludioxonil, but also It has a very obvious synergistic effect, and the control effect on plant diseases caused by fungi is significantly improved, especially the control effect on gray mold is significantly improved, thereby completing the present invention.

That is, in order to achieve the above object, according to the first aspect of the present invention, the present invention provides a fungicide composition, wherein the active ingredients of the fungicide composition include fludioxonil and pyrazole amide compounds, said The pyrazole amide compound is a compound shown in the following formula (I) and/or a compound shown in formula (II),

According to the second aspect of the present invention, the present invention provides the application of the above fungicide composition in the control of Botrytis cinerea.

According to the third aspect of the present invention, the present invention provides a preparation prepared from the above-mentioned fungicide composition, wherein, the dosage form of the preparation is emulsifiable concentrate, water emulsion, microemulsion, soluble liquid, water suspension, suspension Emulsions, ultra-low volume sprays, oil suspensions, microcapsule suspensions, water surface coating oils, wettable powders, water dispersible granules, dry suspensions, soluble powders or soluble granules, emulsifiable powders, emulsifiable granules formulations, granules, solid microcapsules, effervescent tablets, effervescent granules, water-floating dispersible granules or seed coatings.

According to the fourth aspect of the present invention, the present invention provides the application of the above-mentioned preparation in the control of Botrytis cinerea.

According to the bactericide composition provided by the present invention, it has obvious synergistic effect, good bactericidal effect, low drug cost, is not easy to produce resistance, and has good safety to crops. In particular, the fungicide composition provided by the invention has remarkable control effect on Botrytis cinerea.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

detailed description

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The active ingredients of the fungicide composition provided by the present invention include fludioxonil and pyrazole amide compounds, and the pyrazole amide compounds are compounds represented by the following formula (I) and/or compounds represented by formula (II)

The pyrazole amide compounds shown in the formula (I) in the present invention can be synthesized using the synthetic route shown in the following synthetic route (1):

The pyrazole amide compounds shown in the formula (II) in the present invention can be synthesized using the synthetic route shown in the following synthetic route (2):

In addition, fludioxonil can be obtained synthetically or commercially, for example, it can be purchased from Shangyu Yingtai Fine Chemical Co., Ltd.

In the present invention, the active ingredient includes fludioxonil and the pyrazole amide compound, and the weight ratio of fludioxonil and the pyrazole amide compound can be changed in a wide range, specifically, for example, pyrazole The weight ratio of bacterionitrile to the pyrazole amide compound is 1:1000-1000:1. Although in the present invention, as long as the active ingredient includes the fludioxonil and the pyrazole amide compounds, it can show a significant synergistic effect, but from the perspective of further improving the synergistic effect, it is preferred The weight ratio of fludioxonil to the pyrazole amide compound is 1:60-60:1; more preferably the weight ratio of fludioxonil to the pyrazole amide compound is 1:20-20:1; more preferably The weight ratio of fludioxonil to the pyrazole amide compound is 1:10˜10:1; more preferably, the weight ratio of fludioxonil to the pyrazole amide compound is 1:5˜5:1.

In the fungicide composition of the present invention, the content of the active ingredient in the fungicide composition can be changed in a wide range, specifically, the content of the active ingredient in the composition is 1 to 95% by weight, preferably 5-80% by weight.

In the fungicide composition of the present invention, in addition to the active ingredient, the fungicide composition usually also contains various surfactants and carriers commonly used in pesticides.

The above-mentioned surfactants can be various surfactants known in the field of pesticide formulations, and the present invention is preferably one or more of emulsifiers, dispersants and wetting agents.

Other carriers except the above-mentioned surfactants can be various carriers known in the field of pesticide formulations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, synthetic Vector class. Specifically, for example: white carbon black, kaolin, diatomaceous earth, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine fertilizer, mixture of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, anhydrous potassium carbonate and anhydrous bicarbonate One or more of a mixture of potassium and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.

Above-mentioned emulsifier can be the various emulsifiers known in the field of agricultural formulations, specifically, this emulsifier can be calcium dodecylbenzenesulfonate, tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene Ether, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct , polyol fatty acid ester and its ethylene oxide adduct, styrylphenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrylphenol Formaldehyde resin polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ether, or a combination of two or more.

The above-mentioned dispersant can be various dispersants known in the field of pesticide formulations, specifically, the dispersant is acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalenesulfonic acid formaldehyde condensate sodium salt, rosin block polymer Oxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, tristyrylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate, p-hydroxyphenyl One or more combinations of lignosulfonic acid sodium salts.

The above-mentioned wetting agent can be various wetting agents known in the field of pesticide formulations, specifically, the wetting agent can be sodium lauryl sulfate, secondary alkyl sodium sulfate, sodium dodecylbenzenesulfonate, fat One or more of alcohol polyoxyethylene ether, alkylnaphthalene sulfonate, alkylphenol resin polyoxyethylene ether sulfate.

The fungicide composition of the present invention, the fungicide composition can also contain various auxiliary agents commonly used in the field of pesticide formulations, specifically, the auxiliary agents for preparation can be solvents, cosolvents, thickeners, antifreezing agents , one or more of capsule material, protective agent, defoamer, disintegrant, stabilizer, preservative and binder.

The above-mentioned solvent can be various solvents known in the field of pesticide formulations, specifically, the solvent can be one or more of organic solvents, vegetable oils, mineral oils, mineral spirits and water.

Wherein, the organic solvent includes N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethyldecylamide, N,N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, One or more of toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1,4-dioxane and cyclohexanone.

The vegetable oil includes one or more of methylated vegetable oil, turpentine-based vegetable oil, turpentine oil, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine nut oil.

The mineral oil includes one or more of liquid wax, machine oil, kerosene and lubricating oil.

At the same time, the above-mentioned solvents can also be used as auxiliary solvents.

The above-mentioned antifreezing agent can be various antifreezing agents known in the field of pesticide formulations, and the present invention is preferably one or more of ethylene glycol, propylene glycol, glycerin and urea.

Above-mentioned thickening agent can be various thickening agents known in the field of pesticide dosage form, specifically, this thickening agent can be xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon black, diatom One or more of clay, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organic bentonite.

The above-mentioned capsule material can be various capsule materials known in the field of pesticide formulations, and in the present invention, it is preferably polyurethane, polyurea or urea-formaldehyde resin.

The above-mentioned protective agent can be various protective agents known in the field of pesticide formulations, and the present invention is preferably polyvinyl alcohol and/or polyethylene glycol.

The above-mentioned defoamer can be various defoamers known in the field of pesticide formulations, and the present invention is preferably one or more of organosiloxane, tributyl phosphate and silicone.

Above-mentioned stabilizer is selected from triphenyl phosphite, epichlorohydrin, acetic anhydride. The above-mentioned preservatives are selected from one or more of benzoic acid, sodium benzoate, 1,2-benzisothiazolin-3-one (abbreviated as BIT), Cathone and potassium sorbate.

The present invention also provides the application of the above fungicide composition in preventing and treating diseases caused by Botrytis cinerea.

The present invention also provides a preparation prepared from the above-mentioned fungicide composition, the dosage form of the preparation is emulsifiable concentrate, water emulsion, microemulsion, soluble liquid, water suspension, suspoemulsion, ultra-low volume spray, oil suspension agent, microcapsule suspension, water-surface film-forming oil, wettable powder, water-dispersible granule, dry suspension, soluble powder or soluble granule, emulsifiable powder, emulsifiable granule, granule, solid microcapsule preparation, Effervescent tablets, effervescent granules, water floating dispersible granules or seed coatings.

The dosage form of the fungicide composition of the present invention can be various dosage forms known in the field of pesticide formulations, specifically, it can be emulsifiable concentrate, water emulsion, microemulsion, soluble liquid, water suspension, suspoemulsion, ultra-low volume spray , oil suspension, microcapsule suspension, water-surface film-forming oil, wettable powder, water-dispersible granule, dry suspension, soluble powder or soluble granule, emulsifiable powder, emulsifiable granule, granule, solid micro Capsule preparations, effervescent tablets, effervescent granules, water floating dispersible granules or seed coatings, the above dosage forms can be prepared by conventional methods in the art.

Preferably, the composition of the emulsifiable concentrate preparation is 1-95% of active ingredient, 0-20% of co-solvent, 1-30% of emulsifier, and 100% of solvent.

The preparation method of the above-mentioned emulsifiable concentrate preparation may include, for example, mixing and stirring each active component, solvent, co-solvent and emulsifier to form a uniform transparent oil phase to obtain an emulsifiable concentrate preparation.

Preferably, the composition of the emulsifiable concentrate preparation is 1-95% of active ingredient, 0-20% of co-solvent, 1-30% of emulsifier, and 100% of solvent.

The preparation method of the above-mentioned emulsifiable concentrate preparation may include, for example, mixing and stirring each active component, solvent, co-solvent and emulsifier to form a uniform transparent oil phase to obtain an emulsifiable concentrate preparation.

Preferably, the aqueous emulsion or microemulsion consists of 1-95% active ingredient, 1-30% emulsifier, 0-30% co-solvent, 1-30% solvent, and 0-10% antifreeze , Thickener 0-10%, water make up to 100%.

Preferably, the preparation method of the water emulsion may include, for example, mixing the active ingredient, emulsifier, co-solvent and solvent to make it a uniform oil phase; mixing water, thickener, antifreeze, etc. to make it a uniform water phase. Mutually. Under high-speed shear, add the water phase to the oil phase or add the oil phase to the water phase to form a water emulsion with good dispersibility.

Preferably, the microemulsion is prepared by mixing and stirring active ingredients, emulsifiers, and solvents to form a uniform and transparent oil phase. under stirring conditions. Gradually add water to form a uniform and transparent microemulsion.

Preferably, the water suspension consists of 1-95% active ingredient, 1-30% surfactant, 1-10% antifreeze, 0.1-5% thickener, and 100% water .

Preferably, the oil suspension consists of 1-95% active ingredient, 1-30% emulsifier, 0.1-10% dispersant, 0.1-5% thickener, and 100% oil .

The preparation method of the water/oil suspension: use water or oil as the medium, add active components, surfactants, and other additives into a sand mill, grind to a certain particle size, and then filter. Then add the measured thickener into the ground mother liquor, and shear and disperse evenly. Made into oil suspension or water suspension.

Preferably, the soluble granules, soluble powders, water-dispersible granules or wettable powders consist of 1-95% active ingredient, 1-30% surfactant, and other carriers to make up 100% by weight.

Wherein, the preparation method of the water-dispersible granule and the soluble granule is as follows: each active component, a dispersant, and a wetting agent are mixed. The carrier and the like are mixed evenly, then pulverized to a certain particle size by airflow, then kneaded by adding water, and finally added to a granulator for granulation, and after drying, water-dispersible granules or soluble granules can be obtained.

The preparation method of the soluble powder and the wettable powder is as follows: fully mixing various active components, various auxiliary agents and other fillers such as carriers, and pulverizing with an ultrafine pulverizer.

Preferably, the above-mentioned microcapsule suspension consists of 1-95% active ingredient, 1-30% solvent, 0.1-5.0% protective agent, 0.05-1.0% defoamer, and 1-30% capsule material by weight percentage, 1-30% dispersant, 0-30% wetting agent, 0-10% antifreeze, 0.1-5% thickener, and 100% water.

Preparation method: mix the solvent and capsule material, then add the active ingredient; then add it into the mixture composed of protective agent, antifreeze, defoamer and water to emulsify, stir until the polymerization reaction is completed; then add thickener, disperse agent and wetting agent to obtain a stable suspension of microcapsules.

The present invention also provides the application of the above preparation in preventing and treating Botrytis cinerea.

The fungicide composition of the present invention can be provided in the form of a finished preparation, that is, each substance in the composition has been mixed; it can also be provided in the form of a separate preparation, which is mixed in a barrel or tank before use, and selected according to the concentration of the required active substance Simply mix with water for dilution.

The composition of the present invention can also be used in combination with other compounds with bactericidal, insecticidal or herbicidal properties, and can also be used in combination with nematicides, protective agents, growth regulators, plant nutrients or soil regulators.

The use method of the fungicide composition of the present invention is simple. Before or after the germination of plant diseases, it is applied to crops and crop growth places according to conventional methods, such as soil mixing, spraying, spraying, pouring, etc., and the application amount depends on the climate conditions. Or depending on the state of the crop, generally apply 1-100g per mu and dilute to 1-2000mg/L for application. The diluent is preferably water.

The bactericidal effect of the fungicide composition of the present invention is generally related to external factors such as climate, but the influence of climate can be slowed down by using an appropriate dosage form.

The present invention is further described through specific examples below, but the present invention is not limited only to the following examples.

Fludioxonil in the following test examples and preparation examples was purchased from Shangyu Yingtai Fine Chemical Co., Ltd. (purity: 98% by weight).

In the following preparation examples, the percentages in all formulation ratios are percentages by weight.

In the following test examples and preparation examples, the compounds shown in formula (I) and formula (II) (hereinafter also referred to as Y12196 and Y13149 respectively for compounds shown in formula (I) and formula (II)) are as previously described Said synthetic route (1) and synthetic route (2) are synthesized, and its specific synthetic method is as follows.

1. Synthesis of 2,4-dichloro-1-(2-nitrophenoxy)benzene

Add 2.82g (20mmol) 2-fluoronitrobenzene and 4.89g (30mmol) 2,4-dichlorophenol, 4.15g (30mmol) K ₂ CO ₃ and 50ml DMF to a 100ml single-necked bottle, heat to reflux for 5h , DMF was removed under reduced pressure, washed three times with 10% NaOH aqueous solution, extracted with ethyl acetate, dried over anhydrous Na ₂ SO ₄ and precipitated to obtain 2,4-dichloro-1-(2-nitrophenoxy) Benzene 5.50g, yield 97%.

2. Synthesis of 2-(2,4-dichlorophenoxy)aniline

Dissolve 5.50g (19.36mmol) of 2,4-dichloro-1-(2-nitrophenoxy)benzene in 100ml of ethanol, add 1.04g (19.36mmol) of ammonium chloride and 10ml of water, heat to reflux and add Three batches of 3.24g (58.08mmol) iron powder were reacted for 6 hours and the reaction system was filtered with silica gel, ethanol was spun off, 100ml of ethyl acetate was added, washed with 60ml×3 times of saturated saline, dried and then precipitated to obtain 2-( 4.50 g of 2,4-dichlorophenoxy)aniline, yield 91%.

3. Synthesis of 2-(2-chloro-4-trifluoromethylphenoxy)aniline

Add 5.00g (45.82mmol) 2-aminophenol and 9.10g (45.82mmol) ₃ -chloro-4-fluorobenzotrifluoride, 9.50g ( _68.73mmol ) K2CO3 and 100ml DMF to a 250ml single-necked bottle, After heating to reflux for 5 h, DMF was removed under reduced pressure, washed three times with 10% NaOH aqueous solution, extracted with ethyl acetate, dried over anhydrous Na ₂ SO ₄ and then precipitated to obtain 2-(2-chloro-4-trifluoromethylbenzene Oxy)aniline 9.53g, yield 72%.

4, the synthesis of the compound shown in formula (I)

Dissolve 0.50g (1.97mmol) of 2-(2,4-dichlorophenoxy)aniline in 20ml of dichloromethane, add 0.30g (2.95mmol) of triethylamine, and slowly add 3 - 0.46 g (2.36 mmol) of difluoromethyl-1-methyl-1H-pyrazole-4-carbonyl chloride. After the completion of the reaction monitored by TLC, 30ml of dichloromethane was added to the system, washed with 50ml x 3 times of saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.70g of compound I with a yield of 86%.

5, the synthesis of the compound shown in formula (II)

Dissolve 0.57g (1.97mmol) of 2-(2-chloro-4-trifluoromethylphenoxy)aniline in 20ml of dichloromethane, add 0.30g (2.95mmol) of triethylamine, and then 0.46 g (2.36 mmol) of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbonyl chloride was slowly added dropwise. After the completion of the reaction monitored by TLC, 30ml of dichloromethane was added to the system, washed with 50ml x 3 times of saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 0.75g of compound I with a yield of 85%.

The relevant nuclear magnetic data of the compound shown in the formula (I) that makes and formula (II) are as follows:

Compound represented by formula (I): ¹ H NMR (600MHz, CDCl ₃ ) δ8.67(s, 1H), 8.55(d, J=8.4Hz, 1H), 7.99(s, 1H), 7.48(t, J＝8.4Hz, 1H), 7.21(m, 2H), 7.04(s, 1H), 6.92(t, J＝48.6Hz, 1H), 6.74(d, J＝13.8Hz, 1H), 3.95(s, 3H).MS:m/z＝411.29(M+).mp:102.5-103.6℃.

Compound represented by formula (II): ¹ H NMR (600MHz, CDCl ₃ ) δ8.62(s, 1H), 8.58(d, J=8.4Hz, 1H), 7.99(s, 1H), 7.75(s, 1H), 7.46(d, J=9Hz, 1H), 7.24(d, J=7.8Hz, 1H), 7.11(t, J=7.8Hz, 1H), 6.99(d, J=9Hz, 1H), 6.87 (t,J=53.4Hz,1H),6.86(s,1H),3.92(s,3H).MS:m/z=445.15(M+).mp:114.3-115.4℃.

test case 1

This test example is used to illustrate the indoor toxicity determination of fludioxonil and pyrazole amide compounds against gray mold of cucumber

Test object: Cucumber Botrytis cinerea

Test method: refer to the method of mycelial growth rate in "Agricultural Industry Standard of the People's Republic of China NY/T 1156.2-2006". Each agent is treated with 5 doses according to the content of active ingredients, and the above-mentioned pathogenic bacteria are cultivated with PDA medium. The bacteria block was moved to the center of the pre-prepared toxic PDA medium, and then cultured in a 25°C incubator, and each treatment was repeated 4 times. Depending on the growth of the CK colony, use the cross method to measure the colony diameter cm of each treatment with a caliper, and calculate the corrected inhibition percentage. Through the linear regression analysis between the probability value of the inhibition rate and the logarithmic value of the serial concentration, the EC ₅₀ value of each drug was obtained, and then the co-toxicity coefficient (CTC) was calculated according to Sun Yunpei's method.

Calculation of drug efficacy: Measure two diameters of each colony cross, and use the average number to represent the colony size. Calculate the colony growth inhibition rate according to the following formula: colony growth inhibition rate%=(blank control colony growth diameter-medicine treatment colony growth diameter)×100/blank control colony growth diameter.

Results The 3.11 professional version of DPS was used for data analysis and statistics, and the regression line, EC ₅₀ and correlation coefficient were obtained. According to Sun Yunpei (YP Sun) method, the _EC50 of each treatment measured was converted into actual toxicity index (ATI); according to the proportioning of the mixture, the theoretical toxicity index (TTI) was obtained, and the co-toxicity coefficient of the mixture was calculated by the following formula ( CTC).

Co-toxicity coefficient (CTC) = [mixture actual toxicity index (ATI) / mixture theoretical toxicity index (TTI)] × 100

Mixture Actual Toxicity Index (ATI) = (EC ₅₀ of standard drug / EC ₅₀ of mixture) × 100

Mixture theoretical toxicity index (TTI) = TI of agent A × content of A in the active ingredient of the mixture + TI of agent B × content of B in the active ingredient of the mixture

Toxicity index (TI) = (EC ₅₀ of standard drug / EC ₅₀ of test drug) × 100 (one of A and B is used as the standard drug)

Agent A and agent B are respectively two kinds of mixed active ingredients, and the mixed agent is a mixture of agent A and agent B mixed together.

Evaluation criteria: when CTC ≥ 120, it shows a synergistic effect; when CTC ≤ 80, it shows an antagonistic effect; 80 < CTC < 120, it shows an additive effect.

The results are shown in Table 1.

Table 1

potion _EC50 (μg/mL) ATI TTI Co-toxicity coefficient CTC Fludioxonil (A) 0.06235 100.00 Y12196(B1) 2.08570 2.99 Y13149(B2) 1.53012 4.07 A+B1(60:1) ⁽¹⁾ 0.0442 141.16 98.41 143.44 A+B1(40:1) 0.0405 153.95 97.63 157.68 A+B1(20:1) 0.0462 134.96 95.38 141.49 A+B1(12:1) 0.0326 191.55 92.54 207.00 A+B1(8:1) 0.0334 186.68 89.22 209.23 A+B1(4:1) 0.0357 174.65 80.60 216.69 A+B1(2:1) 0.0326 191.55 67.66 283.09 A+B1(1:1) 0.0327 190.73 51.50 370.39 A+B1(1:2) 0.0377 165.43 35.33 468.28 A+B1(1:4) 0.0563 110.79 22.39 494.75 A+B1(1:8) 0.1325 47.06 13.77 341.76 A+B1(1:12) 0.2758 22.61 10.45 216.29 A+B1(1:20) 0.3849 16.20 7.61 212.88 A+B1(1:40) 0.5982 10.42 5.36 194.60 A+B1(1:60) 0.7084 8.80 4.58 192.16 A+B2(60:1) 0.0399 156.27 98.43 158.76 A+B2(40:1) 0.0401 155.49 97.66 159.21 A+B2(20:1) 0.0396 157.45 95.43 164.99 A+B2(12:1) 0.0319 195.45 92.62 211.03 A+B2(8:1) 0.0286 218.01 89.34 244.02 A+B2(4:1) 0.0287 217.25 80.81 268.82 A+B2(2:1) 0.0312 199.84 68.02 293.78 A+B2(1:1) 0.0322 193.63 52.04 372.12 A+B2(1:2) 0.0354 176.13 36.05 488.62 A+B2(1:4) 0.0508 122.74 23.26 527.76 A+B2(1:8) 0.1298 48.04 14.73 326.13 A+B2(1:12) 0.2687 23.20 11.45 202.67 A+B2(1:20) 0.3809 16.37 8.64 189.50 A+B2(1:40) 0.5786 10.78 6.41 168.12 A+B2(1:60) 0.6999 8.91 5.64 157.88

Remarks: ⁽¹⁾ The numerical ratio in the brackets indicated is the weight ratio of the two medicaments.

Preparation Example 1

This preparation example is used to illustrate the preparation of suspending agent

Weigh 10% fludioxonil, 20% Y13149, 2% TERSPERSE 2500 (purchased from Huntsman, hereinafter the same), 3% TERSPERSE 4896 (purchased from Huntsman, hereinafter the same), 0.2% xanthan gum, 3% white carbon black, 5% ethylene glycol, 0.3% benzoic acid, 0.5% silicone defoamer (trade name: s-29 produced by Nanjing Sixin Applied Chemicals Company), and deionized water to 100%.

Preparation method: Mix the active ingredients, wetting agent, dispersant, antifreeze, etc. evenly, add to a sand mill and grind to a certain particle size, then filter. Then add the prepared xanthan gum and stir until uniform to obtain 30% fludioxonil-Y13149 suspension concentrate Y1.

Preparation example 2

This preparation example is used to illustrate the preparation of suspending agent

Weigh 25% fludioxonil, 25% Y12196, 2% NNO (purchased from Shanghai Tiantan Auxiliary Co., Ltd., the same below), 2% TERSPERSE 2500, 0.1% xanthan gum, 3% white carbon black, 5% propylene glycol, Add 0.5% sodium benzoate, 0.5% silicone defoamer, and deionized water to 100%.

Preparation method: Mix the active ingredients, wetting agent, dispersant, antifreeze, etc. evenly, add to a sand mill and grind to a certain particle size, then filter. Then add the prepared xanthan gum and stir until uniform to obtain 50% fludioxonil-Y12196 suspension concentrate Y2.

Preparation example 3

This preparation example is used to illustrate the preparation of wettable powder

Weigh 30% fludioxonil, 30% Y12196, 5% calcium lignosulfonate, 2% pull open powder BX (purchased from Shanghai Tiantan Auxiliary Co., Ltd., the same below), 1% sodium lauryl sulfate, 5% % white carbon black, kaolin added to 100%.

Preparation method: The above-mentioned raw materials are mixed and jet-milled to prepare 60% fludioxonil-Y12196 wettable powder Y3.

Preparation Example 4

This preparation example is used to illustrate the preparation of wettable powder

Weigh 12% fludioxonil, 48% Y13149, 4% calcium lignosulfonate, 3% TERSPERSE 2700, 2% pull open powder BX, 2% sodium lauryl sulfate, 5% white carbon black, light calcium plus to 100%.

Preparation method: The above-mentioned raw materials are mixed and jet-milled to prepare 60% fludioxonil-Y13149 wettable powder Y4.

Preparation Example 5

This preparation example is used to illustrate the preparation of microemulsion

Weigh 5% fludioxonil, 10% Y12196, 4% TX-10 (purchased from Xingtai Lanxing Auxiliary Company, the same below), 5% Nongru 700# (purchased from Nanjing Taihua Chemical Co., Ltd., the same below) , 6% Nongru 500# (purchased from Nanjing Taihua Chemical Co., Ltd., the same below), 4% Nongru 1601# (purchased from Nanjing Taihua Chemical Co., Ltd., the same below), 15% cyclohexanone, 5% N -Methylpyrrolidone, 5% n-butanol, 1% epichlorohydrin, dissolved completely and mixed uniformly, deionized water was added to 100%, after stirring, 15% fludioxonil-Y12196 microemulsion Y5 was obtained.

Preparation example 6

This preparation example is used to illustrate the preparation of microemulsion

Weigh 10% fludioxonil, 10% Y13149, 5% agricultural milk 400#, 4% agricultural milk 500#, 6% agricultural milk 1601#, 25% cyclohexanone, 10% trimethylbenzene, 5% isopropanol, 3% calcium dodecylbenzenesulfonate, dissolved completely and mixed evenly, added deionized water to 100%, stirred to obtain 20% fludioxonil-Y13149 microemulsion Y6.

Preparation Example 7

This preparation example is used to illustrate the preparation of emulsion in water

Weigh 5% fludioxonil, 5% Y12196, 3% Nongru 2201# (purchased from Nanjing Taihua Chemical Co., Ltd., the same below), 1.5% nonylphenol polyoxyethylene (EO=10) ether phosphate (purchased Nanjing Taihua Chemical Co., Ltd., the same below), 2.5% tristyrylphenol polyoxyethylene ether phosphate (Nongru 600# acid phospholipid, purchased from Nanjing Taihua Chemical Co., Ltd.), 2% Span-60# ( Purchased from Xingtai Bluestar Auxiliary Company, the same below), 1% epichlorohydrin, 20% xylene, 10% cyclohexanone, 0.1% xanthan gum, 0.5% benzoic acid, and deionized water to 100%.

Preparation method: after dissolving the above active ingredients, emulsifier and dispersant in a solvent, add them into the water phase under high shear conditions, then add xanthan gum and stir evenly to prepare 10% fludioxonil-Y12196 aqueous emulsion Y7.

Preparation example 8

This preparation example is used to illustrate the preparation of emulsion in water

Weigh 6% fludioxonil, 6% Y13149, 2% Nongru 2201#, 10% nonylphenol polyoxyethylene (EO=10) ether phosphate, 2% Span-60#, 2% emulsifier T-60 (purchased from Xingtai Bluestar Auxiliary Company), 1% triphenyl phosphite, 15% mesitylene, 10% cyclohexanone, 0.3% xanthan gum, 0.5% benzoic acid, and deionized water to 100%.

Preparation method: After dissolving the above active ingredients, emulsifier and dispersant in a solvent, add them into the water phase under high shear conditions, then add xanthan gum and stir evenly to prepare 12% fludioxonil-Y13149 aqueous emulsion Y8.

Preparation Example 9

This preparation example is used to illustrate the preparation of water-dispersible granules

Weigh 35% fludioxonil, 35% Y13149, 3% TERSPERSE 2700, 2% diffusion agent NNO (alkyl naphthalene sulfonate formaldehyde condensate), 3% pull-off powder BX (sodium dibutyl naphthalene sulfonate), Add 4% K-12 (sodium lauryl sulfate), 3% diatomaceous earth, 5% glucose, and kaolin to 100%.

According to the formula ratio, the original drug, dispersant, wetting agent, binder, etc. are mixed by the conventional method of preparing water-dispersible granules, pulverized by ultra-fine airflow, and added to a granulator equipped with a certain size screen for granulation. Then it is dried and sieved to obtain a granular product to obtain 70% fludioxonil-Y13149 water-dispersible granule Y9.

Preparation Example 10

This preparation example is used to illustrate the preparation of water-dispersible granules

Weigh 40% fludioxonil, 20% Y12196, 3% TERSPERSE 2700, 2% diffusion agent NNO (alkyl naphthalene sulfonate formaldehyde condensate), 3% pull-off powder BX (sodium dibutyl naphthalene sulfonate), Add 4% K-12 (sodium lauryl sulfate), 3% diatomaceous earth, 5% glucose, and kaolin to 100%.

According to the formula ratio, the original drug, dispersant, wetting agent, binder, etc. are mixed by the conventional method of preparing water-dispersible granules, pulverized by ultra-fine airflow, and added to a granulator equipped with a certain size screen for granulation. Then it is dried and sieved to obtain a granular product to obtain 60% fludioxonil-Y12196 water-dispersible granule Y10.

Comparative Preparation Example 1

Weigh 24% Y12196, 2% TERSPERSE 2500, 3% TERSPERSE 2425, 0.2% xanthan gum, 3% white carbon black, 5% ethylene glycol, 0.3% benzoic acid, 0.5% silicone defoamer (trade name: s-29 produced by Nanjing Sixin Applied Chemicals Company), deionized water was added to 100%.

Preparation method: Mix the active ingredients, wetting agent, dispersant, antifreeze, etc. evenly, add to a sand mill and grind to a certain particle size, then filter. Then add the prepared xanthan gum and stir until uniform to prepare 24% Y12196 suspending agent.

Comparative preparation example 2

Weigh 24% Y13149, 2% TERSPERSE 2500, 3% TERSPERSE 2425, 0.2% xanthan gum, 3% white carbon black, 5% ethylene glycol, 0.3% benzoic acid, 0.5% silicone defoamer (trade name: s-29 produced by Nanjing Sixin Applied Chemicals Company), deionized water was added to 100%.

Preparation method: Mix the active ingredients, wetting agent, dispersant, antifreeze, etc. evenly, add to a sand mill and grind to a certain particle size, then filter. Then add the prepared xanthan gum and stir until uniform to prepare 24% Y13149 suspending agent.

Comparative Preparation Example 3

Weigh 2.5% fludioxonil, 30% N-methylpyrrolidone, 5% 505#, 7% 602#, trimethylbenzene and add to 100%.

Preparation method: Mix and stir the active ingredient, emulsifier, cosolvent, etc. until uniform to prepare 2.5% fludioxonil emulsifiable oil.

test case 2

This test example is used to illustrate the field efficacy test of controlling cucumber gray mold

Field application example 1. Field efficacy test on controlling cucumber gray mold

The field efficacy test of controlling cucumber gray mold refers to the "Guidelines for Field Efficacy Test of Pesticides (1) GB/T17980.28-2000 Fungicide Control of Vegetable Botrytis" by the Institute of Drug Control, Ministry of Agriculture. The experimental field is located in Zhejiang Shaoxing Academy of Agricultural Sciences. The plots of test drug, control drug and blank control were arranged in random blocks with an area of 15m ² , repeated 4 times, and the disease base was investigated before application, and the drug was applied twice. Five-point sampling was adopted in each plot, and 2 plants were investigated at each point, and all leaves and fruits of each plant were investigated.

Leaf disease classification criteria are as follows:

Level 0: no disease;

Grade 1: 3 diseased spots on a single leaf;

Grade 3: There are 4 to 6 diseased spots on a single leaf;

Grade 5: 7 to 10 diseased spots on a single leaf;

Grade 7: There are 11 to 20 diseased spots on a single leaf, some of which are densely integrated into sheets;

Grade 9: A single leaf has dense diseased spots accounting for more than a quarter of the leaf area.

The classification criteria for fruit diseases are as follows:

Level 0: no disease;

Grade 1: residual flower disease;

Grade 3: Onset of fruit navel;

Grade 5: The lesion length accounts for less than 10% of the fruit;

Grade 7: The lesion length accounts for 11% to 25% of the fruit;

Grade 9: Lesions account for more than 26% of the fruit.

Drug efficacy calculation method:

According to the survey results, calculate the disease index and control effect according to the formulas (1) and (2) below. The experimental data were statistically analyzed using Duncan's new multiple range method (DMRT).

In the formula: CK ₀ , CK ₁ are the disease index of the blank control area before and after application of the drug, respectively; PT ₀ , PT ₁ are the disease index of the drug treatment area before and after the drug application, respectively.

In addition, the applied drugs, the amount of active ingredients and the test results are shown in Table 2

Table 2

It can be seen from the above effect data that the fungicidal composition provided by the present invention can be used to prevent gray mold with special effects, reasonable components, treatment plus protection, good bactericidal effect, reduced number of medications, low cost of medication, and its activity and bactericidal The effect is not a simple superposition of the activities of each component, but a significant synergistic effect, which slows down the generation of resistance, is safe for crops, and meets the safety requirements of pesticide preparations.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (7)

1. a bactericide composition, is characterized in that, the active ingredient of this bactericide composition comprises fludioxonil and pyrazole amide compound, and described pyrazole amide compound is the compound shown in following formula (I) and / or the compound shown in formula (II), Wherein, the weight ratio of the fludioxonil to the pyrazole amide compound is 1:60-60:1. 2. The fungicide composition according to claim 1, wherein the content of the active ingredient in the fungicide composition is 1-95% by weight. 3. The fungicide composition according to claim 2, wherein the content of the active ingredient in the fungicide composition is 5-80% by weight. 4. The fungicide composition according to claim 1, wherein the weight ratio of the fludioxonil to the pyrazole amide compound is 1:20˜20:1. 5. The application of the fungicide composition described in any one of claims 1-4 in the control of Botrytis cinerea. 6. the preparation prepared by the fungicide composition described in any one of claims 1-4, wherein, the dosage form of described preparation is emulsifiable concentrate, water emulsion, microemulsion, soluble liquid, water suspension, suspoemulsion, Ultra-low volume sprays, oil suspensions, microcapsule suspensions, water surface film-forming oils, wettable powders, water-dispersible granules, dry suspensions, soluble powders or soluble granules, emulsifiable powders, emulsifiable granules, Granules, solid microcapsule preparations, effervescent tablets, effervescent granules, water floating dispersible granules or seed coatings. 7. the application of the preparation described in claim 6 in the prevention and treatment of Botrytis cinerea.