Bactericidal composition, bactericidal preparation and application
The bactericidal composition formed by combining triazole sulfonamide compounds with fluthiazolypyriethylone solves the problems of increased pesticide resistance and increased drug use in the prior art, and achieves efficient prevention and treatment of plant diseases such as cucumber downy mildew, which has fast-acting and long-term effectiveness, and reduces the risk of environmental pollution.
Patent Information
- Application Number
- CN202110256050.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2021-03-09
- Publication Date
- 2025-08-01
- Estimated Expiration
- 2041-03-09
AI Technical Summary
In the prevention and control of plant diseases, existing chemicals have problems such as increased pesticide resistance, increased drug use and environmental pollution, especially the poor effect of preventing and treating downy mildew in cucumber.
Triazole sulfonamide compounds (such as bromocyclazole or cycloflucazole) are combined with fluthiazolypyriethylone to form a bactericidal composition for the prevention and treatment of plant diseases, especially cucumber downy mildew.
It has achieved the reduction of drug usage, improved the rapid effect and effectiveness of prevention and treatment effects, broadened the sterilization spectrum, slowed down the generation of resistance, and improved the safety of use.
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Figure CN115039786B_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of pesticides, and in particular to a bactericidal composition, and a bactericidal preparation comprising the bactericidal composition and applications thereof. Background Art
[0002] Plants are often attacked by diseases during their growth. If left uncontrolled, the resulting yield reductions and harvest losses can have serious adverse impacts on the socioeconomic landscape. Currently, the use of chemical pesticides is undoubtedly one of the most effective methods for controlling plant diseases. However, the long-term, repeated use of a single pesticide and other irregular usage practices can lead to the rapid development of resistance to the pesticides, resulting in increased pesticide usage, pesticide residues, environmental pollution, and other problems.
[0003] Similarly, for plant diseases caused by fungi, chemical agents are a common means of prevention and control. However, due to the increasing resistance of plants to pesticides, the use of pesticides has increased year by year, resulting in increasingly serious environmental pollution.
[0004] For example, cucumber downy mildew is a cucumber disease caused by the fungus Pseudocoperonospora from the phylum Oomycetes. It is the most common and most devastating cucumber disease. The spores of the pathogen are spread by air currents and rainwater. In greenhouses, human activities are the primary source of infection. The most suitable temperature for cucumber downy mildew is 16-24°C. It is less likely to develop at temperatures below 10°C or above 28°C, and it is unlikely to develop at temperatures below 5°C or above 30°C. The ideal humidity for infection is above 85%, especially when leaves are covered with a film of water, which makes them most susceptible to infection. When the humidity is below 70%, the pathogen's spores have difficulty germinating and infecting, and below 60%, spores cannot form.
[0005] Oxathiapiprolin, commonly known as Oxathiapiprolin, CAS registration number: 1003318-67-9, is the first piperidinylthiazole isoxazoline fungicide developed by DuPont. Its structural formula is as follows:
[0006]
[0007] Fluoxathiapiprolin has a unique site of action against Oomycete pathogens, achieving a fungicidal effect by inhibiting oxysterol-binding protein (OSBP). It has excellent control over downy mildew and blight in cucumbers, grapes, vegetables, and other specialty crops. However, fluoxathiapiprolin has a single site of action, and the Fungicide Resistance Action Committee (FRAC) believes it carries a medium-to-high resistance risk, necessitating resistance management. Fluoxathiapiprolin is currently a commonly used chemical for cucumber downy mildew control, generally used alone. This has led to increased resistance to the pesticide and an annual increase in pesticide usage.
[0008] Therefore, there is an urgent need to develop a bactericidal composition that has a significant control effect on plant diseases, especially plant diseases caused by fungi. Summary of the Invention
[0009] The first object of the present invention is to provide a bactericidal composition that can effectively solve the problem of excessive dosage of existing chemical control drugs.
[0010] Specifically, the present invention provides a bactericidal composition, and the active components of the bactericidal composition include: active ingredient a and active ingredient b; the active ingredient a includes triazolesulfonamide compounds represented by the general formula (I), and the active ingredient b includes fluopyram.
[0011]
[0012] In the general formula (I), R1 to R5 each independently represent hydrogen, halogen, or substituted or unsubstituted alkyl group, and at least one of R1 to R5 is halogen or substituted or unsubstituted alkyl group.
[0013] In some embodiments, in the general formula (I), among R1 to R5, any one of R2 and R4 represents halogen or substituted or unsubstituted alkyl group, and the remaining four groups all represent hydrogen atoms.
[0014] In some embodiments, the halogen is fluorine, chlorine, or bromine.
[0015] As a specific embodiment, the halogen is bromine.
[0016] In some embodiments, the substituted or unsubstituted alkyl group is substituted or unsubstituted C1 - C4 alkyl group, preferably substituted or unsubstituted C1 - C2 alkyl group.
[0017] The substituted alkyl group is further preferably halogenated C1 - C2 alkyl group, that is, when representing a substituted alkyl group, the substituting group is preferably halogen, more preferably fluorine.
[0018] As a specific embodiment, the substituted alkyl group is trifluoromethyl.
[0019] As a preferred embodiment, the triazolesulfonamide compound represented by the general formula (I) is bromuconazole or cyflufenamid.
[0020] Furthermore, the triazolesulfonamide compound represented by the general formula (I) is bromuconazole.
[0021] The bromuconazole is a novel triazolesulfonamide fungicide independently developed by Dongyangguang Pesticide R & D Co., Ltd. in Dongguan City, Guangdong Province. The chemical name of the bromuconazole is N 3 -(3 - bromobenzyl)-N 3-Cyclopropyl-N 1 ,N 1 -Dimethyl-1H-1,2,4-triazole-1,3-disulfonamide, and its structure is:
[0022]
[0023] Bromocyclazole is stable in nature and safe for the environment. Its mechanism of action is to indirectly inhibit the germination of free spores, has certain systemic permeability, and has a relatively long effective period. Bromocyclazole has good control effects on powdery mildew, downy mildew, etc. of crops.
[0024] Further, the triazolesulfonamide compound shown in the general formula (I) is cyflufenamid.
[0025] The cyflufenamid is a novel triazolesulfonamide fungicide independently developed by Dongyangguang Pesticide R & D Co., Ltd., Dongguan City, Guangdong Province. The chemical name of the cyflufenamid is N 3 -Cyclopropyl-N 1 ,N 1 -Dimethyl-N 3 -(3-(Trifluoromethyl)benzyl)-1H-1,2,4-triazole-1,3-disulfonamide, and its specific structure is:
[0026]
[0027] Cyflufenamid is stable in nature and safe for the environment. Its mechanism of action is to indirectly inhibit the germination of free spores, has certain systemic permeability, and has a relatively long effective period. Cyflufenamid has good control effects on powdery mildew, downy mildew, etc. of crops.
[0028] As a preferred embodiment, the active ingredient b is fluopyram.
[0029] As a preferred embodiment, the active components of the bactericidal composition include: active ingredient a and active ingredient b, wherein, the active ingredient a is bromocyclazole or cyflufenamid, and the active ingredient b is fluopyram.
[0030] As a preferred embodiment, the active components of the bactericidal composition are active ingredient a and active ingredient b, wherein, the active ingredient a is bromocyclazole or cyflufenamid, and the active ingredient b is fluopyram.
[0031] Further, as a preferred embodiment, the active components of the bactericidal composition include bromocyclazole and fluopyram.
[0032] Further, as a preferred embodiment, the active components of the bactericidal composition include cyflufenamid and fluopyram.
[0033] As a more preferred embodiment, the active components of the bactericidal composition are bromuconazole and fluxapyroxad.
[0034] As a more preferred embodiment, the active components of the bactericidal composition are cyflufenconazole and fluxapyroxad.
[0035] As a preferred embodiment, in the bactericidal composition, the mass ratio of the active ingredient a to the active ingredient b is (1 - 20):(20 - 1), preferably (1 - 15):(15 - 1).
[0036] As a more specific embodiment, in the bactericidal composition, the mass ratio of the active ingredient a to the active ingredient b is 1:20, 1:15, 1:10, 1:5, 1:3, 1:1, 3:1, 5:1, 10:1, 15:1 or 20:1.
[0037] As a preferred embodiment, in the bactericidal composition, the active ingredient a is bromuconazole and the active ingredient b is fluxapyroxad; more preferably, the mass ratio of bromuconazole to fluxapyroxad is (1 - 20):(20 - 1), preferably (1 - 15):(15 - 1).
[0038] As a preferred embodiment, in the bactericidal composition, the active ingredient a is cyflufenconazole and the active ingredient b is fluxapyroxad; more preferably, the mass ratio of cyflufenconazole to fluxapyroxad is (1 - 20):(20 - 1), preferably (1 - 15):(15 - 1).
[0039] The second object of the present invention is to provide a bactericidal preparation.
[0040] Specifically, the present invention provides a bactericidal preparation, and the bactericidal preparation contains the bactericidal composition of the present invention.
[0041] As a preferred embodiment, in the bactericidal preparation, based on the total mass percentage of the bactericidal preparation raw materials being 100%, the sum of the mass percentages of the active ingredient a and the active ingredient b in the bactericidal preparation raw materials is 1 - 99%, preferably 1 - 90%, more preferably 1 - 85%, more preferably 10 - 85%, more preferably 10 - 80%.
[0042] As a preferred embodiment, the dosage form of the bactericidal preparation is powder, wettable powder, microcapsule, water dispersible granule, granule, aqueous solution, suspension, emulsifiable concentrate, microemulsion, water emulsion, spray, seed coating agent or smoke agent.
[0043] As a more preferred embodiment, the dosage form of the bactericidal preparation is an emulsifiable concentrate, a suspension concentrate, a water dispersible granule, a microemulsion, an emulsion in water or a wettable powder.
[0044] The third object of the present invention is to provide the application of the bactericidal composition or the bactericidal preparation.
[0045] Specifically, the present invention provides the application of the bactericidal composition or the bactericidal preparation in preventing or treating plant diseases.
[0046] As a preferred embodiment, the bactericidal composition or the bactericidal preparation provided by the present invention is applied in preventing or treating plant diseases caused by fungi.
[0047] As a more preferred embodiment, the bactericidal composition or the bactericidal preparation provided by the present invention is applied in preventing or treating cucumber downy mildew, grape downy mildew, potato late blight, tomato late blight and / or pepper blight.
[0048] Further preferably, the bactericidal composition or the bactericidal preparation provided by the present invention is applied in preventing or treating plant diseases caused by fungi of the genus Pseudoperonospora in the Oomycetes.
[0049] As a more preferred embodiment, the bactericidal composition or the bactericidal preparation provided by the present invention is applied in preventing or treating cucumber downy mildew.
[0050] The present invention also provides a method for preventing or treating plant diseases by using the bactericidal composition or the bactericidal preparation of the present invention.
[0051] As a preferred embodiment, the method includes: treating a plant or a certain / some parts of the plant with an effective amount of the bactericidal composition or the bactericidal preparation of the present invention.
[0052] The bactericidal composition and the bactericidal preparation provided by the present invention have an obvious synergistic effect, can effectively solve the problem of excessive dosage of existing chemical control drugs for crop diseases, improve the safety of prevention and control; and significantly improve the quick-acting property of the drug and extend the effective period. Detailed Embodiments
[0053] The technical solutions of the present invention will be described in detail below.
[0054] In the present invention, the terms "comprising" and "including" are open expressions, that is, including the content specified by the present invention, but not excluding other aspects of the content.
[0055] The present invention provides a bactericidal composition, and the active components of the composition include: active ingredient a and active ingredient b; the active ingredient a includes a triazolesulfonamide compound represented by the general formula (I), and the active ingredient b includes fluopyram.
[0056]
[0057] In general formula (I), R1 to R5 are defined as described above.
[0058] The present invention studies and discovers that when fluxametpyr is used in combination with the triazolesulfonamide compounds represented by general formula (I), especially when fluxametpyr is combined with bromuconazole or cyproconazole, it has an obvious synergistic effect, and an ideal pest and disease control effect can be achieved with a lower dosage of the drug; while reducing the application amount of the active ingredient, the same good effect is maintained, which substantially broadens the bactericidal spectrum on the one hand and improves the use safety on the other hand.
[0059] In some embodiments, the active components of the bactericidal composition include active ingredient a and active ingredient b, wherein active ingredient a is bromuconazole or cyproconazole, and active ingredient b is fluxametpyr.
[0060] In some embodiments, the active components of the bactericidal composition include active ingredient a and active ingredient b, wherein active ingredient a is bromuconazole and active ingredient b is fluxametpyr.
[0061] In some embodiments, the active components of the bactericidal composition include active ingredient a and active ingredient b, wherein active ingredient a is cyproconazole and active ingredient b is fluxametpyr.
[0062] In some embodiments, the active components of the bactericidal composition are active ingredient a and active ingredient b, wherein active ingredient a is bromuconazole and active ingredient b is fluxametpyr.
[0063] In some embodiments, the active components of the bactericidal composition are active ingredient a and active ingredient b, wherein active ingredient a is cyproconazole and active ingredient b is fluxametpyr.
[0064] In some embodiments, in the bactericidal composition, the mass ratio of active ingredient a to active ingredient b is (1 - 20):(20 - 1), preferably (1 - 15):(15 - 1).
[0065] As a more specific embodiment, in the bactericidal composition, the mass ratio of active ingredient a to active ingredient b is 1:20, 1:15, 1:10, 1:5, 1:3, 1:1, 3:1, 5:1, 10:1, 15:1 or 20:1.
[0066] In some embodiments, in the bactericidal composition of the present invention, the active ingredient a is bromuconazole and the active ingredient b is fluxapyroxad; wherein, the mass ratio of bromuconazole to fluxapyroxad is (1-20):(20-1).
[0067] In some embodiments, the mass ratio of bromuconazole to fluxapyroxad is (1-15):(15-1).
[0068] In some embodiments, in the bactericidal composition of the present invention, the active ingredient a is cyflufenconazole and the active ingredient b is fluxapyroxad; wherein, the mass ratio of cyflufenconazole to fluxapyroxad is (1-20):(20-1).
[0069] In some embodiments, the mass ratio of cyflufenconazole to fluxapyroxad is (1-15):(15-1).
[0070] The bactericidal composition of the present invention not only includes a ready-to-use composition (which can be applied to plants or seeds using a suitable device), but also includes a commercially available concentrate (which must be diluted with water before use).
[0071] The present invention further provides a bactericidal preparation, which comprises the bactericidal composition of the present invention.
[0072] In some embodiments, in the bactericidal preparation, the mass ratio of the active ingredient a to the active ingredient b is (1-20):(20-1), preferably (1-15):(15-1).
[0073] As a specific embodiment, in the bactericidal preparation, the mass ratio of the active ingredient a to the active ingredient b is 1:20, 1:15, 1:10, 1:5, 1:3, 1:1, 3:1, 5:1, 10:1, 15:1 or 20:1.
[0074] In some embodiments, in the bactericidal preparation of the present invention, the active ingredient a is bromuconazole and the active ingredient b is fluxapyroxad; wherein, the mass ratio of bromuconazole to fluxapyroxad is (1-20):(20-1).
[0075] In some embodiments, the mass ratio of bromuconazole to fluxapyroxad is (1-15):(15-1).
[0076] In some embodiments, in the bactericidal preparation of the present invention, the active ingredient a is cyflufenconazole and the active ingredient b is fluxapyroxad; wherein, the mass ratio of cyflufenconazole to fluxapyroxad is (1-20):(20-1).
[0077] In some embodiments, the mass ratio of epoxiconazole to isopyrazam is (1 to 15):(15 to 1).
[0078] The present invention further provides a bactericidal preparation comprising the bactericidal composition of the present invention. The preparation types provided by the present invention are extensive and can also solve the problems of excessive dosage and insufficient control efficacy in the prior art, and can achieve the effects of expanding the bactericidal spectrum, quick-acting and long-acting. In addition to containing the active ingredients a and b, the bactericidal preparation usually also contains auxiliaries commonly used in pesticides. The auxiliaries are wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreezing agents, defoaming agents, solvents, preservatives, stabilizers, synergists, carriers, etc., which can be appropriately added according to the needs of the preparation, and can vary according to different situations, and there is no special limitation.
[0079] Auxiliaries are auxiliary substances added during the processing or use of pesticide preparations to improve the physical and chemical properties of the agents. The auxiliaries themselves have basically no biological activity, but can affect the control effect.
[0080] Among them, the wetting agent is selected from alkylphenol polyoxyethylene ethers (such as nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, dodecylphenol ether, dinonylphenol ether, and mixed alkylphenol ethers, etc.), fatty alcohol polyoxyethylene ethers, fatty acid or fatty acid ester sulfates, alkylnaphthalenesulfonates (such as sodium dibutylnaphthalenesulfonate, sodium isopropylnaphthalenesulfonate), alkylbenzenesulfonates (such as sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate), alkyl sulfates, etc., one or more of which. Typical representatives of suitable wetting agents include, but are not limited to -WET / MAX (alkylnaphthalenesulfonate), (alkylated naphthalenesulfonate), BX (alkylated naphthalenesulfonate), MT 804 (alkylated naphthalenesulfonate), GY-WS10 (non-ionic compound).
[0081] The dispersants selected are one or more of naphthalene sulfonates, naphthalene sulfonate formaldehyde condensates, lignin sulfonates, alkylbenzene sulfonates, alkylphenol polyoxyethylene ether formaldehyde condensate sulfates, high molecular weight polycarboxylates, alkylbenzene polyoxyethylene ethers, ethylene oxide-propylene oxide block polyethers, and organic phosphates, etc. For wettable powder formulations, the most common dispersant is sodium lignosulphonate. For suspension concentrates, polyelectrolytes such as sodium naphthalene sulphonate formaldehyde condensate are used to achieve very good adsorption and stabilization effects. Tristyrylphenol ethoxylate phosphate ester can also be used. Typical representatives of suitable dispersants include but are not limited to 2700, 2500, 4894, NA, GY-900, Morwet D-425, Borresperse CA, Borresperse NA, SUPRAGIL MNS / 90, 700 or Ethylan NS-500LQ.
[0082] The emulsifiers selected are one or more of fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, alkylphenol polyoxyethylene polyoxypropylene ethers, fatty amines, ethylene oxide adducts of fatty amides, fatty acid polyoxyethylene esters, ethylene oxide adducts of castor oil and their derivatives, ethylene oxide adducts of rosin acid and analogues, polyhydric alcohol fatty acids and their ethylene oxide adducts, and polyoxyethylene-polyoxypropylene block copolymers, etc. Typical representatives of suitable emulsifiers include but are not limited to agricultural emulsifier 500#, agricultural emulsifier 601#, agricultural emulsifier 602#, agricultural emulsifier 700#, agricultural emulsifier 1601#, agricultural emulsifier 1602#, TERMUL 2507, EMULPON CO-360 or Ethylan 992.
[0083] The thickeners selected are one or more of silica, kaolin, bentonite, xanthan gum, gum arabic, polyacrylic acid, and sodium carboxymethyl cellulose, etc.
[0084] The disintegrants selected are one or more of urea, bentonite, aluminum chloride, ammonium sulfate, succinic acid, sodium bicarbonate, etc.
[0085] The antifreezes selected are one or more of glycerol, ethylene glycol, propylene glycol, etc.
[0086] The defoamer selected from silicone defoamers, C 8-10 fatty alcohol defoamers, polyureas, polyethylene glycol fatty acid esters, etc., one or more of them.
[0087] The solvent is one or more of toluene, xylene, cyclohexanone, aromatic solvent, methanol, ethyl acetate, soybean oil, epoxidized soybean oil, castor oil, methyl oleate, rapeseed oil, N-octyl pyrrolidone, etc.
[0088] The preservative selected from sodium benzoate, benzoic acid, potassium sorbate, Kathon, etc., one or more of them.
[0089] The stabilizer selected from phosphoric acid, pyrophosphoric acid, phthalic acid, benzoic acid, triphenyl phosphite, acetic anhydride, epichlorohydrin, resorcinol, sodium citrate, etc., one or more of them.
[0090] The synergist has no biological activity itself, but can inhibit the detoxifying enzymes in organisms. When mixed with certain pesticides, it can greatly improve the toxicity and efficacy of pesticides, such as one or more of synergistic phosphorus, synergistic ether, etc.
[0091] The carrier selected from modified corn starch, kaolin, clay, talc, chalk, quartz, magnesium silicate, montmorillonite, diatomaceous earth, silicon dioxide, alumina, natural or artificial silicate, resin, wax, solid fertilizer, water, alcohol (especially butanol), organic solvent, mineral oil and vegetable oil and their derivatives, etc., one or more of them.
[0092] Of course, if appropriate, other additional components may also be present, such as protective colloids, binders, adhesives, thixotropic substances, penetrants, chelating agents, complexing formers, dyes, etc. Generally, the active compound can be combined with any solid or liquid additive commonly used for formulation purposes.
[0093] The bactericidal composition provided by the present invention can be used as it is or in a formulated form or a form of use prepared therefrom according to its physical properties and / or chemical properties, such as aerosol, capsule suspension, cold atomization concentrate, hot atomization concentrate, granule encapsulated in a capsule, fine granule, flowable concentrate for treating seeds, ready-to-use solution, dustable powder, emulsifiable concentrate, oil-in-water emulsion, water-in-oil emulsion, large granule, microgranule, oil-dispersible powder, oil-soluble flowable concentrate, oil-soluble liquid, foam, paste, pesticide-coated seed, suspension concentrate, suspoemulsion concentrate, soluble concentrate, suspension, wettable powder, soluble powder, powder and granule, water-soluble granule or tablet, water-soluble powder for treating seeds, wettable powder impregnated with an active compound, microcapsules in coating materials of natural products, synthetic substances, polymeric substances and seeds, and ULV cold atomization and hot atomization formulations.
[0094] For the bactericidal preparation provided by the present invention, based on the total mass percentage content of the bactericidal preparation raw materials being 100%, the sum of the mass percentage contents of active ingredient a and active ingredient b in the bactericidal preparation raw materials is 1-99%.
[0095] Preferably, the sum of the mass percentage contents of active ingredient a and active ingredient b in the bactericidal preparation raw materials is 1-90%.
[0096] More preferably, the sum of the mass percentage contents of active ingredient a and active ingredient b in the bactericidal preparation raw materials is 1-85%.
[0097] Even more preferably, the sum of the mass percentage contents of active ingredient a and active ingredient b in the bactericidal preparation raw materials is 10-85%.
[0098] Even more preferably, the sum of the mass percentage contents of active ingredient a and active ingredient b in the bactericidal preparation raw materials is 10-80%.
[0099] As a more specific embodiment, in the bactericidal preparation, based on the total mass percentage content of the bactericidal preparation raw materials being 100%, the sum of the mass percentage contents of active ingredient a and active ingredient b in the bactericidal preparation raw materials can be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or other values within the range of 10-80%.
[0100] The typical preparation dosage forms of the bactericidal preparation provided by the present invention are powder, wettable powder, microcapsule, water-dispersible (granular) particle, granule, aqueous solution, suspension, emulsifiable concentrate, microemulsion, water-in-oil emulsion, ultra-low volume spray, seed coating agent or smoke agent.
[0101] In some embodiments, the bactericidal preparation may be a powder. The powder (DP) is a preparation in which the active substance is added with a certain amount of inert powder, such as clay, kaolin, talcum powder, etc., and is mechanically processed into a powdery substance with a particle diameter of less than 100 microns.
[0102] In some embodiments, the bactericidal preparation may be a wettable powder. The wettable powder (WP) is a mixture composed of a composition in a certain proportion with a suitable surfactant and an inert substance (kaolin powder). The wettable powder is a preparation that can be uniformly dispersed in water. In addition to the active ingredient and the inert substance (kaolin powder), it also contains a certain amount of anionic or non-ionic surfactants (dispersants, wetting agents).
[0103] In some embodiments, the bactericidal preparation may be a microcapsule. The microcapsule (MC) is a preparation in which the active substance is first coated in an adhesive, film-forming agent, etc. to form a tiny capsule-like preparation, and then processed into the required dosage form; it is divided into capsule suspensions (CS), encapsulated granules (CG), capsulated dry flowables (CDF), etc.
[0104] In some embodiments, the bactericidal preparation may be a water-dispersible (granular) granule. The water-dispersible (granular) granule (WDG) is a mixture composed of a composition in a certain proportion with a suitable surfactant and an inert substance (kaolin powder). It is pulverized by air flow to make the particle fineness meet the requirements, and a double-screw mixer and a plowshare mixer are used for mixing multiple times to make the product evenly mixed. Then, it is granulated by conventional methods such as fluidized bed granulation, spray granulation, and pan granulation.
[0105] In some embodiments, the bactericidal preparation may be a granule. The granule (GR) is a mixture composed of a composition in a certain proportion with a suitable surfactant, diluent, and inert substance (kaolin powder). Granulation is carried out by a granulator, such as the fluidized bed granulation method, which is a granulation method in which the powder is kept in a flowing state and a binder solution is sprayed to make it agglomerate. This method can complete the processes of mixing, kneading, granulation, drying, and classification in one device in a short time under a closed state.
[0106] In some embodiments, the bactericidal preparation may be an aqueous solution. The aqueous solution (AS) is a liquid directly prepared by water using the property that certain technical drugs can dissolve in water without decomposition.
[0107] In some embodiments, the bactericidal preparation may be a suspension concentrate. A suspension concentrate (SC), also known as a water suspension, thick suspension, or colloidal suspension, is a homogeneous and stable dispersion system in which the technical material that is insoluble or poorly soluble in water is dispersed in water under the action of auxiliaries (such as wetting and dispersing agents, thickeners, structure regulators, and defoamers).
[0108] In some embodiments, the bactericidal preparation may be an emulsifiable concentrate. An emulsifiable concentrate (EC) is prepared by dissolving the composition in an organic solvent such as benzene, toluene, xylene, or cyclohexanone in a certain proportion and adding a certain amount of anionic or non-ionic surfactants (emulsifiers).
[0109] In some embodiments, the bactericidal preparation may be a microemulsion. A microemulsion (ME) generally consists of a liquid pesticide, surfactants (emulsifiers), water, stabilizers, etc.; its characteristic is that it uses water as the medium and contains little or no organic solvent. The droplet size in a microemulsion is generally a few nanometers to dozens of nanometers, less than one-quarter of the visible light wavelength.
[0110] In some embodiments, the bactericidal preparation may be an emulsion in water. An emulsion in water (EW) is a pesticide formulation in which the liquid technical material that is insoluble in water or a solution of the technical material dissolved in an organic solvent that is insoluble in water is dispersed in water. The technical material is dispersed in water as small droplets with a size of 0.5 - 1.5 microns, and the appearance is a milky white liquid like milk.
[0111] In some embodiments, the bactericidal preparation may be an ultra-low volume spray. An ultra-low volume spray refers to a special formulation for ultra-low volume spraying, in which the liquid medicine sprayed onto the target crop is ejected as extremely fine droplets with an extremely low dosage.
[0112] In some embodiments, the bactericidal preparation may be a seed coating agent. A seed coating agent (SD) is prepared by grinding and mixing the active ingredient and auxiliaries, and can be directly or after dilution coated on the surface of seeds to form a protective film with a certain strength and permeability.
[0113] In some embodiments, the bactericidal preparation may be a fumigant. A fumigant (FU), also known as a smoke agent, is a medicament in which the active ingredient is mixed with a combustible substance, etc., and after combustion, the pesticide is vaporized and condensed into smoke particles or directly dispersed into smoke particles.
[0114] The above preferred formulation types can improve the physical and chemical properties of the medicament, such as stability, uniformity, quick-acting property, or sustained-release property, etc., and can also improve the control effect.
[0115] Due to differences in expression, there may be differences in understanding regarding the meanings of various adjuvants and various preparations. It should be understood that all the various adjuvants and preparations disclosed in this field fall within the scope covered by the present invention. For example, those described in "Pesticide Formulation Processing Technology" by Luo Yanping and Song Weiwei, Chemical Industry Press, 2015; "Pesticide Formulation Science" by Wang Kaiyun, China Agriculture Press, 2009; "Modern Pesticide Formulation Processing Technology Series" by Liu Guangwen, Chemical Industry Press, 2018; "Pesticide Formulations, Their Formulation and Use Methods" by Tu Yuqin, Golden Shield Press, 2008; "China Pesticides" by China Pesticide Industry Association; and so on. The preparation methods of various preparations include, but are not limited to, those described in the present invention.
[0116] The above-mentioned preparations can be prepared in a manner known per se, for example, by mixing the active compound or the active compound combination with at least one additive. Suitable additives are all conventional formulation auxiliaries, such as organic solvents, fillers, solvents or diluents, solid carriers and fillers, surfactants (such as adjuvants, emulsifiers, dispersants, protective colloids, wetting agents and thickeners), dispersants and / or binders or fixatives, preservatives, dyes and pigments, defoamers, inorganic and organic thickeners, water repellents, and if appropriate, driers and UV stabilizers, gibberellins, as well as water and other processing aids can also be added. In each case, depending on the type of preparation to be prepared, other processing steps may be required, such as wet grinding, dry grinding or granulation.
[0117] The bactericidal preparation of the present invention can achieve the same effects as the bactericidal composition described above, which will not be elaborated here.
[0118] The present invention provides the use of the bactericidal composition or the bactericidal preparation. Specifically, the present invention provides the use of the bactericidal composition or the bactericidal preparation in the prevention or treatment of plant diseases.
[0119] As a preferred embodiment, the present invention provides the use of the bactericidal composition or the bactericidal preparation in the prevention or treatment of plant diseases caused by fungi.
[0120] As a preferred embodiment, the use of the bactericidal composition or the bactericidal preparation in the prevention or treatment of cucumber downy mildew, grape downy mildew, potato late blight, tomato late blight and / or pepper blight.
[0121] More preferably, the present invention provides the use of the bactericidal composition or the bactericidal preparation in the prevention or treatment of plant diseases caused by fungi of the genus Pseudoperonospora in the phylum Oomycota.
[0122] In some embodiments, the bactericidal composition or the bactericidal preparation provided by the present invention can be used for the prevention or treatment of cucumber downy mildew.
[0123] The present invention also provides a method for preventing or treating plant diseases by using the described bactericidal composition or the described bactericidal preparation.
[0124] As a preferred embodiment, the method includes: treating a plant or a certain / some parts of the plant with an effective amount of the described bactericidal composition or bactericidal preparation. The following is a specific description.
[0125] Furthermore, the present invention provides a method for controlling plant diseases, which includes simultaneously applying, separately applying, or successively applying the active ingredient a and the active ingredient b to the pathogen and / or its environment, or to a plant, a plant part, a seed, soil, an area, a material, or a space.
[0126] The method of the present invention can specifically adopt common usage methods in the art such as soaking and spraying.
[0127] As a specific embodiment of the present invention, the described composition or fungicide of the present invention can be sprayed onto the leaf surface of the plant.
[0128] For the simultaneous application, difenoconazole or cyproconazole can be directly applied after being uniformly mixed with isofetamid, or can be prepared into a preparation and then applied after being uniformly mixed with isofetamid.
[0129] For the separate application, difenoconazole or cyproconazole and isofetamid can be separately applied, or can be separately prepared into preparations and then separately applied.
[0130] For the successive application, difenoconazole or cyproconazole and isofetamid can be successively applied, or can be separately prepared into preparations and then successively applied. When applying successively, difenoconazole or cyproconazole (active ingredient or preparation) can be applied first and then isofetamid (active ingredient or preparation), or isofetamid (active ingredient or preparation) can be applied first and then difenoconazole or cyproconazole (active ingredient or preparation).
[0131] The bactericidal composition or bactericidal preparation provided by the present invention can be used to treat all plants and plant parts. Plants refer to all plants and plant populations, such as desired and undesired wild plants, cultivated species and plant varieties (whether protected by plant variety rights or plant breeder rights). Cultivated species and plant varieties can be plants obtained by conventional propagation and breeding methods (assisted or supplemented by one or more biotechnological methods, such as by using doubled haploids, protoplast fusion, random mutagenesis and directed mutagenesis, molecular markers or genetic markers), or by methods of bioengineering and genetic engineering. Plant parts refer to all above-ground and underground parts of plants and plant organs, which are listed, for example, buds, leaves, flowers and roots, such as leaves, needles, stems, branches, flowers, fruiting bodies, fruits and seeds, as well as roots, bulbs and rhizomes. Crops and asexual and sexual propagation materials, such as cuttings, bulbs, rhizomes, tillers and seeds, also belong to plant parts.
[0132] For the purposes of the present invention, the term "effective amount" means the amount of the composition of the present invention sufficient to reduce the incidence of sudden death syndrome. This amount varies within a wide range depending on the fungus to be controlled, the plant species, the climatic conditions and the compounds contained in the composition of the present invention.
[0133] The treatment of plants and plant parts with the bactericidal composition or bactericidal preparation containing active ingredient a and active ingredient b provided by the present invention can be carried out directly using conventional treatment methods or acting on their surrounding environment, habitat or storage place, such as by dipping, spraying, atomizing, irrigation, evaporation, dusting, fogging, broadcasting, foaming, smearing, coating, watering (irrigation), dripping, and in the case of propagation materials, especially in the case of seeds, also by incrusting, coating with one or more coatings, etc. to treat dry seeds with a powder, treat seeds with a solution, treat slurries with a water-soluble powder. The composition or preparation can also be injected into the soil.
[0134] Among the plants that can be protected by the method of the present invention, mention may be made of major crops such as maize, soybean, cotton, rape, rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet, triticale, flax, vines, as well as various fruits and vegetables from various plant taxa, horticultural and forest crops; ornamental plants; and genetically modified homologues of these crops.
[0135] The present invention also includes a method for treating seeds. The bactericidal composition of the present invention can be applied directly, that is, without including other components and without dilution. Generally, it is preferred to apply the composition of the present invention in a suitable formulation form to the seeds. Suitable formulations and methods for treating seeds are conventional in the art. The bactericidal composition of the present invention can be converted into conventional seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating materials for seeds, as well as ULV formulations.
[0136] Depending on the plant species or plant cultivar, their location and growth conditions (soil, climate, vegetative period, nutrients), the treatment according to the invention can also bring about supra-additive ("synergistic") effects. Thus, for example, at least one of the following effects exceeding the actual expectation can be brought about: reduction of the application rate of the composition comprising active ingredient a and active ingredient b that can be used according to the invention and / or broadening of the activity spectrum and / or increase in activity, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or water or soil salinity, improved flowering quality, easier harvesting, accelerated ripening, higher harvesting yield, larger fruits, higher plant height, greener leaf color, earlier flowering, higher quality and / or higher nutritional value of the harvested product, higher sugar concentration in the fruits, better storage stability and / or processability of the harvested product.
[0137] The bactericidal composition or bactericidal preparation provided by the invention has been experimentally proven to be able to produce a synergistic effect and maintain the same good effect while reducing the application amount of the active ingredient. On the one hand, this substantially broadens the bactericidal spectrum, and on the other hand, it improves the use safety. In addition to the bactericidal synergistic activity, the bactericidal composition or bactericidal preparation provided by the invention has a strong synergistic effect.
[0138] In terms of broadening the bactericidal spectrum, for example: the bactericidal spectrum can be broadened to other plant pathogens (such as resistant strains of plant diseases).
[0139] Moreover, it also has at least one of the following advantages: favorable characteristics during formulation or use (such as grinding, sieving, emulsifying, dissolving or dispersing); enhanced storage stability and light stability; favorable residue formation; improved toxicological and ecotoxicological characteristics; improved plant characteristics, such as better growth, increased harvesting yield, more developed root systems, larger leaf areas, greener leaves, stronger shoots, less seed requirement, lower phytotoxicity, mobilization of the plant defense system, and good compatibility with plants.
[0140] Therefore, using the composition and preparation comprising bromuconazole and fluxapyroxad or cyproconazole and fluxapyroxad provided by the invention is very helpful for keeping plants healthy and can also guarantee the quality and yield. In a similar way, the composition and preparation comprising bromuconazole and fluxapyroxad or cyproconazole and fluxapyroxad provided by the invention can not only improve the quick-acting property of the compound medicament, but also have a longer persistent period.
[0141] In summary, compared with the prior art, the bactericidal composition and bactericidal preparation of the present invention have the following beneficial effects: (1) The compounding of bromuconazole or cyflufenconazole with fluopyramine has a synergistic effect, and has certain quick-acting and long-acting properties; (2) It delays the generation of drug resistance and improves the safety of crops; (3) It reduces the dosage of drugs, reduces costs and labor consumption; (4) It broadens the bactericidal spectrum.
[0142] The following will describe the implementation embodiments of the present invention in detail in conjunction with the examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention.
[0143] In the following examples, the bromuconazole technical and cyflufenconazole technical were self-made. Cyflufenconazole was prepared according to the preparation method of Example 12 in the application number PCT / CN2019 / 108170; bromuconazole was prepared according to the preparation method of Example 8 in the application number PCT / CN2018 / 081979; the fluopyramine technical was purchased from Hubei Xinhe Chemical Co., Ltd. For those not specified in the examples, they were carried out under conventional conditions or conditions recommended by the manufacturer. For the reagents or instruments whose manufacturers were not specified, they were all conventional products that could be prepared by the methods described in the prior art records or obtained through commercial purchase.
[0144] Synthesis and characterization of cyflufenconazole:
[0145]
[0146] Add N 3 -(3-(trifluoromethyl)benzyl)-N 1 ,N 1 -dimethyl-1H-1,2,4-triazole-1,3-disulfonamide (0.41 g, 1.0 mmol), potassium carbonate (0.28 g, 2.0 mmol) and N,N-dimethylformamide (10 mL) into a 100 mL three-necked flask, and then slowly add bromocyclopropane (0.24 g, 2.0 mmol) to the reaction system. React at room temperature for 8 hours; quench with water (20 mL), extract with ethyl acetate (15 mL × 3), wash the organic phase with saturated brine, dry over anhydrous magnesium sulfate, filter, and remove the solvent from the filtrate under reduced pressure with a rotary evaporator. Purify by column chromatography (ethyl acetate / petroleum ether (v / v) = 1 / 3) to obtain 0.24 g of white solid, yield: 53%.
[0147] 11H NMR (400 MHz, CDCl3): δ (ppm) 8.76 (s, 1H), 7.49 - 7.16 (m, 4H), 3.82 (s, 2H), 2.67 (s, 6H), 1.36 - 1.32 (m, 1H), 0.71 - 0.68 (m, 2H), 0.22 - 0.19 (m, 2H).
[0148] LC-MS: (M + 1) m / z = 454.0.
[0149] Synthesis and Characterization of Bromocyclazole:
[0150]
[0151] Potassium carbonate (0.276 g, 2.0 mmol), N3-cyclopropyl-N 1 ,N 1 -dimethyl-1H-1,2,4-triazole-1,3-disulfonamide (0.40 g, 1.36 mmol), 1-bromo-3-(bromomethyl)benzene (0.48 g, 2.0 mmol) and N,N-dimethylformamide (15 ml) were added to a 50 mL three-necked flask and stirred at room temperature for 12 hours. Water (30 mL) was added, and the mixture was extracted with ethyl acetate (20 mL × 3). The organic phase was washed with saturated brine (10 ml), dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The residue was purified by column chromatography (ethyl acetate / petroleum ether (v / v) = 1 / 5) to obtain 0.287 g of a white solid with a yield of 45%.
[0152] 1 1H NMR (400 MHz, CDCl3) δ (ppm): 8.63 (s, 1H), 7.52 (s, 1H), 7.44 (d, J = 7.9 Hz, 1H), 7.33 (d, J = 7.7 Hz, 1H), 7.21 (t, J = 7.8 Hz, 1H), 4.54 (s, 2H), 3.08 (s, 6H), 2.58 - 2.53 (m, 1H), 0.87 - 0.83 (m, 2H), 0.77 - 0.73 (m, 2H).
[0153] LC-MS: (M + 1) m / z = 464.0.
[0154] Example 1: Indoor Bioassay
[0155] Experiments were conducted on cucumber downy mildew. Using the potting method indoors, the inhibitory effects of different pesticides on the growth of the cucumber downy mildew pathogen (Pseudoperonospora cubensis (Berk. et Curt.) Rostov, collected from the Zengcheng Experimental Base of South China Agricultural University and preserved in the living generation) were determined, and the EC 50 values of each pesticide against the pathogen were calculated.
[0156] Pesticide application: Pot-grown cucumber seedlings with consistent growth at the two-leaf stage were selected for the experiment. Single agents or each composition (specifically shown in Table 1 and Table 2) were dissolved in solvent DMSO and then diluted with 0.1 wt% Tween 80 water to appropriate concentration gradients (bromocylconazole / epoxiconazole: 5 mg / L, 2.5 mg / L, 1.25 mg / L, 0.625 mg / L, 0.3125 mg / L, 0.15625 mg / L; fluopyram: 2 mg / L, 1 mg / L, 0.5 mg / L, 0.25 mg / L, 0.125 mg / L, 0.0625 mg / L; composition: 2 mg / L, 1 mg / L, 0.5 mg / L, 0.25 mg / L, 0.125 mg / L, 0.0625 mg / L). After foliar spraying treatment, the test materials were air-dried for 24 h. The control group was sprayed with the same amount of solvent.
[0157] Inoculation: Fresh sporangia on cucumber diseased leaves were washed with an aqueous solution of 0.1 wt% Tween 80, filtered through four layers of gauze, and made into a sporangia suspension with a concentration of 6×10 5 CFU / mL. Then, it was evenly sprayed onto the cucumber seedlings with an inoculation sprayer (pressure 0.1 MPa) until the surface was wet. After spray inoculation, the seedlings were transferred to a phytotron with a relative humidity > 90%, a temperature of 22 °C, and a light intensity greater than 2000 lx. The disease situation was investigated after 7 days.
[0158] The grading standard refers to "Guidelines for Field Efficacy Trials of Pesticides (I) Fungicides for Controlling Cucumber Downy Mildew" as follows:
[0159] Grade 0: No disease spots;
[0160] Grade 1: The diseased area accounts for 5% or less of the entire leaf area;
[0161] Grade 3: The diseased area accounts for 6% - 10% of the entire leaf area;
[0162] Grade 5: The diseased area accounts for 11% - 25% of the entire leaf area;
[0163] Grade 7: The diseased area accounts for 26% - 50% of the entire leaf area;
[0164] Grade 9: The diseased area accounts for more than 50% of the entire leaf area.
[0165] The formula for calculating the control effect is as follows:
[0166]
[0167]
[0168] Based on the concentrations of each single agent and the composition and the corresponding control effects, perform corresponding regression analysis to obtain the EC 50 value and 95% confidence interval of each composition.
[0169] Adopt the co-toxicity coefficient calculation method introduced by Sun Yunpei to calculate the co-toxicity coefficient (CTC) of the mixture and determine the synergistic effect of the mixture.
[0170] Take a single agent in the mixture as the standard agent (usually select the one with a lower EC 50 ) for calculation:
[0171] Single-agent toxicity index = standard agent EC 50 / EC of a certain single agent 50 × 100;
[0172] Theoretical toxicity index (TTI) = toxicity index of single agent A × proportion of single agent A in the mixture + toxicity index of single agent B × proportion of single agent B in the mixture;
[0173] Actual toxicity index (ATI) = EC of the standard single agent 50 value / EC of the mixture 50 value × 100;
[0174] Co-toxicity coefficient (CTC) = actual toxicity index / theoretical toxicity index × 100.
[0175] Among them, the standard single agent is the one with a smaller EC 50 selected from the two single agents as the standard single agent.
[0176] When the co-toxicity coefficient CTC is greater than 120, it indicates that the mixture has a synergistic effect; when CTC is less than 80, it indicates that the mixture has an antagonistic effect; when CTC is between 80 and 120, it indicates that the mixture has an additive effect.
[0177] The determination results of the co-toxicity coefficients of the single agent and each compound composition against cucumber downy mildew are shown in Table 1 and Table 2 respectively.
[0178] Table 1: Determination results of co-toxicity coefficients of different ratios (mass ratio) of bromocyclazole and fluopyram against cucumber downy mildew
[0179]
[0180] As can be seen from the data in Table 1, the bactericidal composition prepared by compounding bromuconazole and fluxapyroxad has a high synergistic effect on the pathogen of cucumber downy mildew. When the mass ratio of bromuconazole to fluxapyroxad is (1-15):(15-1), the co-toxicity coefficient is greater than 120, showing a synergistic effect.
[0181] The above experiments show that the bactericidal composition prepared by compounding bromuconazole and fluxapyroxad is an ideal agent for controlling cucumber downy mildew.
[0182] Table 2: Determination results of co-toxicity coefficient of different ratios (mass ratio) of cyflufenamid and fluxapyroxad on cucumber downy mildew
[0183]
[0184] As can be seen from the data in Table 2, the bactericidal composition prepared by compounding cyflufenamid and fluxapyroxad has a high synergistic effect on the pathogen of cucumber downy mildew. When the mass ratio of cyflufenamid to fluxapyroxad is (1-15):(15-1), the co-toxicity coefficient is greater than 120, showing a synergistic effect.
[0185] The above experiments show that the bactericidal composition prepared by compounding cyflufenamid and fluxapyroxad is an ideal agent for controlling cucumber downy mildew.
[0186] Example 2: 20% compound emulsifiable concentrate of bromuconazole and fluxapyroxad
[0187] 18.75 g of bromuconazole technical and 1.25 g of fluxapyroxad technical were added to a mixed solvent of 40 g of toluene (Aladdin reagent) and 30 g of xylene (Aladdin reagent). Then, 5 g of triphenylvinylphenol polyoxyethylene polyoxypropylene ether (trade name: Nongru 1601#, Xingtai Yancheng Chemical Auxiliary Co., Ltd.) and 5 g of castor oil polyoxyethylene ether (trade name: EMULPON CO-360, Nanjing Jierun Technology Co., Ltd.) were added and slowly stirred until completely dissolved to obtain a 20% compound emulsifiable concentrate of bromuconazole and fluxapyroxad with an effective ingredient mass content.
[0188] Example 3: 30% compound suspension concentrate of bromuconazole and fluxapyroxad
[0189] 1. Preparation of pulverized slurry
[0190] Disperse 2 g of a non-alkylphenol-based highly efficient dispersant (trade name: TERSPERSE 4894, Huntsman), 1 g of a comb-shaped polymer compound dispersant (trade name: GY-D900, Beijing Guangyuan Yinnong Chemical Co., Ltd.), 4 g of a wetting agent (trade name: GY-WS10, Beijing Guangyuan Yinnong Chemical Co., Ltd.) and 0.3 g of a highly efficient silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) in 42.7 g of water. Disperse 1.88 g of bromuconazole technical and 28.12 g of fluxapyroxad in it. Use glass beads with a diameter of 0.6 - 0.8 mmφ and perform wet grinding for 2.0 h with a sand mill (Shenyang New Micro Motor Factory) to obtain 80 g of a ground slurry.
[0191] 2. Preparation of the dispersion medium
[0192] Disperse 0.3 g of xanthan gum (Aladdin reagent), 0.4 g of magnesium aluminum silicate (Aladdin reagent), 4 g of ethylene glycol (Aladdin reagent) and 0.1 g of sodium benzoate (Aladdin reagent) in 15.2 g of water to obtain 20 g of a dispersion medium.
[0193] 3. Preparation of the aqueous suspension pesticide composition
[0194] Mix 80 g of the above-mentioned ground slurry and 20 g of the dispersion medium to obtain 100 g of an aqueous suspension pesticide composition. Under high shear (4000 revolutions per minute) for 30 minutes with a high-speed disperser (trade name: TG25, IKA, Germany), a compound suspension concentrate of bromuconazole and fluxapyroxad with an active ingredient mass content of 30% is prepared.
[0195] Example 4: 50% compound water dispersible granule of bromuconazole and fluxapyroxad
[0196] Add 25 g of bromuconazole technical, 25 g of fluxapyroxad, 6 g of naphthalene sulfonate (trade name: SUPRAGIL MNS / 90, Solvay), 4 g of lignin (trade name: Borresperse NA, Borregaard Industries Ltd.), 2 g of alkylnaphthalene sulfonate (trade name: GEROPON L-WET / MAX, Solvay), 10 g of ammonium sulfate (Aladdin reagent) and kaolin (Hangzhou Zuotu New Materials Co., Ltd.) to 100 g. First, pre-grind and mix evenly, then grind to the required particle size by air flow grinding (Kunshan Younaike Machinery Co., Ltd.), add an appropriate amount of water for kneading, and then perform extrusion granulation with a rotary granulator to obtain a compound water dispersible granule of bromuconazole and fluxapyroxad with an active ingredient mass content of 50%.
[0197] Example 5: 10% compound suspension concentrate of bromuconazole and fluxapyroxad
[0198] 1. Preparation of the ground slurry
[0199] Disperse 2 g of a non-alkylphenol-based highly efficient dispersant (trade name: TERSPERSE 4894, Huntsman), 3 g of a comb-shaped polymer compound dispersant (trade name: GY-D900, Beijing Guangyuan Yinnong Chemical Co., Ltd.), 2 g of a wetting agent (trade name: GY-WS10, Beijing Guangyuan Yinnong Chemical Co., Ltd.) and 0.3 g of a highly efficient silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) in 62.7 g of water. Disperse 1.67 g of bromuconazole technical and 8.33 g of fluxapyroxad in it. Use glass beads with a diameter of 0.6 - 0.8 mmφ and perform wet grinding for 2.0 h with a sand mill (Shenyang New Micro Motor Factory) to obtain 80 g of a ground slurry.
[0200] 2. Preparation of the dispersion medium
[0201] Disperse 0.3 g of xanthan gum (Aladdin reagent), 0.4 g of magnesium aluminum silicate (Aladdin reagent), 4 g of ethylene glycol (Aladdin reagent) and 0.1 g of sodium benzoate (Aladdin reagent) in 15.2 g of water to obtain 20 g of a dispersion medium.
[0202] 3. Preparation of the aqueous suspension pesticide composition
[0203] Mix 80 g of the above-mentioned ground slurry and 20 g of the dispersion medium to obtain 100 g of an aqueous suspension pesticide composition. Under high shear (4000 revolutions per minute) for 30 minutes with a high-speed disperser (trade name: TG25, IKA, Germany), a compound suspension agent of bromuconazole and fluxapyroxad with an active ingredient mass content of 10% is prepared.
[0204] Example 6: 80% compound water dispersible granule of bromuconazole and fluxapyroxad
[0205] Add 60 g of bromuconazole technical, 20 g of fluxapyroxad, 6 g of naphthalene sulfonate (trade name: SUPRAGIL MNS / 90, Solvay), 2 g of lignin (trade name: Borresperse NA, Borregaard Industries Ltd.), 2 g of alkylnaphthalene sulfonate (trade name: GEROPON L-WET / MAX, Solvay), 5 g of ammonium sulfate (Aladdin reagent) and kaolin (Hangzhou Zuotu New Materials Co., Ltd.) to 100 g. First, pre-grind and mix evenly, then grind to the required particle size by air flow grinding (Kunshan Younaike Machinery Co., Ltd.), add an appropriate amount of water for kneading, and then perform extrusion granulation with a rotary granulator to obtain a compound water dispersible granule of bromuconazole and fluxapyroxad with an active ingredient mass content of 80%.
[0206] Example 7: 30% compound microemulsion of cyflufenamid and fluxapyroxad
[0207] Weigh 28.12 g of cyflufenamid technical, 1.88 g of fluxapyroxad, 10 g of solvent xylene (Aladdin reagent), 5 g of solvent cyclohexanone (Aladdin reagent), 9 g of emulsifier phenethylphenol polyoxyethylene polyoxypropylene ether (trade name: Nongru 1601#, Xingtai Yancheng Chemical Auxiliary Co., Ltd.), 5 g of emulsifier dodecylbenzenesulfonate (trade name: Nongru 500#, Xingtai Yancheng Chemical Auxiliary Co., Ltd.), and 5 g of antifreeze propylene glycol (Aladdin reagent). After fully dissolving cyflufenamid and fluxapyroxad with the solvent, add the emulsifier and antifreeze and mix evenly. Finally, add 36 g of deionized water and stir evenly to obtain a compounded microemulsion of cyflufenamid and fluxapyroxad with an active ingredient mass content of 30%.
[0208] Example 8: 40% compounded aqueous emulsion of cyflufenamid and fluxapyroxad
[0209] 1. Preparation of oil phase
[0210] Add 10 g of cyflufenamid technical and 30 g of fluxapyroxad to a mixed solvent of 3 g of cyclohexanone (Aladdin reagent) and 3 g of xylene (Aladdin reagent). After ultrasonic mixing evenly, then add 2 g of emulsifier (trade name: TERMUL 2507, Huntsman) and 2 g of castor oil polyoxyethylene ether (trade name: EMULPON CO-360, AkzoNobel) and slowly stir until completely dissolved.
[0211] 2. Preparation of water phase
[0212] Add 4 g of ethylene glycol (Aladdin reagent), 0.2 g of magnesium aluminum silicate (Aladdin reagent), 0.1 g of high-efficiency organosilicon defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.), and add 45.7 g of water and stir evenly.
[0213] 3. Preparation of aqueous emulsion
[0214] Slowly add the water phase to the oil phase and continuously stir until completely added. Then, under high shear (4000 revolutions per minute) of a high-speed disperser (trade name: TG25, IKA, Germany) for 30 minutes, a compounded aqueous emulsion of cyflufenamid and fluxapyroxad with an active ingredient mass content of 40% is obtained.
[0215] Example 9: 60% compounded wettable powder of cyflufenamid and fluxapyroxad
[0216] Weigh 30 g of cyflufenamid technical, 30 g of isoflucypram, 5 g of alkylnaphthalenesulfonate (trade name: Morwet D-425, AkzoNobel), 5 g of calcium lignosulfonate (trade name: Borresperse CA, Borregaard), 5 g of ammonium sulfate (Aladdin reagent), 0.5 g of magnesium aluminum silicate (Aladdin reagent), and add kaolin (Hangzhou Zuotu New Materials Co., Ltd.) to make up to 100 g. First, pre-crush and mix evenly, and then air crush (model: SJM-100, Kunshan Younaike Machinery Co., Ltd.) to the required particle size (10 - 15 microns) to obtain a 60% wettable powder of the cyflufenamid and isoflucypram mixture.
[0217] Example 10: 10% Suspension Concentrate of Cyflufenamid and Isoflucypram Mixture
[0218] 1. Preparation of the grinding slurry
[0219] Disperse 3 g of non-alkylphenol-based high-efficiency dispersant (trade name: AG TP1, Clariant), 3 g of comb-shaped polymer dispersant (trade name: GY-D800, Beijing Guangyuan Yinuo Chemical Co., Ltd.), 2 g of wetting agent (trade name: GY-WS10, Beijing Guangyuan Yinuo Chemical Co., Ltd.), and 0.3 g of high-efficiency silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) in 61.7 g of water. Disperse 1.67 g of cyflufenamid technical and 8.33 g of isoflucypram in it. Use 0.6 - 0.8 mm φ glass beads and wet grind for 2.0 h with a sand mill (Shenyang New Micro Motor Factory) to obtain 80 g of the grinding slurry.
[0220] 2. Preparation of the dispersion medium
[0221] Disperse 0.3 g of xanthan gum (Aladdin reagent), 0.4 g of magnesium aluminum silicate (Aladdin reagent), 4 g of ethylene glycol (Aladdin reagent), and 0.1 g of sodium benzoate (Aladdin reagent) in 15.2 g of water to obtain 20 g of the dispersion medium.
[0222] 3. Preparation of the aqueous suspension pesticide composition
[0223] Mix 80 g of the above grinding slurry and 20 g of the dispersion medium to obtain 100 g of the aqueous suspension pesticide composition. High-shear mix for 30 minutes at 4000 revolutions per minute with a high-speed disperser (trade name: TG25, IKA, Germany) to prepare a 10% suspension concentrate of the cyflufenamid and isoflucypram mixture.
[0224] Example 11: 70% Water Dispersible Granules of Cyflufenamid and Isoflucypram Mixture
[0225] Add 65.62 g of cyproconazole technical, 4.38 g of isoflucypram, 5 g of naphthalene sulfonate (trade name: 8906, BASF), 5 g of lignin (trade name: Borresperse NA, Borregaard Industries), 2 g of alkyl naphthalene sulfonate (trade name: GEROPON L-WET / MAX, Solvay), 5 g of ammonium sulfate (Aladdin reagent), and kaolin (Hangzhou Zuotu New Materials Co., Ltd.) to 100 g. First, pre-crush and mix evenly, then grind by air flow (Kunshan Younaike Machinery Co., Ltd.) to the required particle size, add an appropriate amount of water for kneading, and then use a rotary granulator for extrusion granulation to obtain a 70% compound water dispersible granule of cyproconazole and isoflucypram.
[0226] Control Example 1: 25% bromuconazole suspension
[0227] 1. Preparation of grinding slurry
[0228] Disperse 2 g of non-alkylphenol-based highly efficient dispersant (trade name: SP-SC3275, Jiangsu Qingyu Chemical Technology Co., Ltd.), 2 g of comb-shaped polymer dispersant (trade name: GY-D180, Beijing Guangyuan Yinong Chemical Co., Ltd.), 2 g of wetting agent (trade name: GY-WS10, Beijing Guangyuan Yinong Chemical Co., Ltd.) and 0.3 g of highly efficient silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) in 48.7 g of water. Disperse 25 g of bromuconazole technical in it, use 0.6 - 0.8 mm φ glass beads, and carry out wet grinding for 1.5 h with a sand mill (Shenyang New Micro Motor Factory) to obtain 80 g of grinding slurry.
[0229] 2. Preparation of dispersion medium
[0230] Disperse 0.3 g of xanthan gum (Aladdin reagent), 0.4 g of magnesium aluminum silicate (Aladdin reagent), 4 g of ethylene glycol (Aladdin reagent) and 0.1 g of sodium benzoate (Aladdin reagent) in 15.2 g of water to obtain 20 g of dispersion medium.
[0231] 3. Preparation of suspension
[0232] Mix 80 g of the above grinding slurry and 20 g of the dispersion medium to obtain 100 g of an aqueous suspension pesticide composition. High shear (4000 revolutions per minute) for 30 minutes with a high-speed disperser (trade name: TG25, IKA, Germany) to prepare a bromuconazole suspension with an active ingredient mass content of 25%.
[0233] Control Example 2: 25% cyproconazole suspension
[0234] 1. Preparation of grinding slurry
[0235] Disperse 2 g of a non-alkylphenol-based highly efficient dispersant (trade name: Envi-pol 871, Nanjing Shanhu Chemical Co., Ltd.), 3 g of a comb-shaped polymer compound dispersant (trade name: CP86, BASF), 1 g of a wetting agent (trade name: GY-WS10, Beijing Guangyuan Yinuo Chemical Co., Ltd.) and 0.3 g of a highly efficient silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) in 48.7 g of water. Disperse 25 g of the original cyflufenamid drug in it. Use glass beads with a diameter of 0.6 - 0.8 mmφ and perform wet grinding for 1.5 h with a sand mill (Shenyang New Micro Motor Factory) to obtain 80 g of a pulverized slurry.
[0236] 2. Preparation of the dispersion medium
[0237] Disperse 0.3 g of xanthan gum (Aladdin reagent), 0.4 g of magnesium aluminum silicate (Aladdin reagent), 4 g of ethylene glycol (Aladdin reagent) and 0.1 g of sodium benzoate (Aladdin reagent) in 15.2 g of water to obtain 20 g of a dispersion medium.
[0238] 3. Preparation of the suspension concentrate
[0239] Mix 80 g of the above pulverized slurry and 20 g of the dispersion medium to obtain 100 g of an aqueous suspension pesticide composition. Stir at high shear (4000 revolutions per minute) for 30 minutes with a high-speed disperser (trade name: TG25, IKA, Germany) to prepare a cyflufenamid suspension concentrate with an active ingredient mass content of 25%.
[0240] Control Example 3: 25% fluxapyroxad suspension concentrate
[0241] 1. Preparation of the pulverized slurry
[0242] Disperse 2.5 g of a non-alkylphenol-based highly efficient dispersant (trade name: LVS, BASF), 2 g of a comb-shaped polymer compound dispersant (trade name: HMK-D1008, Beijing Hanhanmoke Chemical Technology Co., Ltd.), 3 g of a wetting agent (trade name: GY-WS10, Beijing Guangyuan Yinuo Chemical Co., Ltd.) and 0.4 g of a highly efficient silicone defoamer (trade name: ETXP-40, Hangzhou Zuotu New Materials Co., Ltd.) in 47.1 g of water. Disperse 25 g of the original fluxapyroxad drug in it. Use glass beads with a diameter of 0.6 - 0.8 mmφ and perform wet grinding for 1.5 h with a sand mill (Shenyang New Micro Motor Factory) to obtain 80 g of a pulverized slurry.
[0243] 2. Preparation of the dispersion medium
[0244] Disperse 0.25 g of xanthan gum (Aladdin reagent), 0.45 g of magnesium aluminum silicate (Aladdin reagent), 4 g of ethylene glycol (Aladdin reagent) and 0.1 g of sodium benzoate (Aladdin reagent) in 15.2 g of water to obtain 20 g of a dispersion medium.
[0245] 3. Suspension preparation
[0246] 80 g of the above-mentioned pulverized slurry and 20 g of the dispersion medium were mixed to obtain 100 g of an aqueous suspension pesticide composition. The composition was then dispersed in a high-speed disperser (trade name: TG25, IKA, Germany) under high shear (5000 rpm) for 30 minutes to obtain a fluazifop-ethyl pyraclostrobin suspension with an active ingredient content of 25% by mass.
[0247] Comparative Example 4:
[0248] Blank water.
[0249] Experimental Example 1: Field Efficacy Test
[0250] Plot setting: Each treatment was repeated 4 times, and the area of each plot was 30m 2 , randomized block arrangement.
[0251] Time and method of application: Apply the agent at the early stage of cucumber downy mildew, spray on the leaves, and spray the liquid in an amount that does not drip; apply the agent twice, investigate the disease base before the first application, apply the agent once every 7 days, investigate the disease index 7 days after each application, and calculate the prevention effect.
[0252] Survey method: Four points were randomly selected in each plot, two plants were surveyed at each point, all leaves of each plant were surveyed, and the total number of leaves and the number of diseased leaves at various levels were recorded.
[0253] The specific grading indicators are as follows:
[0254] Level 0: no lesions;
[0255] Level 1: The lesion area accounts for 5% or less of the entire leaf area;
[0256] Level 3: The lesion area accounts for 6-10% of the entire leaf area;
[0257] Level 5: The lesion area accounts for 11-25% of the entire leaf area;
[0258] Level 7: The lesion area accounts for 26-50% of the entire leaf area;
[0259] Level 9: The area of lesions accounts for more than 50% of the entire leaf area.
[0260] Calculation of drug efficacy:
[0261]
[0262]
[0263] Where: CK0: disease index of blank control area before medication;
[0264] CK1: post-drug disease index of blank control area;
[0265] PT0: pre-drug disease index of the drug-treated area;
[0266] PT1: Post-drug disease index in the drug-treated area.
[0267] The test results are shown in Table 3.
[0268] Table 3: Effects of different pesticides on cucumber downy mildew
[0269]
[0270]
[0271] As can be seen from Table 3, the control effects of the compounding agents of epoxiconazole and fluthiazolinone, cyfluthiazolinone and fluthiazolinone on cucumber downy mildew are significantly better than those of the control agent.
[0272] Combining the two active ingredients in a specific ratio not only improves the compound's rapid effectiveness but also prolongs its duration of action. Specifically, compared to the control agent alone, the compound still achieves a good level of control seven days after application, extending its duration of action.
[0273] In addition, no phytotoxicity of the combined pesticides to cucumbers was found in the entire indoor and outdoor biotests. Therefore, the combination of the two pesticides is highly safe for cucumbers.
[0274] Therefore, compounding pesticides can play a role in complementing each other's strengths and weaknesses. Compounding pesticides can not only reduce the use of pesticides and production costs, but also save farmers the number of times they need to spray pesticides. At the same time, it can also slow down the development of pesticide resistance.
[0275] In addition to cucumber downy mildew, the fungicidal composition and fungicidal preparation of the present invention can also be used for the prevention and treatment of grape downy mildew, potato late blight, tomato late blight, pepper blight, etc.
[0276] Although the present invention has been described in detail above using general explanations, specific embodiments, and experiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the present invention. Therefore, such modifications and improvements, which do not depart from the spirit of the present invention, are intended to be within the scope of protection claimed herein.
Claims
1. A bactericidal composition, characterized in that, The active components of the bactericidal composition include: active ingredient a and active ingredient b; the active ingredient a includes triazolesulfonamide compounds, and the active ingredient b includes flutriafol; the mass ratio of the active ingredient a to the active ingredient b is (1-15):(15-1); Among them, the triazolesulfonamide compound is bromuconazole or cyflufenamid, The structure of the bromuconazole is , The structure of the cyflufenamid is 。 2. A bactericidal preparation, characterized in that, The bactericidal preparation contains the bactericidal composition described in claim 1.
3. The bactericidal preparation according to claim 2, characterized in that, Based on the total mass percentage of the bactericidal preparation raw materials being 100%, the sum of the mass percentages of the active ingredient a and the active ingredient b in the bactericidal preparation raw materials is 1-99%.
4. The bactericidal preparation according to claim 3, characterized in that, Based on the total mass percentage of the bactericidal preparation raw materials being 100%, the sum of the mass percentages of the active ingredient a and the active ingredient b in the bactericidal preparation raw materials is 1-90%.
5. The bactericidal preparation according to claim 4, characterized in that, Based on the total mass percentage of the bactericidal preparation raw materials being 100%, the sum of the mass percentages of the active ingredient a and the active ingredient b in the bactericidal preparation raw materials is 1-85%.
6. The bactericidal preparation according to claim 5, characterized in that, Based on the total mass percentage of the bactericidal preparation raw materials being 100%, the sum of the mass percentages of the active ingredient a and the active ingredient b in the bactericidal preparation raw materials is 10-85%.
7. The bactericidal preparation according to claim 6, characterized in that, Based on the total mass percentage of the bactericidal preparation raw materials being 100%, the sum of the mass percentages of the active ingredient a and the active ingredient b in the bactericidal preparation raw materials is 10-80%.
8. The bactericidal preparation according to any one of claims 2-7, characterized in that, The dosage form of the bactericidal preparation is powder, wettable powder, microcapsule, water dispersible granule, granule, aqueous solution, suspension, emulsifiable concentrate, microemulsion, water emulsion, spray, seed coating agent or smoke agent.
9. The bactericidal preparation according to claim 8, characterized in that, The dosage form of the bactericidal preparation is emulsifiable concentrate, suspension, water dispersible granule, microemulsion, water emulsion or wettable powder.
10. Use of the bactericidal composition described in claim 1 or the bactericidal preparation described in any one of claims 2-9 in the prevention or treatment of plant diseases.
11. The application according to claim 10, characterized in that, The use is in the prevention or treatment of plant diseases caused by fungi.
12. The application according to claim 10, wherein Use of the bactericidal composition or bactericidal preparation in the prevention or treatment of cucumber downy mildew, grape downy mildew, potato late blight, tomato late blight and / or pepper blight.
13. Method for preventing or treating plant diseases by using the bactericidal composition described in claim 1 or the bactericidal preparation described in any one of claims 2-9; The method includes: Treat the plant or part of the plant with an effective amount of the bactericidal composition or bactericidal preparation.
Citation Information
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