CN110754472A

CN110754472A - Bactericidal composition containing fluorobenzene ether amide and cyproconazole

Info

Publication number: CN110754472A
Application number: CN201810830199.9A
Authority: CN
Inventors: 李义涛; 董江强; 梁任龙; 刘新烁; 刘杨润琦
Original assignee: Dongguan Dongyangjunyang Hydrogen Patent Pesticide Co Ltd
Current assignee: Dongguan Dongyangjunyang Hydrogen Patent Pesticide Co Ltd
Priority date: 2018-07-26
Filing date: 2018-07-26
Publication date: 2020-02-07

Abstract

The invention relates to a bactericidal composition containing fluorophenylether amide and cyproconazole, a preparation and an application thereof, wherein the mass ratio of the effective components of fluorophenylether amide and cyproconazole is 1-10: 10-1, and the total content of fluorophenylether amide and cyproconazole in the bactericidal composition/preparation is 10-60% by mass. The bactericidal composition/preparation provided by the invention has an obvious synergistic effect on prevention and treatment of soybean rust. The bactericidal composition and the preparation are suitable for preventing and treating wheat powdery mildew, wheat sharp eyespot, soybean rust disease, soybean gray spot, soybean gray mold, soybean anthracnose or leaf spot of melons, fruits and vegetables.

Description

Bactericidal composition containing fluorobenzene ether amide and cyproconazole

Technical Field

The invention relates to the technical field of pesticide compounding, and particularly relates to a bactericidal composition containing fluorobenzene ether amide and cyproconazole.

Background

Fluorophenylamide (development code: Y13149) is a novel succinate dehydrogenase inhibitor (SDHI) and has high bactericidal activity against powdery mildew and banded sclerotial blight. The fluorophenylether amide has internal absorption conductivity, and has the characteristics of rain water leaching resistance, low dosage (5-7 g/mu), low cost (less than 20 ten thousand yuan/ton) and the like. The control effect and the cost of the thifluzamide are obviously superior to those of similar products. The structural formula of the fluorophenylene ether amide is as follows:

cyproconazole (cyproconazole) is a triazole agricultural bactericide with a molecular formula of C₁₅H₁₈ClN₃O, the mechanism of action is to inhibit the demethylation of sterols, and is effective against the Erysipheles, Puccinales, Sporotrichum, Rhinocephalus, Septoria, Venturia species on cereal crops, coffee, sugar beet, fruit trees and grapes. The chemical name of the cyproconazole is 2- (4-chlorphenyl) -3-cyclopropyl-1- (1H-1,2, 4-triazole-1 group) butan-2-ol, and the structural formula is as follows:

soybean rust is a main disease in tropical and subtropical soybean production, often attacks in the grain swelling period, affects crop growth and finally reduces grain yield; it has been reported that soybean production areas worldwide lose 10-80% of yield due to soybean rust.

However, the bactericidal composition or/and the preparation containing the fluorophenylether amide and cyproconazole, and the application thereof in controlling soybean rust disease are not disclosed or suggested.

In addition, the application of chemical agents is the most effective means for controlling plant diseases. Because of the non-standard use of the existing pesticide, the resistance of the disease to the pesticide is stronger and stronger, so that the use amount of the pesticide is increased year by year, and the environmental pollution is more and more serious. Therefore, reasonable use of pesticides and preparation of compounded fungicides to expand the bactericidal spectrum and reduce the resistance to diseases are imminent.

Disclosure of Invention

Based on the above situation, in one aspect, the invention provides a bactericidal composition, and the effective components of the bactericidal composition are fluophenylamide and cyproconazole.

Further, the mass ratio of the fluorobenzene ether amide to the cyproconazole is 1-10: 10 to 1.

Furthermore, the mass ratio of the fluorobenzene ether amide to the cyproconazole is 1:10 to 1.

Further, the total content of the fluorobenzene ether amide and the cyproconazole in the bactericidal composition is 10-60% by mass.

Furthermore, the total content of the fluorobenzene ether amide and the cyproconazole in the bactericidal composition is 10-40% by mass.

Preferably, the total content of the fluorobenzene ether amide and the cyproconazole in the bactericidal composition is 10-30% by mass.

More preferably, the total content of the fluorobenzene ether amide and the cyproconazole in the bactericidal composition is 10-25 mass%.

On the other hand, the invention provides application of the bactericidal composition containing the fluorophenyletheramide and the cyproconazole in preventing and treating wheat powdery mildew, wheat sharp eyespot, soybean rust disease, soybean gray spot disease, soybean gray mold, soybean anthracnose or leaf spot of melons, fruits and vegetables.

In another aspect, the invention provides a preparation prepared from the bactericidal composition containing the fluorophenylether amide and the cyproconazole, and the preparation is in the form of missible oil, aqueous emulsion, microemulsion, suspending agent, wettable powder or water dispersible granules.

Further, the invention provides application of a preparation containing fluorophenylether amide and cyproconazole in preventing and treating wheat powdery mildew, wheat sharp eyespot, soybean rust disease, soybean gray spot disease, soybean gray mold, soybean anthracnose or melon, fruit and vegetable leaf spot disease.

In yet another aspect, the present invention provides a method for controlling plant diseases, the method comprising applying to the plant or plant part an effective amount of a fungicidal composition comprising a fluorophenylether amide and cyproconazole, or a formulation comprising a fluorophenylether amide and cyproconazole.

Detailed description of the invention

The preparation containing the composition of the fluorobenzene ether amide and the cyproconazole provided by the invention can generate a synergistic effect, and the same good effect is kept while the application amount of the fluorobenzene ether amide and the cyproconazole is reduced. On one hand, the bactericidal spectrum is widened, and on the other hand, the use safety is improved.

In addition to the bactericidal synergistic activity, the formulation provided by the present invention comprising the combination of fluorophenylether amide and cyproconazole has other excellent characteristics, which may also be referred to as synergy in a broad sense, for example: the spectrum of activity broadens to other plant pathogens (e.g. diseases on resistant strains); reducing the amount of active compound applied; even at application rates at which the individual compounds show no or virtually no activity, the compounding with the active compounds according to the invention is still sufficient for controlling diseases; advantageous properties during formulation or use (e.g. grinding, sieving, emulsification, dissolution or dispersion); enhanced storage stability and light stability; the environmental protection of the formed residues is enhanced; improved toxicological and ecotoxicological properties; improved plant characteristics (e.g. better growth, increased harvest yield, more developed root system, greater leaf area, greener leaves, stronger shoots, less seed requirements, lower phytotoxicity, mobilization of the plant's defense system, good compatibility with plants). Therefore, the preparation containing the composition of the fluorophenylether amide and the cyproconazole provided by the invention is beneficial to keeping plants healthy, so that the quality and the yield of crops are guaranteed. In addition, the preparation containing the composition of the fluorophenylether amide and the cyproconazole provided by the invention can be used for enhancing the systemic action (systemic action). Even if a single compound of the composition does not have sufficient systemic properties, the formulation provided by the present invention comprising the combination of fluorophenylether amide and cyproconazole may still have such properties. Similarly, the preparation containing the composition of the fluorobenzene ether amide and the cyproconazole provided by the invention can bring about a more durable bactericidal effect.

Therefore, in order to achieve the purpose, the technical scheme adopted by the invention is as follows:

in one aspect, the invention provides a bactericidal composition, and the effective components of the bactericidal composition are fluophenyl ether amide and cyproconazole.

Specifically, the mass ratio of the fluorobenzene ether amide to the cyproconazole is 1: 1. 1: 3. 1: 5. 1: 10. 3: 1. 5:1 or 10: 1.

Further preferably, the total content of the fluorobenzene ether amide and the cyproconazole in the bactericidal composition is 10-25 mass%.

More preferably, the total content of the fluorophenylether amide and cyproconazole in the bactericidal composition is 11 mass%, 20 mass%, 24 mass%, or 25 mass%.

Further, the total content of the fluorobenzene ether amide and cyproconazole in the preparation is 10-60% by mass.

Furthermore, the total content of the fluorobenzene ether amide and the cyproconazole in the preparation is 10-40% by mass.

Preferably, the total content of the fluorobenzene ether amide and the cyproconazole in the preparation is 10-30 mass%, the toxicity and the residue are well balanced, and the cost is low.

Further preferably, the total content of the fluorobenzene ether amide and the cyproconazole in the preparation is 10-25 mass%.

More preferably, the total content of the fluorophenylether amide and cyproconazole in the preparation is 11 mass%, 20 mass%, 24 mass%, or 25 mass%.

The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.

In the compositions or formulations of the present invention, the mass ratio of the fluorophenylether amide to cyproconazole may vary within a relatively wide range. Is present in a synergistically effective mass ratio of fluorophenylether amide to cyproconazole in the range of 1000:1 to 1:1000, preferably in the range of 100:1 to 1:100, more preferably in the range of 50:1 to 1:50, even more preferably in the range of 20:1 to 1:20, and even more preferably in the range of 10:1 to 1: 10. Other mass ratios of fluorophenylether amide to cyproconazole which can be used according to the invention are: 95:1 to 1:95, 90:1 to 1:90, 85:1 to 1:85, 80:1 to 1:80, 75:1 to 1:75, 70:1 to 1:70, 65:1 to 1:65, 60:1 to 1:60, 55:1 to 1:55, 45:1 to 1:45, 40:1 to 1:40, 35:1 to 1:35, 30:1 to 1:30, 25:1 to 1:25, 15:1 to 1:15, 10:1 to 1:10, 5:1 to 1:5, 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2, 1: 1. In view of further improving the synergistic effect, the mass ratio of the fluorobenzene ether amide to the cyproconazole is preferably 1-10: 10-1; synergy outside this range is significantly weaker than this range.

If the fluorophenylene ether amide or cyproconazole can be present in stereoisomeric, optically isomeric or tautomeric forms, it is to be understood that, where applicable, such compounds also include the corresponding isomeric forms in the context, even if not explicitly mentioned in each case.

If the fluorophenylene ether amide or cyproconazole is capable of forming a salt, e.g. with an acidAddition salts, for example, the acids are strong mineral acids, such as mineral acids (e.g., perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid, or hydrohalic acids); strong organic carboxylic acids, e.g. unsubstituted or substituted C₁-C₄Alkanecarboxylic acids (e.g. acetic acid), saturated or unsaturated dicarboxylic acids (e.g. oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid and phthalic acid), hydroxycarboxylic acids (e.g. ascorbic acid, lactic acid, malic acid, tartaric acid and citric acid or benzoic acid); or organic sulfonic acids, e.g. unsubstituted or substituted C₁-C₄Alkanesulfonic or arylsulfonic acids (e.g. methanesulfonic acid or p-toluenesulfonic acid). Or, for example, with a base, a metal salt, such as an alkali metal salt or alkaline earth metal salt (e.g., sodium, potassium or magnesium salt); or salts with ammonia or organic amines, such as morpholine, piperidine, pyrrolidine, mono-, di-or tri-lower alkylamines (e.g. ethylamine, diethylamine, triethylamine or dimethylpropylamine) or mono-, di-or trihydroxy-lower alkylamines (e.g. mono-, di-or triethanolamine). Or, optionally, forming the corresponding internal salt. In the context of the present invention, agrochemically advantageous salts are preferred. In view of the close relationship between the free form of the fluorophenylether amide or cyproconazole and the form of the salt thereof, it is to be understood that, where advantageous and appropriate, reference to fluorophenylether amide or cyproconazole or a salt thereof anywhere in the context of the present invention also includes the corresponding salt or fluorophenylether amide or cyproconazole, respectively. The same applies to stereoisomers, optical isomers or tautomers of fluorophenylether amide or cyproconazole and salts thereof.

The composition of the present invention contains, in addition to the active ingredients of fluorophenyletheramide and cyproconazole, adjuvants commonly used in agricultural chemicals, such as wetting agents, dispersants, emulsifiers, thickeners, gelling agents, anti-settling agents, disintegrants, antifreezes, antifoaming agents, solvents, preservatives, stabilizers, synergists, fillers, or carriers, and the like, and may be added as appropriate according to the needs of the preparation, and may be changed depending on the circumstances, and is not particularly limited.

The adjuvant is an auxiliary substance added in the processing or use of pesticide preparations and used for improving the physicochemical property of the pesticide preparation, and the adjuvant has basically no biological activity but can influence the control effect.

Wetting agents are substances that, when added to a liquid, increase the spreading or penetration capacity of the liquid by reducing the interfacial tension between the liquid and the surface on which the liquid is spread. Wetting agents perform two main functions in agrochemical formulations: increasing the rate of wetting of the powder in water during processing and manufacture to produce a concentrate that is soluble in water or a mixture suspended in water; it is also possible to reduce the wetting time of the wettable powder and improve the penetration of the aqueous phase into the dispersible granules before the product is applied with water for spraying in an aerosol can. The wetting agent is selected from alkyl benzene sulfonate (such as sodium dodecyl benzene sulfonate and calcium dodecyl benzene sulfonate), alkyl naphthalene sulfonate (such as dibutyl naphthalene sulfonate and isopropyl naphthalene sulfonate), lignosulfonate (such as sodium lignosulfonate and calcium lignosulfonate), Sodium Dodecyl Sulfate (SDS), dioctyl sodium sulfosuccinate, Alkylphenol Polyoxyethylene Ether (APEO) (such as nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether, dodecylphenol ether, dinonyl phenol ether and mixed alkylphenol ether), alkylphenol ethoxylate (APES), fatty alcohol ethoxylate, fatty alcohol polyoxyethylene ether sodium sulfate (ethoxylated alkyl sodium sulfate, AES), nekal, silkworm excrement, Chinese honeylocust powder, soapberry powder, SOPA, detergent, emulsifier 2000 series, penetrant JFC, wetting penetrant F, wetting penetrant T, sodium alkyl sulfonate, sodium alkyl phenol polyoxyethylene ether (APEO), One or more of NP-10. Typical representatives of suitable wetting agents are for example SDS (sodium dodecyl sulfate),

EFW (alkylated naphthalene sulfonate),

BX (alkylated naphthalene sulfonate),

MT 804 (alkylated naphthalene sulfonate). The wetting agent is one or more of the wetting agents.

Dispersants are substances that adsorb onto the surface of particles and help maintain the dispersed state of the particles and prevent the particles from reaggregating. The addition of dispersants to agrochemical formulations helps to disperse and suspend during manufacture and helps to ensure that the particles are redispersed in water in the spray tank. They are widely used in wettable powders, suspensions and water dispersible granules. Surfactants used as dispersants have the ability to adsorb strongly to the surface of the particles and provide a two electron layer barrier or steric hindrance against reaggregation of the particles. The most commonly used surfactants are anionic surfactants, nonionic surfactants or mixtures of the two types. For wettable powders, the most common dispersant is sodium lignosulfonate (sodium lignosulphonate). For the suspending agent, polyelectrolytes such as sodium naphthalene sulfonate formaldehyde condensate (sodium naphthalene sulfonate formaldehyde condensate) are used to obtain very good adsorption and stabilization. Tristyrylphenol ethoxylate phosphate ester (tristyrylphenol ethoxylate phosphate ester), nonionic surfactants such as alkylaryl ethylene oxide condensates (alkyl arylethylene oxide condensates) and EO-PO block copolymers are also used. Nonionic surfactants are sometimes used in combination with anionic surfactants as dispersing agents for suspending agents. In recent years, new classes of very high molecular weight polymeric surfactants have been developed as dispersants. These dispersants have a very long hydrophobic "backbone" and form a "comb" type structure with many ethylene oxide chains as their "teeth" fixing the bulk drug. These high molecular weight polymers may provide very good long term stability to the suspension, since the hydrophobic backbone has multiple anchor points to be fixed to the particle surface. Examples of commonly used dispersants are sodium lignosulfonate, sodium naphthalene sulfonate formaldehyde condensate, tristyrylphenol ethoxylate phosphate, fatty alcohol ethoxylates, alkyl ethoxylates, alkylphenol ethoxylate methyl ether condensate sulfate, fatty amine ethoxylates, glycerol fatty acid ester ethoxylates, EO-PO block copolymers and graft copolymers. Suitable dispersantsIs typically represented by

2700、

2500. Ufoxane NA, Morwet D425 or Ethylan NS-500 LQ. The dispersant is one or more of the dispersants.

An emulsifier is a substance that improves the surface tension of one liquid phase after it is added dropwise to another liquid phase, stabilizing the mixture. In the absence of an emulsifier, the two liquids would separate into two immiscible liquid phases. The most commonly used emulsifier blends contain an alkylphenol or fatty alcohol having 12 or more ethylene oxide units and an oil soluble calcium salt of dodecylbenzene sulfonic acid. Emulsifiers having a hydrophilic-lipophilic balance ("HLB") value in the range of 8 to 18 generally provide good emulsion stability. Emulsion stability can also sometimes be improved by adding small amounts of EO-PO block copolymer surfactant. The emulsifier is selected from one or more of calcium dodecyl benzene sulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenethyl phenol polyoxyethylene polyoxypropylene ether, fatty alcohol ethylene oxide and cyclohexene oxide copolymer, styryl phenol polyoxyethylene ether, castor oil polyoxyethylene ether and alkylphenol ether phosphate. Typical representatives of suitable dispersants are, for example, farm milk 500#, farm milk 600#, farm milk 700#, farm milk 1601# or ethyllan 992. The emulsifier is one or more of the above emulsifiers.

Thickeners or gelling agents are used primarily in suspending agents, aqueous emulsions and suspoemulsions to modify the rheology or flowability of the liquid and to prevent separation or settling of the dispersed particles or oil droplets. Thickeners, gelling agents and anti-settling agents are generally divided into two categories, namely water-insoluble particles and water-soluble polymers. It is possible to use clays and silica to prepare the suspending agent. Examples of these types of materials include, but are not limited to, montmorillonite, such as bentonite; magnesium aluminum silicate; and activated clay (attapulgite). Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The most common types of polysaccharides are natural extracts of seeds or seaweeds or synthetic derivatives of cellulose. Examples of these types of materials include, but are not limited to, guar gum, locust bean gum (locust beans), carrageenan (carrageenam), alginates, methylcellulose, sodium carboxymethylcellulose (SCMC), Hydroxyethylcellulose (HEC). Other types of anti-settling agents such as modified starch, polyacrylate, polyvinyl alcohol and polyethylene oxide. Another good anti-settling agent is xanthan gum. The thickening agent is one or more of the thickening agents.

The disintegrating agent is selected from one or more of sodium sulfate, ammonium sulfate, aluminum chloride, sodium chloride, ammonium chloride, bentonite, glucose, sucrose, starch, cellulose, urea, sodium carbonate, sodium bicarbonate, citric acid and tartaric acid.

The antifreezing agent includes alcohols, alcohol ethers, chlorinated hydrocarbons, inorganic salts, etc. Common antifreeze agents include methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, ethylene glycol butyl ether, propylene glycol butyl ether, ethylene glycol butyl ether acetate, methylene chloride, 1-dichloroethane, 1, 2-dichloroethane, dimethyl sulfoxide, formamide, calcium chloride, sodium acetate, magnesium chloride, etc. The antifreezing agent is one or more of the antifreezing agents.

The use of surfactants often results in a tendency of water-based formulations to foam during manufacture and application. To reduce foaming tendency, antifoams are usually added at the production stage or before bottling. In general, there are two types of defoamers, namely silicone and non-silicone. The silicone is typically an aqueous emulsion of polydimethylsiloxane, while the non-silicone antifoam agent is a water-insoluble oil such as octanol and nonanol. In the case of both types of defoamers, the function of the defoamer is to displace the surfactant from the air-water interface. The defoaming agent is selected from C_10-20Saturated fatty acid compound, silicone oil, silicone compound, C_8-10One or more of fatty alcohols.

The solvent is an organic substance used for dissolving and diluting the active ingredients of the pesticide, so that the pesticide is convenient to process and use. Commonly used solvents are benzene, toluene, xylene, durene, methanol, ethanol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, cyclohexanone, alkylene carbonate, diesel oil, solvent oil, soybean oil, epoxidized soybean, oil castor oil, water, etc. The solvent is one or more of the solvents.

Microorganisms are susceptible to spoilage of formulated products, and preservatives are used to eliminate or reduce the effects of such microorganisms. Examples of such agents include, but are not limited to, propionic acid and its sodium salt, sorbic acid and its sodium or potassium salt, benzoic acid and its sodium salt, parahydroxybenzoic acid sodium salt, methylparaben, carbazone (CIT/MIT), and 1, 2-benzisothiazolin-3-one (BIT). The preservative is one or more of the preservatives.

The stabilizer can be divided into two types, one type can inhibit or slow down the decomposition of the effective components of the pesticide, such as an antioxidant, an anti-photolysis agent and the like; and the other can improve the physical stability of the preparation, such as an anti-caking agent and an anti-sedimentation agent. The stabilizer is selected from disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2, 6-di-tert-butyl-p-cresol, triethanolamine oleate, epoxidized vegetable oil, kaolin, bentonite, attapulgite, white carbon black, talcum powder, montmorillonite or starch and the like. The stabilizer is one or more of the above stabilizers.

The synergist has no bioactivity, but can greatly improve the performance of active matters, and when the synergist is mixed with certain pesticides, the toxicity and the efficacy of the pesticides can be greatly improved, such as synergistic phosphorus, synergistic ether and the like.

By carrier is meant a natural or synthetic organic or inorganic substance, which is mixed or combined with the active compound for better application, especially on plants or plant parts or seeds. The carrier may be a solid or a liquid. Are generally inert and should be suitable for use in agriculture. Suitable solid or liquid carriers are: ammonium salts and ground natural minerals (e.g. kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth), and ground artificial minerals (e.g. finely divided silica, alumina) and natural or artificial silicates, resins, waxes, solid fertilizers, water, alcohols (in particular butanol), organic solvents, mineral and vegetable oils and derivatives thereof. Mixtures containing these carriers are also possible. Suitable solid carriers for granules are: crushed and fractionated natural minerals (for example calcite, marble, pumice, sepiolite, dolomite), as well as inorganic and organic powder artificial granules and organic materials (for example granules of wood chips, coconut shells, maize cobs, or tobacco stalks). The filler is one or more of the above fillers.

Suitable liquefied gaseous extenders or carriers are those which are gaseous at ambient temperature and atmospheric pressure, such as aerosol propellants (e.g. butane, propane, nitrogen and carbon dioxide).

If the filler used is water, an organic solvent may also be used as an auxiliary solvent. Suitable liquid solvents are mainly: aromatic compounds such as xylene, toluene or alkylnaphthalene; chlorinated aromatic compounds and chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffins, such as mineral oil fractions, mineral oils and vegetable oils; alcohols (e.g., butanol or ethylene glycol) and ethers and esters thereof; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; strongly polar solvents such as dimethylformamide and dimethylsulfoxide; and water.

If appropriate, further additional components may also be present, such as protective colloids, binders, adhesives, thixotropic substances, penetrants, chelating agents, complexing agents, colorants and the like. In general, the active compounds may be combined with any solid or liquid additive conventionally used in the preparation of formulations.

Typically, the compositions or formulations of the present invention comprise 0.05 to 99 mass%, 0.01 to 98 mass%, 0.1 to 95 mass%, 0.5 to 90 mass%, 10 to 70 mass%, 10 to 60 mass%, 10 to 40 mass%, 10 to 30 mass%, 10 to 25 mass% of the active compounds fluorophenyletheramide and cyproconazole.

The compositions comprising fluorophenyletheramide and cyproconazole provided by the present invention can be used as such or in the form of their formulations or use forms prepared therefrom according to their respective physical or chemical properties, for example, aerosol powders, microcapsule suspensions, aerosols, microcapsule granules, powders, suspension seed coatings, powder granules, emulsifiable concentrates, pastes, insecticide-coated seed treatments, suspension concentrates, suspoemulsions, suspension dressings, wettable powders, tablets, wettable powder seed coatings impregnated with active compounds, microcapsules in natural and synthetic substances and coating materials for polymeric substances and seeds, and ULV cold and hot atomized formulations.

Typical preparation formulations are powder, wettable powder, microcapsule, water dispersible granule, suspending agent, missible oil, microemulsion, aqueous emulsion, ultra-low volume spray and seed coating.

The powder (DP) is prepared by adding a certain amount of inert powder such as clay, kaolin, and pulvis Talci into active substance, and mechanically processing into powder with particle diameter below 100 μm.

Wettable Powders (WP) refer to a mixture of the composition in a certain proportion mixed with a suitable surfactant and an inert substance (kaolin powder). Wettable powders are formulations which are uniformly dispersible in water and which contain, in addition to the active ingredient and inert substances (kaolin powder), a certain amount of anionic or nonionic surfactants (dispersants, wetting agents).

Microcapsule (CJ) is prepared by coating active substance in binder, film-forming agent, etc. to form micro capsule, and processing into desired dosage form; the microcapsule suspension is divided into microcapsule suspending agents (CS), microcapsule granules (CG), microcapsule Dry suspending agents (CDF) and the like.

Water Dispersible Granules (WDG) refer to a mixture of the composition in a certain proportion mixed with suitable surfactant and inert substance (kaolin) powder. The powder fineness reaches the requirement by airflow crushing, and the product is uniformly mixed by using a double-screw mixer and a coulter mixer for multiple times. And then by conventional methods such as fluidized bed granulation, spray granulation, pan granulation. Finally, the solid mixture with a certain range of particle size is obtained through screening and drying treatment.

Granules (GR) refers to a mixture of the composition in certain proportions with suitable surfactants, diluents and inerts (kaolin powder). Granulation by a granulator, for example, a fluidized bed granulation method, is a granulation method in which a binder solution is sprayed and agglomerated while keeping a powder in a fluidized state. The method can complete the procedures of mixing, kneading, granulating, drying, grading and the like in a device in a closed state for a short time.

The suspending agent (SC) is prepared by mixing the composition with proper surfactant, water or organic solvent according to a certain proportion, uniformly grinding by a colloid mill, and grinding for 1-2 times by a sand mill to a certain fineness.

Emulsifiable Concentrates (EC) refer to liquids prepared by dissolving the composition in a certain proportion in an organic solvent such as benzene, toluene, xylene, cyclohexanone, and adding a certain amount of a mixture of anionic or nonionic surfactants (emulsifiers).

Microemulsions (ME) generally consist of a liquid pesticide, a surfactant (emulsifier), water, a stabilizer, etc.; it features that water is used as medium and contains no or less organic solvent. The droplet size in microemulsions is typically from a few nanometers to tens of nanometers, less than a quarter of the wavelength of visible light.

The aqueous Emulsion (EW) is a preparation in which a raw pesticide liquid insoluble in water or a solution obtained by dissolving a raw pesticide in an organic solvent insoluble in water is dispersed in water, and the prepared liquid raw pesticide is dispersed in water in small droplets of 0.5-1.5 microns, and is milky-white milk-like liquid in appearance.

The ultra-low volume spray (ULV) is a special agent for ultra-low volume spray application, wherein the liquid medicine sprayed on target crops is sprayed in extremely fine droplets with extremely low dosage.

The seed coating agent (SD) is prepared by grinding and mixing active ingredients and an auxiliary agent, and can be directly coated on the surface of seeds or diluted to form a protective film with certain strength and permeability.

The meaning of each adjuvant and each preparation will cause a difference in understanding due to a difference in expression. It should be understood that various adjuvants and formulations disclosed in the art are within the scope of the present invention, such as pesticide formulation processing technology, hunyan plane, songwang, chemical industry publishers, 2015; "pesticide formulation science, king shipment, chinese agriculture press, 2009; the "processing technology of modern pesticide formulation works, liu guang text, chemical industry press, 2018; agricultural chemical formulations and methods of use, tunzhi, jindun press, 2008; chinese pesticide, China Association for the pesticide industry; and the like.

The above-mentioned formulations can be prepared in a known manner, for example by mixing the active compound or active compound combination with at least one additive. Suitable additives are all customary formulation auxiliaries, such as organic solvents, fillers, solvents or diluents, solid carriers and fillers, surfactants (e.g. adjuvants, emulsifiers, dispersants, protective colloids, wetting agents and tackifiers), binders or fixatives, preservatives, dyes and pigments, defoamers, inorganic and organic thickeners, water repellents, if appropriate siccatives and UV stabilizers, gibberellins and also water and other processing aids. In each case, depending on the type of formulation to be prepared, further processing steps may be required, such as wet grinding, dry grinding or granulation. Methods of preparation of various formulations, including but in no way limited to those described herein.

The compositions of the invention comprise not only ready-to-use compositions, which can be applied to plants or seeds with a suitable device, but also commercial concentrates, which have to be diluted with water before use.

According to the invention, all plants and plant parts can be treated. Plants are understood to mean all plants and plant populations, such as desired and undesired wild plants, cultivars and plant varieties (whether protected by plant variety rights or plant breeder rights). Cultivars and plant varieties may be plants obtained by conventional propagation and breeding methods (assisted or supplemented by one or more biotechnological methods, for example by using dihaploids, protoplast fusions, random and directed mutagenesis, molecular or genetic markers), or by methods of bioengineering and genetic engineering. Plant parts refer to all parts and organs of the plant above and below the ground, such as shoots, leaves, needles, stems, branches, flowers, fruit bodies, fruits and seeds and roots, bulbs and rhizomes, to name a few; crops and vegetative and generative propagation material, for example cuttings, bulbs, rhizomes, cork tree and seeds, also belong to the plant parts.

For the purposes of the present invention, the term "effective amount" means an amount of a composition of the invention sufficient to reduce the incidence of sudden death syndrome. This amount varies within wide limits depending on the fungus to be controlled, the plant species, the climatic conditions and the compounds contained in the composition according to the invention. The term "plurality" means two or more.

The treatment of plants and plant parts with the compositions or formulations comprising fluorophenyletheramide and cyproconazole provided by the invention can be carried out directly or by acting on their surroundings, habitat or storage area using customary treatment methods, for example by dipping, spraying, misting, irrigating, evaporating, dusting, atomizing, broadcasting, foaming, painting, coating, watering (pouring), dripping, and in the case of propagation material, in particular in the case of seeds, also dry seeds can be treated with powder, seeds can be treated with solution, slurries can be treated with water-soluble powder by encrustation, coating one or more coats and the like. The composition or formulation may also be injected into the soil.

Among the plants which can be protected by the method of the invention, mention may be made of primary crops, such as maize, soybean, cotton, oilseed rape, rice, wheat, sugar beet, sugarcane, oats, rye, barley, millet, triticale, flax, vines, and also various fruits and vegetables from various plant taxonomic groups, horticultural and forest crops; an ornamental plant; and genetically modified homologues of these crops.

The invention also encompasses methods of treating seeds. The composition of the invention may be applied directly, i.e. without the inclusion of other components and without dilution. Generally, it is preferred that the compositions of the present invention are applied to the seed in a suitable formulation. Suitable formulations and methods for treating seeds are conventional in the art. The compositions of the invention can be converted into conventional seed dressing formulations, such as suspended seed coatings, suspended seed dressings, dry powder seed coatings, aqueous emulsion seed coatings or other coating materials for seeds, and ULV formulations.

Depending on the plant species or plant cultivars, their location and growth conditions (soil, climate, vegetative phase, nutrition), the treatment according to the invention may also bring about superadditive ("synergistic") effects. Thus, for example, the following effects beyond the actual expectation can be brought about: the compositions comprising fluorophenylene ether amide and cyproconazole which can be used according to the invention have a reduced application rate and/or a broadened activity spectrum and/or an increased activity, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, larger fruits, higher plant height, greener leaf colour, earlier flowering, higher quality and/or nutritional value of the harvested products, higher sugar concentration in the fruits, better storage stability and/or processability of the harvested products.

Compared with the prior art, the bactericidal composition has the beneficial effects that: (1) the two effective components are compounded, so that the composition has a good synergistic effect; (2) the bactericidal spectrum is expanded, and the application range is widened; (3) the generation of drug resistance is delayed; (4) the production cost and the use cost are reduced; (5) is safe to crops.

Detailed Description

The present invention will be described in further detail below with reference to specific examples, but the present invention is by no means limited to these examples. The technical product fluorobenzene ether amide is prepared by self, and the preparation method refers to CN104557709A example 1; other raw materials, adjuvants, formulations and the like used are commercially available, with a 40% cyproconazole suspension being purchased from Jiangsu Fengden crop protection GmbH.

Indoor bioassay test

Measuring the growth inhibition effect of different agents on soybean rust (Phakopsora pachyrhizi) by adopting a potting method indoors, and calculating the EC of each agent on pathogenic bacteria₅₀The value is obtained.

Application of the medicine: the first pair of potted soybean seedlings with fully expanded true leaves and consistent growth were selected for the experiments. The single dose or each composition (see Table 1) was dissolved in dimethyl sulfoxide and diluted to 50mg/L with 0.1% Tween 80 in water. Drying the test material in shade for 24h after spraying the stem leaves.

Inoculation: shearing soybean leaves with rust disease sporophyte, adding into Tween water, washing off spores on the diseased leaves with a writing brush, filtering with two layers of gauze to obtain spore suspension, and uniformly spraying and inoculating on soybean seedlings with a sprayer. And (3) culturing the inoculated potted soybean seedlings in an artificial climate chamber (25 ℃, the humidity is more than 80 percent), and carrying out grading investigation according to the disease condition of a blank control for about 10 days.

Grading standard:

level 0: no disease; level 1: the area of the lesion spots accounts for less than 5% of the area of the whole leaf;

and 3, level: the area of the lesion spots accounts for 6 to 10 percent of the area of the whole leaf; and 5, stage: the area of the lesion spots accounts for 11 to 25 percent of the area of the whole leaf;

and 7, stage: the area of the lesion spots accounts for 26 to 50 percent of the area of the whole leaf; and 9, stage: the area of the lesion spots accounts for more than 50 percent of the area of the whole leaf.

And (3) calculating the drug effect:

corresponding regression analysis is carried out according to the concentration of each composition and the corresponding control effect to obtain the EC of each composition₅₀The value is obtained.

And (3) calculating a co-toxicity coefficient (CTC) of the mixture by adopting a co-degree coefficient calculation method introduced by Sun Yunpei, and determining the synergy of the mixture.

Using a single dosage of the mixture as a standard medicament (EC is usually selected)₅₀Lower), the calculation is performed:

single dose virulence index (standard dose EC)₅₀A certain single agent EC₅₀×100

Theoretical virulence index (TTI) is the virulence index of A single agent multiplied by the proportion of A single agent in the mixture and the virulence index of B single agent multiplied by the proportion of B single agent in the mixture.

Measured virulence index (ATI) ═ EC for standard single dose₅₀EC of value/blend₅₀Value x 100

Co-toxicity coefficient is measured toxicity index/theoretical toxicity index multiplied by 100

The mixture has synergistic effect when CTC is greater than 120, is antagonistic when CTC is less than 80, and has additive effect between 80 and 120.

Table 1: determination result of soybean rust co-toxicity coefficients of fluorophenylether amide and cyproconazole in different ratios

Medicament	Virulence equation	EC₅₀(mg/L)	Co-toxicity coefficient
				Fluorophenylate amides	Y＝2.45189+3.69662x	4.89	-
Cyproconazole	Y＝3.16254+2.45081x	5.62	-
				Fluorobenzene ether amide: 1:1 of cyproconazole	Y＝2.83212+4.62879x	2.94	177.88
Fluorobenzene ether amide: 1:3 cyproconazole	Y＝3.62877+2.70004x	3.22	168.25
				Fluorobenzene ether amide: 1:5 of cyproconazole	Y＝3.09576+3.66321x	3.31	165.66
Fluorobenzene ether amide: 1:10 cyproconazole	Y＝4.12251+1.61283x	3.50	158.42
				Fluorobenzene ether amide: cyproconazole 3:1	Y＝4.58345+0.90973x	2.87	176.10
Fluorobenzene ether amide: cyproconazole 5:1	Y＝4.63327+0.86984x	2.64	189.33
				Fluorobenzene ether amide: 10:1 of cyproconazole	Y＝3.98441+2.54103x	2.51	197.15

The compound takes the fluorobenzene ether amide and the cyproconazole as effective components, has obvious synergistic effect on soybean rust when being compounded according to different mass ratios, and can become an ideal medicament for preventing and treating the soybean rust by compounding the fluorobenzene ether amide and the cyproconazole.

Preparation example 1: preparation of 25% fluorobenzene ether amide-cyproconazole suspension

1. Preparation of sanding slurries

25g of a crude drug (12.5 g of a fluorobenzene ether amide crude drug, 12.5g of a cyproconazole crude drug), 2g of a dispersant hydroxypolyethylene oxide block copolymer [ trade name: ethylan NS-500LQ, Acksonobel, 2g of a polymerized acrylic polymer graft copolymer [ trade name:

2500, hensman, 2g sodium lauryl sulfate [ avadin reagent ], 0.5g magnesium aluminum silicate [ avadin reagent ], 0.4g defoamer [ trade name: high-efficiency organic silicon defoamer, Hangzhou left soil new material Co., Ltd.). After sufficiently stirring, the mixture was added to a vertical sand mill (Shenyang chemical research institute) and used

The glass beads were sanded to obtain 90g of sanded slurry.

2. Modulation of homogeneous media

0.3g of xanthan gum (avastin reagent) was dissolved in 5g of ethylene glycol (avastin reagent), and 0.2g of sodium benzoate (avastin reagent) was dissolved in 4.5g of water, and the two were mixed and stirred sufficiently and uniformly to obtain 10g of a homogeneous medium.

3. Preparation of suspension pesticide composition

90g of the sand grinding slurry and 10g of the homogeneous medium are mixed to obtain 100g of the pesticide composition of the suspending agent, and the suspending agent with the mass content of the effective component of 25% is prepared.

Preparation example 2: preparation of 11% fluorobenzene ether amide-cyproconazole microemulsion

1. Emulsification

In a beaker, 5g of cyclohexanone (alatin reagent), 8g of ethanol (alatin reagent), 11g of a drug substance (1 g of a fluorobenzene ether amide drug substance, 10g of a cyproconazole drug substance), 8g of calcium dodecylbenzenesulfonate (trade name: 500# agricultural milk, yanchen chemical assistant company from chenge, 12g phenethylphenol polyoxyethylene polyoxypropylene ether (trade name: farm milk 1601#, from chentai, yancheng chemical assistants, inc. Fully and uniformly stirring to obtain an oil phase. 56g of water was added to the oil phase with stirring to obtain a water-in-oil microemulsion.

2. Phase inversion

The microemulsion is placed in warm water bath and converted into oil-in-water microemulsion, and microemulsion with the mass content of active ingredients of 11% is prepared.

Preparation example 3: preparation of 24% aqueous emulsion of fluorobenzene ether amide-cyproconazole

1. Preparation of the oil phase

In a beaker, 8g of cyclohexanone [ alatin reagent ], 18g of durene [ alatin reagent ], 24g of a drug substance (4 g of a fluorophenyletheramide drug substance, 20g of a cyproconazole drug substance), 5g of a copolymer of aliphatic alcohol, ethylene oxide and hexane oxide [ trade name: ethyl 992, aksunobel, 2g calcium dodecylbenzenesulfonate [ trade name: 500# agricultural milk, yancheng chemical auxiliaries from chenge, 5g ethylene glycol (avadin reagent), 0.2g antifoam agent (trade name: high-efficiency organic silicon defoamer, Hangzhou left soil new material Co., Ltd.). Fully and uniformly stirring to obtain the oil phase.

2. Emulsification

37.8g of water was slowly added to the oil phase with stirring, and the mixture was dispersed in a high-speed disperser [ trade name: TG25 German IKA is cut under high shear (8000 rpm) for 20 minutes to prepare the aqueous emulsion with the mass content of the active ingredient of 24 percent.

Preparation example 4: preparation of 20% fluorobenzene ether amide-cyproconazole emulsion oil agent

20g of a crude drug (5 g of a fluorobenzene ether amide crude drug, 15g of a cyproconazole crude drug), 3g of calcium dodecylbenzenesulfonate [ trade name: 500# agricultural milk, yancheng chemical auxiliaries from chenge, 4g styryl phenol polyoxyethylene ether (trade name: agricultural milk 600#, from Yancheng chemical assistants, from the Chenge company ], 73g of xylene. After sufficiently and uniformly stirred, the mixture was dispersed in a high-speed disperser [ trade name: TG25 German IKA was subjected to high shear (5000 rpm) for 20 minutes to obtain an emulsifiable concentrate containing 20% by mass of the active ingredient.

Preparation example 5: 40% fluorobenzene ether amide-cyproconazole water dispersible granule

1. Pulverizing

40g of raw drug (30 g of fluorobenzene ether amide raw drug and 10g of cyproconazole raw drug) is crushed by a jet mill to obtain raw drug with the particle size of less than 20 mu m. The crude drug was mixed with 2g of a polymerized acrylic graft copolymer [ trade name:

2700, hensman, 5g lignosulfonate [ trade name: ufoxane NA, aksunobel, 3g ammonium sulfate [ avastin reagent ], 50g white carbon black [ avastin reagent ]. And fully and uniformly mixing to obtain a mixed material.

2. Granulating

Adding 15g of water into the mixture, carrying out extrusion granulator, heating in an electric heating constant temperature blast drier for 2h at 60 ℃, and taking out.

3. Sieving

And (3) screening the dried particles by using a sieve of 20 meshes or 60 meshes according to requirements, and discarding small particles at the bottom and large particles at the upper part to obtain the water dispersible granule with the active ingredient mass content of 40%.

Preparation example 6: preparation of 55% fluorobenzene ether amide-cyproconazole wettable powder

55g of a crude drug (50 g of a fluorobenzene ether amide crude drug and 5g of a cyproconazole crude drug) was mixed with 2g of sodium dodecyl sulfate [ an latin reagent ], 4g of an alkyl naphthalene formaldehyde condensate sulfonate [ trade name: d-425, Acksonobel, 10g of white carbon black (Aladdin reagent) and 29g of bentonite (Aladdin reagent) are fully mixed and then crushed by a jet mill to prepare wettable powder with the mass content of the effective component of 55 percent.

Comparative example 1: preparation of 30% Fluorophenyl Ether amide suspension

1. Preparation of sanding slurries

Adding 30g of raw fluorobenzene ether amide in a beaker in sequence,2g of dispersant hydroxy polyethylene oxide block copolymer [ trade name: ethylan NS-500LQ, Acksonobel, 2g of a polymerized acrylic polymer graft copolymer [ trade name:

2500, hensman, 2g sodium lauryl sulfate [ avadin reagent ], 0.5g magnesium aluminum silicate [ avadin reagent ], 0.4g defoamer [ trade name: high-efficiency organic silicon defoamer, Hangzhou left soil new material Co., Ltd.). After sufficiently stirring, the mixture was added to a vertical sand mill (Shenyang chemical research institute) and usedThe glass beads were sanded to obtain 90g of sanded slurry.

2. Modulation of homogeneous media

3. Preparation of suspension pesticide composition

90g of the sand grinding slurry and 10g of the homogeneous medium are mixed to obtain 100g of the pesticide composition of the suspending agent, and the suspending agent with the mass content of the effective component of 30% is prepared.

Test of field drug effect

And (3) test treatment: the test drugs of preparation examples 1 to 3 were each set with three effective ingredient dosages according to the test design of the test drugs in table 2. The control agents were a commercial pesticide 40% cyproconazole SC and 30% fluorophenyletheramide SC prepared in comparative 1 and clear water blank, respectively.

Table 2: test design of test agent

Setting a cell: each cell area is 66.7m²；

The application method comprises the following steps: the agent is applied at the early stage of soybean rust disease, and sprayed on the leaf surface, and the spraying amount is mainly no water drop;

the application times are as follows: 2 times, windy day or expected rainfall within 1 hour, no drug application. The disease condition base is investigated before the first application, the subsequent application is carried out for 1 time every 7 days, and the control effect is investigated 7 days after the 2 nd application.

Investigation time and number of times: the base number was investigated 1 day after the administration of the drug, and the index of disease was investigated 7 days and 14 days after the administration of the drug.

The investigation method comprises the following steps: and (4) grading according to the damage symptom degree of the soybean leaves, taking the soybean leaves as a unit, sampling five points on the diagonal line of each cell, surveying and connecting 5 clusters at each point for 25 clusters, and recording the total number of the soybean leaves, the number of diseased soybean leaves and the number of diseased soybean leaves.

The method for investigating before pesticide application and checking the pesticide effect after prevention and treatment comprises the following steps: randomly sampling 5 points in the test treatment area, and recording the total leaf number, the diseased leaf number and the diseased stage number. The standard method of classification is as follows:

And (3) calculating the drug effect:

the results are detailed in table 3.

Table 3: prevention effect of different agents on soybean rust

After the fluorophenylether amide and the cyproconazole are compounded, the control effect on the soybean rust is obviously better than that of a control medicament, after the fluorophenylether amide and the cyproconazole are compounded, the bactericidal spectrum is enlarged, the bactericidal effect is obviously improved compared with that of a single agent, and the synergistic effect can be shown after the fluorophenylether amide and the cyproconazole are compounded, so that the administration frequency can be reduced. In addition, no phytotoxicity of the pesticide composition on soybean is found in the application range, which shows that the bactericidal composition has good safety on crops and can be popularized and applied.

In conclusion, the bactericidal composition provided by the invention with the fluorophenylether amide and cyproconazole as the active ingredients has a good control effect on soybean rust and is safe for target crops. The compound preparation not only improves the control effect, but also expands the bactericidal spectrum, widens the application range, reduces the cost, has good curative effect on soybean rust, reduces manpower and material resources and improves the production benefit. Therefore, the invention and the popularization of the compound preparation have very important significance to the society.

Claims

1. A germicidal composition, characterized by: the effective components of the bactericidal composition are the fluorophenylene ether amide and the cyproconazole.

2. The germicidal composition of claim 1, wherein: the mass ratio of the fluorophenylether amide to the cyproconazole is 1-10: 10 to 1.

3. The germicidal composition of claim 2, wherein: the mass ratio of the fluorophenylene ether amide to the cyproconazole is 1:10 to 1.

4. The germicidal composition of claim 1, wherein: the total content of the fluorobenzene ether amide and the cyproconazole in the bactericidal composition is 10-60% by mass.

5. The germicidal composition of claim 4, wherein: the total content of the fluorobenzene ether amide and the cyproconazole in the bactericidal composition is 10-40% by mass.

6. The germicidal composition of claim 5, wherein: the total content of the fluorobenzene ether amide and the cyproconazole in the bactericidal composition is 10-30% by mass.

7. The use of the fungicidal composition of any one of claims 1 to 6 for the control of wheat powdery mildew, wheat sharp eyespot, soybean rust, soybean gray leaf spot, soybean gray mold, soybean anthracnose or fruit and vegetable leaf spot.

8. A formulation prepared from the germicidal composition of any of claims 1-6, wherein: the preparation is in the form of missible oil, aqueous emulsion, microemulsion, suspending agent, wettable powder or water dispersible granule.

9. The use of the formulation of claim 8 for controlling wheat powdery mildew, wheat sharp eyespot, soybean rust, soybean gray leaf spot, soybean gray mold, soybean anthracnose, or fruit and vegetable leaf spot.

10. A method for controlling plant diseases, which comprises applying to the plant or plant part an effective amount of the fungicidal composition of any one of claims 1 to 6 or the formulation of claim 8.