CN110810419A

CN110810419A - Sterilization composition containing fluorobenzene ether amide and triflumizole

Info

Publication number: CN110810419A
Application number: CN201810900205.3A
Authority: CN
Inventors: 李义涛; 陈锦昌; 梁任龙; 刘新烁; 钟乐荣; 董江强
Original assignee: Dongguan Dongyangjunyang Hydrogen Patent Pesticide Co Ltd
Current assignee: Dongguan Dongyangjunyang Hydrogen Patent Pesticide Co Ltd
Priority date: 2018-08-09
Filing date: 2018-08-09
Publication date: 2020-02-21

Abstract

The invention relates to a bactericidal composition or preparation containing fluorophenylether amide and triflumizole and application thereof, wherein the mass ratio of the effective components of fluorophenylether amide and triflumizole is 1-10: 10-1, and the total content of fluorophenylether amide and triflumizole in the bactericidal composition or preparation is 10-60% by mass. The bactericidal composition or the preparation of the invention has obvious synergistic effect on the prevention and treatment of cucumber powdery mildew. The bactericidal composition or the preparation is suitable for preventing and treating powdery mildew, banded sclerotial blight, bakanae disease, anthracnose, epidemic disease, rust disease, gray mold or rice blast.

Description

Sterilization composition containing fluorobenzene ether amide and triflumizole

Technical Field

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

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:

triflumizole is an imidazole bactericide, mainly plays a role by inhibiting the synthesis of pathogenic bacteria ergosterol, and has the advantages of high efficiency, low toxicity, low residue and the like. In the aspect of disease control, triflumizole is widely used for controlling powdery mildew and rust disease of crops such as cereals, vegetables, melons and fruits, and has certain control effects on stripe disease and smut of wheat, bakanae disease and rice blast of rice, anthracnose of tea trees and melons and fruits, and the like. The structural formula of triflumizole is:

the powdery mildew of cucumber is one of the common diseases in cucumber cultivation, influences the photosynthesis of leaves and causes great yield loss in the later growth stage of cucumber; the yield reduction in the general year is about 10 percent, and the yield reduction in the popular year is about 20 to 40 percent. In recent years, powdery mildew has certain drug resistance and can be attacked all the year round, so that certain difficulty is brought to prevention and treatment.

However, the bactericidal composition or/and formulation comprising flubenconazole and flubenconazole according to the present invention and the use thereof for controlling cucumber powdery mildew 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 or a preparation, and the effective components of the bactericidal composition or the preparation are fluophenylamide and triflumizole.

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

Furthermore, the mass ratio of the fluorobenzene ether amide to the triflumizole is 1-3: 10 to 1.

Further, the total content of the fluorobenzene ether amide and the triflumizole in the sterilization composition or the preparation is 1-95% by mass.

Furthermore, the total content of the fluorobenzene ether amide and the triflumizole in the sterilization composition or the preparation is 5-70% by mass.

Preferably, the total content of the fluorobenzene ether amide and the triflumizole in the sterilization composition or the preparation is 10-60 mass%.

More preferably, the total content of the fluorobenzene ether amide and the triflumizole in the sterilizing composition or the preparation is 30-50 mass%.

On the other hand, the invention provides application of the bactericidal composition containing the fluorophenylether amide and the triflumizole in preventing and treating powdery mildew, banded sclerotial blight, bakanae disease, anthracnose, epidemic disease, rust disease, gray mold or rice blast.

In another aspect, the invention provides a preparation prepared from the bactericidal composition containing the flubendiamide and the triflumizole, and the preparation is missible oil, a suspending agent, wettable powder, water dispersible granules, a microemulsion, an emulsion in water or a microcapsule suspending agent.

Further, the invention provides application of a preparation containing fluorophenylether amide and triflumizole in preventing and treating powdery mildew, banded sclerotial blight, bakanae disease, anthracnose, epidemic disease, rust disease, gray mold or rice blast.

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 triflumizole, or a formulation comprising a fluorophenylether amide and triflumizole.

Detailed description of the invention

The preparation containing the composition of the fluorobenzene ether amide and the triflumizole 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 triflumizole is reduced. On one hand, the bactericidal spectrum is widened, and on the other hand, the use safety is improved.

In addition to the fungicidal synergistic activity, the present invention provides formulations comprising a combination of fluorophenylether amide and triflumizole having other excellent properties, which in a broad sense may also be referred to as synergy, 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 triflumizole provided by the invention is beneficial to keeping plants healthy, so that the quality and yield of crops are guaranteed. In addition, the preparation containing the composition of the fluorophenylether amide and the triflumizole provided by the invention can be used for enhancing the 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 triflumizole may still have such properties. Similarly, the preparation containing the composition of the fluorophenylether amide and the triflumizole provided by the invention can bring about a more lasting 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 sterilization composition, and the effective components of the sterilization composition are fluophenylamide and triflumizole.

Further, the mass ratio of the fluorobenzene ether amide to the triflumizole in the sterilization composition is 1-10: 10 to 1.

Furthermore, the mass ratio of the fluorobenzene ether amide to the triflumizole in the bactericidal composition is 1-3: 10 to 1.

Specifically, the mass ratio of the fluorophenylether amide to the triflumizole in the bactericidal composition is 1: 1. 1: 3. 1: 5. 1: 10. 3: 1. 5: 1. 10: 1. 2: 3. 1: 6. 2:1 or 3: 10.

in another aspect, the invention provides a formulation comprising as active ingredients flufenoxanil and triflumizole.

Furthermore, the preparation formulation is missible oil, suspending agent, wettable powder, water dispersible granules, microemulsion, emulsion in water or microcapsule suspending agent.

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

Furthermore, the mass ratio of the fluorobenzene ether amide to the triflumizole in the preparation is 1-3: 10 to 1.

Specifically, the mass ratio of the fluorobenzene ether amide to the triflumizole in the preparation is 1: 1. 1: 3. 1: 5. 1: 10. 3: 1. 5: 1. 10: 1. 2: 3. 1: 6. 2:1 or 3: 10.

More preferably, the total content of the fluorobenzene ether amide and the triflumizole in the sterilization composition or the preparation is 30-50 mass%; the toxicity and the residue reach better balance, and the cost is lower.

Most preferably, the total content of the fluorophenyletheramide and triflumizole in the bactericidal composition or preparation is 13 mass%, 30 mass%, 35 mass%, or 50 mass%.

The total content of the fluorobenzene ether amide and the triflumizole in the sterilization composition or the preparation refers to the percentage of the total mass of the fluorobenzene ether amide and the triflumizole in the whole sterilization composition or the preparation. For example, the total content of the fluorophenylether amide and the triflumizole in the sterilization composition is 30-50% by mass, namely the total mass of the fluorophenylether amide and the triflumizole accounts for 30-50% by mass of the whole sterilization composition.

In still another aspect, the invention provides an application of a bactericidal composition or a preparation containing fluorophenylether amide and triflumizole in controlling powdery mildew, banded sclerotial blight, bakanae disease, anthracnose, epidemic disease, rust disease, gray mold or rice blast.

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

The mass ratio of the fluorophenyletheramide to triflumizole in the compositions or formulations according to the invention can be varied within a relatively wide range. Is present in a synergistically effective mass ratio of fluorophenyletheramide to triflumizole 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 triflumizole 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 fluorophenylether amide to the triflumizole is preferably 1-10: 10-1; synergy outside this range is significantly weaker than this range.

If the flufenoxanil or triflumizole 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 flufenoxanil or triflumizole can form salts, for example, acid addition salts with acids, for example, 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 flufenoxanil or triflumizole and the form of its salt, reference to either flufen amide or triflumizole or its salt anywhere in the context of the present invention is understood to also include the corresponding salt or flufen amide or triflumizole, respectively, where advantageous and appropriate. The same applies to stereoisomers, optical isomers or tautomers of fluorophenyletheramide or triflumizole and to salts thereof.

The composition of the present invention contains, in addition to the active ingredients of fluorophenyletheramide and triflumizole, 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 can 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),

OTB (dioctyl sulfosuccinate),EFW (alkylated naphthalene sulfonate),

BX (alkyl)A sulfonated naphthalene sulfonate),

MT 804 (alkylated naphthalene sulfonate).

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 suspension 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 customary dispersants are sodium lignosulfonates, sodium naphthalenesulfonate formaldehyde condensates, tristyrylphenol ethoxylate phosphate esters, fatty alcohol ethoxylates, alkyl ethoxylates, alkylphenolsPolyoxyethylene ether, alkylphenol polyoxyethylene ether methyl ether condensation compound sulfate, fatty amine polyoxyethylene ether, glycerin fatty acid ester polyoxyethylene ether, EO-PO block copolymer and graft copolymer. Typical representatives of suitable dispersants are e.g.

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.

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 selected from one or more of xanthan gum, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose or white carbon black.

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 composition or formulation of the present invention comprises 0.05 to 99 mass%, 0.01 to 98 mass%, 0.1 to 95 mass%, 0.5 to 90 mass%, 1 to 95 mass%, 5 to 70 mass%, 10 to 60 mass%, 10 to 50 mass% of the fluorophenylether amide and triflumizole.

The compositions comprising flubendiamide with triflumizole provided by the 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, microencapsulated granules, powders, suspension seed coatings, granules, emulsifiable concentrates, emulsions in water, microemulsions, effervescent granules, microgranules, oil-dispersed powders, oil suspensions, oils, 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 in coatings of polymeric substances and seeds, and ULV cold and hot fogging 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.

Ultra-low volume spray (ULV) refers to a liquid medicine sprayed onto target crops, which is sprayed in extremely fine droplets with extremely low dosage, and is a special preparation for ultra-low volume spray application.

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.

Smoke agent (FU), also called smoke agent, is a chemical agent which mixes the effective components with combustible substances, etc. and then burns them to gasify the pesticide and condense it into smoke particles or directly disperse the pesticide into smoke particles.

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 triflumizole provided according to the invention can be carried out directly or by applying to their surroundings, habitat or storage area conventional 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 by treating dry seeds with powder, by treating the seeds with solution, by treating the slurry with water-soluble powder by coating (incrustation), by 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 triflumizole 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 of the fluophenyl ether amide is prepared by self, and the preparation method refers to CN104557709A example 1; other useful prodrugs, adjuvants, formulations, etc. are commercially available, with the triflumizole prodrug being purchased from Chongqing Sabinasi technologies, Inc.

Indoor bioassay test

Measuring the growth inhibition effect of different agents on cucumber powdery mildew (Sphaerotheca fuliginea) by adopting a potting method indoors, and calculating the EC of each agent on pathogenic bacteria₅₀The value is obtained.

Application of the medicine: potted cucumber seedlings with two leaf periods of consistent vigor are selected for experiments. The single dose or each composition (see table 1) is dissolved by dimethyl sulfoxide, and then is diluted to 100, 50, 25, 12.5, 6.25 and 3.125mg/L by adding 0.1 percent of Tween 80 aqueous solution. Drying the test material in shade for 24h after spraying the stem leaves.

Inoculation: washing fresh spores on cucumber leaves with water containing a small amount of Tween, filtering with double-layer gauze to obtain spore suspension, and uniformly spraying the spore suspension on seedlings with an inoculation sprayer. And (4) placing the inoculated potted cucumber seedlings in a greenhouse for normal culture, and carrying out grading investigation according to the blank control morbidity situation for about 7 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 20 percent of the area of the whole leaf;

and 7, stage: the area of the lesion spots accounts for 21 to 40 percent of the area of the whole leaf;

and 9, stage: the area of the lesion spots accounts for more than 40 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 different proportions of flubendiamide and triflumizole for cucumber powdery mildew co-toxicity coefficient

Medicament	Virulence equation	EC₅₀(mg/L)	Co-toxicity coefficient
				Fluorophenylate amides	Y＝3.79041+1.51981x	6.25	-
Triflumizole	Y＝2.71209+2.17978x	11.21	-
				Fluorobenzene ether amide: triflumizole 1:1	Y＝4.09117+1.21851x	5.57	144.08
Fluorobenzene ether amide: triflumizole 1:3	Y＝3.49823+1.87714x	6.31	148.24
				Fluorobenzene ether amide: triflumizole 1:5	Y＝3.24981+2.01485x	7.39	133.94
Fluorobenzene ether amide: triflumizole 1:10	Y＝3.10045+2.06680x	8.30	125.96
				Fluorobenzene ether amide: triflumizole 3:1	Y＝3.96518+1.44866x	5.18	135.66
Fluorobenzene ether amide: triflumizole 5:1	Y＝3.86477+1.60248x	5.11	132.07
				Fluorobenzene ether amide: triflumizole ═10:1	Y＝3.80164+1.70185x	5.06	128.70

When the flufenoxanil and the triflumizole are compounded as effective components in different proportions, the synergistic effect on the control capability of cucumber powdery mildew is obvious. Therefore, the complex formulation of the fluorobenzene ether amide and the triflumizole can become an ideal medicament for preventing and treating powdery mildew of cucumber.

Preparation example 1: 50% fluorobenzene ether amide triflumizole wettable powder

30g of triflumizole technical, 20g of fluorobenzene ether amide technical, and lignosulfonate (trade name: borresperse NA, pall industries, Inc. ] 8g, Morwet EFW (Acksonobel company) 2g, white carbon black (Aladdin reagent) 5g and kaolin (Hangzhou left soil new material Co., Ltd.) are added to 100g, and the mixture is pre-crushed, mixed evenly and then crushed into required particle size by a dry method through airflow crushing (Kunshan Yongke machinery Co., Ltd.) to prepare wettable powder with the mass content of the effective components of 50%.

Preparation example 2: 35% fluorobenzene ether amide-triflumizole water dispersible granule

30g of triflumizole technical, 5g of fluorobenzene ether amide technical, and an alkyl naphthalene sulfonate formaldehyde condensate (trade name: MorwetD425, Acksonobel company 6g, sodium dodecyl sulfate (Aladdin reagent) 2g, urea (Aladdin reagent) 3g, xanthan gum (Aladdin reagent) 0.5g, and kaolin (Hangzhou left soil new material Co., Ltd.) to 100g, pre-crushing and uniformly mixing, then crushing by air flow crushing (Kunshan Yonak machinery Co., Ltd.) by dry method to required particle size, and then granulating by adopting a rotary granulator to prepare the water dispersible granule with the active ingredient mass content of 35%.

Preparation example 3: 30% fluorophenyletheramide-triflumizole suspension

1. Preparation of pulverized slurry

The EOPO front-stage copolymer was dispersed in 38.5g of water [ trade name: ethylan NS-500LQ, AksuNobel company 1g, sodium lignosulfonate (trade name: borreperse NA, pallizine industries, Ltd. ] 3g, sodium dodecyl sulfate (Alistin reagent) 2g and organic silicon defoamer (Hangzhou left soil new materials, Ltd.) 0.5g, wherein 10g of triflumizole raw material and 20g of fluorobenzene ether amide raw material are dispersed and used

The glass beads were wet-pulverized by a sand mill (Shenyang chemical research institute) to obtain 75g of a pulverized slurry.

2. Preparation of Dispersion Medium

In 18.55g of water, 0.2g of xanthan gum (avastin reagent), 0.75g of magnesium aluminum silicate (Hangzhou left soil new materials Co., Ltd.), 5g of ethylene glycol (avastin reagent) and 0.5g of sodium benzoate (avastin reagent) were dispersed to obtain 25g of a dispersion medium.

3. Preparation of the suspending agent

The above pulverized slurry (75 g) was mixed with a dispersion medium (25 g) to obtain 100g of an aqueous suspension-type agricultural chemical composition, and a suspension concentrate containing 30% by mass of the active ingredient was prepared.

Preparation example 4: 30% fluorophenyletheramide-triflumizole suspension

1. Preparation of pulverized slurry

A polycarboxylate salt was dispersed in 35.5g of water [ trade name: GY-D07, Beijing Guangyuan agricultural chemistry LLC 4g, Morwet EFW 2g, wetting agent (GY-WS 10, Beijing Guangyuan Yinong) 3g and organic silicon defoamer 0.5g, wherein 15g of triflumizole and 15g of fluorophenyletheramide are dispersed in the organic silicon defoamer, and the organic silicon defoamer is prepared by

2. Preparation of Dispersion Medium

In 20.66g of water were dispersed 0.3g of xanthan gum (avastin reagent), 4g of ethylene glycol (avastin reagent), and a preservative [ trade name: 0.04g of WJB-20, Shanghai Wanjin auxiliary agent Co., Ltd., and 25g of a dispersion medium was obtained.

3. Preparation of the suspending agent

Preparation example 5: 13% aqueous emulsion of fluorophenyletheramide and triflumizole

10g of triflumizole original drug, 3g of fluorobenzene ether amide original drug, 10g of cyclohexanone (an latin reagent) and 10g of dimethylbenzene (an latin reagent) are mixed and soaked, slowly stirred until the materials are dissolved to prepare an oil phase, and then castor oil polyoxyethylene ether (trade name: BY-125, 4g of swallow-honest chemical auxiliary agent (from chen tai), 2g of calcium alkylbenzene sulfonate (swallow-honest chemical auxiliary agent (from chen tai), 5g of ethylene glycol (avastin reagent), and 0.1g of silicone defoamer (from left soil new materials limited, hangzhou) were dissolved in 55.9g of water to prepare a water phase, and an oil phase was added to the water phase or the water phase was added to the oil phase, and the mixture was dispersed in a high-speed dispersion machine (trade name: TG25, German IKA) is subjected to high shear (5000 r/min) for 10 minutes to prepare an aqueous emulsion with the mass content of the active ingredient of 13 percent.

Comparative example 1: 30% fluorophenyletheramide suspending agent

1. Preparation of pulverized slurry

Castor oil polyoxyethylene ether [ trade name: BY-125, Switzerland chemical auxiliary agent from Chenge Taiwan, 2g, polymeric dispersant (trade name: TERSPERSE 2500 g, Hensmei 3g, wetting agent (GY-WS 10, Beijing Guangyuan Yinong) 2g and organic silicon defoamer (Hangzhou left soil new material Co., Ltd.) 0.5g, wherein 30g of fluorobenzene ether amide raw material is dispersed therein for use

2. Preparation of Dispersion Medium

In 19.56g of water were dispersed 0.4g of xanthan gum (avastin reagent), 5g of ethylene glycol (avastin reagent), and a preservative [ trade name: 0.04g of WJB-20, Shanghai Wanjin auxiliary agent Co., Ltd., and 25g of a dispersion medium was obtained.

3. Preparation of the suspending agent

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 30% fluorophenyletheramide SC prepared in control example 1 and 30% triflumizole WP as a commercial pesticide and a blank clear water test, 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 medicament is applied at the early stage of powdery mildew of cucumber, and sprayed on the leaf surface, and the spraying amount is mainly no water drops;

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) according to the grading of the damage symptom degree of the cucumber leaves, taking the cucumber 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 plants, the number of diseased plants and the number of disease stages.

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:

grading standard:

level 0: no disease;

And (3) calculating the drug effect:

the results are detailed in table 3.

Table 3: control effect of different medicaments on cucumber powdery mildew

After the fluorophenyletheramide and the triflumizole are compounded, the control effect on the powdery mildew of cucumber is obviously better than that of a control medicament, after the fluorophenyletheramide and the triflumizole are compounded, the quick action is good, the lasting period is prolonged, the synergistic effect is good after the fluorophenyletheramide and the triflumizole are compounded, the medicine using frequency can be reduced, and the labor amount of farmers is reduced. In addition, no adverse effect of the pesticide composition on cucumbers is found in the application range, which shows that the bactericidal composition disclosed by the invention is good in safety to crops and can be popularized and applied.

Claims

1. The bactericidal composition is characterized in that the effective components of the bactericidal composition are fluophenylamide and triflumizole.

2. The bactericidal composition according to claim 1, wherein the mass ratio of the fluorophenylether amide to the triflumizole is 1-10: 10 to 1.

3. The bactericidal composition according to claim 2, wherein the mass ratio of the fluorophenylether amide to the triflumizole is 1-3: 10 to 1.

4. The bactericidal composition according to claim 1, wherein the sum of the contents of the fluorophenyletheramide and the triflumizole in the bactericidal composition is 1 to 95% by mass.

5. The bactericidal composition according to claim 4, wherein the sum of the contents of the fluorophenyletheramide and the triflumizole in the bactericidal composition is 5 to 70% by mass.

6. The bactericidal composition according to claim 5, wherein the sum of the contents of the fluorophenyletheramide and the triflumizole in the bactericidal composition is 10 to 60% by mass.

7. The use of the fungicidal composition of any one of claims 1 to 6 for the control of powdery mildew, banded sclerotial blight, bakanae disease, anthracnose, epidemic disease, rust disease, gray mold or rice blast.

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

9. Use of the formulation of claim 8 for the control of powdery mildew, sheath blight, bakanae disease, anthracnose, epidemic disease, rust disease, gray mold or rice blast.

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.