CN112753701A - Composition containing imazalil and Ipflufenoquin, preparation and preparation method and application thereof - Google Patents

Abstract

The invention relates to a composition containing imazalil and Iflufenoquin, a preparation method and application thereof. A composition comprising a pharmaceutically active ingredient; the pharmacodynamic active components comprise imazalil and Iflufenoquin. The composition is used as a bactericide, has wide application range, good effect, low cost and low residue, is safe to people, livestock, environment and the like, and the two active ingredients show excellent synergistic effect in preventing and treating diseases related to cereal crops caused by fungi.

Description

Composition containing imazalil and Ipflufenoquin, preparation and preparation method and application thereof

Technical Field

The invention relates to the field of pesticides, and particularly relates to a composition, a preparation method and application thereof.

Background

Iflufenoquin is a quinoline bactericide developed by Nippon-Soda, Japan. The code NF-180 is developed, the name of Chinese culture is 2- [ (7, 8-difluoro-2-methyl-3-quinolyl) oxy ] -6-fluoro-a, a-dimethyl benzyl alcohol, the name of English chemistry is 2- [ (7, 8-difluoro-2-methyl-3-quinolyl) oxy ] -6-fluoro-a, a-dimethyl lbenzemethanol, the CAS accession number is 1314008-27-9, and the structural formula is as follows:

imazalil is a systemic fungicide and has a preventive effect against many fungal diseases affecting fruits, vegetables and ornamental plants. The Chinese chemical name is 1- [2- (2, 4-dichlorophenyl) -2- (2-propenyloxy) ethyl ] -1H-imidazole, the CAS accession number is 35554-44-0, and the imazalil structural formula is as follows:

the chemical agent is an effective means for preventing and treating grape anthracnose. The pesticide usage amount is increased year by year due to the fact that the grape anthracnose has stronger and stronger resistance to the pesticide at present, and the pollution to the environment is more and more serious.

Therefore, the development of a pesticide composition with a remarkable effect on controlling the grape anthracnose is urgently needed.

Disclosure of Invention

The invention aims to provide a composition, the pharmacodynamic active components of which comprise imazalil and Iflufenoquin, which not only solves the problems of over high dosage and insufficient control effect in the prior art, but also has the effects of wider bactericidal spectrum, higher quick action, longer lasting period and the like.

The invention also aims to provide a preparation which has wide preparation types, can also solve the problems of overhigh dosage and insufficient control effect in the prior art, and can achieve the effects of enlarging bactericidal spectrum, improving quick action and prolonging lasting period.

In order to achieve the above purpose, the invention provides the following technical scheme:

in one aspect, the present invention provides a composition comprising a pharmaceutically active ingredient; the pharmacodynamic active components comprise imazalil and Iflufenoquin.

Furthermore, the mass ratio of imazalil to Ipfenoquin in the composition is 1-20: 20-1.

Furthermore, the mass ratio of imazalil to Iflufenoquin in the composition is 1-5: 5-1.

Preferably, the mass ratio of imazalil to Ipflufenoquin in the composition is 1-3: 5-1.

More preferably, the mass ratio of imazalil to Ipflufenoquinb in the composition is 1-2: 3-1.

Specifically, the mass ratio of imazalil to Ipflufenoquin in the composition is 20:1, 15:1, 10:1, 5:1, 3:1, 2:1, 1:2, 1:3, 1:5, 1:10, 1:15 or 1: 20. In the invention, when the mass ratio of imazalil to Iflufenoquin in the composition is in the range, the composition has synergistic bactericidal effect.

The composition of the invention can contain common auxiliary agents for pesticides besides the pharmacodynamic active components, the auxiliary agents are auxiliary substances added in the processing or use of pesticide preparations and used for improving the physicochemical property of the pesticide preparations, and the auxiliary agents basically have no biological activity but can influence the control effect. The adjuvants may include at least one of a wetting agent, a dispersing agent, an emulsifier, a thickener, a disintegrant, an antifreeze, a defoamer, a solvent, a preservative, a stabilizer, a synergist, a carrier, and the like. The above-mentioned auxiliary agents may be added as appropriate according to the requirements of the composition, and may be changed depending on the case, and are not particularly limited.

Preferably, the wetting agent is selected from one or more of alkylphenol ethoxylates (e.g., nonylphenol ethoxylates, octylphenol ethoxylates, dodecylphenol ethers, dinonylphenol ethers, mixed alkylphenol ethers, and the like), fatty acid or fatty acid ester sulfates, alkylnaphthalene sulfonates (e.g., sodium dibutylnaphthalene sulfonate, sodium isopropylnaphthalene sulfonate), alkylbenzene sulfonates (e.g., sodium dodecylbenzene sulfonate, calcium dodecylbenzene sulfonate), alkyl sulfates and lignosulfonates (e.g., sodium lignosulfonate, calcium lignosulfonate), and the like. Suitable wetting agents are

OTB (dioctyl sulfosuccinate),

EFW (alkylated naphthalenesulfonates),

BX (alkylated naphthalenesulfonates) or

MT 804 (alkylated naphthalene sulfonate).

The dispersing agent is selected from one or more of naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, lignosulfonate, alkylbenzene sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, high-molecular polycarboxylate, alkylbenzene polyoxyethylene ether, ethylene oxide propylene oxide block polyether, organic phosphate and the like. For wettable powder formulations, a common dispersing agent is sodium lignosulfonate (sodium lignosulphonate). For suspension concentrates, polyelectrolytes such as sodium naphthalene sulfonate formaldehyde condensate are used to achieve adsorption and stabilization. Tristyrylphenol ethoxylate phosphate (trisstyrylphenol ethylatephosphateester) was also used. Typical representatives of suitable dispersants are, in particular

2700、

2500、

2510、YUS-EP60P、SP-3498D、

4894. Ufoxane NA, Morwet D425, GY-D800, Antraox B/848, Morwet D425 or Ethylan NS-500 LQ.

The emulsifier is selected from one or more of castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide addition product of fatty amide, fatty acid polyoxyethylene ester, castor oil ethylene oxide addition product and derivatives thereof, rosin acid ethylene oxide addition product and analogs, polyol fatty acid and ethylene oxide addition product thereof, polyoxyethylene polyoxypropylene block copolymer and the like. Typical representatives of suitable dispersants are, inter alia, lignin a, 3A high-purity modified wood sodium, agro-milk 500#, agro-milk 601#, agro-milk 602#, agro-milk 700#, agro-milk 1601#, agro-milk 1602#, TERMUL2507, emulson CO-360 or ethyalan 992.

The thickening agent is one or more selected from white carbon black, kaolin, bentonite, xanthan gum, Arabic gum, polyacrylic acid, sodium carboxymethylcellulose and the like.

The disintegrating agent is selected from one or more of urea, modified starch, bentonite, aluminum chloride, ammonium sulfate, succinic acid, sodium bicarbonate, etc.

The antifreezing agent is one or more selected from glycerol, ethylene glycol, propylene glycol and the like.

The defoaming agent is selected from silicone defoaming agent, silicone defoaming agent (such as ETXP-40), and C_8-10And one or more of fatty alcohol antifoaming agents, polyureas, polyethylene glycol fatty acid esters, and the like.

The solvent is one or more of toluene, xylene, cyclohexanone, aromatic solvent, methanol, ethyl acetate, soybean oil, epoxidized soybean oil, castor oil, corn oil, epoxidized corn oil, methyl oleate, rapeseed oil, N-octyl pyrrolidone and the like.

The preservative is selected from one or more of sodium benzoate, benzoic acid, potassium sorbate, kasong, and the like.

The stabilizer is selected from one or more of phosphoric acid, pyrophosphoric acid, phthalic acid, benzoic acid, triphenyl phosphite, acetic anhydride, epichlorohydrin, magnesium aluminum silicate, resorcinol, sodium citrate and the like.

The synergist has no bioactivity, but can inhibit detoxifying enzyme in organism, and when mixed with some pesticides, can greatly improve the toxicity and the efficacy of the pesticides, such as one or more of synergistic phosphorus, synergistic ether and the like.

The carrier is selected from one or more of kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, silica, alumina, natural or artificial silicates, resins, waxes, solid fertilizers, water, alcohols (especially butanol), organic solvents, mineral and vegetable oils and their derivatives, and the like.

In addition, 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 pharmacodynamically active component can be combined with any solid or liquid additive commonly used for formulation purposes.

In some embodiments, imazalil and Ipflufenoquin are present in the composition in a total amount of 1 to 95 mass%.

Preferably, the total content of imazalil and Ipflufenoquin in the composition is 20-80% by mass.

More preferably, the total content of imazalil and Ipflufenoquin in the composition is 30-60 mass%.

Specifically, the total content of imazalil and Ipflufenoquin in the composition is 30 mass%, 40 mass%, 50 mass%, or 60 mass%. In the present invention, the synergistic effect of sterilization is further enhanced when the total content of imazalil and Ipflufenoquin in the composition is within the above range.

In another aspect, the present invention provides a formulation prepared from the composition of the present invention.

In some embodiments, the mass ratio of imazalil to Ipflufenoquin in the formulations of the present invention is 1-20: 20-1.

Preferably, the mass ratio of imazalil to Iflufenoquin in the preparation is 1-5: 5-1.

More preferably, the mass ratio of imazalil to Ipflufenoquin in the preparation is 1-3: 5-1.

More preferably, the mass ratio of imazalil to Ipflufenoquin in the preparation is 1-2: 3-1.

Specifically, the mass ratio of imazalil to Ipflufenoquin in the preparation provided by the invention is 20:1, 15:1, 10:1, 5:1, 3:1, 2:1, 1:2, 1:3, 1:5, 1:10, 1:15 or 1: 20.

In some embodiments, imazalil and Ipflufenoquin are present in the formulations of the present invention in a total amount of 1-95% by mass.

Preferably, the total content of imazalil and Ipflufenoquin in the preparation is 20-80% by mass.

More preferably, the total content of imazalil and Ipflufenoquin in the preparation is 30-60 mass%.

Specifically, the total content of imazalil and Ipflufenoquin in the preparation is 30 mass%, 40 mass%, 50 mass%, or 60 mass%.

In some embodiments, the above formulation may further comprise at least one of the following additional technical features:

the compositions and/or formulations comprising imazalil and Ipflufenoquin provided by one or more embodiments of the present invention may be used as such or in their formulated form or use forms prepared therefrom according to their respective physical and/or chemical properties, e.g., aerosols, capsule suspensions, cold atomized concentrates, hot atomized concentrates, particles encapsulated with capsules, fine particles, flowable concentrates for treating seeds, ready to use solutions, sprayable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, large particles, microparticles, oil dispersible powders, oil soluble flowable concentrates, oil soluble liquids, foams, pastes, pesticide coated seeds, suspension concentrates, suspoemulsions concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water soluble particles or tablets, water soluble granules or tablets, Water-soluble powders for the treatment of seeds, wettable powders 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. Preferred formulations include powders, wettable powders, microcapsules, water dispersible granules, aqueous solutions, suspensions, emulsifiable concentrates, microemulsions, aqueous emulsions, ultra-low volume sprays, seed coatings and/or smoke formulations.

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

Wettable Powders (WP) are mixtures of the compositions in a certain proportion with suitable surfactants and inert substances (kaolin powders). 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 an anionic or nonionic surfactant (dispersant, wetting agent).

The Microcapsule (MC) is prepared by coating pharmaceutically active components 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) means a mixture of the composition in a certain proportion with a suitable surfactant and an inert substance (kaolin powder). Pulverizing with air flow to make the fineness of powder meet the requirement, mixing with a double helix mixer and a colter mixer for several times to make the product mix uniformly, and granulating with conventional method such as fluidized bed granulation, spray granulation, and disc granulation.

Granules (GR) are mixtures 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 to coagulate a powder while keeping the powder in a fluid 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 aqueous Agent (AS) is a liquid prepared by directly using water by utilizing the characteristic that some raw medicines can be dissolved in the water without decomposition.

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) are 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 pesticide formulation in which a water-insoluble raw drug liquid or a solution obtained by dissolving a raw drug in a water-insoluble organic solvent is dispersed in water. The aqueous emulsion is a preparation prepared by dispersing a liquid pesticide raw pesticide prepared by mixing with an organic solvent into water in small drops of 0.5-1.5 mu m, and the appearance of the aqueous emulsion is milky white milk-like liquid.

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

The seed coating agent (SD) is prepared by grinding and mixing pharmacodynamic active components and an auxiliary agent, and can be coated on the surface of seeds directly or after being 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 active components with combustible substances, etc. and burns them to gasify the agricultural chemicals and condense them into smoke particles or directly disperse them 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. Methods of preparation of various formulations, including but in no way limited to those described herein.

The above-mentioned formulations can be prepared in a manner known per se, 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), dispersants and/or binders or fixatives, preservatives, dyes and pigments, defoamers, inorganic and organic thickeners, hydrophobicizers and, if appropriate, siccatives and UV stabilizers, gibberellins and also water and other processing auxiliaries. 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.

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.

The invention provides some preferable preparation compositions, which are as follows:

preferably, when the formulation is a suspension concentrate, the adjuvant comprises at least one of water, a dispersing agent, a wetting agent, a defoaming agent, a thickening agent, a stabilizer, an anti-freezing agent, and a preservative;

the dispersant preferably comprises at least one of non-alkyl phenols and polycarboxylates, preferably TERSPERSE 4894 in combination with GY-D800, preferably in a total amount of 2 to 6 mass% in the formulation;

the wetting agent is preferably GY-WS03, and the total content in the preparation is preferably 3-5 mass%;

the defoaming agent is preferably organic silicon, and the total content of the defoaming agent in the preparation is preferably 0.5-1.5 mass%;

the thickening agent is preferably xanthan gum, and the total content of the thickening agent in the preparation is preferably 0.1-0.3 mass%;

the stabilizer is preferably magnesium aluminum silicate, and the total content of the stabilizer in the preparation is preferably 0.2-0.4 mass%;

the antifreezing agent is preferably propylene glycol, and the total content of the antifreezing agent in the preparation is preferably 4-5 mass%;

the preservative is preferably sodium benzoate, and the total content in the preparation is preferably 0.05-0.15% by mass.

Preferably, when the preparation is missible oil, the auxiliary agent comprises a solvent and an emulsifier;

the solvent is preferably mineral spirit 200 #;

the emulsifier is preferably at least one of anionic and nonionic compound emulsifiers, and the total content in the preparation is preferably 5-15% by mass.

Preferably, when the preparation is a water dispersible granule, the auxiliary agent comprises at least one of a dispersing agent, a carrier, an antifoaming agent, a disintegrating agent and a stabilizing agent;

the dispersing agent is preferably at least one of lignin and ethylene oxide and propylene oxide block copolymer, preferably the combination of the lignin and the ethylene oxide and propylene oxide block copolymer, and the total content of the dispersing agent in the preparation is preferably 7-10 mass%;

the carrier is preferably kaolin;

the defoaming agent is preferably organic silicon, and the total content of the defoaming agent in the preparation is preferably 0.1-0.3 mass%;

the disintegrant is preferably at least one of ammonium sulfate and organic bentonite, preferably the combination of the ammonium sulfate and the organic bentonite, and the total content of the disintegrant in the preparation is preferably 4-6 mass%;

the stabilizer is preferably magnesium aluminum silicate, and the total content of the stabilizer in the preparation is preferably 0.3-0.6 mass%.

Preferably, when the formulation is a wettable powder, the adjuvant includes at least one of a dispersant, a disintegrant, a stabilizer, a defoamer, and a carrier;

the dispersant preferably comprises at least one of lignin and a naphthalene sulfonate polycondensate, preferably a combination of the two, and the total content in the preparation is preferably 8-12 mass%;

the stabilizer is preferably magnesium aluminum silicate, and the total content of the stabilizer in the preparation is preferably 0.3-0.6 mass%;

the defoaming agent is preferably organic silicone, and the total content of the defoaming agent in the preparation is preferably 0.2-0.4 mass%;

the disintegrant is preferably ammonium sulfate, and the total content of the disintegrant in the preparation is preferably 3-5% by mass;

the carrier is preferably kaolin.

Preferably, when the preparation is an aqueous emulsion, the auxiliary agents comprise an organic solvent, an antifreezing agent, an emulsifier, a stabilizer, a defoaming agent and water;

the organic solvent preferably comprises at least one of cyclohexanone and xylene, preferably the mixture of cyclohexanone and xylene, and the total content in the preparation is preferably 15-20 mass%;

the antifreezing agent is preferably ethylene glycol, and the total content of the antifreezing agent in the preparation is preferably 3-5 mass%;

the emulsifier preferably comprises at least one of castor oil polyoxyethylene ether and TERMUL2507, and the total content of the emulsifier in the preparation is preferably 5-7 mass%;

the stabilizer is preferably magnesium aluminum silicate, and the total content of the stabilizer in the preparation is preferably 0.1-0.3 mass%;

the defoaming agent is preferably silicone, and the total content in the preparation is preferably 0.05-0.15 mass%.

The above preferred formulation type composition can improve physicochemical properties of the agent, such as stability, uniformity, quick-acting property and/or sustained-release property, and can also improve control effect.

In another aspect, the invention provides the use of a composition according to the invention and/or a formulation according to the invention for controlling plant diseases caused by fungi.

Preferably, the plant diseases comprise grape anthracnose, cucumber gray mold, wheat scab, rice sheath blight, cucumber powdery mildew, pear scab, melon leaf spot and/or cucumber target spot.

Preferably, the grape anthracnose (glomerillaricingula) is caused by anthrax. The composition and/or the preparation show more remarkable synergistic effect on preventing and treating diseases caused by the anthrax.

In still another aspect, the present invention provides a method for controlling plant diseases, comprising: an effective amount of a composition according to the invention and/or a formulation according to the invention is applied to the plants and/or plant parts to be treated.

Preferably, the plant comprises a cereal crop, a melon, a fruit and/or a vegetable.

More preferably, the plant comprises grape, cucumber, wheat, rice, pear, melon, corn, soybean, cotton, rape, sugar beet, sugar cane and/or oat.

Further, the present invention provides a method for controlling plant diseases, which comprises applying the effective ingredients of Iflufenoquin and imazalil simultaneously, or separately, or sequentially to the plant or plant part to be treated.

The simultaneous application can be directly applied after uniformly mixing the effective components of the Ipfenoquin and the imazalil, or can be prepared into a preparation for application after uniformly mixing the Ipfenoquin and the imazalil.

The separate application can be realized by respectively applying the effective components of the Ipflufenoquin and the imazalil, or respectively applying the Ipflufenoquin and the imazalil after being prepared into preparations.

The sequential administration may be carried out by sequentially administering the active ingredients of Iflufenoquin and imazalil, or by sequentially administering Iflufenoquin and imazalil each in the form of a preparation. When the administration is performed sequentially, Ipflufenoquin (active ingredient or preparation) may be administered first and then imazalil (active ingredient or preparation), or Ipflufenoquin (active ingredient or preparation) may be administered first and then.

In practice, the compositions and/or formulations of the present invention may be used to treat all plants and/or plant parts. 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 breeding 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, flowers and roots, for example leaves, needles, stems, branches, flowers, fruit bodies, fruits and seeds as well as 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.

In the present invention, the term "effective amount" means the total amount of each active ingredient in an amount sufficient to exhibit a desired controlling effect. 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.

In the present invention, the terms "comprising", "including" or "containing" are open-ended expressions, i.e. include what is indicated by the present invention, but do not exclude other aspects.

In the present invention, "prevention" means prevention and/or treatment.

The compound imazalil or Ipflufenoquin having at least one basic center can form acid addition salts with acids, for example, strong inorganic 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). Imazalil or Ipflufenoquin having at least one acidic group can form a salt with a base, the salt being a metal saltFor example alkali metal salts or alkaline earth metal salts, such as sodium, potassium or magnesium salts; 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). In addition, the corresponding internal salts may optionally be formed. In the present invention, an agrochemically advantageous salt may be selected. In view of the close relationship between imazalil and Ipflufenoquin in their free form and their salt forms, it is to be understood that any reference to imazalil or Ipflufenoquin or salts thereof in this invention includes the corresponding salts or imazalil and Ipflufenoquin, respectively, where advantageous and appropriate.

If, in the context of the present invention, imazalil or ifluorequiquin exist in stereoisomeric, optically isomeric or tautomeric forms, it is to be understood that, where applicable, such compounds also include the corresponding isomeric forms, even if not explicitly mentioned in each case.

In the treatment of plants and/or plant parts with the compositions and/or preparations provided by the invention, the treatment 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 by treating dry seeds with a powder, by treating the seeds with a solution, by treating the slurry with a water-soluble powder by encrusting, by coating one or more coats or the like, and also by applying the compositions and/or preparations to the soil.

The invention also provides a method for treating seeds. The compositions and/or formulations of the present invention may be administered 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 seeds 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 solutions, emulsions, suspensions, powders, foams, slurries or other coating materials for seeds, and ULV formulations.

In addition to the synergistic bactericidal activity, the compositions and/or formulations of the present invention comprising imazalil and Ipflufenoquin have other surprising properties that can bring about effects beyond those actually expected, and in a broad sense, these properties can also be referred to as synergy. For example: reduced application rates, broader spectrum of activity, broader spectrum of kill, higher quick-acting properties, longer duration, increased activity, increased tolerance to high or low temperatures, increased tolerance to drought and/or water and/or soil salt content, better plant growth, easier harvesting, earlier ripening, higher harvest yields, larger fruits, more developed root systems, higher plant height, greener leaf color, larger leaf area, higher flowering performance, stronger shoots, less seed demand, lower toxicity in cereal crops, better compatibility with cereal crops, higher quality and/or higher nutritional value of harvested products, higher sugar concentration in the fruits, better storage stability and/or processability of harvested products; more importantly, the composition can play a role in synergy after being combined in a proper proportion; meanwhile, the generation of drug resistance can be delayed, the safety of crops is improved, the drug cost is reduced and the labor force is saved by compounding the two pesticides.

In summary, compared with the prior art, the invention achieves the following technical effects:

(1) the imazalil and the Iflufenoquin are combined to play a role in synergy, and have certain quick-acting property and long-acting property;

(2) the generation of drug resistance is delayed, and the safety of crops is improved;

(3) the dosage is reduced, and the cost and labor consumption are reduced;

(4) the bactericidal spectrum is expanded.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. In the following examples, the Ipflufenoquin technical material is self-made, and the preparation method refers to WO2011081174A1 example; imazalil is purchased from Zhejiang Hebei science and technology Co., Ltd, and in comparative example 2, 20% imazalil aqueous emulsion is purchased from Jiangxi Heyi chemical industry Co., Ltd. The rest of the reagents or instruments used are not indicated by manufacturers, and are all conventional products which can be prepared by the methods described in the prior art or obtained by commercial purchase.

Indoor bioassay test

Measuring the inhibition effect of different agents on the growth of grape anthracnose (glomerillaricingula) by adopting a hypha growth rate method indoors, and calculating the EC of each agent on pathogenic bacteria₅₀The value is obtained.

Activated bacterial strain

Selecting strains (purchased from China agricultural microbial culture Collection center, ACCC36264), placing the strains in the middle of a Potato Dextrose Agar (PDA) culture medium, placing the strains in an incubator at 26 ℃ for culturing for 2d, then selecting strains from cultured colonies, placing the strains in the middle of a new PDA culture medium, and placing the strains in the incubator at 26 ℃ for culturing for 2 d.

Weighing and preparing of samples

Weighing a certain amount of single dose or a certain proportion of the composition (shown in table 1), dissolving with a solvent of dimethyl sulfoxide, adding sterile water containing 0.1% Tween 80, mixing uniformly to prepare a solution with a certain concentration, and diluting by a half dilution method to 5mL of solutions with concentration gradients of 2mg/L, 1mg/L, 0.5mg/L, 0.25mg/L, 0.125mg/L and 0.0625mg/L respectively for later use.

Plate addition method

Preparing a toxic plate by adopting the compound and a culture medium: in a clean bench, 5mL of the sterilized compound solution was added to 45mL of PDA medium (cooled to 45-50 ℃ C.) (sterilization mode: UV sterilization), mixed well, poured onto a plate (diameter 90mm), cooled, and 3 plates were repeated. PDA medium with the addition of an equal amount of sterile water containing the same solvent emulsifier instead of compound solution served as blank.

The inoculated pellet (diameter 6mm) was picked and placed upside down in the center of the plate and incubated in an incubator at 26 ℃ for 2 days (incubation time should be determined according to growth conditions, typically when the diameter of the colony in the blank grows to 70-80 mm). The colony diameter was measured by the cross method.

Colony spread diameter (mm) ═ average diameter of colony (mm) -6(mm)

The biometric data values are obtained by looking up a table based on the relative inhibition rates. And (3) taking the concentration logarithm as an abscissa, and converting the inhibition percentage into a biological probability value according to a biological statistic probability value conversion table as an ordinate to draw a toxicity regression equation. The mass concentration when the value of the several degrees is 5 is obtained by the equation and is the EC₅₀(MillotM,Girardot M,Dutreix L,et al..Antifungaland anti-biofilm activities ofacetone lichen extracts against Candida albicans.[J].Molecules,2017,22(4):651.)。

And (3) calculating the co-toxicity coefficient (CTC) of the mixture by adopting a co-toxicity coefficient calculation method of the 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 agent virulence index (EC of standard agent)₅₀A certain single agent EC₅₀)×100

Theoretical virulence index (TTI) ═ A virulence index of single agent, x proportion of single agent in mixed agent + B virulence index, x proportion of single agent in mixed agent

Measured virulence index (ATI) ═ EC (standard single dose)₅₀EC of value/blend₅₀Value) × 100

Co-toxicity coefficient (CTC) ═ (measured/theoretical virulence index) × 100

When the CTC is more than 120, the mixture has synergistic effect (namely, the addition is obviously improved compared with the simple addition of single dose), when the CTC is less than 80, the antagonism is realized, and the addition effect of the CTC is realized between 80 and 120.

Table 1: determination result of co-toxicity coefficient of grape anthracnose caused by different ratios (mass ratio) of imazalil and Iflufenoquin

And (4) conclusion: as can be seen from the table 1, the imazalil and the Iflufenoquin are taken as effective components, and when the imazalil and the Iflufenoquin are compounded according to different mass ratios, the effect of preventing and treating the grape anthracnose is remarkable. When the mass ratio of imazalil to Ipfenoquin is 1-3: 5-1, the co-toxicity coefficient is greater than 120, and the synergistic effect is obvious; when the mass ratio of imazalil to Ipfenoquin is 1-2: 3-1, the co-toxicity coefficient is more than 150, and the synergistic effect is obvious. Therefore, the composition of imazalil and Iflufenoquin can be an ideal medicament for preventing and treating grape anthracnose.

Example 130% suspension of Iflufenoquin and imazalil

1. Preparation of comminuted slurry

1.8g of non-alkylphenol high-efficiency dispersant (trade name: TERSPERSE 4894, Huntsman), 1.2g of high molecular compound dispersant with a comb-shaped structure (trade name: GY-800, Beijing Guangyuan Yinong), 4g of wetting agent (GY-WS 03, Beijing Guangyuan Yinong) and 1g of high-efficiency organic silicon defoamer (New left soil Material Co., Ltd., Hangzhou) are dispersed in 42g of water, 15g of Ipfufenoquin raw drug and 15g of imazalil raw drug are dispersed in the water, and the water is used

Glass beads were wet-pulverized for 2.0 hours by a sand mill to obtain 80g of a pulverized slurry.

2. Preparation of Dispersion Medium

0.2g of xanthan gum, 0.3g of magnesium aluminum silicate, 4.2g of 1, 2-propanediol and 0.1g of sodium benzoate were dispersed in 15.2g of water to obtain 20g of a dispersion medium.

3. Preparation of aqueous suspension pesticide composition

80g of the ground slurry and 20g of a dispersion medium were mixed to obtain 100g of an aqueous suspension-type agricultural chemical composition, and the aqueous suspension-type agricultural chemical composition was cut at a high speed (4000 rpm) for 30 minutes by a high-speed dispersion machine to obtain a suspension concentrate containing 30% by mass of active ingredients (Ipfufenoquin and imazalil).

Example 240% emulsifiable concentrate of Iflufenoquin and imazalil

10g of Iflufenoquin technical, 30g of imazalil technical, 5g of anion and nonionic compound emulsifier (trade name: YUS-2010CX, bamboo oil) and 5g of anion and nonionic compound emulsifier (trade name: YUS-2011CX, bamboo oil) are added to 100g of solvent oil (Yangzhou Tianda chemical Co., Ltd.), cut at high speed of a high-speed dispersion machine for 10 minutes (4000 revolutions per minute) and ultrasonically heated to prepare the missible oil preparation with the mass content of effective components (Iflufenoquin and imazalil) of 40%.

Example 350% Iflufenoquin and imazalil Water dispersible granules

40g of Iflufenoquin raw drug, 10g of imazalil raw drug, 5g of EOPO block copolymer (trade name: Antraox B/848, Rhodia), 3g of lignin (trade name: WG4, Shanghai Jie's chemical industry), 5g of ammonium sulfate, 0.5g of magnesium aluminum silicate, 0.2g of organic bentonite and 0.2g of high-efficiency organic silicon defoamer (New left soil material Co., Ltd. of Hangzhou), adding kaolin to 100g, pre-crushing and uniformly mixing, crushing by air flow to obtain the required particle size, and granulating by a rotary granulator to obtain the water dispersible granule with the mass content of effective components (Iflufenoquin and imazalil) of 50%.

Example 460% Iflufenoquin and imazalil Water dispersible granules

50g of Iflufenoquin raw drug, 10g of imazalil raw drug, 5g of EOPO block copolymer (trade name: Antraox B/848, Rhodia), 3g of lignin (trade name: WG4, Shanghai Jie's chemical industry), 5g of ammonium sulfate, 0.5g of magnesium aluminum silicate, 0.2g of organic bentonite and 0.2g of high-efficiency organic silicon defoamer (New left soil material Co., Ltd. of Hangzhou), adding kaolin to 100g, pre-crushing and uniformly mixing, crushing by air flow to obtain the required particle size, and granulating by a rotary granulator to obtain the water dispersible granule with the mass content of effective components (Iflufenoquin and imazalil) of 60%.

EXAMPLE 560% wettable powder of Iflufenoquin and imazalil

15g of Ipflufenoquin raw drug, 45g of imazalil raw drug, 6g of naphthalenesulfonate polycondensate (trade name: Morwet D-425, Acksonobel), 4g of lignin (trade name: WG4, Shanghai Jie's chemical industry), 4g of ammonium sulfate, 0.5g of magnesium aluminum silicate and 0.3g of organic silicone (trade name: DOW CORNING ANTIFOAM C EMULSION, DOW CORNING) are mixed, kaolin is added to 100g, the mixture is pre-crushed and uniformly mixed, and then airflow crushing is carried out to obtain wettable powder with the mass content of active ingredients (Ipflufenoquin and imazalil) of 60%.

Example 630% aqueous emulsion of Iflufenoquin and imazalil

1. Preparation of the oil phase

Adding 15g of Iflufenoquin technical material and 15g of imazalil technical material into a mixed solvent of 10g of cyclohexanone and 7g of xylene, uniformly mixing by ultrasonic waves, adding 2g of emulsifier (trade name: TERMUL2507, Huntsman) and 4g of castor oil polyoxyethylene ether (trade name: EMULPON CO-360, Acksonobel) and slowly stirring until the components are completely dissolved.

2. Preparation of aqueous phase

4g of ethylene glycol, 0.2g of magnesium aluminum silicate and 0.1g of high-efficiency organic silicon defoamer (Hangzhou left soil new material Co., Ltd.) are mixed, 42.7g of water is added and stirred uniformly.

3. Blending of pesticide composition aqueous emulsion

Slowly adding the water phase into the oil phase, continuously stirring until the water phase is completely added, and then shearing at high speed (4000 revolutions per minute) for 30 minutes in a high-speed dispersion machine to prepare the aqueous emulsion with the mass content of the effective components (Ipfufenoquin and imazalil) of 30 percent.

Comparative example 130% Ipfufenoquin Water dispersible granule

30g of Ipfenoquin raw pesticide, 6g of naphthalenesulfonate polycondensate (trade name: Morwet D-425, Acksonobel), 4g of lignin (trade name: WG4, Shanghai Jie chemical industry), 4g of ammonium sulfate, 0.5g of magnesium aluminum silicate and 0.3g of organic silicone (trade name: DOW CORNING ANTIFOAM C EMULSION, DOW CORNING) are mixed, 100g of kaolin is added, the mixture is pre-crushed and mixed uniformly, and then airflow crushing is carried out to obtain the water dispersible granule with the mass content of the active ingredient (Ipfenoquin) of 30%.

Comparative example 2

Outsourcing of commercial drugs: 20% imazalil emulsion in water

Comparative example 3

100g of blank clear water.

Test of field drug effect

And (3) test treatment: the test agents of examples 1 to 6 were each set with three effective ingredient amounts according to the test design of the test agents in Table 2. The control agents were control 1, control 2 and control 3, respectively.

Table 2: test design of test agent

Setting a cell: each cell area is 66.7m²；

The application method comprises the following steps: applying the pesticide at the early growth stage of grape anthracnose, and spraying on leaf surfaces, wherein the spraying amount is mainly no water drops;

the application times are as follows: and 3 times, if the rainfall is expected to be in strong wind weather or within 1 hour, the pesticide is not applied. 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 3 rd application.

Investigation time and number of times: base number was investigated 1 day after application, and grape growth was investigated 7 days, 14 days, and 21 days after application.

The investigation method comprises the following steps: according to the growing condition of grape anthracnose, taking a grape as a unit, sampling five points on the diagonal line of each cell, surveying 5 connected clusters at each point, and recording the total number of the plants and the growing condition, wherein the total number of the clusters is 25.

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

level 0: the whole plant is disease-free;

level 1: the fourth leaf and the leaf sheaths below the fourth leaf, wherein the leaf is diseased (the sword leaf is taken as the first leaf);

and 3, level: the third leaf and the leaf sheaths below the third leaf cause diseases;

and 5, stage: the second leaf and the leaf sheaths below the second leaf cause diseases;

and 7, stage: the scabies of the sword leaf and the leaf sheaths below the sword leaf are attacked;

and 9, stage: the whole plant is attacked and withered in advance.

And (3) calculating the drug effect:

the results are detailed in table 3.

Table 3: prevention effect of different medicaments on grape anthracnose

And (4) conclusion: as can be seen from the table 3, after the imazalil and the Ipfenoquin are compounded according to a certain proportion, the control effect on grape anthracnose is obviously better than that of a control medicament, and the two components are compounded according to a certain proportion, so that compared with the control medicament used alone, the control medicament can reach more than 80% after being used for 7 days, and the quick-acting property is improved; the control effect is still over 80 percent in 21 days, the lasting period is prolonged, and the synergistic effect is realized. In addition, the composition of the embodiment of the invention is not found to have phytotoxicity on grapes in the application range, which indicates that the bactericidal composition of the invention is good in safety to crops.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. A composition comprising a pharmaceutically active ingredient;

the pharmacodynamic active components comprise imazalil and Iflufenoquin.

2. The composition according to claim 1, wherein the mass ratio of imazalil to Ipflufenoquin is 1-20: 20-1; preferably, the mass ratio of imazalil to Ipfenoquin is 1-5: 5-1; more preferably, the mass ratio of imazalil to Ipfenoquin is 1-3: 5-1.

3. The composition according to any one of claims 1-2, wherein the mass ratio of imazalil to Ipflufenoquin is 1-2: 3-1.

4. A composition according to any one of claims 1 to 3, wherein imazalil and Ipflufenoquin are present in the composition in a total amount of 20 to 80% by mass.

5. The composition according to any one of claims 1 to 4, wherein imazalil and Ipfufenoquin are present in the composition in a total amount of 30 to 60% by mass.

6. The composition according to any one of claims 1 to 5, wherein the composition further comprises: pesticidally acceptable adjuvants including wetting agents, dispersing agents, emulsifiers, thickeners, disintegrants, antifreeze agents, antifoam agents, solvents, preservatives, stabilizers, synergists and/or carriers.

7. A formulation prepared from the composition of any one of claims 1-6.

8. The formulation of claim 7, wherein the formulation is in the form of a powder, a wettable powder, a microcapsule, a water dispersible granule, a granule, an aqueous solution, a suspension, an emulsifiable concentrate, a microemulsion, an aqueous emulsion, an ultra-low volume spray, a seed coating, and/or a smoke formulation.

9. Use of a composition according to any one of claims 1 to 6 or a formulation according to any one of claims 7 to 8 for controlling plant diseases caused by fungi;

preferably, the plant diseases comprise grape anthracnose, cucumber gray mold, wheat scab, rice sheath blight, cucumber powdery mildew, pear scab, melon leaf spot and/or cucumber target spot.

10. A method for controlling plant diseases, characterized in that an effective amount of the composition according to any one of claims 1 to 6 or the formulation according to any one of claims 7 to 8 is applied to the plant or plant part to be treated;

preferably, the plant comprises a cereal crop, a melon, a fruit and/or a vegetable.