WO2021143307A1 - 一种含四氟醚唑和醚菌酯的杀菌颗粒组合物及其制备方法 - Google Patents

一种含四氟醚唑和醚菌酯的杀菌颗粒组合物及其制备方法 Download PDF

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WO2021143307A1
WO2021143307A1 PCT/CN2020/126965 CN2020126965W WO2021143307A1 WO 2021143307 A1 WO2021143307 A1 WO 2021143307A1 CN 2020126965 W CN2020126965 W CN 2020126965W WO 2021143307 A1 WO2021143307 A1 WO 2021143307A1
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Prior art keywords
kresoxim
methyl
active substance
tetraflurane
granule composition
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PCT/CN2020/126965
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English (en)
French (fr)
Inventor
罗昌炎
布里斯托•詹姆斯•T
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江苏龙灯化学有限公司
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Publication of WO2021143307A1 publication Critical patent/WO2021143307A1/zh

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A01N25/14—Powders or granules wettable
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides

Definitions

  • the invention relates to the technical field of pesticide preparations, in particular to a bactericidal granule composition containing tetrafluraneconazole and kresoxim-methyl and a preparation method thereof.
  • tetraflurane 2-(2,4-dichlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propyl 1,1,2,2-tetrafluoro Ethyl ether
  • the pure product is a colorless viscous liquid with a solubility of 156.6mg/L in water. It belongs to the second generation of triazole bactericides.
  • the molecular structure contains fluorine.
  • the bactericidal activity is 2-3 times that of the first generation.
  • the bactericidal spectrum is broad, highly effective, and lasts for 4-6 weeks. It has protective and therapeutic effects. And has very good internal absorption and conduction performance.
  • the chemical name of Kresoxim-methyl is (E)-2-methoxyimino-2-[2-(o-methylphenoxymethyl)phenyl]methyl acetate.
  • the pure product is white crystal with aromatic odor. Solid, melting point 101.6-102.5°C, solubility in water 2mg/L. It has good activity against various diseases caused by deuteromycetes, ascomycetes, basidiomycetes, oomycetes and other fungi, such as grape powdery mildew, wheat rust, potato blight, pumpkin blight, rice blast, etc., especially against diseases such as grape powdery mildew, wheat rust, potato blight, pumpkin blight, and rice blast. Strawberry powdery mildew, melon powdery mildew, cucumber powdery mildew, and pear scab are effective.
  • CN101700032A protects a bactericidal composition, which contains a combination of tetrafluraneconazole and the bactericidal active substance B-Kresoxim-methyl to prevent and control a variety of plant diseases caused by pathogenic fungi, to achieve synergy, concurrent treatment, overcoming or delaying the development of pathogen resistance And the purpose of reducing the cost of medication.
  • emulsifiable concentrates and water emulsions need to use a large amount of organic solvents, which have a great impact on the environment and are gradually eliminated.
  • Suspoemulsions are usually used to prepare the preferred formulations of liquid pesticides and solid pesticides.
  • the liquid tetraflurane pesticide to the solid Kresoxim-methyl suspoemulsion in the preparation of the tetraflurane and Kresoxim-methyl suspoemulsion Pesticides have a certain dissolving effect, which leads to the occurrence of Austenite maturation during long-term storage, which leads to the growth of suspended particles, agglomeration and unstable formulations.
  • the oil suspension concentrate also causes product instability due to the slight dissolution of tetraflurane to kresoxim-methyl, and the active components are easy to crystallize out of the formulation.
  • the microcapsule dosage form can also solve the problem of mixing liquid pesticides and solid pesticides to a certain extent, due to the high processing cost and many technical difficulties, it is difficult to prepare qualified microcapsules, and it is not ideal to prepare tetraflurane and ether.
  • the dosage form of strobilurin is also solve the problem of mixing liquid pesticides and solid pesticides to a certain extent, due to the high processing cost and many technical difficulties, it is difficult to prepare qualified microcapsules, and it is not ideal to prepare tetraflurane and ether.
  • the object of the present invention is to provide a stable antiseptic granule composition containing tetrafluoroconazole and Kresoxim-methyl and a preparation method thereof.
  • the antiseptic granule composition is physicochemically stable and has Good storage and redispersibility, and it is also stable in the conventional test of accelerated stability, which represents two-year storage stability.
  • the present invention adopts the following technical solutions:
  • the present invention provides a stable bactericidal granule composition containing tetrafluoroconazole and kresoxim-methyl, which contains the following components:
  • the liquid tetraflurane active substance is reduced under the action of the viscosity reducer.
  • the powders containing solid particles of Kresoxim-methyl are uniformly adsorbed, so that the active ingredients of tetrafluraneconazole and Kresoxim-methyl contained in the granulated particles can maintain stability for a long time, and have good storage and redispersion. performance.
  • viscosity reducer in the present invention refers to a solvent used to reduce the viscosity of the tetraflurane azole active substance that is liquid at room temperature, so as to facilitate the adsorption of the carrier or the powder, so that the liquid tetraflurane azole active agent is more uniform Distributed in the granulated granules to ensure the consistency of the active ingredients of tetraflurane and kresoxim-methyl.
  • the viscosity reducing agent includes aromatic hydrocarbon solvents, such as benzene, toluene, xylene, mixed trimethylbenzene, solvesso 100, solvesso 200, solvesso 150, etc.; alcohols, linear or branched fatty alcohols, such as ethanol, methanol, propanol, Butanol, hexanol, octanol, cyclohexanol, and may also include polyols, such as propylene glycol, glycerol, polyethylene glycol, polyglycerol, etc.; alkyl ketones, linear, branched or cyclic ketones Etc., such as acetone, methyl ethyl ketone, pentanone, cyclohexanone, etc.; vegetable oils, such as soybean oil, corn oil, sesame oil, castor oil, peanut oil, sunflower oil, etc.; vegetable oil esters, such as methyl oleate, palmitic
  • the emulsifier is used as an emulsifying liquid when the particles are diluted with water to make the tetraflurane azole active substance evenly distributed in the water-diluted liquid in the form of fine oil droplets.
  • Suitable emulsifiers can be selected from any substances used for this purpose in agrochemical formulations, such as reactants of alkylphenols with ethylene oxide and/or propylene oxide, ethoxylated nonylphenols, castor Sesame oil ethoxylates, mixtures of polyalkoxylated alcohols (Atlox 4894), alkyl calcium salts, alkyl benzene sulfonate calcium salts, sorbitan derivatives or polyethylene oxide-sorbitan fatty acids ester.
  • the optional other functional surfactants are suitable functional surfactants, which can be selected from surfactants commonly used for this purpose in agrochemical formulations, such as dispersants, wetting agents, defoamers , PH adjusters, inert fillers, etc.
  • Suitable dispersants are fatty alcohol ethoxylates, fatty alcohol alkoxylates, EO/PO block copolymers, sulfonic acids of ethoxylated alcohols, sulfosuccinates, fatty acid methyl taurates, Tristyrylphenol ethoxylate and alkoxylate, tri-sec-butylphenol ethoxylate, sulfated cresol-formaldehyde condensate, sulfated condensate of naphthalene and alkylnaphthalene, lignosulfonate , Ethoxylated fatty alcohols, phosphate esters of tristyryl phenol and tri-sec-butyl phenol, as well as ethoxylated fatty alcohols, polyacrylic acid, polymethacrylic acid and acrylate copolymers, tristyryl phenol and One or more of ether sulfate of tri-sec-butylphenol and polymer
  • Suitable wetting agents are preferably anionic wetting agents, such as alkali metal, alkaline earth metal or ammonium salts of anionic wetting agents.
  • Suitable wetting agents are naphthalene sulfonates (e.g. disodium methylene dinaphthalene sulfonate, sodium naphthalenesulfonate-formaldehyde condensate, ammonium naphthalenesulfonate-formaldehyde condensate), alkyl naphthalene sulfonates (e.g.
  • alkyl naphthalene sulfonate benzene sulfonate, alkyl benzene sulfonate (such as sodium cumene sulfonate, potassium cumene sulfonate, sodium xylene sulfonate, sodium toluene sulfonate), alkane sulfonate ( Such as sodium tetradecene sulfonate), ⁇ -olefin sulfonate (such as sodium ⁇ -olefin sulfonate), sulfosuccinate (such as sodium dioctyl sulfosuccinate), alkyl phosphate (such as laurel Base myristyl phosphate), alkyl sulfates (such as sodium lauryl sulfate, sodium cetyl stearyl sulfate, sodium cetyl sulfate, sodium myristyl sulfate, sodium
  • Suitable defoamers are silicone, low-carbon alcohols and fatty acid salt defoamers.
  • Suitable pH regulators are phosphoric acid, acetic acid, citric acid, sodium carbonate, sodium bicarbonate, potassium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate and other substances that can provide proton acid or proton base.
  • Suitable inert carriers are selected from one or more of sodium sulfate, kaolin, calcined kaolin, talc, white carbon black, montmorillonite, diatomaceous earth, potassium phosphate and the like.
  • the adsorption carrier is selected from any one or a combination of at least two of white carbon black, diatomaceous earth, attapulgite, molecular sieve, starch, cellulose, calcium silicate, montmorillonite or bentonite.
  • the bactericidal granule composition of the present invention contains the following components in weight percentage:
  • the tetraflurane azole active substance as component (a) has a weight percentage of 1-20%, such as 1%, 2%, 5%, 8%, 10%. %, 12.2%, 14.5%, 15%, 17.8%, 19% or 20%, preferably 2-15%.
  • the active substance of Kresoxim-methyl as the component (b) in the germicidal granule composition has a weight percentage of 1-50%, for example, 1%, 2%, 5%, 10%, 15.5% , 19.8%, 25%, 28.8%, 30%, 35%, 38.1%, 40%, 44%, 48%, 49% or 50%, preferably 5-30%.
  • the viscosity reducing agent as component (c) has a weight percentage of 0.5-15%, such as 0.5%, 0.8%, 1%, 2%, 3.6%, 5 %, 7%, 9%, 10%, 12%, 12.9%, 14% or 15%, preferably 1-10%.
  • the emulsifier as the component (d) in the germicidal granule composition has a weight percentage of 1-15%, such as 1%, 2%, 4%, 5.5%, 7%, 9% , 10%, 12.3%, 13%, 14% or 15%, preferably 2-10%.
  • the weight percentage of optional other functional surfactants as component (e) in the antimicrobial granule composition is 1-15%, such as 1%, 2%, 4%, 5.5% , 6%, 7%, 9%, 10%, 12.3%, 13%, 14% or 15%, preferably 2-10%.
  • the weight percentage is 20-80%, such as 20%, 25%, 28%, 30%, 35%, 40% , 45.5%, 50%, 53.6%, 58.9%, 62%, 65%, 68%, 70%, 72.2%, 75.4%, 77%, 79% or 80%, preferably 30-70%.
  • the bactericidal granule composition of the present invention consists of the following components:
  • Viscosity reducing agent its weight percentage is 1-10%
  • Emulsifier its weight percentage is 2-10%;
  • the present invention also provides a preparation method of the antibacterial granule composition, which comprises the following steps:
  • Step I Mix the components (a), (c) and (d) in any order, and stir to obtain a homogeneous oil phase.
  • Step II Mix the components (b), (e) and (f) in any order, and then pulverize them to obtain a powder with an average particle size of ⁇ 4 ⁇ m containing the kresoxim-methyl active substance;
  • Step III Mixing the materials of Step I and Step II, granulating and forming to obtain a bactericidal granule composition containing tetraflurane and Kresoxim-methyl.
  • the preparation method provided in the present invention adopts the method of first preparing the tetrafluraneconazole active substance and the kresoxim-methyl active substance into a uniform oil phase and pulverized powder, that is, combining the tetrafluraneconazole active substance and the reduced Viscosity and emulsifier are formulated into a uniform oil phase, kresoxim-methyl active substance is mixed with functional surfactant and adsorption carrier and then pulverized to obtain powder with an average particle size ⁇ 4 ⁇ m, and then the oil phase is mixed with the powder. Granulation and molding.
  • the preparation method not only has simple processing technology and convenient operation, but also can obtain a granular composition of tetrafluraneconazole and kresoxim-methyl with a uniform content.
  • the product quality is stable for long-term storage, and the granules are not sticky or agglomerated, and have good fluidity.
  • the particle size D50 of the powder containing the kresoxim-methyl active substance in step II is less than or equal to 4 ⁇ m, such as 0.5 ⁇ m, 0.8 ⁇ m, 1 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 2.8 ⁇ m, 3 ⁇ m, 3.5 ⁇ m or 4 ⁇ m,
  • the preferred D50 is between 1.5 ⁇ m and 3 ⁇ m.
  • the materials of step I and step II are mixed so that the oil phase of step I is uniformly and completely absorbed into the powder of step II, and suitable granulation equipment is selected according to the properties of the mixed powder containing the oil phase. Pelletizing and molding. If necessary, appropriate amount of water can be added during the process to assist the pelletizing and molding.
  • Suitable methods for granulation and molding include agglomeration (granulation) methods, such as fluidized bed, plate, disc, high shear rate (also known as Schugi method), spray drying, etc., and paste extrusion .
  • granulation granulation methods
  • the particles prepared by these methods are usually classified by sieving to adjust the diameter and uniformity of the particles.
  • the "too large” and “fine powder” fractions removed by sieving in this process are often reprocessed in another preparation.
  • the stable preparation of the bactericidal granular composition containing tetrafluraneconazole and kresoxim-methyl prepared according to the present invention can be stored stably even if stored under high temperature or cold conditions, and no particle aggregation and inconvenient use have been found Quality issues. If it is diluted with water, the formulation can be transformed into a homogeneous spray liquid, and the nozzle is free from clogging caused by the incompatibility between the solid active ingredient of Kresoxim-methyl and the liquid active ingredient of Tetraflurane in the spray liquid.
  • the present invention technically solves the problem that the liquid tetraflurane azole active material has a dissolving effect on the solid kresoxim-methyl active material, and the two different properties of the active material are prepared into a physical and chemically stable preparation product, which is compared with the conventional preparation into an emulsifiable concentrate, Compared with water emulsions, it does not need to use a lot of organic solvents, is environmentally friendly, and has low environmental pressure; compared with the preparation of microcapsule suspensions, it has low cost, simple processing technology, low operation requirements, and is more suitable for actual production; compared with the preparation of oil suspensions , Water suspension, suspoemulsion, water dispersible granules and other formulations are more stable than other formulations, and these formulations can not be prepared into qualified products, more or less because liquid pesticides and solid pesticides cannot be processed together or because of liquid pesticides The dissolution of solid pesticides leads to unstable product quality, particle size growth, agglomeration and other
  • the present invention has at least the following beneficial effects:
  • the liquid tetraflurane active matter is in the viscosity reducing agent.
  • the preparation method provided by the present invention is to first prepare the tetrafluraneconazole active substance and the kresoxim-methyl active substance into a homogeneous oil phase and pulverized powder, that is, to combine the tetrafluraneconazole active substance and the reduced Viscosity and emulsifier are formulated into a uniform oil phase, kresoxim-methyl active substance is mixed with functional surfactant and adsorption carrier and then pulverized to obtain powder with an average particle size ⁇ 4 ⁇ m, and then the oil phase is mixed with the powder.
  • Granulation molding has the advantages of simple processing technology and convenient operation, and makes the performance of the sterilizing granule composition more stable.
  • Tetraflurane+Kresoxim-methyl 2%+50% granules are composed of the following components by weight percentage:
  • Step I Mix tetraflurane, propylene glycol, and Tween 80 to obtain an oil phase;
  • Step II After mixing kresoxim-methyl, naphthalene sulfonate formaldehyde polycondensate, sodium dodecylbenzene sulfonate, solid defoamer, white carbon black and diatomaceous earth, pulverize with a jet mill to obtain an average particle size. Powder containing kresoxim-methyl with diameter ⁇ 4 ⁇ m;
  • Step III Add the oil phase of Step I to the powder of Step II under stirring, and after stirring until the adsorption is uniformly mixed, the extrusion granulation method is used for granulation and molding.
  • Tetraflurane + Kresoxim-methyl 20% + 5% granules are composed of the following components by weight percentage:
  • Step I Mix tetraflurane, methyl oleate and castor oil ethoxylate to obtain an oil phase;
  • Step II After mixing kresoxim-methyl, naphthalenesulfonate formaldehyde polycondensate, sodium dodecylbenzenesulfonate, solid defoaming agent and diatomaceous earth, pulverize with a jet mill to obtain an average particle size ⁇ 4 ⁇ m Powders containing kresoxim-methyl;
  • Step III Using a fluidized bed granulation method, spray the oil phase of step I into the powder of step II to complete the granulation and molding.
  • Tetraflurane+Kresoxim-methyl 10%+35% granules are composed of the following components by weight percentage:
  • Step I Mix tetraflurane, polyethylene glycol and calcium dodecylbenzene sulfonate to obtain an oil phase;
  • Step II After mixing the kresoxim-methyl, lignin sulfonate, fatty alcohol ethoxylate, solid defoamer and corn starch uniformly, pulverize with a jet mill to obtain the kresoxim-containing with an average particle size ⁇ 4 ⁇ m Powder
  • Step III Using spray granulation equipment, spray the oil phase of Step I into the powder of Step II to complete the granulation and molding.
  • Tetraflurane+Kresoxim-methyl 10%+25% granules are composed of the following components by weight percentage:
  • Step I Mix tetraflurane, soybean oil, and Tween 20 to obtain an oil phase;
  • Step II After mixing the kresoxim-methyl, polycarboxylate, octyl sulfonate succinate, solid defoaming agent, white carbon black and sodium sulfate, pulverize with a jet mill to obtain ether-containing ether with an average particle size of ⁇ 4 ⁇ m Strobilurin powder;
  • Step III Add the oil phase of Step I to the powder of Step II under stirring, and after stirring until the adsorption and mixing are uniform, use the extrusion granulation method to granulate and shape.
  • Tetraflurane+Kresoxim-methyl 2%+5% granules are composed of the following components by weight percentage:
  • Step I Mix and stir a mixture of tetraflurane, propylene glycol and polyalkoxylated alcohol to obtain an oil phase;
  • Step II After kresoxim-methyl, lignin sulfonate, sodium dodecylbenzene sulfonate, solid defoamer and diatomaceous earth are mixed uniformly, they are pulverized with a jet mill to obtain ether-containing ether with an average particle size of ⁇ 4 ⁇ m Strobilurin powder;
  • Step III Add the oil phase of step I to the powder of step II under stirring, stir until the adsorption and mixing are uniform, then use the extrusion granulation method to granulate and shape, and if necessary, add an appropriate amount during this process The water performs auxiliary mixing and granulation molding.
  • Tetraflurane+Kresoxim-methyl 15%+30% granules are composed of the following components by weight percentage:
  • Step 1 Mix tetraflurane, propylene glycol, and castor oil ethoxylate to obtain an oil phase;
  • Step II After kresoxim-methyl, naphthalene sulfonate formaldehyde condensation polymer, sodium dodecyl benzene sulfonate, solid defoamer and white carbon black are mixed uniformly, they are pulverized with a jet mill to obtain an average particle size ⁇ 4 ⁇ m Powders containing kresoxim-methyl;
  • Step III Using a fluidized bed granulation method, spray the oil phase of step I into the powder of step II to complete the granulation and molding.
  • Tetraflurane+Kresoxim-methyl 15%+30% granules are composed of the following components by weight percentage:
  • Step I Mix tetraflurane and castor oil ethoxylate to obtain an oil phase
  • Step II After kresoxim-methyl, naphthalene sulfonate formaldehyde polycondensate, sodium dodecylbenzene sulfonate, solid defoamer and white carbon black are mixed uniformly, they are pulverized with a jet mill to obtain a powder containing kresoxim-methyl material;
  • Step III Step I and Step II are mixed. Due to the excessive viscosity of the oil phase, mechanical mixing or spray mixing using a nozzle cannot be mixed uniformly, resulting in uneven granules content and failure.
  • Tetraflurane+Kresoxim-methyl 15%+30% water-dispersible granules are composed of the following components by weight percentage:
  • the preparation is carried out according to the conventional processing method of water-dispersible granules, and the processing fails due to the inability of jet pulverization due to the liquid original medicine.
  • Tetraflurane+Kresoxim-methyl 15%+30% oil suspension concentrate is composed of the following components by weight percentage:
  • tetraflurane+Kresoxim-methyl 15%+30% oil suspension can be prepared.
  • Tetraflurane+Kresoxim-methyl 10%+20% suspoemulsion is composed of the following components by weight percentage:
  • tetrafluraneconazole + kresoxim-methyl 10%+20% suspoemulsion can be prepared.
  • Tetraflurane+Kresoxim-methyl 15%+30% EC is composed of the following components by weight percentage:
  • tetraflurane + kresoxim-methyl 15%+30% emulsifiable concentrate can be prepared.
  • Tetraflurane+Kresoxim-methyl 15%+30% microcapsule suspension-suspending agent is composed of the following components by weight percentage:
  • microcapsule suspension-suspension agent tetraflurane+Kresoxim-methyl 15%+30% microcapsule suspension-suspension agent can be prepared.
  • the bactericidal granular composition containing tetrafluranconazole and kresoxim-methyl solves the problem of reducing the activity of liquid tetrafluranconazole and solid kresoxim-methyl. It is difficult to process the product into granular products, and the processing technology is simple, the operation is convenient, and the cost is low. It avoids the use of a large amount of organic solvents and is environmentally friendly.
  • the prepared product has good thermal storage stability, is stable when diluted with water, will not cause incompatibility due to the mutual influence of the liquid original drug and the solid original drug, and has stable physical and chemical quality.

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Abstract

提供了一种含四氟醚唑和醚菌酯的杀菌颗粒组合物，所述杀菌颗粒组合物含有以下组分：(a)四氟醚唑活性物；(b)醚菌酯活性物；(c)减粘剂；(d)乳化剂；(e)任选的其他表面活性剂；(f)吸附载体；其中减粘剂有效降低了液体四氟醚唑活性物的粘度，使四氟醚唑活性物均匀地分布在颗粒中；还提供了所述杀菌颗粒组合物的制备方法。所述的含四氟醚唑和醚菌酯的杀菌颗粒组合物，有效解决了液体的四氟醚唑活性物对固体颗粒醚菌酯活性物的影响，所制备的颗粒产品在加速稳定性测试中表现出较好的贮存稳定性，具有重要的颗粒产品应用价值。

Description

一种含四氟醚唑和醚菌酯的杀菌颗粒组合物及其制备方法 技术领域
本发明涉及农药制剂技术领域，尤其涉及一种含四氟醚唑和醚菌酯的杀菌颗粒组合物及其制备方法。
背景技术
四氟醚唑化学名称为2-(2，4-二氯苯基)-3-(1H-1，2，4-三唑-1-基)丙基1，1，2，2-四氟乙基醚，纯品为无色黏性液体，水中溶解度为156.6mg/L。属于第二代三唑类杀菌剂，分子结构中含氟，杀菌活性是第一代的2-3倍，杀菌谱广、高效、持效期长达4-6周，具有保护和治疗作用，并有很好的内吸传导性能。适宜作为谷类作物如小麦、大麦、燕麦、黑麦等，果实如香蕉、葡萄、梨、苹果等，蔬菜如瓜类，甜菜，观赏性植物等的杀菌剂。可以防治白粉菌属、柄锈菌属、喙孢属、核腔菌属和壳针孢属菌引起的病害如小麦白粉病、小麦散黑穗病、小麦锈病、小麦腥黑穗病、小麦颖枯病、大麦云纹病、大麦散黑穗病、大麦纹枯病、玉米丝黑穗病、高粱丝黑穗病、瓜果白粉病、香蕉叶斑病、苹果斑点落叶病、梨黑星病和葡萄白粉病等。既可茎叶处理，也可作种子处理使用。
醚菌酯化学名称为(E)-2-甲氧亚氨基-2-[2-(邻甲基苯氧基甲基)苯基]乙酸甲酯，纯品为白色具有芳香性气味的结晶状固体，熔点101.6-102.5℃，水中溶解度为2mg/L。对半知菌、子囊菌、担子菌、卵菌纲等真菌引起的多种病害具有很好的活性，如：葡萄白粉病、小麦锈病、马铃薯疫病、南瓜疫病、水稻稻瘟病等病害，特别对草莓白粉病、甜瓜白粉病、黄瓜白粉病、梨黑星病有效。
目前关于四氟醚唑与醚菌酯的杀菌组合物的专利也有报道。CN101700032A保护一种杀菌组合物，其含有四氟醚唑和杀菌活性物B醚菌酯的组合用以防治 由病原真菌引起的多种植物病害，达到增效、兼治、克服或延缓病菌抗性发展以及降低用药成本的目的。
尽管相关专利中都描述了四氟醚唑与醚菌酯复配组合增效的用途，但未从制剂加工技术角度真正解决四氟醚唑与醚菌酯制备成剂型的技术难题。这是由于：四氟醚唑是液体农药，醚菌酯是高熔点固体原药。通常这样的液体农药和固体农药组合只可以开发成乳油、水乳剂、微胶囊、悬乳剂、油悬浮剂这些剂型。然而乳油和水乳剂需要使用大量有机溶剂，对环境影响较大而逐步淘汰。悬乳剂通常用来制备液体农药和固体农药复配的优选剂型，然而通过大量实验发现制备四氟醚唑与醚菌酯复配的悬乳剂中液体的四氟醚唑农药对固体的醚菌酯农药有一定的溶解作用，从而导致长期贮存过程中发生奥氏熟化现象而导致悬浮颗粒粒子增长，团聚而制剂不稳定。油悬浮剂也因四氟醚唑对醚菌酯的微溶解而导致产品不稳定，并且活性组分容易从制剂中结晶析出。虽然微胶囊剂型在一定程度上也能解决液体农药和固体农药复配的问题，但由于加工成本高，技术难点多，制备合格的微胶囊困难重重，也不是理想的制备四氟醚唑和醚菌酯的剂型。
因此，如何提供一种稳定的含四氟醚唑和醚菌酯的杀菌颗粒组合物，使其具有良好的贮存和再分散性能，并且提供一种加工工艺简单、操作方便的颗粒剂制备方法，已成为目前亟待解决的技术难题。
发明内容
为解决上述技术问题，本发明的目的是提供一种稳定的含四氟醚唑和醚菌酯的杀菌颗粒组合物及其制备方法，该杀菌颗粒组合物在物理化学上是稳定的，其具有良好的贮存和再分散性能，并且在代表两年贮存稳定性的加速稳定性的常规试验中也是稳定的。
为达此目的，本发明采用以下技术方案：
本发明提供了一种稳定的含四氟醚唑和醚菌酯的杀菌颗粒组合物，其含有以下组分：
(a)室温下为液体的四氟醚唑活性物；
(b)室温下为固体的醚菌酯活性物；
(c)减粘剂；
(d)乳化剂；
(e)任选的其他功能性表面活性剂；
(f)吸附载体。
本发明提供的含四氟醚唑和醚菌酯的杀菌颗粒组合物中，通过添加用于降低液体四氟醚唑粘度的溶剂，液体的四氟醚唑活性物在减粘剂的作用下被含固体颗粒醚菌酯的粉料所均匀吸附，使得造粒成型后的颗粒中所含有的四氟醚唑和醚菌酯活性成分可以在长时间内保持稳定性，具有良好的贮存和再分散性能。
本发明中所述“减粘剂”意指用于降低室温下为液体的四氟醚唑活性物粘度的溶剂，便于吸附载体或者吸附粉料，使得液体的四氟醚唑活性剂更均匀地分布在造粒成型的颗粒中，确保四氟醚唑和醚菌酯活性成分的一致性。
所述的减粘剂包括芳烃溶剂，例如苯、甲苯、二甲苯、混三甲苯、solvesso 100、solvesso 200、solvesso150等；醇，直链或支链的脂肪醇，例如乙醇、甲醇、丙醇、丁醇、己醇、辛醇、环己醇，还可以包括多元醇，例如丙二醇、丙三醇、聚乙二醇、聚丙三醇等；烷基酮，直链、支链或环状的酮等，例如丙酮、丁酮、戊酮、环己酮等；植物油，例如大豆油、玉米油、芝麻油、蓖麻油、花生油、葵花籽油等；植物油酯化物，例如油酸甲酯、棕榈酸异辛酯、环氧大豆油等。
所述的乳化剂是在颗粒兑水稀释时作为乳化液体的四氟醚唑活性物的用途， 使得四氟醚唑活性物以细小的油珠形式均匀地分布在兑水稀释液中。合适的乳化剂可以选自在农业化学配制剂中用于该目的的任何物质，例如烷基酚与环氧乙烷和/或环氧丙烷的反应物、乙氧基化的壬基酚、蓖麻油乙氧基化物、多烷氧基化的醇的混合物(Atlox 4894)、烷基钙盐、烷基苯磺酸钙盐、脱水山梨醇衍生物或聚环氧乙烷-脱水山梨醇脂肪酸酯。
所述的任选的其他功能性表面活性剂是合适的功能性表面活性剂，可以选自在农业化学配制剂中常用于该目的的表面活性剂，例如分散剂、润湿剂、消泡剂、pH调节剂、惰性填料等。
合适的分散剂选用脂肪醇乙氧基化物、脂肪醇烷氧基化物、EO/PO嵌段共聚物、乙氧基化醇的磺酸，磺基琥珀酸盐，脂肪酸甲基牛磺酸盐，三苯乙烯基苯酚乙氧基化物和烷氧基化物，三仲丁基苯酚乙氧基化物，硫酸化甲酚-甲醛缩合物、萘和烷基萘的硫酸化缩合物，木素磺酸盐，乙氧基化脂肪醇、三苯乙烯基苯酚和三仲丁基苯酚的磷酸酯，以及乙氧基化脂肪醇、聚丙烯酸、聚甲基丙烯酸和丙烯酸酯共聚物、三苯乙烯基苯酚和三仲丁基苯酚的醚硫酸盐和聚合物分散剂中的一种或多种。
合适的润湿剂优选阴离子润湿剂，例如阴离子润湿剂的碱金属、碱土金属或铵盐。合适的润湿剂为萘磺酸盐(例如亚甲基二萘磺酸二钠盐，萘磺酸钠-甲醛缩合物，萘磺酸铵-甲醛缩合物)，烷基萘磺酸盐(例如烷基萘磺酸钠)，苯磺酸盐，烷基苯磺酸盐(例如枯烯磺酸钠、枯烯磺酸钾、二甲苯磺酸钠、甲苯磺酸钠)，烷烃磺酸盐(例如十四碳烯磺酸钠)，α-烯烃磺酸盐(例如α-烯烃磺酸钠)，磺基琥珀酸盐(例如二辛基磺基琥珀酸钠)，烷基磷酸盐(例如月桂基肉豆蔻基磷酸盐)，烷基硫酸盐(例如月桂基硫酸钠、鲸蜡基硬脂基硫酸钠、鲸蜡基硫酸钠、肉豆蔻基硫酸钠、鲸蜡基硬脂基硫酸钠)中的一种或多种
合适的消泡剂选用有机硅类、低碳醇类和脂肪酸盐类消泡剂。
合适的pH调节剂选用磷酸、醋酸、柠檬酸、碳酸钠、碳酸氢钠、磷酸钾、磷酸一氢钾、磷酸二氢钾等能提供质子酸或质子碱的物质。
合适的惰性载体选用硫酸钠、高岭土、煅烧高岭土、滑石粉、白炭黑、蒙脱土、硅藻土、磷酸钾等一种或多种。
所述的吸附载体选自白炭黑、硅藻土、凹凸棒土、分子筛、淀粉、纤维素、硅酸钙、蒙脱土或膨润土中的任意一种或至少两种的组合。
优选地，本发明中所述杀菌颗粒组合物包含如下重量百分比的各组分：
(a)重量百分比为1-20％的室温下为液体的四氟醚唑活性物；
(b)重量百分比为1-50％的室温下为固体的醚菌酯活性物；
(c)重量百分比为0.5-15％的减粘剂；
(d)重量百分比为1-15％的乳化剂；
(e)重量百分比为1-15％的任选的其他功能性表面活性剂；
(f)重量百分比为20-80％的吸附载体。
在本发明中，所述杀菌颗粒组合物中，作为(a)组分的四氟醚唑活性物，其重量百分比为1-20％，例如1％、2％、5％、8％、10％、12.2％、14.5％、15％、17.8％、19％或20％，优选为2-15％。
在本发明中，所述杀菌颗粒组合物中，作为(b)组分的醚菌酯活性物，其重量百分比为1-50％，例如1％、2％、5％、10％、15.5％、19.8％、25％、28.8％、30％、35％、38.1％、40％、44％、48％、49％或50％，优选为5-30％。
在本发明中，所述杀菌颗粒组合物中，作为(c)组分的减粘剂，其重量百分比为0.5-15％，例如0.5％、0.8％、1％、2％、3.6％、5％、7％、9％、10％、12％、12.9％、14％或15％，优选为1-10％。
在本发明中，所述杀菌颗粒组合物中，作为(d)组分的乳化剂，其重量百分比为1-15％，例如1％、2％、4％、5.5％、7％、9％、10％、12.3％、13％、14％或15％，优选为2-10％。
在本发明中，所述杀菌颗粒组合物中，作为(e)组分的任选的其他功能性表面活性剂的重量百分比为1-15％，例如1％、2％、4％、5.5％、6％、7％、9％、10％、12.3％、13％、14％或15％，优选为2-10％。
在本发明中，所述杀菌颗粒组合物中，作为(f)组分的吸附载体，其重量百分比为20-80％，例如20％、25％、28％、30％、35％、40％、45.5％、50％、53.6％、58.9％、62％、65％、68％、70％、72.2％、75.4％、77％、79％或80％，优选为30-70％。
进一步优选地，本发明中所述杀菌颗粒组合物由以下组分组成：
(a)室温下为液体的四氟醚唑活性物，其重量百分比为2-15％；
(b)室温下为固体的醚菌酯活性物，其重量百分比为5-30％；
(c)减粘剂，其重量百分比为1-10％；
(d)乳化剂，其重量百分比为2-10％；
(e)任选的其他功能性表面活性剂，其重量百分比为2-10％；
(f)吸附载体，其重量百分比为30-70％。
另一方面，本发明还提供了一种所述的杀菌颗粒组合物的制备方法，其包含以下步骤：
步骤I：以任意顺序混合组分(a)、(c)和(d)，搅拌均匀得均一油相。
步骤II：以任意顺序混合组分(b)、(e)和(f)，混合均匀后进行粉碎得平均粒径≤4μm的含醚菌酯活性物的粉料；
步骤III：混合步骤I和步骤II的物料，造粒成型得到含四氟醚唑和醚菌酯 的杀菌颗粒组合物。
本发明中所提供的制备方法，其采用的是先将四氟醚唑活性物和醚菌酯活性物分别配制成均一油相和粉碎后粉料，即，将四氟醚唑活性物与减粘剂和乳化剂配制成均一油相，将醚菌酯活性物与功能性表面活性剂和吸附载体混合后粉碎得到平均粒径≤4μm的粉料，然后再将油相与粉料进行混合，造粒成型。该制备方法不仅加工工艺简单、操作方便，同时该配制方法能够获得含量均一的四氟醚唑和醚菌酯的颗粒组合物，长期贮存产品质量稳定，颗粒不粘结、不团聚，流动性好，加水稀释分散快，易形成均匀的喷雾液，便于农户计量和施用。
优选地，步骤II中所述粉碎含醚菌酯活性物的粉料的颗粒粒径D50≤4μm，例如0.5μm、0.8μm、1μm、2μm、2.5μm、2.8μm、3μm、3.5μm或4μm，优选的D50在1.5μm-3μm之间。
优选地，所述混合步骤I和步骤II的物料，使得步骤I的油相均匀完全地吸附到步骤II的粉料中，根据混合好含有油相的粉料的性状选择合适的造粒设备进行造粒成型，该过程中如有需要可添加适量的水用以辅助造粒成型。
合适的造粒成型的方法包括凝聚(成粒)方法，例如流化床、板、圆盘、高切变速率(也称为Schugi方法)、喷雾干燥等，以及糊体挤出(paste extrusion)。通过这些方法制备的颗粒通常接下来通过筛分进行分级以调整所述颗粒的直径和均匀性。然后常将在该过程中通过筛分除去的“过大”和“细粉”级分在另外的制备中再处理。
根据本发明制备得到的稳定的含四氟醚唑和醚菌酯的杀菌颗粒组合物的制剂，即使在高温或者寒冷条件下存放，仍可保存稳定，且未发现任何颗粒聚集和使用不方便的质量问题。如以水稀释，制剂则可转变成均相喷雾液，而喷嘴并无因喷雾液中有固体的醚菌酯活性成分和液体的四氟醚唑活性成分不兼容出 现的堵塞现象。
本发明在技术上解决了液体的四氟醚唑活性物对固体的醚菌酯活性物有溶解效应而将这两种不同性状的活性物制备成理化稳定的制剂产品，与常规制备成乳油、水乳剂相比，不需要使用大量有机溶剂，环保，对环境压力小；与制备微胶囊悬浮剂相比，成本低，加工工艺简单，对操作要求低，更适合实际生产；与制备油悬浮剂、水悬浮剂、悬乳剂、水分散颗粒剂等剂型相比稳定性更高，而这些剂型都不能制备成合格的产品，或多或少会因为液体农药和固体农药不能一起加工或者因为液体农药对固体农药有溶解而导致制备的产品质量不稳定，粒径增长、团聚等质量问题。
与现有技术相比，本发明至少具有以下有益效果：
(1)本发明提供的含四氟醚唑和醚菌酯的杀菌颗粒组合物中，通过添加用于降低液体四氟醚唑粘度的溶剂，液体的四氟醚唑活性物在减粘剂的作用下被含固体颗粒醚菌酯的粉料所均匀吸附，使得造粒成型后的颗粒中所含有的四氟醚唑和醚菌酯活性成分可以在长时间内保持稳定性，对其进行加速贮存实验，热贮54℃并在14天后进行样品观察和性能测试，其仍表现出颗粒流动性好，入水分散性能好，因此良好的贮存和再分散性能；
(2)本发明所提供的制备方法是通过采用先将四氟醚唑活性物和醚菌酯活性物分别配制成均一油相和粉碎后粉料，即，将四氟醚唑活性物与减粘剂和乳化剂配制成均一油相，将醚菌酯活性物与功能性表面活性剂和吸附载体混合后粉碎得到平均粒径≤4μm的粉料，然后再将油相与粉料进行混合，造粒成型，其具有加工工艺简单、操作方便的优点，并使得杀菌颗粒组合物性能更稳定。
具体实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了， 所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
四氟醚唑+醚菌酯2％+50％颗粒剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000001
按以下步骤制备所述的杀菌颗粒组合物：
步骤I：将四氟醚唑、丙二醇和吐温80，混合搅拌均匀得油相；
步骤II：将醚菌酯、萘磺酸盐甲醛缩聚物、十二烷基苯磺酸钠、固体消泡剂、白炭黑和硅藻土混合均匀后，用气流粉碎机粉碎以获得平均粒径≤4μm的含有醚菌酯的粉料；
步骤III：将步骤I的油相在搅拌的情况下加入到步骤II的粉料中，搅拌直至吸附混合均匀后，使用挤压造粒法造粒成型。
实施例2
四氟醚唑+醚菌酯20％+5％颗粒剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000002
Figure PCTCN2020126965-appb-000003
按以下步骤制备所述的杀菌颗粒组合物：
步骤I：将四氟醚唑、油酸甲酯和蓖麻油乙氧基化物，混合搅拌均匀得油相；
步骤II：将醚菌酯、萘磺酸盐甲醛缩聚物、十二烷基苯磺酸钠、固体消泡剂和硅藻土混合均匀后，用气流粉碎机粉碎以获得平均粒径≤4μm的含有醚菌酯的粉料；
步骤III：采用流化床造粒法，将步骤I的油相喷涂到步骤II的粉料中，完成造粒成型。
实施例3
四氟醚唑+醚菌酯10％+35％颗粒剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000004
Figure PCTCN2020126965-appb-000005
按以下步骤制备所述的杀菌颗粒组合物：
步骤I：将四氟醚唑、聚乙二醇和十二烷基苯磺酸钙，混合搅拌均匀得油相；
步骤II：将醚菌酯、木质素磺酸盐、脂肪醇乙氧基化物、固体消泡剂和玉米淀粉混合均匀后，用气流粉碎机粉碎以获得平均粒径≤4μm的含有醚菌酯的粉料；
步骤III：采用喷雾造粒设备，将步骤I的油相喷涂到步骤II的粉料中，完成造粒成型。
实施例4
四氟醚唑+醚菌酯10％+25％颗粒剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000006
按以下步骤制备所述的杀菌颗粒组合物：
步骤I：将四氟醚唑、大豆油和吐温20，混合搅拌均匀得油相；
步骤II：将醚菌酯、聚羧酸盐、琥珀酸辛基磺酸盐、固体消泡剂、白炭黑和 硫酸钠混合均匀后，用气流粉碎机粉碎以获得平均粒径≤4μm的含有醚菌酯的粉料；
步骤III：将步骤I的油相在搅拌的情况下加入到步骤II的粉料中，搅拌直至吸附混合均匀后，使用挤压造粒法造粒成型。
实施例5
四氟醚唑+醚菌酯2％+5％颗粒剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000007
按以下步骤制备所述的杀菌颗粒组合物：
步骤I：将四氟醚唑、丙二醇和多烷氧基化的醇的混合物，混合搅拌均匀得油相；
步骤II：将醚菌酯、木质素磺酸盐、十二烷基苯磺酸钠、固体消泡剂和硅藻土混合均匀后，用气流粉碎机粉碎以获得平均粒径≤4μm的含有醚菌酯的粉料；
步骤III：将步骤I的油相在搅拌的情况下加入到步骤II的粉料中，搅拌直至吸附混合均匀后，使用挤压造粒法造粒成型，该过程中如有必要可添加适量的水进行辅助混合和造粒成型。
实施例6
四氟醚唑+醚菌酯15％+30％颗粒剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000008
按以下步骤制备所述的杀菌颗粒组合物：
步骤I：将四氟醚唑、丙二醇和蓖麻油乙氧基化物，混合搅拌均匀得油相；
步骤II：将醚菌酯、萘磺酸盐甲醛缩聚物、十二烷基苯磺酸钠、固体消泡剂和白炭黑混合均匀后，用气流粉碎机粉碎以获得平均粒径≤4μm的含有醚菌酯的粉料；
步骤III：采用流化床造粒法，将步骤I的油相喷涂到步骤II的粉料中，完成造粒成型。
对比例1
四氟醚唑+醚菌酯15％+30％颗粒剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000009
Figure PCTCN2020126965-appb-000010
按以下步骤制备所述的杀菌颗粒组合物
步骤I：将四氟醚唑和蓖麻油乙氧基化物，混合搅拌均匀得油相；
步骤II：将醚菌酯、萘磺酸盐甲醛缩聚物、十二烷基苯磺酸钠、固体消泡剂和白炭黑混合均匀后，用气流粉碎机粉碎以获得含有醚菌酯的粉料；
步骤III：步骤I和步骤II混合，由于油相粘度过大，机械混合或使用喷嘴喷涂混合都不能混合均匀，导致制备的颗粒剂含量不均匀而失败。
对比例2
四氟醚唑+醚菌酯15％+30％水分散颗粒剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000011
按常规的水分散颗粒剂的加工方法进行制备，由于含有液体原药，无法进行气流粉碎而导致加工失败。
对比例3
四氟醚唑+醚菌酯15％+30％油悬浮剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000012
按常规的油悬浮剂加工方法，可制备四氟醚唑+醚菌酯15％+30％油悬浮剂。
对比例4
四氟醚唑+醚菌酯10％+20％悬乳剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000013
Figure PCTCN2020126965-appb-000014
按常规的悬乳剂加工方法，可制备四氟醚唑+醚菌酯10％+20％悬乳剂。
对比例5
四氟醚唑+醚菌酯15％+30％乳油，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000015
按常规的乳油加工方法，可制备四氟醚唑+醚菌酯15％+30％乳油。
对比例6
四氟醚唑+醚菌酯15％+30％微胶囊悬浮-悬浮剂，按重量百分含量由以下组分组成：
Figure PCTCN2020126965-appb-000016
Figure PCTCN2020126965-appb-000017
按常规的微胶囊悬浮-悬浮剂加工方法，可制备四氟醚唑+醚菌酯15％+30％微胶囊悬浮-悬浮剂。
将实施例1-6和对比例1-6的样品进行加速贮存实验，热贮54℃在14天后进行样品观察和性能测试，结果见表1。
表1
Figure PCTCN2020126965-appb-000018
Figure PCTCN2020126965-appb-000019
从表1所示的结果可以看出，本发明提供的含四氟醚唑和醚菌酯的杀菌颗粒组合物，在加工上很好地解决了将液体四氟醚唑和固体醚菌酯活性物加工成颗粒产品的难题，并且加工工艺简单，操作方便，成本低，避免了使用大量的有机溶剂，对环境友好。制备成的产品热贮稳定性好，对水稀释稳定，不会因为液体原药和固体原药的相互影响而导致不兼容，理化质量稳定。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (9)

  1. 一种含四氟醚唑和醚菌酯的杀菌颗粒组合物，其特征在于，含有以下组分：
    (a)室温下为液体的四氟醚唑活性物；
    (b)室温下为固体的醚菌酯活性物；
    (c)减粘剂；
    (d)乳化剂；
    (e)任选的其他功能性表面活性剂；
    (f)吸附载体。
  2. 根据权利要求1所述的杀菌颗粒组合物，其特征在于，所述减粘剂是降低室温下为液体的四氟醚唑活性物粘度的溶剂；
    优选地，所述减粘剂选自芳烃溶剂、多元醇、烷基酮、植物油或植物油酯化物中的任意一种或至少两种的组合。
  3. 根据权利要求1所述的杀菌颗粒组合物，其特征在于，所述任选的其他功能性表面活性剂为消泡剂、分散剂、润湿剂、抗氧化剂、惰性载体或pH调节剂中的任意一种或至少两种的组合。
  4. 根据权利要求1所述的杀菌颗粒组合物，其特征在于，所述吸附载体选自白炭黑、硅藻土、凹凸棒土、分子筛或淀粉中的任意一种或至少两种的组合。
  5. 根据权利要求1-4任一项所述的杀菌颗粒组合物，其特征在于，所述杀菌颗粒组合物包含如下重量百分比的各组分：
    (a)重量百分比为1-20％的室温下为液体的四氟醚唑活性物；
    (b)重量百分比为1-50％的室温下为固体的醚菌酯活性物；
    (c)重量百分比为0.5-15％的减粘剂；
    (d)重量百分比为1-15％的乳化剂；
    (e)重量百分比为1-15％的任选的其他功能性表面活性剂；
    (f)重量百分比为20-80％的吸附载体。
  6. 根据权利要求5所述的杀菌颗粒组合物，其特征在于，所述室温下为液体的四氟醚唑活性物的重量百分比为2-15％；
    优选地，所述室温下为固体的醚菌酯活性物的重量百分比为5-30％；
    优选地，所述减粘剂的重量百分比为1-10％；
    优选地，所述乳化剂的重量百分比为2-10％；
    优选地，所述任选的其他功能性表面活性剂的重量百分比为2-10％；
    优选地，所述吸附载体的重量百分比为30-70％。
  7. 根据权利要求1-6任一项所述的杀菌颗粒组合物的制备方法，其特征在于，所述制备方法包括以下步骤：
    步骤I：以任意顺序混合组分(a)、(c)和(d)，搅拌均匀得均一油相；
    步骤II：以任意顺序混合组分(b)、(e)和(f)，混合均匀后进行粉碎得平均粒径≤4μm的含醚菌酯活性物的粉料；
    步骤III：混合步骤I和步骤II的物料，造粒成型得到含四氟醚唑和醚菌酯的杀菌颗粒组合物。
  8. 根据权利要求7所述的制备方法，其特征在于，所述造粒成型包括挤压造粒、流化床造粒或喷雾塔造粒。
  9. 根据权利要求7所述的制备方法，其特征在于，所述步骤III中在混合物料时加水辅助；
    优选地，所述步骤III中在造粒成型时加水辅助。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1864484A (zh) * 2005-05-18 2006-11-22 安徽华星化工股份有限公司 基于醚菌酯的复配杀菌组合物
CN101700032A (zh) * 2009-11-30 2010-05-05 青岛星牌作物科学有限公司 一种含有四氟醚唑的杀菌组合物及应用
CN108522515A (zh) * 2017-03-02 2018-09-14 江苏龙灯化学有限公司 一种含有醚菌酯与四氟醚唑的杀菌组合物的应用
CN111109260A (zh) * 2018-10-31 2020-05-08 江苏龙灯化学有限公司 一种含醚菌酯和四氟醚唑的悬乳剂
CN111109268A (zh) * 2018-10-31 2020-05-08 江苏龙灯化学有限公司 一种含有醚菌酯与四氟醚唑的杀菌组合物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003055102A (ja) * 2001-08-15 2003-02-26 Kumiai Chem Ind Co Ltd 粒状農薬組成物及びその製造方法
CN104336012A (zh) * 2014-10-17 2015-02-11 山东潍坊润丰化工股份有限公司 一种可湿性粉剂及其制备方法
CN106538580A (zh) * 2016-11-14 2017-03-29 江苏丰山集团股份有限公司 一种含氟啶嘧磺隆的除草组合物及其应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1864484A (zh) * 2005-05-18 2006-11-22 安徽华星化工股份有限公司 基于醚菌酯的复配杀菌组合物
CN101700032A (zh) * 2009-11-30 2010-05-05 青岛星牌作物科学有限公司 一种含有四氟醚唑的杀菌组合物及应用
CN108522515A (zh) * 2017-03-02 2018-09-14 江苏龙灯化学有限公司 一种含有醚菌酯与四氟醚唑的杀菌组合物的应用
CN111109260A (zh) * 2018-10-31 2020-05-08 江苏龙灯化学有限公司 一种含醚菌酯和四氟醚唑的悬乳剂
CN111109268A (zh) * 2018-10-31 2020-05-08 江苏龙灯化学有限公司 一种含有醚菌酯与四氟醚唑的杀菌组合物

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