WO2023173248A1 - 一种含四氟醚唑和苯菌酮的杀菌组合物 - Google Patents

一种含四氟醚唑和苯菌酮的杀菌组合物 Download PDF

Info

Publication number
WO2023173248A1
WO2023173248A1 PCT/CN2022/080612 CN2022080612W WO2023173248A1 WO 2023173248 A1 WO2023173248 A1 WO 2023173248A1 CN 2022080612 W CN2022080612 W CN 2022080612W WO 2023173248 A1 WO2023173248 A1 WO 2023173248A1
Authority
WO
WIPO (PCT)
Prior art keywords
room temperature
bactericidal composition
tris
liquid
phenylethyl
Prior art date
Application number
PCT/CN2022/080612
Other languages
English (en)
French (fr)
Inventor
罗昌炎
布里斯托詹姆斯·蒂莫西
Original Assignee
江苏龙灯化学有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 江苏龙灯化学有限公司 filed Critical 江苏龙灯化学有限公司
Priority to PCT/CN2022/080612 priority Critical patent/WO2023173248A1/zh
Priority to CN202280023920.8A priority patent/CN117377388A/zh
Publication of WO2023173248A1 publication Critical patent/WO2023173248A1/zh

Links

Classifications

    • 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
    • A01N25/30—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 characterised by the surfactants
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aldehyde or keto groups, or thio analogues thereof, directly attached to an aromatic ring system, e.g. acetophenone; Derivatives thereof, e.g. acetals
    • 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 present application relates to the technical field of pesticide preparations, and in particular, to a fungicidal composition containing tetrafluoroethazole and mesotrione.
  • tetrafluoroetherazole 2-(2,4-dichlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propyl 1,1,2,2-tetrafluoro Ethyl ether, pure product is a yellow viscous liquid with a solubility in water of 156.6mg/L. It belongs to the second generation of triazole fungicides. It contains fluorine in its molecular structure. Its bactericidal activity is 2-3 times that of the first generation. It has a broad bactericidal spectrum, high efficiency, and a long-lasting effect of 4-6 weeks. It has protective and therapeutic effects. And it has good internal suction conduction performance.
  • benzophenone 3′-bromo-2,3,4,6′-tetramethoxy-2′,6-dimethylbenzophenone.
  • the pure product is a white crystalline solid with a solubility in water of 0.492 mg. /L. It is a benzophenone fungicide and is mainly used to control diseases such as powdery mildew and eyespot in crops such as cereals, cucumbers and grapes. It has attracted much attention due to its unique mechanism of action.
  • CN103053538A discloses a bactericidal composition.
  • the combination of tetraflurozolin and oxyprodione has an obvious synergistic effect on powdery mildew and improves the resistance of powdery mildew.
  • it can significantly reduce the amount of pesticides used in the field, effectively reduce environmental pollution and pesticide residues, reduce production and use costs, and overcome and delay the development of disease resistance.
  • CN102805083A discloses a composition of mesotriazole and triazole fungicides. It also does not discuss and solve the problem of storage compatibility of tetrafluoroethazole active substance and mesotriazole active substance and the problem of aggregate settlement during the dilution process of the composition after storage. .
  • the present application provides a stable storage-compatible bactericidal composition of tetrafluoropropazole and meclofenac.
  • the bactericidal composition is physically and chemically stable and has good storage and dilution stability, especially reducing or avoiding This solves the problem of dilution, aggregation and sedimentation of the composition after storage.
  • the present application provides a bactericidal composition containing tetrafluoroetherazole and meclofenac, which contains the following components:
  • the diluent refers to a substance that can dilute the concentration of the active ingredient, and can be a liquid diluent or a solid diluent.
  • Liquid diluents are usually: aliphatic hydrocarbons such as cyclohexane or paraffin such as petroleum distillates, mineral and vegetable oils, alcohols such as ethanol or ethylene glycol and their ethers and esters, ketones such as methyl isobutyl ketone or cyclohexanone, strong solvents such as dimethyldecylamide and propylene carbonate, or water.
  • Solid diluents are usually: for example ammonium salts and pulverized natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or silicates; and pulverized synthetic minerals such as highly dispersed silica , alumina and silicates; particles of natural minerals, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth; and particles of synthetic minerals, such as highly dispersed silicic acid, alumina and silicates; crushed and graded natural rocks such as calcite, marble, pumice, sepiolite and dolomite; and inorganic synthetic granules and organic powders; and granules of organic products, such as sawn wood, coconut shells, corn cobs and tobacco stems; and inorganic salts, such as ammonium sulfate, potassium sulfate; and organic substances, such as sucrose, star
  • the present application further includes one or more functional surfactants.
  • Surfactants themselves do not have biological activity, but they can improve the dispersion, wetting, and emulsification effects of active ingredients in the preparation system and the spreading, wetting, penetration, and adhesion of active ingredients on plant surfaces. They have the ability to activate active molecules.
  • Functional additive compounds include anionic, nonionic, cationic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof.
  • Such surfactants can be used as emulsifiers, dispersants, wetting agents, defoaming agents, pH adjusters, antifreeze agents, thickeners, preservatives, antioxidants, colorants, etc.
  • Suitable emulsifiers include mixtures of alkylphenols with ethylene oxide and/or propylene oxide, ethoxylated nonylphenols, castor oil ethoxylates, polyalkoxylated alcohols (Atlox 4894), alkyl calcium salts, alkyl benzene sulfonate calcium salts, sorbitan derivatives or polyethylene oxide-sorbitan fatty acid esters.
  • Suitable dispersants include fatty alcohol ethoxylates, fatty alcohol alkoxylates, EO/PO block copolymers, sulfonic acids of ethoxylated alcohols, sulfosuccinates, fatty acid methyltaurate, Tristyrylphenol ethoxylates and alkoxylates, tris-sec-butylphenol ethoxylates, sulfated cresol-formaldehyde condensates, sulfated condensates of naphthalene and alkylnaphthalene, lignosulfonates , phosphate esters of ethoxylated fatty alcohols, tristyrylphenol and tri-sec-butylphenol, as well as ethoxylated fatty alcohols, polyacrylic acid, polymethacrylic acid and acrylate copolymers, tristyrylphenol and One or more of tri-sec-butylphenol ether sulfate and poly
  • Suitable wetting agents are preferably anionic wetting agents, for example 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 naphthalene sulfonate-formaldehyde condensate, ammonium naphthalene sulfonate-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 ( For example, sodium tetradecene sulfonate), alpha-olefin sulfonate (for example, sodium alpha-olefin sulfonate), sulfosuccinate (for example, sodium dioctyl sulfosuccinate), alkyl phosphate (for example, sodium lauryl sulfonate) Myristyl phosphate), alkyl sulfates (such as sodium lauryl sulfate, sodium cetyl stearyl sulfate, sodium cetyl sulfate,
  • Suitable defoaming agents include silicone, low carbon alcohol and fatty acid salt defoaming agents.
  • Suitable pH adjusters include phosphoric acid, acetic acid, citric acid, sodium carbonate, sodium bicarbonate, potassium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate and other substances that can provide protonic acid or protonic base.
  • Suitable antifreeze agents include all substances customarily used for this purpose in agrochemical compositions, preferably propylene glycol and/or ethylene glycol.
  • Suitable thickeners include all substances commonly used for this purpose in agrochemical compositions, preferably the thickener is xanthan gum.
  • Suitable preservatives include all substances commonly used for this purpose in agrochemical compositions, preferably the preservatives are selected from the Proxel series and/or Nipacide series of preservatives.
  • Suitable antioxidants include all substances commonly used for this purpose in agrochemical compositions, preferably the antioxidant is 2,6-di-tert-butyl-4-methylphenol.
  • Suitable colorants include all substances commonly used for this purpose in agrochemical compositions.
  • the colorant is any one of titanium dioxide, zinc oxide, blue pigments or Pigment Red BBN. or a combination of at least two.
  • the germicidal composition described in this application contains the following weight percentages of each component:
  • the weight percentage of the tetrafluoroetherazole active substance as component (a) is 1-20%, such as 1%, 2%, 5%, 8%, 10% , 12.2%, 14.5%, 15%, 17.8%, 19% or 20%, preferably 5-15%.
  • the weight percentage of mefendizone active material as component (b) is 1-50%, such as 1%, 2%, 3.2%, 5%, 10%, 15.5%, 19.8%, 25%, 28.8%, 30%, 35%, 38.1%, 40%, 44%, 48%, 49% or 50%, preferably 10-30%.
  • the weight percentage of the optional functional surfactant as component (d) in the bactericidal composition is 1-20%, such as 1%, 2%, 4%, 5.5%, 7%, 9%, 10%, 12.3%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%, preferably 3-15%.
  • the diluent of component (e) its weight percentage is 15-90%, such as 15%, 20%, 25%, 28%, 30%, 35%, 40%, 45.5%, 50%, 53.6%, 58.9%, 62%, 65%, 68%, 70%, 74%, 75%, 78%, 80%, 82.2%, 85.4%, 87%, 89% Or 90%, preferably 30-70%.
  • the bactericidal composition described in this application contains the following weight percentages of each component:
  • this application also provides a preparation method of the bactericidal composition, which includes the following steps:
  • Step I Mix components (a), (b), (c), (d) and (e) in any order under stirring conditions, and mix evenly;
  • Step II Crush or grind the mixture of Step I to a mixture with an average particle size D50 ⁇ 4 ⁇ m;
  • Step III Formulate the mixture of Step II.
  • the preparation method provided in this application uses [2,4,6-tris( 1-Phenylethyl)phenyl] ether, other functional surfactants and diluents are mixed together and then ground or pulverized to obtain the mother liquor or master powder of the semi-finished product, and then the mother liquor or master powder is formulated according to the final dosage form requirements. chemical treatment.
  • Suitable dosage forms include suspensions, suspoemulsions, microcapsule suspension-suspensions, macrogranules, water-dispersible granules, emulsions, wettable powders, and dry suspensions.
  • Preferred dosage forms are suspensions, suspoemulsions, and water-dispersible formulations. Granules and emulsions.
  • the preparation method has a simple processing technology and is convenient to operate. At the same time, the preparation method can obtain a bactericidal composition of tetrafluoroetherazole and benzofenone with uniform content, solving the problem of long-term problem of liquid tetrafluoroetherazole active material and solid benzofendione active material. Storage compatibility issues reduce or avoid the accumulation and settlement of granular oil droplets after dilution with water, thereby reducing the risk of clogging the sprayer or nozzle.
  • the average particle diameter D50 of the pulverized or ground mixture described in step II is ⁇ 4 ⁇ m, such as 0.5 ⁇ m, 0.85 ⁇ m, 1 ⁇ m, 1.2 ⁇ m, 1.5 ⁇ m, 1.8 ⁇ m, 2.1 ⁇ m, 2.5 ⁇ m, 2.9 ⁇ m. , 3 ⁇ m, 3.2 ⁇ m, 3.5 ⁇ m, 3.85 ⁇ m or 4 ⁇ m, the preferred D50 is between 1.2 ⁇ m-2.5 ⁇ m.
  • the dosage form described in step III is to process the mixture of step II into a liquid dosage form of suspension, suspoemulsion or microcapsule suspension-suspension, or into a solid dosage form of large granules, water-dispersed granules, or emulsions. Granules or wettable powder.
  • the preparation of the bactericidal composition containing tetraflurozolin and mefendizone prepared according to the present application solves the problem of storage compatibility of tetraflurozolin and mefendizone, and particularly solves the problem of the dilution of the stored bactericidal composition.
  • the mutual aggregation and sedimentation problem between the tetrafluoroetherazole in the form of oil beads and the benzophenone in the form of particles reduces the risk of clogging the sprayer.
  • This application is technically made by adding ethylene oxide and propylene oxide polymerized with the general formula: C 30 H 30 O(C 3 H 6 O) m (C 2 H 4 O) n (I) [2,4 , 6-tris(1-phenylethyl)phenyl] ether, overcomes the incompatibility between liquid tetrafluoroetherazole and solid mexifenone in the composition and the problem of mutual aggregation and sedimentation when the composition is diluted with water. , avoiding the risk of the spray liquid clogging the sprayer.
  • Example 1 Preparation method of Example 1: Stir vegetable oil, ethoxylated castor oil and tetrafluoroetherazole evenly and then polymerize [2,4,6-tris(1-benzene) with oxybenzophenone, ethylene oxide and propylene oxide. Ethyl)phenyl] ether, propylene glycol, methacrylic acid copolymer, etc.
  • Example 1 and Comparative Examples 1-5 Before storing the samples of Example 1 and Comparative Examples 1-5 above at room temperature and after 12 months of storage, observe changes in the appearance of each sample and dilute each sample 100 times with water. Shake evenly and let stand for 10 minutes to observe changes in the dilution. The experimental results are shown in Table 2.
  • Spray liquid pressure test Dilute the stored samples of Example 1 and Comparative Examples 1-5 with water to obtain 20L of spray liquid, and the preparation amount is 500g.
  • 20L of diluent circulates and passes through a fine screen.
  • the pressure of the liquid passing through the fine sieve was recorded every hour, and the liquid passing through the fine sieve was taken once an hour, and the total content (ppm) of tetrafluorozoate and mefenodine in the diluent was analyzed by liquid chromatography. An increase in the pressure gauge indicates that the nozzle and fine screen are clogged.
  • Table 3 The results are shown in Table 3.
  • Example 2 [2,4,6-tris(1-phenylethyl ethane) polymerized by tetrafluoroetherazole, oxybenzone, calcium dodecylbenzene sulfonate, ethylene oxide and propylene oxide base) phenyl] ether, lignosulfonate, solid defoaming agent and calcined kaolin are mixed evenly, and then air-pulverized through a jet mill to obtain a master powder with an average particle size of less than 3 ⁇ m. The master powder is kneaded and granulated by adding water.
  • Example 2 and Comparative Examples 6-10 Before storing the samples of Example 2 and Comparative Examples 6-10 above at room temperature and after 12 months of storage, observe changes in the appearance of each sample and dilute each sample 100 times with water. Shake evenly and let stand for 10 minutes to observe changes in the dilution. The experimental results are shown in Table 5.
  • Spray liquid pressure test Dilute the stored samples of Example 2 and Comparative Examples 6-10 with water to obtain 20L of spray liquid, and the preparation amount is 500g.
  • 20L of diluent circulates and passes through a fine screen.
  • the pressure of the liquid passing through the fine sieve was recorded every hour, and the liquid passing through the fine sieve was taken once an hour, and the total content (ppm) of tetrafluorozoate and mefenodine in the diluent was analyzed by liquid chromatography. An increase in the pressure gauge indicates that the nozzle and fine screen are clogged. The results are shown in Table 6.
  • Example 3 Preparation method: Mix tetrafluoroetherazole, methyl oleate and ethoxylated vegetable oil evenly, and then mix [2,4,6-tris( 1-Phenylethyl)phenyl] ether, lignosulfonate, defoaming agent, and diatomaceous earth are mixed evenly, and then air-pulverized through a jet mill to obtain a master powder with an average particle size of less than 3 ⁇ m. Add water to the master powder. The mixture is kneaded and granulated, granulated, and dried to obtain tetraflurozolin + 8% + 30% emulsion granules.
  • Example 4 Preparation method: [2,4,6-tris(1-phenylethyl)phenyl polymerized with tetrafluoroetherazole, oxybenzone, silicone defoaming agent, ethylene oxide and propylene oxide ] ether, naphthalene sulfonate formaldehyde condensation polymer, polycarboxylate dispersant, white carbon black, lactose and appropriate amount of water are mixed to obtain a mixed solution with a solid content of about 50%, and the average particle size is obtained by wet grinding with a sand mill 2.0 ⁇ m suspension, move the suspension into a spray tower for spray granulation, and dry to obtain tetrafluoroethazole + 6% meclozolin + 24% dry suspension.
  • Spray liquid pressure test Dilute the stored samples of Examples 3 and 4 with water to obtain 20L of spray liquid, with a preparation volume of 500g. Under the action of the pump, 20L of diluent circulates and passes through a fine screen. The pressure of the liquid passing through the fine sieve was recorded every hour, and the liquid passing through the fine sieve was taken once an hour, and the total content (ppm) of tetrafluorozoate and mefenodine in the diluent was analyzed by liquid chromatography. An increase in the pressure gauge indicates that the nozzle and fine screen are clogged. The results are shown in Table 8.
  • compositions listed in the examples of this application can well overcome the compatibility problem of liquid tetrafluoroetherazole and solid meclozolin by adding a specific structure or amount of ethylene oxide and propylene oxide polymerized [2,4 , 6-tris(1-phenylethyl)phenyl] ether, effectively improves the room temperature storage compatibility problem of tetrafluoroethazole and meclofenac, and the prepared preparation has good dilution stability; at high temperatures Under the dilution factor, tetrafluorozofen and mefendizone still have good compatibility, and the diluted solution or spray solution will not flocculate, aggregate and settle, and has good productization value.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

本申请涉及一种含四氟醚唑和苯菌酮的杀菌组合物，所述组合物含有以下组分：(a)室温下液体的四氟醚唑活性物；(b)室温下固体的苯菌酮活性物；(c)环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚；(d)任选的功能性表面活性剂；环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚有效解决了两种不同形态的四氟醚唑和苯菌酮贮存兼容性问题，尤其是解决了贮存后组合物在稀释过程中油珠形态的四氟醚唑和颗粒形态的苯菌酮之间的相互聚集沉降问题，减少了堵塞喷雾器的风险。本申请所述杀菌组合物，有效解决了液体的四氟醚唑活性物和固体的苯菌酮的兼容性问题，所制备产品在贮存稳定性中表现出较好的性能。

Description

一种含四氟醚唑和苯菌酮的杀菌组合物 技术领域
本申请涉及农药制剂技术领域，尤其涉及一种含四氟醚唑和苯菌酮的杀菌组合物。
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，纯品为黄色黏性液体，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。
苯菌酮化学名称为3′-溴-2,3,4,6′-四甲氧基-2′,6-二甲基二苯甲酮，纯品为白色结晶固体，水中溶解度为0.492mg/L。属于二苯酮类杀菌剂，主要用于防治谷类、黄瓜和葡萄等作物的白粉病和眼点病等病害，由于其独特的作用机制而备受关注。其通过干扰孢子萌发时的附着胞的发育与形成，抑制了白粉病的孢子萌发，可作用于真菌生命循环全过程；其次，通过干扰极性肌动蛋白组织的建立和形成，使病菌的菌丝体顶端细胞的形成受到干扰和抑制，从而阻碍了菌丝体的正常发育与生长，抑制和阻碍了白粉病菌的侵害，有效地控制白粉病的危害，具有明显的预防和治疗作用。
目前关于四氟醚唑和苯菌酮的杀菌组合也有专利报道，CN103053538A公开了一种杀菌组合物，其含有四氟醚唑和苯菌酮的组合对白粉病有明显的增效作用，提高了防治效果；另外可以大幅减少田间用药量，有效减少环境污染和农药残留，降低生产和使用成本；以及克服和延缓病害抗药性的产生。说明书中虽然列举了配置苯菌酮和四氟醚唑悬浮剂、水分散粒径实例，但并未探讨和解 决四氟醚唑活性物和苯菌酮活性物贮存兼容性问题和贮存后组合物在稀释过程中的聚集沉降问题。CN102805083A公开了苯菌酮和三唑类杀菌剂的组合物，同样未探讨和解决四氟醚唑活性物和苯菌酮活性物贮存兼容性问题和贮存后组合物在稀释过程中聚体沉降问题。
因此，如何提供一种稳定的四氟醚唑和苯菌酮贮存兼容的杀菌组合物，使其具有良好的贮存兼容性和稀释稳定性能，减少或避免稀释聚集沉降问题，已成为目前组合物亟待解决的技术难题。
发明内容
本申请提供了一种稳定的四氟醚唑和苯菌酮贮存兼容的杀菌组合物，该杀菌组合物在物理化学上是稳定的，其具有良好的贮存和稀释稳定性，尤其是减少或避免了贮存后组合物稀释聚集沉降的问题。
本申请提供了一种含四氟醚唑和苯菌酮的杀菌组合物，其含有以下组分：
(a)室温下液体的四氟醚唑活性物；
(b)室温下固体的苯菌酮活性物；
(c)环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚，通式为：C 30H 30O(C 3H 6O) m(C 2H 4O) n  (I)，其中，1≤m≤50，1≤n≤50；
(d)任选的功能性表面活性剂；和
(e)稀释剂。
本申请提供的含四氟醚唑和苯菌酮的杀菌组合物中，通过添加式I的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚这类物质，有效地使液体的四氟醚唑活性物和固体的苯菌酮活性物组合在一起，提升了液体的四氟醚唑活性物和固体的苯菌酮活性物的贮存兼容性；尤其是提升了液体的四氟醚唑活性物和固体的苯菌酮活性物贮存后的兑水稀释兼容稳定性，减少了四氟醚唑油珠和苯菌酮颗粒之间的聚集沉降问题，最终得到了合格的喷雾液。
本申请中所述式I的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚，其中1≤m≤50，1≤n≤50；m可以选自1、2、5、8、10、12、15、17、19、20、21、24、26、30、35、38、42、44、45、46、48、49或50；n可以选自1、2、5、8、10、12、15、17、19、20、21、24、26、30、35、38、42、44、45、46、48、49或50；m和n是相互独立的整数，可以相同或不同，优选相同。这 些环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚可以为市售品，例如可适宜使用SOPROPHOR 796/P(Solvay USA lnc.)、STEP-FLOW 1500(Stepan Company)等。
就本申请中使用的式I的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚，通常为1≤m≤50，1≤n≤50，优选2≤m≤30，2≤n≤30，更优选5≤m≤25，5≤n≤25。当m＝0或n＝0时，由于通式结构变化而存在功能性能的变化的风险，另一方面，当m＞50或n＞50时，存在难以加工塑性的风险。
出人意料的发现，本申请中通过加入式I的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚这类物质，有效地解决了含有四氟醚唑和苯菌酮的杀菌组合物贮存兼容性问题，尤其是在组合物贮存后兑水稀释过程中的聚集沉降的问题。
所述稀释剂是指能稀释活性成分浓度的物质，可以是液体稀释剂和固体稀释剂。液体稀释剂通常为：脂肪烃例如环己烷或石蜡例如石油馏分，矿物及植物油，醇例如乙醇或乙二醇及其醚及酯，酮例如甲基异丁基酮或环己酮，强极性溶剂例如二甲基癸酰胺和碳酸丙烯酯，或水。固体稀释剂通常为：例如铵盐及粉碎的天然矿物，例如高岭土、粘土、滑石粉、白垩、石英、凹凸棒石、蒙脱石或硅酸盐；以及粉碎的合成矿物例如高分散二氧化硅、氧化铝及硅酸盐；天然矿物的颗粒，如高岭土，粘土，滑石，白垩，石英，硅镁土，蒙脱土或硅藻土；和合成矿物颗粒，如高分散的硅酸，氧化铝和硅酸盐；粉碎并分级的天然岩石例如方解石、大理石、浮石、海泡石及白云石；以及无机合成的颗粒和有机粉末；和有机产物的颗粒，例如锯木、椰壳、玉米穗轴及烟草茎；以及无机盐，例如硫酸铵，硫酸钾；以及有机物，例如蔗糖、淀粉、乳糖、尿素、纤维素、聚乙烯醇、甲基吡咯烷酮。
本申请进一步包含一种或多种功能性表面活性剂。表面活性剂本身不具有生物活性，但能提升活性成分在制剂体系中的分散、润湿、乳化效果以及活性成分在植物表面的铺展、润湿、渗透、粘附等性能，具有活化活性分子一些功能性助剂化合物。这些表面活性剂包括阴离子、非离子、阳离子和两性表面活性剂，嵌段聚合物，聚电解质，以及它们的混合物。这类表面活性剂可以用作乳化剂、分散剂、润湿剂、消泡剂、pH调节剂、抗冻剂、增稠剂、防腐剂、抗氧化剂、着色剂等。
合适的乳化剂选用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。
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。
合适的抗冻剂包括所有的在农业化学组合物中常用于此目的的物质，优选地，所述抗冻剂为丙二醇和/或乙二醇。
合适的增稠剂包括所有的在农业化学组合物中常用于此目的的物质，优选地，所述增稠剂为黄原胶。
合适的防腐剂包括所有的在农业化学组合物中常用于此目的的物质，优选地，所述防腐剂选自Proxel系列和/或Nipacide系列防腐剂。
合适的抗氧化剂包括所有的在农业化学组合物中常用于此目的的物质，优选地，所述抗氧化剂为2,6-二叔丁基-4-甲基苯酚。
合适的着色剂包括所有的在农业化学组合物中常用于此目的的物质，优选 地，所述着色剂为二氧化钛、氧化锌、蓝颜料或Pigment Red BBN(即耐晒大红BBN)中的任意一种或至少两种的组合。
优选地，本申请中所述杀菌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％的室温下液体的四氟醚唑活性物；
(b)重量百分比为1-50％的室温下固体的苯菌酮活性物；
(c)重量百分比为2-15％的式I所示的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚；
(d)重量百分比为1-20％的任选的功能性表面活性剂；和
(e)重量百分比为15-90％的稀释剂。
在本申请中，所述杀菌组合物中，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5-15％。
在本申请中，所述杀菌组合物中，作为(b)组分的苯菌酮活性物，其重量百分比为1-50％，例如1％、2％、3.2％、5％、10％、15.5％、19.8％、25％、28.8％、30％、35％、38.1％、40％、44％、48％、49％或50％，优选为10-30％。
在本申请中，所述杀菌组合物中，作为(c)组分的式I的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚，其重量百分比为2-15％，例如2％、3％、3.6％、5％、7％、9％、10％、12％、12.9％、14％或15％，优选为3-10％。当配比用量百分比小于2％时，由于用量过低而不能完全解决兼容性问题，另一方面当配比用量大于15％时，存在难以制剂化的风险。
在本申请中，所述杀菌组合物中，作为(d)组分的任选的功能性表面活性剂，其重量百分比为1-20％，例如1％、2％、4％、5.5％、7％、9％、10％、12.3％、13％、14％、15％、16％、17％、18％、19％或20％，优选为3-15％。
在本申请中，所述杀菌组合物中，作为(e)组分的稀释剂，其重量百分比为15-90％，例如15％、20％、25％、28％、30％、35％、40％、45.5％、50％、53.6％、58.9％、62％、65％、68％、70％、74％、75％、78％、80％、82.2％、85.4％、87％、89％或90％，优选为30-70％。
进一步优选地，本申请中所述杀菌组合物，包含如下重量百分比的各组分：
(a)重量百分比为5-15％的室温下液体的四氟醚唑活性物；
(b)重量百分比为10-30％的室温下固体的苯菌酮活性物；
(c)重量百分比为5-12％的式I的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚；
(d)重量百分比为3-15％的任选的功能性表面活性剂；和
(e)重量百分比为30-70％的稀释剂。
另一方面，本申请还提供了一种所述的杀菌组合物的制备方法，其包含以下步骤：
步骤I：在搅拌的条件下以任意顺序混合组分(a)、(b)、(c)、(d)和(e)，混合均匀；
步骤II：粉碎或者研磨步骤I的混合物至平均粒径D50≤4μm的混合物；以及
步骤III：将步骤II的混合物进行剂型化。
本申请中所提供的制备方法，其采用的是将四氟醚唑活性物、苯菌酮活性物、和式I的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚、其他功能性表面活性剂以及稀释剂一起混合后进行研磨或者粉碎，得到半成品的母液或母粉，然后根据最终剂型需求，将母液或母粉进行剂型化处理。
合适的剂型例如悬浮剂、悬乳剂、微胶囊悬浮-悬浮剂、大颗粒剂、水分散颗粒剂、乳粒剂、可湿性粉剂、干悬浮剂，优选的剂型是悬浮剂、悬乳剂、水分散颗粒剂和乳粒剂。该制备方法加工工艺简单、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苯菌酮的杀菌组合物，解决了液体四氟醚唑活性物和固体的苯菌酮活性物长期贮存兼容性问题，减少或避免了兑水稀释后的颗粒油珠的聚集沉降，从而减少了堵塞喷雾器或喷头风险。
优选地，步骤II中所述的粉碎或研磨后的混合物的颗粒平均粒径D50≤4μm，例如0.5μm，0.85μm，1μm，1.2μm，1.5μm，1.8μm，2.1μm，2.5μm，2.9μm，3μm，3.2μm，3.5μm，3.85μm或4μm，优选的D50在1.2μm-2.5μm之间。
优选地，步骤III中所述的剂型化是将步骤II混合物加工成液体剂型的悬浮剂、悬乳剂或微胶囊悬浮-悬浮剂，或者加工成固体剂型的大颗粒剂、水分散颗粒剂、乳粒剂或可湿性粉剂。
根据本申请制备得到的含四氟醚唑和苯菌酮的杀菌组合物的制剂，解决了四氟醚唑和苯菌酮的贮存兼容性问题，特别是解决了贮存后的杀菌组合物在稀释过程中油珠形态的四氟醚唑和颗粒形态的苯菌酮之间的相互聚集沉降问题， 减少了堵塞喷雾器的风险。
本申请在技术上通过添加通式为：C 30H 30O(C 3H 6O) m(C 2H 4O) n  (I)的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚，克服了液体的四氟醚唑和固体的苯菌酮在组合物中的不兼容性以及组合物兑水稀释的相互聚集沉降问题，避免了喷雾液堵塞喷雾器的风险。
具体实施方式
为便于理解本申请，本申请列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实验1：四氟醚唑+苯菌酮10％+20％悬乳剂
表1：组合物
Figure PCTCN2022080612-appb-000001
Figure PCTCN2022080612-appb-000002
实施例1的制备方法：将植物油、乙氧基蓖麻油与四氟醚唑搅拌均匀后与苯菌酮、环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚、丙二醇、甲基丙烯酸共聚物等一起混合到去离子水中，搅拌均匀后通过砂磨机湿法砂磨至平均粒径在2.5μm左右，所得的砂磨液加入一定量的消泡剂和黄原胶，搅拌均匀即得含四氟醚唑和苯菌酮10％+20％悬乳剂。(对比例1-5按实施例1的制备方法制备，保持加工参数基本一致)。
将上述实施例1和对比例1-5的样品常温贮存前和贮存12个月后，观察各样品外观变化及各样品兑水稀释100倍，摇匀静置10分钟后观察稀释液变化。实验结果见表2。
表2
Figure PCTCN2022080612-appb-000003
Figure PCTCN2022080612-appb-000004
应用例1：喷雾液压力测试：将实施例1和对比例1-5贮存后的样品，加水稀释得到20L的喷雾液，制剂量500g。在泵的作用下，20L稀释液循环流动，并且通过一个细筛。液体通过细筛的压力每一小时记录一次，并且1小时取一次通过细筛的液体，通过液相色谱分析法分析稀释液中四氟醚唑和苯菌酮的总含量(ppm)。压力表的升高说明喷嘴和细筛被堵塞。结果见表3。
表3
Figure PCTCN2022080612-appb-000005
Figure PCTCN2022080612-appb-000006
实验2：四氟醚唑+苯菌酮5％+50％水分散颗粒剂
表4：组合物
Figure PCTCN2022080612-appb-000007
Figure PCTCN2022080612-appb-000008
实施例2的制备方法：将四氟醚唑、苯菌酮、十二烷基苯磺酸钙、环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚、木质素磺酸盐、固体消泡剂和煅烧高岭土混合均匀，然后通过气流粉碎机进行气流粉碎，得到平均粒径3μm以下的母粉，母粉加水进行捏合造粒，整粒，干燥得到四氟醚唑+苯菌酮5％+50％水分散颗粒剂。(对比例6-10按实施例2的制备方法制备，保持加工参数基本一致)
将上述实施例2和对比例6-10的样品常温贮存前和贮存12个月后，观察各样品外观变化及各样品兑水稀释100倍，摇匀静置10分钟后观察稀释液变化。实验结果见表5。
表5：
Figure PCTCN2022080612-appb-000009
Figure PCTCN2022080612-appb-000010
应用例2：喷雾液压力测试：将实施例2和对比例6-10贮存后的样品，加水稀释得到20L的喷雾液，制剂量500g。在泵的作用下，20L稀释液循环流动，并且通过一个细筛。液体通过细筛的压力每一小时记录一次，并且1小时取一次通过细筛的液体，通过液相色谱分析法分析稀释液中四氟醚唑和苯菌酮的总含量(ppm)。压力表的升高说明喷嘴和细筛被堵塞。结果见表6。
表6
Figure PCTCN2022080612-appb-000011
Figure PCTCN2022080612-appb-000012
实施例3
四氟醚唑+苯菌酮8％+30％乳粒剂
Figure PCTCN2022080612-appb-000013
实施例3制备方法：将四氟醚唑和油酸甲酯、乙氧基化植物油混合均匀，然后和苯菌酮、环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚、木质素磺酸盐、消泡剂、硅藻土混合均匀，然后通过气流粉碎机进行气流粉碎，得到平均粒径3μm以下的母粉，母粉加水进行捏合造粒，整粒，干燥得到四氟醚 唑+苯菌酮8％+30％乳粒剂。
实施例4
四氟醚唑+苯菌酮6％+24％干悬浮剂
Figure PCTCN2022080612-appb-000014
实施例4制备方法，将四氟醚唑、苯菌酮、有机硅消泡剂、环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚、萘磺酸盐甲醛缩聚物、聚羧酸盐分散剂、白炭黑、乳糖与适量的水混合，得到固含量约50％的混合液，通过砂磨机湿法研磨得到平均粒径2.0μm的悬浮液，将悬浮液移入喷雾塔喷雾造粒，干燥得四氟醚唑+苯菌酮6％+24％干悬浮剂。
将上述实施例3-4的样品常温贮存前和贮存12个月后，观察各样品外观变化及各样品兑水稀释100倍，摇匀静置10分钟后观察稀释液变化。实验结果见表7。
表7
Figure PCTCN2022080612-appb-000015
应用例3：喷雾液压力测试：将实施例3和4贮存后的样品，加水稀释得到 20L的喷雾液，制剂量500g。在泵的作用下，20L稀释液循环流动，并且通过一个细筛。液体通过细筛的压力每一小时记录一次，并且1小时取一次通过细筛的液体，通过液相色谱分析法分析稀释液中四氟醚唑和苯菌酮的总含量(ppm)。压力表的升高说明喷嘴和细筛被堵塞。结果见表8。
表8
Figure PCTCN2022080612-appb-000016
本申请实施例列举的组合物都能很好地克服了液体四氟醚唑和固体苯菌酮兼容性问题，通过添加特定结构或量的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚，有效的改善了四氟醚唑和苯菌酮的常温贮存兼容性问题，同时制备的制剂具有很好的稀释稳定性；在高稀释倍数下，四氟醚唑和苯菌酮仍然具有较好的兼容性，稀释液或喷雾液不会絮凝聚集和沉降，具有很好的产品化价值。

Claims (8)

  1. 一种含四氟醚唑和苯菌酮的杀菌组合物，其含有以下组分：
    (a)室温下液体的四氟醚唑活性物；
    (b)室温下固体的苯菌酮活性物；
    (c)环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚，通式为：C 30H 30O(C 3H 6O) m(C 2H 4O) n(I)其中1≤m≤50，1≤n≤50；
    (d)任选的功能性表面活性剂；和
    (e)稀释剂。
  2. 根据权利要求1所述的杀菌组合物，其中，所述式I的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚，2≤m≤30，2≤n≤30。
  3. 根据权利要求1所述的杀菌组合物，其中，所述稀释剂为水或固体填料。
  4. 根据权利要求1所述的杀菌组合物，其中，所述任选的功能性表面活性剂为消泡剂、分散剂、润湿剂、乳化剂、抗氧化剂、pH调节剂、增稠剂、抗冻剂或崩解剂中的任意一种或至少两种的组合。
  5. 根据权利要求1-4任一项所述的杀菌组合物，其中，所述杀菌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％的室温下液体的四氟醚唑活性物；
    (b)重量百分比为1-50％的室温下固体的苯菌酮活性物；
    (c)重量百分比为2-15％的式I所示的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚；
    (d)重量百分比为1-20％的任选的功能性表面活性剂；和
    (e)重量百分比为15-90％的稀释剂。
  6. 根据权利要求5所述的杀菌组合物，其中，所述室温下液体的四氟醚唑活性物的重量百分比为5-15％；
    优选地，所述室温下固体的苯菌酮活性物的重量百分比为10-30％；
    优选地，所述式I所示的环氧乙烷与环氧丙烷聚合的[2,4,6-三(1-苯基乙基)苯基]醚的重量百分比为3-10％；
    优选地，所述任选的功能性表面活性剂的重量百分比为3-15％；
    优选地，所述稀释剂的重量百分比为30-70％。
  7. 一种稳定的水喷雾液，其含有如权利要求1-6中任一项所述含四氟醚唑和苯菌酮的杀菌组合物和水。
  8. 一种如权利要求7所述的稳定的水喷雾液的制备方法，其包括：混合水和如权利要求1-6中任一项所述含四氟醚唑和苯菌酮的杀菌组合物，得到所述稳定的水喷雾液。
PCT/CN2022/080612 2022-03-14 2022-03-14 一种含四氟醚唑和苯菌酮的杀菌组合物 WO2023173248A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2022/080612 WO2023173248A1 (zh) 2022-03-14 2022-03-14 一种含四氟醚唑和苯菌酮的杀菌组合物
CN202280023920.8A CN117377388A (zh) 2022-03-14 2022-03-14 一种含四氟醚唑和苯菌酮的杀菌组合物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2022/080612 WO2023173248A1 (zh) 2022-03-14 2022-03-14 一种含四氟醚唑和苯菌酮的杀菌组合物

Publications (1)

Publication Number Publication Date
WO2023173248A1 true WO2023173248A1 (zh) 2023-09-21

Family

ID=88022009

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/080612 WO2023173248A1 (zh) 2022-03-14 2022-03-14 一种含四氟醚唑和苯菌酮的杀菌组合物

Country Status (2)

Country Link
CN (1) CN117377388A (zh)
WO (1) WO2023173248A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102428913A (zh) * 2011-11-11 2012-05-02 山东荣邦化工有限公司 一种微乳剂杀虫剂及其生产工艺
CN102805083A (zh) * 2012-09-02 2012-12-05 陕西上格之路生物科学有限公司 一种含苯菌酮和三唑类杀菌剂的杀菌组合物
CN103053538A (zh) * 2011-10-21 2013-04-24 深圳诺普信农化股份有限公司 杀真菌组合物
CN111685117A (zh) * 2020-06-30 2020-09-22 青岛润农化工有限公司 一种含苯菌酮和氟酰胺的杀菌组合物及其应用
CN113115773A (zh) * 2020-01-15 2021-07-16 江苏龙灯化学有限公司 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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103053538A (zh) * 2011-10-21 2013-04-24 深圳诺普信农化股份有限公司 杀真菌组合物
CN102428913A (zh) * 2011-11-11 2012-05-02 山东荣邦化工有限公司 一种微乳剂杀虫剂及其生产工艺
CN102805083A (zh) * 2012-09-02 2012-12-05 陕西上格之路生物科学有限公司 一种含苯菌酮和三唑类杀菌剂的杀菌组合物
CN113115773A (zh) * 2020-01-15 2021-07-16 江苏龙灯化学有限公司 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
CN111685117A (zh) * 2020-06-30 2020-09-22 青岛润农化工有限公司 一种含苯菌酮和氟酰胺的杀菌组合物及其应用

Also Published As

Publication number Publication date
CN117377388A (zh) 2024-01-09

Similar Documents

Publication Publication Date Title
WO2002087701A1 (fr) Composition agrochimique conferant une resistance aux maladies et stimulant la croissance
JPH02250806A (ja) 殺菌組成物
CN109964940A (zh) 一种杀螨组合物及其制剂、杀螨组合物和制剂的应用
WO2017166565A1 (zh) 具有增效作用的植物生长调节剂组合物
WO2018086634A1 (zh) 包含噻苯隆和极细链格孢激活蛋白的组合物
WO2018059605A2 (zh) 一种植物生长调节剂
CN103749452B (zh) 一种拌种剂
WO2019072061A1 (zh) 包含噻苯隆和聚谷氨酸的农药组合物
WO2018086633A1 (zh) 一种包含苯并异噻唑啉酮类和乙蒜素的杀菌剂组合物
WO2018157649A1 (zh) 一种包含大黄素衍生物与苯并异噻唑啉酮的杀菌剂组合物
WO2017166564A1 (zh) 一种植物生长调节剂组合物
WO2018126878A1 (zh) 一种包含苯并异噻唑啉酮类和四氟醚唑的杀菌剂组合物
JPS63162604A (ja) 殺真菌剤に関する改良
WO2023173248A1 (zh) 一种含四氟醚唑和苯菌酮的杀菌组合物
WO2018068773A2 (zh) 含苯并异噻唑啉酮类和极细链格孢激活蛋白的杀菌组合物
CN104757006A (zh) 一种包含噻呋酰胺的农药组合物
WO2018036294A1 (zh) 一种农药组合物
WO2021143307A1 (zh) 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
WO2018036289A1 (zh) 一种农药组合物
CN102258024A (zh) 一种除草组合物
CN106070245B (zh) 一种杀菌剂组合物
CN101564041B (zh) 一种咪鲜胺和嘧霉胺复配的杀菌组合物
CN109938034A (zh) 除草剂组合物、其制备方法及应用
WO2020038070A1 (zh) 一种除草剂组合物及其制备方法和应用
CN111165499A (zh) 包含Quinofumelin和氟苯醚酰胺的杀菌组合物及其用途和制备方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 202280023920.8

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22931288

Country of ref document: EP

Kind code of ref document: A1