WO2017185559A1 - 一种杀菌剂组合物 - Google Patents

一种杀菌剂组合物 Download PDF

Info

Publication number
WO2017185559A1
WO2017185559A1 PCT/CN2016/094036 CN2016094036W WO2017185559A1 WO 2017185559 A1 WO2017185559 A1 WO 2017185559A1 CN 2016094036 W CN2016094036 W CN 2016094036W WO 2017185559 A1 WO2017185559 A1 WO 2017185559A1
Authority
WO
WIPO (PCT)
Prior art keywords
mancozeb
active component
composition according
mbit
bbit
Prior art date
Application number
PCT/CN2016/094036
Other languages
English (en)
French (fr)
Inventor
郑尊涛
仲汉根
季红进
Original Assignee
江苏辉丰农化股份有限公司
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
Priority to MX2018012244A priority Critical patent/MX2018012244A/es
Priority to EA201892136A priority patent/EA201892136A1/ru
Priority to CA3017537A priority patent/CA3017537C/en
Priority to NZ745272A priority patent/NZ745272A/en
Priority to EP16900068.4A priority patent/EP3420820B1/en
Priority to AU2016404643A priority patent/AU2016404643B2/en
Application filed by 江苏辉丰农化股份有限公司 filed Critical 江苏辉丰农化股份有限公司
Priority to BR112018071895-5A priority patent/BR112018071895B1/pt
Priority to US16/097,474 priority patent/US10694746B2/en
Priority to UAA201809159A priority patent/UA122269C2/uk
Publication of WO2017185559A1 publication Critical patent/WO2017185559A1/zh
Priority to PH12018501990A priority patent/PH12018501990A1/en
Priority to CONC2018/0011392A priority patent/CO2018011392A2/es

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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14—Di-thio analogues thereof
    • 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
    • A01N25/02—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 containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the invention belongs to the field of agricultural plant protection, in particular to a germicidal composition with improved properties, in particular to a germicidal composition comprising benzisothiazolinones and mancozeb.
  • Benzoisothiazolinones are a new type of broad-spectrum fungicide mainly used for the prevention and treatment of various bacterial and fungal diseases such as cereal crops, vegetables and fruits.
  • the mechanism of bactericidal action mainly includes destroying the nuclear structure of the pathogen, causing it to lose the heart part and failing to death and interfering with the metabolism of the pathogenic cells, causing its physiological disorder and ultimately leading to death. It can effectively protect plants from pathogens in the early stage of disease occurrence. Increasing the dosage after disease occurrence can obviously control the spread of pathogens, thus achieving the dual functions of protection and eradication.
  • Mancozeb is a kind of protective fungicide with high efficiency, low toxicity, low residue and wide spectrum of sterilization. It is mainly used to control various fungal diseases such as wheat, fruits and vegetables.
  • the bactericidal mechanism can form a dense protective membrane of gas, water and light on the surface of the leaves and fruits after use, inhibiting the germination and invasion of the spores of the bacteria, and destroying the activities of various enzymes required for the normal physiological metabolism of the bacteria, thereby To achieve the purpose of sterilization and disease prevention.
  • the object of the present invention is to solve the resistance of the bactericide in practical application and the problem of soil residue, and to screen out the fungicides with different sterilization principles to obtain a new fungicide composition, so as to improve the control effect of the bactericide and delay the resistance.
  • Sexual production reducing the amount of application, reducing the cost of prevention.
  • Another object of the present invention is to provide a process for the preparation of a bactericidal composition comprising two active ingredients A and B and for the control of crop diseases in the agricultural sector.
  • the object of the invention can be achieved by the following measures:
  • a synergistic fungicidal composition comprising two active components A and B, wherein active component A is a structural compound having formula (I) and active component B is mancozeb.
  • R is selected from H or a C 1 - C 8 alkyl group.
  • the C 1 -C 8 alkyl group in the present invention means a linear or branched alkyl group having 1 to 8 carbon atoms, and includes a C 1 alkyl group (e.g., methyl group) and a C 2 alkyl group (e.g., ethyl group). , C 3 alkyl (such as n-propyl, isopropyl), C 4 alkyl (such as n-butyl, isobutyl, tert-butyl, sec-butyl), C 5 alkyl (such as n-pentyl, etc.) , C 6 alkyl, C 7 alkyl, C 8 alkyl. It includes, but is not limited to, C 1 -C 6 alkyl, C 1 -C 5 alkyl, C 1 -C 4 alkyl, and the like.
  • R is selected from H or a C 1 -C 4 alkyl group.
  • R is selected from the group consisting of H, -CH 3 or -C 4 H 9 .
  • A is 1,2-benzisothiazolin-3-one (abbreviated as BIT in the specification).
  • R is CH 3
  • A is 2-methyl-1,2-benzisothiazolin-3-one (abbreviated as MBIT in the specification).
  • the inventors have found through experiments that the composition of the present invention is effective for controlling bacterial or fungal diseases of crops, and more importantly, the application amount is reduced and the use cost is lowered.
  • the compounds containing component A and component B have different structural types and different mechanisms of action. The combination of the two can expand the bactericidal spectrum, and can delay the generation and development of pathogen resistance to a certain extent, and component A and group There is no cross-resistance between points B.
  • the weight ratio between the two components in the bactericidal composition of the present invention is from 1:3 to 300, and a preferred embodiment is that the weight ratio of the active component A to the active component B is from 1:4 to 280.
  • the weight ratio between the components of component A and component B can be further optimized to 1:10 to 270.
  • the weight ratio between the two components of A and B can be arbitrarily adjusted within the range of the following ratios: 1:3, 1:4, 1:5, 1:6, 1: 7, 1:8, 1:9, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:190, 1:200, 1:210, 1:220, 1: 230, 1:240, 1:250, 1:260, 1:270, 1:280, 1:290, 1:300, and may also be selected within the range of any two of the above ratios.
  • composition of the present invention can be made into a pesticide-acceptable dosage form from the active ingredient and agrochemical adjuvant or adjuvant.
  • the active ingredient in the composition has a mass content of from 2 to 95%, preferably from 5 to 95%.
  • the composition comprises from 10 to 90% by weight of the active ingredient and from 90 to 10% by weight of the pesticide adjuvant to a pesticide-acceptable dosage form.
  • the present invention provides the use of a bactericidal composition comprising component A and component B for controlling crop diseases in the agricultural sector, in particular for controlling fungi or bacteria of certain crops.
  • composition may specifically comprise an agrochemical adjuvant or an auxiliary such as one or more of a carrier, a solvent, a dispersing agent, a wetting agent, an adhesive, a thickener, a binder, a surfactant or a fertilizer.
  • auxiliary such as one or more of a carrier, a solvent, a dispersing agent, a wetting agent, an adhesive, a thickener, a binder, a surfactant or a fertilizer.
  • auxiliary such as one or more of a carrier, a solvent, a dispersing agent, a wetting agent, an adhesive, a thickener, a binder, a surfactant or a fertilizer.
  • auxiliary such as one or more of a carrier, a solvent, a dispersing agent, a wetting agent, an adhesive, a thickener, a binder, a surfactant or a fertilizer.
  • Common auxiliaries can be mixed during the application.
  • auxiliaries or auxiliaries may be solid or liquid, they are usually materials commonly used in the processing of dosage forms, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders. .
  • the method of application of the compositions of the invention comprises the use of the compositions of the invention for aerial parts of plants, in particular leaves or foliage. You can choose to soak or apply to the surface of the control object.
  • the frequency of administration and the amount administered will depend on the biological and climatic conditions of the pathogen.
  • the plant growth site such as rice fields, may be wetted with a liquid formulation of the composition, or the composition may be applied to the soil in solid form, such as in the form of granules (soil application), the composition may be passed from the soil to the plant through the roots of the plant. In vivo (systemic action).
  • composition of the present invention can be prepared into various pesticide-acceptable dosage forms including, but not limited to, emulsifiable concentrates, suspending agents, wettable powders, water-dispersible granules, powders, granules, aqueous preparations, aqueous emulsions, microemulsions, poison baits.
  • the dosage form of the invention employs a wettable powder, a suspending agent, a water-dispersible granule, an aqueous emulsion or a microemulsion.
  • the compositions may be applied by spraying, misting, dusting, spreading or pouring, and the like.
  • composition of the present invention can be prepared into various dosage forms by a known method, and the active ingredient and the auxiliary agent, such as a solvent, a solid carrier, and, if necessary, can be uniformly mixed and ground together with the surfactant to prepare a desired preparation. Dosage form.
  • the above solvent may be selected from aromatic hydrocarbons, preferably containing from 8 to 12 carbon atoms, such as a mixture of xylenes or substituted benzenes, phthalates such as dibutyl phthalate or dicaprylic acid, aliphatic hydrocarbons such as rings.
  • aromatic hydrocarbons preferably containing from 8 to 12 carbon atoms, such as a mixture of xylenes or substituted benzenes, phthalates such as dibutyl phthalate or dicaprylic acid, aliphatic hydrocarbons such as rings.
  • Alkenes or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl
  • ketones such as cyclohexanone
  • highly polar solvents such as N-methyl-2 Pyrrolidone, dimethyl sulfoxide or dimethylformamide
  • vegetable or vegetable oils such as soybean oil.
  • the above solid carriers are typically natural mineral fillers such as talc, kaolin, montmorillonite or activated clay.
  • a highly dispersible silicic acid or a highly dispersible adsorbent polymer carrier such as a particulate adsorbent carrier or a non-adsorbing carrier, and a suitable particulate adsorbent carrier is porous, such as floating. Stone, bentonite or bentonite; suitable non-adsorbing carriers such as calcite or sand.
  • a large amount of pre-granulated materials of inorganic or organic nature can be used as a carrier, in particular dolomite.
  • Suitable surfactants are lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, alkaline earth metal or amine salts, alkylarylsulfonates, alkyl groups Sulfates, alkyl sulfonates, fatty alcohol sulphates, fatty acids and sulfated fatty alcohol glycol ethers, as well as condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, naphthalene or naphthalene sulfonic acid with phenol and formaldehyde Condensate, polyoxyethylene octyl phenyl ether, ethoxylated isooctyl phenol, octyl phenol, nonyl phenol, alkyl aryl polyglycol ether, tributyl benzene poly
  • the active component A may be first dissolved in a basic substance to form a benzisothiazolin metal salt.
  • Suitable basic substances include: alkali metal carbonates, alkali metal hydroxides (such as hydroxides). Sodium, potassium hydroxide), alkali metal alkoxy carbonate, alkali metal alkoxide or magnesium methoxide.
  • the two active ingredients in the compositions of the present invention exhibit synergistic effects, the activity of which is more pronounced than the expected sum of activity using a single compound, and the individual activity of a single compound.
  • the synergistic effect is manifested by allowing for a reduced application rate, a broader fungicidal control profile, quicker effect, longer lasting control effect, better control of plant harmful fungi by only one or a few applications, and broadening of possible application. Intervals. These properties are particularly desirable in the practice of plant fungi control.
  • the bactericidal composition of the invention can be applied to the agricultural field for controlling crop diseases, and the specific diseases targeted include, but are not limited to, peach perforated bacterial perforation, tobacco wildfire, rice sheath blight, cucumber bacterial angular spot, cucumber Downy mildew, rice bacterial stripe disease, rice bacterial base rot, corn bacterial wilt, watermelon wilt, grape downy mildew, tomato bacterial wilt, eggplant bacterial wilt, rice blast, rice bacterium Stripe disease, pepper anthracnose, litchi ulcer disease, grape anthracnose, tobacco bacterial wilt, cucumber anthracnose, celery spot blotch, lotus root blight, strawberry powdery mildew, lettuce downy mildew, celery gray mold, Apricot bacterial perforation, peach tree canker, onion downy mildew, cotton bacterial leaf spot, cucumber bacterial leaf blight and so on.
  • the other characteristics exhibited by the bactericidal composition of the present invention are mainly as follows: 1.
  • the compounding of the composition of the present invention has obvious synergistic effect; 2. Since the chemical composition of the two single agents of the present composition is greatly different, the effect The mechanism is completely different, there is no cross-resistance, and the problem of resistance caused by the separate use of the two single agents can be delayed; 3.
  • the composition of the present invention is safe and safe for crops. It has been proved by experiments that the bactericidal composition of the invention has stable chemical properties, remarkable synergistic effect, and exhibits obvious synergistic effect and complementary effect on the control object.
  • the active ingredient active group A and the active component B, and the auxiliary agent and the filler are uniformly mixed according to the formula, and are pulverized into a wettable powder by a jet stream, and then added with a certain amount of water to be mixed and extruded, granulated, and dried and sieved.
  • a water dispersible granule product A water dispersible granule product.
  • Active component A BIT
  • active component B to prepare water-dispersible granules
  • Example 1 71% BIT ⁇ Desenmanganese Zinc Water Dispersible Granules
  • BIT 1% mancozebium 70%, potassium dodecylsulfate 5%, ammonium sulfate 3%, alkyl naphthalenesulfonate 4%, light calcium carbonate to 100%.
  • Example 2 50.5% BIT ⁇ Desenmanganese Zinc Water Dispersible Granules
  • Example 3 25.1% BIT ⁇ Desenmanganese Zinc Water Dispersible Granules
  • Active component A MBIT
  • active component B to prepare water-dispersible granules
  • Example 5 50.5% MBIT ⁇ Dyson Manganese Zinc Water Dispersible Granules
  • Example 6 25.1% MBIT ⁇ Desenmanganese Zinc Water Dispersible Granules
  • Active component A BBIT
  • active component B to prepare water-dispersible granules
  • Example 7 71% BBIT ⁇ Dyson Manganese Zinc Water Dispersible Granules
  • Example 8 50.5% BBIT ⁇ Dyson Manganese Zinc Water Dispersible Granules
  • Example 9 25.1% BBIT ⁇ Dyson Manganese Zinc Water Dispersible Granules
  • the active ingredient active group A and the active component B, and the components such as a dispersing agent, a wetting agent, a thickener and water are uniformly mixed according to the formula, and after being sanded and/or sheared at a high speed, a semi-finished product is obtained. After the analysis, the water is mixed and evenly filtered to obtain the finished product.
  • Active component A (BIT) and active component B to prepare suspension agent
  • Example 10 4% BIT ⁇ Mancozeb Suspension
  • Example 12 21% BIT ⁇ Mancozeb Suspension
  • Example 13 5% BIT ⁇ Mancozeb Suspension
  • Example 14 4% MBIT ⁇ Mancozeb Suspension
  • Example 17 5% MBIT ⁇ Mancozeb Suspension
  • Example 18 4% BBIT ⁇ Dyson Manganese Zinc Suspension
  • Example 20 21% BBIT ⁇ Dyson Manganese Zinc Suspension
  • Example 21 5% BBIT ⁇ Mancozeb Suspension
  • the active ingredient A and the B active ingredient are sufficiently mixed with various auxiliary agents and fillers, and are pulverized by an ultrafine pulverizer to obtain a wettable powder.
  • Active component A BIT
  • active component B wettable powder
  • Example 22 60.2% BIT ⁇ Desenmanganese Zinc Wettable Powder (1:300)
  • Example 23 40.2% BIT ⁇ Desenmanganese Zn Wettable Powder (1:200)
  • Example 24 51% BIT ⁇ Desenmanganese Zn Wettable Powder (1:50)
  • BIT 1% mancozeb 50%, sodium lignin sulfonate 6%, alkyl sulfonate 7%, white carbon black 10%, kaolin to 100%.
  • Active component A MBIT
  • active component B active component B
  • Example 25 60.2% MBIT ⁇ Desenmanganese Zn Wettable Powder
  • Example 26 40.2% MBIT ⁇ Dyson Manganese Zinc Wettable Powder
  • Example 27 51% MBIT ⁇ Dyson Manganese Zinc Wettable Powder
  • Active component A (BBIT) and active component B to prepare wettable powder
  • Example 28 60.2% BBIT ⁇ Desenmanganese Zn Wettable Powder
  • Example 29 40.2% BBIT ⁇ Desenmanganese Zn Wettable Powder
  • Example 30 51% BBIT ⁇ Dyson Manganese Zinc Wettable Powder
  • the control effect is converted into the probability value (y), the liquid height ( ⁇ g/ml) is converted into a logarithmic value (x), the virulence equation is calculated by the least squares method, and the neutral concentration EC50 is suppressed, and the virulence of the drug is calculated according to the method of Sun Yunpei. Exponential Co-toxicity Factor (CTC).
  • CTC Exponential Co-toxicity Factor
  • Measured virulence index (ATI) (standard drug EC50 / test drug EC50) * 100
  • Theoretical virulence index (TTI) A virulence index * Percentage of A in the mixture + B virulence index * Percentage of B in the mixture
  • CTC Co-toxicity coefficient [mixture measured virulence index (ATI) / mixed theory virulence index (TTI)] * 100
  • CTC ⁇ 80 the composition showed antagonism, 80 ⁇ CTC ⁇ 120, the composition showed an additive effect, CTC ⁇ 120, and the composition showed synergistic effect.
  • Test method In the early stage of the disease, the first spray was immediately performed, and after 7 days, the second application was carried out, each treatment of 4 cells, 20 square meters per cell. The incidence of the disease was investigated before the drug and 11 days after the second drug. Each plot was randomly sampled at 5 points, and 5 crops were investigated at each point. The percentage of the lesion area per leaf on the whole plant was counted and graded. Disease index and control effect.
  • Grade 1 less than 5 leaf lesions, less than 1 cm in length;
  • Grade 3 6-10 leaf lesions, some lesions are longer than 1 cm;
  • Grade 5 11-25 leaf lesions, some lesions are connected into pieces, and the lesion area accounts for 10-25% of the leaf area;
  • Grade 7 more than 26 leaf lesions, the lesions are connected into pieces, and the lesion area accounts for 26-50% of the leaf area;
  • Grade 9 The lesions are connected into pieces, and the area of the lesions accounts for more than 50% of the leaf area or the whole leaves are dead.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

提供了一种杀菌剂组合物，其包含两种有效成分A和B，活性组分A为具有式(Ⅰ)的结构化合物，活性组分B为代森锰锌，两组分之间的重量比为1:1～400。还提供了该组合物的制备方法及用途。试验结果表明，上述杀菌组合物增效明显，更重要的是施用量减少，使用成本降低。该杀菌组合物能有效防治作物的某些特定的真菌病害。通过将不同作用机制和作用方式的杀菌剂进行复配，有效降低各单剂的施用量，对于扩大杀菌谱和延缓真菌、真菌抗性以及提高防治效果等方面具有很好的作用。

Description

一种杀菌剂组合物 技术领域
本发明属于农业植物保护领域，特别是涉及一种具有改进性能的杀菌组合物，具体地说是涉及一种包含苯并异噻唑啉酮类和代森锰锌的杀菌组合物。
背景技术
苯并异噻唑啉酮类化合物是一种新型、广谱杀菌剂，主要用于防治和治疗禾谷类作物、蔬菜、水果等多种细菌、真菌性病害。其杀菌作用机理，主要包括破坏病菌细胞核结构，使其失去心脏部位而衰竭死亡和干扰病菌细胞的新陈代谢，使其生理紊乱，最终导致死亡两个方面。在病害发生初期使用可有效保护植株不受病原物侵染，病害发生后酌情增加用药量可明显控制病菌的蔓延，从而达到保护和铲除的双重作用。
代森锰锌是一种高效、低毒、低残留、杀菌谱广的保护性杀菌剂，主要用于防治麦类、水果、蔬菜等多种真菌病害。其杀菌作用机理，使用后可在叶片、果实的表面形成一层透气、透水、透光的致密保护膜，抑制病菌孢子的萌发和入侵，破坏病菌正常生理代谢所需各种酶的活性，从而达到杀菌防病的目的。
实际的农药经验已经表明，重复且专一施用一种活性化合物来防治有害真菌在很多情况下将导致真菌菌株的快速选择性，为降低抗性真菌菌株选择性的危险性，目前通常使用不同活性化合物的混合物来防治有害真菌。通过将具有不同作用机理的活性化合物进行组合，可延缓抗性产生，降低施用量，减少防治成本。
发明内容
本发明的目的是针对杀菌剂在实际应用中抗性以及土壤残留问题，筛选出不同杀菌原理的杀菌剂进行复配，得到新的一种杀菌剂组合物，以提高杀菌剂防治效果，延缓抗性产生，降低施用量，减少防治成本。
本发明的另一个目的是提供包含两种有效成分A和B杀菌组合物的制备方法及在农业领域防治农作物病害的应用。
本发明的目的可以通过以下措施达到：
一种具有增效作用的杀菌剂组合物，该组合物包含A和B两种活性组分，其中活性组分A为具有式(Ⅰ)的结构化合物，活性组分B为代森锰锌。
Figure PCTCN2016094036-appb-000001
式(Ⅰ)中，R选自H或C1～C8烷基。
本发明中的C1～C8烷基是指含有1至8个碳原子的直链或支链烷基，它包括C1烷基(如甲基)、C2烷基(如乙基)、C3烷基(如正丙基、异丙基)、C4烷基(如正丁基、异丁基、叔丁基、仲丁基)、C5烷基(如正戊基等)、C6烷基、C7烷基、C8烷基。它包括但不限于C1～C6烷基、C1～C5烷基、C1～C4烷基等。
在一种优选方案中，R选自H或C1～C4烷基。
在一种更优选的方案中，R选自H、-CH3或-C4H9。
式(Ⅰ)中，当R为H时，A为1,2-苯并异噻唑啉-3-酮(说明书中简称BIT)。
式(Ⅰ)中，当R为CH3时，A为2-甲基-1,2-苯并异噻唑啉-3-酮(说明书中简称MBIT)。
式(Ⅰ)中，当R为C4H9时，A为2-正丁基-1,2-苯并异噻唑啉-3-酮，该式中的“丁基”为正丁基(说明书中简称BBIT)。
发明人通过试验发现，本发明的组合物是用于防治农作物细菌或真菌性病害防治增效明显，更重要的是施用量减少，降低使用成本。含有组分A与组分B的化合物结构类型不同，作用机制各异，两者复配能够扩大杀菌谱，并且可以在一定程度上延缓病原菌抗性的产生和发展速度，且组分A与组分B之间无交互抗性。
本发明杀菌剂组合物中的两组分之间的重量比为1:3～300，有一种优选方案为活性组分A与活性组分B的重量比为1:4～280。为使两组分间的药效增效作用更为显著，组分A和组分B的重量两组分之间的重量比可以进一步优化至1:10～270。
在一种优选的方案中，A和B两组分之间的重量比可以任意地在下述配比的范围内进行调整：1：3、1：4、1：5、1：6、1：7、1：8、1：9、1：10、1：20、1：30、1：40、1：50、1：60、1：70、1：80、1：90、1：100、1：110、1：120、1：130、1：140、1：150、1：160、1：170、1：180、1：190、1：200、1：210、1：220、1：230、1：240、1：250、1：260、1：270、1：280、1：290、1：300，也可以在以上任意两个配比所组成的范围内进行选择。
本发明的组合物可以由活性成分和农药助剂或辅料制成农药上允许的剂型。
在一种方案中，组合物中的活性成分的质量含量为2～95％，优选5～95％。
在另一种方案中，该组合物由10～90％重量份的活性组分与90～10％重量份的农药助剂组成农药上允许的剂型。
本发明提供了包含组分A和组分B的杀菌组合物在农业领域防治农作物病害方面的用途，特别是在防治某些作物的真菌或细菌方面的用途。
上述组合物具体可包含农药助剂或辅料，例如载体、溶剂、分散剂、润湿剂、胶粘剂、增稠剂、粘合剂、表面活性剂或肥料等中的一种或几种。在施用的过程中可以混合常用的助剂。
合适的助剂或辅料可以是固体或液体，它们通常是剂型加工过程中常用的物质，例如天然的或再生的矿物质，溶剂、分散剂、润湿剂、胶粘剂、增稠剂、粘合剂。
本发明组合物的施用方法包括将本发明的组合物用于植物生长的地上部分，特别是叶部或叶面。可以选择浸种或涂抹于防治对象表面。施用的频率和施用量取决于病原体的生物学和气候生存条件。可以将植物的生长场所，如稻田，用组合物的液体制剂浸湿，或者将组合物以固体形式施用于土壤中，如以颗粒形式(土壤施用)，组合物可以由土壤经植物根部进入植物体内(内吸作用)。
本发明的组合物可以制备成农药上可接受的各种剂型，包括但不限于乳油、悬浮剂、可湿性粉剂、水分散粒剂、粉剂、粒剂、水剂、水乳剂、微乳剂、毒饵、母液、母粉等，在一种优选方案中，本发明的剂型采用可湿性粉剂、悬浮剂、水分散粒剂、水乳剂或微乳剂。根据这些组合物的性质以及施用组合物所要达到的目的和环境情况，可以选择将组合物以喷雾、弥雾、喷粉、撒播或泼浇等之类的方法施用。
可用已知的方法可以将本发明的组合物制备成各种剂型，可以将有效成分与助剂，如溶剂、固体载体，需要时可以与表面活性剂一起均匀混合、研磨，制备成所需要的剂型。
上述的溶剂可选自芳香烃，优选含8-12个碳原子，如二甲苯混合物或取代的苯，酞酸酯类，如酞酸二丁酯或酞酸二辛酸，脂肪烃类，如环已烷或石蜡，醇和乙二醇和它们的醚和酯，如乙醇，乙二醇，乙二醇单甲基；酮类，如环已酮，强极性的溶剂，如N-甲基-2-吡咯烷酮，二甲基亚砜或二甲基甲酰胺，和植物油或植物油，如大豆油。
上述的固体载体，如用于粉剂和可分散剂的通常是天然矿物填料，例如滑石、高岭土，蒙脱石或活性白土。为了管理组合物的物理性能，也可以加入高分散性硅酸或高分散性吸附聚合物载体，例如粒状吸附载体或非吸附载体，合适的粒状吸附载体是多孔型的，如浮 石、皂土或膨润土；合适的非吸附载体如方解石或砂。另外，可以使用大量的无机性质或有机性质的预制成粒状的材料作为载体，特别是白云石。
根据本发明的组合物中的有效成分的化学性质，合适的表面活性剂为木质素磺酸、萘磺酸、苯酚磺酸、碱土金属盐或胺盐，烷基芳基磺酸盐，烷基硫酸盐，烷基磺酸盐，脂肪醇硫酸盐，脂肪酸和硫酸化脂肪醇乙二醇醚，还有磺化萘和萘衍生物与甲醛的缩合物，萘或萘磺酸与苯酚和甲醛的缩合物，聚氧乙烯辛基苯基醚，乙氧基化异辛基酚，辛基酚，壬基酚，烷基芳基聚乙二醇醚，三丁基苯聚乙二醇醚，三硬脂基苯基聚乙二醇醚，烷基芳基聚醚醇，乙氧基化蓖麻油，聚氧乙烯烷基醚，氧化乙烯缩合物、乙氧基化聚氧丙烯，月桂酸聚乙二醇醚缩醛，山梨醇酯，木质素亚硫酸盐废液和甲基纤维素。
在制备液体剂型时，可以先将活性组分A溶于碱性物质，形成苯并异噻唑啉金属盐，合适的碱性物质包括：碱金属碳酸盐、碱金属氢氧化物(如氢氧化钠、氢氧化钾)、碱金属烷氧基碳酸盐、碱金属醇盐或甲醇镁。
本发明的组合物中两种有效成分表现为增效效果，该组合物的活性比使用单个化合物的活性预期总和，以及单个化合物的单独活性更为显著。增效效果表现为允许施用量减少、更宽的杀真菌控制谱、见效快、更持久的防治效果、通过仅仅一次或少数几次施用更好的控制植物有害真菌、以及加宽了可能的施用间隔时间。这些特性是植物真菌控制实践过程中特别需要的。
本发明的杀菌剂组合物可应用于农业领域防治农作物病害方面，所针对的具体病症包括但不限于桃树细菌性穿孔病、烟草野火病、水稻纹枯病、黄瓜细菌性角斑病、黄瓜霜霉病、水稻细菌性条斑病、水稻细菌性基腐病、玉米细菌性枯萎病、西瓜枯萎病、葡萄霜霉病、番茄青枯病、茄子青枯病、水稻稻曲病、水稻细菌性条斑病、辣椒炭疽病、荔枝溃疡病、葡萄炭疽病、烟草青枯病、黄瓜炭疽病、芹菜斑枯病、莲藕立枯病、草莓白粉病、莴苣霜霉病、芹菜灰霉病、杏细菌性穿孔病、桃树溃疡病、洋葱霜霉病、棉花细菌性角斑病、黄瓜细菌性叶枯病等。
本发明的杀菌组合物的表现出的其它特点主要表现为：1、本发明的组合物混配具有明显的增效作用；2、由于本组合物的两个单剂化学结构差异很大，作用机理完全不同，不存在交互抗性，可延缓两单剂单独使用所产生的抗性问题；3、本发明的组合物对作物安全、防效好。经试验证明，本发明杀菌剂组合物化学性质稳定，增效显著，对防治对象表现出明显的增效以及互补作用。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明，凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
以下实施例所有配方中百分比均为重量百分比。本发明组合物各种制剂的加工工艺均为现有技术，根据不同情况可以有所变化。
一、剂型制备实施例
(一)水分散粒剂的加工及实施例
将活性成分活性分组A与活性组分B，与助剂和填料按配方的比例混合均匀，经气流粉碎成可湿性粉剂，再加入一定量的水混合挤压造粒，经干燥筛分后制得水分散粒剂产品。
1、活性组分A(BIT)与活性组分B制备水分散粒剂
实施例1：71％BIT·代森锰锌水分散粒剂
BIT 1％，代森锰锌70％，十二烷基磺酸钾5％，硫酸铵3％，烷基萘磺酸钾4％，轻质碳酸钙补足至100％。
实施例2：50.5％BIT·代森锰锌水分散粒剂
BIT 0.5％，代森锰锌50％，甲基萘磺酸钠甲醛缩合物5％，十二烷基硫酸钠3％，木质素磺酸钠6％,硅藻土补足至100％。
实施例3：25.1％BIT·代森锰锌水分散粒剂
BIT 0.1％，代森锰锌25％，羧甲基淀粉钠2％，十二烷基磺酸钠4％，黄原胶2％，木质素磺酸钠6％,凹凸棒土补足至100％。
2、活性组分A(MBIT)与活性组分B制备水分散粒剂
实施例4：71％MBIT·代森锰锌水分散粒剂
MBIT 1％，代森锰锌70％，其余组分按照实施例1的方法制备。
实施例5：50.5％MBIT·代森锰锌水分散粒剂
MBIT 0.5％，代森锰锌50％，其余组分按照实施例2的方法制备。
实施例6：25.1％MBIT·代森锰锌水分散粒剂
MBIT 0.1％，代森锰锌25％，其余组分按照实施例3的方法制备。
3、活性组分A(BBIT)与活性组分B制备水分散粒剂
实施例7：71％BBIT·代森锰锌水分散粒剂
BBIT 1％，代森锰锌70％，其余组分按照实施例1的方法制备。
实施例8：50.5％BBIT·代森锰锌水分散粒剂
BBIT 0.5％，代森锰锌50％，其余组分按照实施例2的方法制备。
实施例9：25.1％BBIT·代森锰锌水分散粒剂
BBIT 0.1％，代森锰锌25％，其余组分按照实施例3的方法制备。
(二)悬浮剂的加工及实施例
将活性成分活性分组A与活性组分B，与分散剂、润湿剂、增稠剂和水等各组分按配方的比例混合均匀，经砂磨和/或高速剪切后，得到半成品，分析后补加水混合均匀过滤即得成品。
1、活性组分A(BIT)与活性组分B制备悬浮剂
实施例10：4％BIT·代森锰锌悬浮剂
BIT 1％，代森锰锌3％，黄原胶3％，膨润土4％，硅酸铝镁2％，乙二醇2％，木质素磺酸钠7％,水补足至100％。
实施例11：15.1％BIT·代森锰锌悬浮剂
BIT 0.1％，代森锰锌15％，膨润土4％，丙三醇3％，甲基萘磺酸钠甲醛缩合物5％，水补足至100％。
实施例12：21％BIT·代森锰锌悬浮剂
BIT 1％，代森锰锌20％，白炭黑3％，丙三醇6％，苯甲酸钠2％，脂肪醇聚氧乙烯醚磷酸酯7％,水补足至100％。
实施例13：5％BIT·代森锰锌悬浮剂
BIT 1％，代森锰锌4％，白炭黑4％，乙二醇5％，木质素磺酸钠7％,黄原胶2％，水补足至100％。
2、活性组分A(MBIT)与活性组分B制备悬浮剂
实施例14：4％MBIT·代森锰锌悬浮剂
MBIT 1％，代森锰锌3％，其余组分按照实施例10的方法制备。
实施例15：15.1％MBIT·代森锰锌悬浮剂
MBIT 0.1％，代森锰锌15％，其余组分按照实施例11的方法制备。
实施例16：21％MBIT·代森锰锌悬浮剂
MBIT 1％，代森锰锌20％，其余组分按照实施例12的方法制备。
实施例17：5％MBIT·代森锰锌悬浮剂
MBIT 1％，代森锰锌4％，其余组分按照实施例13的方法制备。
3、活性组分A(BBIT)与活性组分B制备悬浮剂
实施例18：4％BBIT·代森锰锌悬浮剂
BBIT 1％，代森锰锌3％，其余组分按照实施例10的方法制备。
实施例19：15.1％BBIT·代森锰锌悬浮剂
BBIT 0.1％，代森锰锌15％，其余组分按照实施例11的方法制备。
实施例20：21％BBIT·代森锰锌悬浮剂
BBIT 1％，代森锰锌20％，其余组分按照实施例12的方法制备。
实施例21：5％BBIT·代森锰锌悬浮剂
BBIT 1％，代森锰锌4％，其余组分按照实施例13的方法制备。
(三)可湿性粉剂的加工及实施例
将活性成分A与B活性成分与各种助剂及填料等按比例充分混合，经超细粉碎机粉碎后制得可湿性粉剂。
1、活性组分A(BIT)与活性组分B制备可湿性粉剂
实施例22:60.2％BIT·代森锰锌可湿性粉剂(1:300)
BIT 0.2％，代森锰锌60％，十二烷基苯磺酸钠2％，木质素磺酸钙3％，膨润土3％，凹凸棒土补足至100％。
实施例23:40.2％BIT·代森锰锌可湿性粉剂(1:200)
BIT 0.2％，代森锰锌40％，拉开粉2％，膨润土1.5％，烷基聚氧乙基醚磺酸盐1％，白炭黑2％，硅藻土补足至100％。
实施例24:51％BIT·代森锰锌可湿性粉剂(1:50)
BIT 1％，代森锰锌50％，木质素磺酸钠6％，烷基磺酸盐7％，白炭黑10％，高岭土补足至100％。
2、活性组分A(MBIT)与活性组分B制备可湿性粉剂
实施例25：60.2％MBIT·代森锰锌可湿性粉剂
MBIT 0.2％，代森锰锌60％，其余组分按照实施例22的方法制备。
实施例26：40.2％MBIT·代森锰锌可湿性粉剂
MBIT 0.2％，代森锰锌40％，其余组分按照实施例23的方法制备。
实施例27：51％MBIT·代森锰锌可湿性粉剂
MBIT 1％，代森锰锌50％，其余组分按照实施例24的方法制备。
3、活性组分A(BBIT)与活性组分B制备可湿性粉剂
实施例28：60.2％BBIT·代森锰锌可湿性粉剂
BBIT 0.2％，代森锰锌60％，其余组分按照实施例22的方法制备。
实施例29：40.2％BBIT·代森锰锌可湿性粉剂
BBIT 0.2％，代森锰锌40％，其余组分按照实施例23的方法制备。
实施例30：51％BBIT·代森锰锌可湿性粉剂
BBIT 1％，代森锰锌50％，其余组分按照实施例24的方法制备。
二、药效验证试验
(一)生物测定实施例
按照试验分级标准调查整株叶片的发病情况，计算病情指数和防治效果。
将防治效果换算成几率值(y)，药液弄高度(μg/ml)转换成对数值(x)，以最小二乘法计算毒力方程和抑制中浓度EC50，依孙云沛法计算药剂的毒力指数级共毒系数(CTC)。
实测毒力指数(ATI)＝(标准药剂EC50/供试药剂EC50)*100
理论毒力指数(TTI)＝A药剂毒力指数*混剂中A的百分含量+B药剂毒力指数*混剂中B的百分含量
共毒系数(CTC)＝[混剂实测毒力指数(ATI)/混剂理论毒力指数(TTI)]*100
CTC≤80,组合物表现为拮抗作用,80＜CTC＜120，组合物表现为相加作用,CTC≥120，组合物表现为增效作用。
1、BIT与代森锰锌复配对毒力测定试验
表1.BIT与代森锰锌复配对黄瓜霜霉病毒力测定结果分析
药剂名称 EC50(μg/ml) ATI TTI 共毒系数(CTC)
BIT 13.5 100.00 / /
代森锰锌 75.17 17.96 / /
BIT：代森锰锌＝1：300 60.79 22.21 18.233 121.81
BIT：代森锰锌＝1：250 58.32 23.15 18.287 126.58
BIT：代森锰锌＝1：200 56.70 23.81 18.368 129.62
BIT：代森锰锌＝1：150 54.14 24.94 18.503 134.76
BIT：代森锰锌＝1：100 50.88 26.53 18.772 141.35
BIT：代森锰锌＝1：75 50.41 26.78 18.233 146.87
BIT：代森锰锌＝1：50 48.29 27.95 19.569 142.85
BIT：代森锰锌＝1：20 46.56 28.99 21.867 132.59
BIT：代森锰锌＝1：10 41.88 32.24 25.418 126.83
BIT：代森锰锌＝1：4 31.70 42.59 34.368 123.91
BIT：代森锰锌＝1：3 29.06 46.45 38.470 120.75
BIT：代森锰锌＝1：2 25.70 52.52 45.307 115.93
结果(表1)表明，BIT与代森锰锌复配对黄瓜霜霉病的防治效果显著提高，说明二者复配对黄瓜霜霉病防治有显著的增效作用。
2、MBIT与代森锰锌复配对毒力测定试验
表2.MBIT与代森锰锌复配对马铃薯晚疫病毒力测定结果分析
药剂名称 EC50(μg/ml) ATI TTI 共毒系数(CTC)
MBIT 14.81 100.00 / /
代森锰锌 68.27 21.69 / /
MBIT：代森锰锌＝1：300 54.53 27.16 21.950 123.740
MBIT：代森锰锌＝1：250 51.61 28.69 22.002 130.414
MBIT：代森锰锌＝1：200 50.28 29.45 22.080 133.393
MBIT：代森锰锌＝1：150 48.17 30.74 22.209 138.431
MBIT：代森锰锌＝1：100 45.50 32.55 22.465 144.889
MBIT：代森锰锌＝1：75 45.50 32.55 21.950 148.298
MBIT：代森锰锌＝1：50 44.48 33.30 23.225 143.359
MBIT：代森锰锌＝1：20 42.75 34.65 25.419 136.304
MBIT：代森锰锌＝1：10 39.34 37.64 28.809 130.659
MBIT：代森锰锌＝1：4 31.27 47.36 37.352 126.798
MBIT：代森锰锌＝1：3 29.25 50.64 41.268 122.701
MBIT：代森锰锌＝1：2 26.04 56.86 47.793 118.977
结果(表2)表明，MBIT与代森锰锌复配对马铃薯晚疫病的防治效果显著提高，说明二者复配对马铃薯晚疫病防治有显著的增效作用。尤其是MBIT与代森锰锌配比在1:3～300之间，增效作用明显。
3、BBIT与代森锰锌复配对毒力测定试验
表3.BBIT与代森锰锌复配对苹果树炭疽病毒力测定结果分析
药剂名称 EC50(μg/ml) ATI TTI 共毒系数(CTC)
BBIT 19.09 100 / /
代森锰锌 92.36 20.67 / /
BBIT：代森锰锌＝1：300 75.22 25.38 20.934 121.237
BBIT：代森锰锌＝1：250 72.22 26.43 20.986 125.959
BBIT：代森锰锌＝1：200 68.16 28.01 21.065 132.969
BBIT：代森锰锌＝1：150 65.71 29.05 21.195 137.058
BBIT：代森锰锌＝1：100 61.97 30.81 21.455 143.583
BBIT：代森锰锌＝1：75 62.44 30.57 20.934 146.048
BBIT：代森锰锌＝1：50 60.89 31.35 22.225 141.068
BBIT：代森锰锌＝1：20 58.31 32.74 24.448 133.910
BBIT：代森锰锌＝1：10 52.58 36.30 27.882 130.207
BBIT：代森锰锌＝1：4 41.36 46.15 36.536 126.316
BBIT：代森锰锌＝1：3 38.57 49.49 40.503 122.187
BBIT：代森锰锌＝1：2 34.22 55.79 47.113 118.415
结果(表3)表明，BBIT与代森锰锌复配对苹果树炭疽病的防治效果显著提高，说明二者复配对苹果树炭疽病防治有显著的增效作用。
(二)田间药效验证试验
试验方法：在发病初期，立即进行第一次喷雾，7天后进行第二次施药，每个处理4个小区，每个小区20平米。于药前和第二次药后11天调查统计发病情况，每个小区5点随机取样，每点调查5株作物，调查整株上每叶片的病斑面积占叶片面积的百分率并分级，计算病情指数和防治效果。
Figure PCTCN2016094036-appb-000002
Figure PCTCN2016094036-appb-000003
预期防效(％)＝X+Y-XY/100(其中，X，Y为单剂防效)
分级标准：
0级：无病斑；
1级：叶片病斑少于5个，长度小于1cm；
3级：叶片病斑6-10个，部分病斑长度大于1cm；
5级：叶片病斑11-25个，部分病斑连成片，病斑面积占叶面积的10-25％；
7级：叶片病斑26个以上，病斑连成片，病斑面积占叶面积的26-50％；
9级：病斑连成片，病斑面积占叶面积的50％以上或全叶枯死。
1、BIT与代森锰锌复配田间药效实验
表4 BIT与代森锰锌混配对苹果轮纹病防治效果
Figure PCTCN2016094036-appb-000004
Figure PCTCN2016094036-appb-000005
Figure PCTCN2016094036-appb-000006
测定结果(表4)表明，BIT与代森锰锌混配对苹果轮纹病的防效明显提高，说明二者复配对苹果轮纹病有显著的增效作用。
2、MBIT与代森锰锌复配田间药效实验
表5 MBIT与代森锰锌混配对番茄早疫病防治效果
Figure PCTCN2016094036-appb-000007
Figure PCTCN2016094036-appb-000008
Figure PCTCN2016094036-appb-000009
测定结果(表5)表明，MBIT与代森锰锌混配对番茄早疫病的防效明显提高，说明二者复配对番茄早疫病有显著的增效作用。
3、BBIT与代森锰锌复配田间药效实验
表6 BBIT与代森锰锌混配对梨树黑星病防治效果
Figure PCTCN2016094036-appb-000010
Figure PCTCN2016094036-appb-000011
Figure PCTCN2016094036-appb-000012
测定结果(表6)表明，BBIT与代森锰锌混配对梨树黑星病的防效明显提高，说明二者复配对梨树黑星病有显著的增效作用。

Claims (10)

  1. 一种杀菌剂组合物，其特征在于所述的组合物包含A和B两种活性组分，其中活性组分A为具有式(Ⅰ)的结构化合物，活性组分B为代森锰锌，两组分之间的重量比为1:3～300，
    Figure PCTCN2016094036-appb-100001
    式(Ⅰ)中，R选自H或C1～C8烷基。
  2. 根据权利要求1所述的杀菌剂组合物，其特征在于式(Ⅰ)中，R选自H或C1～C4烷基。
  3. 根据权利要求2所述的杀菌剂组合物，其特征在于式(Ⅰ)中，R选自H、-CH3或-C4H9，对应的活性组分A分别为1,2-苯并异噻唑啉-3-酮、2-甲基-1,2-苯并异噻唑啉-3-酮或2-正丁基-1,2-苯并异噻唑啉-3-酮。
  4. 根据权利要求1所述的杀菌剂组合物，其特征在于活性组分A和活性组分B的重量比为1:4～280。
  5. 根据权利要求4所述的杀菌剂组合物，其特征在于活性组分A和活性组分B的重量比为1:10～260。
  6. 根据权利要求1～5中任意一项所述的杀菌剂组合物，其特征在于该组合物由活性成分和农药助剂或辅料制成农药上允许的剂型。
  7. 根据权利要求6所述的杀菌剂组合物，其特征在于所述活性成分的质量含量为2～95％。
  8. 根据权利要求6所述的杀菌剂组合物，其特征在于所述的剂型为可湿性粉剂、悬浮剂或水分散粒剂。
  9. 根据权利要求6所述的杀菌剂组合物，其特征在于所述农药助剂或辅料选自载体、溶剂、分散剂、润湿剂、胶粘剂、增稠剂、粘合剂、表面活性剂或肥料中的一种或几种。
  10. 权利要求1～9中任意一项所述的杀菌剂组合物在农业领域防治农作物病害方面的用途。
PCT/CN2016/094036 2016-04-29 2016-08-08 一种杀菌剂组合物 WO2017185559A1 (zh)

Priority Applications (11)

Application Number Priority Date Filing Date Title
EA201892136A EA201892136A1 (ru) 2016-04-29 2016-08-08 Бактерицидная и фунгицидная композиция
CA3017537A CA3017537C (en) 2016-04-29 2016-08-08 Fungicidal composition
NZ745272A NZ745272A (en) 2016-04-29 2016-08-08 Fungicidal composition
EP16900068.4A EP3420820B1 (en) 2016-04-29 2016-08-08 Fungicidal composition
AU2016404643A AU2016404643B2 (en) 2016-04-29 2016-08-08 Anti-microbial composition
MX2018012244A MX2018012244A (es) 2016-04-29 2016-08-08 Composicion fungicida.
BR112018071895-5A BR112018071895B1 (pt) 2016-04-29 2016-08-08 Composição fungicida
US16/097,474 US10694746B2 (en) 2016-04-29 2016-08-08 Fungicidal composition
UAA201809159A UA122269C2 (uk) 2016-04-29 2016-08-08 Фунгіцидна композиція
PH12018501990A PH12018501990A1 (en) 2016-04-29 2018-09-14 Fungicidal composition
CONC2018/0011392A CO2018011392A2 (es) 2016-04-29 2018-10-25 Composición fungicida

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610287269 2016-04-29
CN201610287269.1 2016-04-29

Publications (1)

Publication Number Publication Date
WO2017185559A1 true WO2017185559A1 (zh) 2017-11-02

Family

ID=57666040

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/094036 WO2017185559A1 (zh) 2016-04-29 2016-08-08 一种杀菌剂组合物

Country Status (13)

Country Link
US (1) US10694746B2 (zh)
EP (1) EP3420820B1 (zh)
CN (1) CN106259387A (zh)
AU (1) AU2016404643B2 (zh)
BR (1) BR112018071895B1 (zh)
CA (1) CA3017537C (zh)
CO (1) CO2018011392A2 (zh)
EA (1) EA201892136A1 (zh)
MX (1) MX2018012244A (zh)
NZ (1) NZ745272A (zh)
PH (1) PH12018501990A1 (zh)
UA (1) UA122269C2 (zh)
WO (1) WO2017185559A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106259387A (zh) * 2016-04-29 2017-01-04 江苏辉丰农化股份有限公司 一种杀菌剂组合物
CN106259366B (zh) * 2016-06-26 2019-06-21 江苏辉丰农化股份有限公司 一种杀菌剂组合物
CN106489965A (zh) * 2016-09-23 2017-03-15 江苏辉丰农化股份有限公司 一种杀菌剂组合物
WO2019241058A1 (en) * 2018-06-10 2019-12-19 Troy Corporation Formaldehyde-free preservatives for highly susceptible products

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1566113A (zh) * 1998-06-17 2005-01-19 拜尔公司 防治植物害虫的组合物
CN1566104A (zh) * 1998-06-10 2005-01-19 拜尔公司 防治植物有害生物的组合物
CN1878469A (zh) * 2003-11-11 2006-12-13 巴斯福股份公司 杀微生物组合物及其应用
CN106259387A (zh) * 2016-04-29 2017-01-04 江苏辉丰农化股份有限公司 一种杀菌剂组合物

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060084573A1 (en) * 2004-10-12 2006-04-20 Biagro Western Sales, Inc. High calcium fertilizer composition
TW200740369A (en) * 2005-11-01 2007-11-01 Dow Agrosciences Llc Pesticidally active compositions having enhanced activity
CA2707819C (en) * 2007-06-21 2013-06-18 Rohm And Haas Company Microbicidal composition comprising n-methyl-1,2-benzisothiazolin-3-one and formaldehyde
MX2010010729A (es) * 2008-04-01 2010-11-01 Dow Agrosciences Llc Composiciones y metodos para controlar los patogenos fungicos de oomiceto.
CN101984809B (zh) * 2010-07-22 2012-11-21 福建诺德生物科技有限责任公司 一种以松脂基植物油为载体的油悬制剂及其制备方法
CN101999372B (zh) * 2010-12-14 2015-11-25 陕西西大华特科技实业有限公司 含有噻霉酮和苯醚甲环唑的杀菌组合物
CN102172240B (zh) * 2011-03-01 2015-09-30 陕西西大华特科技实业有限公司 一种含有噻霉酮和甲氧基丙烯酸酯类杀菌剂的杀菌组合物
JP5575179B2 (ja) * 2011-06-07 2014-08-20 ローム アンド ハース カンパニー 安定な殺生物剤組成物
CN104094946B (zh) * 2013-06-09 2015-11-18 江苏辉丰农化股份有限公司 具有增效作用的杀菌组合物
CN103960264B (zh) * 2014-05-05 2015-07-01 河北双吉化工有限公司 一种含有吡唑醚菌酯、代森锰锌和复硝酚钠的杀菌组合物
CN104488534A (zh) * 2014-12-31 2015-04-08 天津市金三农农业科技开发有限公司 一种温室种植山药的方法
CN105685061A (zh) * 2016-02-29 2016-06-22 陕西西大华特科技实业有限公司 噻霉酮在防治马铃薯种传病害及促根发芽上的应用
WO2019241058A1 (en) * 2018-06-10 2019-12-19 Troy Corporation Formaldehyde-free preservatives for highly susceptible products

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1566104A (zh) * 1998-06-10 2005-01-19 拜尔公司 防治植物有害生物的组合物
CN1566113A (zh) * 1998-06-17 2005-01-19 拜尔公司 防治植物害虫的组合物
CN1878469A (zh) * 2003-11-11 2006-12-13 巴斯福股份公司 杀微生物组合物及其应用
CN106259387A (zh) * 2016-04-29 2017-01-04 江苏辉丰农化股份有限公司 一种杀菌剂组合物

Also Published As

Publication number Publication date
AU2016404643A1 (en) 2018-08-30
BR112018071895A2 (pt) 2019-02-05
CA3017537A1 (en) 2017-11-02
EA201892136A1 (ru) 2019-05-31
US20190150446A1 (en) 2019-05-23
EP3420820A4 (en) 2019-08-28
BR112018071895B1 (pt) 2022-06-21
EP3420820B1 (en) 2022-02-16
UA122269C2 (uk) 2020-10-12
EP3420820A1 (en) 2019-01-02
CO2018011392A2 (es) 2018-11-13
CN106259387A (zh) 2017-01-04
US10694746B2 (en) 2020-06-30
NZ745272A (en) 2020-08-28
AU2016404643B2 (en) 2021-05-06
MX2018012244A (es) 2019-02-07
PH12018501990A1 (en) 2019-07-01
CA3017537C (en) 2020-12-22

Similar Documents

Publication Publication Date Title
AU2016202645B2 (en) Synergistic Fungicide Composition
WO2018059606A1 (zh) 含有苯并异噻唑啉酮类和双炔酰菌胺的杀菌组合物
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
WO2018040775A1 (zh) 一种杀菌剂组合物
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
WO2017121019A1 (zh) 一种杀菌剂组合物
CN105432620B (zh) 杀菌组合物及其应用
WO2017166565A1 (zh) 具有增效作用的植物生长调节剂组合物
WO2017185559A1 (zh) 一种杀菌剂组合物
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
WO2017206825A1 (zh) 具有增效作用的除草组合物
WO2015196951A1 (zh) 具有增效作用的杀虫杀螨剂组合物
WO2018001152A1 (zh) 一种杀菌剂组合物
WO2018024067A1 (zh) 一种杀菌剂组合物
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
WO2018006462A1 (zh) 一种杀菌剂组合物
CN106719646A (zh) 一种包含蒽醌类化合物和甲氧基丙烯酸酯类的杀菌剂组合物
CN105211075A (zh) 杀菌组合物及其应用
WO2018028324A1 (zh) 具有增效作用的除草组合物
WO2018036294A1 (zh) 一种农药组合物
WO2018040764A1 (zh) 具有增效作用的除草组合物
WO2018001189A1 (zh) 一种杀菌剂组合物
WO2018054396A1 (zh) 一种杀菌剂组合物
WO2018040788A1 (zh) 一种杀菌剂组合物
WO2018068772A1 (zh) 包含苯并异噻唑啉酮类和唑嘧菌胺的杀菌组合物

Legal Events

Date Code Title Description
DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2016404643

Country of ref document: AU

Date of ref document: 20160808

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 3017537

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2016900068

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 201892136

Country of ref document: EA

ENP Entry into the national phase

Ref document number: 2016900068

Country of ref document: EP

Effective date: 20180926

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112018071895

Country of ref document: BR

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

Ref document number: 16900068

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 112018071895

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20181024