WO2018000528A1 - 一种杀菌剂组合物 - Google Patents

一种杀菌剂组合物 Download PDF

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Publication number
WO2018000528A1
WO2018000528A1 PCT/CN2016/094040 CN2016094040W WO2018000528A1 WO 2018000528 A1 WO2018000528 A1 WO 2018000528A1 CN 2016094040 W CN2016094040 W CN 2016094040W WO 2018000528 A1 WO2018000528 A1 WO 2018000528A1
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WIPO (PCT)
Prior art keywords
thiazolone
composition
composition according
fluconazole
active component
Prior art date
Application number
PCT/CN2016/094040
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English (en)
French (fr)
Inventor
仲汉根
季红进
Original Assignee
江苏辉丰农化股份有限公司
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Filing date
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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 BR112018072574-9A priority Critical patent/BR112018072574B1/pt
Priority to EA201892129A priority patent/EA201892129A1/ru
Priority to US16/307,423 priority patent/US11219213B2/en
Priority to MX2018012513A priority patent/MX2018012513A/es
Priority to EP16906925.9A priority patent/EP3420819B1/en
Priority to UAA201900561A priority patent/UA124307C2/uk
Priority to AU2016413017A priority patent/AU2016413017C1/en
Priority to CA3017543A priority patent/CA3017543C/en
Publication of WO2018000528A1 publication Critical patent/WO2018000528A1/zh
Priority to PH12018502010A priority patent/PH12018502010A1/en

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Classifications

    • 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
    • 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
    • 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
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures 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
    • 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
    • A01N25/08—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 solids as carriers or diluents
    • 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
    • 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

Definitions

  • the present invention belongs to the field of agricultural plant protection, and more particularly to a bactericidal composition having improved properties, and more particularly to a bactericidal composition comprising thiaminone and fluconazole.
  • Tetazin is 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.
  • Fumazolidinol is a broad-spectrum systemic fungicide with good protection and treatment for various diseases caused by basidiomycetes and ascomycetes. It can effectively control wheat crops, powdery mildew, rust, smut, corn. Smut and so on. Its mechanism of action is mainly to inhibit the biosynthesis of ergosterol, which can cause fungal cell wall rupture and hyphal growth.
  • Fumazol is also a fungicide with eradication, protection, contact and systemic activity. It has good protection and therapeutic effects on many diseases caused by basidiomycetes and ascomycetes, and has certain fumigation effects, but is inactive against oomycetes and bacteria.
  • the drug has a good systemic action, which is absorbed by the roots, stems and leaves of the plant, and then transferred upward by the vascular bundle.
  • the internal suction capacity of the root is greater than that of the stem and the leaf, and it cannot be laterally or directionally transduced in the phloem. Therefore, fluconazole inhibits the growth of fungi in plants or in vitro. Famazole alcohol has a scavenging effect on the spore heap of wheat powdery mildew. After 5-10 days of application, the original lesion can disappear.
  • 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 preparation method comprising the two active ingredients A and B germicidal compositions and in agriculture The application of the field to control crop diseases.
  • 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 thiazolone and active component B is fluconazole.
  • 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 bactericide composition of the present invention is 1:30 to 30:1.
  • the weight ratio of the active component A to the active component B is 1:20 ⁇ 20:1, in order to make the effect more apparent, the weight ratio may further preferably be 1:10 to 10:1.
  • the two active components A and B can be selected from 30:1, 29:1, 28:1, 27:1, 26:1, 25:1, 24:1, 23:1, 22 : 1, 21: 1, 20: 1, 19: 1, 18: 1, 17: 1, 16: 1: 15: 1, 14: 1, 13: 1, 12: 1, 11: 1, 10: 1 , 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1 :5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17 , 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1 A more specific ratio of 30 or the like can also be selected within the range of any of the above two ratios.
  • composition of the present invention can be made into a pesticide-acceptable dosage form from the active ingredient and agrochemical adjuvant or adjuvant. Further, the composition comprises 4 to 80% by weight of the active ingredient and 96 to 20% by weight of the pesticide adjuvant to form 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 and amount of application depends on the pathogen's health Material science and climate survival conditions.
  • 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 is a liquid preparation, a suspension, a wettable powder, a water-dispersible granule 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 pumice, bentonite or Bentonite; a suitable non-adsorbing carrier 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 can be first dissolved in a basic substance to form a metal salt of thiazolone.
  • Suitable basic substances include: alkali metal carbonates, alkali metal hydroxides (such as sodium hydroxide, Potassium hydroxide), an alkali metal alkoxy carbonate, an 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 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.
  • Example 1 52% thiazolone ⁇ folconazole wettable powder
  • Example 2 44% thiazolone ⁇ folconazole wettable powder
  • Example 3 12% thiazolone ⁇ folconazole wettable powder
  • Example 5 31% thiazolone ⁇ folconazole wettable powder
  • 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.
  • Example 8 10% thiazolone ⁇ Folconazole suspension
  • Tefmosone 20% fluconazole 1%, bentonite 3%, glycerol 5%, sodium lignosulfonate 4%, sodium methylnaphthalene sulfonate formaldehyde condensate 5%, water to 100%.
  • 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.
  • Example 10 10.5% thiazolone ⁇ folconazole water dispersible granules
  • Example 11 30% thiazolone ⁇ folconazole water dispersible granules
  • Example 12 22% thiazolone ⁇ folconazole water dispersible granules
  • Example 13 52% thiazolone ⁇ folconazole water dispersible granules
  • 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.
  • Table 2 Mixture of thiazolone and fluconazole to control the control effect of strawberry powdery mildew

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  • Life Sciences & Earth Sciences (AREA)
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  • Pest Control & Pesticides (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

一种杀菌剂组合物，该组合物包含两种有效成分A和B,活性组分A为噻霉酮，活性组分B为粉唑醇，两组分之间的重量比为1:30〜30:1。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抗性产生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噻霉酮和粉唑醇的杀菌组合物。
背景技术
噻霉酮是一种新型、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。
粉唑醇是一种广谱性内吸杀菌剂，对担子菌和子囊菌引起的多种病害具有良好的保护和治疗作用，可有效地防治麦类作物白粉病、锈病、黑穗病、玉米黑穗病等。其作用机理是主要抑制麦角甾醇的生物合成，能引起真菌细胞壁破裂和菌丝的生长。粉唑醇也是具有铲除、保护、触杀和内吸活性的杀菌剂。对担子菌和子囊菌引起的许多病害具有良好的保护和治疗作用，并兼有一定的熏蒸作用，但对卵菌和细菌无活性。该药有较好的内吸作用，通过植物的根、茎、叶吸收，再由维管束向上转移。根部的内吸能力大于茎、叶，单不能在韧皮部作横向或向基输导。故粉唑醇不论在植物体内或体外都能抑制真菌的生长。粉唑醇对麦类白粉病的孢子堆具有铲除作用，施药后5～10d，原来形成的病斑可消失。
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为噻霉酮，活性组分B为粉唑醇。
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1：30～30：1，在一种优选方案中，活性组分A和活性组分B的重量比为为1：20～20：1，为使作用效果更明显两者重量比可进一步优选1：10～10：1。
在一些具体实施方式中，两种活性组分A和B可选用30:1、29:1、28:1、27:1、26:1、25:1、24:1、23:1、22:1、21:1、20:1、19:1、18:1、17:1、16:1、15:1、14:1、13:1、12:1、11:1、10:1、9:1、8:1、7:1、6:1、5:1、4:1、3:1、2:1、1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9、1:10、1:11、1:12、1:13、1:14、1:15、1:16、1:17、1:18、1:19、1:20、1:21、1:22、1:23、1:24、1:25、1:26、1:27、1:28、1:29、1:30等更具体的配比，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。进一步的，该组合物由4～80％重量份的活性组分与96～20％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，本发明的剂型采用水剂、悬浮剂、可湿性粉剂、水分散粒剂或微乳剂。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，形成噻霉酮金属盐，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)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。
实施例1:52％噻霉酮·粉唑醇可湿性粉剂
噻霉酮2％，粉唑醇50％，拉开粉5％，膨润土3％，烷基聚氧乙基醚磺酸盐4％，白炭黑5％，硅藻土补足至100％。
实施例2:44％噻霉酮·粉唑醇可湿性粉剂
噻霉酮4％，粉唑醇40％，木质素磺酸钠5％，烷基聚氧乙基醚磺酸盐6％，白炭黑10％，硅藻土补足至100％。
实施例3:12％噻霉酮·粉唑醇可湿性粉剂
噻霉酮10％，粉唑醇2％，木质素磺酸钠5％，烷基磺酸盐5％，白炭黑10％，高岭土补足至100％。
实施例4:64％噻霉酮·粉唑醇可湿性粉剂
噻霉酮60％，粉唑醇4％，皂土3％，烷基磺酸盐5％，白炭黑5％，硅藻土补足至100％。
实施例5:31％噻霉酮·粉唑醇可湿性粉剂
噻霉酮30％，粉唑醇1％，苯甲酸钠5％，烷基聚氧乙基醚磺酸盐6％，白炭黑10％，高岭土补足至100％。
(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。
实施例6：15.5％噻霉酮·粉唑醇悬浮剂
噻霉酮0.5％，粉唑醇15％，白炭黑5％，乙二醇5％，脂肪醇聚氧乙烯醚磷酸酯6％，水补足至100％。
实施例7：32％噻霉酮·粉唑醇悬浮剂
噻霉酮2％，粉唑醇30％，白炭黑3％，丙三醇4％，苯甲酸钠2％，甲基萘磺酸钠甲醛缩合物5％,水补足至100％。
实施例8：10％噻霉酮·粉唑醇悬浮剂
噻霉酮5％，粉唑醇5％，膨润土4％，乙二醇5％，苯甲酸钠7％,黄原胶2％，水补足至100％。
实施例9：21％噻霉酮·粉唑醇悬浮剂
噻霉酮20％，粉唑醇1％，，膨润土3％，丙三醇5％，木质素磺酸钠4％，甲基萘磺酸钠甲醛缩合物5％,水补足至100％。
(三)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。
实施例10：10.5％噻霉酮·粉唑醇水分散粒剂
噻霉酮0.5％，粉唑醇10％，十二烷基磺酸钾5％，硫酸铵5％，烷基萘磺酸钾4％，轻质碳酸钙补足至100％。
实施例11：30％噻霉酮·粉唑醇水分散粒剂
噻霉酮5％，粉唑醇25％，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12：22％噻霉酮·粉唑醇水分散粒剂
噻霉酮20％，粉唑醇2％，十二烷基磺酸钾3％，硫酸铵5％，甲基萘磺酸钠甲醛缩合物5％，轻质碳酸钙补足至100％。
实施例13：52％噻霉酮·粉唑醇水分散粒剂
噻霉酮50％，粉唑醇2％，甲基萘磺酸钠甲醛缩合物5％，十二烷基硫酸钠5％，硫酸铵5％,硅藻土补足至100％。
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、噻霉酮与粉唑醇复配对毒力测定试验
表1.噻霉酮与粉唑醇复配对小麦叶锈病毒力测定结果分析
药剂名称 EC50(μg/ml) ATI TTI 共毒系数(CTC)
粉唑醇 67.34 100.00 \ \
噻霉酮 40.23 167.39 \ \
噻霉酮：粉唑醇＝1：30 53.25 126.45 102.17 123.76
噻霉酮：粉唑醇＝1：25 52.15 129.13 102.59 125.87
噻霉酮：粉唑醇＝1：20 48.61 138.54 103.21 134.23
噻霉酮：粉唑醇＝1：15 46.94 143.47 104.21 137.67
噻霉酮：粉唑醇＝1：10 42.85 157.16 106.13 148.09
噻霉酮：粉唑醇＝1：5 40.30 167.10 111.23 150.23
噻霉酮：粉唑醇＝1：1 33.02 203.94 133.69 152.54
噻霉酮：粉唑醇＝5：1 28.56 235.76 156.16 150.98
噻霉酮：粉唑醇＝10：1 28.11 239.57 161.26 148.56
噻霉酮：粉唑醇＝15：1 29.91 225.15 163.18 137.98
噻霉酮：粉唑醇＝20：1 30.33 222.02 164.18 135.23
噻霉酮：粉唑醇＝25：1 32.19 209.21 164.80 126.95
噻霉酮：粉唑醇＝30：1 32.85 204.98 165.21 124.07
结果(表1)表明，噻霉酮与粉唑醇复配对小麦叶锈病的防治效果显著提高，说明二者复配对小麦叶锈病防治有显著的增效作用。实验发现，当噻霉酮与粉唑醇的配比超出本发明的配比范围时，其共素系数低于120。
(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 PCTCN2016094040-appb-000001
Figure PCTCN2016094040-appb-000002
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、噻霉酮与粉唑醇复配田间药效实验
表2噻霉酮与粉唑醇混配对草莓白粉病防治效果
Figure PCTCN2016094040-appb-000003
Figure PCTCN2016094040-appb-000004
Figure PCTCN2016094040-appb-000005
测定结果(表2)表明，噻霉酮与粉唑醇混配对草莓白粉病的防效明显提高，说明二者复配对草莓白粉病有显著的增效作用。

Claims (9)

  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为噻霉酮，活性组分B为粉唑醇，两组分之间的重量比为1：30～30：1。
  2. 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1：20～20：1。
  3. 根据权利要求2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1：10～10：1。
  4. 根据权利要求1～3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。
  5. 根据权利要求4所述的杀菌剂组合物，其特征在于该组合物由4～80％重量份的活性组分与96～20％重量份的农药助剂组成农药上允许的剂型。
  6. 根据权利要求4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。
  7. 根据权利要求4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。
  8. 权利要求1～3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。
  9. 权利要求1～3中任意一项所述的杀菌剂组合物在农业领域防治小麦叶锈病或草莓白粉病方面的用途。
PCT/CN2016/094040 2016-06-26 2016-08-08 一种杀菌剂组合物 WO2018000528A1 (zh)

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US16/307,423 US11219213B2 (en) 2016-06-26 2016-08-08 Fungicidal composition
MX2018012513A MX2018012513A (es) 2016-06-26 2016-08-08 Composicion fungicida.
EP16906925.9A EP3420819B1 (en) 2016-06-26 2016-08-08 Fungicidal composition
UAA201900561A UA124307C2 (uk) 2016-06-26 2016-08-08 Фунгіцидна композиція
AU2016413017A AU2016413017C1 (en) 2016-06-26 2016-08-08 Bactericide composition
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