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CN109169676A - A kind of bactericidal composition containing Isoflucypram and methoxy acrylic bactericide - Google Patents

A kind of bactericidal composition containing Isoflucypram and methoxy acrylic bactericide Download PDF

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Publication number
CN109169676A
CN109169676A CN201811155184.3A CN201811155184A CN109169676A CN 109169676 A CN109169676 A CN 109169676A CN 201811155184 A CN201811155184 A CN 201811155184A CN 109169676 A CN109169676 A CN 109169676A
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CN
China
Prior art keywords
isoflucypram
bactericidal composition
preparation
agent
methoxy acrylic
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Legal status (The legal status 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 status listed.)
Withdrawn
Application number
CN201811155184.3A
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Chinese (zh)
Inventor
李义涛
董江强
梁任龙
刘新烁
郭文举
陈锦昌
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Dongguan dongyangjunyang hydrogen patent pesticide Co., Ltd
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Dongguan Dongyang Guangke Research and Development Co Ltd
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Priority to CN201811155184.3A priority Critical patent/CN109169676A/en
Publication of CN109169676A publication Critical patent/CN109169676A/en
Withdrawn legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N47/00Biocides, 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
    • A01N47/08Biocides, 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
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof

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

Abstract

The present invention relates to a kind of bactericidal composition containing Isoflucypram and methoxy acrylic bactericide and preparation and its applications, methoxy acrylic bactericide is pyraclostrobin, ZEN 90160, kresoxim-methyl, any one in coumoxystrobin, wherein the mass ratio of effective component Isoflucypram and methoxy acrylic bactericide is 1~15: 15~1, and the total content of Isoflucypram and methoxy acrylic bactericide in bactericidal composition/preparation is 1~80 mass %.Bactericidal composition/preparation of the present invention shows apparent synergistic effect to the prevention and treatment of uncinula necator.Bactericidal composition and preparation of the present invention are suitable for the prevention and treatment of the diseases such as powdery mildew, rust, glume blight, net blotch, downy mildew, rice blast.The composition has outstanding practical value for having apparent synergistic effect between active component, having delayed the generation of germ drug resistance, reduced the pollution to environment when preventing and treating crop disease.

Description

A kind of sterilization group containing Isoflucypram and methoxy acrylic bactericide Close object
Technical field
The present invention relates to technical field of pesticide compounding, contain Isoflucypram and methoxyl group propylene more particularly to one kind The bactericidal composition of bactericide of phosphate (phosphinium) ester.
Background technique
Isoflucypram (exploitation code name: BCS-CN88460) is pyrazole carboxamides fungicide, belongs to novel succinic acid Dehydrogenase inhibitor (SDHI), the fungicide are by inhibiting in pathogen mitochondrial respiratory mechanism in tricarboxylic acid cycle Succinate dehydrogenase and play a role.The chemical name of Isoflucypram is N- [[the chloro- 2- of 5- (1- Methylethyl) phenyl] first Base] the fluoro- 1- methyl-1 H- pyrazole-4-carboxamide of-N- cyclopropyl -3- (difluoromethyl) -5-.Isoflucypram is passed with interior suction The property led, and the characteristic with resistance to rainwater shower and to powdery mildew, gray mold have efficient sterilizing activity.Isoflucypram structure Formula are as follows:
Pyraclostrobin is methoxy acrylic bactericide, is a kind of mitochondrial respiratory inhibitor i.e. by thin Electronics transfer is prevented in born of the same parents' pigment synthesis.The appearance of pyraclostrobin is white to oldlace tasteless crystalline solid, fusing point 63.7~ 65.2 DEG C, it is 1.9mg/L that 20 DEG C, which are lauched middle solubility,.There is pyraclostrobin protection, treatment, blade to permeate conduction, right Powdery mildew of cucumber, downy mildew and banana freckle, leaf spot, sclerotiniose etc. have preferable control efficiency.Pyraclostrobin structure Formula are as follows:
ZEN 90160 is methoxy acrylic bactericide, is a kind of mitochondrial respiratory inhibitor i.e. by cell Electronics transfer is prevented in pigment synthesis.The appearance of ZEN 90160 is white powder, and 68~69 DEG C of fusing point, 20 DEG C are lauched middle solubility For 3.1mg/L.There is ZEN 90160 protection, treatment, blade to permeate conduction, to wheat leaf blessing disease, net blotch and moire disease Etc. there is preferable control efficiency.ZEN 90160 structural formula are as follows:
Kresoxim-methyl is methoxy acrylic bactericide, is a kind of mitochondrial respiratory inhibitor i.e. by cell color Electronics transfer is prevented in element synthesis.The appearance of kresoxim-methyl is white powder crystalline solid, and 97.2-101.7 DEG C of fusing point, 20 DEG C are lauched Solubility is 2mg/L.There is kresoxim-methyl protection, treatment, blade to permeate conduction, to powdery mildew of strawberry, melon powdery mildew, Huang Melon powdery mildew, pear scab etc. have preferable control efficiency.Kresoxim-methyl structural formula are as follows:
Coumoxystrobin is methoxy acrylic bactericide, is a kind of mitochondrial respiratory inhibitor i.e. by cell Electronics transfer is prevented in pigment synthesis.The appearance of coumoxystrobin is powder creamy white or light yellow, 109~111 DEG C of fusing point, readily soluble In DMF, acetone, ethyl acetate, methanol, it is slightly soluble in petroleum ether, is practically insoluble in water.Coumoxystrobin has protection, treatment, blade Permeate conduction, to apple tree canker, ring spot, spot disease, sigatoka, scab, sclerotinia sclerotiorum etc. have compared with Good control efficiency.Coumoxystrobin structural formula are as follows:
However, not disclosing or implying and is of the invention comprising Isoflucypram and methoxy acrylic bactericide The bactericidal composition of (methoxy acrylic bactericide is selected from pyraclostrobin, ZEN 90160, kresoxim-methyl, coumoxystrobin) Or/preparation, and its application in prevention and treatment uncinula necator.
In addition, application chemical agent is the most effective means of current controlling plant diseases.Single medicament is used for a long time, It is easy to cause the drug resistance of disease to greatly promote, is greatly increased so as to cause formulation rate, and then more serious dirt is caused to environment Dye.And compound the effective component of two kinds of not no cross tolerances, the promotion of disease drug resistance can be delayed significantly, expansion is killed Bacterium spectrum, improves drug effect, to reduce the usage amount of pesticide, and then reduces the pollution to environment.
Summary of the invention
Summary of the invention
Based on the above circumstances, on the one hand, the present invention provides a kind of bactericidal composition, and the effective component of the bactericidal composition is Isoflucypram and methoxy acrylic bactericide, the acrylic bactericide are selected from pyraclostrobin, pyridine Any one in oxygen bacterium ester, kresoxim-methyl and coumoxystrobin.
Further, the mass ratio of Isoflucypram and methoxy acrylic bactericide is 1~15:15~1.
Further, the total content of Isoflucypram and methoxy acrylic bactericide in bactericidal composition For 1~80 mass %.
Preferably, the total content of Isoflucypram and methoxy acrylic bactericide in bactericidal composition is 10 ~45 mass %.
On the other hand, the present invention provides a kind of sterilization comprising Isoflucypram and methoxy acrylic bactericide Application of the composition in the diseases such as prevention and treatment powdery mildew, rust, glume blight, net blotch, downy mildew, rice blast.
Another aspect, the present invention provide a kind of sterilization comprising Isoflucypram and methoxy acrylic bactericide Preparation prepared by composition, the dosage form of the preparation are missible oil, aqueous emulsion, microemulsion, suspending agent, wettable powder or moisture Shot agent.
Preferably, the mass ratio of Isoflucypram and methoxy acrylic bactericide is 1~5:5 in the preparation ~1.
Specifically, the mass ratio of Isoflucypram and pyraclostrobin is 1~5:3~1 in the preparation;
Specifically, the mass ratio of Isoflucypram and ZEN 90160 is 1~3:2~1 in the preparation;
Specifically, the mass ratio of Isoflucypram and kresoxim-methyl is 1~2:2~1 in the preparation;
Specifically, the mass ratio of Isoflucypram and pyraclostrobin is 1~3:2~1 in the preparation.
Further, the present invention provides the preparation comprising Isoflucypram and methoxy acrylic bactericide anti- Control the application in the diseases such as powdery mildew, rust, glume blight, net blotch, downy mildew, rice blast.
Also on the one hand, the present invention is provided to control the method for plant disease, the method includes to the plant or plant Object part apply a effective amount of bactericidal composition comprising Isoflucypram and methoxy acrylic bactericide or comprising The preparation of Isoflucypram and methoxy acrylic bactericide.
Detailed description of the invention
Preparation provided by the invention comprising Isoflucypram and methoxy acrylic bactericide composition, can Synergistic effect is generated, is maintained like while the amount of application of Isoflucypram and methoxy acrylic bactericide reduces Good effect.On the one hand fungicidal spectrum has been widened, has on the other hand improved safety in utilization.
It is provided by the invention to be sterilized comprising Isoflucypram and methoxy acrylic in addition to sterilizing synergistic activity The preparation of agent composition has other excellent characteristics, and in a broad sense, these characteristics alternatively referred to as act synergistically, such as: activity Spectrum is widened to other plant pathogen (such as disease on resistant strain);Reduce the amount of application of reactive compound;Even if in list One compound shows inactive or almost without under active amount of application, is still enough to prevent by reactive compound compounding of the invention It cures the disease evil;The advantageous feature of (such as grind, screening, emulsification, dissolve or disperse) in preparation or use process;The storage of enhancing is steady Qualitative and photostability;Reinforce being formed the feature of environmental protection of residue;Improved toxicology and ecological toxicology characteristic;Improved plant Characteristic (such as preferably growth, the harvesting raising of yield, more flourishing root system, bigger leaf area, greener leaf, stronger The transfer, good compatible with plant of strong spray, less seed demand, lower phytotoxicity, plant defense system Property).Therefore, using the system provided by the invention comprising Isoflucypram and methoxy acrylic bactericide composition Agent helps that plant is made to keep fit, to ensure the quality and yield of crop.In addition, provided by the invention include The preparation of Isoflucypram and methoxy acrylic bactericide composition can help to enhancing systemic action (systemic action).Even if the single compound of composition does not have enough absorbabilities, provided by the invention to include The preparation of Isoflucypram and methoxy acrylic bactericide composition can still have the property.Similarly, the present invention mentions The preparation comprising Isoflucypram and methoxy acrylic bactericide composition supplied can bring more longlasting sterilization to make With.
Therefore, in order to achieve the above objectives, The technical solution adopted by the invention is as follows:
On the one hand, the present invention provides a kind of bactericidal composition, and the effective component of the bactericidal composition includes Isoflucypram and methoxy acrylic bactericide.
Further, methoxy acrylic bactericide is pyraclostrobin, ZEN 90160, kresoxim-methyl, coumoxystrobin In any one.
The mass ratio of the bactericidal composition, Isoflucypram and pyraclostrobin is 1~15:15~1.
Further, the mass ratio of Isoflucypram and pyraclostrobin is 1~10:10~1.
Preferably, the mass ratio of Isoflucypram and pyraclostrobin is 1~5:3~1.
The mass ratio of the bactericidal composition, Isoflucypram and ZEN 90160 is 1~15:15~1.
Further, the mass ratio of Isoflucypram and ZEN 90160 is 1~10:5~1.
Preferably, the mass ratio of Isoflucypram and ZEN 90160 is 1~3:2~1.
The mass ratio of the bactericidal composition, Isoflucypram and kresoxim-methyl is 1~15:15~1.
Further, the mass ratio of Isoflucypram and kresoxim-methyl is 1~5:5~1.
Preferably, the mass ratio of Isoflucypram and kresoxim-methyl is 1~2:2~1.
The mass ratio of the bactericidal composition, Isoflucypram and coumoxystrobin is 1~15:15~1.
Further, the mass ratio of Isoflucypram and coumoxystrobin is 1~10:10~1.
Preferably, the mass ratio of Isoflucypram and coumoxystrobin is 1~3:2~1.
Specifically, Isoflucypram and the mass ratio of each in methoxy acrylic bactericide can be 1: 15,1:10,1:5,1:3,1:2,1:1,2:1,3:1,5:1,10:1 or 15:1.
Further, the total content of Isoflucypram and pyraclostrobin in bactericidal composition is 10~45 matter Measure %.
Preferably, the total content of Isoflucypram and pyraclostrobin in bactericidal composition is 20~30 mass %.
It is highly preferred that the total content of Isoflucypram and pyraclostrobin in bactericidal composition is 20 mass %, 24 Quality % or 30 mass %.
Further, the total content of Isoflucypram and ZEN 90160 in bactericidal composition is 10~45 matter Measure %.
Preferably, the total content of Isoflucypram and ZEN 90160 in bactericidal composition is 10~25 mass %.
It is highly preferred that the total content of Isoflucypram and ZEN 90160 in bactericidal composition is 10 mass %, 21 matter Measure % or 25 mass %.
Further, the total content of Isoflucypram and kresoxim-methyl in bactericidal composition is 10~45 mass %.
Preferably, the total content of Isoflucypram and kresoxim-methyl in bactericidal composition is 30~45 mass %.
It is highly preferred that the total content of Isoflucypram and kresoxim-methyl in bactericidal composition is 30 mass % or 45 matter Measure %.
Further, the total content of Isoflucypram and coumoxystrobin in bactericidal composition is 10~45 matter Measure %.
Preferably, the total content of Isoflucypram and coumoxystrobin in bactericidal composition is 12~36 mass %.More Preferably, the total content of Isoflucypram and coumoxystrobin in bactericidal composition is 12 mass %, 25 mass % or 36 matter Measure %.
On the other hand, the present invention provides a kind of sterilization comprising Isoflucypram and methoxy acrylic bactericide Application of the composition in the diseases such as prevention and treatment powdery mildew, rust, glume blight, net blotch, downy mildew, rice blast.
Another aspect, the present invention provide a kind of sterilization comprising Isoflucypram and methoxy acrylic bactericide Preparation prepared by composition, the dosage form of the preparation are missible oil, aqueous emulsion, microemulsion, suspending agent, wettable powder or moisture Shot agent.
Further, the present invention provides the preparation comprising Isoflucypram and methoxy acrylic bactericide anti- Control the application in the diseases such as powdery mildew, rust, glume blight, net blotch, downy mildew, rice blast.
Also on the one hand, the present invention is provided to control the method for plant disease, the method includes to the plant or plant Object part apply a effective amount of bactericidal composition comprising Isoflucypram and methoxy acrylic bactericide or comprising The preparation of Isoflucypram and methoxy acrylic bactericide.
Term "comprising" is open language, that is, includes content specified by the present invention, but be not precluded otherwise Content.
In composition of the present invention or preparation, the matter of Isoflucypram and methoxy acrylic bactericide Amount in relatively wide range than that can change.With Isoflucypram: the range of methoxy acrylic bactericide is 1000: The effective mass ratio of 1 to 1:1000 collaboration exists, and preferred mass ratio is 100:1 to 1:100, and further preferred mass ratio is 50:1 to 1:50, still more preferably mass ratio are 20:1 to 1:20, and even more preferably mass ratio is 10:1 to 1:10.It can basis Other mass ratioes for the Isoflucypram: methoxy acrylic bactericide that the present invention uses are: 95:1 to 1:95,90:1 To 1:90,85:1 to 1:85,80:1 to 1:80,75:1 to 1:75,70:1 to 1:70,65:1 to 1:65,60:1 to 1:60,55:1 To 1:55,45:1 to 1:45,40:1 to 1:40,35:1 to 1:35,30:1 to 1:30,25:1 to 1:25,15:1 to 1:15,10:1 To 1:10,5:1 to 1:5,4:1 to 1:4,3:1 to 1:3,2:1 to 1:2,1:1.In terms of further increasing the synergistic function To consider, it is preferable that the mass ratio of Isoflucypram and methoxy acrylic bactericide is 1~15: 15~1;Herein Synergistic function except range is markedly less than this range.
If Isoflucypram or methoxy acrylic bactericide can be with alloisomerism, optical siomerism or interconversions The form of isomery exists, then it should be understood that even if being not expressly mentioned in each example, under usable condition, such compound is upper and lower It further include corresponding isomeric form in text.
If Isoflucypram or methoxy acrylic bactericide can form acid-addition salts with acid, for example, described Acid can be strong inorganic acid, such as mineral acid (such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or halogen acids);It is strong organic Carboxylic acid, such as unsubstituted or substituted C1-C4Alkanoic acid (such as acetic acid), saturated or unsaturated dicarboxylic acids (such as oxalic acid, Malonic acid, succinic acid, maleic acid, fumaric acid and phthalic acid), hydroxycarboxylic acid (such as ascorbic acid, lactic acid, malic acid, wine Stone acid and citric acid or benzoic acid);Or organic sulfonic acid, such as unsubstituted or substituted C1-C4Alkanesulfonic acid or aryl sulfonic acid (example Such as methanesulfonic acid or p-methyl benzenesulfonic acid).If Isoflucypram or methoxy acrylic bactericide can with alkali forming salt, The salt can be metal salt, such as alkali metal salt or alkali salt (such as sodium salt, sylvite or magnesium salts);Or with ammonia or organic The salt that amine is formed, such as morpholine, piperidines, pyrrolidines, mono-, two- or three-low-grade alkylamines (such as ethamine, diethylamine, triethylamine Or dimethyl propylamine) or mono-, two- or trihydroxy-low-grade alkylamine (such as mono-, two- or triethanolamine).In addition, can be optional Ground forms corresponding inner salt.In the context of the present invention, advantageous salt preferably on agriculture chemistry.In view of Isoflucypram or Substantial connection between the free form of methoxy acrylic bactericide and the form of its salt, in advantageous and appropriate situation Under, the Isoflucypram or methoxy acrylic bactericide that refer in the context of the invention any place or its salt should be understood that To respectively further comprise corresponding salt or Isoflucypram or methoxy acrylic bactericide.Same situation is also applied for The stereoisomer of Isoflucypram or methoxy acrylic bactericide, optical isomer or tautomer and its Salt.
Composition of the present invention removes and includes effective component Isoflucypram and methoxy acrylic bactericide Outside, usually also containing common adjuvant on pesticide, the adjuvant is wetting agent, dispersing agent, emulsifier, thickener, gelling Agent, antisettling agent, disintegrating agent, antifreezing agent, defoaming agent, solvent, preservative, stabilizer, synergist, filler or carrier etc., according to The needs of preparation can be properly added, and can be varied, be not particularly limited according to different situations.
Adjuvant is added in Pesticide formulation or use, for improving the auxiliary substance of medicament physicochemical property, is helped The basic inactive of agent itself, but control efficiency can be influenced.
Wetting agent is such substance, and when being added into liquid, the substance is by reducing liquid and liquid at it Interfacial tension between the surface of upper spread increases the spread or penetrating power of liquid.Wetting agent is sent out in agrochemical formulations It waves two kinds of major functions: increasing the wetting rate of powder in water during processing and manufacture, so that preparation can dissolve in water Concentrate or the mixture that suspends in water;Wettable powder can also be reduced before product and water are applied to aerosol can sprinkling Wetting time and improve water phase in the infiltration into dispersible particle.The wetting agent select alkylbenzene sulfonate (such as Neopelex, calcium dodecyl benzene sulfonate), alkylnaphthalene sulfonate (such as nekal, isopropyl naphthalene sulphur Sour sodium), lignosulfonates (such as sodium lignin sulfonate, calcium lignosulfonate), lauryl sodium sulfate (SDS), succinic acid Dibutyl ester sodium sulfonate, dioctyl sodium sulphosuccinate, alkyl phenol polyoxyethylene ether (APEO) (such as nonylphenol polyoxyethylene ether, Octyl phenol polyoxyethylene ether, dodecane phenolic ether, dinonyl phenolic ether and mixing alkane phenolic ether etc.), alkylphenol ethoxylate (APES), Alcohol ethoxylate, sodium sulfate of polyethenoxy ether of fatty alcohol (ethoxylated alkyl sulfate, AES), pull open powder, silkworm excrement, Spaonin powder, spaonin powder, SOPA, detergent, 2000 series of emulsifier, penetrating agent JFC, wet bleeding agent F, wetting and penetrating agent are fast T, the mixing of one or more of NP-10.The Typical Representative of suitable wetting agent such as SDS, AES, Morwet EFW, JR-P. The wetting agent is one of above-mentioned wetting agent or a variety of.
Dispersing agent is such substance, is adsorbed on the surface of particle and helps to maintain the dispersity of particle and prevent Tablet reassembles.Dispersing agent is added in agrochemical formulations to dispersion and suspension during facilitating manufacture, and is helped In ensuring that particle is re-dispersed into water in aerosol can.They are widely used in wettable powder, suspending agent and water dispersible granules In.Surfactant as dispersing agent, which has the ability being securely adsorbed on particle surface and provides confrontation particle, to reassemble Electric double layer barrier or steric hindrance.Most common surfactant is anionic surfactant, non-ionic surface The mixture of activating agent or both types.For wettable powder, the most common dispersing agent is sodium lignin sulfonate (sodium lignosulphonate).For suspending agent, polyelectrolyte (polyelectrolyte) such as naphthalene sulfonic acids are used Sodium formaldehyde condensation product (sodium naphthalene sulphonate formaldehyde condensate) obtains very Good absorption and stabilization.Also tristyrylphenol ethoxylates phosphate (tristyrylphenol is used Ethoxylate phosphate ester), nonionic surface active agent such as alkylaryl ethylene oxide condensation product (alkylarylethylene oxide condensate) and EO-PO block copolymer.Sometimes living using non-ionic surface Property agent and anionic surfactant are in combination as the dispersing agent for suspending agent.In recent years, molecular weight has been developed New type of the very high polymeric surfactant as dispersing agent.These dispersing agents have very long hydrophobicity " skeleton " " tooth " of raw medicine is fixed using many ethylene oxide chains as it with formation " comb " type structure.These heavy polymers can be Suspending agent provides extraordinary long-time stability, this is because hydrophobic skeleton has the multiple anchors being fixed on particle surface Point.The example of common dispersants has sodium lignin sulfonate, naphthalenesulfonic acid-formaldehyde condensate, tristyrylphenol ethoxylates Phosphate, alcohol ethoxylate, alkyl ethoxylate, alkyl phenol polyoxyethylene ether, alkyl phenol polyoxyethylene ether methyl ether Condensate sulfate, aliphatic amine polyoxyethylene ether, glycerol fatty acid ester polyoxyethylene ethe, EO-PO block copolymer and grafting are altogether Polymers.The Typical Representative of suitable dispersing agent such as TERSPERSE2700, TERSPERSE2500, Ufoxane NA, Morwet D425 or Ethylan NS-500LQ etc..The dispersing agent is one of above-mentioned dispersing agent or a variety of.
Emulsifier is that a kind of liquid phase dropwise addition is made to improve its surface tension after another liquid phase, makes the object of its stabilized with mixture Matter.In the case where no emulsifier, two kinds of liquid can be separated into two immiscible liquid phases.Most common emulsifier is blended Object contains the oil-soluble calcium of alkyl phenol or fatty alcohol and dodecyl benzene sulfonic acid with 12 or more ethylene oxide units Salt.Range can usually provide good emulsion stability for the emulsifier of 8 to 18 hydrophile-lipophile balance (" HLB ") value.Emulsion Stability can also be improved sometimes by the way that a small amount of EO-PO block copolymer surfactant is added.The emulsifier is selected from ten Dialkyl benzene sulfonic acids calcium, alkyl phenol formaldehyde resin polyoxyethylene ether, phenethyl phenol polyoxyethylene poly-oxygen propylene aether, fatty alcohol ring Oxidative ethane oxepane copolymer, styrylphenol polyoxyethylene ether, castor oil polyoxyethylene base ether, alkyl phenol ether phosphate One of or it is a variety of.The Typical Representative of suitable dispersing agent such as agriculture breast 500#, agriculture breast 601P, TERSPERSE200, Emulpon CO-360 or Ethylan 992.The emulsifier is one of mentioned emulsifier or a variety of.
Thickener or gelling agent are used primarily in the rheology or flowing for changing liquid in suspending agent, aqueous emulsion and suspoemulsion Property and prevent dispersed particle or small oil droplet from separation or sedimentation occurs.Thickener, gelling agent and antisettling agent are generally divided into two Class, that is, water-insoluble particle and water-soluble polymer.It is feasible that suspending agent is prepared using clay and silica.These types The example of substance includes but is not limited to montmorillonite, such as bentonite;Aluminium-magnesium silicate and atlapulgite (attapulgite).It is water-soluble Polysaccharide has been used as thickening-gelling agent for many years.Most common polysaccharide type is the natural extract or cellulose of seed or seaweed Synthesis of derivatives.The example of the substance of these types includes but is not limited to guar gum, carob gum (locust beangum), angle Pitch dish glue (carrageenam), alginates, methylcellulose, sodium carboxymethylcellulose (SCMC), hydroxyethyl cellulose (HEC). Other types of antisettling agent such as converted starch, polyacrylate, polyvinyl alcohol and polyethylene glycol oxide.It is another good anti-heavy Depressant prescription is xanthan gum.The thickener is one of above-mentioned thickener or a variety of.
The disintegrating agent is selected from sodium sulphate, ammonium sulfate, aluminium chloride, sodium chloride, ammonium chloride, bentonite, glucose, sugarcane One or more of sugar, starch, cellulose, urea, sodium carbonate, sodium bicarbonate, citric acid, tartaric acid.
Antifreezing agent has alcohols, alcohol ethers, chlorinated hydrocarbon, inorganic salts etc..Common antifreezing agent has methanol, ethyl alcohol, isopropyl Alcohol, ethylene glycol, propylene glycol, glycerine, diethylene glycol (DEG), butyl glycol ether, propandiol butyl ether, 2-Butoxyethyl acetate, dichloromethane Alkane, 1,1- dichloroethanes, 1,2- dichloroethanes, dimethyl sulfoxide, formamide, calcium chloride, sodium acetate, magnesium chloride etc..Described Antifreezing agent is one of above-mentioned antifreezing agent or a variety of.
The application of surfactant normally results in aqua type preparation and generates foaming tendency in production and application.For Reduction foaming tendency, usually in production phase or the preceding addition defoaming agent in being fitted into bottle.In general, disappearing there are two types of type Infusion, that is, siloxanes and non-silicone.Siloxanes is usually the aqueous emulsion of dimethyl silicone polymer, rather than silicone antifoam agent For water-insoluble oil such as octanol and nonyl alcohol.Using the defoaming agent of both types, the function of defoaming agent is all from sky Surfactant is replaced in gas-water interface.The defoaming agent is selected from C10-20Saturated fat acids compound, silicone oil, silicone Compound, C8-10Fatty alcohol it is one or more.
Solvent is to make it easy to the organic matter processed and used for dissolving and diluting pesticide active ingredient.It is common molten Agent have benzene,toluene,xylene, durol, methanol, ethyl alcohol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, Cyclohexanone, N-Methyl pyrrolidone, alkylene carbonate, diesel oil, solvent naphtha, soybean oil, epoxidized soybean oil, castor oil, water etc..Institute The solvent stated is one of above-mentioned solvent or a variety of.
Microorganism easily causes the corruption of prepared product, therefore preservative be used to eliminate or reduce this microorganism Effect.The example of these reagents includes but is not limited to propionic acid and its sodium salt, sorbic acid and its sodium salt or sylvite, benzoic acid and its sodium Salt, P-hydroxybenzoic acid sodium salt, methyl p-hydroxybenzoate, Kathon CG (CIT/MIT) and 1,2- benzisothiazole-3-ketone (BIT).The preservative is one of foregoing preservatives or a variety of.
Stabilizer is divided to two classes, and one kind can inhibit or slow down pesticide active ingredient decomposition, such as antioxidant, anti-light solution agent; It is another kind of that preparation physical stability can be improved, such as anti-caking agent and antisettling agent.The stabilizer is selected from disodium hydrogen phosphate, grass It is acid, succinic acid, adipic acid, borax, DBPC 2,6 ditertiary butyl p cresol, triethanolamine oleate, epoxidized vegetable oil, kaolin, swollen Moisten soil, attapulgite, white carbon black, talcum powder, montmorillonite or starch etc..The stabilizer be one of above stabilizer or It is a variety of.
Synergist inactive itself, but the performance of active matter can be increased substantially, it, can be big when with certain combined use of pesticides Amplitude improves pesticide virulence and drug effect, such as Synergistic Phosphorus, Butacide.
Carrier refers to natural or synthetic organic matter or inorganic matter, it is mixed or combined to have more with reactive compound Good application, especially in the application on plant or plant part or seed.Carrier can be solid or liquid.It is usually lazy Property and should be suitable for used in agricultural.Suitable solid or liquid-carrier are as follows: ammonium salt and the natural minerals ground (such as kaolinite Soil, clay, talcum, chalk, quartz, Attagel, montmorillonite or diatomite), and the artificial mineral ground is (such as finely divided Silica, aluminium oxide) and natural or synthetic silicates, resin, wax, solid fertilizer, water, alcohol (especially butanol), You Jirong Agent, mineral oil and vegetable oil and its derivative.It can also be the mixture containing these carriers.Solid suitable for granule carries Body are as follows: the natural minerals (such as calcite, marble, float stone, sepiolite, dolomite) that crush and be classified and inorganic and have Machine powder manufactured particles and organic material (such as sawdust, coconut husk, corncob or tobacco stem particle).The filler For one of above-mentioned filler or a variety of.
It is gaseous liquid under environment temperature and atmospheric pressure that suitable liquefied gaseous state filler or carrier, which are those, Such as aerosol propellants (such as butane, propane, nitrogen and carbon dioxide).
If filler used is water, also it can be used organic solvent as secondary solvent.Suitable liquid solvent is main Are as follows: aromatic compound such as dimethylbenzene, toluene or alkylnaphthalene;Chlorinated aromatic compound and chloro fat race hydrocarbon, such as chlorobenzene, Vinyl chloride or methylene chloride;Aliphatic hydrocarbon, such as hexamethylene or paraffin, such as mineral oil fractions, mineral oil and vegetable oil;Alcohol (example Such as butanol or ethylene glycol) and its ether and ester;Ketone, such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or cyclohexanone;It is highly polar Solvent such as dimethylformamide and dimethyl sulfoxide;And water.
If appropriate, other additional components, such as protective colloid, adhesive (binder), sticker also may be present (adhesive), thixotroping substance, bleeding agent, chelating agent, complexing forming agent, coloring agent etc..In general, the reactive compound can In conjunction with any solid or liquid additive for being usually used in preparation preparation.
In general, composition or preparation of the invention include 0.05 to 99 quality %, 0.01 to 98 quality %, 0.1 to 95 matter Measure %, 0.5 to 90 quality %, 10 to 70 quality %, 10 to 60 quality %, 10 to 45 quality % reactive compounds Isoflucypram and methoxy acrylic bactericide.
Composition provided by the invention comprising Isoflucypram and methoxy acrylic bactericide can be as former state Use such as gas molten with its dosage form or use form prepared therefrom using or according to its each physical property or chemical property Pulvis, microcapsule suspending agent, aerosol, microcapsulated granule, pulvis, suspension seed-coating agent, dust granule, missible oil, aqueous emulsion, microemulsion, bubble Rise granule, fine granule, oil loose powder, oil-suspending agent, finish, paste, the coated seed treatment of insecticide, suspension concentration Agent, suspoemulsion, suspension seed dressing, wettable powder, tablet, with reactive compound impregnate can wet-milling seed coat agent, natural products With the microcapsule formulations and ULV harl and hot atomization preparation in the coating material of synthetic and polymeric material and seed.
Typical preparation formulation be pulvis, wettable powder, microcapsule formulations, water dispersion granule, granule, suspending agent, Missible oil, microemulsion, aqueous emulsion, ultra-low volume spray agent, seed coat agent.
Pulvis (DP) is that a certain amount of inert dust, such as clay, kaolin, talcum powder is added in active material, is added through machinery Work is at powdered object, and powder diameter is at 100 microns or less.
Wettable powder (WP) refer to by composition by a certain percentage with suitable surfactant and inert substance (kaolinite Native powder) mixing mixture.Wettable powder is the preparation caning be uniformly dispersed in water, wherein in addition to active constituent and inertia Other than substance (kaolin powder), also contain a certain amount of anion or nonionic surface active agent (dispersing agent, wetting agent).
Microcapsule formulations (CJ) are first to be coated on active matter to form small cryptomere preparation in adhesive, film forming agent etc., so It is reprocessed into the dosage form of needs afterwards;It is divided into micro-capsule suspension (Capsule Suspensions, CS) and microcapsules granula (Encapsulated Granule, CG), microcapsules dry suspending agent (Capsulated Dry Flowable, CDF) etc..
Water dispersible granules (WDG) refer to composition is (high with suitable surfactant and inert substance by a certain percentage Ridge soil) powder mixing mixture.Through air-flow crushing, particle size is made to reach requirement, and uses double helical form mixing machine and plough Blade mixing machine keeps product mix uniform through repeatedly mixing.Again by conventional method as fluidized bed prilling, mist projection granulating, disc type are made Grain.The solid mixture of obtained a certain range partial size is finally dried by screening.
Granule (GR) refer to by composition by a certain percentage with suitable surfactant, diluent and inert substance The mixture of (kaolin powder).It is granulated such as fluidized bed prilling method by pelletizer, is to keep powder under flow regime, spray Upper binder solution is allowed to the prilling process being aggregated.This method makes the processes such as mixing, kneading, granulation, dry, classification one In a device, the short time is completed under air-tight state.
Suspending agent (SC) refer to composition is mixed with suitable surfactant, water or organic solvent by a certain percentage, It is uniformly levigate through colloid mill, then grind 1 to 2 time through sand mill and be made to certain fineness.
Missible oil (EC), which refers to, to be dissolved composition in organic solvent by a certain percentage such as benzene,toluene,xylene, hexamethylene Ketone, and the liquid being prepared in the mixture of a certain amount of anion or nonionic surface active agent (emulsifier) is added.
Microemulsion (ME) is generally made of liquid pesticide, surfactant (emulsifier), water, stabilizer etc.;Its main feature is that Using water as medium, be free of or less containing organic solvent.Drop size in microemulsion is generally several nanometers to tens nanometers, and being less than can The a quarter of light-exposed wavelength.
Aqueous emulsion (EW) is insoluble in the raw medicine liquid of water or raw medicine is dissolved in organic solvent acquired solution not soluble in water point It dissipates in water, the preparation that liquid pesticidal raw medicine obtained is dispersed in water with 0.5-1.5 microns of droplet, appearance is milky Milk shape liquid.
Ultra-low volume spray agent (ULV) refers to the medical fluid being sprayed onto being denoted as on object, with superfine droplet, extremely low dosage spray It out, is a kind of special dosage form applied for ultra-low volume spray.
Seed coat agent (SD) is mixed effective component and auxiliary agent are ground, can be coated on kind of a sublist directly or after dilution Face forms the protective film with some strength and permeability.
About the meaning of various adjuvants, various preparations, due to the difference in statement, the difference on understanding will cause.It answers When understanding, various adjuvants disclosed in this field, preparation belong to the range that the present invention covers, such as " pesticidal preparations add Work technology ", Luo Yanping, Song Weiwei, Chemical Industry Press, 2015;" pesticidal preparations ", Wang Kaiyun, Chinese agriculture publishing house, 2009;" Preparation Forms of Modern Pesticide processing technology book series ", Liu Guangwen, Chemical Industry Press, 2018;" formulations of pesticide and preparation and Application method ", Tu Yuqin, Golden Shield publishing house, 2008;" Chinese pesticide ", described in Chinese pesticide industry association etc. that A bit.
Above-mentioned preparation can be prepared in known manner, such as by by reactive compound or active agent combinations It is mixed at least one additive.Suitable additive is all conventional pharmaceutical adjuncts, such as organic solvent, filler, molten Agent or diluent, solid carrier and filler, surfactant (such as adjuvant, emulsifier, dispersing agent, protective colloid, wetting agent And tackifier), adhesive or fixative, preservative, dyestuff and pigment, defoaming agent, inorganic and organic thickening agent, hydrophober, such as Fruit is suitable, can also add drier and UV stabilizer, gibberellin and water and other processing aids.In each case, according to Preparation type to be prepared, it may be necessary to other procedure of processings, such as wet lapping, dry grinding or granulation.The system of various preparations Preparation Method includes but is not limited to those of described in the invention.
Composition of the invention not only include ready-to-use composition (can be used suitable device be applied to plant or Seed), and include commercially available concentrate (must be diluted with water before use).
According to the present invention, all plant and plant part can be handled.Plant refers to all plant and plant population, example As wanted (whether to be weighed by Plant variety right or plant breeder with undesired wild plant, cultivar and plant variety Protection).Cultivar and plant variety can be through Sterile culture and breeding method (by one or more biotechnology methods It is assisted or is supplemented, such as by using dihaploid, protoplast fusion, random mutagenesis and directed mutagenesis, molecular labeling Or genetic marker), or the plant obtained by bioengineering and the method for genetic engineering.Plant part refers to all grounds of plant With under ground portion and organ, wherein listing such as bud, leaf, needle, stem, branch, flower, fructification, fruit and seed and root, bulb And rhizome;Crop and asexual and case of propagation material, such as cutting, bulb, rhizome, bark of a cork tree and seed is divided to also belong to plant portion Point.
For the present invention, term " effective quantity " indicates the composition of the invention for being enough to reduce sudden death syndrome incidence Amount.This amount depend on fungi, floristics, weather conditions and the present composition to be controlled in include compound and Change in a wide range.
With the composition or preparation provided by the invention comprising Isoflucypram and methoxy acrylic bactericide To the processing that plant and plant part carry out can be used conventional treatment method directly carry out or act on its ambient enviroment, habitat or Storage ground, for example, by dipping, sprinkling, be sprayed, irrigation, evaporation, dusting, atomizing, broadcast sowing, foam, smear, be coated with, water and (pour Fill), instil, and in the case of propagation materials, especially in the case of seed, can also pass through involucrum (incrust), packet Slurries are handled with powder-processed dry seeds, with solution processing seed, with water-soluble powder by one or more layers coating etc..It can also incite somebody to action Composition or preparation are injected into soil.
In the plant that can be protected by the method for the invention, can be mentioned that staple crops, as corn and soybean, cotton, Rape, rice, wheat, beet, sugarcane, oat, rye, barley, grain, triticale, flax, liana and come from various plants The various fruit of taxon and vegetables, gardening and forest crop;Ornamental plant;And the homology of the genetic modification of these crops Object.
The present invention also includes the method for handling seed.Composition of the invention can be applied directly, that is, not include other groups Divide and without dilution.Generally, it is preferred to which the present composition is applied to seed with suitable dosage form.Handle seed Suitable preparation and method be that this field is conventional.The present composition can be converted into conventional Seed dressing formulations, such as outstanding Floating seed coat agent, suspension seed dressing, dry-powder seed coating agent, water and milk seed coat agent or other be used for the coating material and ULV system of seed Agent.
According to plant species or plant cultivars, their position and growth conditions (soil, weather, trophophase, nutrition), Processing of the invention can also bring superadditivity (" collaboration ") effect.Thus, for example, the following effect more than actual desired can be brought Fruit: the rate of application of the composition comprising Isoflucypram and methoxy acrylic bactericide that can be used according to the invention It reduces and/or activity profile is widened and/or active increases, better plant growth, improves the tolerance to high temperature or low temperature, raising To the tolerance of arid or water or soil salt content, raising Flowering quality, it is easier harvesting, hasting of maturity, higher harvesting Yield, bigger fruit, higher plant height, greener leaf color, make to bloom earlier, the quality of harvested products it is higher And/or nutritive value is higher, the sugared concentration in fruit is higher, harvested products storage stabilities and/or processability are more preferable.
Compared with prior art, bactericidal composition of the invention has the beneficial effect that (1) two kind of effective component compounding, tool There is good synergistic effect;(2) fungicidal spectrum is expanded, use scope has been widened;(3) delay the generation of drug resistance;(4) interior suction is made With strong, antibacterial action is lasting, reduces production cost and use cost;(5) to crop safety and the plant characteristic of improvement can be brought.
Specific embodiment
The following specific examples are used to further explain the present invention in detail, but the present invention be only limited to absolutely not it is following these Embodiment.Raw medicine Isoflucypram is self-control, and preparation method refers to CN102421757;Other used raw medicines, auxiliary agent, Preparation etc. is commercially available, wherein the purchase of 25% pyraclostrobin suspending agent is in the Jiangsu bumper harvest limited public affairs of crop protection share Department, the purchase of 22.5% chlorfenapyr suspending agent is in Kai Bang agricultural science and technology Co., Ltd of Weifang City, the purchase of 30% kresoxim-methyl suspending agent In Co., Ltd of Shandong Weifang Shuangxing Pesticide Co., Ltd., 20% coumoxystrobin suspending agent is bought in Bada Pesticide Co., Ltd., Jilin Province.
1 indoor biometrics experiment of experimental example
Pot-culture method, the suppression that measurement different agents grow grape powdery mildew (Uncinula necator) are used indoors Production is used, and calculates each medicament to the EC of pathogen50Value.
Application: the two consistent grape pot seedlings of leaf phase growing way of selection are for experiment.Single dose or each composition (being shown in Table 1~4) 50mg/L is diluted to 0.1% Tween 80 water is added after dmso solution respectively.Test material is dried in the shade after cauline leaf spraying treatment 24h。
Inoculation: with the water added with a small amount of tween, the Fresh spores taken on grape disease leaf is washed, filters, is made through double gauze Spore suspension, with inoculation sprayer, even spraying is inoculated on seedling.Grape pot seedling after inoculation is placed in greenhouse normally to cultivate, 7d or so is classified according to blank control incidence and investigates.
Grade scale:
0 grade: disease-free;1 grade: lesion area accounts for 5% or less full wafer leaf area;
3 grades: lesion area accounts for the 6%~10% of full wafer leaf area;5 grades: lesion area account for full wafer leaf area 11%~ 20%;
7 grades: lesion area accounts for the 21%~40% of full wafer leaf area;9 grades: lesion area account for the 40% of full wafer leaf area with On.
Drug effect calculates:
Corresponding regression analysis is done according to each composition concentration and corresponding preventive effect, finds out the EC of each composition50Value.
Coefficient calculation method is spent together using the abundant introduction of Sun Yun, the co-toxicity coefficient (CTC) of mixture is calculated, determines mixture It is building performance.
(EC is generally selected using single dose a certain in mixture as standard agent50Junior), it is calculated:
Single dose toxicity index=standard agent EC50/ certain single dose EC50×100
Theoretical toxicity index (TTI)=A single dose toxicity index × A single dose proportion+B single dose in mixture virulence Index × B single dose proportion in mixture.
Survey toxicity index (ATI)=standard single dose EC50 value/mixture EC50Value × 100
Co-toxicity coefficient=survey toxicity index/theoretical toxicity index × 100
Mixture has synergetic when CTC is greater than 120, is antagonism when CTC is less than 80, and CTC is phase between 80-120 Add effect.
The measurement result of table 1:Isoflucypram and pyraclostrobin different ratio to uncinula necator co-toxicity coefficient
It can be obtained from table 1: when Isoflucypram and pyraclostrobin proportion are between 10~1:1~10, co-toxicity coefficient All 120 or more, there is apparent synergistic effect.
The measurement result of table 2:Isoflucypram and ZEN 90160 different ratio to uncinula necator co-toxicity coefficient
Can obtain from table 2: when Isoflucypram and ZEN 90160 proportion are between 10~1:1~5, co-toxicity coefficient all exists 120 or more, there is apparent synergistic effect.
The measurement result of table 3:Isoflucypram and kresoxim-methyl different ratio to uncinula necator co-toxicity coefficient
Can obtain from table 3: when Isoflucypram and kresoxim-methyl proportion are between 5~1:1~5, co-toxicity coefficient is all 120 More than, there is apparent synergistic effect.
The measurement result of table 4:Isoflucypram and coumoxystrobin different ratio to uncinula necator co-toxicity coefficient
Can obtain from table 4: when Isoflucypram and coumoxystrobin proportion are between 10~1:1~10, co-toxicity coefficient is all 120 or more, there is apparent synergistic effect.
So the present invention is using Isoflucypram and methoxy acrylic bactericide as effective component, with it is above-mentioned not When homogenous quantities ratio compounds, there is apparent synergistic effect to uncinula necator, it is seen then that Isoflucypram and methoxyl group propylene The compounding of bactericide of phosphate (phosphinium) ester can become the favourable agents of prevention and treatment uncinula necator.
The preparation of preparation example 1:30%Isoflucypram pyraclostrobin suspending agent
1. the preparation of slurry is sanded
30g raw medicine (wherein Isoflucypram raw medicine 15g, pyraclostrobin raw medicine 15g), 2g are sequentially added in beaker Phosphate (trade name: JR-P, Akzo Nobel), 2g sodium sulfate of polyethenoxy ether of fatty alcohol (trade name: AES, big thousand country New high-tech enterprise), the macromolecular grafted copolymer of 2g polypropylene acids (trade name: TERSPERSE 2500, Hensel is graceful), 0.5g aluminium-magnesium silicate (Hangzhou Zuo Tu new material Co., Ltd), (trade name: XP40, the left soil in Hangzhou are new for 0.2g organic silicon defoamer Materials Co., Ltd), the sodium benzoate (Aladdin reagent) and 57.6g water of 0.2g.After stirring, it is added into vertical Sand mill (Shenyang Chemical Research Institute) usesBead is sanded, and obtains and slurry 94.5g is sanded.
2. homogeneous
0.3g xanthan gum (Aladdin reagent) is dissolved with 5g ethylene glycol (Aladdin reagent), above-mentioned sand milling slurry is added 94.5g, 0.2g organic silicon defoamer (trade name: XP40, Hangzhou Zuo Tu new material Co., Ltd), after mixing, use height Fast dispersion machine (trade name: TG25, German IKA) carries out homogenous disperse with 5000r/min, and effective component mass content is made and is 30% Isoflucypram pyraclostrobin suspending agent.
The preparation of preparation example 2:20%Isoflucypram pyraclostrobin aqueous emulsion
1. oily mutually prepare
It is sequentially added in beaker 5g toluene (Aladdin reagent), 10g durol (trade name: raise by No. 150 solvent naphthas State day reaches chemical industry), 20g raw medicine (wherein Isoflucypram raw medicine 5g, pyraclostrobin raw medicine 15g) is stirred mixing, makes It is dissolved into transparence mixed liquor.Then 3g fatty alcohol EOPO block copolymer (trade name: Ethylan is added to mixed liquor 992, Akzo Nobel), 2g alkyl phenol ether phosphate (trade name: 601P, Xingtai City Yan Cheng chemical assistant company) sufficiently stirs It mixes uniformly, oil phase is made.
2. emulsification
The water of 60g is added in beaker, then the oil of upper step is mutually slowly added dropwise into beaker in the case of stirring, Homogeneous 20min is finally carried out with 12000r/min with high speed disperser (trade name: TG25, German IKA), effective component matter is made Measure the Isoflucypram pyraclostrobin aqueous emulsion that content is 20%.
The preparation of preparation example 3:24%Isoflucypram pyraclostrobin wettable powder
46g diatomite (Hangzhou Zuo Tu new material Co., Ltd) and 20g white carbon black (Aladdin reagent) is taken to be dried, so Filler mixture is obtained by airslide disintegrating mill (the excellent nanogram Mechanology Inc. in Kunshan) processing afterwards.(wherein by 24g raw medicine Isoflucypram raw medicine 20g, pyraclostrobin raw medicine 4g) and 4g sodium lignin sulfonate (trade name: Ufoxane NA, Bao Li Pueraria lobota), the alkylated naphthalene sulfonate of 3g (trade name: Morwet EFW, Akzo Nobel), 3g modified acrylic ester copolymer (trade name: Agrilan700, Akzo Nobel) after mixing, filler mixture obtained, then passes through before being added The Isoflucypram that effective component mass content is 24% is made in airslide disintegrating mill (the excellent nanogram Mechanology Inc. in Kunshan) processing Pyraclostrobin wettable powder.
The preparation of preparation example 4:25%Isoflucypram chlorfenapyr suspending agent
1. the preparation of slurry is sanded
25g raw medicine (wherein Isoflucypram raw medicine 12.5g, ZEN 90160 raw medicine 12.5g) is sequentially added in beaker, 1g phosphate (trade name: JR-P, Akzo Nobel), 1g sodium sulfate of polyethenoxy ether of fatty alcohol (trade name: AES, big thousand state New high-tech enterprise of family), and 3gEOPO block copolymer (trade name: 848, Klein), 0.4g aluminium-magnesium silicate (the left native green wood in Hangzhou Expect Co., Ltd), 0.2g organic silicon defoamer (trade name: XP40, Hangzhou Zuo Tu new material Co., Ltd), the benzoic acid of 0.2g Sodium (Aladdin reagent) and 63.7g water.After stirring, it is added into vertical grinding machine (Shenyang Chemical Research Institute), is made WithBead is sanded, and obtains and slurry 94.5g is sanded.
2. homogeneous
0.3g xanthan gum (Aladdin reagent) is dissolved with 5g ethylene glycol (Aladdin reagent), above-mentioned sand milling slurry is added 94.5g, 0.2g organic silicon defoamer (trade name: XP40, Hangzhou Zuo Tu new material Co., Ltd), after mixing, use height Fast dispersion machine (trade name: TG25, German IKA) carries out homogenous disperse with 5000r/min, and effective component mass content is made and is 25% Isoflucypram chlorfenapyr suspending agent.
The preparation of preparation example 5:10%Isoflucypram ZEN 90160 microemulsion
1. oily mutually prepare
It is sequentially added in beaker 5g methanol (Aladdin reagent), 12g dimethylbenzene (Aladdin reagent), 10g raw medicine is (wherein Isoflucypram raw medicine 7.5g, ZEN 90160 raw medicine 2.5g), it is stirred mixing, makes it dissolve into transparence mixed liquor, is made Obtain oily phase.
2. indirect emulsification
The water of addition 57g in beaker, 8g alkyl phenol block polyether copolymer (trade name: TERMUL 200, Hensel is graceful), 8g castor oil polyoxyethylene ether (trade name: Emulpon CO-360, Akzo Nobel) is uniformly mixed, then in the feelings of stirring The oil of upper step is mutually slowly added dropwise into beaker under condition, is stirred, it is 20% that effective component mass content, which is made, Isoflucypram ZEN 90160 aqueous emulsion.
The preparation of preparation example 6:21%Isoflucypram ZEN 90160 aqueous emulsion
1. oily mutually prepare
It is sequentially added in beaker 5gN- methyl pyrrolidone (Aladdin reagent), 9g durol (trade name: No. 150 Solvent naphtha, Yangzhou day reach chemical industry), 21g raw medicine (wherein Isoflucypram raw medicine 7g, ZEN 90160 raw medicine 14g) is stirred Mixing, makes it dissolve into transparence mixed liquor.Then to mixed liquor be added 3g alkyl phenol block polyether copolymer (trade name: TERMUL 200, Hensel is graceful), 1g calcium dodecyl benzene sulfonate (trade name: agriculture breast 500, Xingtai City Yan Cheng chemical assistant company), It stirs, oil phase is made.
2. emulsification
The water of 61g is added in beaker, then the oil of upper step is mutually slowly added dropwise into beaker in the case of stirring, Homogeneous 20min is finally carried out with 12000r/min with high speed disperser (trade name: TG25, German IKA), effective component matter is made Measure the Isoflucypram ZEN 90160 aqueous emulsion that content is 21%.
The preparation of preparation example 7:30%Isoflucypram kresoxim-methyl suspending agent
1. the preparation of slurry is sanded
30g raw medicine (wherein Isoflucypram raw medicine 15g, kresoxim-methyl raw medicine 15g), 1g phosphoric acid are sequentially added in beaker Ester (trade name: JR-P, Akzo Nobel), the alkylated naphthalene sulfonate of 2g (trade name:EFW, Aksu promise shellfish You), 2gEOPO block copolymer (trade name: 848, Klein), 0.4g bentonite (Hangzhou Zuo Tu new material Co., Ltd), 0.2g organic silicon defoamer (trade name: XP40, Hangzhou Zuo Tu new material Co., Ltd), sodium benzoate (the Aladdin examination of 0.2g Agent) and 58.7g water.It after stirring, is added into vertical grinding machine (Shenyang Chemical Research Institute), uses Bead is sanded, and obtains and slurry 94.5g is sanded.
2. homogeneous
0.3g xanthan gum (Aladdin reagent) is dissolved with 5g ethylene glycol (Aladdin reagent), above-mentioned sand milling slurry is added 94.5g, 0.2g organic silicon defoamer (trade name: XP40, Hangzhou Zuo Tu new material Co., Ltd), after mixing, use height Fast dispersion machine (trade name: TG25, German IKA) carries out homogenous disperse with 5000r/min, and effective component mass content is made and is 25% Isoflucypram kresoxim-methyl suspending agent.
The preparation of preparation example 8:45%Isoflucypram water dispersion granules agent of Kresoxim
1. crushing
33g diatomite (Hangzhou Zuo Tu new material Co., Ltd) and 10g white carbon black (Aladdin reagent) is taken to be dried, so Filler mixture is obtained by airslide disintegrating mill (the excellent nanogram Mechanology Inc. in Kunshan) processing afterwards.(wherein by 45g raw medicine Isoflucypram raw medicine 15g, kresoxim-methyl raw medicine 20g) and 3g modified acrylic ester copolymer (trade name: Agrilan700, Ah Gram Soviet Union Nobel), the alkylated naphthalene sulfonate of 1g (trade name:EFW, Akzo Nobel), 5g polymeric acrylic acid Quasi-graft copolymer (trade name:2700, Hensel is graceful) after mixing, filler mixing obtained before being added Then object obtains mixed material by airslide disintegrating mill (the excellent nanogram Mechanology Inc. in Kunshan) processing.
2. being granulated
15g water is added in mixed material, 3g ammonium sulfate (Aladdin reagent) is granulated by Squeezinggranulator, then It is taken out after drying 2h in electric heating constant temperature blast drier with 60 DEG C of heating.
3. screening
It selects 20 mesh and the sieve of 60 mesh to sieve as requested the particle of drying, gives up top bulky grain and bottom The dust of filtering can be prepared by the Isoflucypram water dispersion granules agent of Kresoxim that effective component mass content is 45%.
The preparation of preparation example 9:45%Isoflucypram kresoxim-methyl wettable powder
47g kaolin (Hangzhou Zuo Tu new material Co., Ltd) is taken to be dried, then (Kunshan is excellent by airslide disintegrating mill Nanogram Mechanology Inc.) processing obtain precomminution filler.By 45g raw medicine (wherein Isoflucypram raw medicine 30g, kresoxim-methyl raw medicine 15g) with 4g alkylnaphthalene sulfonate formaldehyde condensation products (trade name:D-425, Akzo Nobel), 4g modified propylene Acid ester copolymer (trade name: Agrilan700, Akzo Nobel) after mixing, is added precomminution obtained before and fills out Material, then being handled by airslide disintegrating mill (the excellent nanogram Mechanology Inc. in Kunshan) and effective component mass content is made is 45% Isoflucypram kresoxim-methyl wettable powder.
The preparation of preparation example 10:25%Isoflucypram coumoxystrobin suspending agent
1. the preparation of slurry is sanded
25g raw medicine (wherein Isoflucypram raw medicine 12.5g, coumoxystrobin raw medicine 12.5g) is sequentially added in beaker, 3g phosphate (trade name: JR-P, Akzo Nobel), 2g sodium sulfate of polyethenoxy ether of fatty alcohol (trade name: AES, big thousand state New high-tech enterprise of family), the anion-modified polymers of carboxylic acid of 2g (trade name: Agrilan 788, Akzo Nobel), 0.5g Aluminium-magnesium silicate (Hangzhou Zuo Tu new material Co., Ltd), 0.2g organic silicon defoamer (trade name: XP40, the left native new material in Hangzhou Co., Ltd), the sodium benzoate (Aladdin reagent) and 57.6g water of 0.2g.After stirring, it is added into vertical sand milling Machine (Shenyang Chemical Research Institute) usesBead is sanded, and obtains and slurry 94.5g is sanded.
2. homogeneous
0.3g xanthan gum (Aladdin reagent) is dissolved with 5g ethylene glycol (Aladdin reagent), above-mentioned sand milling slurry is added 94.5g, 0.2g organic silicon defoamer (trade name: XP40, Hangzhou Zuo Tu new material Co., Ltd), after mixing, use height Fast dispersion machine (trade name: TG25, German IKA) carries out homogenous disperse with 5000r/min, and effective component mass content is made and is 30% Isoflucypram pyraclostrobin suspending agent.
The preparation of preparation example 11:36%Isoflucypram coumoxystrobin water dispersible granules
1. the preparation of spraying slurry
360g raw medicine (wherein Isoflucypram raw medicine 12g, coumoxystrobin raw medicine 24g) is sequentially added in beaker, 100g polymeric acrylic acid quasi-graft copolymer (trade name: TERSPERSE 2700, Hensel is graceful), 50g alkylnaphthalene sulfonate formaldehyde Condensation product (trade name: Morwet D-425, Akzo Nobel), 3g organic silicon defoamer (trade name: XP40, the left soil in Hangzhou New material Co., Ltd), 400g aluminium-magnesium silicate (Hangzhou Zuo Tu new material Co., Ltd) and 87g white carbon black (Aladdin reagent), It is soaked with 200g water, after stirring, is added into horizontal sand mill (Shenyang Chemical Research Institute), used Bead is sanded, and spraying slurry 1200g is obtained.
2. mist projection granulating
Spraying slurry obtained by upper step is made using drying machine with centrifugal spray (the dry Co., Ltd of Jiangyin City Zhuo Ying) Grain, adjusts temperature, and evaporation water obtains granulated.
3. screening
It selects 20 mesh and the sieve of 60 mesh to sieve as requested for granulated obtained by upper step, gives up big of top The dust of grain and bottom filtering can be prepared by the Isoflucypram coumoxystrobin moisture that effective component mass content is 36% Shot agent.
The preparation of preparation example 12:12%Isoflucypram coumoxystrobin missible oil
It is sequentially added in beaker 5g cyclohexanone (Aladdin reagent), 30g toluene (Aladdin reagent), 12g raw medicine is (wherein Isoflucypram raw medicine 9g, coumoxystrobin raw medicine 3g), it is stirred mixing, makes it dissolve into transparence mixed liquor.Then to 3g fatty alcohol EOPO block copolymer (trade name: Ethylan992, Akzo Nobel) is added in mixed liquor, 2g detergent alkylate Sulfoacid calcium (trade name: agriculture breast 500, Xingtai City Yan Cheng chemical assistant company) is supplemented residue 48g toluene (Aladdin reagent), is filled Divide and stir evenly, the Isoflucypram coumoxystrobin missible oil that effective component mass content is 12% is made.
The preparation of reference examples 1:30%Isoflucypram suspending agent
1. the preparation of slurry is sanded
30g Isoflucypram raw medicine, 2g phosphate (trade name: JR-P, Aksu promise shellfish are sequentially added in beaker You), 2g sodium sulfate of polyethenoxy ether of fatty alcohol (trade name: AES, big thousand national new high-tech enterprises), 2g polypropylene acids Macromolecular grafted copolymer (trade name:2500, Hensel is graceful), 0.5g aluminium-magnesium silicate (the left native new material in Hangzhou Co., Ltd), 0.2g organic silicon defoamer (trade name: XP40, Hangzhou Zuo Tu new material Co., Ltd), the sodium benzoate of 0.2g (Aladdin reagent) and 57.6g water.It after stirring, is added into vertical grinding machine (Shenyang Chemical Research Institute), usesBead is sanded, and obtains and slurry 94.5g is sanded.
2. homogeneous
0.3g xanthan gum (Aladdin reagent) is dissolved with 5g ethylene glycol (Aladdin reagent), above-mentioned sand milling slurry is added 94.5g, 0.2g organic silicon defoamer (trade name: XP40, Hangzhou Zuo Tu new material Co., Ltd), after mixing, use height Fast dispersion machine (trade name: TG25, German IKA) carries out homogenous disperse with 5000r/min, and effective component mass content is made and is 30% Isoflucypram suspending agent.
2 field control effectiveness test of embodiment
Test process: according to the reagent agent experimental design in table 1~4, phase is set to the test medicine of preparation example 1-12 Same effective ingredient consumption.Comparison medicament is commercially available 25% pyraclostrobin SC of pesticide, 22.5% ZEN 90160 SC, 30% ether respectively 30%Isoflucypram SC and blank clear water prepared by bacterium ester SC, 20% coumoxystrobin SC and reference examples 1.
Cell setting: test sets 12 processing, and every processing is repeated 4 times;Plot area is 15~30m2, random district's groups row Column;
Application method: medicament is administered in uncinula necator early stage, foliar spray processing, and spouting liquid is with drop of not dripping It is main;
Spraying times: 2 times, strong wind day or it is expected that rainfall in 1 hour, is not administered.State of an illness radix is investigated before application for the first time, with It was administered afterwards every 7 days 1 time, 7 days investigation preventive effects after the 2nd application.
Control time and number: 3 times, strong wind day or it is expected that rainfall in 1 hour, please don't be administered.Investigation disease before application for the first time Feelings radix is administered 1 time every 7d later, and 7~14d investigates preventive effect after the 3rd application.
Investigation method: every cell takes 5 points of investigation at random, and every is investigated 2~3 plants, and the whole blades of every plant of investigation record total leaf Number, the sick number of sheets, sick series.Grade scale method is as follows:
0 grade: disease-free spot;
1 grade: lesion area accounts for 5% or less entire blade area;
3 grades: lesion area accounts for the 6%-10% of entire blade area;
5 grades: lesion area accounts for the 11%-20% of entire blade area;
7 grades: lesion area accounts for the 21%-40% of entire blade area;
9 grades: lesion area accounts for 40% or more of entire blade area.
Drug effect calculates:
See Table 5 for details for test result.
Table 5: preventive effect of the different agents to uncinula necator
Processing number Medicament Active ingredient amount (g/ mus) Control efficiency (14 days)
Preparation example 1 30%Isoflucypram pyraclostrobin SC 6 80.5
Preparation example 2 20%Isoflucypram pyraclostrobin EW 6 74.9
Preparation example 3 24%Isoflucypram pyraclostrobin WP 6 75.2
Preparation example 4 25%Isoflucypram ZEN 90160 SC 6 80.2
Preparation example 5 10%Isoflucypram ZEN 90160 ME 6 79.5
Preparation example 6 21%Isoflucypram ZEN 90160 EW 6 86.3
Preparation example 7 30%Isoflucypram kresoxim-methyl SC 6 81.5
Preparation example 8 45%Isoflucypram kresoxim-methyl WG 6 87.4
Preparation example 9 45%Isoflucypram kresoxim-methyl WP 6 85.3
Preparation example 10 25%Isoflucypram coumoxystrobin SC 6 79.2
Preparation example 11 36%Isoflucypram coumoxystrobin WG 6 77.5
Preparation example 12 12%Isoflucypram coumoxystrobin EC 6 80.5
Reference examples 1 30%Isoflucypram SC 6 79.1
Reference examples 2 25% pyraclostrobin SC 6 80.6
Reference examples 3 22.5% ZEN 90160 SC 6 79.9
Reference examples 4 30% kresoxim-methyl SC 6 75.4
Reference examples 5 20% coumoxystrobin SC 6 76.2
Reference examples 6 The control of blank clear water -- --
As can be seen from the above data, provided by the present invention to be killed containing Isoflucypram and methoxy acrylic The bactericidal composition of microbial inoculum has significant curative effect on uncinula necator, has delayed the generation of Disease Resistance.In addition, in medication model It does not find that composition pesticide of the invention has phytotoxicity generation to grape in enclosing, shows bactericidal composition of the invention to crop safety Property is good, can promote and apply.

Claims (9)

1. a kind of bactericidal composition, it is characterised in that: the effective component of the bactericidal composition includes Isoflucypram and methoxy Base acrylic bactericide, wherein methoxy acrylic bactericide is pyraclostrobin, ZEN 90160, kresoxim-methyl, fourth Any one in fragrant bacterium ester.
2. bactericidal composition according to claim 1, it is characterised in that: Isoflucypram and methoxy acrylic The mass ratio of fungicide is 1~15:15~1.
3. bactericidal composition according to claim 2, it is characterised in that: Isoflucypram and methoxy acrylic The mass ratio of fungicide is 1~10:10~1, more preferable 1~5:5~1.
4. bactericidal composition according to claim 1 to 3, it is characterised in that: Isoflucypram and methoxyl group Total content of the acrylic bactericide in bactericidal composition is 1~80 mass %.
5. bactericidal composition according to claim 4, it is characterised in that: Isoflucypram and methoxy acrylic Total content of the fungicide in bactericidal composition is 10~45 mass %.
6. bactericidal composition described in claim 1-5 any one is in prevention and treatment powdery mildew, rust, glume blight, net blotch, downy mildew Application in the diseases such as disease, rice blast.
7. preparation prepared by bactericidal composition described in claim 1-5 any one, it is characterised in that: the agent of the preparation Type is missible oil, aqueous emulsion, microemulsion, suspending agent, wettable powder or water dispersible granules.
8. preparation as claimed in claim 7 is in diseases such as prevention and treatment powdery mildew, rust, glume blight, net blotch, downy mildew, rice blast In application.
9. the method for controlling plant disease, the method includes applying a effective amount of right to the plant or plant part It is required that bactericidal composition described in 1-5 any one or preparation as claimed in claim 7.
CN201811155184.3A 2018-09-30 2018-09-30 A kind of bactericidal composition containing Isoflucypram and methoxy acrylic bactericide Withdrawn CN109169676A (en)

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Publication number Priority date Publication date Assignee Title
CN113453555A (en) * 2019-02-20 2021-09-28 巴斯夫欧洲公司 Pesticidal mixtures comprising pyrazole compounds
CN115251066A (en) * 2022-08-04 2022-11-01 青岛海利尔生物科技有限公司 Cyprodinil-containing bactericidal composition

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CN104735985A (en) * 2012-10-19 2015-06-24 拜尔农科股份公司 Method for enhancing tolerance to abiotic stress in plants using carboxamide or thiocarboxamide derivatives
CN105357967A (en) * 2012-10-19 2016-02-24 拜尔农科股份公司 Method of plant growth promotion using carboxamide derivatives

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WO2012143127A1 (en) * 2011-04-22 2012-10-26 Bayer Cropsciences Ag Active compound combinations comprising a (thio)carboxamide derivative and a fungicidal compound
CN104735985A (en) * 2012-10-19 2015-06-24 拜尔农科股份公司 Method for enhancing tolerance to abiotic stress in plants using carboxamide or thiocarboxamide derivatives
CN105357967A (en) * 2012-10-19 2016-02-24 拜尔农科股份公司 Method of plant growth promotion using carboxamide derivatives

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Publication number Priority date Publication date Assignee Title
CN113453555A (en) * 2019-02-20 2021-09-28 巴斯夫欧洲公司 Pesticidal mixtures comprising pyrazole compounds
CN113453555B (en) * 2019-02-20 2023-08-08 巴斯夫欧洲公司 Pesticidal mixtures comprising pyrazole compounds
CN115251066A (en) * 2022-08-04 2022-11-01 青岛海利尔生物科技有限公司 Cyprodinil-containing bactericidal composition
CN115251066B (en) * 2022-08-04 2024-04-09 青岛海利尔生物科技有限公司 Sterilization composition containing cyprodinil

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