CN105594709A - Sterilization composition containing florothiazolylpyrithylone and metrafenone - Google Patents

Sterilization composition containing florothiazolylpyrithylone and metrafenone Download PDF

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CN105594709A
CN105594709A CN201510732114.XA CN201510732114A CN105594709A CN 105594709 A CN105594709 A CN 105594709A CN 201510732114 A CN201510732114 A CN 201510732114A CN 105594709 A CN105594709 A CN 105594709A
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Prior art keywords
metrafenone
ethyl ketone
pyrrole ethyl
thiazole pyrrole
fluorine thiazole
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葛尧伦
陈健
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Hailir Pesticides and Chemicals Group Co Ltd
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Hailir Pesticides and Chemicals Group Co Ltd
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Abstract

The invention relates to a sterilization composition containing florothiazolylpyrithylone and metrafenone. The effective component of the sterilization composition is a florothiazolylpyrithylone and metrafenone binary complex. A mass ratio of florothiazolylpyrithylone to metrafenone is 1-40:40-1, and the above preparation contains 1-80 mass% of the effective component florothiazolylpyrithylone and metrafenone, and the balance of auxiliary components allowed and accepted in pesticides. The dosage form of the sterilization composition can be a missible oil, a suspension, a wettable pulvis, a water dispersible granule, an emulsion in water and a micro-emulsion. The sterilization composition is mainly used to prevent and treat grape downy mildew, late blight and various powdery mildews.

Description

A kind of bactericidal composition that contains fluorine thiazole pyrrole ethyl ketone and metrafenone
Technical field
The present invention relates to agriculture chemical compounding technical field, particularly relate to a kind of killing of fluorine thiazole pyrrole ethyl ketone and metrafenone of containingBacteria composition.
Background technology
Fluorine thiazole pyrrole ethyl ketone is a kind of new piperidine series bactericidal agent of E.I.Du Pont Company's exploitation. It is formulated in Merck & Co., Inc. and reportsMedicinal actives compound (IV), find to there is better Fungicidal active compound (V) through high flux screening, and then optimize researchFind the specific Oxathi-apiprolin of downy mildew. Active component Bao Han oxazole ring in this molecular structure, pyrazole ring,Thiazole ring, can significantly strengthen the control to special product corps diseases such as potato, grape, vegetables. Within 2012, obtain the approval of ISO common nameNew varieties of pesticides [2], by being widely used in the control of crop germ in the future.
Metrafenone is the new type bactericide of a Benzophenones of BASF AG's exploitation, has good to all kinds of powdery mildewsPrevention effect. The chemical name of metrafenone: (the bromo-6-methoxyl group-2-of 3-aminomethyl phenyl)-(2,3,4-trimethoxy-6-methylbenzeneBase) ketone, its chemical structural formula is
Using chemical agent is the most effectively means of controlling plant diseases. But use single long-term continuous high doseChemical bactericide, easily cause the problems such as residual, the environmental pollution of medicament and resistance to resistance to the action of a drug fungi development. Reasonably chemistryBactericide compounded or mixture has expansion fungicidal spectrum, improve prevention effect, extend the optimum period for applying fertilizer, reduce dosage, reduce poisoning,Reduce residual, delay the actively feature such as Antifungal resistance and drug-fast generation and development, bactericide compounded is to solve above-mentioned askingOne of effective method the most of topic. Develop new product bactericide price constantly soaring, and by contrast, develop and study efficiently,It is short and be subject to domestic and international attention that the composite and mixture of low toxicity, low-residual has small investment, lead time, and numerous and confused increasing developsDynamics. We filter out fluorine thiazole pyrrole ethyl ketone and metrafenone and carry out compositely on the basis of lab screening and field test, haveSignificantly synergistic effect. And composite bactericidal composition and application about fluorine thiazole pyrrole ethyl ketone and metrafenone there is no people's report at presentRoad mistake.
Summary of the invention
Based on above situation, the object of the invention is to provide a kind of new and effective pesticide sterilizing composite. Be mainly used inPrevent and treat downy mildew of garpe, late blight and all kinds of powdery mildew.
Technical scheme of the present invention realizes by following measures:
One contains fluorine thiazole pyrrole ethyl ketone and metrafenone bactericidal composition, the active ingredient fluorine thiazole pyrrole of this bactericidal compositionTwo yuan of ethyl ketone and metrafenones are composite, and all the other are auxiliary element. Active ingredient fluorine thiazole pyrrole ethyl ketone in wherein said Pesticidal combinationWith the mass ratio of metrafenone be 1~40: 40~1, described bactericidal composition of the present invention is through toxicity test experimental verification, fluorine thiazoleThe mass ratio of pyrrole ethyl ketone and metrafenone is 1~40: 40~1 o'clock, and synergistic effect is better.
The formulations of pesticide that described bactericidal composition of the present invention can be prepared are missible oil, suspending agent, wettable powder, moistureShot agent, aqueous emulsion, microemulsion. Wherein active ingredient fluorine thiazole pyrrole ethyl ketone and the gross mass of metrafenone in preparation account for whole system1%~80% of agent quality, while wherein accounting for 15%~50%, toxicity and residually reach good balance, cost is also lower.
The specific embodiments of the formulations of pesticide that bactericidal composition of the present invention is mixed with is as follows:
Described bactericidal composition is cream preparation, and the mass fraction of component is: 1~40 part of fluorine thiazole pyrrole ethyl ketone; Benzene bacterium1~40 part of ketone; 10~30 parts of conventional emulsifiers; 20~50 parts of conventional solvents; 1~5 part of conventional synergist. The tool of this cream preparationBody production stage for first active ingredient fluorine thiazole pyrrole ethyl ketone and metrafenone are added add again after dissolving completely in solvent emulsifying agent,After stirring, synergist becomes the oily liquids of transparent and homogeneous, and filling, can be made into the cream preparation of the present composition.
Described bactericidal composition is suspending agent, and the mass fraction of component is: 1~40 part of fluorine thiazole pyrrole ethyl ketone; Metrafenone 1~40 parts; 5~20 parts of dispersants; 1~5 part of antifreezing agent; 0.1~2 part of thickener; 0.1~0.8 part of defoamer; Penetrating agent 0~10Part; 0.1~5 part of pH value conditioning agent; Water, surplus. The concrete production stage of this suspending agent is for first mixing other auxiliary agents, through high speedShear-mixed is even, adds active ingredient fluorine thiazole pyrrole ethyl ketone and metrafenone, and in ball crusher, abrading-ball 2~3 hours, makes a diameterAll, below 5mm, can be made into the suspending agent preparation of the present composition.
Described bactericidal composition is wettable powder, and the mass fraction of component is: 1~40 part of fluorine thiazole pyrrole ethyl ketone; Benzene1~40 part of bacterium ketone; 3~10 parts of dispersants; 1~5 part of wetting agent; Filler, surplus. The concrete production stage of this wettable powderFor: by above-mentioned formula, active ingredient fluorine thiazole pyrrole ethyl ketone is mixed with metrafenone and dispersant, wetting agent and filler, stirringUniform stirring in still is mixing after airslide disintegrating mill, can be made into the wettable powder of the present composition.
Described bactericidal composition is water dispersible granules, and the mass fraction of component is: 1~40 part of fluorine thiazole pyrrole ethyl ketone; Benzene1~40 part of bacterium ketone; 3~10 parts of dispersants; 1~10 part of wetting agent; 1~5 part of disintegrant; Filler, surplus. This water dispersible granulesConcrete production stage is: by above-mentioned formula by active ingredient fluorine thiazole pyrrole ethyl ketone and metrafenone and dispersant, wetting agent, disintegrantAnd filler mixes, pulverize with micro jet, through mediating, then add in fluidized bed prilling drying machine and makeAfter grain, dry, screening, through sample analysis, can be made into the water dispersible granules of the present composition.
Described bactericidal composition is aqueous emulsion, and the mass fraction of component is: 1~40 part of fluorine thiazole pyrrole ethyl ketone; Metrafenone 1~40 parts; 3~30 parts of emulsifying agents; 5~15 parts of solvents; 2~15 parts of stabilizing agents; 1~5 part of antifreezing agent; 0.1~8 part of defoamer; IncreaseThick dose 0.2~2 part; Water, surplus. The concrete production stage of this aqueous emulsion is: first by fluorine thiazole pyrrole ethyl ketone and metrafenone, solventBe added together with emulsifying agent, cosolvent, make to be dissolved into uniform oil phase; By part water, antifreeze, antimicrobial etc. otherInsecticides adjuvant mixes into uniform water; When reactor high speed stirs, oil phase is added to water, slowly addWater until reach phase inversion point, is opened cutter and is carried out high speed shear, and add remaining water, shears about half an hour, forms water bagThe aqueous emulsion of oil type, can be made into the aqueous emulsion of the present composition.
Described bactericidal composition is microemulsion, and the mass fraction of component is: 1~40 part of fluorine thiazole pyrrole ethyl ketone; Metrafenone 1~40 parts; 10~30 parts of emulsifying agents, 1~8 part of antifreezing agent, 0.5~10 part of stabilizing agent, 20~50 parts of conventional solvent cosolvents. WillFluorine thiazole pyrrole ethyl ketone and metrafenone dissolve completely with cosolvent, then add other compositions such as emulsifying agent, antifreezing agent stabilizing agent, evenlyMix, finally add water, after fully stirring, can be made into microemulsion.
Wherein above-described emulsifying agent is selected from calcium dodecyl benzene sulfonate and aliphatic acid polyethenoxy ether, alkyl phenol polyoxyVinethene sulfosuccinate, styrylphenol polyoxyethylene ether, NPE, castor oil polyoxyethylene ether,Aliphatic acid polyethenoxy base ester, any or more than one any mixtures than forming in polyoxyethylene aliphatic alcohol ether.
Described solvent is dimethylbenzene or biodiesel, toluene, diesel oil, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, turpentineOil, solvent naphtha, dimethyl formamide, dimethyl sulfoxide (DMSO), one or more in water equal solvent are arbitrarily than the mixing of compositionThing.
Described dispersant is selected from polycarboxylate, lignosulfonates, APES methyl ether condensation product sulfuric acidSalt, alkylsulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, APES, polyoxyethylene carboxylate, fatAmine APEO, one or more in fatty acid glyceride APEO.
Described wetting agent is selected from lauryl sodium sulfate, calcium dodecyl benzene sulfonate, and Nekal BX, moistening bleeding agent F,Alkylbenzenesulfonate polyoxyethylene triphen phosphenylic acid salt dimly, spaonin powder, silkworm excrement, one or more in soapberry powder.
Described disintegrant is selected from bentonite, urea, and ammonium sulfate, aluminium chloride, citric acid, succinic acid, in sodium acid carbonateOne or more.
Described thickener is selected from xanthans, carboxymethyl cellulose, and carboxyethyl cellulose, methylcellulose, Magnesiumaluminumsilicate,In polyvinyl alcohol one or more.
Described stabilizing agent is selected from natrium citricum, the one in resorcinol.
Described antifreezing agent is selected from ethylene glycol, propane diols, one or more in glycerine.
Described defoamer is selected from silicone oil, silicone compound, C10-20Saturated fat acid compounds, C8-10Fatty alcoholOne or more.
Described filler is selected from kaolin, diatomite, and bentonite, attapulgite, white carbon, starch, in precipitated calcium carbonateOne or more.
The present invention has obvious synergistic effect taking fluorine thiazole pyrrole ethyl ketone and metrafenone as the composite bactericide of active ingredient,Delay the drug-fast generation in key, and reduced to become to produce cost and use cost, can be used for the improvement of resistance disease. Be mainly used inPrevent and treat downy mildew of garpe, late blight and all kinds of powdery mildew.
Detailed description of the invention
For making technical scheme of the present invention, object and advantage are clearer, the following specific embodiment of the present inventionDescribe, but the present invention is not limited to these examples. Effect experiment of the present invention adopts indoor biometrics and field test phaseIn conjunction with mode, if no special instructions, the ratio of below mentioning is all ratio of quality and the number of copies.
Embodiment: fluorine thiazole pyrrole ethyl ketone proportioning co-toxicity experiments different from metrafenone.
1.1 reagent agent
The former medicine of 96% fluorine thiazole pyrrole ethyl ketone, the former medicine of 95% metrafenone, above-mentioned former medicine is by the limited public affairs of extra large rel medicine company shareResearch and development department of department provides.
1.2 test targets
Never executed fluorine thiazole pyrrole ethyl ketone and metrafenone from Shouguang, Shandong and cucumber of the same type gathers and separates potted plantly,For trying cucumber variety: Chang Chun Mi Ci.
1.3 test method
1.3.1 medicament preparation
First use the former medicine of acetone solution, according to the result of preliminary experiment, two appropriate former medicines are made into different proportionings, then use thirdIt is stand-by that each processing is diluted to respectively some concentration gradients by ketone.
Susceptible cucumber variety Chang Chun Mi Ci is cultivated in pot for growing seedlings, be placed in greenhouse and cultivate, plant grows to three to four leavesAfter date, gathers the blade of identical leaf age, for cultivation and the mensuration of powdery mildew of cucumber bacterium.
1.3.2 the cultivation of powdery mildew of cucumber bacterium and the preparation of spore suspension
Powdery mildew of cucumber bacterium adopts plants method to cultivate under 20 DEG C, the condition of 12h alternation of light and darkness, and every 30d turns and is commissioned to trainSupport 1 time. When inoculation, with the conidium on sterilized water wash-out incidence of leaf, being mixed with spore concentration is l × 106Individual/mL's is outstandingSupernatant liquid.
1.3.3 strains tested sensitivity testing
Adopt leaf dish moisturizing method to carry out toxicity test. First the blade of collection is prepared into the leaf dish that diameter is 1.5cm, randomMix, be placed in respectively the series concentration liquid configuring and soak lh, 50 leaf dishes of each concentration, test is with locating of adding medicine notReason is blank, and after immersion finishes, leaf faces up and puts on the wetting blotting paper of identical liquor strength, on leaf dishLiquid blot, the spore suspension l0L preparing is inoculated in to leaf dish central authorities, room temperature is placed after 5min, is placed in 20 DEG C, 12hUnder the condition of alternation of light and darkness, cultivate, after 10d, measure the onset area on leaf dish, calculate EC50
On the basis of pilot study, respectively single dose fluorine thiazole pyrrole ethyl ketone and metrafenone are carried out to virulence survey in order to upper methodFixed, the two EC50Value is respectively 8.69 ㎎/l and 8.26 ㎎/l.
The percentage that accounts for leaf disc area according to lesion area is divided sick level
0 grade: anosis;
1 grade: sorus area accounts for below 5% of whole leaf area;
3 grades: sorus area accounts for below the 6%-10% of whole leaf area;
5 grades: sorus area accounts for below the 11%-20% of whole leaf area;
7 grades: sorus area accounts for below the 21%-50% of whole leaf area;
9 grades: sorus area accounts for the more than 50% of whole leaf area.
1.3.4 mixture toxicity test and interpretation of result
Carry out the toxicity test of mixture according to mixed ratio by single dose toxicity test method.
If the contrast death rate < 5%, does not proofread and correct, the contrast death rate, between 5%-20%, is proofreaied and correct by formula 2, contrastThe death rate > 20%, test need be reformed.
Taking the logarithm value of drug concentration (mg/L) as independent variable x, taking the probability value of corrected mortality as dependent variable y, respectivelySet up virulence regression equation formula, adopt DPS software to calculate the EC of single dose and each proportioning mixture50Calculate poison altogether according to the abundant method of Sun YunCoefficient (CTC). Co-toxicity coefficient CTC, computing formula is as follows: (taking fluorine thiazole pyrrole ethyl ketone as standard medicament, its toxicity index is100):
The EC of toxicity index (TI)=fluorine thiazole pyrrole ethyl ketone of metrafenone50The EC of/metrafenone50×100
The EC of true toxicity index (ATI)=fluorine thiazole pyrrole ethyl ketone of M50The EC of/M50×100
TI × P benzene of TI × P fluorine thiazole pyrrole ethyl ketone+metrafenone of theoretical toxicity index (TTI)=fluorine thiazole pyrrole ethyl ketone of MBacterium ketone
TTI × 100 of the ATI/M of co-toxicity coefficient (CTC)=M of M
In formula:
M is fluorine thiazole pyrrole ethyl ketone and the mixture of the different proportionings of metrafenone
P fluorine thiazole pyrrole ethyl ketone is fluorine thiazole pyrrole ethyl ketone shared ratio in mixture
P metrafenone is metrafenone shared ratio in mixture.
2.1 toxicity test results
Table 1 fluorine thiazole pyrrole ethyl ketone and the toxicity test of metrafenone to powdery mildew of cucumber
As can be seen from the table, the result of the test of different proportion proportioning shows, dilutes respectively all tables in active ingredient ratioReveal stronger synergistic effect, wherein taking fluorine thiazole pyrrole ethyl ketone: metrafenone is the good suggestion of synergistic effect as 1:20~20:1 timeSuitable proportion 1:20~20:1 left and right mixture preparation is carried out to further field control effectiveness test, to evaluate its field practical applicationEffect.
3 field tests are prevented and treated powdery mildew of cucumber, the experimental result of downy mildew of garpe
3.1 field tests are prevented and treated powdery mildew of cucumber
3.1.1 test method
Test is on Shandong Pingdu City cucumber ground, and 4 points of every community investigation, investigate 2 strains at every, by staging record morbidity journeyDegree, grade scale is as follows:
0 grade: anosis;
1 grade: sorus area accounts for below 5% of whole leaf area;
3 grades: sorus area accounts for below the 6%-10% of whole leaf area;
5 grades: sorus area accounts for below the 11%-20% of whole leaf area;
7 grades: sorus area accounts for below the 21%-50% of whole leaf area;
9 grades: sorus area accounts for the more than 50% of whole leaf area.
3.1.2 control time and number of times
Test is investigated 4 times altogether, and radix investigation before medicine is investigated after 7 days, 7 days for the second time and medicine after medicine for the first time for 15 days.
3.1.3 drug effect computational methods
The total number of sheets × 100 of sick leaf rate (%)=sick number of sheets/investigate
Disease index=∑ (the sick number of sheets × relative level numerical value at different levels)/(investigating the total number of sheets × 9) × 100
Prevention effect (%)=(1-(disease index after the front disease index × treatment region medicine of blank district medicine)/(blank rightAccording to disease index before disease index × treatment region medicine after district's medicine)) × 100.
3.1.4 poisoning investigation method
After dispenser, whether 15d range estimation medicament has poisoning to crop continuously.
3.1.5 result of the test and analysis
Each effect of preventing and treating powdery mildew of cucumber of processing. (table 2)
The each effect of preventing and treating powdery mildew of cucumber of processing of table 2
48% fluorine thiazole pyrrole ethyl ketone as shown in Table 2: metrafenone with 24:24 ratio composite bactericide for powdery mildew of cucumberControl successful higher than fluorine thiazole pyrrole ethyl ketone and metrafenone single dose, bactericidal effect increases progressively with the increase of dosage. According to field orderSurvey, within the scope of test dose, plant growth is normal, and the poisoning phenomenon to cucumber does not all appear in each treatment agent, illustrates that it is rightCucumber is safe. Advise that the bactericide different from the mechanism of action mixes use to delay the drug-fast generation of germ.
4.1 field tests are prevented and treated downy mildew of garpe
4.1.1 test method
Test is on Shandong Pingdu City wine-growing ground, and 4 points of every community investigation, investigate 2 strains at every, record and send out by stagingCourse of disease degree, grade scale is as follows:
0 grade: anosis;
1 grade: sorus area accounts for below 5% of whole leaf area;
3 grades: sorus area accounts for below the 6%-10% of whole leaf area;
5 grades: sorus area accounts for below the 11%-20% of whole leaf area;
7 grades: sorus area accounts for below the 21%-50% of whole leaf area;
9 grades: sorus area accounts for the more than 50% of whole leaf area.
4.1.2 control time and number of times
Test is investigated 4 times altogether, radix investigation before medicine, for the first time after medicine 14 days, after 14 days and medicine, within 21 days, enter after medicine for the second timeRow investigation.
4.1.3 drug effect computational methods
The total number of sheets × 100 of sick leaf rate (%)=sick number of sheets/investigate
Disease index=∑ (the sick number of sheets × relative level numerical value at different levels)/(investigating the total number of sheets × 9) × 100
Prevention effect (%)=(1-(disease index after the front disease index × treatment region medicine of blank district medicine)/(blank rightAccording to disease index before disease index × treatment region medicine after district's medicine)) × 100.
4.1.4 poisoning investigation method
After dispenser, whether 14d range estimation medicament has poisoning to crop continuously.
4.1.5 result of the test and analysis
Each effect (table 3) of processing control cucumber downy mildew
The each effect of processing control cucumber downy mildew of table 3
The Mixed Pharmacy of different proportion as can be seen from Table 3, tests by different consumptions, and after medicine, it is to oeninThe control of mildew is all better than contrasting medicament, and bactericidal effect increases progressively with the increase of dosage. According to field range estimation, at test dose modelIn enclosing, plant growth is normal, and the poisoning phenomenon to grape does not all appear in each treatment agent, illustrates that it is safe to grape. BuildDiscuss the bactericide different from the mechanism of action and mix use to delay the drug-fast generation of germ.
In sum, the bactericidal composition that the present invention contains fluorine thiazole pyrrole ethyl ketone and metrafenone, to powdery mildew of cucumber and PortugalGrape downy mildew has good prevention effect, and it is to target crop safety. Complex preparation has not only improved preventive effect, and expandsFungicidal spectrum, so this compounded combination tool in production practices is of great significance.

Claims (4)

1. a bactericidal composition that contains fluorine thiazole pyrrole ethyl ketone and metrafenone, is characterized in that: this bactericidal composition effectivelyComposition is fluorine thiazole pyrrole ethyl ketone and metrafenone binary built, and all the other are auxiliary element, wherein active ingredient fluorine thiazole pyrrole ethyl ketone withThe mass ratio of metrafenone is 1~40: 40~1.
2. bactericidal composition according to claim 1, is characterized in that: fluorine thiazole pyrrole ethyl ketone and metrafenone are in preparationGross weight accounts for 1%~80% of the whole quality of the pharmaceutical preparations.
3. bactericidal composition according to claim 2, is characterized in that: fluorine thiazole pyrrole ethyl ketone and metrafenone are in preparationGross weight accounts for 5%~50% of the whole quality of the pharmaceutical preparations.
4. according to the bactericidal composition described in claim 1 or 2 or 3, it is characterized in that: the formulation of this bactericidal composition is breastOil, suspending agent, wettable powder, water dispersible granules, aqueous emulsion, microemulsion.
CN201510732114.XA 2015-10-31 2015-10-31 Sterilization composition containing florothiazolylpyrithylone and metrafenone Withdrawn CN105594709A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106912488A (en) * 2017-05-01 2017-07-04 佛山市瑞生通科技有限公司 A kind of combination containing biological bactericide
CN107950543A (en) * 2017-12-10 2018-04-24 广东中迅农科股份有限公司 A kind of bactericidal composition containing benziothiazolinone and fluorine thiazole pyrrole ethyl ketone
CN108184864A (en) * 2017-12-25 2018-06-22 山东省烟台市农业科学研究院 A kind of complex composition and its application containing fluorine thiazole pyrrole ethyl ketone and frutus cnidii

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106912488A (en) * 2017-05-01 2017-07-04 佛山市瑞生通科技有限公司 A kind of combination containing biological bactericide
CN107950543A (en) * 2017-12-10 2018-04-24 广东中迅农科股份有限公司 A kind of bactericidal composition containing benziothiazolinone and fluorine thiazole pyrrole ethyl ketone
CN108184864A (en) * 2017-12-25 2018-06-22 山东省烟台市农业科学研究院 A kind of complex composition and its application containing fluorine thiazole pyrrole ethyl ketone and frutus cnidii
CN108184864B (en) * 2017-12-25 2020-07-14 山东省烟台市农业科学研究院 Compound composition containing oxathiapiprolin and osthole and application thereof

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