CN102283228B - Sterilization composite containing pyraclostrobin and propineb - Google Patents

Sterilization composite containing pyraclostrobin and propineb Download PDF

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CN102283228B
CN102283228B CN 201010210668 CN201010210668A CN102283228B CN 102283228 B CN102283228 B CN 102283228B CN 201010210668 CN201010210668 CN 201010210668 CN 201010210668 A CN201010210668 A CN 201010210668A CN 102283228 B CN102283228 B CN 102283228B
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propineb
pyraclostrobin
bactericidal composition
composite
leaf
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CN102283228A (en
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张绪芬
任玉英
白复芹
冯涵丽
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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 discloses a sterilization composite containing pyraclostrobin and propineb and a preparation method and applications thereof. The sterilization composite is characterized by containing the pyraclostrobin, the propineb and other assistants, wherein the weight ratio of the pyraclostrobin to the propineb is (1:80)-(50:9). The sterilization composite can be applied to controlling the diseases of cereals, fruit trees, melons, vegetables and the like. The composite has a wide application range, low cost and a good effect. Proved by indoor efficacy trials, the composite has an obvious synergistic effect. Moreover, blending the pyraclostrobin with the propineb is not reported yet at home and abroad, therefore, the invention is disclosed.

Description

A kind of bactericidal composition that contains pyraclostrobin and Propineb
Technical field
The invention belongs to the agriculture chemical compounding field, relate to a kind of bactericidal composition and application thereof, especially a kind of bactericidal composition and application thereof take pyraclostrobin and Propineb as main active.
Background technology
Using chemical agent is the most effectively means of control fungal diseases of plants.But long-term use single chemical bactericide continuously high dose, easily cause the problems such as residual, the environmental pollution of medicament and anti-pesticide resistance fungi development.Reasonably chemical bactericide is composite or be mixed and have the expansion fungicidal spectrum, improve control efficiency, extend the optimum period for applying fertilizer, reduce dosage, reduce poisoning, reduce residual, delay Antifungal resistance and the positive characteristics such as drug-fast generation and development, bactericide compounded or to be mixed be one of the effective method the most that addresses the above problem.Exploitation new product bactericide price is constantly soaring, and by contrast, exploitation is efficient with research, low toxicity, low-residual composite be mixed have small investment, the lead time is short and be subject to domestic and international attention, the numerous and confused dynamics that develops that strengthens.
Pyraclostrobin (pyraclostrobin): methyl (N)-[[[1-(4-chlorobenzene) pyrazoles-3 base)-oxygen]-the O-methoxyl group]-the N-methoxymethyl carbamate
Figure BSA00000160454600011
Outward appearance: white is to oldlace crystalloid solid, and is tasteless.Proportion: 1.367g/cm3, molten some 63.7-65.2 ℃.Be the mitochondrial respiratory inhibitor, namely by stoping electronics to shift in cytochrome b cl is synthetic.Have protection, treatment, blade infiltration conduction.Pyraclostrobin missible oil shows that through the field control effectiveness test result powdery mildew of cucumber, downy mildew and banana freckle, leaf spot are had control efficiency preferably.The dosage of preventing and treating powdery mildew of cucumber, downy mildew is active ingredient 75~150g/hm 2(being converted into the missible oil commodity amount is 20-40mL/667m2).In the their early stage even spraying, generally spray medicine 3~4 times after thin up, interval 7d sprays 1 medicine.The active ingredient concentration of control banana freckle, leaf spot is 83.3-250mg/kg (extension rate is 1000-3000 times), begins spraying in their early stage.General spray medicine 3 times is asked every 1 medicine of 10d spray, spray medicine number of times depending on the state of an illness.To cucumber, banana safety, have no poisoning and occur.
Propineb (propineb): acrylic bisdithiocarbamic zinc
Figure BSA00000160454600021
White or micro-yellow powder decomposing more than 160 ℃, only have a small amount of residue in ℃ left and right and stay.Solvability (20 ℃):<1mg/L water;<0.1g/L carrene, hexane, propyl alcohol-2, toluene.K0w0.55 (estimated value) (20 ℃).Stable upon storage under dry cryogenic conditions, hydrolysis (22 ℃) DT50 (estimated value) 1 day (PH4), approximately 1 day (PH7),>2 days (PH9).Act on the synthetic of fungal cell wall and protein, can suppress infecting and sprouting of spore, can suppress mycelial growth simultaneously, cause its distortion, death.And this medicine contains and is easy to zinc element absorbed by crops, the quality that is conducive to promote plant growth and improves fruit.
Summary of the invention
The present invention be directed to the problems referred to above a bactericidal composition that contains pyraclostrobin and Propineb applied widely, that cost is low, effective is provided.
A further object of the invention is to provide the purposes of this bactericidal composition.
A kind of bactericidal composition, it contains pyraclostrobin and Propineb, and wherein the weight ratio of pyraclostrobin and Propineb is 1: 80~50: 9.
Described bactericidal composition, wherein the more excellent weight ratio of pyraclostrobin and Propineb is 1: 50~5: 1.
Described bactericidal composition, wherein to account for the weight fraction ratio of preparation be 10~81% to active ingredient.
Described bactericidal composition, pyraclostrobin and Propineb and auxiliary agent, carrier etc. are processed into any one formulation that allows on agricultural chemicals.
Described bactericidal composition is characterized in that the formulation that can be processed into is wetting powder, water dispersible granules, suspending agent etc.
The application of described bactericidal composition aspect the multiple diseases of control Cereal and fruit tree, melon, vegetables etc.
When said composition was made wetting powder, constituent content was:
Pyraclostrobin 1~50%
Propineb 9~80%
Dispersant 3~20%
Wetting agent 3~10%
Filler 10~70%
The concrete procedure of processing of this bactericidal composition wetting powder is: press above-mentioned formula with pyraclostrobin and Propineb and dispersant, wetting agent and filler mixing, uniform stirring in stirred tank, mixing after airslide disintegrating mill, namely can be made into the wetting powder of the present composition.
When said composition was made water dispersible granules, constituent content was:
Pyraclostrobin 1~50%
Propineb 9~80%
Dispersant 3~20%
Wetting agent 3~10%
Disintegrant 2~5%
Filler 10~70%
The concrete procedure of processing of this bactericidal composition water dispersible granules is: by above-mentioned formula, pyraclostrobin, Propineb and dispersant, wetting agent, disintegrant and filler are mixed, pulverize with micro jet, through mediating, then add and carry out granulation, drying, screening in the fluidized bed prilling dryer by sample analysis, make the water dispersible granules that contains the bactericidal composition of pyraclostrobin of the present invention.
When said composition was processed into suspending agent, constituent content was:
Pyraclostrobin 1~50%
Propineb 9~80%
Dispersant 5~20%
Antifreezing agent 0.5~3%
Thickener 0.1~2%
Defoamer 0.1~0.8%
Water surplus
The concrete production stage of this bactericidal composition suspending agent is for first mixing other auxiliary agents, mix through high speed shear, add the former medicine of pyraclostrobin and Propineb, abrading-ball is 2~3 hours in ball crusher, make a diameter all below 5mm, make the suspending agent preparation that contains the bactericidal composition of mebenil and tricyclazole of the present invention.
Described dispersant is selected from one or more in polycarboxylate, lignosulfonates, alkylphenol polyoxyethylene formaldehyde condensation products sulphate, alkyl benzene sulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, alkylphenol polyoxyethylene, aliphatic amine polyoxyethylene ether, polyoxyethylene carboxylate, fatty acid glyceride APEO.
Described wetting agent is selected from: lauryl sodium sulfate, calcium dodecyl benzene sulfonate, Nekal BX., one or more in wetting and penetrating agent F, alkylnaphthalene sulfonate, polyoxyethylene triphenylethylene phosphenylic acid salt, spaonin powder, silkworm excrement, soapberry powder.
Described disintegrant is selected from: one or more in bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, sodium bicarbonate.
Described filler is selected from: one or more in kaolin, diatomite, bentonite, attapulgite, white carbon, starch, precipitated calcium carbonate.
Described thickener is selected from: one or more in xanthans, CMC, hydroxyethylcellulose, methylcellulose, Magnesiumaluminumsilicate, polyvinyl alcohol.
Described antifreezing agent is selected from: one or more in ethylene glycol, propane diols, glycerine, diethylene glycol (DEG), triethylene glycol.
Described defoamer is selected from: silicone oil, silicone compound, C 10-20Saturated fat acid compounds, C 8-10One or more in aliphatic alcohols compound and polyoxyethylene glycerol ether.
The invention has the beneficial effects as follows:
1, the present invention's pyraclostrobin used is a kind of mitochondria electron transfer inhibitor, and Propineb is gloomy class protective fungicide of generation, and phase spray medicine must or start before disease occurs.Pyraclostrobin and Propineb mutually are mixed and can produce conflict, but Synergistic reduces dosage, reduces costs.
2, this composition scope of application increases, be applicable to the multiple diseases of Cereal and fruit tree, melon, vegetables etc., as rice blast, rice sheath blight disease, rice green smut, wheat scab, wheat powdery mildew, grape powdery mildew, ring rot of apple, alternaria leaf spot of apple, apple mildew, pear scab, sigatoka etc.
3, two kinds of composite bactericide double action mechanism, delay the drug-fast generation of germ.
4, the pathogen that produces resistance there is good preventive effect.
Specific embodiment: pyraclostrobin and Propineb composite
1 materials and methods
1.1 test material
1.1.1 reagent agent
The 95% former medicine of pyraclostrobin is produced by shake agriculture chemical industry Co., Ltd of Nanjing; The 89% former medicine of Propineb is produced by Limin Chemical Co., Ltd.;
1.1.2 the bacterium sample gathers
Yellow Pseudoperonospora cubensis was not executed the cucumber cultivation ground collection of pyraclostrobin and Propineb and similar medicament from Shandong.The area of base acrylic bactericide gathers.The fresh sick leaf that the gathers plastic sack of packing into is taken back the laboratory with the low temperature incubator, rinse with clear water, and in the triangular flask that the petiole insertion is filled with water, moisturizing 24h under 18~22 ℃ of conditions promotes fresh sporangial generation.Wash fresh sporangium with the distilled water flushing blade, 2 layers of filtered through gauze, then centrifugal 3 times of centrifuge 2500r/rain uses distilled water diluting, adjusts sporangia suspension concentration to 5~100,000/mL at microscopically, is used for biologicall test.
1.1.3 test plant
The cucumber variety Chang Chun Mi Ci of the high sense of plantation downy mildew in the greenhouse, when plant to be planted is grown to 7~8 leaves, the picking leaves sheet is for examination.
1.2 test method and Tests of Synergistic Actions
1.2.1 the liquid of single dose toxicity test preparation
Two kinds of former medicinal dimethyl formamides (DMF) are dissolution with solvents, are made into 10000 μ g/ml mother liquors, then with the Tween solution of 0.1% Tween solution, mother liquor are diluted to 5~6 concentration gradients.
Adopt leaf dish moisturizing method to carry out toxicity test.First the blade that gathers is prepared into the leaf dish that diameter is 1.5cm, random mixing, be placed in respectively the series concentration liquid that configures and soak 1h, 50 leaf dishes of each concentration, test is with the blank that is treated to of adding medicine not, after soaking end, leaf faces up and puts on the wetting blotting paper of identical liquor strength, liquid on the leaf dish is blotted, the sporangia suspension 10 μ l that prepare are inoculated in the leaf dish central, be placed under the condition of 12h alternation of light and darkness and cultivate, measure the onset area on the leaf dish after 7d, calculate EC 50
On the basis of preliminary experiment, respectively single dose pyraclostrobin and Propineb are carried out toxicity test, both EC in order to upper method 50Value is respectively 3.46mg/l and 34.12mg/l.
The percentage that accounts for the leaf disc area according to lesion area is divided sick level:
0 grade: scab
1 grade: lesion area accounts for 1%~20% of leaf disc area
2 grades: lesion area accounts for 21%~50% of leaf disc area
3 grades: lesion area accounts for more than 50% of leaf disc area
Use the Wadley method, estimate the synergistic effect of pharmacy mix according to coefficient of synergism (SR), namely SR<1.0 are antagonism, and 1.0≤SR≤1.5 are summation action, and SR>1.5 are synergistic effect.
EC 50Theoretical value=(a+b)/((a/EC (A)+b/EC (B))
SR=EC50 theoretical value/EC50 measured value
In formula: a, b are respectively the percentage composition of pyraclostrobin and Propineb in mixture;
EC (A), EC (B) is respectively the EC of A and B 50Value.
Data see Table 1 different proportioning pyraclostrobin Propineb mixtures to virulence and the synergistic effect of bacterium of downy mildew of cucumber
Combination arranges 1.2.2 be mixed
60% pyraclostrobin Propineb mass ratio is respectively 6%+54%, 7.5%+52.5%, 10%+50%, 15%+45% and 30%+30% totally 5 combinations that are mixed.
1.2.3 mixture toxicity test
Carry out the toxicity test of mixture according to mixed ratio with single dose toxicity test method.
EC that each that will measure according to the abundant method of Sun Yun processed 50Value is converted into actual mixed toxicity index (ATI); According to the proportioning of mixture, obtain theoretical mixed toxicity index (TTI), calculate the co-toxicity coefficient (CTC) of mixture by following formula.
Single dose toxicity index=(standard medicament EC 50/ reagent agent EC 50) * 100
ATI=(standard medicament EC 50/ reagent agent (using with) EC 50) * 100
The content (%) of toxicity index * B in mixed of the content (%) of toxicity index * A of TII=A in mixed+B
CTC=(ATI/TTI)×100
If co-toxicity coefficient is large 120, showing has synergistic effect; If be starkly lower than 100 (below 80), be indicated as antagonism; Between 100~120, be indicated as summation action
Data see Table 1
Virulence and the synergistic effect of the different proportioning pyraclostrobin of table 1 Propineb mixture to bacterium of downy mildew of cucumber
Figure BSA00000160454600061
The composite co-toxicity to bacterium of downy mildew of cucumber of table 2 pyraclostrobin Propineb
2 results and analysis
According to bactericide joint toxicity measuring result, pyraclostrobin Propineb mass ratio be the co-toxicity coefficient of 1: 7 o'clock all greater than 100, show as synergistic effect, the synthesise various factor is thought 1: 7 and is best proportioning.
3 field trials are measured the control efficiency to cucumber downy mildew and downy mildew of garpe
3.1 field trial is measured the control efficiency to cucumber downy mildew
3.1.1 application method
Test is total to dispenser 3 times, check plot spray equivalent clear water.When making up a prescription, after first with a small amount of water, medicament fully being dissolved, then add suitable quantity of water to carry out complete stool spraying processing, even spraying.Adopt power driven sprayer during the spray medicine, operating pressure is 2.0~2.3kg/cm 2, shower nozzle aperture 1.2mm.The residential quarter spouting liquid is used by 675 liters/hectare, and liquid is sprayed application to crop leaf positive and negative two sides uniformly, does not drip as the best take wish.
3.1.2 investigation method
Random 4 samplings in every residential quarter are fixed 2 strain cucumber (grape) at every, amount to 8 strains, the whole blades of every strain investigation, and a situation arises for the statistics disease.
Every leaf accounts for the percentage classification of leaf area by scab, record total number of sheets, the sick number of sheets at different levels, calculates the blade incidence of disease, disease index, refers to comparison with the contrast disease, calculates relative control effect.
Severity Scaling standard (take blade as unit)
Sick level victimization state
0 grade: without scab;
1 grade: lesion area accounts for below 5% of whole leaf area;
3 grades: lesion area accounts for 6%~10% of whole leaf area;
5 grades: lesion area accounts for 11%~25% of whole leaf area;
7 grades: lesion area accounts for 26%~50% of whole leaf area;
9 grades: lesion area accounts for more than 50% of whole leaf area;
3.1.3 control time and number of times
Test is investigated 4 times altogether, respectively investigates 1 time in 7 days after 7 days, the 3rd time medicine after 7 days, the 2nd time medicine before medicine, after the 1st medicine.
3.1.4 drug effect computational methods
Sick leaf rate (%)=sick number of sheets/investigate total number of sheets * 100
Disease index=∑ (the sick numbers of sheets at different levels * relative level numerical value)/(investigating total number of sheets * 9) * 100
Control efficiency (%)=(1-(disease index after disease index before blank district medicine * treatment region medicine)/(after blank district medicine before disease index * treatment region medicine disease index)) * 100
3.1.5 poisoning investigation method
After dispenser, whether continuous 7d range estimation medicament has poisoning to crop.
3.1.6 result of the test and analysis
Each processes the effect of control cucumber downy mildew table 3
Interpretation of result:
As can be seen from Table 3, the effect of the 60% pyraclostrobin Propineb WP combination control cucumber downy mildew that is mixed of 1: 7 is very remarkable.The evidence complex preparation significantly is better than effect under the low concentration consumption in control efficiency under the consumption of high concentration.Complex preparation has significant synergistic effect, its quick result, and the lasting period is long, and the highest preventive effect of 7 days can reach 86% left and right after the 3rd medicine, and is relatively outstanding.And the highest preventive effect of single dose pyraclostrobin and Propineb is respectively 78% and 73% left and right, and is relatively relatively poor.Use safety under recommended dose.
3.2 field trial is measured the control efficiency to downy mildew of garpe
Each processes the effect of preventing and treating downy mildew of garpe table 4
Figure BSA00000160454600091
Interpretation of result:
As can be seen from Table 4, to prevent and treat the effect of downy mildew of garpe very remarkable in the combination that is mixed of 60% pyraclostrobin Propineb WP 1: 7.The effect of complex preparation is significantly higher than single dose, its instant effect, and the lasting period is also better, is the desirable medicament of preventing and treating downy mildew, and to grape safety.
In sum, the present invention contains the Bactericidal composite of pyraclostrobin and Propineb, cucumber downy mildew and Plasmopara viticola are had good control efficiency, and it is to the target crop safety.Complex preparation has not only improved preventive effect, and has enlarged fungicidal spectrum, and tool is of great significance in production practices.

Claims (3)

1. bactericidal composition that contains pyraclostrobin and Propineb, it is characterized in that: the active ingredient of this bactericidal composition is pyraclostrobin and Propineb binary built, all the other are auxiliary element, and wherein the mass ratio of active ingredient pyraclostrobin and Propineb is 1:7.
2. bactericidal composition according to claim 1, it is characterized in that: pyraclostrobin and the Propineb gross mass in preparation accounts for 10 ~ 81% of the whole quality of the pharmaceutical preparations.
3. bactericidal composition according to claim 1 and 2, it is characterized in that: the formulation of this bactericidal composition is suspending agent, wetting powder and water dispersible granules.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102302025A (en) * 2011-03-12 2012-01-04 陕西汤普森生物科技有限公司 Bactericidal composition containing pyraclostrobin and thiocarbamate
CN103404523A (en) * 2013-08-21 2013-11-27 陕西康禾立丰生物科技药业有限公司 Pesticide for preventing crop diseases such as powdery mildews, leaf spots and downy mildews and preparation thereof
CN104396979B (en) * 2014-10-24 2016-01-20 北京富力特农业科技有限责任公司 A kind of bactericide and uses thereof
CN105145602A (en) * 2015-09-25 2015-12-16 安徽美兰农业发展股份有限公司 Pyraclostrobin and propineb compound wettable powder and preparation method thereof
CN105394073A (en) * 2015-11-18 2016-03-16 无锡市稼宝药业有限公司 Bactericide for controlling apple Alternaria leaf spot

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1216897A (en) * 1996-04-26 1999-05-19 巴斯福股份公司 Fungicide mixtures
CN101400259A (en) * 2006-03-14 2009-04-01 巴斯夫欧洲公司 Method of inducing tolerance of plants against bacterioses
CN101437396A (en) * 2006-03-24 2009-05-20 巴斯夫欧洲公司 Method for combating phytopathogenic fungi

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1216897A (en) * 1996-04-26 1999-05-19 巴斯福股份公司 Fungicide mixtures
CN101400259A (en) * 2006-03-14 2009-04-01 巴斯夫欧洲公司 Method of inducing tolerance of plants against bacterioses
CN101437396A (en) * 2006-03-24 2009-05-20 巴斯夫欧洲公司 Method for combating phytopathogenic fungi

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