CN103931624A - Fungicidal composition containing prothioconazole and cyazofamid - Google Patents
Fungicidal composition containing prothioconazole and cyazofamid Download PDFInfo
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- CN103931624A CN103931624A CN201410179390.3A CN201410179390A CN103931624A CN 103931624 A CN103931624 A CN 103931624A CN 201410179390 A CN201410179390 A CN 201410179390A CN 103931624 A CN103931624 A CN 103931624A
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- cyazofamid
- prothioconazoles
- fungicidal composition
- bactericidal composition
- prothioconazole
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Abstract
The invention relates to a fungicidal composition containing prothioconazole and cyazofamid. The fungicidal composition has the effective components of prothioconazole and the cyazofamid which are compounded, wherein the mass ratio of the prothioconazole to the cyazofamid is (1-50):(50-1); in the preparation, the mass part ratio of the prothioconazole to the cyazofamid is 1-80%, and the fungicidal composition also comprises the balance of auxiliary components which are allowable and acceptable in pesticide. The fungicidal composition can be prepared into missible oil, a suspending agent, wettable powder, water dispersible granules, an emulsion in water, a microemulsion, granules or microcapsules. The fungicidal composition is mainly used for controlling diseases such as powdery mildew, banded sclerotial blight, fusarium wilt, leaf spot disease, rust disease, sclerotinia sclerotiorum, downy mildew, epidemic disease and gray mold of crops such as wheat, barley, vegetables, peanut and rice.
Description
Technical field
The present invention relates to agriculture chemical compounding technical field, particularly relate to a kind of bactericidal composition that contains prothioconazoles and cyazofamid.
Background technology
Prothioconazoles is a kind of New-type wide-spectrum triazolinthione series bactericidal agent of Beyer Co., Ltd's development, its chemistry (RS)-2-(2-(1-chlorine cyclopropyl)-3-(2-chlorphenyl)-2-hydroxypropyl-1-2-dihydro-3-1,2,4-triazole-3-thioketones by name.Prothioconazoles toxicity is low, and without teratogenesis, mutagenesis type, to embryo's avirulence, to human and environment safety.Prothioconazoles is mainly used in preventing and treating cereal crop as numerous diseases such as wheat, barley, rape, peanut, paddy rice and legume crops.Almost all wheat class diseases are had to good control efficiency, as the powdery mildew of Wheat and barley, banded sclerotial blight, fusarium wilt, leaf spot, rust, stalk break, net blotch, moire disease etc.Can also prevent and treat the soil-borne disease of oily Lay and peanut, as stalk break, and main foliage disease, as gray mold, black spot, brown spot, balck shank, stalk break and rust etc.
Cyazofamid is the sulphaguanidine azoles fungicide that Japanese Ishihara Sangyo Kaisha, Ltd. produces; super protective fungicide; its chemistry chloro-2-cyano group-N of 4-by name; N-dimethyl-5-p-methylphenyl imidazoles-1-sulfonamide; cyazofamid is mitochondrial respiratory inhibitor; the all vegetative stages of oomycetes are all had to effect, and the germ that metalaxyl is produced to resistance or sensitivity all has activity.To downy mildew, epidemic disease, club root, damping off etc. have special efficacy, for the bacteria-treating on potato, grape, vegetables (cucumber, Chinese cabbage, tomato, onion, lettuce), lawn.To crop, the mankind, Environmental security.
Using chemical agent is the most effectively means of controlling plant diseases.But long-term use single chemical bactericide continuously high dose, easily cause the problems such as residual, the environmental pollution of medicament and resistance to pesticide resistance fungi development.Reasonably chemical bactericide is composite or be mixed and have 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 feature such as drug-fast generation and development, bactericide compounded is one of the effective method the most addressing 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 there is small investment, the lead time is short and be subject to domestic and international attention, the numerous and confused dynamics that develops that strengthens.We filter out prothioconazoles and cyazofamid and carry out compositely on the basis of lab screening and field trial, have obvious synergistic effect.And about the composite bactericidal composition of prothioconazoles and cyazofamid and application, there is no at present people reported.
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 in preventing and treating the diseases such as powdery mildew on the crops such as wheat, barley, vegetables, peanut, paddy rice, banded sclerotial blight, fusarium wilt, leaf spot, rust, stalk break, downy mildew, epidemic disease, gray mold.
Technical scheme of the present invention realizes by following measures:
A bactericidal composition that contains prothioconazoles and cyazofamid, two yuan of the active ingredient prothioconazoles of this bactericidal composition and cyazofamids are composite, and all the other are auxiliary element.In wherein said bactericidal composition, the mass ratio of active ingredient prothioconazoles and cyazofamid is 1～50: 50～1, described bactericidal composition of the present invention is through toxicity test experimental verification, the mass ratio of prothioconazoles and cyazofamid is 1～20: 20～1 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, wetting powder, water dispersible granules, aqueous emulsion, microemulsion, granule, microcapsule formulations.Wherein active ingredient prothioconazoles and the cyazofamid gross mass in preparation accounts for 1%～80% of the whole quality of the pharmaceutical preparations, while wherein accounting for 10%～60%, and 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: 1～50 part of prothioconazoles; 1～50 part of cyazofamid; 10～30 parts of conventional emulsifiers; 20～50 parts of conventional solvents; 1～5 part of conventional synergist.The concrete production stage of this cream preparation is for first adding active ingredient prothioconazoles and cyazofamid in solvent the oily liquids that becomes transparent and homogeneous after adding again emulsifier, synergist to stir after dissolving completely, 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: 1～50 part of prothioconazoles; 1～50 part of cyazofamid; 5～20 parts of dispersants; 1～5 part of antifreezing agent; 0.1～2 part of thickener; 0.1～0.8 part of defoamer; 0～10 part of penetrating agent; 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 speed shear, mix, add active ingredient prothioconazoles and cyazofamid, in ball crusher, abrading-ball is 2～3 hours, make a diameter all below 5mm, can be made into the suspending agent preparation of the present composition.
Described bactericidal composition is wetting powder, and the mass fraction of component is: 1～50 part of prothioconazoles; 1～50 part of cyazofamid; 3～10 parts of dispersants; 1～5 part of wetting agent; Filler, surplus.The concrete production stage of this wetting powder is: by above-mentioned formula, active ingredient prothioconazoles is mixed with cyazofamid and dispersant, wetting agent and filler, uniform stirring in stirred tank, after airslide disintegrating mill, mixing, can be made into the wetting powder of the present composition.
Described bactericidal composition is water dispersible granules, and the mass fraction of component is: 1～50 part of prothioconazoles; 1～50 part of cyazofamid; 3～10 parts of dispersants; 1～10 part of wetting agent; 1～5 part of disintegrant; Filler, surplus.The concrete production stage of this water dispersible granules is: by above-mentioned formula, active ingredient prothioconazoles is mixed with cyazofamid and dispersant, wetting agent, disintegrant and filler, with micro jet, pulverize, through mediating, then add and in fluidized bed prilling dryer, carry out granulation, dry, screening by 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: 1～50 part of prothioconazoles; 1～50 part of cyazofamid; 3～30 parts of emulsifier; 5～15 parts of solvents; 2～15 parts of stabilizing agents; 1～5 part of antifreezing agent; 0.1～8 part of defoamer; 0.2～2 part of thickener; Water, surplus.The concrete production stage of this aqueous emulsion is: first prothioconazoles and cyazofamid, solvent and emulsifier, cosolvent are added together, make to be dissolved into uniform oil phase; By part water, antifreeze, other the insecticides adjuvant such as antimicrobial mixes into uniform water; When reactor high speed stirs, oil phase is added to water, slowly add water until reach phase inversion point, open clipper and carry out high speed shear, and add remaining water, shear about half an hour, form the aqueous emulsion of oil-in-water type, can be made into the aqueous emulsion of the present composition.
Described bactericidal composition is microemulsion, and the mass fraction of component is: 1～50 part of prothioconazoles; 1～50 part of cyazofamid; 10～30 parts of emulsifier, 1～8 part of antifreezing agent, 0.5～10 part of stabilizing agent, 20～50 parts of conventional solvent cosolvents.Prothioconazoles and cyazofamid are dissolved completely with cosolvent, then add other compositions such as emulsifier, antifreezing agent stabilizing agent, evenly mix, finally add water, after fully stirring, can be made into microemulsion.
Described bactericidal composition is granule, and the mass fraction of component is: 1～50 part of prothioconazoles; 1～50 part of cyazofamid; 1～10 part of wetting dispersing agent; 0.1～5 part of thickener; 0.1～5 part of defoamer; Castor oil, surplus is supplied.Each components such as active ingredient prothioconazoles and cyazofamid, dispersant, stabilizing agent, defoamer and solvent are mixed in the ratio of formula, put into after the grinding of sand milling still, send in mixer for well-distribution and mix and get product.
Described bactericidal composition is microcapsule formulations, and the mass fraction of component is: 1～50 part of prothioconazoles; 1～50 part of cyazofamid; 5～20 parts, urea; 5～20 parts, formaldehyde; 5～20 parts of emulsifying dispersants; 1～5 part of antifreezing agent; 0.1～2 part of thickener; 0.1～0.8 part of defoamer; Water, surplus.In being housed, the there-necked flask of agitating device adds urea and formaldehyde (amount of substance ratio is about l:1.5～2.0), left and right, pH value to 8～9 with sodium hydroxide solution regulator solution, then be warming up to 70～80 ℃, reaction obtains stable urea resin prepolymer.Get a certain amount of prothioconazoles and cyazofamid and be dissolved in cyclohexane, and add emulsifying dispersant in solution, follow vigorous stirring, the O/W type stable emulsion that to be made into the aqueous solution of take containing emulsifying dispersant be water.Above-mentioned urea resin prepolymer is added in emulsion, regulate pH value, polymerization reaction take place under acid catalysis condition, is wrapped oil phase substance, forms microcapsule granule.Slowly heat up, solidify, temperature is controlled at 40～50 ℃, hardening time 1h.Selection adds appropriate auxiliary agent, the microcapsules that gets final product stablely.
Wherein above-described emulsifier is selected from calcium dodecyl benzene sulfonate and aliphatic acid polyethenoxy ether, alkylphenol polyoxyethylene sulfosuccinate, styrylphenol polyoxyethylene ether, polyoxyethylene nonylphenol ether, 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, turpentine-based vegetable oil code name is ND-45, solvent naphtha, dimethyl formamide, dimethyl sulfoxide (DMSO), one or more in water equal solvent are arbitrarily than the mixture forming.
It is LG-3, GY-D1252, GY-D1256, SNWGF-01 that described dispersant is selected from polycarboxylate code name, lignosulfonates code name is 201107,21108, alkylphenol polyoxyethylene methyl ether condensate sulfate, alkylsulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, aliphatic amine polyoxyethylene ether, 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 is phosphenylic acid salt dimly, spaonin powder, silkworm excrement, one or more in soapberry powder.
Described disintegrant is selected from bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, one or more in sodium bicarbonate.
Described thickener is selected from xanthans, carboxymethyl cellulose, carboxyethyl cellulose, methylcellulose, Magnesiumaluminumsilicate, in polyvinyl alcohol one or more.
Described stabilizing agent is selected from sodium citrate, a kind of 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, C
10-20saturated fat acid compounds, C
8-10one or more of fatty alcohol.
Described filler is selected from kaolin, diatomite, bentonite, attapulgite, white carbon, starch, one or more in precipitated calcium carbonate.
The present invention be take the composite bactericide that prothioconazoles and cyazofamid be active ingredient and is had obvious synergistic effect, delay the drug-fast generation in key, and reduced and become to have produced cost and use cost, be mainly used in preventing and treating the diseases such as powdery mildew on the crops such as wheat, barley, vegetables, peanut, paddy rice, banded sclerotial blight, fusarium wilt, leaf spot, rust, stalk break, downy mildew, epidemic disease, gray mold.
Embodiment
For making technical scheme of the present invention, object and advantage are clearer, and the present invention describes with following specific embodiment, but the present invention is not limited to these examples.The mode that effect experiment of the present invention adopts indoor biometrics and field trial to combine, if no special instructions, the ratio of below mentioning is all ratio of quality and the number of copies.
Embodiment: prothioconazoles proportioning co-toxicity experiments different from cyazofamid.
1.1 reagent agent
The former medicine of 96% cyazofamid, the former medicine of 95% prothioconazoles, above-mentioned former medicine provides by research and development department of extra large rel medicine company limited company.
1.2 test targets
Wheat powdery mildew germ, separation and purification gained the wheat powdery mildew incidence of leaf taking back from Fengyang County is cultivated and is preserved in 4 ℃ of refrigerators on PDA inclined-plane.
For examination medium
:
PDA medium
:potato 200g, glucose 20g, agar 20g, water 1000ml.
AEA medium
:dusty yeast 5g/L, glycerine 20mL/L, MgSO
40.25g/L, NaNO
36g/L, KCl 0.5g/L, KH
2pO
41.5g/L, agar powder 20g/L, deionized water 1L.
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 several different proportionings, then it is stand-by with acetone, each processing to be diluted to respectively to several concentration gradients.
Susceptible wheat cultivation, in pot for growing seedlings, is placed in to greenhouse and cultivates, and plant grows to three to four leaf after dates, gathers the blade of identical leaf age, for cultivation and the mensuration of wheat powdery mildew.
1.3.2 the cultivation of wheat powdery mildew and the preparation of spore suspension
Wheat powdery mildew adopts plants method to cultivate under 20 ℃, the condition of 12h alternation of light and darkness, and every 30 d turn culture 1 time.During inoculation, with the conidium on sterile water wash-out incidence of leaf, being mixed with spore concentration is l * 10
6the suspension of individual/mL.
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, mix at random, be placed in respectively the series concentration liquid configuring and soak lh, 50 leaf dishes of each concentration, test is with the blank that is treated to of adding medicine not, after immersion finishes, leaf faces up and puts on the wetting blotting paper of identical liquor strength, liquid on leaf dish is blotted, the spore suspension l0L preparing is inoculated in to leaf dish central authorities, and room temperature is placed after 5 min, is placed under 20 ℃, the condition of 1 2h alternation of light and darkness and cultivates, after 10d, measure the onset area on leaf dish, calculate EC
50.
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
By single dose toxicity test method, according to mixed ratio, carry out the toxicity test of mixture.
If contrast lethality <5%, does not proofread and correct, contrast lethality, between 5%-20%, is proofreaied and correct by formula 2, contrast lethality >20%, and test need be reformed.
The logarithm value of drug concentration (mg/L) of take is independent variable x, and the probability value of corrected mortality of take is dependent variable y, sets up respectively virulence regression equation formula, adopts DPS software to calculate the EC of single dose and each proportioning mixture
50according to the abundant method of Sun Yun, calculate co-toxicity coefficient (CTC).Co-toxicity coefficient CTC, computing formula is as follows: (take prothioconazoles as standard medicament, its toxicity index is 100):
The EC of the toxicity index of cyazofamid (TI)=prothioconazoles
50the EC of/cyazofamid
50* 100
The EC of true toxicity index (ATI)=prothioconazoles of M
50the EC of/M
50* 100
TI * P cyazofamid of TI * P prothioconazoles+cyazofamid of theoretical toxicity index (TTI)=prothioconazoles of M
TTI * 100 of the ATI/M of the co-toxicity coefficient of M (CTC)=M
In formula:
M is prothioconazoles and the mixture of the different proportionings of cyazofamid
P prothioconazoles is prothioconazoles shared ratio in mixture
P cyazofamid is cyazofamid shared ratio in mixture.
2.1 toxicity test results
Table 1 cyazofamid and the prothioconazoles toxicity test to wheat powdery mildew
As can be seen from the table, the result of the test of different proportion proportioning shows, in active ingredient ratio, dilute respectively and all show stronger synergistic effect, wherein take prothioconazoles and cyazofamid as 1:20～20:1 time the good suggestion of synergistic effect suitable proportion 1:10～10:1 left and right mixture preparation is carried out to further field control effectiveness test, to evaluate its field practical application effect.
3, field trial control wheat powdery mildew, the experimental result of cucumber downy mildew
3.1 field trial control wheat powdery mildews
3.1.1 test method
Test site, in great Tong Qiao village, capital town, Fengyang County, is wheat for studying thing, and kind is short morning 781, broadcasts sowing, and growing way is better, and test is established every mu and established contrast totally 10 processing.Every processing repeats 4 times, and random district group is arranged, 30 square metres of community areas.
3.1.2 control time and number of times
Before dispenser, after the 1st medicine after 7 days and the 2nd dispenser 7 days, 14 days, every community adopted 5 samplings of diagonal, every some investigation 20 strains, before blooming, 2 leaves are got in every strain from upper end, after blooming, sword-like leave 2 leaves are got in every strain, by leaf classification investigation occurring degree, calculate disease and refer to and control efficiency.
Grade scale is as follows:
0 grade: anosis;
1 grade: lesion area accounts for below 5% of one-piece blade area;
3 grades: lesion area accounts for the 6%-15% of one-piece blade area;
5 grades: lesion area accounts for the 16%-25% of one-piece blade area;
7 grades: lesion area accounts for the 26%-50% of one-piece blade area;
9 grades: lesion area accounts for the more than 50% of one-piece blade area.
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
Control efficiency (%)=(disease index after the front disease index * treatment region medicine of 1-(blank district medicine)/(the front disease index of disease index * treatment region medicine after blank district medicine)) * 100.
3.1.4 poisoning investigation method
After dispenser, whether 14d range estimation medicament has poisoning to crop continuously.
3.1.5 result of the test and analysis
Each processes the effect of control wheat powdery mildew.Table 2
As shown in Table 2 24% prothioconazoles cyazofamid composite bactericide for wheat powdery mildew control successful higher than prothioconazoles and cyazofamid single dose, bactericidal effect increases progressively with the increase of dosage.According to field range estimation, within the scope of test dose, plant growth is normal, and the poisoning phenomenon to wheat does not all appear in each treatment agent, illustrates that it is safe to wheat.Advise that the bactericide different from the mechanism of action mixes use to delay the drug-fast generation of germ.
3.2 field trial control cucumber downy mildews
3.2.1 test method
Test site, in the Pingdu herbary of Shandong, is cucumber for examination vegetables, and growing way is better, and test is established every mu and established contrast totally 10 processing.Every processing repeats 4 times, and random district group is arranged, 14 square metres of community areas.
3.2.2 control time and number of times
Before dispenser, after the 1st medicine after 7 days and the 2nd dispenser 7 days, 14 days, every community adopted 5 samplings of diagonal, every some investigation 2 strains, and totally 10 strains, investigation complete stool blade, by leaf classification investigation occurring degree, calculates disease and refers to and control efficiency.
Grade scale is as follows:
0 grade: anosis;
1 grade: lesion area accounts for below 5% of one-piece blade area;
3 grades: lesion area accounts for the 6%-15% of one-piece blade area;
5 grades: lesion area accounts for the 16%-25% of one-piece blade area;
7 grades: lesion area accounts for the 26%-50% of one-piece blade area;
9 grades: lesion area accounts for the more than 50% of one-piece blade area.
3.2.3 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
Control efficiency (%)=(disease index after the front disease index * treatment region medicine of 1-(blank district medicine)/(the front disease index of disease index * treatment region medicine after blank district medicine)) * 100.
3.2.4 poisoning investigation method
After dispenser, whether 14d range estimation medicament has poisoning to crop continuously.
3.2.5 result of the test and analysis
Each processes the effect of control cucumber downy mildew.(table 3)
The Mixed Pharmacy of different proportion, tests by different consumptions as can be seen from Table 3, and 24% its right control of prothioconazoles cyazofamid composite bactericide is all better than contrasting medicament and bactericidal effect and increases progressively with the increase of dosage.According to field range estimation, 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 safe to cucumber.Advise that the bactericide different from the mechanism of action mixes use to delay the drug-fast generation of germ.
In sum, the bactericidal composition that the present invention contains prothioconazoles and cyazofamid, has good control efficiency to wheat powdery mildew, cucumber downy mildew, and it is to target crop safety.Complex preparation has not only improved preventive effect, and has expanded fungicidal spectrum, widens the scope of application, reduces costs, and multiple diseases is played to the double effect of controlling of a medicine, alleviates manpower and materials, improves productivity effect.So the invention of this complex preparation is of great significance social tool with popularization.
Claims (4)
1. a bactericidal composition that contains prothioconazoles and cyazofamid, it is characterized in that: the active ingredient of this bactericidal composition is prothioconazoles and cyazofamid binary built, all the other are auxiliary element, and wherein the mass ratio of active ingredient prothioconazoles and cyazofamid is 1～50: 50～1.
2. bactericidal composition according to claim 1, is characterized in that: prothioconazoles and the cyazofamid gross weight in preparation accounts for 1%～80% of the whole quality of the pharmaceutical preparations.
3. bactericidal composition according to claim 2, is characterized in that: prothioconazoles and the cyazofamid gross weight in preparation accounts for 5%～60% 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 missible oil, suspending agent, wetting powder, water dispersible granules, aqueous emulsion, microemulsion, granule, microcapsule formulations
.
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|---|---|---|---|
| CN201410179390.3A CN103931624A (en) | 2014-04-30 | 2014-04-30 | Fungicidal composition containing prothioconazole and cyazofamid |
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|---|---|---|---|
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ID=51179708
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112998028A (en) * | 2021-03-04 | 2021-06-22 | 中国农业科学院植物保护研究所 | Metal-prothioconazole nano pesticide and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923001A (en) * | 2002-03-21 | 2007-03-07 | 巴斯福股份公司 | Fungicidal mixtures |
-
2014
- 2014-04-30 CN CN201410179390.3A patent/CN103931624A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923001A (en) * | 2002-03-21 | 2007-03-07 | 巴斯福股份公司 | Fungicidal mixtures |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112998028A (en) * | 2021-03-04 | 2021-06-22 | 中国农业科学院植物保护研究所 | Metal-prothioconazole nano pesticide and preparation method and application thereof |
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Application publication date: 20140723 |