CN103975932B - A kind of bactericidal composition containing prothioconazoles and flumorph - Google Patents
A kind of bactericidal composition containing prothioconazoles and flumorph Download PDFInfo
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Abstract
The present invention relates to a kind of bactericidal composition containing prothioconazoles and flumorph, its active ingredient is prothioconazoles and flumorph binary built.Wherein the mass ratio of prothioconazoles and flumorph is 1 ~ 50: 50 ~ 1, the ratio of quality and the number of copies 1% ~ 80% of active ingredient prothioconazoles and flumorph in preparation, all the other are for allowing the auxiliary element using and accept in agricultural chemicals, the formulation of bactericidal composition of the present invention is missible oil, suspending agent, wetting powder, water dispersible granules, aqueous emulsion, microemulsion, granule, microcapsule formulations.Be mainly used in downy mildew, the phytophthora root rot on the powdery mildew of control cereal crop, banded sclerotial blight, fusarium wilt, leaf spot, rust, stalk break, net blotch, moire disease, gray mold and grape, potato and tomato.
Description
Technical field
The present invention relates to technical field of pesticide combination, particularly relate to a kind of bactericidal composition containing prothioconazoles and flumorph.
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 by name, 2,4-triazole-3-thioketones.Prothioconazoles toxicity is low, and without teratogenesis, mutagenesis type, to embryo's avirulence, to human and environment safety.Prothioconazoles is mainly used in control cereal crop as numerous diseases such as wheat, barley, rape, peanut, paddy rice and legume crops.Almost there is good control efficiency, as the powdery mildew, banded sclerotial blight, fusarium wilt, leaf spot, rust, stalk break, net blotch, moire disease etc. of Wheat and barley to all wheat class diseases.The soil-borne disease of oily Lay and peanut can also be prevented and treated, as stalk break, and main foliage disease, as gray mold, black spot, brown spot, balck shank, stalk break and rust etc.
Flumorph belongs to morpholine class disinfectant use in agriculture, and its chemical name is 4-[3-(3,4-Dimethoxyphenyl)-3-(4-fluorophenyl) acryloyl] morpholine, and flumorph is effective especially to Peronospora, epidemic disease mycin germ.To the Oomycete on grape, potato and tomato, especially Peronosporaceae and Phytophthora bacterium have fungicidal effectiveness.
Use the most effective means that chemical agent is controlling plant diseases.But long-term use single chemical bactericide continuously high dose, easily cause the problems such as the remaining of medicament, environmental pollution and resistance to pesticide resistance fungi development.Composite or the mixture of rational chemical bactericide has expansion fungicidal spectrum, improve control efficiency, extend the optimum period for applying fertilizer, reduce dosage, reduce poisoning, minimizing remains, delay Antifungal resistance and the actively feature such as drug-fast generation and development, bactericide compounded is one of the effective method the most solved the problem.Develop new product bactericide price constantly rises, and by contrast, exploitation is efficient with research, low toxicity, low-residual composite and mixture has small investment, the lead time is short and be subject to domestic and international attention, numerous and confused increasing develops dynamics.We are on the basis of lab screening and field trial, filter out prothioconazoles and flumorph carries out composite, have obvious synergistic effect.And about prothioconazoles and flumorph composite bactericidal composition and apply and there is no people at present and 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 downy mildew, the phytophthora root rot on the powdery mildew of control cereal crop, banded sclerotial blight, fusarium wilt, leaf spot, rust, stalk break, net blotch, moire disease, gray mold and grape, potato and tomato.
Technical scheme of the present invention is realized by following measures:
Contain a bactericidal composition for prothioconazoles and flumorph, active ingredient prothioconazoles and the flumorph two yuan of this bactericidal composition are composite, and all the other are auxiliary element.In wherein said bactericidal composition, the mass ratio of active ingredient prothioconazoles and flumorph is 1 ~ 50: 50 ~ 1, described bactericidal composition of the present invention is through toxicity test experimental verification, when the mass ratio of prothioconazoles and flumorph is 1 ~ 20: 20 ~ 1, 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 flumorph gross mass in the formulation accounts for 1% ~ 80% of the whole quality of the pharmaceutical preparations, and when wherein accounting for 10% ~ 60%, toxicity reaches good balance with residual, and 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: prothioconazoles 1 ~ 50 part; Flumorph 1 ~ 50 part; Conventional emulsifier 10 ~ 30 parts; Conventional solvents 20 ~ 50 parts; Conventional synergist 1 ~ 5 part.The concrete production stage of this cream preparation be first active ingredient prothioconazoles and flumorph are added dissolve completely in solvent after add emulsifier again, synergist becomes transparent and homogeneous oily liquids after stirring, filling, namely can be made into the cream preparation of the present composition.
Described bactericidal composition is suspending agent, and the mass fraction of component is: prothioconazoles 1 ~ 50 part; Flumorph 1 ~ 50 part; Dispersant 5 ~ 20 parts; Antifreezing agent 1 ~ 5 part; Thickener 0.1 ~ 2 part; Defoamer 0.1 ~ 0.8 part; Penetrating agent 0 ~ 10 part; PH value regulator 0.1 ~ 5 part; Water, surplus.The concrete production stage of this suspending agent is for first to mix other auxiliary agents, mix through high speed shear, add active ingredient prothioconazoles and flumorph, abrading-ball 2 ~ 3 hours in ball crusher, make a diameter all at below 5mm, namely can be made into the aqueous suspension formulations of the present composition.
Described bactericidal composition is wetting powder, and the mass fraction of component is: prothioconazoles 1 ~ 50 part; Flumorph 1 ~ 50 part; Dispersant 3 ~ 10 parts; Wetting agent 1 ~ 5 part; Filler, surplus.The concrete production stage of this wetting powder is: mixed with flumorph and dispersant, wetting agent and filler by active ingredient prothioconazoles by above-mentioned formula, uniform stirring in stirred tank, mixing after airslide disintegrating mill, namely 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: prothioconazoles 1 ~ 50 part; Flumorph 1 ~ 50 part; Dispersant 3 ~ 10 parts; Wetting agent 1 ~ 10 part; Disintegrant 1 ~ 5 part; Filler, surplus.The concrete production stage of this water dispersible granules is: mixed with flumorph and dispersant, wetting agent, disintegrant and filler by active ingredient prothioconazoles by above-mentioned formula, pulverize with micro jet, through mediating, then add in fluidized-bed granulation dryer and to carry out after granulation, drying, screening, through sample analysis, namely 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: prothioconazoles 1 ~ 50 part; Flumorph 1 ~ 50 part; Emulsifier 3 ~ 30 parts; Solvent 5 ~ 15 parts; Stabilizing agent 2 ~ 15 parts; Antifreezing agent 1 ~ 5 part; Defoamer 0.1 ~ 8 part; Thickener 0.2 ~ 2 part; Water, surplus.The concrete production stage of this aqueous emulsion is: first prothioconazoles and flumorph, solvent and emulsifier, cosolvent are added together, and makes to be dissolved into uniform oil phase; By part water, antifreeze, other the insecticides adjuvant such as antimicrobial mixes uniformly aqueous phase; While high-speed stirred, oil phase is added aqueous phase in a kettle., 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, namely can be made into the aqueous emulsion of the present composition.
Described bactericidal composition is microemulsion, and the mass fraction of component is: prothioconazoles 1 ~ 50 part; Flumorph 1 ~ 50 part; Emulsifier 10 ~ 30 parts, antifreezing agent 1 ~ 8 part, stabilizing agent 0.5 ~ 10 part, Conventional solvents cosolvent 20 ~ 50 parts.Prothioconazoles and flumorph cosolvent are dissolved completely, then add other compositions such as emulsifier, antifreezing agent stabilizing agent, Homogeneous phase mixing, finally adds water, can be made into microemulsion after fully stirring.
Described bactericidal composition is granule, and the mass fraction of component is: prothioconazoles 1 ~ 50 part; Flumorph 1 ~ 50 part; Wetting dispersing agent 1 ~ 10 part; Thickener 0.1 ~ 5 part; Defoamer 0.1 ~ 5 part; Castor oil, surplus is supplied.Each components such as active ingredient prothioconazoles and flumorph, dispersant, stabilizing agent, defoamer and solvent are mixed in the ratio of filling a prescription, after putting into the grinding of sand milling still, sends into mixing in mixer for well-distribution and get product.
Described bactericidal composition is microcapsule formulations, and the mass fraction of component is: prothioconazoles 1 ~ 50 part; Flumorph 1 ~ 50 part; 5 ~ 20 parts, urea; 5 ~ 20 parts, formaldehyde; Emulsifying dispersant 5 ~ 20 parts; Antifreezing agent 1 ~ 5 part; Thickener 0.1 ~ 2 part; Defoamer 0.1 ~ 0.8 part; Water, surplus.Urea and formaldehyde (amount of substance ratio is about l:1.5 ~ 2.0) is added in the there-necked flask that agitating device is housed, regulate the pH value of solution to about 8 ~ 9 with sodium hydroxide solution, then be warming up to 70 ~ 80 DEG C, be obtained by reacting stable urea resin prepolymer.Get a certain amount of prothioconazoles and flumorph is dissolved in cyclohexane, and add emulsifying dispersant in the solution, with vigorous stirring, the O/W type stable emulsion that to be made into the aqueous solution containing emulsifying dispersant be aqueous phase.Above-mentioned urea resin prepolymer is added in emulsion, adjust ph, polymerization reaction take place under acid catalysed conditions, oil phase substance is wrapped, form microcapsule granule.Slow intensification, solidification, temperature controls at 40 ~ 50 DEG C, hardening time 1h.Select to add appropriate auxiliary agent, stable microcapsules.
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 one in polyoxyethylene aliphatic alcohol ether or more than one any mixtures than composition.
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 of composition.
It is LG-3, GY-D1252, GY-D1256, SNWGF-01 that described dispersant is selected from polycarboxylate code name, lignosulfonates code name is 201107,201108, 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, 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, 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, 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, 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 composite bactericide that the present invention is active ingredient with prothioconazoles and flumorph has obvious synergistic effect, delay the drug-fast generation in key, and reduce into product cost and use cost, be mainly used in downy mildew, phytophthora root rot on the powdery mildew of control cereal crop, banded sclerotial blight, fusarium wilt, leaf spot, rust, stalk break, net blotch, moire disease, gray mold and grape, potato and tomato.
Embodiment
For making technical scheme of the present invention, object and advantage are clearly understood, the following specific embodiment of the present invention is described, but the present invention is not limited to these examples.The mode that effect experimental of the present invention adopts indoor biometrics and field trial to combine, if no special instructions, the ratio below mentioned is all ratio of quality and the number of copies.
Embodiment: prothioconazoles and flumorph different ratio co-toxicity are tested.
1.1 reagent agent
The former medicine of 96% flumorph, 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 from the wheat powdery mildew incidence of leaf that Fengyang County is taken back, PDA inclined-plane is cultivated in 4 DEG C of refrigerators and preserves.
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, appropriate two former medicines are made into several different ratio by the result according to preliminary experiment, then it is stand-by with acetone, each process to be diluted to several concentration gradients respectively.
By susceptible wheat cultivation in pot for growing seedlings, be placed in greenhouse and cultivate, 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 adopt plants method 20 DEG C, cultivate under the condition of 12h alternation of light and darkness, every 30 d turn culture 1 time.With the conidium on sterile water wash-out incidence of leaf during inoculation, being mixed with spore concentration is l × 10
6the suspension of individual/mL.
1.3.3 strains tested sensitivity testing
Leaf dish moisturizing method is adopted to carry out toxicity test.First the blade of collection is prepared into the leaf dish that diameter is 1.5cm, random mixing, be placed in the series concentration liquid configured respectively and soak lh, each concentration 50 leaf dishes, test with the process of not adding medicine as blank, after immersion terminates, leaf faces up and puts on the blotting paper that identical liquor strength is wetting, liquid on leaf dish is blotted, the spore suspension l0L prepared is inoculated in leaf dish central authorities, after room temperature places 5 min, is placed in 20 DEG C, cultivates under the condition of 1 2h alternation of light and darkness, measure the onset area on leaf dish after 10d, calculate EC
50.
The percentage accounting for leaf disc area according to lesion area divides disease level
0 grade: anosis;
1 grade: sorus area accounts for less than 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 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 contrast lethality <5%, does not correct, contrast lethality, between 5%-20%, corrects by formula 2, and contrast lethality >20%, test need be reformed.
Be independent variable x with the logarithm value of drug concentration (mg/L), with the probability value of corrected mortality for dependent variable y, set up virulence regression equation formula respectively, adopt DPS software to calculate the EC of single dose and each proportioning mixture
50co-toxicity coefficient (CTC) is calculated according to the abundant method of Sun Yun.Co-toxicity coefficient CTC, computing formula is as follows: (take prothioconazoles as standard agent, its toxicity index is 100):
The EC of toxicity index (the TI)=prothioconazoles of flumorph
50the EC of/flumorph
50× 100
The EC of true toxicity index (the ATI)=prothioconazoles of M
50the EC of/M
50× 100
TI × P flumorph of TI × P prothioconazoles+flumorph of theoretical toxicity index (the TTI)=prothioconazoles of M
TTI × 100 of the ATI/M of co-toxicity coefficient (the CTC)=M of M
In formula:
M is the mixture of prothioconazoles and flumorph different ratio
P prothioconazoles is the ratio of prothioconazoles shared by mixture
P flumorph is the ratio of flumorph shared by mixture.
2.1 toxicity test results
Table 1 flumorph and prothioconazoles are to the toxicity test of wheat powdery mildew
As can be seen from the table, the result of the test of different proportion proportioning shows, dilute respectively in active ingredient ratio and all show stronger synergistic effect, wherein with prothioconazoles and flumorph for the good suggestion of synergistic effect when 1:20 ~ 20:1 carries out further field control effectiveness test to suitable proportion about 1:10 ~ 10:1 mixture preparation, 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 is in great Tong Qiao village, capital town, Fengyang County, and be wheat for studying thing, kind is short morning 781, broadcasts sowing, and growing way is better, and test establishes every mu to establish contrast totally 10 process.Often process repetition 4 times, random district group arranges, plot area 30 square metres.
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 diagonal 5 sampling, investigates 20 strains at often, before blooming, 2 leaves are got in every strain from upper end, sword-like leave 2 leaf is got in the every strain of Post flowering, 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 less than 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 more than 50% of one-piece blade area.
3.1.3 drug effect computational methods
Sick leaf rate (%)=sick number of sheets/investigate the total number of sheets × 100
Disease index=∑ (the sick number of sheets × relative level numerical value at different levels)/(investigating the total number of sheets × 9) × 100
Control efficiency (%)=(before 1-(blank district medicine after disease index × treatment region medicine disease index)/(after blank district medicine before disease index × treatment region medicine disease index)) × 100.
3.1.4 poisoning investigation method
Whether after dispenser, continuous 14d estimates medicament has poisoning to crop.
3.1.5 result of the test and analysis
The effect of each process control wheat powdery mildew.Table 2
Prothioconazoles flumorph controls successful higher than prothioconazoles and flumorph single dose with 1:3 ratio composite bactericide for wheat powdery mildew as shown in Table 2, and 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 is used in combination to delay the drug-fast generation of germ.
3.2 field trials prevent and treat powdery mildew of cucumber
3.2.1 test method
Test site is in the Pingdu herbary of Shandong, and be cucumber for examination vegetables, growing way is better, and test establishes every mu to establish contrast totally 10 process.Often process repetition 4 times, random district group arranges, plot area 14 square metres.
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 diagonal 5 sampling, often some investigation 2 strains, totally 10 strains, investigation complete stool blade, and by leaf classification investigation occurring degree, calculating disease refers to and control efficiency.
Grade scale is as follows:
0 grade: anosis;
1 grade: lesion area accounts for less than 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 more than 50% of one-piece blade area.
3.2.3 drug effect computational methods
Sick leaf rate (%)=sick number of sheets/investigate the total number of sheets × 100
Disease index=∑ (the sick number of sheets × relative level numerical value at different levels)/(investigating the total number of sheets × 9) × 100
Control efficiency (%)=(before 1-(blank district medicine after disease index × treatment region medicine disease index)/(after blank district medicine before disease index × treatment region medicine disease index)) × 100.
3.2.4 poisoning investigation method
Whether after dispenser, continuous 14d estimates medicament has poisoning to crop.
3.2.5 result of the test and analysis
Each process prevents and treats the effect of powdery mildew of cucumber.(table 3)
The Mixed Pharmacy of different proportion as can be seen from Table 3, tests by different consumptions, and prothioconazoles flumorph is all better than contrast medicament with its right control of 1:3 ratio composite bactericide and 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 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 is used in combination to delay the drug-fast generation of germ.
In sum, the present invention contains the bactericidal composition of prothioconazoles and flumorph, have good control efficiency, and it is to Target crops safety to wheat powdery mildew, powdery mildew of cucumber.Complex preparation not only increases preventive effect, and expands fungicidal spectrum, widens the scope of application, reduces costs, and plays the double effect controlled of a medicine, alleviate manpower and materials to multiple diseases, improves productivity effect.So the invention of this complex preparation is of great significance social tool with popularization.
Claims (4)
1. one kind contains the bactericidal composition of prothioconazoles and flumorph, it is characterized in that: the active ingredient of this bactericidal composition is prothioconazoles and flumorph binary built, all the other are auxiliary element, wherein the mass ratio of active ingredient prothioconazoles and flumorph be 1: 3,1:2,1:1,2:1 or 3:1.
2. bactericidal composition according to claim 1, is characterized in that: prothioconazoles and flumorph gross weight in the formulation 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 flumorph gross weight in the formulation accounts for 5% ~ 60% of the whole quality of the pharmaceutical preparations.
4. the bactericidal composition according to claim 1 or 2 or 3, 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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| CN111567538A (en) * | 2020-06-01 | 2020-08-25 | 沈阳化工研究院（南通）化工科技发展有限公司 | Bactericide composition containing flumorph and prothioconazole |
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| CN105409976B (en) * | 2015-12-19 | 2022-02-11 | 青岛奥迪斯生物科技有限公司 | Sterilization composition containing metalaxyl-M and flumorph |
| CN105794797A (en) * | 2016-05-19 | 2016-07-27 | 东莞市瑞德丰生物科技有限公司 | Sterilization composition containing flumorph, prothioconazole and penthiopyrad |
| CN107535501A (en) * | 2017-09-26 | 2018-01-05 | 安徽国星生物化学有限公司 | A kind of bactericidal composition and its application containing prothioconazoles and dimethomorph |
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