CN102308808A - Antibacterial composition containing cyflufenamid and triazole bactericides - Google Patents

Antibacterial composition containing cyflufenamid and triazole bactericides Download PDF

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CN102308808A
CN102308808A CN201110304829A CN201110304829A CN102308808A CN 102308808 A CN102308808 A CN 102308808A CN 201110304829 A CN201110304829 A CN 201110304829A CN 201110304829 A CN201110304829 A CN 201110304829A CN 102308808 A CN102308808 A CN 102308808A
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cyflufenamid
bactericidal composition
preparation
composition preparation
bactericidal
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杜秀斌
葛尧伦
杨波涛
韩先正
葛大鹏
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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 preparation of an antibacterial composition, which belongs to the pesticide compounding field. Affective ingredients of the antibacterial composition are prepared through mixing two components of cyflufenamid and several triazole bactericides, wherein the weight ratio of cyflufenamid to the triazole bactericides is 90:1-1:90, and preferably 60:3-2:70; the total weight percentage of the active ingredients in the antibacterial composition is 1-90%, and preferably 8-75%, the rest is pesticide allowable and acceptable auxiliary components. A wettable pulvis, a suspending agent, a soluble liquid formulation, an emulsion in water, a water dispersed granule, and a particulate agent can be prepared from the antibacterial composition with known methods. The antibacterial composition is mainly used for controlling fungal diseases of crops of grains, cotton, oil, fruits, vegetables and flowers.

Description

A kind of bactericidal composition that contains cyflufenamid and triazole bactericidal agent
Technical field
The present invention relates to the agriculture chemical compounding technical field, be specifically related to a kind of with one of any in cyflufenamid and part triazole class compounds prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Cyproconazole, the Difenoconazole be two yuan of composite bactericidal compositions of active ingredient.
Background technology
Cyflufenamid is the bactericide with novel precursor structure of Japanese Cao Da company exploitation, and its chemical structural formula is following:
Figure BDA0000097461350000011
It has good effect and characteristic to powdery mildew, the peach grey scab bacterium of various vegetables and wheat class, simultaneously triazole, imidazoles, methoxy acrylate class resistance bacterium and sensitive bacteria is had same isoreactivity.Cyflufenamid is extremely low to people and animals' toxicity, do not exist follow-on influence, teratogenesis, mutagenicity test all is negative, on producing also not to the stimulation and the allergy of eye, skin.In addition, this agent can not influence environment and beneficial organism yet, and is minimum to honeybee and silkworm influence yet.
Prothioconazole The mechanism of action is the inhibition of fungal sterol precursors - lanosterol or 24 - methylene-dihydro-14 Mi hair drunk demethylation the role that the demethylation inhibitor (DMIS).Have good systemic activity, excellent protection, treat and root out activity, the lasting period is long.Crop is had good safety, and preventing disease theraping effect is good, and production-increasing function is obvious, compares with the triazole type biocide agent, and prothioconazoles has the more bactericidal activity of wide spectrum.Be mainly used in control cereal crop such as numerous diseases such as wheat, barley, rape, peanut, paddy rice and legume crop.Almost all wheat class diseases all there is good control efficiency, like 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, like stalk break, and main foliage disease, like gray mold, black spot, brown spot, balck shank, stalk break and rust etc.
Simeconazoles is the Japan three siliceous triazole bactericidal agent of company's exploitation altogether; Be a kind of ergosterol class synthetic inhibitor, but the mechanism of action is comparatively unique, this medicament has remarkable root absorption; In making object on divide a word with a hyphen at the end of a line; So have dividing a word with a hyphen at the end of a line property of infiltration and bactericidal effect in the good crop, very wide fungicidal spectrum is arranged, it all has very high antibacterial activity and can prevent and treat numerous diseases simultaneously ascomycetes, basidiomycetes and numerous fungi imperfect.Triazole type agricultural chemicals in the past has inhibitory action to the growth of paddy rice usually, but simeconazoles especially has excellent control efficiency to rice diseases such as rice sheath blight disease, false smut, and does not have the poisoning generation.
Tetraconazole is the environment-friendly novel triazole type agricultural chemicals of a kind of low toxicity, efficient, applied range, and absorption in it has well can be rapidly by plant absorbing and in the inside plants conduction, and drug effect is remarkable, and is safe in utilization.Can prevent and treat Erysiphe, Puccinia, Rhynchosporium spp, nuclear cavity Pseudomonas and the microbial disease of Septoria such as wheat powdery mildew, loose smut of wheat, wheat rust, the bunt of wheat, wheat grain husk blessing disease, barley leaf blotch, loose smut of barley, barley banded sclerotial blight, maize head smut, head smut of sorghum, melon and fruit powdery mildew, sigatoka, alternaria leaf spot of apple, pear scab and grape powdery mildew etc.Suitable cereal crop such as wheat, barley, oat, rye etc., fruit tree such as banana, grape, pears, apple etc., vegetables such as melon, beet, ornamental plants etc.
The triazole bactericidal agent that Tebuconazole is a kind of efficient, wide spectrum, interior absorption is strong has protection, treats, roots out three big functions, and fungicidal spectrum is wide, the lasting period is long.These article are used to prevent and treat sclerotinia rot of colza, and not only preventive effect is good, and have resistant to lodging, characteristics such as production-increasing function is obvious.Can prevent and treat multiple rust, powdery mildew, net blotch, root rot, the head blight of cereal crop effectively, smut and kind pass diseases such as zonate spot.
Cyproconazole is a sterol demethylation inhibitor, has prevention and therapeutic action.All effective to the Erysiphales on cereal crop, coffee, beet, fruit tree and the grape, Uredinales, the mould genus of genus spore, Rhynchosporium spp, Septoria, Venturia bacterium.Use with other bactericide, can fine cereal eye spot disease, leaf spot and the net blotch of preventing and treating.
Difenoconazole has protection, treatment and systemic activity; To Ascomycetes, Basidiomycetes with comprise that half of Alternaria, Ascochyta, the mould genus of tail spore, Colletotrichum, ball Cuo Pseudomonas, Phoma, Ramularia, Septoria, Venturia know sickly, Erysiphaceae, Uredinales and some are planted and are passed pathogen lasting protection and therapeutic action are arranged.Also fine to bitter rot or anthracnose of grape, white rot effect.
Triazole bactericidal agent through using for a long time, has produced very big pesticide resistance, and in used in daily field, dosage strengthened, and problems such as lasting period shortening are more remarkable, are unfavorable for very much the sustainable development of environment.But triazole bactericidal agent, interior absorption is better, and treatment and protective effect are obvious, at pesticide field, see that from the mode of action and cost cost performance is higher, and the bigger market space is arranged.I research staff of company attempts with the new type bactericide of different effects mechanism composite with it, to improve its preventive effect, reduces its agricultural cost; Through test of indoor virulence repeatedly and field experiment, in the screening of indoor biometrics prescription, chance on, composite new type bactericide cyflufenamid and the above part triazole bactericidal agent; Synergistic effect is obvious; Can obviously improve its preventive effect, enlarge fungicidal spectrum, improve germicidal efficiency.And, do not see relevant report at present at home and abroad as yet about the research in new type bactericide cyflufenamid and the composite field of triazole class compounds.
Summary of the invention
I research staff of company is devoted for years in the research in the composite field of agriculture chemicals fungicide, through a large amount of test recipe screenings, has proposed a kind of new and effective bactericidal composition, the problem that present triazole bactericidal agent resistance in practical application is big to solve, the lasting period is short.Bactericidal composition of the present invention be with one of any in new type bactericide cyflufenamid and part triazole class compounds prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Cyproconazole, the Difenoconazole be that two yuan of carrying out of active ingredient are mixed, other are relevant auxiliary agent of agricultural chemicals and complementary component.Can be used for preventing and treating numerous diseases such as cereal crop such as wheat, barley, rape, peanut, paddy rice and legume crop, can obviously improve actual preventive effect, delay the drug-fast generation of germ, reduce drug cost.
The present invention for a kind of with one of any in new type bactericide cyflufenamid and part triazole bactericidal agent prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Cyproconazole, the Difenoconazole be that active ingredient is carried out two yuan of bactericidal composition preparations that are mixed; In the bactericidal composition wherein of the present invention in active ingredient new type bactericide cyflufenamid and several kinds of triazole bactericidal agent prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Cyproconazole, the Difenoconazole one of any percentage by weight be 90: 1~1: 90; At some targetedly on the basis of test recipe screening test; Can percentage by weight one of any in active ingredient new type bactericide cyflufenamid and part triazole bactericidal agent prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Cyproconazole, the Difenoconazole be preferably 60: 3~2: 70; Synergistic effect is more obvious under this proportioning, but be not limited in this optimum ratio synergistic effect arranged.
The formulations of pesticide that pesticide sterilizing composite of the present invention uses the preparation method in pesticidal preparations field to be prepared into are wetting powder, suspending agent, soluble liquid, aqueous emulsion and water dispersible granules, granule; The gross mass of two kinds of active ingredients accounts for 1%~90% of total formulation gross mass in the preparation; Can further be preferably 8%~75%, all the other prepare complementary component for relevant auxiliary agent and formulation in the agricultural chemicals.
Pesticide sterilizing composite of the present invention to grain, cotton, oil, really, a large amount of fungal diseases of vegetables, flowers all have favorable effect, especially numerous Pseudomonas such as the Erysiphales on the crops such as cereal crop such as wheat, barley, rape, peanut, paddy rice and beans, Uredinales, the mould genus of genus spore, Rhynchosporium spp, Septoria, Venturia bacterium are had excellent preventive effect.For example prevent and treat powdery mildew of wheat and barley; Sclerotinia rot of colza; Cotton disease; Sweet potato black rot; Cucurbits powdery mildew, anthracnose, gray mold; The Kidney bean gray mold; Powdery mildew of pea, brown spot; Floral crops diseases, downy mildew of garpe, wheat rust, melon anthracnose and downy mildew etc. for making effect disease of the present invention clearer, are enumerated above typical disease, have only these but do not represent, and are all good to the fungal disease preventive effect.Wherein the composite rice field that can be used for of cyflufenamid and simeconazoles prevents and treats rice diseases such as rice sheath blight disease, false smut, and effect is excellent.
In addition, bactericidal composition of the present invention is compared similar bactericidal agent also has a lot of other obvious advantages, and the first, it is more lasting to compare the single-dose effect, and quick-acting also has raising; The second, delayed the drug-fast generation of crop greatly, reduced the access times repeatedly of agricultural chemicals, reduced the agricultural chemicals usage amount, reduced agricultural cost; The 3rd, this bactericidal composition drug effect after date decomposes than being easier to, and the residual quantity of medicine is lower, and is friendly more to environment; At last in the practical application of this bactericidal composition, crops are had general fresh-keeping, production-increasing function, the increasing both production and income of agricultural region is significant.
Embodiment:
In order to make the object of the invention, technical scheme and advantage clearer, the present invention describes with following specific embodiment, but the present invention only limits to these examples absolutely not.The method that the present invention adopts indoor bioassay and field trial to combine.If no special instructions, the ratio of below mentioning (comprising percentage) all is a mass ratio.Should be pointed out that all any modifications of within spirit of the present invention and principle, being made, be equal to replacement and improvement etc., all should be included within protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with accompanying claims.
Wherein prepare required necessary basis component about the formulations of pesticide and the easy manufacture implementation method following:
Cyflufenamid is represented with active principle A in following implementer's case, and active principle B represents in triazole bactericidal agent compound prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Cyproconazole, the Difenoconazole one of any.
One of technical scheme of the present invention, described bactericidal composition are wetting powder, and the percentage by weight of component is:
Figure BDA0000097461350000041
The concrete procedure of processing of this bactericidal composition wetting powder is: press above-mentioned prescription with active principle A and active principle B and dispersant, wetting agent and filler mixing; In stirred tank, evenly stir; Behind airslide disintegrating mill, mixing, promptly can be made into the wetting powder of the present composition.
Two of technical scheme of the present invention, described bactericidal composition are suspending agent, and the percentage by weight of component is:
Figure BDA0000097461350000042
The concrete production stage of this suspending agent is earlier other auxiliary agents to be mixed; Mix through high speed shear, add active principle A and active principle B, abrading-ball is 2~3 hours in ball crusher; Make a diameter all below 5mm, make the suspending agent preparation of bactericidal composition of the present invention.
Three of technical scheme of the present invention, described bactericidal composition are aqueous emulsion, and the percentage by weight of component is:
Figure BDA0000097461350000051
The concrete production stage of this aqueous emulsion is: at first former medicine active principle A is added with active principle B, solvent and emulsifier, cosolvent and be in the same place, make and be dissolved into uniform oil phase; With part water, antifreeze, other insecticides adjuvant such as antimicrobial mixes into uniform aqueous phase; When the agitated reactor high speed stirs, oil phase is added water, slowly add water, open clipper and carry out high speed shear, and add remaining water, shear half an hour approximately, form the aqueous emulsion of oil-in-water type until reaching the phase inversion point.Promptly make the aqueous emulsion of bactericidal composition of the present invention.
Four of technical scheme of the present invention, described bactericidal composition are water dispersible granules, and the percentage by weight of component is:
Figure BDA0000097461350000052
The concrete procedure of processing of this bactericidal composition water dispersible granules is: by above-mentioned prescription active principle A, active principle B and dispersant, wetting agent, disintegrant and filler are mixed; Pulverize with micro jet; Through mediating; Add then and carry out granulation, drying, screening in the fluidized bed prilling dryer after sample analysis, promptly make the water dispersible granules of bactericidal composition of the present invention.
Described emulsifier is selected from any one or more mixtures formed with arbitrary proportion in calcium dodecyl benzene sulfonate and aliphatic acid polyethenoxy ether, APES sulfosuccinate, styryl phenol APEO, NPE, castor oil polyoxyethylene ether, aliphatic acid polyethenoxy base ester, the polyoxyethylene aliphatic alcohol ether.
Said solvent is any one or more mixed solvents formed with arbitrary proportion in xylol or biodiesel, toluene, diesel oil, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, turpentine oil, solvent naphtha, dimethyl formamide, dimethyl sulfoxide (DMSO), the water equal solvent.
Described dispersant is selected from one or more in polycarboxylate, lignosulfonates, APES formaldehyde condensation products sulphate, alkyl benzene sulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, APES, aliphatic amine polyoxyethylene ether, polyoxyethylene carboxylate, the fatty acid glyceride APEO.
Described wetting agent is selected from: lauryl sodium sulfate, calcium dodecyl benzene sulfonate, draw back in powder copper rosinate X, wetting and penetrating agent F, alkylnaphthalene sulfonate, polyoxyethylene triphenylethylene phosphenylic acid salt, spaonin powder, silkworm excrement, the soapberry powder one or more.
Described disintegrant is selected from: one or more in bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, the sodium bicarbonate.
Described thickener is selected from: one or more in xanthans, CMC, hydroxyethylcellulose, methylcellulose, Magnesiumaluminumsilicate, the polyvinyl alcohol.
Described stabilizing agent is selected from: a kind of in sodium citrate, the resorcinol.
Described antifreezing agent is selected from: one or more in ethylene glycol, propane diols, the glycerine.
Described antifoaming agent is selected from: silicone oil, silicone compound, C 10-20Saturated fat acid compounds, C 8-10In the aliphatic alcohols compound one or more.
Described filler is selected from: one or more in kaolin, diatomite, bentonite, attapulgite, white carbon, starch, the precipitated calcium carbonate.
Indoor virulence test and field experiment
The indoor virulence measuring:
Biologicall test instance 1:
(1) experimental subjects:
The wheat powdery mildew germ, separation and purification gained from the powdery mildew incidence of leaf of wheat paddock is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
Supply the 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, KCl0.5g/L, KH 2PO 41.5g/L, agar powder 20g/L, deionized water 1L.
(2) experimental pharmacy:
The former medicine of 95% cyflufenamid, Tso Tat Co., Ltd., Japan, the former medicine of 94% prothioconazoles, Beyer Co., Ltd.
Combination setting is mixed:
19% cyflufenamid prothioconazoles percentage composition was respectively 4: 15,6: 13,8: 11,10: 9,12: 7, i.e. 4%+15%, 6%+13%, 8%+11%, 10%+9%, 12%+7% totally 5 combinations that are mixed.
(3) test method:
Single agent is to the toxicity test of wheat powdery mildew germ:
Cyflufenamid and prothioconazoles dissolve with proper amount of acetone, are made into the mother liquor of 10000 μ g/ml, preserve in 4 ℃ of following low temperature, and be for use, is diluted to a series of concentration with sterile water before the test.
The wheat powdery mildew germ after cultivating in advance on the AEA medium, is inoculated in the bacterium dish of diameter 5mm respectively on the AEA flat board that contains the variable concentrations gradient, cultivates down in 25 ℃ of dark conditions.Every processing repetition 3 times.When control strain colony diameter length is above to 6.5cm, adopt " right-angled intersection method " to measure.According to the linear regression analysis between the logarithm value of the probit value of inhibiting rate and medicine series concentration, obtain the EC that two kinds of single agent suppress mycelial growths 50Value, correlation coefficient and virulence regression equation.
On the basis of preliminary experiment, respectively single agent cyflufenamid and prothioconazoles are carried out toxicity test, EC in order to last method 50Value is followed successively by 4.07mg/l and 6.39mg/l.
The mixture toxicity test:
Carry out the toxicity test of mixture according to mixed ratio with single agent toxicity test method.
EC that each that will measure according to the abundant method of Sun Yun handled 50Value is converted into the actual toxicity index (ATI) of using with; According to the proportioning of mixture, obtain theory and use toxicity index (TTI) with, calculate the co-toxicity coefficient (CTC) of mixture by following formula.
Single agent toxicity index=(standard medicament EC 50/ confession reagent agent EC 50) * 100
ATI=(standard medicament EC 50/ confession reagent agent (using with) EC 50) * 100
The content (%) of toxicity index * B in using with of content (the %)+B of toxicity index * A of TII=A in using with
CTC=(ATI/TTI)×100
If co-toxicity coefficient is greater than 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.
(4) result and analysis:
The composite co-toxicity test of table 1 cyflufenamid and prothioconazoles to the wheat powdery mildew germ
The pharmacy quality ratio Virulence regression equation Correlation coefficient (r) EC 50(mg/L)
Cyflufenamid (A) Y=3.1544X+3.0771 0.9743 4.07
Prothioconazoles (B) Y=3.2437X+2.3871 0.9662 6.39
A: B is 4: 15 Y=3.6102X+3.0386 0.9801 3.49
A: B is 6: 13 Y=3.5906X+3.2388 0.9655 3.09
A: B is 8: 11 Y=3.3015X+3.3223 0.9714 3.22
A: B is 10: 9 Y=3.4743X+3.2208 0.9578 3.25
A: B is 12: 7 Y=3.2258X+3.3396 0.9639 3.27
The composite co-toxicity test of table 2 cyflufenamid and prothioconazoles to the wheat powdery mildew germ
Test medicine Mass ratio The actual measurement poison refers to Theoretical poison refers to Co-toxicity coefficient Conclusion
Cyflufenamid (A) 1∶0 100.00 100.00 / /
Prothioconazoles (B) 0∶1 63.69 63.69 / /
A∶B 4∶15 116.50 71.34 163.31 Synergy
A∶B 6∶13 131.56 75.16 175.04 Synergy
A∶B 8∶11 126.31 78.98 159.92 Synergy
A∶B 10∶9 125.17 82.80 151.17 Synergy
A∶B 12∶7 124.42 86.62 143.63 Synergy
Measuring the result according to above indoor virulence test shows; Cyflufenamid and prothioconazoles all have synergistic effect preferably by the percentage composition of experiment; Wherein with cyflufenamid: prothioconazoles is that 6: 13 o'clock co-toxicity coefficient is the highest; Be 175.04, we can think that the percentage composition of cyflufenamid and prothioconazoles is that 6: 13 o'clock synergistic effects are best.So suggestion is carried out further field control effectiveness test to the mixture preparation of suitable proportion about 6: 13, to estimate its actual field effect.
Biologicall test instance 2: the composite Toxicity Determination of cyflufenamid and tetraconazole to the powdery mildew of cucumber germ.
The former medicine of 94% tetraconazole, Italian Sai Ge company.
The powdery mildew of cucumber germ, separation and purification gained from the powdery mildew of cucumber incidence of leaf of Shouguang, Shandong cucumber booth is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
Single agent cyflufenamid and tetraconazole are carried out toxicity test, EC 50Value is followed successively by 3.66 and 8.53mg/l.
Combination setting is mixed:
22% cyflufenamid tetraconazole percentage composition was respectively 4: 18,6: 16,8: 14,10: 12,12: 10, i.e. 4%+18%, 6%+16%, 8%+14%, 10%+12%, 12%+10% totally 5 combinations that are mixed.
Test method is with biologicall test embodiment 1
Experimental result and analysis:
The composite virulence experiment of table 3 cyflufenamid and tetraconazole to the powdery mildew of cucumber germ
The pharmacy quality ratio Virulence regression equation Correlation coefficient (r) EC 50(mg/L)
Cyflufenamid (A) Y=2.5418X+3.5677 0.9521 3.66
Tetraconazole (B) Y=2.4329X+2.7351 0.9639 8.53
A: B is 4: 18 Y=2.6007X+33982 0.9408 4.13
A: B is 6: 16 Y=2.5583X+3.6341 0.9755 3.42
A: B is 8: 14 Y=2.7101X+34667 0.9492 3.68
A: B is 10: 12 Y=2.6944X+3.5081 0.9613 3.58
A: B is 12: 10 Y=2.5002X+3.6325 0.9805 3.52
The composite co-toxicity test of table 4 cyflufenamid and tetraconazole to the powdery mildew of cucumber germ
Test medicine Mass ratio The actual measurement poison refers to Theoretical poison refers to Co-toxicity coefficient Conclusion
Cyflufenamid (A) 1∶0 100.00 100.00 / /
Tetraconazole (B) 0∶1 42.91 42.91 /
A∶B 4∶18 88.63 53.29 166.33 Synergy
A∶B 6∶16 107.05 58.48 183.06 Synergy
A∶B 8∶14 99.48 63.67 156.25 Synergy
A∶B 10∶12 102.28 68.86 148.54 Synergy
A∶B 12∶10 103.88 74.05 140.29 Synergy
Measuring the result according to above indoor virulence test shows; The used cyflufenamid and the percentage composition of tetraconazole all have synergistic effect in the experiment; Wherein the co-toxicity coefficient when the percentage composition of cyflufenamid and tetraconazole is 6: 16 is 183.06 to the maximum, thinks that promptly 6: 16 o'clock synergistic effects of percentage composition of cyflufenamid and tetraconazole are best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 6: 16 left and right sides scopes of suitable proportion, to estimate its actual field effect.
Biologicall test instance 3: the composite Toxicity Determination of cyflufenamid and simeconazoles to rice green smut.
The former medicine of 95% simeconazoles, Japan three is chemical company altogether.
The rice green smut germ, separation and purification gained from the rice pathogenesis paddy rice spike of rice of Hunan is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
Single agent cyflufenamid and simeconazoles are carried out toxicity test, EC 50Value is followed successively by 4.37mg/l and 6.03mg/l.
Combination setting is mixed:
The percentage composition of 18% cyflufenamid simeconazoles was respectively 3: 15,5: 13,7: 11,9: 9,11: 7, i.e. 3%+15%, 5%+13%, 7%+11%, 9%+9%, 11%+7% totally 5 combinations that are mixed.
Test method is similar with biologicall test embodiment 1
Result and analysis:
The composite co-toxicity of table 5 cyflufenamid and simeconazoles to the rice green smut germ
The pharmacy quality ratio Virulence regression equation Correlation coefficient (r) EC 50(mg/L)
Cyflufenamid (A) Y=2.8741X+3.1592 0.9502 4.37
Simeconazoles (B) Y=2.6435X+29372 0.9614 6.03
A: B is 3: 15 Y=2.5109X+3.5665 0.9783 3.72
A: B is 5: 13 Y=2.5543X+36804 0.9802 3.29
A: B is 7: 11 Y=2.7004X+3.5923 0.9596 3.32
A: B is 9: 9 Y=2.6912X+3.5348 0.9665 3.50
A: B is 11: 7 Y=2.7322X+3.5000 0.9711 3.54
The composite co-toxicity of table 6 cyflufenamid and simeconazoles to the rice green smut germ
Test medicine Mass ratio The actual measurement poison refers to Theoretical poison refers to Co-toxicity coefficient Conclusion
Cyflufenamid (A) 1∶0 100.00 100.00 / /
Simeconazoles (B) 0∶1 72.47 72.47 / /
A∶B 3∶15 117.38 77.06 152.33 Synergy
A∶B 5∶13 133.01 80.12 166.02 Synergy
A∶B 7∶11 131.58 83.18 158.19 Synergy
A∶B 9∶9 124.76 86.24 144.67 Synergy
A∶B 11∶7 123.45 89.29 138.25 Synergy
Mensuration result according to the test of bactericide co-toxicity; When cyflufenamid and simeconazoles percentage composition are above experiment ratio; Result of the test shows all has synergistic effect; And the co-toxicity coefficient when ratio is 5: 13 is 166.02 to the maximum, and we can think that the percentage composition of cyflufenamid and simeconazoles is at 5: 13 o'clock, and synergistic effect is best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 5: 13 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
Biologicall test instance 4: the composite Toxicity Determination of cyflufenamid and Cyproconazole to the grape powdery mildew germ.
The former medicine of 95% Cyproconazole, Fengdeng Pesticide Co., Ltd., Jiangsu.
The grape powdery mildew germ, separation and purification gained on the grape powdery mildew incidence of leaf in the vineyard of Qingdao, Shandong Province Pingdu City is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
Single agent cyflufenamid and Cyproconazole are carried out toxicity test, EC 50Value is followed successively by 3.59 and 7.38mg/l.
Combination setting is mixed:
19% cyflufenamid Cyproconazole percentage composition was respectively 4: 15,6: 13,8: 11,10: 9,12: 7, i.e. 4%+15%, 6%+13%, 8%+11%, 10%+9%, 12%+7% totally 5 combinations that are mixed.
Test method is with biologicall test embodiment 1
Experimental result and analysis:
The composite virulence experiment of table 7 cyflufenamid and Cyproconazole to the grape powdery mildew germ
The pharmacy quality ratio Virulence regression equation Correlation coefficient (r) EC 50(mg/L)
Cyflufenamid (A) Y=2.1007X+3.8339 0.9619 3.59
Cyproconazole (B) Y=2.3015X+3.0021 0.9507 7.38
A: B is 4: 15 Y=2.2254X+3.7021 0.9655 3.83
A: B is 6: 13 Y=2.1758X+3.9439 0.9726 3.06
A: B is 8: 11 Y=2.3361X+3.9045 0.9694 2.94
A: B is 10: 9 Y=2.1983X+3.9747 0.9688 2.93
A: B is 12: 7 Y=2.0966X+4.0154 0.9711 2.95
The composite co-toxicity test of table 8 cyflufenamid and Cyproconazole to the grape powdery mildew germ
Test medicine Mass ratio The actual measurement poison refers to Theoretical poison refers to Co-toxicity coefficient Conclusion
Cyflufenamid (A) 1∶0 100.00 100.00 / /
Cyproconazole (B) 0∶1 48.64 48.64 /
A∶B 4∶15 93.73 59.46 157.64 Synergy
A∶B 6∶13 117.41 64.86 181.02 Synergy
A∶B 8∶11 121.95 70.27 173.55 Synergy
A∶B 10∶9 122.66 75.67 162.09 Synergy
A∶B 12∶7 121.77 81.08 150.18 Synergy
Show according to above Toxicity Determination result of the test; The used cyflufenamid and the percentage composition of Cyproconazole all have synergistic effect in the experiment; Wherein the co-toxicity coefficient when the percentage composition of cyflufenamid and Cyproconazole is 6: 13 is 181.02 to the maximum, thinks that promptly 6: 13 o'clock synergistic effects of percentage composition of cyflufenamid and Cyproconazole are best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 6: 13 left and right sides scopes of suitable proportion, to estimate its actual field effect.
Biologicall test instance 5: the composite Toxicity Determination of cyflufenamid and Difenoconazole to the pear scab germ.
97% difenoconazole technical material, Zhejiang Heben Science & Technology Co., Ltd..
The pear scab germ, separation and purification gained on the scab incidence of leaf in the pear tree garden in Laiyang, Shandong is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
Single agent cyflufenamid and Difenoconazole are carried out toxicity test, EC 50Value is followed successively by 4.63 and 8.99mg/l.
Combination setting is mixed:
12% cyflufenamid Difenoconazole percentage composition was respectively 2: 10,4: 8,6: 6,8: 4,10: 2, i.e. 2%+10%, 4%+8%, 6%+6%, 8%+4%, 10%+2% totally 5 combinations that are mixed.
Test method is similar with biologicall test embodiment 1
Experimental result and analysis:
The composite co-toxicity experiment of table 9 cyflufenamid and Difenoconazole to the pear scab germ
The pharmacy quality ratio Virulence regression equation Correlation coefficient (r) EC 50(mg/L)
Cyflufenamid (A) Y=3.7536X+2.5016 0.9742 4.63
Difenoconazole (B) Y=3.6917X+1.4790 0.9635 8.99
A: B is 2: 10 Y=3.5574X+2.7165 0.9519 4.38
A: B is 4: 8 Y=3.8805X+2.8676 0.9816 3.54
A: B is 6: 6 Y=3.7116X+3.0485 0.9641 3.36
A: B is 8: 4 Y=3.9028X+2.9561 0.9577 3.34
A: B is 10: 2 Y=3.6049X+3.9214. 0.9809 3.27
The composite co-toxicity test of table 10 cyflufenamid and Difenoconazole to the pear scab germ
Test medicine Mass ratio The actual measurement poison refers to Theoretical poison refers to Co-toxicity coefficient Conclusion
Cyflufenamid (A) 1∶0 100.00 100.00 / /
Difenoconazole (B) 0∶1 51.50 51.50 /
A∶B 2∶10 105.61 59.58 177.24 Synergy
A∶B 4∶8 130.64 67.67 193.06 Synergy
A∶B 6∶6 137.98 75.75 182.15 Synergy
A∶B 8∶4 138.64 83.83 165.37 Synergy
A∶B 10∶2 141.63 91.92 154.09 Synergy
Show according to above Toxicity Determination result of the test; All has synergistic effect under the content per distribution ratio of used cyflufenamid and Difenoconazole in the experiment; Wherein the co-toxicity coefficient when the percentage composition of cyflufenamid and Difenoconazole is 4: 8 is 193.06 to the maximum, thinks that promptly the percentage composition of cyflufenamid and Difenoconazole is that 4: 8 o'clock synergistic effects are best.Suggestion is carried out further field control effectiveness test to 4: 8 interior mixture preparations of left and right sides scope of suitable proportion, to estimate its actual field effect.
Field trial 1: to the preventive effect of pear scab
(1) investigation method
Experimental field be located at 5 years living theatre, Laiyang, Shandong and carry out, 4 repetitions are established in every processing, every repetition 10 strains, and randomized arrangement, guard row is established in the centre.Every fixing investigation 4 strains, 10 at every strain investigation spring tip, 60 blades, 30 of young fruits of repeating.April 20, Mays 10 daily adopt knapsack sprayer to spray tree crown, and each sprays medicine once, and the soup consumption is 1201/667m 2
Come classification according to the pear scab grade scale, grade scale does
0 grade: blade does not have scab, young fruit does not have scab;
1 grade: blade 1~5 scab, young fruit have a small amount of scab;
2 grades: 6~15 scabs of blade, young fruit 1/3 fruit face have scab;
3 grades: 16 above scabs of blade, but blade is non-warping, young fruit 1/2 fruit face has scab;
4 grades: the leaf malformation distortion, full fruit has scab;
(2) control time and number of times
Test is investigated 3 times altogether, i.e. disease index investigation before the medicine, preventive effect investigation in 10 days behind the 1st medicine, 10 days and preventive effect investigation in 20 days behind 2 medicines.
(3) drug effect computational methods
Sick leaf rate (the %)=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 behind disease index before the blank district medicine * treatment region medicine)/(disease index before disease index behind the blank district medicine * treatment region medicine)) * 100
(4) poisoning investigation method
Whether continuous 7d range estimation medicament has poisoning to crop after the dispenser.
(5) experimental result and analysis
Table 11 is respectively organized the test medicine processing and is prevented and treated the test effect of pear scab
Interpretation of result:
Can know by table 11; The effect that 4: 8 the combination that is mixed of 12% cyflufenamid Difenoconazole prevents and treats pear scab is more remarkable; Behind the medicine 10 days for the first time, 10 days and 20 days preventive effects 89.97%, 91.46% and 92.23% the highest behind the medicine for the second time, 20 days preventive effects the highest are 84.18% behind the single agent 10% cyflufenamid EC medicine second time; 20 days preventive effect is up to 82.98% behind the 10% Difenoconazole WG medicine second time; The effect of complex preparation significantly is superior to two kinds of single agent, has not only significantly improved the effect for pear scab, and has further prolonged its lasting period.
Field trial 2: to the preventive effect of powdery mildew of cucumber
(1) investigation method
Experimental field be located at Shouguang, Shandong, publish the medium cucumber field of course of disease degree for experimental field, soil fertility is medium, and irrigation and drainage are convenient.Adopt the bilinear sampling method, 5 points are got in every sub-district, look into 5 caves at every, and 2 blades in the fixing middle part of every strain fix a point to check during investigation.
Come classification according to the powdery mildew of cucumber grade scale, write down total strain number, diseased plant number, degree of being in a bad way, calculate diseased plant rate, disease index and preventive effect.The powdery mildew of cucumber grade scale is:
0 grade: no 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.
Test is investigated 3 times altogether, i.e. disease index investigation before the medicine, preventive effect investigation in 10 days behind the 1st medicine, 10 days and preventive effect investigation in 20 days behind 2 medicines.
(2) control time and number of times
Test is investigated 3 times altogether, i.e. disease index investigation before the medicine, preventive effect investigation in 10 days behind the 1st medicine, 10 days and preventive effect investigation in 20 days behind 2 medicines.
(3) drug effect computational methods
Sick leaf rate (the %)=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 behind disease index before the blank district medicine * treatment region medicine)/(disease index before disease index behind the blank district medicine * treatment region medicine)) * 100
(4) poisoning investigation method
Whether continuous 7d range estimation medicament has poisoning to crop after the dispenser.
(5) experimental result and analysis
Table 12 is respectively organized the test medicine processing and is prevented and treated the test effect of powdery mildew of cucumber
Figure BDA0000097461350000141
Figure BDA0000097461350000151
Interpretation of result:
Can know that by table 12 effect that 6: 16 the combination that is mixed of 22% cyflufenamid tetraconazole prevents and treats powdery mildew of cucumber is very remarkable.Under same 10 milliliters every mu consumption, the effect of complex preparation significantly is superior to two kinds of single agent, and its quick-acting and lasting effect are all relatively good, and is the most outstanding with lasting effect especially.Complex preparation significantly is superior to the effect under the low concentration consumption in control efficiency under the consumption of high concentration.20 days preventive effects reach 95.57% after 10 days best control efficiency behind the 1st, 2 medicine reaches 92.54% and 94.86%, the 2 medicine respectively.And single agent 10% cyflufenamid EC; 10 days the highest preventive effect is 84.51% behind the 2nd medicine; 20 days preventive effects are 82.69% behind the 2nd medicine of single agent 4% tetraconazole aqueous emulsion; The effect of complex preparation significantly is superior to two kinds of single agent, has not only significantly improved the effect for the powdery mildew of cucumber germ, and has further prolonged its lasting period.
Comprehensive above experiment is said; With new type bactericide cyflufenamid and part triazole bactericidal agent prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Cyproconazole, Difenoconazole is that active ingredient is carried out two yuan of bactericidal composition preparations that are mixed diseases such as the black star of powdery mildew, leaf spot, rust, downy mildew, eqpidemic disease, anthracnose and the drupe of various crop, grey scab is all had the better prevention effect; Can effectively suppress further developing of disease; Simultaneously to crop safety; Suggestion is promoted the use of, and in use should be used alternatingly with other different mechanisms medicines, to delay the pesticide resistance of plant.

Claims (5)

1. pesticide sterilizing composite preparation; It is characterized in that: this bactericidal composition is to be the preparation that active ingredient is carried out two yuan of composite bactericidal compositions with one of any (representing with B) in new type bactericide cyflufenamid (representing with A) and several kinds of triazole bactericidal agent prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Cyproconazole, the Difenoconazole; All the other components are that formulation prepares required auxiliary agent and complementary component in the agricultural chemicals, and wherein the percentage by weight of two kinds of effective constituents A and B is 90: 1~1: 90 in this bactericidal composition preparation.
2. bactericidal composition preparation according to claim 1 is characterized in that: on the basis of specific aim experimental formula screening, the percentage by weight of effective constituents A and B can be preferably 60: 3~2: 70 in this bactericidal composition preparation.
3. bactericidal composition preparation according to claim 1 and 2 is characterized in that: to account for the percentage of total formulation gross weight be 1%~90% to the total content of two kinds of effective constituents A and B in the bactericidal composition preparation of the present invention.
4. bactericidal composition preparation according to claim 3 is characterized in that: effective constituents A and the B total content percentage in preparation is preferably 8%~75% in the bactericidal composition preparation of the present invention.
5. according to the described bactericidal composition preparation of claim 1 to 4, it is characterized in that: the preparation formulation that bactericidal composition preparation of the present invention can be mixed with is wetting powder, suspending agent, soluble liquid, aqueous emulsion and water dispersible granules, granule.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103190421A (en) * 2013-04-07 2013-07-10 海南正业中农高科股份有限公司 Cyflufenamid-containing sterilizing composite
CN103271038A (en) * 2013-05-20 2013-09-04 联保作物科技有限公司 Bactericidal composition and preparation thereof
CN103583564A (en) * 2012-08-17 2014-02-19 陕西美邦农药有限公司 High-efficiency bactericidal composition containing simeconazole and triazoles
CN104041491A (en) * 2014-07-14 2014-09-17 陕西上格之路生物科学有限公司 Bactericidal composition containing cyflufenamid and cuppric nonyl phenolsulfonate
CN104957146A (en) * 2015-06-24 2015-10-07 广东中迅农科股份有限公司 Sterilization composition containing tetraconazole and cyflufenamid
WO2015189110A1 (en) * 2014-06-11 2015-12-17 Bayer Cropscience Aktiengesellschaft Active compound combinations comprising cyflufenamid and bixafen or spiroxamine and optionally prothioconazole
CN105165836A (en) * 2015-07-19 2015-12-23 广东中迅农科股份有限公司 Sterilization composition containing prothioconazole and cyflufenamid
CN106942232A (en) * 2017-04-17 2017-07-14 北京科发伟业农药技术中心 Fungicidal composition containing cyflufenamid
CN109717191A (en) * 2017-10-31 2019-05-07 江苏龙灯化学有限公司 A kind of application of the bactericidal composition containing cyflufenamid and Tebuconazole

Citations (3)

* Cited by examiner, † Cited by third party
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
CN102007916A (en) * 2010-10-28 2011-04-13 江苏龙灯化学有限公司 Agricultural and gardening antifungal composition
WO2011056463A2 (en) * 2009-11-04 2011-05-12 E. I. Du Pont De Nemours And Company Fungicidal mixtures

Patent Citations (3)

* Cited by examiner, † Cited by third party
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
WO2011056463A2 (en) * 2009-11-04 2011-05-12 E. I. Du Pont De Nemours And Company Fungicidal mixtures
CN102007916A (en) * 2010-10-28 2011-04-13 江苏龙灯化学有限公司 Agricultural and gardening antifungal composition

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103583564A (en) * 2012-08-17 2014-02-19 陕西美邦农药有限公司 High-efficiency bactericidal composition containing simeconazole and triazoles
CN103583564B (en) * 2012-08-17 2016-01-13 陕西美邦农药有限公司 A kind of efficient bactericidal composite containing simeconazoles and triazole type
CN103999861B (en) * 2013-04-07 2015-07-15 海南正业中农高科股份有限公司 Bactericidal composition containing cyflufenamid and fenamidone
CN103190421A (en) * 2013-04-07 2013-07-10 海南正业中农高科股份有限公司 Cyflufenamid-containing sterilizing composite
CN103190421B (en) * 2013-04-07 2014-06-11 海南正业中农高科股份有限公司 Cyflufenamid-containing sterilizing composite
CN103999858A (en) * 2013-04-07 2014-08-27 海南正业中农高科股份有限公司 Fungicidal composition containing cyflufenamid and ethylicin
CN103999861A (en) * 2013-04-07 2014-08-27 海南正业中农高科股份有限公司 Bactericidal composition containing cyflufenamid and fenamidone
CN103271038A (en) * 2013-05-20 2013-09-04 联保作物科技有限公司 Bactericidal composition and preparation thereof
CN103271038B (en) * 2013-05-20 2014-08-13 联保作物科技有限公司 Bactericidal composition and preparation thereof
WO2015189110A1 (en) * 2014-06-11 2015-12-17 Bayer Cropscience Aktiengesellschaft Active compound combinations comprising cyflufenamid and bixafen or spiroxamine and optionally prothioconazole
EA032148B1 (en) * 2014-06-11 2019-04-30 Байер Кропсайенс Акциенгезельшафт Active compound fungicide combination comprising cyflufenamid and spiroxamine, use thereof, fungicide composition comprising this combination, seed treated with this combination, method for controlling phytopathogenic fungi in plants or crops
CN104041491A (en) * 2014-07-14 2014-09-17 陕西上格之路生物科学有限公司 Bactericidal composition containing cyflufenamid and cuppric nonyl phenolsulfonate
CN104957146A (en) * 2015-06-24 2015-10-07 广东中迅农科股份有限公司 Sterilization composition containing tetraconazole and cyflufenamid
CN105165836A (en) * 2015-07-19 2015-12-23 广东中迅农科股份有限公司 Sterilization composition containing prothioconazole and cyflufenamid
CN106942232A (en) * 2017-04-17 2017-07-14 北京科发伟业农药技术中心 Fungicidal composition containing cyflufenamid
CN109717191A (en) * 2017-10-31 2019-05-07 江苏龙灯化学有限公司 A kind of application of the bactericidal composition containing cyflufenamid and Tebuconazole

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