Background technology
Fluorine azoles bacterium acyl azanol, English common name pydiflumetofen, chemical name：3-（Difluoromethyl）- N- methoxyl groups-1- methyl-N- [（RS）- 1- methyl -2-（2,4,6- trichlorophenyls）Ethyl] pyrazole-4-carboxamide.It is that Switzerland is first just being protected up to cropA kind of succinate dehydrogenase inhibitors series bactericidal agent of shield Co., Ltd research and development.Fluorine azoles bacterium acyl azanol wide spectrum, efficiently, it is adaptable to manyCrop is planted, especially to leaf spot and powdery mildew activity highest, to the disease such as botrytis for being agriculturally difficult to prevent and treat（Botrytisspp.）, sclerotinite（Sclerotinia spp.）With rod spore bacterium（Corynespora spp.）It is high etc. the microbial disease of cause of diseaseEffect, the generation of these diseases can cause the heavy losses of grape, peanut and potatoes and other crops yield, and peasant is selectable anti-Control means limited.Fluorine azoles bacterium acyl azanol is prevented and treated on cereal by sickle-like bacteria also breakthroughly（Fusarium）The disease for causing, it is such as redMildew etc..
Tebuconazole, English common name tebuconazole, chemical name：(RS) the p- chlorphenyl -4,4- dimethyl -3 of -1-(1H-1,2,4- triazol-1-yls methyl) amylalcohol.Tebuconazole is a kind of efficient, wide spectrum, absorbability triazole type sterilization pesticide, is hadProtect, treat, rooting out three zones, wide sterilization spectrum, lasting period are long.As all of triazole bactericidal agent, Tebuconazole canSuppress the biosynthesis of the ergosterol of fungi.
Hexaconazole, English common name hexaconazole, chemical name：(RS) -2- (2,4 dichloro benzene bases）-1-（1H-1,2,4- triazol-1-yls）- hex- 2- alcohol.Hexaconazole belongs to triazole bactericidal agent, and sterol demethylation inhibitors are especially carried on a shoulder pole to fungiThe disease that daughter bacteria door and Ascomycota cause has the protection and therapeutic action of broad spectrum activity.The cell membrane of destruction and prevention germ is importantThe biosynthesis of constituent ergosterol, causes cell membrane to be formed, and makes germ dead.With interior suction, protection and treatmentActivity.
Difenoconazole, English common name difenoconazole, chemical name：1- (2- [4- (4- chlorobenzenes oxygen) -2- chlorinePhenyl] -4- methyl isophthalic acids, 3- dioxin-pentane -2- ylmethyls)-H-1,2,4- triazoles.It is that wide-spectrum bactericide is inhaled in one kind, to ascusGammaproteobacteria, Basidiomycetes and including Alternaria, Ascochyta, Cercospora, Colletotrichum, ball Cuo Pseudomonas, Phoma, post everySpore category, Septoria, Venturia partly know disease in interior, and Erysiphaceae, Uredinales and some Seedborne pathogens have lasting guarantorShield and therapeutic action.It is also fine to bitter rot or anthracnose of grape, white rot effect.Foliar treatment or Seed Treatment can improve the yield of cropAnd guaranteed quality.
Epoxiconazole, English common name epoxiconazole, chemical name：(2RS, 3SR) -3- (2- chlorphenyls) -2- (4-Fluorophenyl) -2- [(1H1,2,4- triazol-1-yls) methyl] oxirane.Epoxiconazole is C-14 demethylations in sterol biosynthesisChange enzyme inhibitor, have protection and therapeutic action concurrently.Suitable for crop wheat, barley, paddy rice, beet, rape, legume, vegetables,Grape and apple etc..To under crop safety recommended dose to crop safety, without poisoning.
Flusilazole, English common name flusilazole, chemical name：Double (4- fluorophenyls) methyl (1H-1,2,4- triazoles-1- bases methylene is supportted) silane.Flusilazole is triazole bactericidal agent, mainly destroys and prevent the cell membrane important composition composition of germThe biosynthesis of ergosterol, causes cell membrane to be formed, and makes germ dead.Gammaproteobacteria, Basidiomycetes and Fungi Imperfecti in antithetical phraseDisease caused by the germ of class is effectively, invalid to disease caused by Oomycete germ.
Triticonazole, English common name triticonazole, chemical name：(±)-(E) -5- (4- benzyl chlorides alkenyl) -2,2-Dimethyl -1- (1H-1,2,4- triazol-1-yls methyl) cyclopentanol.Triticonazole belongs to triazole bactericidal agent, sterol biosynthesisMiddle C-14 demethylations enzyme inhibitor, security is higher, is mainly used as seed treatment.Suitable cereal crop, legume,Fruit tree etc..
Metconazole, English common name metconazole, chemical name：(1RS, 5RS；1RS, 5SR) -5- (4- chlorphenyls) -2,2- dimethyl -1- (1- hydrogen-l, 2,4- triazole-l- methyl) cyclopentanol.Metconazole is that C-14 takes off in ergosterol biosynthesisMethylase inhibitors, antifungal spectrum is wide.Metconazole field is applied to be had to cereal crops septoria musiva, fusarium and handle rest fungus plant diseaseExcellent effect.Metconazole compared with traditional biocide agent, dosage is extremely low and prevent and treat cereal to plant sick scope very wide, it is suitable wheat, bigThe crops such as wheat, oat, rye, triticale, to non-target organism low toxicity.
Kind bacterium azoles, English common name ipconazole, chemical name：2- [(4- chlorphenyls) methyl] -5- (1- isopropyls) -1- (1H-1,2,4- triazol-1-yls methyl) cyclopentanol.Kind bacterium azoles are mainly used in paddy rice, and rice bakanae disease is prevented and treated by Seed TreatmentDisease, leaf spot and rice blast etc., and the seed-borne disease for preventing and treating other crops.
Propiconazole, English common name propiconazol, chemical name：1- [2- (2,4 dichloro benzene base) -4- propyl group -1,3- dioxolanes-Alpha-Methyl] -1- hydrogen -1,2,4- triazoles.Propiconazole is that a kind of absorbability with protection and therapeutic action is sterilizedAgent, can be absorbed, and soon can be conducted upwards in plant body by root, stem, leaf portion, can prevent and treat sac fungus, basidiomycetes and halfKnow the disease caused by bacterium, particularly there is preferable prevention effect to root rotof flax, powdery mildew, bakanae disease of rice, but it is rightOomycetes disease is invalid.
Prothioconazoles, English common name prothioconazole, chemical name：(RS) -2- [2- (1- chlorine cyclopropyl) -3-(2- chlorphenyls) -2- hydroxypropyls] -2,4- dihydro -1,2,4- triazole -3- thioketones.Prothioconazoles are a kind of new triazolinonesSystemic fungicide, as a kind of demethylation inhibitors (DMI), plays precursor --- the lanosterol for suppressing sterol in fungiThe demethylation effect on 14- or -24 methylene lanostenols.The active ingredient have fabulous protection, treatment andEradicate activity.
Applicant has been surprisingly found that through experiment, by the different fluorine azoles bacterium acyl azanol of the mechanism of action and Tebuconazole, hexaconazole, phenylateOne or more compounding in methyl cyclic-azole, epoxiconazole, Flusilazole, triticonazole, metconazole, kind bacterium azoles, propiconazole, prothioconazoles,The preventing and treating of gibberella zeaze petch of wheat and barley, apple marssonina leaf spot, sigatoka, wheat sharp eyespot, rice sheath blight disease is applied to, synergistic effect showsWrite.
The content of the invention
It is an object of the invention to provide a kind of component it is reasonable, synergistic effect is notable, bactericidal effect good, drug cost is low,To the fluorine-containing azoles bacterium acyl azanol and the bactericidal composition of triazole bactericidal agent of crop safety.
Bactericidal composition formulation another object of the present invention is to provide fluorine-containing azoles bacterium acyl azanol and triazole bactericidal agent.
It is still another object of the present invention to provide above-mentioned composition in preventing and treating gibberella zeaze petch of wheat and barley, apple marssonina leaf spot, Banana LeafApplication in pinta, wheat sharp eyespot, rice sheath blight disease.
To achieve the above object, the technical scheme is that so solve：
A kind of bactericidal composition of fluorine-containing azoles bacterium acyl azanol and triazole bactericidal agent, it is characterised in that：
（1）First active component：Fluorine azoles bacterium acyl azanol；
（2）Second active component：Tebuconazole, hexaconazole, Difenoconazole, epoxiconazole, Flusilazole, triticonazole, metconazole, kind bacteriumOne or more in azoles, propiconazole, prothioconazoles.
The weight ratio of the first active component and the second active component is 1:50~30:1, content sum is that the composition is totalThe 1%~90% of weight.
Further, the weight ratio of the first active component and the second active component is 1：20~10：1, content sum is describedThe 2%~80% of composition total weight.
Further, the weight ratio of the first active component and the second active component is 1：4~1：1, content sum is describedThe 5%~70% of composition total weight.
The bactericidal composition of a kind of fluorine-containing azoles bacterium acyl azanol of the present invention and triazole bactericidal agent is according to the art technologyThe preparation formulation that method well known to personnel can be prepared is suspending agent, dispersible oil-suspending agent, wettable powder, water-dispersible grainAgent, missible oil, microemulsion.
To suspending agent, usable auxiliary agent has：Emulsifying agent such as calcium dodecyl benzene sulfonate（Agriculture breast 500#）, Nongru-700 #,Agriculture breast 2201, this disk -60#, emulsifying agent T-60（Common name：Anhydrous sorbitol single-hard ester acid ester APEO）、TX-10（It is logicalWith name：Octyl phenol polyoxyethylene（10）Ether）, agriculture breast 1601#, agriculture breast 600#, agriculture breast 400#；Dispersant such as polycarboxylate, woodenOne or more in plain sulfonate, alkylnaphthalene sulfonate；In wetting agent such as alkyl sulfate, alkylsulfonate, naphthalene sulfonateOne or more；One or more in antifreezing agent such as ethylene glycol, propane diols, glycerine, urea, inorganic salts such as sodium chloride；IncreaseOne or more in thick dose such as white carbon, polyvinyl alcohol, bentonite, aluminium-magnesium silicate；Defoamer for example silicone oil, silicone compound,One or more in C10-20 saturated fat acid compounds, C8-10 aliphatic alcohols, hexanol, butanol, octanol；Disintegrant is such asOne or more in ammonium sulfate, urea, sucrose, glucose；Stabilizer such as triphenyl phosphite, epoxychloropropane, aceticanhydride；Water isDeionized water.
To dispersibling oil-suspending agent, usable auxiliary agent has：Dispersant such as polycarboxylate, lignosulfonates, alkylnaphthaleneSulfonate（Dispersing agent NNO）、TERSPERSE 2020（Huntsman Corporation of U.S. HUNTSMAN produces, alkyl naphthalene sulfonic acid salt）InOne or more；Emulsifying agent such as BY（Castor oil polyoxyethylene ether）Serial emulsifying agent（BY-110、BY-125、BY-140）, agriculture breast700#（Common name：Alkyl phenol formaldehyde resin polyoxyethylene ether）, agriculture breast 2201, this disk -60#（Common name：Sorbitol anhydride list is stearicAcid esters）, Tween-60 #（Common name：Sorbitan monostearate APEO）, agriculture breast 1601#（Common name：PhenethylPhenol polyoxyethylene poly-oxygen propylene aether）、TERSPERSE 4894（Huntsman Corporation of the U.S. produces）In one or more；WettingAgent such as alkylphenol-polyethenoxy base ether formaldehyde condensation products sulfate, APES phosphate, phenethyl phenol polyoxy secondAlkenyl ether phosphate, alkyl sulfate, alkylsulfonate, naphthalene sulfonate, TERSPERSE 2500（Huntsman Corporation of the U.S. goes outProduct）In one or more；One or more in thickener such as white carbon, polyvinyl alcohol, bentonite, aluminium-magnesium silicate；Antifreezing agent is such asOne or more in ethylene glycol, propane diols, glycerine, urea, inorganic salts such as sodium chloride；Decentralized medium for example soybean oil, rapeseed oil,One or more in small wheat oil, methyl oleate, diesel oil, machine oil, mineral oil.
To wettable powder, usable auxiliary agent has：Dispersant such as polycarboxylate, lignosulfonates, polyoxyethylene gatherOxypropylene group ether block copolymers, alkyl naphthalene formaldehyde condensate sulfonates, alkylphenol-polyethenoxy base ether phosphate, poly alkyl alcoholOxygen ethene ether phosphate, one or more in alkylphenol-polyethenoxy base ether sulfonate；Wetting agent such as alkyl sulfate, alkyl sulphurOne or more in hydrochlorate, alkylnaphthalene sulfonate；Filler for example ammonium sulfate, urea, sucrose, glucose, diatomite, kaolin,One or more in white carbon, fine particle calcium carbonate, talcum powder, attapulgite, potter's clay.
To water dispersible granules, usable auxiliary agent has：Dispersant such as polycarboxylate（TERSPERSE 2700、T36、GY-D06 etc.）, lignosulfonates, one or more in alkylnaphthalene sulfonate；Wetting agent for example alkyl sulfate, alkylsulfonate,One or more in naphthalene sulfonate；It is disintegrant such as ammonium sulfate, sodium sulphate, polyvinylpyrrolidone, starch and its derivative, swollenOne or more in profit soil；Binding agent such as starch, glucose, polyvinyl alcohol, polyethylene glycol, sodium carboxymethylcellulose, sucroseIn one or more；One kind in filler such as diatomite, kaolin, white carbon, fine particle calcium carbonate, talcum powder, attapulgite, potter's clay orIt is various.
To missible oil, usable auxiliary agent has：Agent such as calcium dodecyl benzene sulfonate（Agriculture breast 500#）, Nongru-700 #, agriculture breast2201st, this disk -60#, emulsifying agent T-60（Common name：Anhydrous sorbitol single-hard ester acid ester APEO）、TX-10（Common name：Octyl phenol polyoxyethylene（10）Ether）, agriculture breast 1601#, agriculture breast 600#, agriculture breast 400#；Solvent such as dimethylbenzene, solvent naphtha（S-150、S-180、S-200）, toluene, biodiesel, methylated vegetable oil, 1-METHYLPYRROLIDONE；Cosolvent for example ethyl acetate, methyl alcohol,Dimethylformamide, cyclohexanone, acetone, MEK；Stabilizer such as triphenyl phosphite, epoxychloropropane, aceticanhydride.
To microemulsion, usable auxiliary agent has：Emulsifying agent is selected from calcium dodecyl benzene sulfonate（Agriculture breast 500#）, agriculture breast700#, agriculture breast 2201, this disk-60#, polysorbate60-#, TX-10, agriculture breast 1601（Common name：Phenethyl phenol polyoxyethylene polyoxyPropylene ether）, agriculture breast 600#, one or more in agriculture breast 400# etc.；Assistant for emulsifying agent is selected from methyl alcohol, isopropanol, n-butanol, secondAlcohol；Solvent is selected from cyclohexanone, 1-METHYLPYRROLIDONE, dimethylbenzene, toluene, solvent naphtha（The trade mark：S-150、S-180、S-200）DengIn one or more；Stabilizer is selected from one or more in triphenyl phosphite, epoxychloropropane etc.；Water is deionizationWater.
Instant component is reasonable, to gibberella zeaze petch of wheat and barley, apple marssonina leaf spot, sigatoka, wheat sharp eyespot, rice banded sclerotial blightThe prevention effect of disease is good, and drug cost is low, and its activity and bactericidal effect are not the simple superposition of each component activity, with existing listOne preparation compares, and has significant synergies, good to crop safety, meets the security requirement of pesticidal preparations.
Specific embodiment
, the synergy of wheat scab determined.
In order to prevent and treat the wheat scab in agricultural production, carried out with fluorine azoles bacterium acyl azanol bacterium and metconazole, prothioconazolesThe synergy research of mutual compounding, specific method is as follows.
Subjects are small bakanae disease (FusaHum graminearum).By fluorine azoles bacterium acyl azanol, metconazole, rosickyiteBacterium azoles active compound, according to the matched proportion density of setting, is configured to required liquid, standby.Experiment uses mycelial growth rate method.
Aseptically, the advance culture medium for melting is quantitatively adding in aseptic conical flask, from low concentration to high concentrationLiquid is quantitatively drawn successively, above-mentioned conical flask is separately added into, and is fully shaken up.Then equivalent pours into 4 culture dishes of a diameter of 9cmIn, it is made the pastille flat board of respective concentration.Treatment without medicament is repeated 4 times as blank.
By cultured pathogen, aseptically, with the card punch of diameter 5mm, bacteria cake is cut from colony edge, usedBacterium disease is inoculated in pastille flat board center by inoculator, and mycelia faces up, and covers ware lid, puts the incubator culture of preference temperature.
Growing state according to bacterium in blank culture dish investigates pathogen mycelial growth situation, uses vernier caliper measurementColony diameter, crossing method is vertically respectively surveyed once, is averaged.
Mycelial growth inhibition rate=（Blank colony diameter-chemicals treatment colony diameter）/ blank colony diameter ×100
Fluorine-containing azoles bacterium acyl azanol and metconazole, the bactericidal composition of prothioconazoles that the present invention is provided are evaluated using co-toxicity coefficient methodSynergistic effect to wheat scab, seeks regression equation, and calculate medicament with the logarithm of drug concentration and preventive effect niqueMinTo EC50Value, then tries to achieve co-toxicity coefficient.Synergy of the compound drug to wheat scab is evaluated with co-toxicity coefficient, altogether poisonCoefficient>120 are expressed as synergistic effect, and co-toxicity coefficient is expressed as summation action, co-toxicity coefficient between 80~120<80 are expressed asAntagonism.
Mixture synergy of the fluorine azoles bacterium acyl azanol of table 1 with metconazole mixture to wheat scab is determined
Mixture synergy of the fluorine azoles bacterium acyl azanol of table 2 with prothioconazoles mixture to wheat scab is determined
Synergy measurement result shows：Fluorine azoles bacterium acyl azanol presses 1 with metconazole, prothioconazoles:70~50:1 uses with, to wheatGibberellic hypha shows different activity：When ratio is 1:50~30:When 1, synergistic effect is shown as；Especially when ratio is 1:4~1:When 1, synergistic effect is the most notable.
2nd, the mixture synergy to apple marssonina leaf spot is determined.
In order to prevent and treat the apple marssonina leaf spot in agricultural production, we have been carried out mutually multiple with fluorine azoles bacterium acyl azanol and propiconazoleThe synergy research matched somebody with somebody, specific method is as follows.
Subjects are marssonina coronaria（Marssonina coronaria）.Fluorine azoles bacterium acyl azanol, propiconazole is formerMedicine, according to the matched proportion density of setting, is configured to required liquid, standby.Experiment uses concave slide method.
It is standby after spore to be generated by apple marssonina leaf spot diseased tissues moisturizing culture.By apple marssonina leaf spot spore deionizationWater is eluted from diseased tissues, filtered, centrifugation（1000r/min）5min, removes supernatant, adds deionized water, then be centrifuged.FinallyIt is with deionized water that spore is resuspended floating to 1 × 105Individual~1 × 107Individual spore, and add 0.5% glucose sugar juice.
Single dose and each Mixed Pharmacy are set into 5 various concentrations gradients first（On the basis of pilot study, bacteriostasis rate existsSet by geometric progression in the range of 5%~90%）.With pipette or pipettor from low concentration to high concentration, liquid is drawn successively0.5mL is separately added into small test tube, then draws the spore suspension 0.5mL for preparing, and makes liquid and spore suspension equivalentIt is well mixed.Above-mentioned mixed liquor is drawn with micro sample adding appliance to drip on concave slide, then frame is put in the culture dish with shoaling layerIn, add a cover moisturizing and be incubated in the incubator of preference temperature.If blank is done in the treatment without medicament, often treatment is repeated 4 times.
When blank spore germination rate reaches more than 90%, each treatment spore germination situation is checked.Often process each repetition withMachine observes more than 3 visuals field, and investigation spore sum is no less than 200, and spore germination number and spore sum are recorded respectively.Spore budLength of tube is considered as sprouting more than the short radius of spore.According to survey data, the spore germination relative inhibition of each treatment is calculated, it is singlePosition is percentage（%）.
Spore germination rate（%）Spore sum × 100 of=spore germination number/investigation
Treatment correction spore germination rate（%）=treatment spore germination rate/blank spore germination rate × 100
Spore germination relative inhibition（%）=（The spore germination rate of blank spore germination rate-treatment correction）/ blankSpore germination rate × 100
Regression analysis is made according to each drug concentration logarithm value and corresponding spore germination relative inhibition niqueMin, each medicament is obtainedEC50Value.The co-toxicity coefficient of mixture is calculated with the abundant methods of Sun Yun（CTC）, activity of the reagent agent to germ is evaluated with this.CompoundingThe co-toxicity coefficient of preparation（CTC）>=120 show as synergistic effect；CTC≤80 show as antagonism；80 ＜ CTC ＜ 120 are showedIt is summation action.
Mixture synergy of the fluorine azoles bacterium acyl azanol of table 3 with propiconazole to apple marssonina leaf spot is determined
Synergy measurement result shows：Fluorine azoles bacterium acyl azanol presses 1 with propiconazole:70~50:1 uses with, to marssonina coronariaShow different activity：When ratio is 1:50~30:When 1, synergistic effect is shown as；Especially when ratio is 1:4~1:When 1,Synergistic effect is the most notable.
, the mixture synergy of sigatoka determined.
In order to prevent and treat the sigatoka in agricultural production, we with fluorine azoles bacterium acyl azanol and Tebuconazole, Difenoconazole,Epoxiconazole, Flusilazole have carried out the synergy research of mutual compounding, and specific method is as follows.
Subjects are sigatoka (Cercosproa musae.The test medicine that active compound is configured to need, will be singleAgent and each Mixed Pharmacy set 5 various concentrations gradients（On the basis of pilot study result, model of the bacteriostasis rate 5%~90%Set by geometric progression in enclosing）.If clear water is compareed, it is repeated 4 times.
Experiment uses mycelial growth rate method, and cultured pathogen is aseptically punched with a diameter of 5 mmDevice, bacteria cake is cut from colony edge, and bacteria cake is connected on the culture medium flat plate of different agents concentration with transfer needle, is put 28 DEG C, is satisfiedCultivated with humidity incubator；When control group bacterium colony is covered with, colony diameter is measured, calculate each chemicals treatment and suppress mycelial growthPercentage.
Fluorine-containing azoles bacterium acyl azanol and Tebuconazole, Difenoconazole, fluorine ring that the present invention is provided are evaluated using co-toxicity coefficient methodThe synergistic effect of azoles, the bactericidal composition of Flusilazole to sigatoka, is asked back with the logarithm of drug concentration and preventive effect niqueMinReturn equation, and calculate the EC of medicament pair50Value, then tries to achieve co-toxicity coefficient.Compound drug is evaluated to banana with co-toxicity coefficientThe synergy of leaf spot, co-toxicity coefficient>120 are expressed as synergistic effect, and co-toxicity coefficient is expressed as being added between 80~120 to be madeWith co-toxicity coefficient<80 are expressed as antagonism.
Mixture synergy of the fluorine azoles bacterium acyl azanol of table 4 with Tebuconazole to apple marssonina leaf spot is determined
Mixture synergy of the fluorine azoles bacterium acyl azanol of table 5 with Difenoconazole to apple marssonina leaf spot is determined
Mixture synergy of the fluorine azoles bacterium acyl azanol of table 6 with epoxiconazole to apple marssonina leaf spot is determined
Mixture synergy of the fluorine azoles bacterium acyl azanol of table 7 with Flusilazole to apple marssonina leaf spot is determined
Synergy measurement result shows：Fluorine azoles bacterium acyl azanol presses 1 with Tebuconazole, Difenoconazole, epoxiconazole, Flusilazole:70~50:1 is used with, and different activity are shown to sigatoka bacterium：When ratio is 1:50~30:When 1, synergy work is shown asWith；Especially when ratio is 1:4~1:When 1, synergistic effect is the most notable.
, the mixture synergy of banded sclerotial blight determined.
In order to prevent and treat the banded sclerotial blight in agricultural production, we are entered with fluorine azoles bacterium acyl azanol and hexaconazole, triticonazole, kind bacterium azolesThe synergy research of mutual compounding is gone, specific method is as follows.
Subjects are rice sheath blight disease（Rhizoctonia solani）, wheat sharp eyespot（Rhizotoniacerealis）.The test medicine that active compound is configured to need, 5 various concentrations gradients are set by single dose and each Mixed Pharmacy（On the basis of pilot study result, bacteriostasis rate is set in the range of 5%~90% by geometric progression）.If clear water is compareed, 4 are repeatedIt is secondary.
Experiment uses mycelial growth rate method, and cultured pathogen is aseptically punched with a diameter of 5 mmDevice, bacteria cake is cut from colony edge, and bacteria cake is connected on the culture medium flat plate of different agents concentration with transfer needle, is put 28 DEG C, is satisfiedCultivated with humidity incubator；When control group bacterium colony is covered with, colony diameter is measured, calculate each chemicals treatment and suppress mycelial growthPercentage.
Fluorine-containing azoles bacterium acyl azanol and hexaconazole, triticonazole, the kind bacterium azoles that the present invention is provided are evaluated using co-toxicity coefficient methodSynergistic effect of the bactericidal composition to banded sclerotial blight, seeks regression equation, and calculate with the logarithm of drug concentration and preventive effect niqueMinGo out the EC of medicament pair50Value, then tries to achieve co-toxicity coefficient.Compound drug is evaluated to wheat sharp eyespot, rice banded sclerotial blight with co-toxicity coefficientThe synergy of disease, co-toxicity coefficient>120 are expressed as synergistic effect, and co-toxicity coefficient is expressed as summation action between 80~120,Co-toxicity coefficient<80 are expressed as antagonism.
Mixture synergy of the fluorine azoles bacterium acyl azanol of table 8 with hexaconazole to rice sheath blight disease is determined
Mixture synergy of the fluorine azoles bacterium acyl azanol of table 9 with triticonazole to wheat sharp eyespot is determined
Mixture synergy of the fluorine azoles bacterium acyl azanol of table 10 with kind bacterium azoles to wheat sharp eyespot is determined
Synergy measurement result shows：Fluorine azoles bacterium acyl azanol presses 1 with hexaconazole, triticonazole, kind bacterium azoles:70~50:1 uses with,Different activity are shown to rhizoctonia cerealis and Rhizoctonia solani Kuhn：When ratio is 1:50~30:When 1, synergy is shown asEffect；Especially when ratio is 1:4~1:When 1, synergistic effect is the most notable.
In order to the present invention is better described, present invention is described further with reference to embodiment.
Example of formulations 1
Weigh 100 grams of fluorine azoles bacterium acyl azanols, 100 grams of metconazoles, 50 grams of alkylphenol-polyethenoxy base ether phosphates, 50 grams of ligninSodium sulfonate, 30 grams of alkyl phenol formaldehyde resin polyoxyethylene ethers, 15 grams of bentonites, 10 grams of xanthans, 50 grams of urea, 1 gram of benzoic acid,8 restrain oneself alcohol, and deionized water adds to 1000 gram weights part.Above-mentioned raw materials are blended, high speed shear dispersion 30min, use sand mill sandIt is milled to particle diameter D9020% fluorine azoles bacterium acyl azanol metconazole suspending agent is obtained after less than 10 μm.
Example of formulations 2
Weigh 80 grams of fluorine azoles bacterium acyl azanols, 160 grams of Tebuconazoles, 55 grams of alkyl polyoxyethylene ether sodium sulfonates, 15 grams of alkylphenol formaldehydesResin APEO, 20 grams of aluminium-magnesium silicates, 40 grams of ethylene glycol, 3 grams of benzoic acid, 15 grams of butanol, deionized water add to 1000 gramsWeight portion.Above-mentioned raw materials are blended, high speed shear dispersion 30min, are sanded to particle diameter D with sand mill9024% is obtained after less than 10 μmFluorine azoles bacterium acyl azanol tebuconazole suspension concentrates.
Example of formulations 3
Weigh 100 grams of fluorine azoles bacterium acyl azanols, 150 grams of prothioconazoles, 40 grams of APES phosphates, 50 grams of polyoxy secondAlkene polyoxypropylene block copolymers, 40 grams of Tween-60 #, 30 grams of Nongru-700 #, 30 grams of calcium dodecyl benzene sulfonates, 15 grams it is organicBentonite, 12 grams of polyvinyl alcohol, 10 grams of BHT, cottonseed oil supply 1000 grams.Above-mentioned raw materials are blended, are sanded to grain with sand millFootpath 25% fluorine azoles bacterium acyl azanol prothioconazoles is obtained less than 5 μm and dispersibles oil-suspending agent.
Example of formulations 4
Weigh 50 grams of fluorine azoles bacterium acyl azanols, 200 grams of Difenoconazoles, 60 grams of BY-110,30 grams of TERSPERSE 2020（AlkylnaphthaleneSulfonates）, 50 grams of AEO, 35 grams of agriculture breast 1601#, 20 grams of gas-phase silicas, 25 grams of epoxychloropropane, palm fibrePalmitic acid oil supplies 1000 grams.Above-mentioned raw materials are blended, be sanded to particle diameter with sand mill and 25% fluorine azoles bacterium acyl hydroxyl is obtained less than 5 μmAmine difenoconazole dispersible oil-suspending agent.
Example of formulations 5
Weigh 100 grams of fluorine azoles bacterium acyl azanols, 250 grams of propiconazoles, 50 grams of Nekal BXs（Nekal）, 20 grams of alkyl phenolsPolyoxyethylene groups ether phosphate, 15 grams of lauryl sodium sulfate, talcum powder are filled up to 1000 grams.Above-mentioned raw materials are blended, ultra microAir-flow crushing, hybrid technique step are prepared into 35% fluorine azoles bacterium acyl azanol propiconazole wettable powder.
Example of formulations 6
Weigh 60 grams of fluorine azoles bacterium acyl azanols, 240 grams of epoxiconazoles, 60 grams of T36（Polycarboxylic acid salt）, 30 grams of Ufoxane 3A（It is woodenPlain Sulfonates）, 30 grams of lauryl sodium sulfate, kaolin filled up to 1000 grams.Above-mentioned raw materials are blended, ultra micro air-flow powderBroken, hybrid technique step is prepared into 30% fluorine azoles bacterium acyl azanol epoxiconazole wettable powder.
Example of formulations 7
Weigh 120 grams of fluorine azoles bacterium acyl azanols, 360 grams of Flusilazoles, 30 grams of GY-D06,40 grams of sodium lignin sulfonates, 20 grams of pull open powdersBX（Nekal）, 15 grams of K-12（Lauryl sodium sulfate）, fine particle calcium carbonate adds to 1000 gram weights part.Above-mentioned raw materials are frequentThe method of regulation water intaking dispersible granule is that mixing, ultra micro air-flow crushing, mixing, granulation step produce 48% fluorine azoles bacterium acyl azanolFlusilazole water dispersible granule.
Example of formulations 8
Weigh 150 grams of fluorine azoles bacterium acyl azanols, 300 grams of triticonazoles, 30 grams of GY-D06（Polycarboxylate）, 50 grams of sodium lignin sulfonates,30 grams of lauryl sodium sulfate, 25 grams of sodium alkyl sulfonates, attapulgite add to 1000 gram weights part.The frequent regulation of above-mentioned raw materials takesThe method of water dispersible granules is that mixing, ultra micro air-flow crushing, mixing, granulation step produce 45% fluorine azoles bacterium acyl azanol triticonazoleWater dispersible granules.
Example of formulations 9
Weigh 100 grams of fluorine azoles bacterium acyl azanols, 150 grams of kind bacterium azoles, 40 grams of agriculture breast 500#, 40 grams of Nongru-700 #, 50 grams of agriculture breasts1601#, 30 grams of dimethylformamides, 20 grams of epoxychloropropane, dimethylbenzene add to 1000 gram weights part.Above-mentioned raw materials are blended,Stirring and dissolving is obtained 25% fluorine azoles bacterium acyl azanol kind bacterium azoles missible oil afterwards completely.
Example of formulations 10
Weigh 80 grams of fluorine azoles bacterium acyl azanols, 160 grams of prothioconazoles, 50 grams of Nongru-700 #, 50 grams of agriculture breasts, 2201,50 grams of this disks-60#, 20 grams of cyclohexanone, 30 grams of epoxychloropropane, toluene add to 1000 gram weights part.Above-mentioned raw materials are blended, and stirring and dissolving is completePrepared 24% fluorine azoles bacterium acyl azanol prothioconazoles missible oil after complete.
Example of formulations 11
Weigh 50 grams of fluorine azoles bacterium acyl azanols, 150 grams of hexaconazoles, 45 grams of agriculture breasts, 2201,35 grams of this disk-60#, 40 grams of polysorbate60-#,80 grams of 1-METHYLPYRROLIDONEs, 120 grams of cyclohexanone, 25 grams of n-butanols, 20 grams of epoxychloropropane, through dissolving complete and mixing equalEven, deionized water adds to 1000 gram weights part, and 20% fluorine azoles bacterium acyl azanol hexaconazole microemulsion is obtained after stirring.
Example of formulations 12
Weigh 40 grams of fluorine azoles bacterium acyl azanols, 160 grams of Difenoconazoles, 50 grams of agriculture breasts, 2201,40 grams of this disk -60#, 45 grams of tweens60-#, 60 grams of 1-METHYLPYRROLIDONEs, 110 grams of cyclohexanone, 50 grams of n-butanols, 15 grams of epoxychloropropane, through dissolving complete and mixingClose uniform, deionized water adds to 1000 gram weights part, 20% fluorine azoles bacterium acyl azanol micro-emulsion of phenyl ether methyl cyclic-azole is obtained after stirring.
Biological Examples 1：Preventing and treating gibberella zeaze petch of wheat and barley field test.
Example of formulations 1 has been carried out in Baoji, Shaanxi province city Mei County Ying Touzhen Zhang Jia villages within 2016（20% fluorine azoles bacterium acyl hydroxylAmine metconazole suspending agent）, example of formulations 3（25% fluorine azoles bacterium acyl azanol prothioconazoles dispersible oil-suspending agent）Preventing and treating wheatThe field control effectiveness test of bakanae disease.Suspended by with comparison medicament 200g/L fluorine azoles bacterium acyl azanols suspending agent, 20% metconazoleAgent, the effect of 25% prothioconazoles suspending agent are contrasted, and demonstrate the present invention to the prevention effect of gibberella zeaze petch of wheat and barley and to wheatSecurity.
Trial crops are wheat, and controlling object is wheat scab（Fusarium graminearum）.Experiment is located at treasuredJi Shi Mei Countys Ying Touzhen, experimental plot physical features is flat, and soil is medium loam, middle fertility, pH value 7.1, rich water quality management during experimentIt is medium.Test medicine and dosage refer to table 11.Blank separately is set, 4 repetitions is often processed, often the ㎡ of cell 30, totally 24 cells,Random district's groups arrangement.Using conventional spray-on process, in the first time dispenser of wheat flowering initial stage, interval sprays second, mu dispenser for 7 daysLiquid 45kg, is uniformly sprayed at leave dual sides.
Investigation and statistical method：State of an illness radix, wheat milk stage 10d or so investigation prevention effects to before harvesting are investigated before dispenserReally.Per the 5 points of samplings of cell diagonal, every 100~200 fringes of investigation account for the percentage of whole fringe area to divide with withered fringe areaLevel, records sick spike numbers at different levels and total spike number.Stage division：
0 grade：Full fringe is disease-free；
1 grade：Withered fringe area accounts for less than the 1/4 of full fringe area；
3 grades：Withered fringe area accounts for the 1/4~1/2 of full fringe area；
5 grades：Withered fringe area accounts for the 1/2~3/4 of full fringe area；
7 grades：Withered fringe area accounts for more than the 3/4 of full fringe area.
Disease index=[∑ (sick spike numbers at different levels × relative value of series)/(total spike number × 7 of investigation)] × 100
Prevention effect (%)=（Blank district disease index-chemicals treatment district disease index)/blank district disease index ×100
Table 11 prevents and treats wheat scab field test results
Table of field test results is bright, and example of formulations 1 and 3 pairs of wheat scabs have good prevention effect, to wheat scabThe preventive effect of 10d reaches more than 94% before harvesting, hence it is evident that better than three preventive effects of single dose.Show by harvesting preceding 10d preventive effects differenceWork property analysis, difference reaches the pole level of signifiance.
Security survey to wheat, observes for some days after the 1st day and medicine after spray, and each test process are to wheat without poisoningPhenomenon occurs.
Biological Examples 2：Prevent and treat apple marssonina leaf spot field test.
Example of formulations 5 has been carried out in Xianyang, Shanxi province city Jingyang County Yunyang town East Street village within 2016（35% fluorine azoles bacterium acylAzanol propiconazole wettable powder）Apple marssonina leaf spot field test is prevented and treated, preventing and treating of the medicament to apple marssonina leaf spot is demonstratedEffect and the security to apple tree.
Trial crops are apple tree, and controlling object is apple marssonina leaf spot（Marssonina coronaria）.Experiment is located atJingyang County Yunyang town, experimental plot physical features is flat, and soil is medium loam, middle fertility, pH value 7.9, during experiment in rich water quality managementDeng.Test medicine and dosage refer to table 12.Blank separately is set, 4 repetitions are often processed, set for 2 per cell, totally 16 cells,Random district's groups arrangement.Using conventional spray-on process.
Investigation and statistical method：State of an illness radix is investigated before dispenser, 10d is reinvestigated once after second.Often treatment cell is equalAccording to the principle of tree crown top, Inner thoraxes, periphery and bottom and east, south, west, north, 16 branches are taken, fixed point is listed, by leaf pointLevel periodic investigation its whole blade, record total number of sheets, the sick numbers of sheets at different levels.Stage division：
0 grade：Disease-free spot；
1 grade：Lesion area accounts for less than the 5% of whole leaf area；
3 grades：Lesion area accounts for the 6%~15% of whole leaf area；
5 grades：Lesion area accounts for the 16%~25% of whole leaf area；
7 grades：Lesion area accounts for the 26%~50% of whole leaf area；
9 grades：Lesion area accounts for more than the 50% of whole leaf area.
Disease index=[∑ (the sick numbers of sheets at different levels × relative value of series)/(investigation total leaf number × 9)] × 100
Prevention effect (%)=[1- (disease index after disease index × treatment dispenser before control dispenser)/（The state of an illness refers to after control dispenserDisease index before number × treatment dispenser] × 100
Table 12 prevents and treats apple marssonina leaf spot field test results
Table of field test results is bright, and example of formulations 5 has good prevention effect to apple marssonina leaf spot, by 200mg/kg sprayings 2Secondary, the preventive effect to apple marssonina leaf spot reaches more than 95%, hence it is evident that better than the preventive effect of each single dose.By aobvious to brown spot preventive effect differenceWork property analysis, difference reaches the pole level of signifiance.
Security survey to apple tree, observes for continuous 7 days after spray, and each test process are sent out apple tree without poisoning phenomenonIt is raw.
Biological Examples 3：Prevent and treat sigatoka field test.
In May, 2016 has carried out example of formulations 2 in Hainan Province Dengmai County（24% fluorine azoles bacterium acyl azanol Tebuconazole suspendsAgent）, example of formulations 4（25% fluorine azoles bacterium acyl azanol difenoconazole dispersible oil-suspending agent）, example of formulations 6（30%Fluorine azoles bacterium acyl azanol epoxiconazole wettable powder）, example of formulations 7（48% fluorine azoles bacterium acyl azanol Flusilazole water-dispersible grainAgent）Sigatoka field test is prevented and treated, this several medicament is demonstrated to the prevention effect difference of sigatoka and to bananaSecurity.
Trial crops are banana, and controlling object is sigatoka (Cercosproa musae).Fallen ill over the years heavierBanana garden carry out.Test medicine and extension rate refer to table 13.Blank separately is set, 4 repetitions are often processed, per 10 plants of cellBanana, totally 40 cells, random district's groups arrangement.Using conventional spray-on process, complete stool is uniformly sprayed.1st dispenser is in banana tikkaSick early stage, second medication after 14d, altogether dispenser 2 times.
Investigation and statistical method：14d investigation blade incidence after 14d and second medicine after first time medicine.Per cell withMachine investigates 3 plants, and every plant of banana down investigates 10 leaves from top（Lobus cardiacus is not switched on to disregard）, record the total number of sheets of investigation, eachThe sick number of sheets of level, calculating preventive effect is referred to according to disease.
Stage division：
0 grade：Disease-free spot；
1 grade：Lesion area accounts for less than the 5% of whole leaf area；
3 grades：Lesion area accounts for the 6%~15% of whole leaf area；
5 grades：Lesion area accounts for 16%~25% of whole leaf area
7 grades：Lesion area accounts for the 26%~50% of whole leaf area；
9 grades：Lesion area accounts for more than the 50% of whole leaf area.
In the influence situation after visual observations dispenser after each medicine to Banana Growth, leaf color, flowers and fruits etc., examination medicament is to perfume (or spice)The security of any of several broadleaf plants plant.
Disease index=[∑ (the sick numbers of sheets at different levels × relative value of series)/(investigation total leaf number × 9)] × 100
Prevention effect (%)=[(control disease index-treatment disease index)/control disease index] × 100
Table 13 prevents and treats sigatoka field test results
Table of field test results is bright：4 example of formulations of the above have preventing and treating effect well to sigatoka by upper table formulation rateReally, the preventive effect of 14d is respectively 94.40%, 95.35%, 94.99%, 94.47% after first time medicine, and the preventive effect of 14d is after second medicine94.21%th, 94.72%, 95.13%, 93.85%, better than each single dose to the preventive effect of sigatoka.
Security survey to banana, observes for continuous 7 days after spray, and each test process occur to banana without poisoning phenomenon.
Biological Examples 4：Prevent and treat rice sheath blight disease field test.
Example of formulations 8 has been carried out in Junichiro Koizumi village of xiangtan, hunan province county within 2016（45% fluorine azoles bacterium acyl azanol triticonazoleWater dispersible granules）, example of formulations 9（25% fluorine azoles bacterium acyl azanol kind bacterium azoles missible oil）, example of formulations 11（20% fluorine azoles bacteriumAcyl azanol hexaconazole microemulsion）Prevent and treat rice sheath blight disease field test.By with comparison medicament 200g/L fluorine azoles bacterium acyl azanolsSuspending agent, 20% sterilizing azole suspending agent, 5% kind bacterium azoles microemulsion, the effect of 50% diniconazole water dispersible granule are contrasted, and are verifiedPrevention effect to rice sheath blight disease of the invention and the security to paddy rice.
Trial crops are paddy rice, and controlling object is rice sheath blight disease（Rhizoctonia solani）.Experiment is located at HunanXiangtan County Junichiro Koizumi village of province, experimental plot physical features is flat, and soil is loam, and fertility is higher, pH value 7.2, during experiment in rich water quality managementDeng.Test medicine and dosage refer to table 14.Blank separately is set, 4 repetitions is often processed, often the ㎡ of cell 30, totally 32 cells, withMachine district's groups are arranged.Using conventional spray-on process, mu dispenser liquid 45kg is uniformly sprayed at leave dual sides.
Investigation and statistical method：State of an illness radix is investigated before dispenser, 10d is reinvestigated once after last time dispenser, and 2 are investigated altogetherIt is secondary.According to rice leaf sheath and blade damage symptom grading, in units of strain, per the 5 points of samplings of cell diagonal, every tuneConnected 5 clumps are looked into, totally 25 clumps, record total strain number, diseased plant number and sick series.
0 grade：Complete stool is disease-free；
1 grade：Quaterfoil and its following leaf sheath, blade morbidity（It is first piece leaf with sword-like leave）；
3 grades：Third blade and its following leaf sheath, blade morbidity；
5 grades：Second blade and its following leaf sheath, blade morbidity；
7 grades：Sword-like leave blade and its following leaf sheath, blade morbidity；
9 grades：Complete stool falls ill, withered ahead of time.
Disease index=[∑ (the sick numbers of sheets at different levels × relative value of series)/(investigation total leaf number × 9)] × 100
Prevention effect (%)=[1- (disease index after disease index × treatment dispenser before control dispenser)/（The state of an illness refers to after control dispenserDisease index before number × treatment dispenser] × 100
Table 14 prevents and treats rice sheath blight disease field test results
Table of field test results is bright, and above example of formulations has good prevention effect to rice sheath blight disease, to rice sheath blight diseaseThe preventive effect of 10d reaches more than 95% after 2nd medicine, hence it is evident that better than 4 preventive effects of single dose.The 10d significances of difference after to medicineAnalysis, preventive effect difference reaches the pole level of signifiance.
Security survey to paddy rice, observes for some days after the 1st day and medicine after spray, and each test process are to paddy rice without poisoningPhenomenon occurs.
From above example, fluorine azoles bacterium acyl azanol and triazole bactericidal agent are 1 according to weight ratio:50~30:1 is carried outCompounding, can be made into suspending agent, dispersibles oil-suspending agent, wettable powder, water dispersible granules, missible oil, microemulsion, red to wheat class mouldDisease, apple marssonina leaf spot, sigatoka, wheat sharp eyespot, rice sheath blight disease have significant prevention effect, and synergistic effect is obvious,Dosage and drug cost are reduced, and to having wide practical use on crop safety, therefore production.
In sum, composition of the invention to gibberella zeaze petch of wheat and barley, apple marssonina leaf spot, sigatoka, wheat sharp eyespot,The prevention effect of rice sheath blight disease is that, using two kinds of active components compound scheme, its activity and bactericidal effect are not each groups significantlyDivide the simple superposition of activity, compared with existing unitary agent, in addition to obvious bactericidal effect, also with significant synergyEffect, cost accounting reduction, to crop safety, meets the security requirement of pesticidal preparations.