A kind of bactericidal composition and application thereof containing oxime bacterium ester and cyproconazole
Technical field
The present invention relates to a kind of composition pesticide, being specifically related to a kind of bactericidal composition containing oxime bacterium ester and cyproconazole and said composition preventing and treating the application on fruit tree, vegetable disease, belonging to technical field of pesticide.
Background technology
Cyproconazole (Cyproconazole, chemical name: 2-(4-chlorphenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl) fourth-2-alcohol) belong to triazole bactericidal agent, sterol demethylation inhibitors, all effective to the Erysiphales on cereal crop, coffee, beet, fruit tree and grape, Puccinia, Rhynchosporium spp., septoria musiva Pseudomonas, Venturia bacterium.Mixed with other bactericide, cereal eye spot disease, leaf spot and net blotch can be prevented and treated very well.The control wheat rust lasting period is 4-6 week, and preventing and treating the powdery mildew lasting period is 3-4 week.
Oxime bacterium ester (Trifloxystrobin; chemical name: (2Z)-2-methoxyimino-2-[2-[[1-[3-(trifluoromethyl) phenyl] ethyleneimino] oxygen methyl] phenyl] methyl acetate) extract from natural products Strobilurins, fungicides that the class successfully developed as bactericide lead compound is new, characteristics such as there is efficient, wide spectrum, protection, treat, root out, permeate, systemic activity, resistance of rainwater washing against, lasting period are long.Oxime bacterium ester to Isosorbide-5-Nitrae-demethylation enzyme inhibitor, benzamides, the bacterial strain that dicarboxyl amine and benzimidazole produce resistance is effective, with existing bactericide at present without cross resistance; Good activity is all had to nearly all Mycophytes (Ascomycetes, Basidiomycetes, Oomycete and Fungi Imperfecti) disease such as powdery mildew, rust, Ying's rot, net blotch, downy mildew, rice blast etc.; Except having special efficacy to powdery mildew, leaf spot, there is good activity to rust, downy mildew, damping off, apple apple scab; Because it is at soil, capable of being fast degraded in water, therefore to crop safety, environmentally safe.
The long-term a large amount of of single bactericide use, and easily make disease develop immunity to drugs, and cause dosage increasing, preventive effect reduction, lasting period to shorten, are unfavorable for environment sustainable development.Delaying disease one of the conventional method that develops immunity to drugs is carry out composite to the active ingredient of the different mechanism of action.By lot of experiments, determine best synergistic complex ratio, to expand fungicidal spectrum, improve germicidal efficiency.Oxime bacterium ester is different from the cyproconazole mechanism of action, composite about oxime bacterium ester and cyproconazole, there is not yet relevant report at home and abroad at present.
Summary of the invention
The object of the present invention is to provide a kind of bactericidal composition containing oxime bacterium ester and cyproconazole, said composition function admirable, bactericidal effect is excellent, avoids disease to develop immunity to drugs, and increases the medicine lasting period, is beneficial to environment sustainable development.
Present invention also offers the application of above-mentioned bactericidal composition in control vegetables, fruit diseases.
The present invention is achieved by the following measures:
Contain a bactericidal composition for oxime bacterium ester and cyproconazole, it is characterized in that: active constituents of medicine comprises oxime bacterium ester and the cyproconazole that weight ratio is 1: 1-10: 1, and preferred weight ratio is 1: 1 to 5: 1.
The described bactericidal composition containing oxime bacterium ester and cyproconazole, by the known method of the art personnel, can be made into any formulation agriculturally allowed, more preferably as: suspending agent or water dispersible granules.
When composition makes water dispersible granules, comprise the component of following percentage by weight: active constituents of medicine 30%-90%, dispersant 4-10%, wetting agent 2-10%, disintegrant 1-10%, filler surplus.Preferably, composition is made up of the component of following percentage by weight: active constituents of medicine 30%-90%, dispersant 4.5%, wetting agent 2%, disintegrant 1.25%, filler surplus.More preferably be made up of the component of following percentage by weight: active constituents of medicine 60%-87%, dispersant 4.5%, wetting agent 2%, disintegrant 1.25%, filler surplus.
Water dispersible granules preparation method is: cyproconazole, oxime bacterium ester, dispersant, wetting agent, disintegrant, filler are mixed in mixer, after airslide disintegrating mill is crushed to particle diameter 20-40 μm, mix again, mediate amount of water 20-30%, carry out extruder grain, 40-50 DEG C of oven dry, namely can be made into oxime bacterium ester cyproconazole water dispersible granules product.
Described dispersant be calcium lignosulfonate, maleic acid-acrylic acid copolymer salt, polyox-yethylene-polyoxypropylene block copolymer, alkylphenol sodium sulfonate, alkyl naphthalene sulfonic acid formaldehyde condensation products sodium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, ethylene oxide-propylene oxide block copolymer and polycarboxylate sodium one or more.Preferred dispersants by polycarboxylate sodium and calcium lignosulfonate in mass ratio 2:1 mix.
Described wetting agent is selected from: one or more in lauryl sodium sulfate, a-sulfo methyl ester, sodium tetradecyl sulfate, neopelex, Negel, a-alkene sulfonic acid sodium, alkyl phenol polyethenoxy ether sodium sulfate, sodium lignin sulfonate, Nekal BX, fatty acid sulfates and fatty acid ester sulphate, preferred wetting agent by lauryl sodium sulfate and sodium lignin sulfonate in mass ratio 1:1 mix.
Described disintegrant is selected from: one or more in potassium sulfate, sodium cellulose glycolate, potassium chloride, diammonium hydrogen phosphate, urea, sodium sulphate, ammonium sulfate, ammonium nitrate, calcium chloride and sodium chloride, preferred disintegrant by ammonium sulfate and urea in mass ratio for 1.5:1 mixes.
Described filler is selected from: one or more in kaolin, bentonite, talcum powder, attapulgite, diatomite, white carbon, starch, precipitated calcium carbonate, and preferred filler is white carbon.
When composition makes suspending agent, take water as solvent, each constituent content is: active constituents of medicine 50-600g/L, dispersant 20-100g/L, wetting agent 10-100g/L, defoamer 1-10g/L, thickening stabilizing agent 1-20g/L, antifreeze 1-80g/L, water are surplus.Preferred each constituent content is: active constituents of medicine 50-600g/L, dispersant 50g/L, wetting agent 10g/L, defoamer 5g/L, thickening stabilizing agent 2.5g/L, antifreeze 50g/L, water are surplus.More preferably each constituent content is: active constituents of medicine 100-550g/L, dispersant 50g/L, wetting agent 10g/L, defoamer 5g/L, thickening stabilizing agent 2.5g/L, antifreeze 50g/L, water are surplus.
Suspending agent preparation method is: dispersant, wetting agent, defoamer, thickening stabilizing agent, antifreeze, water in above-mentioned formula are mixed through high speed shear, add cyproconazole, oxime bacterium ester, ball milling 2-3 hour in ball mill, make diameter of particle all below 5 μm, obtained oxime bacterium ester cyproconazole suspending agent product.
Described dispersant be calcium lignosulfonate, maleic acid-acrylic acid copolymer salt, polyox-yethylene-polyoxypropylene block copolymer, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, ethylene oxide-propylene oxide block copolymer and polycarboxylate sodium one or more.Preferred dispersants by naphthalene sulfonic acid-formaldehyde condensation product sodium salt, polycarboxylate sodium and calcium lignosulfonate in mass ratio 1:3:1 mix.
Described wetting agent is selected from: one or more in lauryl sodium sulfate, sodium tetradecyl sulfate, neopelex, Negel, sodium lignin sulfonate and Nekal BX, and preferred wetting agent is lauryl sodium sulfate.
Described defoamer is selected from: silicone oil, silicone compound, C
10-20saturated fat acid compounds, C
8-10one or more in aliphatic alcohols compound, preferred defoamer is silicone compound.
Described thickening stabilizing agent is selected from: one or more in xanthans, aluminium-magnesium silicate, gum Arabic and polyvinyl alcohol, and preferred thickening stabilizing agent is aluminium-magnesium silicate: xanthans is in mass ratio for 1.5:1 mixes.
Described antifreeze is selected from: one or more in ethylene glycol, propane diols and glycerine, and preferred antifreeze is ethylene glycol.
Composition of the present invention is mainly used in preventing and treating the disease in vegetables, fruit tree, the powdery mildew especially in fruit and vegetables, scab and spot defoliation.
Beneficial effect of the present invention: (1) present composition effective active composition oxime bacterium ester and cyproconazole belong to the bactericide of two kinds of different mechanisms of action, and both can not produce conflict at mutual mixture, and expand fungicidal spectrum, improves germicidal efficiency; (2) present composition has good synergistic effect within the specific limits, and preventive effect is higher than single dose, and dosage is little, avoids the pesticide resistance of disease, extends the medicine lasting period, is beneficial to environment sustainable development; (3) present composition can be made into suspending agent and water dispersible granules, and the selection of auxiliary material and formulation improves drug effect; (4) present composition has special efficacy to the powdery mildew on vegetables, fruit tree, scab, spot defoliation.
Embodiment
Below in conjunction with embodiment to further instruction of the present invention, but the present invention is not limited thereto.If no special instructions, the percentage in following embodiment is all weight percentage.
The embodiment of the present invention is the method adopting Toxicity Determination and field trial to combine.First pass through Toxicity Determination, synergy ratio (SR) after clear and definite two kinds of medicaments are composite by a certain percentage, SR < 0.5 is antagonism, 0.5≤SR≤1.5 are summation action, SR > 1.5 is synergistic effect, on this basis, then carry out field trial.
oxime bacterium ester and cyproconazole composite to powdery mildew of cucumber Toxicity Determination
Test medicine provides by Shandong Weifang Rainbow Chemical Co., Ltd..
Determine that after the effective inhibition concentration scope of each medicament, each medicament establishes 7 dosage process respectively by active constituent content through prerun, if clear water contrast.Carry out with reference to " farm-chemical indoor determination test rule bactericide ", adopt mycelial growth rate method to measure medicament to the virulence of powdery mildew of cucumber.Measure colony diameter by right-angled intersection method after 72h, calculate each process net growth, mycelial growth inhibition rate.
Net growth (mm)=measurement colony diameter-5
Mycelial growth inhibition rate is converted into probit value (y), liquor strength (μ g/mL) converts logarithm value (x) to, try to achieve virulence regression equation (y=a+bx) with method of least squares, and calculate the EC50 value of often kind of medicament thus.Calculate two medicament different ratio synergies ratio (SR) according to Wadley method, SR < 0.5 is antagonism, and 0.5≤SR≤1.5 are summation action simultaneously, and SR > 1.5 is synergistic effect.Computing formula is as follows:
Wherein: a, b are respectively oxime bacterium ester and the ratio of cyproconazole shared by combination, and A is oxime bacterium ester, and B is cyproconazole.
Result of the test is as shown in table 1:
As shown in Table 1, oxime bacterium ester, cyproconazole are to the EC of powdery mildew of cucumber
50be respectively 1.79mg/L and 32.41mg/L.The virulence of oxime bacterium ester is apparently higher than the virulence of cyproconazole.Oxime bacterium ester and cyproconazole mixture within the scope of 1:1-10:1 all shows obvious synergistic effect, and wherein, both mixed synergies within the scope of 1:1-5:1 are ideal.
Lower mask body enumerates representative embodiment of the present invention.
embodiment 186% oxime bacterium ester cyproconazole water dispersible granules
Formula is: oxime bacterium ester 43%, cyproconazole 43%, polycarboxylate sodium 3%, calcium lignosulfonate 1.5%, lauryl sodium sulfate 1%, sodium lignin sulfonate 1%, and ammonium sulfate 0.75%, urea 0.5%, white carbon add to 100%.
Preparation method is: cyproconazole, oxime bacterium ester, dispersant, wetting agent, disintegrant, filler are mixed in mixer, after airslide disintegrating mill is crushed to particle diameter 20-40 μm, mix again, mediate amount of water 20-30%, carry out extruder grain, 40-50 DEG C of oven dry, namely can be made into 86% water dispersible granules.
embodiment 287% oxime bacterium ester cyproconazole water dispersible granules
Formula is: oxime bacterium ester 62%, cyproconazole 25%, polycarboxylate sodium 3%, calcium lignosulfonate 1.5%, lauryl sodium sulfate 1%, sodium lignin sulfonate 1%, and ammonium sulfate 0.75%, urea 0.5%, white carbon add to 100%.Preparation method is with embodiment 1.
embodiment 384% oxime bacterium ester cyproconazole water dispersible granules
Formula is: oxime bacterium ester 70%, cyproconazole 14%, polycarboxylate sodium 3%, calcium lignosulfonate 1.5%, lauryl sodium sulfate 1%, sodium lignin sulfonate 1%, and ammonium sulfate 0.75%, urea 0.5%, white carbon add to 100%.Preparation method is with embodiment 1.
embodiment 485.8% oxime bacterium ester cyproconazole water dispersible granules
Formula is: oxime bacterium ester 78%, cyproconazole 7.8%, polycarboxylate sodium 3%, calcium lignosulfonate 1.5%, lauryl sodium sulfate 1%, sodium lignin sulfonate 1%, and ammonium sulfate 0.75%, urea 0.5%, white carbon add to 100%.Preparation method is with embodiment 1.
embodiment 572% oxime bacterium ester cyproconazole water dispersible granules
Formula is: oxime bacterium ester 36%, cyproconazole 36%, maleic acid-acrylic acid copolymer salt 5%, Nekal BX 3%, and ammonium sulfate 15%, sodium sulphate 5%, starch add to 100%.Preparation method is with embodiment 1.
embodiment 634.8% oxime bacterium ester cyproconazole water dispersible granules
Formula is: oxime bacterium ester 24.8%, cyproconazole 10%, polycarboxylate sodium 5%, ethylene oxide-propylene oxide block copolymer 3%, sodium tetradecyl sulfate 1%, sodium lignin sulfonate 1%, calcium chloride 28%, precipitated calcium carbonate add to 100%.Preparation method is with embodiment 1.
embodiment 762.4% oxime bacterium ester cyproconazole water dispersible granules
Formula is: oxime bacterium ester 52%, cyproconazole 10.4%, alkylphenol sodium sulfonate 8%, calcium lignosulfonate 1.5%, lauryl sodium sulfate 1%, sodium lignin sulfonate 1%, and potassium sulfate 15%, urea 7%, sodium cellulose glycolate 5%, bentonite add to 100%.Preparation method is with embodiment 1.
embodiment 836% oxime bacterium ester cyproconazole water dispersible granules
Formula is: oxime bacterium ester 33%, cyproconazole 3%, polycarboxylate sodium 4%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 1.5%, ethylene oxide-propylene oxide block copolymer 2%, lauryl sodium sulfate 1%, a-alkene sulfonic acid sodium 2%, sodium chloride 21%, talcum powder add to 100%.Preparation method is with embodiment 1.
embodiment 9100g/L oxime bacterium ester cyproconazole suspending agent
Formula is: oxime bacterium ester 50g/L, cyproconazole 50g/L, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 10g/L, polycarboxylate sodium 30g/L, calcium lignosulfonate 10g/L, lauryl sodium sulfate 10g/L, ethylene glycol 50g/L, silicone compound 5g/L, aluminium-magnesium silicate 1.5g/L, xanthans 1g/L, water makes surplus.
Preparation method is: by dispersant in above-mentioned formula, wetting agent, defoamer, thickening stabilizing agent, antifreeze,
water,mix through high speed shear, add cyproconazole, oxime bacterium ester, ball milling 2-3 hour in ball mill, make diameter of particle all below 5 μm, to obtain final product.
embodiment 10535g/L oxime bacterium ester cyproconazole suspending agent
Formula is: oxime bacterium ester 375g/L, cyproconazole 160g/L, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 10g/L, polycarboxylate sodium 30g/L, calcium lignosulfonate 10g/L, lauryl sodium sulfate 10g/L, ethylene glycol 50g/L, silicone compound 5g/L, aluminium-magnesium silicate 1.5g/L, xanthans 1g/L, water makes surplus.Preparation method is with embodiment 9.
embodiment 11120g/L oxime bacterium ester cyproconazole suspending agent
Formula is: oxime bacterium ester 100g/L, cyproconazole 20g/L, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 10g/L, polycarboxylate sodium 30g/L, calcium lignosulfonate 10g/L, lauryl sodium sulfate 10g/L, ethylene glycol 50g/L, silicone compound 5g/L, aluminium-magnesium silicate 1.5g/L, xanthans 1g/L, water makes surplus.Preparation method is with embodiment 9.
embodiment 12132g/L oxime bacterium ester cyproconazole suspending agent
Formula is: oxime bacterium ester 120g/L, cyproconazole 12g/L, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 10g/L, polycarboxylate sodium 30g/L, calcium lignosulfonate 10g/L, lauryl sodium sulfate 10g/L, ethylene glycol 50g/L, silicone compound 5g/L, aluminium-magnesium silicate 1.5g/L, xanthans 1g/L, water makes surplus.Preparation method is with embodiment 9.
embodiment 13420g/L oxime bacterium ester cyproconazole suspending agent
Formula is: oxime bacterium ester 210g/L, cyproconazole 210g/L, maleic acid-acrylic acid copolymer salt 10g/L, polycarboxylate sodium 30g/L, calcium lignosulfonate 10g/L, neopelex 10g/L, glycerine 50g/L, C
10-20saturated fat acid compounds 5g/L, gum Arabic 1g/L, water makes surplus.Preparation method is with embodiment 9.
embodiment 14348g/L oxime bacterium ester cyproconazole suspending agent
Formula is: oxime bacterium ester 248g/L, cyproconazole 100g/L, polyox-yethylene-polyoxypropylene block copolymer 50g/L, calcium lignosulfonate 10g/L, lauryl sodium sulfate 10g/L, propane diols 50g/L, silicone compound 5g/L, aluminium-magnesium silicate 1.5g/L, polyvinyl alcohol 1g/L, water makes surplus.Preparation method is with embodiment 9.
embodiment 15240g/L oxime bacterium ester cyproconazole suspending agent
Formula is: oxime bacterium ester 200g/L, cyproconazole 40g/L, polycarboxylate sodium 30g/L, calcium lignosulfonate 20g/L, sodium tetradecyl sulfate 10g/L, ethylene glycol 50g/L, silicone compound 5g/L, aluminium-magnesium silicate 5g/L, water makes surplus.Preparation method is with embodiment 9.
embodiment 1666g/L oxime bacterium ester cyproconazole suspending agent
Formula is: oxime bacterium ester 60g/L, cyproconazole 6g/L, calcium lignosulfonate 60g/L, Negel 0.3g/L, sodium lignin sulfonate 0.3g/L, Nekal BX 0.4g/L, propane diols 50g/L, silicone compound 5g/L, xanthans 2g/L, water makes surplus.Preparation method is with embodiment 9.
The oxime bacterium ester prepare above-described embodiment and cyproconazole complex preparation constant product quality are tested, and the results are shown in following table 2 and table 3.
Known by table 2,3, in embodiment 5,6,7,8,13,14,15,16, after heat storage, quality occurs obviously to be deteriorated, do not meet product quality requirement, and use the embodiment 1,2,3,4,9,10,11,12 of preferred promoter before heat storage and after heat storage, quality is all good, and preferred promoter plays key effect in product quality.
The oxime bacterium ester prepare above-described embodiment and cyproconazole complex preparation are prevented and treated apple mildew situation and are carried out the test of pesticide effectiveness.This experimental establishment is carried out in this locality, and contrast medicament is 50% trifloxystrobin water dispersible granule (commercial), 40% cyproconazole suspending agent (commercial).
In apple mildew their early stage spray pesticide, dispenser in every 7 days once, is total to dispenser 3 times.Within 7 days, investigate disease index before dispenser with after third time dispenser, finally calculate preventive effect.Experimental result is as follows:
As can be seen from Table 4, oxime bacterium ester and cyproconazole composite after effectively can prevent and treat apple mildew, control efficiency be all better than contrast medicament, test scope of medication in target crop is had no adverse effects.The embodiment preventive effect of preferred promoter is used will to be obviously better than other embodiments, and more than 90% is reached to apple mildew preventive effect, also find in process of the test, oxime bacterium ester and cyproconazole compound drug also show excellent control efficiency to alternaria leaf spot of apple, embodiment 2 and 10 preventive effect is more than 95%, and other embodiment preventive effects are at 70-80%.
The oxime bacterium ester prepare above-described embodiment and cyproconazole complex preparation are prevented and treated banana freckle situation and are carried out the test of pesticide effectiveness, this experimental establishment is in Pubei County, Guangxi, and contrast medicament is 50% trifloxystrobin water dispersible granule (commercial), 40% cyproconazole suspending agent (commercial).
In banana freckle their early stage spray pesticide, dispenser in every 7 days once, is total to dispenser 3 times, and within 7 days, investigate disease index before dispenser with after third time dispenser, finally calculate preventive effect, result of the test is as follows:
As can be seen from Table 5, oxime bacterium ester and cyproconazole composite after effectively can prevent and treat the generation of banana freckle, control efficiency is all better than contrasting medicament, and dosage is low, has no adverse effects in this test scope of medication to target crop.In addition, the preventive effect of other embodiments, about 80%, is also better than contrasting medicament.
The oxime bacterium ester prepared above-described embodiment, cyproconazole complex preparation are prevented and treated powdery mildew of cucumber situation and are carried out the test of pesticide effectiveness.This experimental establishment is carried out in locality, and contrast medicament is 50% trifloxystrobin water dispersible granule (commercial), 40% cyproconazole suspending agent (commercial).
In powdery mildew of cucumber their early stage spray pesticide, once, dispenser 3 times altogether, investigates disease index in 7 days before dispenser with after third time dispenser, finally calculates preventive effect in dispenser in every 7 days.Experimental result is as follows:
As can be seen from Table 6, oxime bacterium ester and cyproconazole composite after effectively can prevent and treat the generation of powdery mildew of cucumber, control efficiency is all better than contrasting medicament, has no adverse effects in this test scope of medication to target crop.In addition, the preventive effect of other embodiments, about 80%, is also better than contrasting medicament.