Summary of the invention
The object of this invention is to provide a kind of synergistic effect obvious, to the bactericidal composition that powdery mildew control efficiency is good, cost is low, resistance risk is low.
Another object of the present invention is to provide the application of this bactericidal composition.
Inventor by a large amount of indoor biometricses and field control effectiveness test, finds Pyriofenone and oxime bacterium ester or kresoxim-methyl in certain proportion after mixture unexpectedly, has significant synergistic effect to diseases such as powdery mildews.
Described oxime bacterium ester: English common name trifloxystrobin.Chemical name: (2Z)-2-methoxyimino-2-[2-[[1-[3-(trifluoromethyl) phenyl] ethyleneimino] oxygen methyl] phenyl] methyl acetate, molecular formula: C
20h
19f
3n
2o
4, a kind of methoxy acrylic bactericide developed by Bayer A.G.Oxime bacterium ester all has good activity 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.
Described kresoxim-methyl: English common name kresoxim-methyl, chemical name (E)-2-methoxyimino-[2-(o-methyl-benzene oxygen ylmethyl) phenyl] methyl acetate.Molecular formula: C
18h
19nO
4.Kresoxim-methyl is that the one developed by BASF Aktiengesellschaft is efficient, wide spectrum methoxy acrylic bactericide; have good protection and therapeutic action, the lasting period is long, with other conventional bactericide without cross resistance; to crop, people and animals and beneficial organism safety, substantially pollution-free to environment.
Oxime bacterium ester and kresoxim-methyl are bactericide well known in the art, can be obtained by various commercial channel.
For overcoming the deficiencies in the prior art, technical scheme of the present invention solves like this: a kind of bactericidal composition, containing active ingredient Pyriofenone (A) and oxime bacterium ester or kresoxim-methyl (B), A and B mass ratio is 1 ︰ 100 ~ 100 ︰ 1, and preferred proportion is 1:30 ~ 30:1.
The active ingredient of said composition and auxiliary agent and filler can be processed into any formulation agriculturally allowed, and good formulation has missible oil, microemulsion, aqueous emulsion, suspending agent, wetting powder, water dispersible granules.
In bactericidal composition of the present invention, the mass accumulation percentage composition of A and B is 5% ~ 85%.
The formulation of above-mentioned bactericidal composition except comprising effective constituents A and B, also comprise auxiliary agent and other contribute to drug effect play material.Missible oil comprises organic solvent, cosolvent and emulsifier; Microemulsion comprises organic solvent, emulsifier and water; Aqueous emulsion comprises organic solvent, dispersant, emulsifier and water; Suspending agent comprises water, dispersant, thickener, antifreezing agent and wetting agent; Wetting powder comprises wetting agent, dispersant and filler; Water dispersible granules comprises dispersant, disintegrant, filler and wetting agent.Below be all various compositions that are conventional in pesticidal preparations or permission use, be not particularly limited, concrete composition and consumption are determined by simple experiment according to recipe requirements.Such as:
Organic solvent can select in isopropyl alcohol, dimethylbenzene, DMF, ring ethyl ketone, toluene, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, trimethyl cyclic ethylene ketone, NOP, 1-METHYLPYRROLIDONE, propyl alcohol, butanols, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, butyl ether, ethyl acetate, vegetable oil one or more.
Cosolvent can select in 1-METHYLPYRROLIDONE, dimethyl formamide, ethanol, the third ethanol, acetone one or more.
Dispersant can be selected sodium lignin sulfonate, calcium lignosulfonate, pulls open powder, one or more in calcium dodecyl benzene sulfonate, polycarboxylate, alkyl benzene sulfonate calcium salt, alkylphenol polyoxyethylene, aliphatic amine polyoxyethylene ether, polyoxyethylene carboxylate, fatty acid glyceride APEO.
Emulsifier can select agricultural emulsifier NO.600 (phenyl phenol polyoxyethyl ether), agriculture breast No. 1601 (phenethyl phenol polyoxyethanyl polypropylene-base ether), agriculture breast No. 500 (alkyl benzene calcium sulfonate), OP series phosphate (thermally coupled distillation columns), No. 600 phosphates (phenyl phenol polyoxyethanyl ether phosphate), styrene polyoxyethylene rice ammonium sulfate, alkyl biphenyl ether disulfonic acid magnesium salts, triethanolamine salt, agriculture breast No. 400 (benzyl xylenol polyoxyethyl ether), Nongru-700 number (alkyl phenolic resin polyoxyethyl ether), peaceful newborn No. 36 (phenethyl fluosite polyoxyethyl ether), agriculture breast No. 1600 (phenethyl phenol polyoxyethanyl polypropylene-base ether), ethylene oxide-propylene oxide block copolymer, OP series (polyoxyethylene nonylphenol ether), agriculture breast No. 33 (alkylaryl polyoxyethylene polyoxypropylene ether), agriculture breast No. 34 (alkylaryl polyoxyethylene poly-oxygen propylene aether), Span series (sorbitan monostearate), TWEEN Series (sorbitan fatty acid ester APEO), one or more in AEO series (fat alcohol alcohol APEO).
Antifreezing agent can select in glycerine, urea, ethylene glycol, propane diols one or more.
Wetting agent can select that methyl naphthalene sulfonate formaldehyde condensate, lauryl sodium sulfate, Negel, alkyl benzene calcium sulfonate, tea are withered, spaonin powder, silkworm excrement, soapberry powder, bay alcohol radical sodium sulphate, washing powder, pull open in powder one or more.
Disintegrant can select in ammonium sulfate, urea, bentonite, aluminium chloride, citric acid, succinic acid, sodium bicarbonate one or more.
Thickener can to select in xanthans, CMC, methylcellulose, Magnesiumaluminumsilicate, polyvinyl alcohol one or more.
Filler can select in White Carbon black, ridge soil, precipitated calcium carbonate, talcum, imvite or convex-concave rod stone, float stone, brickbat, sepiolite or bentonite and non-adsorbent calcium soil or sand one or more.
Product described in the invention can finished product preparation form provide, and namely in composition, each material mixes, and the composition of composition also can provide with unit dose form, directly directly mixes in bucket or tank, be then diluted to required concentration before using.
Bactericidal composition of the present invention can be used for preventing and treating on the crop such as cucumber, watermelon, pumpkin, muskmelon, joint melon, bottle gourd, balsam pear, sponge gourd, wax gourd, Hami melon, strawberry, capsicum, Chinese cabbage, eggplant, potato, cucumber by fungus-caused plant diseases such as imperfect fungus, sac fungi, basidiomycetes, be particularly useful for preventing and treating powdery mildew.
Compared with prior art, its advantage is in the present invention: 1, composition synergistic effect is obvious, and preventive effect significantly improves compared with single dose; 2, after drug effect improves, the effective ingredient consumption in field declines, and reduces production and use cost, decreases residue of pesticide and environmental pollution; 3, composition is made up of the active ingredient of different mechanism of action, and action site increases, and is conducive to overcoming and delay the drug-fast generation of germ.
Embodiment
Being undertaken composite by the pesticide active ingredient of different types of structure, is a kind of effective means solving the problem such as cost and resistance in agricultural chemicals single dose application process at present.After the pesticide active ingredient mixing of different types of structure, usually show three kinds of type of action, i.e. summation action, synergistic effect and antagonism, but be specially which kind of effect, unpredictable, only have and just can be known by lot of experiments.Compound synergic is well filled a prescription, and can improve actual control efficiency, and reduce the usage amount of agricultural chemicals, contributing to the generation of delaying drug resistance, is the important means of scientific prevention and cure damage by disease and insect.
The present composition has obvious synergistic function to Powdery Mildew etc., and is not only the simple addition of two kinds of pharmacy effects, is clear that very much this result can tested from following toxicity test.
Biologicall test example 1: composition is to the Toxicity Determination of cucurbits powdery mildew bacterium
Subjects is cucumber powdery mildew's pathogen (Sphaerothecafuliginea).
Test method: with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1156.11-2008 ".Choose the potted plant two panels leaf period cucumber seedling that growth potential is consistent, 5 basins are selected in each process, number for subsequent use.Spray under 50PSI pressure with Potter spray tower, every basin 5mL.Test process is see table 1, table 2, table 3, and each medicament arranges 5 concentration gradients.Carrying out inoculum density after 24h is 3 × 10
5the cucumber powdery mildew's pathogen conidial suspension of individual spore/mL.To spray the cucumber seedling of equivalent clear water for blank.After inoculation, cucumber seedling is put into greenhouse to cultivate.After 10d, according to the morbidity grade scale investigation disease index of powdery mildew of cucumber, and calculate control efficiency.
Powdery mildew of cucumber severity Scaling standard:
0 grade: blade is without scab;
1 grade: lesion area accounts for less than 5% of whole blade area;
3 grades: lesion area accounts for 6% ~ 10% of whole blade area;
5 grades: lesion area accounts for 11% ~ 25% of whole blade area;
7 grades: lesion area accounts for 25% ~ 50% of whole blade area;
9 grades: lesion area accounts for more than 50% of whole blade area.
The expection effect (i.e. theoretical control efficiency, %) of mixture of active principles uses Colby formula to determine and compares with the effect observed:
Colby formula: E=X+Y-X*Y/100
E: when active components A working concentration in composition is a, compositions contemplated effect when active component B working concentration is b.
X: effect when active components A using dosage is a.
Effect when Y: active component B using dosage is b.
Illustrate that mixture has synergistic effect when the actual control efficiency observed exceedes expection preventive effect.
Toxicity test result see table 1 to table 3.
The independent reactive compound of table 1 is to the pot experiment measurement result of powdery mildew of cucumber
Table 2Pyriofenone and the composite pot experiment measurement result to powdery mildew of cucumber of oxime bacterium ester
Table 3Pyriofenone and the composite pot experiment measurement result to powdery mildew of cucumber of kresoxim-methyl
Result of the test shows, Pyriofenone and oxime bacterium ester or kresoxim-methyl is composite within the specific limits prevents and treats powdery mildew of cucumber, has synergistic effect.
In order to make object of the present invention, technical scheme and advantage clearly understand, the following concrete formulation examples of the present invention is described, but the present invention is limited to absolutely not these examples.The following stated is only the good embodiment of the present invention, only in order to explain the present invention, therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that all any amendments done within the spirit and principles in the present invention, equivalent 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 claims.
Missible oil embodiment
Pesticide activity component, emulsifier, partial solvent are mixed in proportion, mix and blend in modulation kettle, until completely dissolved, more remaining solvent is added lentamente, obtain uniform oil phase after fully stirring, make missible oil product.
Embodiment 1,20.2%Pyriofenone oxime bacterium emulsifiable concentrate
Pyriofenone20%, oxime bacterium ester 0.2%, agriculture breast No. 500 2% (emulsifier), dimethylbenzene (solvent) are supplemented to 100%.
Embodiment 2,20.2%Pyriofenone kresoxim-methyl missible oil
Pyriofenone20%, kresoxim-methyl 0.2%, agriculture breast No. 500 2% (emulsifier), toluene (solvent) are supplemented to 100%.
Embodiment 3,15.5%Pyriofenone oxime bacterium emulsifiable concentrate
Pyriofenone15%, oxime bacterium ester 0.5%, agriculture breast No. 500 3% (emulsifier), dimethylbenzene (solvent) are supplemented to 100%.
Embodiment 4,15.5%Pyriofenone kresoxim-methyl missible oil
Pyriofenone15%, kresoxim-methyl 0.5%, agriculture breast No. 500 3% (emulsifier), toluene (solvent) are supplemented to 100%.
Microemulsion, aqueous emulsion embodiment
By each component proportion, active component is dissolved in solvent and cosolvent, adds surfactant, mix obtained oil phase.By water-soluble component and the obtained aqueous phase of water mixing, then add in aqueous phase by oil phase or aqueous phase adds in oil phase, limit edged stirs, obtained microemulsion or aqueous emulsion.
Embodiment 5,5%Pyriofenone oxime bacterium ester microemulsion
Pyriofenone2.5%, oxime bacterium ester 2.5%, toluene 8% (solvent), agriculture breast No. 500 8% (emulsifier), agricultural emulsifier NO.600s 5% (emulsifier), agriculture breast No. 1,600 5% (emulsifier), sldium lauryl sulfate 2% (wetting agent), ethylene glycol 5% (antifreezing agent), water are supplemented to 100%
Embodiment 6,5%Pyriofenone kresoxim-methyl microemulsion
Pyriofenone3%, kresoxim-methyl 2%, dimethylbenzene 8% (solvent), agriculture breast No. 500 8% (emulsifier), agricultural emulsifier NO.600s 5% (emulsifier), agriculture breast No. 1,600 5% (emulsifier), sldium lauryl sulfate 2% (wetting agent), ethylene glycol 5% (antifreezing agent), water are supplemented to 100%
Embodiment 7,15%Pyriofenone trifloxystrobin water emulsion
Pyriofenone5%, oxime bacterium ester 10%, DMF (solvent) 5%, cyclohexanol (solvent) 10%, glycerine (antifreezing agent) 5%, phenethyl phenol polyethenoxy ether (emulsifier) 10%, calcium dodecyl benzene sulfonate (wetting agent) 5%, water are supplemented to 100%
Embodiment 8,15%Pyriofenone kresoxim-methyl aqueous emulsion
Pyriofenone3%, kresoxim-methyl 12%, DMF (solvent) 5%, cyclohexanol (solvent) 10%, glycerine (antifreezing agent) 5%, phenethyl phenol polyethenoxy ether (emulsifier) 10%, calcium dodecyl benzene sulfonate (wetting agent) 5%, water are supplemented to 100%
Suspending agent embodiment
The ratio of each components such as active component, dispersant, defoamer, thickener and water in formula is mixed, after sand milling or high speed shear, obtains semi-finished product, add water after analysis and mix filtration and namely obtain suspending agent.Embodiment 9,31%Pyriofenone oxime bacterium ester suspending agent
Pyriofenone1%, oxime bacterium ester 30%, polyoxyethylene nonylphenol ether 8% (emulsifier), propane diols 2% (cosolvent), xanthans 1% (thickener), organosilicon 2% (defoamer), water are supplemented to 100%
Embodiment 10,31%Pyriofenone kresoxim-methyl suspending agent
Pyriofenone1%, kresoxim-methyl 30%, polyoxyethylene nonylphenol ether 8% (emulsifier), propane diols 2% (cosolvent), xanthans 1% (thickener), organosilicon 2% (defoamer), water are supplemented to 100%
Embodiment 11,30.3%Pyriofenone oxime bacterium ester suspending agent
Pyriofenone0.3%, oxime bacterium ester 30%, polyoxyethylene nonylphenol ether 8% (emulsifier), propane diols 2% (cosolvent), xanthans 1% (thickener), organosilicon 2% (defoamer), water is supplemented to 100% embodiment 12, 30.3%Pyriofenone kresoxim-methyl suspending agent Pyriofenone0.3%, kresoxim-methyl 30%, polyoxyethylene nonylphenol ether 8% (emulsifier), propane diols 2% (cosolvent), xanthans 1% (thickener), organosilicon 2% (defoamer), water is supplemented to 100%
Water dispersible granules embodiment
Pesticide activity component, auxiliary agent and filler are mixed in proportion, through air-flow crushing, then adds the water of 15-20%, obtain water dispersible granules product through kneading, granulation, drying, screening.Capital equipment: mixer, airslide disintegrating mill, kneader, Squeezinggranulator, drying equipment (drying room or fluid bed).
Embodiment 13,85%Pyriofenone trifloxystrobin water dispersible granule
Pyriofenone50%, oxime bacterium ester 35%, neopelex 4% (wetting agent), sodium lignin sulfonate 10% (dispersant), ammonium sulfate 3% (disintegrant), kaolin (filler) are to 100%
Embodiment 14,85%Pyriofenone water dispersion granules agent of Kresoxim
Pyriofenone60%, kresoxim-methyl 25%, neopelex 4% (wetting agent), sodium lignin sulfonate 10% (dispersant), ammonium sulfate 3% (disintegrant), White Carbon black (filler) are to 100%
Wetting powder embodiment
Pesticide activity component, auxiliary agent, filler are mixed in proportion after air-flow crushing, mixes obtained wetting powder again.Capital equipment: mixer, airslide disintegrating mill.
Embodiment 15,50%Pyriofenone oxime bacterium ester wetting powder
Pyriofenone15%, oxime bacterium ester 35%, bay alcohol radical sodium sulphate 4% (wetting agent), mersolates 7% (dispersant), white carbon 8% (filler), kaolin (filler) are to 100%
Embodiment 16,50%Pyriofenone kresoxim-methyl wetting powder
Pyriofenone20%, kresoxim-methyl 30%, bay alcohol radical sodium sulphate 4% (wetting agent), mersolates 7% (dispersant), white carbon 8% (filler), kaolin (filler) are to 100%
Embodiment 17,35%Pyriofenone oxime bacterium ester wetting powder
Pyriofenone25%, oxime bacterium ester 10%, bay alcohol radical sodium sulphate 4% (wetting agent), mersolates 7% (dispersant), white carbon 8% (filler), kaolin (filler) are to 100%
Embodiment 18,35%Pyriofenone kresoxim-methyl wetting powder
Pyriofenone30%, kresoxim-methyl 5%, bay alcohol radical sodium sulphate 4% (wetting agent), mersolates 7% (dispersant), white carbon 8% (filler), kaolin (filler) are to 100%
Field information example 1:Pyriofenone and the composite field control effectiveness test to powdery mildew of cucumber of oxime bacterium ester
Yangjiang, test site Guangdong.Test medicine and consumption, in table 4, often process 4 communities and repeat, each plot area 20 square metres.Carry out first time dispenser at disease initial stage of origination, even spraying, be sprayed onto till blade drips, be treated to blank with clear water.Second time medicine is executed after 7 days.The incidence of 7 days investigation powderys mildew of cucumber before first time medicine and after second time medicine.Every community adopts 5 samplings, often some investigation two strains, and all blades are investigated in every strain, and the percentage accounting for whole leaf area with lesion area carrys out classification record.Calculate each process disease index and control efficiency.
Grade scale:
0 grade: without scab;
1 grade: lesion area accounts for less than 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 50% of whole leaf area.
Drug effect computational methods:
As can be seen from Table 4: Pyriofenone, the preventive effect of oxime bacterium ester single dose to powdery mildew of cucumber are respectively 76.3%, 74.3%, and embodiment of the present invention bactericidal composition is all significantly increased in preventive effect, and minimum preventive effect is 84.7%, has been up to 89.6%.The result of field trial fully shows, Pyriofenone and oxime bacterium ester is composite has significant synergistic function to powdery mildew of cucumber afterwards, and when mu effective ingredient consumption reduces compared with single dose, control efficiency significantly improves.Therefore, the present composition have reduce costs, the beneficial effect of delaying drug resistance, minimizing spraying times and residue of pesticide.
Table 4Pyriofenone and the composite field test results to powdery mildew of cucumber of oxime bacterium ester
Field information example 2:Pyriofenone and the composite field control effectiveness test to powdery mildew of cucumber of kresoxim-methyl
Test site yueyang, hunan.Test medicine and consumption, in table 5, often process 4 communities and repeat, each plot area 20 square metres.Carry out first time dispenser at disease initial stage of origination, even spraying, be sprayed onto till blade drips, be treated to blank with clear water.Second time medicine is executed after 7 days.The incidence of 7 days investigation powderys mildew of cucumber before first time medicine and after second time medicine.Every community adopts 5 samplings, often some investigation two strains, and all blades are investigated in every strain, and the percentage accounting for whole leaf area with lesion area carrys out classification record.Calculate each process disease index and control efficiency.
Grade scale and drug effect computational methods are with Field information example 1.
As can be seen from Table 5: Pyriofenone, the preventive effect of kresoxim-methyl single dose to powdery mildew of cucumber are respectively 79.5%, 77.1%, and embodiment of the present invention bactericidal composition is all significantly increased in preventive effect, and minimum preventive effect is 87.2%, has been up to 91.8%.The result of field trial fully shows, Pyriofenone and kresoxim-methyl is composite has significant synergistic function to powdery mildew of cucumber afterwards, and when mu effective ingredient consumption reduces compared with single dose, control efficiency significantly improves.Therefore, the present composition have reduce costs, the beneficial effect of delaying drug resistance, minimizing spraying times and residue of pesticide.
Table 5Pyriofenone and the composite field test results to powdery mildew of cucumber of kresoxim-methyl