CN102246791A - Compounded pesticide sterilizing composition - Google Patents
Compounded pesticide sterilizing composition Download PDFInfo
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- CN102246791A CN102246791A CN2011101915019A CN201110191501A CN102246791A CN 102246791 A CN102246791 A CN 102246791A CN 2011101915019 A CN2011101915019 A CN 2011101915019A CN 201110191501 A CN201110191501 A CN 201110191501A CN 102246791 A CN102246791 A CN 102246791A
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Abstract
The invention relates to a sterilizing composition in the field of pesticide compounding. An effective component bixafen of the sterilizing composition is subjected to two-element mixing with a few kinds of ergosterol synthetic inhibitor compounds; the weight percentage proportion of the two effective components is (80:1)-(1:80), preferably (1-40):(50-1); the total weight percentage of the effective components in the sterilizing composition is 1-90 percent, preferably 5-55 percent; and the rest in the sterilizing composition is auxiliary components which are allowed to be used and are acceptable in pesticide. By using the known method, the sterilizing composition can be prepared into wettable powder, emulsifiable solution, suspending agent, water dispersible granules, water emulsion or microemulsion.
Description
Technical field
The present invention relates to a kind of Synergistic sterilizing composition pesticide, be specifically related to a kind of bixafen of comprising and the two yuan of composite Synergistic bactericidal compositions of arbitrary fungicide active ingredient that are selected from part ergosterol biosynthesis inhibitor compounds such as pefurazoate, penconazole, Cyproconazole, fluorine ring azoles, fenhexamid, Flusilazole, Prochloraz, propiconazole, prothioconazoles, simeconazoles, volution bacterium amine, Tebuconazole, the tetraconazole.
Background technology
Bixafen (C
18H
12Cl
2F
3N
3O), be a kind of novel SDI pyrazoles bactericide, the chemical structural formula of bixafen is:
Bixafen is the succinate dehydrogenase inhibitor, the control that is used for leaf spot and leaf rust will mainly be developed, but by studies show that, this new compound all has excellent activity to multiple germ, as the comparatively general germ of pesticide resistance such as white powder germ, ash arrhizus bacteria, Pseudoperonospora cubensis, be expected to become the important kind of bactericide resistance management.
Sterol is not only the important living matter of nearly all biology, and the sterol structure of dissimilar biologies and also each difference to some extent of component, the difference of different organism sterol biosynthesis pathways, and SBI provides possibility for the exploitation selectivity.Present known SBI has not only comprised the derivative of different chemical structures type, as compounds such as pyridines, miazines, imidazoles, triazole type, piperazines, piperidines, morpholine class, polyene macrolides and propylamines, and SBI has different action sites in the sterol biosynthesis pathway.
China has been extensive use of all kinds of crop powdery mildews of DMI bactericidal agent for preventing and treating such as triazolone and rust etc. since the mid-80.Though it is still effective that these medicaments use on some crops in most of areas, the susceptibility of germ has been descended several times to tens times, the medicament usage amount obviously improves, and the lasting period shortens.For example on Gongxian County, Sichuan, Xichang and other places, the control wheat powdery mildew keeps 6～8 weeks of drug effect by original per hectare with triazolone active ingredient 75～100g, to present medication 450g, only keep drug effect 5～7d, illustrate that triazolone has lost control efficiency and the use value to wheat powdery mildew basically in these areas.On the Hami melon in Xinjiang, use the also almost completely forfeiture of effect of this class pesticide control powdery mildew.There has been more serious DMI bactericide pesticide resistance problem in these situation explanations in China.
There are above problem equally in wherein several ergosterol synthetic inhibitor compounds such as pefurazoate, penconazole, Cyproconazole, fluorine ring azoles, fenhexamid, Flusilazole, Prochloraz, propiconazole, prothioconazoles, simeconazoles, volution bacterium amine, Tebuconazole, tetraconazole, and resistance problem is on the rise.
Do not have by the different mechanisms of action that rationally to be mixed between the agricultural chemicals of cross resistance be an important directions of present domestic pesticide research, it is a good method that solves resistance problem, research and development with respect to new drug, drop into low, R﹠D cycle is short, it is fast to produce result, and relatively is fit to domestic agricultural chemicals present situation at present.My company also is devoted for years to the prescription screening in the agriculture chemical compounding field, by indoor in a large number, outdoor prescription screening experiment is found, with novel pyrazole series bactericidal agent bixafen and several ergosterol synthetic inhibitor compounds such as pefurazoate, penconazole, Cyproconazole, fluorine ring azoles, fenhexamid, Flusilazole, Prochloraz, propiconazole, prothioconazoles, simeconazoles, volution bacterium amine, Tebuconazole, arbitrary fungicide active ingredient in the tetraconazole is mixed for two yuan the target bacterium is had extremely strong synergistic effect, improved bactericidal activity greatly, preferably resolve the resistance problem of DMI class sterilization, improve actual preventive effect, thereby finished the present invention.And relevant above-described two yuan composite, do not see correlative study or report at present at home and abroad as yet.
Summary of the invention
The purpose of this invention is to provide a kind of wide spectrum, efficient, low toxicity, bactericidal composition that use cost is low, to satisfy the needs of agricultural production, two kinds of active component combination backs produce synergistic effect, use the resistance problem that brings to obtain fine solution to single agent, when improving actual preventive effect, can also avoid the drug-fast generation of germ and delay the drug-fast generation speed of germ.
The research staff of our company finished the present invention on the basis of a large amount of indoor, outdoor experimental formula screenings, the present invention and the objective of the invention is to realize by following measure:
A kind of combination sterilization composition based on bixafen, it is characterized in that with active ingredient (A) bixafen and (B) the arbitrary fungicide active ingredient in several ergosterol synthetic inhibitor compounds such as pefurazoate, penconazole, Cyproconazole, fluorine ring azoles, fenhexamid, Flusilazole, Prochloraz, propiconazole, prothioconazoles, simeconazoles, volution bacterium amine, Tebuconazole, the tetraconazole carry out two yuan composite, wherein the percentage by weight of effective constituents A and B is 1～80: 80～1.
Above-mentioned several ergosterol synthetic inhibitor compounds all is bactericide well known in the art, can obtain by various commercial channel, based on concrete formulation screening test, as a kind of improvement of the present invention, the percentage by weight of effective constituents A and B preferred 1～40: 50～1.
Except active ingredient (A) bixafen and (B) several ergosterol synthetic inhibitor compounds such as pefurazoate, penconazole, Cyproconazole, fluorine ring azoles, fenhexamid, Flusilazole, Prochloraz, propiconazole, prothioconazoles, simeconazoles, volution bacterium amine, Tebuconazole, arbitrary fungicide active ingredient in the tetraconazole is for outside the important technology feature of the present invention, and another important technology of the present invention is characterized as: can be prepared into the suitable agriculture preparation formulation that uses based on the bixafen bactericidal composition more than of the present invention and be wetting powder, missible oil, suspending agent, water dispersible granules, aqueous emulsion or microemulsion.Wherein effective constituents A and B gross weight account for 1%～90% of whole weight of formulation in the preparation, can be preferably 5%～55%.
Bactericidal composition based on bixafen of the present invention can be used for preventing and treating powdery mildew on cereal, the fruit and vegetables such as wheat, downy mildew, rust, tikka class disease, scab, rot etc. to be caused by germ, ergosterol class synthetic inhibitor class agricultural chemicals there have been the disease of certain resistance, preventive effect excellence.
Compare with existing agricultural chemicals, excellent effect of the present invention is: 1, several ergosterol synthetic inhibitor class agricultural chemicals of the present invention and novel pyrazoles bactericide bixafen are composite has an obvious synergistic effect, has enlarged fungicidal spectrum, has improved actual preventive effect; 2, compare with using the one-component bactericide, the risk that produces poisoning reduces, and is safer to crop; 3, composition is made up of two kinds of different active ingredients of the mechanism of action, helps avoiding drug-fast generation and delays the drug-fast generation speed of germ, and the disease that single agent has been developed immunity to drugs has good action effect; 4, medicament is mixed, and has improved bactericidal activity, has reduced dosage, thereby has reduced cost and the pollution that has alleviated environment.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention describes with following specific embodiment, but the present invention only limits to these examples absolutely not.The method that the present invention adopts indoor bioassay and field trial to combine.If no special instructions, the ratio of below mentioning (comprising percentage) all is a mass ratio.Should be pointed out that all any modifications of being made within the spirit and principles in the present invention, be equal to replacement and improvement etc., all should be included within protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
The formulation embodiment:
Wherein necessary component and the easy manufacture implementation method about preparation pesticidal preparations formulation is as follows:
The novel pyrazoles bactericide bixafen of effective constituents A representative in the formulation embodiment wherein, active ingredient B represent one of any in several ergosterol synthetic inhibitor compounds such as pefurazoate, penconazole, Cyproconazole, fluorine ring azoles, fenhexamid, Flusilazole, Prochloraz, propiconazole, prothioconazoles, simeconazoles, volution bacterium amine, Tebuconazole, the tetraconazole.
One of technical scheme of the present invention, described bactericidal composition are wetting powder, and the percentage by weight of component is:
The concrete procedure of processing of this bactericidal composition wetting powder is: press above-mentioned prescription with effective constituents A and active ingredient B and dispersant, wetting agent and filler mixing, in stirred tank, evenly stir, behind airslide disintegrating mill, mixing, promptly can be made into the wetting powder of the present composition.
Two of technical scheme of the present invention, described bactericidal composition are suspending agent, and the percentage by weight of component is:
The concrete production stage of this suspending agent is earlier other auxiliary agents to be mixed, mix through high speed shear, add effective constituents A and active ingredient B, abrading-ball is 2～3 hours in ball crusher, make a diameter all below 5mm, make the suspending agent preparation of the present composition of the present invention.
Three of technical scheme of the present invention, when described Pesticidal combination was microemulsion, the percentage by weight of component was:
The concrete production stage of this microemulsion is: former medicine A, B are dissolved fully with cosolvent, add other compositions such as emulsifier, antifreezing agent stabilizing agent again, evenly mix, add entry at last, can be made into microemulsion after fully stirring.
Four of technical scheme of the present invention, described Pesticidal combination are cream preparation, and the mass percent of component is:
The concrete production stage of this cream preparation adds emulsifier, the synergist back that stirs after the dissolving fully again and becomes the oily liquids of transparent and homogeneous for earlier effective constituents A, B being added in the solvent, and can promptly can be made into the cream preparation of the present composition.
Five of technical scheme of the present invention, described bactericidal composition are aqueous emulsion, and the percentage by weight of component is:
The concrete production stage of this aqueous emulsion is: at first former pharmaceutically active ingredient A is added with active ingredient B, solvent and emulsifier, cosolvent and be in the same place, make and be dissolved into uniform oil phase; With part water, antifreeze, other insecticides adjuvant such as antimicrobial mixes into uniform water; When the reactor high speed stirs, oil phase is added water, slowly add water, open clipper and carry out high speed shear, and add remaining water, shear half an hour approximately, form the aqueous emulsion of oil-in-water type until reaching the phase inversion point.Promptly make the aqueous emulsion of the present composition.
Six of technical scheme of the present invention, described bactericidal composition are water dispersible granules, and the percentage by weight of component is:
The concrete procedure of processing of this bactericidal composition water dispersible granules is: by above-mentioned prescription effective constituents A, active ingredient B and dispersant, wetting agent, disintegrant and filler are mixed, pulverize with micro jet, through mediating, add then and carry out granulation, drying, screening in the fluidized bed prilling dryer after sample analysis, make the water dispersible granules of the present composition.
Described emulsifier is selected from any one or more mixtures formed with arbitrary proportion in calcium dodecyl benzene sulfonate and aliphatic acid polyethenoxy ether, alkylphenol polyoxyethylene sulfosuccinate, styryl phenol APEO, polyoxyethylene nonylphenol ether, castor oil polyoxyethylene ether, aliphatic acid polyethenoxy base ester, the polyoxyethylene aliphatic alcohol ether.
Described solvent is any one or more mixed solvents formed with arbitrary proportion in dimethylbenzene or biodiesel, toluene, diesel oil, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, turpentine oil, solvent naphtha, dimethyl formamide, dimethyl sulfoxide (DMSO), the water equal solvent.
Described dispersant is selected from one or more in polycarboxylate, lignosulfonates, alkylphenol polyoxyethylene formaldehyde condensation products sulphate, alkyl benzene sulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, alkylphenol polyoxyethylene, aliphatic amine polyoxyethylene ether, polyoxyethylene carboxylate, the fatty acid glyceride APEO.
Described wetting agent is selected from: lauryl sodium sulfate, calcium dodecyl benzene sulfonate, draw back in powder active ingredient BX., wetting and penetrating agent F, alkylnaphthalene sulfonate, polyoxyethylene triphenylethylene phosphenylic acid salt, spaonin powder, silkworm excrement, the soapberry powder one or more.
Described disintegrant is selected from: one or more in bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, the sodium bicarbonate.
Described thickener is selected from: one or more in xanthans, CMC, hydroxyethylcellulose, methylcellulose, Magnesiumaluminumsilicate, the polyvinyl alcohol.
Described stabilizing agent is selected from: a kind of in sodium citrate, the resorcinol.
Described antifreezing agent is selected from: one or more in ethylene glycol, propane diols, the glycerine.
Described defoamer is selected from: silicone oil, silicone compound, C
10-20Saturated fat acid compounds, C
8-10In the aliphatic alcohols compound one or more.
Described filler is selected from: one or more in kaolin, diatomite, bentonite, attapulgite, white carbon, starch, the precipitated calcium carbonate.
Biologicall test example 1:
(1) experimental subjects: the powdery mildew of cucumber bacterium, the cucumber cultivation ground collection of not executing bixafen and ergosterol synthetic inhibitor class agricultural chemicals from Shouguang, Shandong separates, and kind is a Chang Chun Mi Ci.
In pot for growing seedlings, place the greenhouse to cultivate susceptible cucumber variety Chang Chun Mi Ci cultivation, plant grows to three to four leaf after dates, gathers the blade of identical leaf age, is used for cultivation and the mensuration of powdery mildew of cucumber bacterium.
The powdery mildew of cucumber bacterium adopts live body plant method to cultivate under 20 ℃, the condition of 12h alternation of light and darkness, and every 30d changes to be commissioned to train and supports 1 time.With the conidium on the sterile water wash-out incidence of leaf, being mixed with spore concentration is 1 * 10 during inoculation
6The suspension of individual/mL.
(2) the former medicine of experimental pharmacy: 90%bixafen, Bayer crop science Co., Ltd, the former medicine of 94% tetraconazole, Italian Yi Saige company.
The soup preparation of single agent toxicity test: the former medicinal acetone of bixafen and tetraconazole is dissolution with solvents, is made into 10000 μ g/ml mother liquors, and is in 4 ℃ of preservations, stand-by.
Combination setting is mixed: 9%bixafen tetraconazole mass ratio is respectively 2%+7%, and 3%+6%, 4%+5%, 5%+4% and 7%+2% be totally 5 combinations that are mixed.
(3) test method: adopt the leaf dish method of preserving moisture to carry out toxicity test.Earlier the blade of gathering is prepared into the leaf dish that diameter is 1.5cm, mixing at random, place the series concentration soup that configures to soak 1h respectively, 50 leaf dishes of each concentration, test is with the blank that is treated to of adding medicine not, after soaking end, leaf faces up and puts on the wetting blotting paper of identical liquor strength, soup on the leaf dish is blotted, the spore suspension 10L for preparing is inoculated in leaf dish central authorities, after room temperature is placed 5min, places under 20 ℃, the condition of 12h alternation of light and darkness and cultivate, measure the onset area on the leaf dish behind the 10d, calculate EC
50
On the basis of preliminary experiment, respectively single agent bixafen and tetraconazole are carried out toxicity test in order to last method, the two EC
50Value is respectively 4.03mg/l and 7.86mg/l.
The percentage that accounts for the leaf disc area according to lesion area is divided sick level:
0 grade: scab
1 grade: lesion area accounts for 1%～20% of leaf disc area
2 grades: lesion area accounts for 21%～50% of leaf disc area
3 grades: lesion area accounts for more than 50% of leaf disc area
The mixture toxicity test:
Carry out the toxicity test of mixture according to mixed ratio with single agent toxicity test method.
EC that each that will measure according to the abundant method of Sun Yun handled
50Value is converted into the actual toxicity index (ATI) of using with; According to the proportioning of mixture, obtain theory and use toxicity index (TTI) with, calculate the co-toxicity coefficient (CTC) of mixture by following formula.
Single agent toxicity index=(standard medicament EC
50/ reagent agent EC
50) * 100
ATI=(standard medicament EC
50/ reagent agent (using with) EC
50) * 100
The content (%) of toxicity index * B in using with of content (the %)+B of toxicity index * A of TII=A in using with
CTC＝(ATI/TTI)×100
If co-toxicity coefficient is big by 120, showing has synergistic effect; If be starkly lower than 100 (below 80), be indicated as antagonism; Between 100～120, be indicated as summation action.
Virulence experiment result and analysis:
Different proportioning bixafen of table 1 and tetraconazole mixture are to the virulence of powdery mildew of cucumber bacterium
| The pharmacy quality ratio | Virulence regression equation | The correlation coefficient r value | EC 50(mg/L) |
| bixafen(A) | Y＝3.1236X+3.1092 | 0.9756 | 4.03 |
| Tetraconazole (B) | Y＝3.2204X+2.1163 | 0.9804 | 7.86 |
| 2∶7 | Y＝3.1007X+3.2373 | 0.9659 | 3.70 |
| 3∶6 | Y＝3.3647X+3.2762 | 0.9834 | 3.25 |
| 4∶5 | Y＝3.1169X+3.4520 | 0.9871 | 3.14 |
| 5∶4 | Y＝3.2045X+3.4448 | 0.9789 | 3.06 |
| 7∶2 | Y＝3.0067X+3.6701 | 0.9803 | 2.77 |
Table 2bixafen and the composite co-toxicity of tetraconazole to the powdery mildew of cucumber bacterium
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| bixafen(A) | 1∶0 | 100.00 | 100.00 | / | / |
| Tetraconazole (B) | 0∶1 | 51.27 | 51.27 | / | / |
| A+B | 2∶7 | 108.85 | 62.10 | 175.28 | Synergy |
| A+B | 3∶6 | 123.88 | 67.51 | 183.49 | Synergy |
| A+B | 4∶5 | 128.44 | 72.93 | 176.11 | Synergy |
| A+B | 5∶4 | 131.83 | 78.34 | 168.27 | Synergy |
| A+B | 7∶2 | 145.55 | 89.17 | 163.22 | Synergy |
Show according to above indoor virulence test measurement result, bixafen and tetraconazole show that by the percentage composition experiment of above experiment synergistic effect is preferably all arranged, wherein with bixafen: tetraconazole is that 3: 6 o'clock co-toxicity coefficient is up to 183.49, thinks that bixafen and tetraconazole mass percent are that 3: 6 o'clock synergistic effects are best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 3: 6 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
The composite Toxicity Determination of biologicall test example 2:bixafen and prothioconazoles to the powdery mildew of cucumber bacterium.
The soup preparation of single agent toxicity test: with bixafen and the former medicinal acetone of prothioconazoles is dissolution with solvents, is made into 10000 μ g/ml mother liquors, in 4 ℃ of preservations, stand-by.
Combination setting is mixed: 11%bixafen prothioconazoles mass ratio is respectively 2%+9%, 4%+7%, 5%+6%, 6%+5% and 8%+3% totally 5 combinations that are mixed.
On the basis of preliminary experiment, respectively single agent bixafen and prothioconazoles are carried out toxicity test in order to last method, the two EC
50Value is respectively 4.79mg/l and 8.01mg/l.
Virulence experiment result and analysis:
Different proportioning bixafen of table 3 and prothioconazoles mixture are to virulence and the synergistic effect of powdery mildew of cucumber bacterium
| The pharmacy quality ratio | Virulence regression equation | The correlation coefficient r value | EC 50(mg/L) |
| bixafen(A) | Y＝2.5744X+3.2485 | 0.9759 | 4.79 |
| Prothioconazoles (B) | Y＝2.6348X+2.6191 | 0.9814 | 8.01 |
| 2∶9 | Y＝2.5705X+3.2328 | 0.9906 | 4.87 |
| 4∶7 | Y＝2.6007X+3.4088 | 0.9835 | 4.09 |
| 5∶6 | Y＝2.5034X+3.4915 | 0.9749 | 4.00 |
| 6∶5 | Y＝2.7113X+3.3558 | 0.9828 | 4.04 |
| 8∶3 | Y＝2.6942X+3.2545 | 0.9841 | 3.81 |
Table 4bixafen and the composite co-toxicity of prothioconazoles to the powdery mildew of cucumber bacterium
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| bixafen(A) | 1∶0 | 100.00 | 100.00 | / | / |
| Prothioconazoles (B) | 0∶1 | 59.80 | 59.80 | / | / |
| A+B | 2∶9 | 98.37 | 67.11 | 146.58 | Synergy |
| A+B | 4∶7 | 117.09 | 74.42 | 157.34 | Synergy |
| A+B | 5∶6 | 119.62 | 78.07 | 153.21 | Synergy |
| A+B | 6∶5 | 118.55 | 81.73 | 145.06 | Synergy |
| A+B | 8∶3 | 125.84 | 89.04 | 141.33 | Synergy |
Show according to above indoor virulence test measurement result, bixafen and prothioconazoles show that by the percentage composition experiment of above experiment synergistic effect is preferably all arranged, wherein with bixafen: prothioconazoles is that 4: 7 o'clock co-toxicity coefficient is up to 157.34, thinks that bixafen and prothioconazoles mass percent are that 4: 7 o'clock synergistic effects are best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 4: 7 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
The composite Toxicity Determination of biologicall test example 3:bixafen and fluorine ring azoles to wheat powdery mildew.
95% epoxiconazole raw drug, Shenyang Kechuang chemicals Co., Ltd.
The soup preparation of single agent toxicity test: with bixafen and the medicinal acetone of epoxiconazole raw is dissolution with solvents, is made into 10000 μ g/ml mother liquors, in 4 ℃ of preservations, stand-by.
Combination setting is mixed: 21%bixafen fluorine ring azoles mass ratio is respectively 3%+18%, 5%+16%, 7%+14%, 9%+12% and 11%+10% totally 5 combinations that are mixed.
On the basis of preliminary experiment, respectively single agent bixafen and fluorine ring azoles are carried out toxicity test, the two EC in order to last method
50Value is respectively 3.87mg/l and 11.03mg/l.
Virulence experiment result and analysis:
Different proportioning bixafen of table 5 and fluorine ring azoles mixture are to the virulence and the synergistic effect of wheat powdery mildew
| The pharmacy quality ratio | Virulence regression equation | The correlation coefficient r value | EC 50(mg/L) |
| bixafen(A) | Y＝2.2436X+3.6814 | 0.9845 | 3.87 |
| Fluorine ring azoles (B) | Y＝2.3147X+2.5867 | 0.9813 | 11.03 |
| 3∶18 | Y＝2.1935X+3.2751 | 0.9711 | 6.11 |
| 5∶16 | Y＝2.2076X+3.4872 | 0.9906 | 4.84 |
| 7∶14 | Y＝2.3009X+3.4750 | 0.9749 | 4.60 |
| 9∶12 | Y＝2.1675X+3.6141 | 0.9716 | 4.36 |
| 11∶10 | Y＝2.1074X+3.7128 | 0.9824 | 4.08 |
Table 6bixafen and the composite co-toxicity of fluorine ring azoles to wheat powdery mildew
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| bixafen(A) | 1∶0 | 100.00 | 100.00 | / | / |
| Fluorine ring azoles (B) | 0∶1 | 35.09 | 35.09 | / | / |
| A+B | 3∶18 | 63.29 | 44.36 | 142.67 | Synergy |
| A+B | 5∶16 | 79.89 | 50.54 | 158.06 | Synergy |
| A+B | 7∶14 | 84.13 | 56.72 | 148.31 | Synergy |
| A+B | 9∶12 | 88.78 | 62.91 | 141.13 | Synergy |
| A+B | 11∶10 | 94.82 | 69.09 | 137.25 | Synergy |
Show according to above indoor virulence test measurement result, bixafen and fluorine ring azoles show that by the mass percent of the above experiment result that experimentizes synergistic effect is preferably all arranged, wherein with bixafen: fluorine ring azoles is that 5: 16 o'clock co-toxicity coefficient is up to 158.06, thinks that bixafen and fluorine ring azoles mass percent are that 5: 16 o'clock synergistic effects are best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 5: 16 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
The composite Toxicity Determination of biologicall test example 4:bixafen and simeconazoles to the powdery mildew of cucumber bacterium.
The soup preparation of single agent toxicity test: with bixafen and the former medicinal acetone of simeconazoles is dissolution with solvents, is made into 10000 μ g/ml mother liquors, in 4 ℃ of preservations, stand-by.
Combination setting is mixed: 13%bixafen simeconazoles mass ratio is respectively 2%+11%, 4%+9%, 6%+7%, 8%+5% and 10%+3% totally 5 combinations that are mixed.
On the basis of preliminary experiment, respectively single agent bixafen and simeconazoles are carried out toxicity test in order to last method, the two EC
50Value is respectively 4.35mg/l and 7.81mg/l.
Virulence experiment result and analysis:
Different proportioning bixafen of table 7 and simeconazoles are to the virulence experiment of powdery mildew of cucumber bacterium
| The pharmacy quality ratio | Virulence regression equation | The correlation coefficient r value | EC 50(mg/L) |
| bixafen(A) | Y＝1.7421X+3.8876 | 0.9847 | 4.35 |
| Simeconazoles (B) | Y＝1.7619X+3.4272 | 0.9732 | 7.81 |
| 2∶11 | Y＝1.6408X+3.8395 | 0.9624 | 5.10 |
| 4∶9 | Y＝1.5324X+4.0396 | 0.9816 | 4.23 |
| 6∶7 | Y＝1.5621X+4.0606 | 0.9711 | 3.99 |
| 8∶5 | Y＝1.4873X+4.1482 | 0.9903 | 3.74 |
| 10∶3 | Y＝1.5006X+4.1716 | 0.9867 | 3.56 |
Table 8bixafen and the composite co-toxicity of simeconazoles to the powdery mildew of cucumber bacterium
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| bixafen(A) | 1∶0 | 100.00 | 100.00 | / | / |
| Simeconazoles (B) | 0∶1 | 55.70 | 55.70 | / | / |
| A+B | 2∶11 | 85.36 | 62.51 | 136.55 | Synergy |
| A+B | 4∶9 | 102.75 | 69.33 | 148.21 | Synergy |
| A+B | 6∶7 | 108.93 | 76.14 | 143.06 | Synergy |
| A+B | 8∶5 | 116.37 | 82.96 | 140.27 | Synergy |
| A+B | 10∶3 | 122.02 | 89.78 | 135.92 | Synergy |
Show according to above indoor virulence test measurement result, bixafen and simeconazoles show that by the mass percent of the above experiment result that experimentizes synergistic effect is preferably all arranged, wherein with bixafen: simeconazoles is that 4: 9 o'clock co-toxicity coefficient is up to 148.21, thinks that bixafen and simeconazoles mass percent are that 4: 9 o'clock synergistic effects are best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 4: 9 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
The composite Toxicity Determination of biologicall test example 5:bixafen and volution bacterium amine to the powdery mildew of cucumber bacterium.
The former medicine of 95% volution bacterium amine, Weiyuan, Hangzhou chemical industry Co., Ltd.
The soup preparation of single agent toxicity test: with bixafen and the former medicinal acetone of volution bacterium amine is dissolution with solvents, is made into 10000 μ g/ml mother liquors, in 4 ℃ of preservations, stand-by.
Combination setting is mixed: 14%bixafen volution bacterium amine mass ratio is respectively 2%+12%, 4%+10%, 6%+8%, 8%+6% and 10%+4% totally 5 combinations that are mixed.
On the basis of preliminary experiment, respectively single agent bixafen and volution bacterium amine are carried out toxicity test, the two EC in order to last method
50Value is respectively 5.13mg/l and 9.35mg/l.
Virulence experiment result and analysis:
Different proportioning bixafen of table 9 and volution bacterium amine are to the virulence of powdery mildew of cucumber bacterium
Table 10bixafen and the composite co-toxicity of volution bacterium amine to the powdery mildew of cucumber bacterium
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| bixafen(A) | 1∶0 | 100.00 | 100.00 | / | / |
| Volution bacterium amine (B) | 0∶1 | 54.87 | 54.87 | / | / |
| A+B | 2∶12 | 87.84 | 61.31 | 143.26 | Synergy |
| A+B | 4∶10 | 101.84 | 67.76 | 150.29 | Synergy |
| A+B | 6∶8 | 119.60 | 74.21 | 161.17 | Synergy |
| A+B | 8∶6 | 123.71 | 80.66 | 153.38 | Synergy |
| A+B | 10∶4 | 127.56 | 87.10 | 146.44 | Synergy |
Show according to above indoor virulence test measurement result, bixafen and volution bacterium amine show that by the mass percent of the above experiment result that experimentizes synergistic effect is preferably all arranged, wherein with bixafen: volution bacterium amine is that 6: 8 o'clock co-toxicity coefficient is up to 161.17, thinks that bixafen and volution bacterium amine mass percent are that 6: 8 o'clock synergistic effects are best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 6: 8 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
The composite Toxicity Determination of biologicall test example 6:bixafen and Cyproconazole to the grape powdery mildew bacterium.
The soup preparation of single agent toxicity test: with bixafen and the former medicinal acetone of Cyproconazole is dissolution with solvents, is made into 10000 μ g/ml mother liquors, in 4 ℃ of preservations, stand-by.
Combination setting is mixed: 16%bixafen Cyproconazole mass ratio is respectively 3%+13%, 5%+11%, 7%+9%, 9%+7% and 11%+5% totally 5 combinations that are mixed.
On the basis of preliminary experiment, respectively single agent bixafen and Cyproconazole are carried out toxicity test in order to last method, the two EC
50Value is respectively 4.65mg/l and 10.44mg/l.
Virulence experiment result and analysis:
Different proportioning bixafen of table 11 and Cyproconazole are to the virulence of powdery mildew of cucumber bacterium
Table 12bixafen and the composite co-toxicity of Cyproconazole to the powdery mildew of cucumber bacterium
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| bixafen(A) | 1∶0 | 100.00 | 100.00 | / | / |
| Cyproconazole (B) | 0∶1 | 44.54 | 44.54 | / | / |
| A+B | 3∶13 | 79.22 | 54.94 | 144.20 | Synergy |
| A+B | 5∶11 | 97.17 | 61.87 | 157.05 | Synergy |
| A+B | 7∶9 | 101.37 | 68.80 | 147.33 | Synergy |
| A+B | 9∶7 | 107.48 | 75.74 | 141.91 | Synergy |
| A+B | 11∶5 | 111.66 | 82.67 | 135.07 | Synergy |
Show according to above indoor virulence test measurement result, bixafen and Cyproconazole show that by the mass percent of the above experiment result that experimentizes synergistic effect is preferably all arranged, wherein with bixafen: Cyproconazole is that 5: 11 o'clock co-toxicity coefficient is up to 157.05, thinks that bixafen and Cyproconazole mass percent are that 5: 11 o'clock synergistic effects are best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 5: 11 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
Field experiment test example 1: field trial is measured bixafen and the composite control efficiency to powdery mildew of cucumber of tetraconazole
(1) investigation method
Experimental field be located in Shandong Province's Qingzhou City cucumber booth, 5 points are investigated in every sub-district, and every some investigation 2 strains are put down in writing occurring degree with staging.
Grade scale is as follows:
0 grade: no scab;
1 grade: lesion area accounts for whole below 5% of leaf area;
3 grades: lesion area accounts for whole leaf area 6%～10%;
5 grades: lesion area accounts for 11%～25% of whole leaf area;
7 grades: lesion area accounts for 26%～50% of whole leaf area;
9 grades: lesion area accounts for whole more than 50% of leaf area.
(2) control time and number of times
Test is investigated 3 times altogether, i.e. disease index investigation before the medicine, preventive effect investigation in 7 days behind the 1st medicine, 7 days and preventive effect investigation in 15 days behind 2 medicines.
(3) drug effect computational methods
Sick leaf rate (the %)=sick number of sheets/investigate total number of sheets * 100
Disease index=∑ (the sick numbers of sheets at different levels * relative level numerical value)/(investigating total number of sheets * 9) * 100
Control efficiency (%)=(1-(disease index behind disease index before the blank district medicine * treatment region medicine)/(disease index before disease index behind the blank district medicine * treatment region medicine)) * 100
(4) poisoning investigation method
Whether continuous 7d range estimation medicament has poisoning to crop after the dispenser.
(5) result of the test and analysis
Each handles the effect of preventing and treating powdery mildew of cucumber table 13
As can be seen from Table 13, to prevent and treat the effect of powdery mildew of cucumber remarkable in the combination that is mixed of 9%bixafen tetraconazole 3: 6.Under the consumption of same every mu 8 gram, the effect of complex preparation significantly is better than two kinds of single agent, and its quick-acting and lasting effect are all relatively good, and be the most outstanding with lasting effect especially.Complex preparation significantly is better than effect under the low concentration consumption in control efficiency under the consumption of high concentration.15 days lasting effect is more remarkable after 7 days control efficiency behind the 1st, 2 medicine reaches 93.71% and 88.68%, the 2 medicine respectively, reaches 91.82%.Result of the test proves that the single agent effect of 10%bixafenEC is better than the single agent of 4% tetraconazole EW.Behind the 2nd medicine 15 days, the highest preventive effect of the single agent of 10%bixafenEC was that the highest preventive effect of the single agent of 84.61%, 4% tetraconazole EW is 80.61%.According to field range estimation, in the test dose scope, plant growth is normal, and each is handled medicament and poisoning phenomenon to cucumber all do not occur, illustrates that it is safe to cucumber.Prevent desirable even more ideal control efficiency at the initial stage of a disease or in advance.
Test example 2: field trial is measured bixafen and the composite control efficiency to powdery mildew of cucumber of prothioconazoles
(1) investigation method
Except that experimental field being located at the Yangling District Li Jia mausoleum, Shaanxi with the composite of fluorine ring azoles, the composite field trial of its excess-three kind compound and bixafen all is located at the cucumber ground in Yangling District Li Tai township, Shaanxi, in the custard squash booth, 5 points are investigated in every sub-district, every some investigation 2 strains, put down in writing occurring degree with staging, grade scale is as follows:
0 grade: no scab;
1 grade: lesion area accounts for whole below 5% of leaf area;
3 grades: lesion area accounts for whole leaf area 6%～10%;
5 grades: lesion area accounts for 11%～25% of whole leaf area;
7 grades: lesion area accounts for 26%～50% of whole leaf area;
9 grades: lesion area accounts for whole more than 50% of leaf area.
(2) control time and number of times
Test is investigated 3 times altogether, i.e. disease index investigation before the medicine, preventive effect investigation in 7 days behind the 1st medicine, 7 days and preventive effect investigation in 15 days behind 2 medicines.
(3) drug effect computational methods
Sick leaf rate (the %)=sick number of sheets/investigate total number of sheets * 100
Disease index=∑ (the sick numbers of sheets at different levels * relative level numerical value)/(investigating total number of sheets * 9) * 100
Control efficiency (%)=(1-(disease index behind disease index before the blank district medicine * treatment region medicine)/(disease index before disease index behind the blank district medicine * treatment region medicine)) * 100
(4) poisoning investigation method
Whether continuous 7d range estimation medicament has poisoning to crop after the dispenser.
(5) result of the test and analysis
Each handles the effect of preventing and treating powdery mildew of cucumber table 14
As can be seen from Table 13, to prevent and treat the effect of powdery mildew of cucumber remarkable in the combination that is mixed of 11%bixafen prothioconazoles 4: 7.Under the consumption of same every mu 8 gram, the effect of complex preparation significantly is better than two kinds of single agent, and its quick-acting and lasting effect are all relatively good, and be the most outstanding with lasting effect especially.Complex preparation significantly is better than effect under the low concentration consumption in control efficiency under the consumption of high concentration.15 days lasting effect is more remarkable after 7 days control efficiency behind the 1st, 2 medicine reaches 82.54% and 90.04%, the 2 medicine respectively reaches 90.79%.Result of the test proves that the single agent effect of 10%bixafenEC obviously is better than the single agent of 25% prothioconazoles SC.Behind the 2nd medicine 15 days, the highest preventive effect of the single agent of 10%bixafenEC was that the highest preventive effect of the single agent of 82.46%, 25% prothioconazoles SC is 81.07%.According to field range estimation, in the test dose scope, plant growth is normal, and each is handled medicament and poisoning phenomenon to cucumber all do not occur, illustrates that it is safe to cucumber.Prevent desirable even more ideal control efficiency at the initial stage of a disease or in advance.
Test example 3: field trial is measured bixafen and the composite control efficiency to wheat powdery mildew of simeconazoles
Test method is with experimental example 2,
Result of the test and analysis:
Each handles the effect of control wheat powdery mildew table 15
As can be seen from Table 15, the effect of 5: 16 the combination control wheat powdery mildew that is mixed of 21%bixafen fluorine ring azoles is remarkable.Under the consumption of same every mu 8 gram, the effect of complex preparation significantly is better than two kinds of single agent, and its quick-acting and lasting effect are all relatively good, and be the most outstanding with lasting effect especially.Complex preparation significantly is better than effect under the low concentration consumption in control efficiency under the consumption of high concentration.15 days lasting effect is more remarkable after 7 days control efficiency behind the 1st, 2 medicine reaches 86.77% and 90.13%, the 2 medicine respectively reaches 91.46%.Result of the test proves, behind the 2nd medicine 15 days, the highest preventive effect of the single agent of 10%bixafenEC was that the highest preventive effect of the single agent of 78.72%, 30% fluorine ring azoles SC is 80.24%.According to field range estimation, in the test dose scope, plant growth is normal, and each is handled medicament and poisoning phenomenon to wheat all do not occur, illustrates that it is safe to wheat.Prevent desirable even more ideal control efficiency at the initial stage of a disease or in advance.
Test example 4: field trial is measured bixafen and the composite control efficiency to the custard squash powdery mildew of volution bacterium amine:
Test method is with experimental example 2,
Result of the test and analysis:
Each handles the effect of control custard squash powdery mildew table 16
As can be seen from Table 16,14%bixafen volution bacterium amine is that 6: 8 the effect of the combination control custard squash powdery mildew that is mixed is remarkable.Under the consumption of same every mu 10 gram, the effect of complex preparation significantly is better than two kinds of single agent, and its quick-acting and lasting effect are all relatively good, and be the most outstanding with lasting effect especially.Complex preparation significantly is better than effect under the low concentration consumption in control efficiency under the consumption of high concentration.7 days control efficiency reaches 84.25% and 88.46% respectively behind the 1st, 2 medicine, 15 days lasting effect is more remarkable behind the 2nd medicine, reach 89.07%, estimate according to the field, in the test dose scope, plant growth is normal, and each is handled medicament and poisoning phenomenon to custard squash all do not occur, illustrates that it is safe to custard squash.Prevent desirable even more ideal control efficiency at the initial stage of a disease or in advance.
In sum, the present invention contains bixafen and the composite Synergistic bactericidal composition of arbitrary fungicide active ingredient that is selected from pefurazoate, penconazole, Cyproconazole, fluorine ring azoles, fenhexamid, Flusilazole, Prochloraz, propiconazole, prothioconazoles, simeconazoles, volution bacterium amine, Tebuconazole, the tetraconazole, powdery mildew of cucumber and custard squash powdery mildew there is good control efficiency, and it is to the target crop safety, compare with single agent, bactericidal composition of the present invention has the advantage that quick-acting is good, the lasting period is long, is difficult for producing poisoning.So research and development of the present invention and popularization have crucial meaning to society.
Claims (5)
1. bactericidal composition is characterized in that: this bactericidal composition is to be C with A novel pyrazole series bactericidal agent bixafen(molecular formula
18H
12Cl
2F
3N
3O) with B pefurazoate, penconazole, Cyproconazole, fluorine ring azoles, fenhexamid, Flusilazole, Prochloraz, propiconazole, prothioconazoles, simeconazoles, volution bacterium amine, Tebuconazole, tetraconazole in one of any be the preparation of two yuan of composite bactericidal compositions of active ingredient, all the other components are usual auxiliaries in the agricultural chemicals, wherein the percentage by weight of effective constituents A and B is 1～80:80～1 in this bactericidal composition
A novel pyrazole series bactericidal agent bixafen.
2. bactericidal composition according to claim 1 is characterized in that: wherein the percentage by weight of effective constituents A and B is preferably 1～40
:50～1.
3. bactericidal composition according to claim 1 is characterized in that: to account for the percentage of gross weight in the preparation be 1%～90% for effective constituents A and B total content in this bactericidal composition.
4. bactericidal composition according to claim 3 is characterized in that: effective constituents A and B total content account for that the percentage of gross weight is preferably 5%～55% in the preparation in this bactericidal composition.
5. bactericidal composition according to claim 1 is characterized in that: the preparation formulation that bactericidal composition of the present invention can be mixed with is wetting powder, missible oil, suspending agent, water dispersible granules, aqueous emulsion or microemulsion.
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| CN104430384A (en) * | 2014-12-03 | 2015-03-25 | 北京燕化永乐生物科技股份有限公司 | Bactericidal composition |
| CN103907616B (en) * | 2012-12-31 | 2016-01-20 | 江苏丰登作物保护股份有限公司 | A kind of composite synergistic bactericidal composition and application thereof containing biphenyl pyrrole bacterium amine and Flutriafol |
| CN105766933A (en) * | 2015-12-24 | 2016-07-20 | 南京华洲药业有限公司 | Bixafen and prothioconazole containing bactericidal composition and application thereof |
| CN105941416A (en) * | 2016-05-25 | 2016-09-21 | 南京华洲药业有限公司 | Sterilizing composition containing bixafen and tebuconazole and application thereof |
| CN105941417A (en) * | 2016-05-25 | 2016-09-21 | 南京华洲药业有限公司 | Sterilization composition containing Bixafen and epoxiconazole and application thereof |
| CN105994294A (en) * | 2016-05-25 | 2016-10-12 | 南京华洲药业有限公司 | Bactericidal composition containing bixafen and propiconazole and application thereof |
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| CN106538546A (en) * | 2016-10-11 | 2017-03-29 | 深圳诺普信农化股份有限公司 | A kind of bactericidal composition of the bacterium of pyrrole containing biphenyl amine and its application |
| CN115697060A (en) * | 2020-04-24 | 2023-02-03 | Upl有限责任公司 | Fungicidal compositions |
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| CN103907616B (en) * | 2012-12-31 | 2016-01-20 | 江苏丰登作物保护股份有限公司 | A kind of composite synergistic bactericidal composition and application thereof containing biphenyl pyrrole bacterium amine and Flutriafol |
| CN104430384A (en) * | 2014-12-03 | 2015-03-25 | 北京燕化永乐生物科技股份有限公司 | Bactericidal composition |
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| CN105766933A (en) * | 2015-12-24 | 2016-07-20 | 南京华洲药业有限公司 | Bixafen and prothioconazole containing bactericidal composition and application thereof |
| CN105941416A (en) * | 2016-05-25 | 2016-09-21 | 南京华洲药业有限公司 | Sterilizing composition containing bixafen and tebuconazole and application thereof |
| CN105941417A (en) * | 2016-05-25 | 2016-09-21 | 南京华洲药业有限公司 | Sterilization composition containing Bixafen and epoxiconazole and application thereof |
| CN105994294A (en) * | 2016-05-25 | 2016-10-12 | 南京华洲药业有限公司 | Bactericidal composition containing bixafen and propiconazole and application thereof |
| CN106472547A (en) * | 2016-10-09 | 2017-03-08 | 江西正邦生物化工有限责任公司 | A kind of composition pesticide containing chlorobenzene ether amide Yu Prochloraz |
| CN106472547B (en) * | 2016-10-09 | 2019-04-16 | 江西正邦作物保护有限公司 | A kind of composition pesticide containing chlorobenzene ether amide and Prochloraz |
| CN106538546A (en) * | 2016-10-11 | 2017-03-29 | 深圳诺普信农化股份有限公司 | A kind of bactericidal composition of the bacterium of pyrrole containing biphenyl amine and its application |
| CN115697060A (en) * | 2020-04-24 | 2023-02-03 | Upl有限责任公司 | Fungicidal compositions |
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