Background technology
Flusilazole (flusilazole) belongs to triazole bactericidal agent, and this medicine mainly is the biosynthesis that destroys and stop the cell membrane important composition composition ergosterol of germ, causes cell membrane not form, and makes germ death.In the antithetical phrase due to the germ of Gammaproteobacteria, Basidiomycetes and Fungi Imperfecti disease effective.
Tebuconazole (tebuconazole) is the wide spectrum triazole bactericidal agent, has superior bioactive, consumption is low, interior absorption is stronger, applied widely, Tebuconazole by plant absorbing after, in plant tissue, shift to the top, can prevent and treat the multiple germ in the various crops, all can prevent and treat effectively Erysiphe, Puccinia, Rhynchosporium spp, nuclear cavity Pseudomonas and the microbial disease of Septoria.Because Flusilazole and Tebuconazole are extensive use of for many years in China, continuously independent all the year round use has made the germ pesticide resistance constantly strengthen, even continue to increase dispenser dosage, also is difficult to effective controlling plant diseases.
Chinese patent application CN101322494 discloses a kind of composition pesticide, and this composition pesticide contains azole active substance and N, N-dialkyl group chain alkyl acid amides.The N that adds q.s in composition, N-dialkyl group chain alkyl acid amides are used for stoping or the crystallization of azole active substance when suppressing to use said composition.Preferred N in the composition, N-dialkyl group chain alkyl acid amides is that general formula is worker's a compound, wherein: (a) represent alkyl for R1 and R2. contain 2 carbon atoms, R represents alkyl, contain 10 to 30 carbon atoms, or (b) R1 and R2 respectively represent alkyl, contain 3 carbon atoms, R represents alkyl, contain 9 to 30 carbon atoms, or (c) R1 and R2 respectively represent alkyl, contain 4 to 12 carbon atoms, R represents alkyl, contains 6 to 30 carbon atoms; When the active substance in the said composition was bactericide, said preparation can be more effective.Particularly bactericide is selected from Tebuconazole, cyproconazole, triticonazole, own azoles alcohol, Flutriafol, nitrile bacterium azoles, Difenoconazole, alkene azoles alcohol, propiconazole, tricyclazole, triticonazole, fluorine bacterium azoles, Flusilazole, metconazole one or more.But said composition does not disclose the proportioning of effective constituent, is suitable for inconvenient.Being mixed of different pesticide species is the common methods of the agriculture resistance disease of control.By the formulation of pesticide screening, filter out rational prescription, can effectively improve actual control efficiency, reduce dosage, reduce cost, delay the generation of disease drug resistance, be the important means of the disease comprehensive regulation.
Summary of the invention
The technical problem that the present invention need solve provides a kind of efficient, low toxicity, quick-acting is good and the lasting period is long, helps the fluorine silicon azoles of the disease comprehensive regulation and the composition pesticide of Tebuconazole.
For addressing the above problem, the technical solution adopted in the present invention is: the composition pesticide of a kind of fluorine silicon azoles and Tebuconazole, comprise usual auxiliaries and Flusilazole and Tebuconazole, the ratio of weight and number of Flusilazole and Tebuconazole is 10: 1-1: 10, and Flusilazole and the percentage by weight of Tebuconazole weight summation in composition pesticide are 1-70%.Flusilazole and the preferred weight percent of Tebuconazole weight summation in composition pesticide are 15-55%.
Further: the above-mentioned fluorine silicon azoles and the composition pesticide of Tebuconazole can be configured to missible oil, microemulsion, aqueous emulsion, suspending agent, wetting powder or water dispersible granules according to well known to a person skilled in the art method.
Preparation during missible oil used auxiliary agent as follows: the solvent of 1-30% and cosolvent by weight, solvent and cosolvent are arene, alcohols, ester class, ketone, amide-type etc., as toluene, dimethylbenzene, trimethylbenzene, dimethyl formamide, methyl alcohol, ethylene glycol, acetone, cyclohexanone, dimethyl sulfoxide (DMSO) etc., solvent and cosolvent can be wherein one or more mixing.The emulsifier of 1-15% by weight, emulsifier can be alkylbenzenesulfonate series, fatty alcohol-polyoxyethylene ether, polyoxyethylene nonyl phenyl propyl group APEO, phenethyl phenol polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ether, phenethyl polyoxy ethyl polyoxyethyl propyl ether, first contract polyoxyethylene nonylphenol ether, phenethyl phenol APEO, alkylphenol polyoxyethylene phosphate etc., and emulsifier can be wherein one or more mixing.The antifreezing agent of 1%-10% by weight, antifreezing agent can be one or more the mixing in glycerine, ethylene glycol, propane diols, sodium chloride, urea, the sorbierite etc.The stabilizing agent of 0.5%-8% by weight, stabilizing agent can be one or more the mixing in xanthan gum, Magnesiumaluminumsilicate, urea, methyl alcohol, benzinum, wettable starch, the cresyl glycidyl ether etc.The defoamer of 0.5%-8% by weight, defoamer can be one or more the mixing in organic silicone oil, methyl alcohol, ethanol, the epoxy soybean wet goods.The pH value conditioning agent of 0%-1% by weight, pH value conditioning agent are one or more the mixing in sodium hydroxide, oxyammonia, acetic acid, the hydrochloric acid etc.
Preparation during microemulsion used auxiliary agent as follows: the solvent of 1-20% and cosolvent by weight, solvent and cosolvent are arene, alcohols, ester class, ketone, amide-type etc., as toluene, dimethylbenzene, trimethylbenzene, dimethyl formamide, methyl alcohol, ethylene glycol, acetone, cyclohexanone, dimethyl sulfoxide (DMSO) etc., can be one or more mixing wherein.The emulsifier of 1-20% by weight, emulsifier can be alkylbenzenesulfonate series, fatty alcohol-polyoxyethylene ether, polyoxyethylene nonyl phenyl propyl group APEO, phenethyl phenol polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ether, phenethyl polyoxy ethyl polyoxyethyl propyl ether, first contract polyoxyethylene nonylphenol ether, phenethyl phenol APEO, alkylphenol polyoxyethylene phosphate etc., and emulsifier can be wherein one or more mixing.The antifreezing agent of 1%-10% by weight, antifreezing agent can be one or more the mixing in glycerine, ethylene glycol, propane diols, sodium chloride, urea, the sorbierite etc.The stabilizing agent of 0.5%-8% by weight, stabilizing agent can be one or more the mixing in xanthan gum, Magnesiumaluminumsilicate, urea, methyl alcohol, benzinum, wettable starch, the cresyl glycidyl ether etc.The defoamer of 0.5%-8% by weight, defoamer can be one or more the mixing in organic silicone oil, methyl alcohol, ethanol, the epoxy soybean wet goods.The pH value conditioning agent of 0%-1% by weight, pH value conditioning agent are one or more the mixing in sodium hydroxide, oxyammonia, acetic acid, the hydrochloric acid etc.
Preparation during suspending agent used auxiliary agent as follows: the solvent of 1%-10% and cosolvent by weight, solvent and cosolvent can be one or more the mixing in castor oil, transformer oil, dimethylbenzene, soya-bean oil, machine oil, diesel oil, dimethyl formamide, methyl alcohol, ethylene glycol, the acetonitrile.The wetting agent of 1%-15% by weight, wetting agent can be alkylbenzenesulfonate series, alkylphenol polyoxyethylene, styryl phenol polyethenoxy ether, castor oil polyoxyethylene ether, fatty acid polyglycol oxy alkylene ester, benzylphenol polyoxyethylene groups polyoxypropylene base ether, phosphoric acid ester etc.Wetting agent can be wherein one or more mixing.The dispersant of 1%-10% by weight, dispersant are one or more the mixing in naphthalene or Fluhyzon formaldehyde condensation products and salt, fatty alcohol ethylene oxide adduct sulfonate, alkylphenol-polyethenoxy base ether sulfonate, lignin and derivative sulfonate thereof, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose etc.The antifreezing agent of 0.5%-8% by weight, antifreezing agent can be one or more the mixing in glycerine, ethylene glycol, propane diols, sodium chloride, urea, the sorbierite etc.The stabilizing agent of 0.5%-8% by weight, stabilizing agent can be one or more the mixing in xanthan gum, Magnesiumaluminumsilicate, urea, methyl alcohol, benzinum, wettable starch, the cresyl glycidyl ether etc.The defoamer of 0.2%-5% by weight, defoamer can be one or more the mixing in organic silicone oil, methyl alcohol, ethanol, the epoxy soybean wet goods.The pH value conditioning agent of 0%-1% by weight, pH value conditioning agent are one or more the mixing in sodium hydroxide, oxyammonia, acetic acid, the hydrochloric acid etc.The thickener of 0%-5% by weight, thickener are one or more the mixing in methylcellulose, polyvinyl alcohol, gum Arabic, the polyvinylpyrrolidone etc.
Preparation during aqueous emulsion used auxiliary agent as follows: the solvent of 3%-30% and cosolvent by weight, solvent and cosolvent can be one or more the mixing in castor oil, transformer oil, dimethylbenzene, soya-bean oil, machine oil, diesel oil, dimethyl formamide, methyl alcohol, ethylene glycol, the acetonitrile etc.The emulsifier of 1%-15% by weight, emulsifier can be alkylbenzenesulfonate series, alkylphenol polyoxyethylene, styryl phenol polyethenoxy ether, castor oil polyoxyethylene ether, fatty acid polyglycol oxy alkylene ester, benzylphenol polyoxyethylene groups polyoxypropylene base ether, phosphoric acid ester etc.Emulsifier can be wherein one or more mixing.The dispersant of 0.1%-10% by weight, dispersant are one or more the mixing in naphthalene or Fluhyzon formaldehyde condensation products and salt, fatty alcohol ethylene oxide adduct sulfonate, lignin and derivative sulfonate thereof, fatty acid ethane addition product phosphate, alkylphenol-polyethenoxy based phosphates, carboxymethyl cellulose, polyvinyl alcohol, N-Methyl pyrrolidone, polyethylene glycol etc.The antifreezing agent of 0.5%-8% by weight, antifreezing agent can be one or more the mixing in glycerine, ethylene glycol, propane diols, sodium chloride, urea, the sorbierite etc.The stabilizing agent of 0.5%-8% by weight, stabilizing agent can be one or more the mixing in xanthan gum, Magnesiumaluminumsilicate, urea, methyl alcohol, benzinum, wettable starch, the cresyl glycidyl ether etc.The defoamer of 0.2%-5% by weight, defoamer can be one or more the mixing in organic silicone oil, C10-20 saturated fat acids, epoxidized soybean oil, iodoxy amine, the ester ethers etc.The pH value conditioning agent of 0%-1% by weight, pH value conditioning agent are one or more the mixing in sodium hydroxide, oxyammonia, acetic acid, the hydrochloric acid etc.The thickener of 0%-5% by weight, thickener are one or more the mixing in methylcellulose, polyvinyl alcohol, gum Arabic, the polyvinylpyrrolidone etc.Mend to 100% with deionized water at last
Preparation during wetting powder used auxiliary agent as follows: the wetting agent of 1%-30% by weight, wetting agent can be that tea is withered, spaonin powder, bay alcohol radical sodium sulphate, neopelex, draw back one or more the mixing in powder, the washing powder etc.The dispersant of 3%-30% by weight, dispersant can be one or more the mixing in lignin and derivative sulfonate, fatty acid ethane addition product phosphate, alkyl phenol polyvinylether sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, naphthalene or Fluhyzon formaldehyde condensation products and salt, the alkylphenol-polyethenoxy based phosphates etc.The filler of 10%-50% by weight, filler can be one or more the mixing in kaolin, white carbon, talcum powder, precipitated calcium carbonate, montmorillonite, diatomite, cellulose powder, urea, bark powder, the ammonium nitrate etc.
Preparation during water dispersible granules used auxiliary agent as follows: the wetting agent of 1%-20% by weight, wetting agent can be one or more the mixing in sodium alkyl benzene sulfonate, sodium lignin sulfonate, fatty alcohol, polyoxyethylene carboxylate sodium sulfonate and ammonium salt, alkyl sulfate, alkylphenol polyoxyethylene, spaonin powder, the withered powder of tea etc.The dispersant of 1%-20% by weight, dispersant can be that ethoxylated dodecyl alcohol, naphthalenesulfonic acid-formaldehyde condensate (NNO), dioctyl sulfosuccinic acid are received, one or more the mixing among JFC, acrylate homopolymer sodium salt etc.The carrier of 5%-50% by weight, carrier can be one or more the mixing in kaolin, white carbon, precipitated calcium carbonate, montmorillonite, the diatomite etc.The disintegrant of 1%-15% by weight, disintegrant can be one or more the mixing in bentonite, urea, ammonium sulfate, sodium chloride, the magnesium chloride etc.The binding agent of 1%-10% by weight, binding agent can be one or more the mixing in starch, gelatin, polyvinyl alcohol, polyethylene glycol, starch, cyclodextrin, soybean lecithin, the rosin etc.The stabilizing agent of 1%-10% by weight, stabilizing agent can be one or more the mixing in benzinum, wettable starch, cresyl glycidyl ether, the sorbierite etc.
Composition pesticide provided by the invention adopts the method for spraying to use usually, also can adopt agricultural to go up other operation techniques of using as required.Chang Yong agricultural chemicals using method for example: spray-on process, bait method, seed treatment method, seed pelleting method, soil treatment method, fumigating system, fumigation method, semar technique etc.
The application of early stage or disease initial stage of origination takes place in plant disease in the composition pesticide that the present invention also provides fluorine silicon azoles and Tebuconazole, especially to the control of apple tree spot defoliation.
Compared with prior art, the present invention includes usual auxiliaries and Flusilazole and Tebuconazole, the ratio of weight and number of Flusilazole and Tebuconazole is 10: 1-1: 10, and Flusilazole and the percentage by weight of Tebuconazole weight summation in composition pesticide are 1-70%.Be that the present invention passes through repetition test, draw preferred prescription, show obvious synergistic effect, the control efficiency of composition is significantly improved than single agent, has reduced the using dosage of agricultural chemicals, has reduced cost.The active ingredient mechanism of action difference of composition pesticide provided by the invention, the application of composition can delay or overcome the drug-fast generation of germ, helps the comprehensive regulation.
Embodiment
The present invention includes usual auxiliaries and Flusilazole and Tebuconazole, the ratio of weight and number of Flusilazole and Tebuconazole is 10: 1-1: 10, and Flusilazole and the percentage by weight of Tebuconazole weight summation in composition pesticide are 1-70%.Be that the present invention passes through repetition test, draw preferred prescription, show obvious synergistic effect, the control efficiency of composition is significantly improved than single agent, has reduced the using dosage of agricultural chemicals, has reduced cost.
Below in conjunction with embodiment content of the present invention is described in further detail, mentioned content is not a limitation of the invention among the embodiment, and Selection of technological conditions such as temperature, time can be suited measures to local conditions and the result be there is no substantial effect among the preparation method.
At first, the basic scheme of summary material prescription of the present invention: the composition pesticide of a kind of fluorine silicon azoles and Tebuconazole, comprise usual auxiliaries and Flusilazole and Tebuconazole, it is characterized in that: the ratio of weight and number of Flusilazole and Tebuconazole is 10: 1-1: 10, and Flusilazole and the percentage by weight of Tebuconazole weight summation in composition pesticide are 1-70%.
Embodiment 1
Following material all is weight percentage: Flusilazole 30%, Tebuconazole 3%, emulsifier fatty alcohol-polyoxyethylene ether 4%, calcium dodecyl benzene sulfonate 5%, triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether 10%, defoamer epoxidized soybean oil 1%, stabilizing agent xanthan gum 0.5%, antifreezing agent glycerine 0.5%, surplus are solvent dimethyl formamide and dimethylbenzene.Above-mentioned prescription is added in the mixing kettle in proportion successively, promptly make 33% Flusilazole Tebuconazole missible oil after stirring.
Embodiment 2
Following material all is weight percentage: Flusilazole 20%, and Tebuconazole 4%, wetting agent draw back powder 3%, dispersant naphthalenesulfonate formaldehyde condensation compound 10%, filler talcum powder 5%, surplus is a filler kaolin.Above-mentioned prescription entered in the blender after the coarse crushing in proportion mix, behind comminution by gas stream, promptly make 24% Flusilazole Tebuconazole wetting powder again.
Embodiment 3
Following material all is weight percentage: Flusilazole 5%, Tebuconazole 10%, emulsifier neopelex 6%, calcium dodecyl benzene sulfonate 5%, dispersant N-Methyl pyrrolidone 8%, antifreezing agent sodium chloride 0.5%, stabilizing agent xanthan gum 0.3%, defoamer organosilicon 0.4%, thickener polyvinyl alcohol 4%, surplus are deionized water.Above-mentioned prescription Central Plains medicine, solvent, emulsifiers dissolve are become even oil phase; With the mixed water that gets of water-soluble component and deionized water in the above-mentioned prescription; Under high-speed stirred, with oil phase and the mixed 15% Flusilazole tebuconazole aqueous emulsion that gets of water.
Embodiment 4
Following material all is weight percentage: Flusilazole 5%, and Tebuconazole 25%, wetting agent lauryl sodium sulfate 6%, dispersant polycarboxylate 4%, disintegrant sodium chloride 2%, binding agent polyethylene glycol 3%, stabilizing agent wettable starch 3%, surplus is a carrier kaolin.Dry pulverization process, granulation, drying, screening make 30% Flusilazole Tebuconazole water-dispersible granules in proportion with above-mentioned prescription.
Embodiment 5
Following material all is weight percentage: Flusilazole 5%, Tebuconazole 50%, emulsifier triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether 12%, wetting agent calcium dodecyl benzene sulfonate 5%, dispersant alkylphenol polyoxyethylene formaldehyde condensation products sulphate 3%, antifreeze glycol 0.2%, stabilizing agent xanthan gum 0.1%, defoamer organosilicon 0.4%, glycerine 5%, thickener gum Arabic 2%, surplus are deionized water.Above-mentioned prescription is pulverized in proportion in advance, added in the sand mill and grind, allotment makes 55% Flusilazole tebuconazole suspension concentrates after high shear mixing.
For the effect of the present composition effectively is described, below that composition of the present invention and single medicament is as follows to the field control effectiveness test comparative analysis as a result of apple tree spot defoliation respectively;
The medicament of optional above-mentioned 1-5 embodiment:
(1) the present invention: weight percentage is a 15%-55% Flusilazole tebuconazole aqueous emulsion (1#);
The contrast medicament:
(1) contain the single medicament of Tebuconazole: weight percentage is 25% tebuconazole aqueous emulsion (2#),
(2) the single medicament of fluorine silicon azoles: weight percentage is 10% Flusilazole aqueous emulsion (3#),
Spraying time: convert the water even spraying at apple tree spot defoliation their early stage.
Result of the test: see Table 1, as can be seen from the test results: after the dispenser 3 days, composition pesticide of the present invention to the control efficiency of apple tree spot defoliation more than 88%, significantly better than single agent; After the dispenser 7 days and 14 days, composition pesticide of the present invention all more than 90%, also significantly better than single agent, illustrate that composition pesticide of the present invention all is being better than single agent aspect quick-acting and the lasting effect, and cost reduced greatly to the control efficiency of apple tree spot defoliation.
The field control effectiveness test result of table 2, control apple tree spot defoliation
Reagent agent |
Extension rate (active ingredient dosage) |
1 day preventive effect (%) behind the medicine |
3 days preventive effects (%) behind the medicine |
7 days preventive effects (%) behind the medicine |
14 days preventive effects (%) behind the medicine |
??1# |
1500 times of liquid (100 mg/kg) |
??58.2 |
??88.5 |
??91.2 |
??92.0 |
??2# |
2500 times of liquid (100 mg/kg) |
??50.7 |
??81.3 |
??86.4 |
??86.9 |
??3# |
2000 times of liquid (50 mg/kg) |
??52.6 |
??82.2 |
??82.6 |
??88.3 |
Be mixed to the virulence of germ for further understanding Flusilazole and Tebuconazole, the inventor is mixed to Flusilazole and Tebuconazole and has carried out a large amount of formulation screening tests.
Test adopts the mycelial growth rate method to measure.To separate the alternaria leaf spot of apple bacterium that obtains from the fresh morbidity material of apple tree spot defoliation and cultivate at oat medium, standby.Under aseptic technique, handle the sterilising medium that will melt in advance according to test and quantitatively add in the aseptic conical flask, from the low concentration to the high concentration, quantitatively draw soup successively, add respectively in the above-mentioned conical flask, fully shake up.To pour 4 diameters into be in the culture dish of 9cm to equivalent then, makes the pastille flat board of respective concentration.From the colony edge cut-off of cultivating 5d oat medium directly is the bacterium cake of 5mm, is inoculated in above-mentioned pastille flat board respectively, and test is established the processing that does not contain medicament and made blank, and every processing repeats for 4 times.26 ℃ of dark conditions are cultivated 5d down, measure colony diameter, calculate the inhibiting rate (%) of each concentration medicament to mycelial growth.
Growing state investigation pathogen mycelial growth situation according to bacterium in the blank culture dish.Use the kind of calliper colony diameter, unit is a millimeter (mm).Each bacterium colony with right-angled intersection method vertical survey diameter is respectively once got its mean value.
According to survey data, calculate each concentration of treatment to mycelial growth inhibition rate by NY/T1156.2-2006 for examination target bacterium, unit is percentage (%).
Logarithm value with drug concentration (mg/L) is independent variable x, is dependent variable y with the probit value of inhibiting rate, sets up the virulence regression equation formula respectively, adopts DPS software to calculate the EC of single agent and each proportioning mixture
50The co-toxicity coefficient (CTC) of (95% confidence limit) and mixture.
According to the NY/T1156.6-2006 bactericide synergy criteria for classifying: co-toxicity coefficient (CTC) 〉=120 shows as synergistic effect; Co-toxicity coefficient (CTC)≤120 shows as antagonism; 120<co-toxicity coefficient (CTC)<120 shows as summation action.
Table 1, Flusilazole and Tebuconazole and different proportioning are to the toxicity test result of apple tree spot defoliation
Reagent agent (active ingredient ratio of quality and the number of copies) |
Virulence regression equation y=a+bx |
Correlation coefficient |
??EC
50(mg/L) (95% confidence limit)
|
Co-toxicity coefficient (CTC value) |
Flusilazole |
??4.9002+1.6402x |
??0.9950 |
??1.15(1.03~1.29) |
??-- |
Tebuconazole |
??4.2327+1.5903x |
??0.9984 |
??3.04(2.86~3.23) |
??-- |
Flusilazole: Tebuconazole (10: 1) |
??4.9177+1.5722x |
??0.9960 |
??1.13(1.03~1.24) |
??147.93 |
Flusilazole: Tebuconazole (5: 1) |
??4.9108+1.6353x |
??0.9978 |
??1.13(1.05~1.22) |
??189.98 |
Flusilazole: Tebuconazole (1: 2) |
??5.0462+1.6013x |
??0.9992 |
??0.94(0.89~0.98) |
??209.86 |
Flusilazole: Tebuconazole (1: 5) |
??4.8156+1.6259x |
??0.9959 |
??1.30(1.17~1.44) |
??176.14 |
Flusilazole: Tebuconazole (1: 10) |
??4.7378+1.6605x |
??0.9931 |
??1.44(1.25~1.66) |
??165.82 |
From result of the test table 2 as can be seen, the composition pesticide of Flusilazole and Tebuconazole is 10 at ratio of quality and the number of copies: 1-1: between 10, co-toxicity coefficient (CTC value) promptly all shows obvious synergistic effect all greater than 120.Flusilazole and Tebuconazole are mixed and have reasonability and feasibility.