CN102258023B - Sterilizing composition containing fludioxonil and metalaxyl - Google Patents

Sterilizing composition containing fludioxonil and metalaxyl Download PDF

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CN102258023B
CN102258023B CN 201010195338 CN201010195338A CN102258023B CN 102258023 B CN102258023 B CN 102258023B CN 201010195338 CN201010195338 CN 201010195338 CN 201010195338 A CN201010195338 A CN 201010195338A CN 102258023 B CN102258023 B CN 102258023B
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metalaxyl
fludioxonil
bactericidal composition
sterilizing composition
agent
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CN102258023A (en
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李雪莲
冯涵丽
白复芹
张珊珊
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Qingdao Audis Bio & Tech Co Ltd
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Qingdao Audis Bio & Tech Co Ltd
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Abstract

The invention discloses a sterilizing composition containing fludioxonil and metalaxyl, a preparation method thereof, and an application thereof. The sterilizing composition is characterized in that: the sterilizing composition comprises fludioxonil, metalaxyl, and other auxiliary agents. A weight ratio of fludioxonil to metalaxyl is 70:1-1:60. The sterilizing composition can be used for controlling paddy rice blast. The sterilizing composition has advantages of low cost and good effect. No report about fludioxonil and metalaxyl blending is found home or abroad. Therefore, the invention is provided.

Description

A kind of bactericidal composition that contains fludioxonil and metalaxyl
Technical field
The invention belongs to the agriculture chemical compounding field, relate to a kind of bactericidal composition, especially a kind of bactericidal composition and the application of this bactericidal composition in agricultural production thereof take fludioxonil and metalaxyl as main active component.
Background technology
Using chemical agent is the most effectively means of controlling plant diseases.But long-term use single chemical bactericide continuously high dose, easily cause the problems such as residual, the environmental pollution of medicament and anti-pesticide resistance fungi development.Reasonably chemical bactericide is composite or be mixed and have the expansion fungicidal spectrum, improve control efficiency, extend the optimum period for applying fertilizer, reduce dosage, reduce poisoning, reduce residual, delay Antifungal resistance and the positive characteristics such as drug-fast generation and development, bactericide compounded is one of the effective method the most that addresses the above problem.Exploitation new product bactericide price is constantly soaring, and by contrast, exploitation is efficient with research, low toxicity, low-residual composite be mixed have small investment, the lead time is short and be subject to domestic and international attention, the numerous and confused dynamics that develops that strengthens.
Fludioxonil:
Figure GSA00000134595900011
The mechanism of action mainly suppresses the relevant transfer of glucose phosphorylated with characteristics, and the mycelial growth of Antifungi, finally causes germ dead, because of the mechanism of action unique, therefore with existing biocide agent without cross resistance.Active ingredient does not move in soil, thereby forms a stable and lasting guard circle around dispenser.Lasting period was more than 4 months.
Metalaxyl:
Figure GSA00000134595900012
The tasteless crystal of white, fusing point 71.8-72.3 ℃, vapour pressure 0.75mPa (25 ℃), density 1.20 (20 ℃), KowlogP=1.75 (distilled water, 25 ℃), solvability water 8.4g/l (22 ℃), ethanol 400, acetone 450, toluene 340, n-hexane 11, n-octyl alcohol 68 (g/L, 25 ℃), stable below 300 ℃, in neutrality, acid medium stable (room temperature).The systemic fungicide of tool protection and therapeutic action; can be absorbed by the root of plant, stem, leaf, and transfer to each organ of plant with moisture content in plant corpus, can make cauline leaf and process; seed treatment and soil treatment are effective to downy mildew, phytophthora, the caused disease of pythium spp.
Summary of the invention
The object of the invention is to for the problems referred to above, for pesticide resistance, enhancing drug effect, the reduction drug cost that overcomes and delay existing agricultural chemicals, thereby provide a kind of bactericidal composition of preventing and treating the various crop fungal disease.
A further object of the invention is to provide the purposes of this bactericidal composition.
Measure of the present invention realizes by following measures.
A kind of bactericidal composition, it contains fludioxonil and metalaxyl, and wherein the weight ratio of fludioxonil and metalaxyl is 70: 1~1: 60.
Described bactericidal composition, wherein the more excellent weight ratio of fludioxonil and metalaxyl is 50: 3~1: 40.
Described bactericidal composition, wherein the weight ratio of two kinds of shared preparations of active principle accumulation of fludioxonil and metalaxyl is 2~71%.
Described bactericidal composition, fludioxonil and metalaxyl and auxiliary agent, carrier etc. are processed into any one formulation that allows on agricultural chemicals.
Described bactericidal composition is characterized in that the formulation that can be processed into is suspending agent, wetting powder, water dispersible granules and microcapsule formulations etc.
Described bactericidal composition is used for preventing and treating the multiple fungal disease of various crop.
Microbicide compositions with synergistic effect takes following measures to realize:
One of technical scheme of the present invention, described bactericidal composition are suspending agent, and the percentage by weight of component is:
Fludioxonil 1~70%
Metalaxyl 1~80%
Dispersant 5~20%
Antifreezing agent 0.5~3%
Thickener 0.1~2%
Defoamer 0.1~0.8%
Water surplus
The concrete production stage of this bactericidal composition suspending agent is for first mixing other auxiliary agents, mix through high speed shear, add fludioxonil and metalaxyl, abrading-ball is 2~3 hours in ball crusher, make a diameter all below 5mm, make the suspending agent preparation that contains the bactericidal composition of fludioxonil and metalaxyl of the present invention.
Two of technical scheme of the present invention, described bactericidal composition are wetting powder, and the percentage by weight of component is:
Fludioxonil 1~70%
Metalaxyl 1~80%
Dispersant 3~20%
Wetting agent 3~10%
Filler 10~70%
The concrete procedure of processing of this bactericidal composition wetting powder is: press above-mentioned formula with fludioxonil and metalaxyl and dispersant, wetting agent and filler mixing, uniform stirring in stirred tank, mixing after airslide disintegrating mill, namely can be made into the wetting powder of the present composition.
Three of technical scheme of the present invention, described bactericidal composition are water dispersible granules, and the percentage by weight of component is:
Fludioxonil 1~70%
Metalaxyl 1~80%
Dispersant 3~20%
Wetting agent 3~10%
Disintegrant 2~5%
Filler 10~70%
The concrete procedure of processing of this bactericidal composition water dispersible granules is: by above-mentioned formula, fludioxonil, metalaxyl and dispersant, wetting agent, disintegrant and filler are mixed, pulverize with micro jet, through mediating, then add and carry out granulation, drying, screening in the fluidized bed prilling dryer by sample analysis, make the water dispersible granules that contains the bactericidal composition of fludioxonil and metalaxyl of the present invention.
Four of technical scheme of the present invention, described bactericidal composition are microcapsule formulations, and the percentage by weight of component is:
Fludioxonil 1~70%
Metalaxyl 1~80%
Urea 5~20%
Formaldehyde 5~20%
Emulsifying dispersant 5~20%
Antifreezing agent 1~5%
Thickener 0.1~2%
Defoamer 0.1~0.8%
Water surplus
This bactericidal composition microcapsule formulations procedure of processing is: add urea and formaldehyde (molar ratio be about 1: 1.5~2.0) in the there-necked flask of agitating device is housed, with the pH value to 8 of sodium hydroxide solution regulator solution~9 left and right, then be warming up to 70~80 ℃, reaction obtains stable urea resin prepolymer.The former medicine of getting a certain amount of fludioxonil and metalaxyl is dissolved in cyclohexane, and adds emulsifying dispersant in solution, follows vigorous stirring, and the aqueous solution that is made into to contain emulsifying dispersant is the O/W type stable emulsion of water.Above-mentioned urea resin prepolymer is added in emulsion, regulate the pH value, polymerization reaction take place under the acid catalysis condition is wrapped oil phase substance, forms microcapsule granule.Slowly heat up, solidify, temperature is controlled at 40~50 ℃, hardening time 1h.Selection adds appropriate auxiliary agent, the microcapsule suspending agent that gets final product stablely.
Described emulsifier is selected from any one or more mixtures that form with arbitrary proportion in calcium dodecyl benzene sulfonate and aliphatic acid polyethenoxy ether, alkylphenol polyoxyethylene sulfosuccinate, styrylphenol polyoxyethylene ether, polyoxyethylene nonylphenol ether, castor oil polyoxyethylene ether, aliphatic acid polyethenoxy base ester, polyoxyethylene aliphatic alcohol ether.
Described dispersant is selected from one or more in polycarboxylate, sodium lignin sulfonate, alkylphenol polyoxyethylene formaldehyde condensation products sulphate, alkyl benzene sulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, alkylphenol polyoxyethylene, aliphatic acid polyethenoxy ether, polyoxyethylene carboxylate, fatty acid glyceride APEO.
Described wetting agent is selected from: one or more in lauryl sodium sulfate, calcium dodecyl benzene sulfonate, Nekal BX, wetting and penetrating agent F, alkylnaphthalene sulfonate, alkylphenol ethoxylate, polyoxyethylene triphenylethylene phosphenylic acid salt, spaonin powder, silkworm excrement, soapberry powder.
Described synergist refers to have enhancing medicament penetration, wetting extended capability, knock down insect speed, improve the resistance of rainwater washing against power of agricultural chemicals, thereby improve a class safety, environmental protection of agricultural insecticide, bactericidal effect, the New-type adjuvant of nontoxic, noresidue, optional any in organic silicon pesticide synergist ZC-650 or organic silicon pesticide bleeding agent spreading agent Agrowet810c, agricultural organic silicon pesticide synergist Silwet408, azone.
Described disintegrant is selected from: one or more in bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, sodium bicarbonate.
Described thickener is selected from: one or more in xanthans, CMC, hydroxyethylcellulose, methylcellulose, Magnesiumaluminumsilicate, polyvinyl alcohol.
Described antifreeze is selected from: one or more in ethylene glycol, propane diols, glycerine, diethylene glycol (DEG), triethylene glycol.
Described defoamer is selected from: silicone oil, silicone compound, C 10-20Saturated fat acid compounds, C 8-10One or more in aliphatic alcohols compound and polyoxyethylene glycerol ether.
Described emulsifying dispersant comprises: wetting agent, dispersant, stabilizing agent, thickener, defoamer and antifreezing agent etc.
Described filler is selected from: one or more in kaolin, diatomite, bentonite, attapulgite, white carbon, starch, precipitated calcium carbonate.
The invention has the beneficial effects as follows:
1, the present invention's fludioxonil used is the mycelium synthetic inhibitor; the mechanism of action is unique; metalaxyl is that the protection with interior absorption adds the curative fungicide agent; have very strong interior absorption, both the mechanism of action is different, and mutually being mixed can not produce conflict; through evidence; but Synergistic reduces dosage, reduces costs.At present fludioxonil and metalaxyl composite not yet has report.
2, two kinds of composite bactericide have double action mechanism, delay the drug-fast generation of germ.
3, reduce the agricultural chemicals usage amount, strengthened the friendly to environment.
Embodiment: fludioxonil and metalaxyl composite
1 materials and methods
1.1 test material
1.1.1 reagent agent
The 95.8% former medicine of fludioxonil is produced by Shaanxi Heng Run chemical industry Co., Ltd; The 98% former medicine of metalaxyl, GuangDong LiWei Chemical Engineering Co., Ltd produces;
1.1.2 for the examination pathogen
The cucumber root rot bacterium gathers sick leaf in Shouguang, Shandong green house, and the separation and purification gained is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and preserved.
1.1.3 for the examination medium
PDA medium: potato 200g, glucose 20g, agar 20g, water 1000ml
1.2 test method and Tests of Synergistic Actions
1.2.1 two kinds of single doses toxicity test to sheath blight fungus
The 95.8% former medicine of fludioxonil and the former medicine of 98% metalaxyl all are made into the mother liquor of 10000 μ g/ml with the methyl alcohol dissolving, preserve in 4 ℃ of lower low temperature, and be stand-by.The Tween 80 aqueous solution with 0.1% before test is diluted to 5 ~ 6 series concentration.
At first be the preparation of bacterial classification and bacterium cake: under sterile working, the cucumber root rot bacterium is seeded on the PDA medium, at 25 ℃, cultivates after 4 days in the mold incubator of RH80%, beat at colony edge with the diameter of the sterilization card punch that is 0.5cm and get bacterium cake number piece, standby.
Next is the preparation of toxic medium: under sterile working, accurately measure successively the liquid that configures from the low concentration to the high concentration adds and melts and be cooled in the medium of 45 ℃ of left and right with liquid-transfering gun, pouring sterilized diameter after mixing into is the interior condensation of culture dish of 9cm, each processes triplicate, not contain medicament as contrast, finally to make the toxic flat board that contains the variable concentrations liquid.
Be that liquid is processed at last: under sterile working, the bacterium cake is moved to toxic dull and stereotyped central authorities, face down is placed in 25 ℃ of incubators and cultivates 4d, when the control strain colony diameter grows to 6.5cm when above, adopts " right-angled intersection method " to measure.According to the linear regression analysis between the logarithm value of the probit value of inhibiting rate and medicine series concentration, obtain the EC that two kinds of single doses suppress mycelial growths 50Value, correlation coefficient and virulence regression equation.
On the basis of preliminary experiment, respectively single dose fludioxonil and metalaxyl are carried out toxicity test, both EC in order to upper method 50Value is respectively 0.12mg/l and 0.18mg/l.
Combination arranges 1.2.2 be mixed
50% fludioxonil metalaxyl mass ratio was respectively 1: 3,1: 2,1: 1,2: 1,3: 1, i.e. 12.5%+37.5%, 16.67%+33.33%, 25%+25%, 33.33%+16.67%, 37.5%+12.5% totally 5 combinations that are mixed.
1.2.3 mixture toxicity test
Carry out the toxicity test of mixture according to mixed ratio with single dose toxicity test method.
EC that each that will measure according to the abundant method of Sun Yun processed 50Value is converted into actual mixed toxicity index (ATI); According to the proportioning of mixture, obtain theoretical mixed toxicity index (TTI), calculate the co-toxicity coefficient (CTC) of mixture by following formula.
Single dose 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 X B in mixed of the content (%) of the toxicity index x A of TII=A in mixed+B
CTC=(ATI/TTI)×100
If co-toxicity coefficient is large 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
Data see Table 1
The composite virulence to the cucumber root rot bacterium of table 1 fludioxonil and metalaxyl
Figure GSA00000134595900061
The composite co-toxicity to the cucumber root rot bacterium of table 2 fludioxonil and metalaxyl
Figure GSA00000134595900071
2 results and analysis
According to bactericide joint toxicity measuring result, fludioxonil and metalaxyl mass ratio are that the co-toxicity coefficient of 1: 2 o'clock is 129.4, and be obviously large 120, shows as synergistic effect, thinks that fludioxonil and metalaxyl mass ratio are best proportioning at 1: 2.
3 field trials are measured the control efficiency to cucumber root rot and root rot
3.1 field trial is measured the control efficiency to cucumber root rot
3.1.1 application method
Adopt and fill with the root test: select root rot that more uniform plot occurs, at the pathogenetic initial stage of root-rot, every kind of medicament is established 3 variable concentrations, and to fill with clear water as contrast, every processing repeats 4 times, and 100 strains, every strain perfusion liquid 250ml are filled with in every residential quarter.
3.1.2 investigation method
Every residential quarter takes immediately disease plant and is not less than 30 strains, records total strain number and diseased plant number at different levels.
The root rot grade scale
0 grade: plants stems base portion and main root are all without scab;
1 grade: plants stems base portion and main root have a small amount of scab;
3 grades: basal part of stem or main root scab are more, and lesion area accounts for 1/4~1/2 of stem and the root gross area;
5 grades: basal part of stem or main root scab are more and larger, and lesion area accounts for 1/2~3/4 of stem and the root gross area;
7 grades: basal part of stem or main root scab form in flakes around the stem phenomenon, but root system is not dead;
9 grades: root system is downright bad, and here above-ground plant parts withers or be dead.
3.1.3 control time and number of times
This test is investigated 4 times altogether, disease index before the investigation medicine before dispenser respectively, and after dispenser, each investigation of 10 days, 30 days and 60 days is once.
3.1.4 drug effect computational methods
Disease index=∑ (diseased plant numbers at different levels * relative level numerical value)/(investigating total strain number * 9) * 100
Figure GSA00000134595900072
3.1.5 result of the test and analysis
Each processes the effect of control cucumber root rot table 3
Figure GSA00000134595900081
Interpretation of result:
As can be seen from Table 3, the effect of the 50% fludioxonil metalaxyl wetting powder combination control cucumber root rot that is mixed of 1: 2 is remarkable.Every mu under same dosage, the effect of complex preparation significantly is better than two kinds of single doses.Complex preparation significantly is better than effect under the low concentration consumption in control efficiency under the consumption of high concentration.Experiment results proved, 50% fludioxonil single dose effect is better than 50% metalaxyl single dose.Under rational proportion, play remarkable synergistic effect.Owing to adopting root-pouring method, the special role mechanism of complex preparation is brought into play drug effect gradually, and the root rot of highly effective control further develops.Significant in production practices again, it is promoted with use and answers undoubtedly the required of market.
3.2 field trial is measured the control efficiency to root rot
3.2.1 result of the test and analysis
Each processes the effect of preventing and treating root rot table 4
Figure GSA00000134595900082
Figure GSA00000134595900091
Interpretation of result:
As can be seen from Table 4, to prevent and treat the effect of root rot remarkable in the combination that is mixed of 50% fludioxonil metalaxyl wetting powder 1: 2.Every mu under same dosage, the effect of complex preparation significantly is better than two kinds of single doses.Complex preparation significantly is better than effect under the low concentration consumption in control efficiency under the consumption of high concentration.Experiment results proved, 50% fludioxonil single dose effect is better than 50% metalaxyl single dose.Complex preparation after medicine 60 days, the highest control efficiency can reach 82% left and right, is the desirable medicament of preventing and treating root rot.
In sum, the present invention contains the Bactericidal composite of fludioxonil and metalaxyl, cucumber root rot and pathogen of soybean root rot there is good control efficiency, and it is to the target crop safety, compare with single dose, bactericidal composition of the present invention has advantages of that the lasting period is long, and is easy to use, environmental pollution is few, is difficult for producing poisoning.Simultaneously, because this complex preparation contains fludioxonil, itself is tagging property bactericide, high-efficiency broad spectrum.The microbial kind biography of many cause of diseases such as sac fungi, basidiomycetes, imperfect fungus and soil-borne disease there is extraordinary preventive effect.Lasting period is long, and is difficult for and other bactericide generation cross resistance, uses wide spectrum.In view of the extremely difficult control of present root rot, larger to causing harm of crop.So research and development of the present invention and popularization are of great significance social tool.

Claims (3)

1. bactericidal composition that contains fludioxonil and metalaxyl, it is characterized in that: the active ingredient of this bactericidal composition is fludioxonil and metalaxyl binary built, and wherein the mass ratio of active ingredient fludioxonil and metalaxyl is 1: 2.
2. bactericidal composition according to claim 1, it is characterized in that: fludioxonil and the metalaxyl gross weight in preparation accounts for 2~71% of the whole quality of the pharmaceutical preparations.
3. bactericidal composition according to claim 1 and 2, it is characterized in that: the formulation of this bactericidal composition is suspending agent, wetting powder, water dispersible granules and microcapsule formulations.
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CN105994324B (en) * 2016-08-03 2017-10-13 顾爱国 A kind of bactericidal composition of pyraclostrobin-containing, metalaxyl and fludioxonil
CN108935477A (en) * 2018-08-31 2018-12-07 济南仕邦农化有限公司 A kind of suspension seed-coating agent and its application
CN113598166A (en) * 2021-08-13 2021-11-05 石家庄农信生物科技集团有限公司 Bactericidal granules and preparation method and application thereof

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Bueno Junior et al..Effect of fungicides on survival of Bradyrhizobium japonicum(Semia 5019 and Semia 5079)and soybean nodulation.《Acta Scientiarum, Agronomy》.2003,第25卷(第1期),231-235.
Effect of fungicides on survival of Bradyrhizobium japonicum(Semia 5019 and Semia 5079)and soybean nodulation;Bueno Junior et al.;《Acta Scientiarum, Agronomy》;20031231;第25卷(第1期);231-235 *

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