CN103960244B - Bactericidal composition containing Shen piperazine mycin - Google Patents
Bactericidal composition containing Shen piperazine mycin Download PDFInfo
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Abstract
The present invention relates to the bactericidal composition containing Shen piperazine mycin, active ingredient is the one of Shen piperazine mycin (A) and Fluoxastrobin (B).Wherein active ingredient (A) is 50: 1 ~ 1: 50 with the mass ratio of (B).Fungicidal composition of the present invention is mainly used in preventing and treating the fungal disease of melon dish crop, apple crop and field crop.
Description
The application is the divisional application of original application " bactericidal composition containing Shen piperazine mycin ", and the application number of original application is 201110437597.2, and on December 18 2011 applying date, patent of invention name is called " bactericidal composition containing Shen piperazine mycin ".
Technical field
The present invention relates to a kind of bactericidal composition, active ingredient is the one of Shen piperazine mycin (A) and methoxy acrylic ester compounds (B).
Background technology
Shen piperazine mycin is by the tunning of Pseudomonas bacterial strain M18, main component is phenazine-1-carboxylic acid (phenazine-1-carboxylic acid), has good inhibitory action to various plants pathogens such as rice sheath blight disease, cucumber blight dis-ease, watermelon blights.Shen piperazine mycin in Shanghai, Hubei, Hainan, Henan, the ground such as Gansu carried out large-area extend trial, shows good field efficacy to rice sheath blight disease, alternaria leaf spot of apple, watermelon blight, gummy stem blight of melon etc.
Methoxy acrylic ester compounds is a kind of extremely outstanding disinfectant use in agriculture, and the mitochondrial respiration of main interference pathogen, T suppression cell energy circulates.This series bactericidal agent mainly comprises kresoxim-methyl, ZEN 90160, Fluoxastrobin etc., has protection, treatment, eradicant action, is widely used in the important disease control of fruit tree, Cereal, vegetable category etc.It is efficient.Low toxicity, environmentally safe, with other conventional bactericide without cross resistance.But this type of compound effects site is single, easily causes the resistance of pathogen.
Under the tillage system reform of high density, high strength, chemical agent is one of important measures of administering day by day serious damage by disease and insect, has played important meaning to guarantee agricultural production.Having an outstanding effect when noval chemical compound is initial, often there is decline to a certain degree in the activity after long-term, single use.As kresoxim-methyl in the world many reports having resistance and occur, the effect of powdery mildew is not equal to before.Agriculture chemical compounding use is the effective means of comprehensive regulation resistance, and noval chemical compound and the composite use of other composition are convenient to applying of noval chemical compound, is beneficial to and controls developing of Disease Resistance.
Given this, the combination of exploitation containing Shen piperazine mycin and methoxy acrylic ester compounds has extremely important application value.
Summary of the invention
The object of the invention is to: a kind of bactericidal composition containing Shen piperazine mycin and methoxy acrylic ester compounds is provided.Through test that is a large amount of, that repeat, unexpected discovery Shen piperazine mycin and methoxy acrylic ester compounds have excellent synergy, and both are composite both can improve control efficiency, increase the control spectrum of Shen piperazine mycin, can delay mutually respective resistance again.
Technical scheme of the present invention is:
A kind of bactericidal composition, active ingredient forms by the one of Shen piperazine mycin (A) and methoxy acrylic ester compounds (B) is composite.
Described bactericidal composition, it is characterized in that active ingredient in composition (A) is 50:1 ~ 1:50 with the mass ratio of (B), preferably mass percent is 30:1 ~ 1:30, and better mass percent is 20:1 ~ 1:20.
Wherein said methoxy acrylic ester compounds comprises:
The molecular formula of kresoxim-methyl (English general kresoxim-methyl by name) is C
18h
19nO
4, chemical name is methyl (E)-2-methoxyimino-2-[2-(0-toloxyl) phenyl] acetate;
The molecular formula of Fluoxastrobin (English common name azoxystrobin) is C
22h
17n
3o
5, chemical name is (E)-2-{2-[6 (2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl } and-3-methoxy acrylate;
The molecular formula of oxime bacterium ester (English general trifloxystrobin by name) is C
20h
19f
3n
2o
4, chemical name is methyl (E)-methoxyl group imido grpup-{ (E)-α-[1-(the fluoro-m-tolyl of α, α-three)-ethyleneimino oxygen base]-o-tolyl } ethyl acetate;
The molecular formula of ZEN 90160 (English general picoxystrobin by name) is C
18h
16f
3nO
4, chemical name is (E)-3-methoxy-2-[2-[6-(trifluoromethyl)-2-pyridine oxygen methyl] phenyl] methyl acrylate;
The molecular formula of Enestroburin (English general enostroburin by name) is C
22h
27c
lnO
4, chemical name is α-[[[[4-(4-chlorphenyl)-Ding-3-alkene-2-base-] imido grpup] methyl] phenyl-'beta '-methoxy acrylic acid methyl esters;
The molecular formula of alkene oxime amine is C
21h
21c
l2n
3o
4, chemical name is N-methyl-2-[((((1-methyl-3-(2,6-dichlorophenyl)-2-acrylic) imido grpup) oxygen base) methyl) phenyl]-2-methoxyimino acetic amide;
The molecular formula of pyraclostrobin (English general pyraclostrobin by name) is C
19h
18cIN
3o
4, chemical name is methyl (N)-[[[1-(4-chlorobenzene) pyrazoles-3 base)-oxygen]-0-methoxyl group] and-N-methoxymethyl carbamate.
Described bactericidal composition, is characterized in that active ingredient accounts for 1% ~ 90% of composition total weight.
Described bactericidal composition, is characterized in that said composition can be made into suspending agent, wetting powder, seed coat agent, aqueous emulsion, microemulsion, missible oil, granule, water dispersible granules, and can need to use corresponding solvent, carrier and auxiliary agent according to exploitation.
Suitable solvent, auxiliary agent comprise: one or more combinations of toluene, dimethylbenzene, carrene, chloroform, paraffin, kerosene, diesel oil, methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, cyclohexanol, phenmethylol, cyclohexanone, isophorone, pyrrolidones, ethyl acetate, butyl acetate, ethylene acetate, methyl-sulfoxide etc.
Carrier comprises one or more combinations of clay, bentonite, attapulgite, calcium sulphate, precipitated calcium carbonate, sucrose, industrial chitin, silica gel, talcum powder, white carbon, sericite in powder etc.;
Available auxiliary agent comprises phosphoric acid salt, hydrochloric acid salt, lignosulphonates, naphthalenesulfonate, phenolsulfonic acid salt, succinic acid Sulfonates, polystyrene-based phenol polyethenoxy ether sulfate, Pluronic PE 6800, molecular weight is the macromolecular grafted copolymer of 20000-30000, triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, polystyrene-based phenol polyethenoxy ethers, polyoxyethylene nonylphenol ether class, polystyrene-based polyethenoxy ether class, alkyl naphthalene sulfonic acid salt, fatty alcohol polyethenoxy ether class, dialkyl succinylsuccinate Sulfonates, branched fatty alcohol polyethenoxy ether class, alkyl polyoxyethylene ether class, carboxyl alkyl cellulose class, hydroxy alkyl cellulose class, Magnesiumaluminumsilicate, xanthans, poly-alkyl silicon ethylene oxide, phosphoric acid, glacial acetic acid, citric acid, maleic acid, dibutyl hydroxy methane, butylated hydroxy anisole, ditert-butylhydro quinone, one or more combinations in n-propyl gallate etc.
Described bactericidal composition is mainly used in the fungal disease of control melon dish crop, apple crop and field crop.The main controlling object of bactericidal composition comprises: cucumber blight dis-ease (Mycosphaerella melonis (Pass.) Chiu et Walker), watermelon blight (Fusarium oxysporum f.sp.Niveum, FON), Fusarium solani (Fusarium solani (Mart.) App.et woll.)), capsicum epidemic disease (Phytophthoracapsici Leonian), pear scab (Venturia pirina (Cooke) Adh.), alternaria leaf spot of apple (Alternaria alternata f.sp.mali), lawn fusarium wilt (Pythium spp.P.aultimum, P.aphanidermatum), rice sheath blight disease (Rhizoctonia solani), false smut (Ustilaginoidea oryzae (Patou.) Bref=U.virens (Cooke) Tak.), rice blast (Pyricularia oryzae Cav.) etc.
Embodiment
Different compound is carried out Combination application, is one of effective control measures of administering the disease-resistant problem of damage by disease and insect.Synergistic combination can improve the control efficiency of medicament significantly, reduces the usage amount of agricultural chemicals.By composite test concrete in a large number, the one of unexpected discovery Shen piperazine mycin and methoxy acrylic ester compounds has significant synergies.The embodiment provided below for elaborating the present invention, and does not form limiting the scope of the invention.Experimental technique used by embodiment, if without specified otherwise, is conventional method; Percentage composition in embodiment, if without specified otherwise, is weight percentage.
Biologicall test example 1: Shen piperazine mycin and the composite Toxicity Determination to rice sheath blight disease of kresoxim-methyl
Subjects: rice sheath blight disease (Rhizoctonia solani), is gathered by field, through indoor separation and purification.
Test method: with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1156.5-2006 ", adopts Broad Bean Leaves method.Select susceptible broad bean potted plant, clip same area, growing way be consistent, be with petiolate blade, moisturizing process, is placed in culture dish.With the former medicine of acetone solution, with the Tween 80 water dilution of 0.1%, prepare 6 series mass concentration.Blade is fully infiltrated 5s in pre-configured liquid, drains unnecessary liquid, after natural air drying, have the one side of mycelia to be inoculated in process central vane diameter 5mm bacterium cake with inoculator, often process inoculation 30 leaves, after mark, moisturizing is cultivated.Test is established and is not made blank containing the process of medicament.Depending on blank incidence, measure the length and width (mm) of lesion diameter, calculate control efficiency.
Control efficiency (%)=(blank lesion diameter-chemicals treatment lesion diameter) × 100/ blank lesion diameter
Concentration EC in suppression is calculated by method of least squares
50, then calculate co-toxicity coefficient (CTC) according to the abundant method of Sun Yun.As CTC < 80, then composition shows as antagonism, and as 80 < CTC < 120, then composition shows as summation action, work as CTC>120, then composition shows as synergistic effect.
Actual measurement toxicity index (ATI)=(standard agent EC50/ reagent agent EC50) × 100
In theoretical toxicity index (TTI)=A medicament toxicity index × mixture A percentage composition+B medicament toxicity index × mixture in the percentage composition of B
Co-toxicity coefficient (CTC)=[the theoretical toxicity index (TTI) of mixture actual measurement toxicity index (ATI)/mixture] × 100
Toxicity test the results are shown in Table 1.
Table 1 Shen piperazine mycin and the composite Toxicity Determination result to rice sheath blight disease of kresoxim-methyl
Process | EC 50(μg/mL) | ATI | TTI | Co-toxicity coefficient CTC |
Shen piperazine mycin | 1.25 | 100.0 | / | / |
Kresoxim-methyl | 0.69 | 181.2 | / | / |
Shen piperazine mycin 50: kresoxim-methyl 1 | 0.98 | 127.6 | 101.6 | 125.6 |
Shen piperazine mycin 30: kresoxim-methyl 1 | 0.73 | 171.2 | 102.6 | 166.9 |
Shen piperazine mycin 20: kresoxim-methyl 1 | 0.6 | 208.3 | 103.9 | 200.6 |
Shen piperazine mycin 10: kresoxim-methyl 1 | 0.33 | 378.8 | 107.4 | 352.8 |
Shen piperazine mycin 1: kresoxim-methyl 1 | 0.27 | 463.0 | 140.6 | 329.3 |
Shen piperazine mycin 1: kresoxim-methyl 10 | 0.31 | 403.2 | 173.8 | 232.0 |
Shen piperazine mycin 1: kresoxim-methyl 20 | 0.37 | 337.8 | 177.3 | 190.6 |
Shen piperazine mycin 1: kresoxim-methyl 30 | 0.43 | 290.7 | 178.5 | 162.8 |
Shen piperazine mycin 1: kresoxim-methyl 50 | 0.57 | 219.3 | 179.6 | 122.1 |
Biologicall test example 2: Shen piperazine mycin and azoxystrobin compound are to the Toxicity Determination of watermelon blight
Subjects: watermelon blight (Fusarium oxysporum f.sp.Niveum, FON), is gathered by field, through indoor separation and purification.
Test method: with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1156.2-2006 ", mycelial growth rate method.
Test method and statistical method, with biologicall test example 1, calculate concentration EC in suppression by method of least squares
50, then calculate co-toxicity coefficient (CTC) according to the abundant method of Sun Yun.As CTC < 80, then composition shows as antagonism, and as 80 < CTC < 120, then composition shows as summation action, work as CTC>120, then composition shows as synergistic effect.
Toxicity test the results are shown in Table 2.
Table 2 Shen piperazine mycin and azoxystrobin compound are to the Toxicity Determination result of watermelon blight
Process | EC 50(μg/mL) | ATI | TTI | Co-toxicity coefficient CTC |
Shen piperazine mycin | 1.168 | 100.0 | / | / |
Fluoxastrobin | 0.61 | 191.5 | / | / |
Shen piperazine mycin 50: Fluoxastrobin 1 | 0.885 | 132.0 | 101.8 | 129.7 |
Shen piperazine mycin 30: Fluoxastrobin 1 | 0.701 | 166.6 | 103.0 | 161.8 |
Shen piperazine mycin 20: Fluoxastrobin 1 | 0.327 | 357.2 | 104.4 | 342.3 |
Shen piperazine mycin 10: Fluoxastrobin 1 | 0.211 | 553.6 | 108.3 | 511.1 |
Shen piperazine mycin 1: Fluoxastrobin 1 | 0.099 | 1179.8 | 145.7 | 809.5 |
Shen piperazine mycin 1: Fluoxastrobin 10 | 0.145 | 805.5 | 183.2 | 439.8 |
Shen piperazine mycin 1: Fluoxastrobin 20 | 0.274 | 426.3 | 187.1 | 227.8 |
Shen piperazine mycin 1: Fluoxastrobin 30 | 0.382 | 305.8 | 188.5 | 162.2 |
Shen piperazine mycin 1: Fluoxastrobin 50 | 0.501 | 233.1 | 189.7 | 122.9 |
Biologicall test example 3: Shen piperazine mycin and the composite Toxicity Determination to cucumber blight dis-ease of oxime bacterium ester
Subjects: cucumber blight dis-ease (Mycosphaerella melonis (Pass.) Chiu et Walker), is gathered by field, through indoor separation and purification.
Test method: with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1156.2-2006 ", mycelial growth rate method.With the former medicine of acetone solution, 0.1% Tween 80 water dilution, is prepared into 6 series mass concentration.Aseptically, get the liquid 5mL configured and mix with 75mL medium, make 4 pastille flat boards, mix in contrast with medium with equivalent sterile water.Cultured cucumber didymella bryoniae is aseptically cut bacterium cake with the sterilizing card punch of diameter 5mm from edge.With inoculator, pure culture biscuits involvng inoculation is dull and stereotyped central in pastille, mycelia faces down, and is placed in 25 DEG C of incubators.Depending on blank growing state investigation result, each bacterium colony right-angled intersection method vertical survey diameter is each once gets its mean value, calculates mycelial growth inhibition rate.Mycelial growth inhibition rate=(blank bacterium colony increases diameter-chemicals treatment bacterium colony and increases diameter) × 100/ blank bacterium colony increases diameter.
Concentration EC in suppression is calculated by method of least squares
50, then calculate co-toxicity coefficient (CTC) according to the abundant method of Sun Yun.Statistical method is with biologicall test example 1.As CTC < 80, then composition shows as antagonism, and as 80 < CTC < 120, then composition shows as summation action, work as CTC>120, then composition shows as synergistic effect.
Toxicity test the results are shown in Table 3.
Table 3 Shen piperazine mycin and the composite Toxicity Determination result to cucumber blight dis-ease of oxime bacterium ester
Process | EC 50(μg/mL) | ATI | TTI | Co-toxicity coefficient CTC |
Shen piperazine mycin | 0.646 | 100.0 | / | / |
Oxime bacterium ester | 0.228 | 283.3 | / | / |
Shen piperazine mycin 50: oxime bacterium ester 1 | 0.494 | 130.8 | 103.6 | 126.2 |
Shen piperazine mycin 30: oxime bacterium ester 1 | 0.365 | 177.0 | 105.9 | 167.1 |
Shen piperazine mycin 20: oxime bacterium ester 1 | 0.228 | 283.3 | 108.7 | 260.6 |
Shen piperazine mycin 10: oxime bacterium ester 1 | 0.098 | 659.2 | 116.7 | 565.0 |
Shen piperazine mycin 1: oxime bacterium ester 1 | 0.038 | 1700.0 | 191.7 | 887.0 |
Shen piperazine mycin 1: oxime bacterium ester 10 | 0.046 | 1404.3 | 266.7 | 526.6 |
Shen piperazine mycin 1: oxime bacterium ester 20 | 0.076 | 850.0 | 274.6 | 309.5 |
Shen piperazine mycin 1: oxime bacterium ester 30 | 0.145 | 445.5 | 277.4 | 160.6 |
Shen piperazine mycin 1: oxime bacterium ester 50 | 0.189 | 341.8 | 279.7 | 122.2 |
Biologicall test example 4: Shen piperazine mycin and the composite Toxicity Determination to cucumber blight dis-ease of ZEN 90160
Subjects: cucumber blight dis-ease (Mycosphaerella melonis (Pass.) Chiu et Walker), is gathered by field, through indoor separation and purification.
Test method: with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1156.2-2006 ", mycelial growth rate method.Test method, statistical method are with biologicall test example 3.Concentration EC in suppression is calculated by method of least squares
50, then calculate co-toxicity coefficient (CTC) according to the abundant method of Sun Yun.As CTC < 80, then composition shows as antagonism, and as 80 < CTC < 120, then composition shows as summation action, work as CTC>120, then composition shows as synergistic effect.
Toxicity test the results are shown in Table 4.
Table 4 Shen piperazine mycin and the composite Toxicity Determination result to cucumber blight dis-ease of ZEN 90160
Process | EC 50(μg/mL) | ATI | TTI | Co-toxicity coefficient CTC |
Shen piperazine mycin | 0.637 | 100.0 | / | / |
ZEN 90160 | 0.177 | 359.9 | / | / |
Shen piperazine mycin 50: ZEN 90160 1 | 0.496 | 128.4 | 105.1 | 122.2 |
Shen piperazine mycin 30: ZEN 90160 1 | 0.283 | 225.1 | 108.4 | 207.7 |
Shen piperazine mycin 20: ZEN 90160 1 | 0.177 | 359.9 | 112.4 | 320.3 |
Shen piperazine mycin 10: ZEN 90160 1 | 0.029 | 2196.6 | 123.6 | 1776.8 |
Shen piperazine mycin 1: ZEN 90160 1 | 0.035 | 1820.0 | 229.9 | 791.5 |
Shen piperazine mycin 1: ZEN 90160 10 | 0.051 | 1249.0 | 336.3 | 371.4 |
Shen piperazine mycin 1: ZEN 90160 20 | 0.066 | 965.2 | 347.5 | 277.7 |
Shen piperazine mycin 1: ZEN 90160 30 | 0.106 | 600.9 | 351.5 | 171.0 |
Shen piperazine mycin 1: ZEN 90160 50 | 0.142 | 448.6 | 354.8 | 126.4 |
Biologicall test example 5: Shen piperazine mycin and the composite Toxicity Determination to rice sheath blight disease of Enestroburin
Subjects: rice sheath blight disease (Rhizoctonia solani), is gathered by field, through indoor separation and purification.
Test method: with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1156.5-2006 ", adopt Broad Bean Leaves method, test method and statistical method are with biologicall test example 1.Concentration EC in suppression is calculated by method of least squares
50, then calculate co-toxicity coefficient (CTC) according to the abundant method of Sun Yun.As CTC < 80, then composition shows as antagonism, and as 80 < CTC < 120, then composition shows as summation action, work as CTC>120, then composition shows as synergistic effect.
Actual measurement toxicity index (ATI)=(standard agent EC
50/ reagent agent EC
50) × 100
In theoretical toxicity index (TTI)=A medicament toxicity index × mixture A percentage composition+B medicament toxicity index × mixture in the percentage composition of B
Co-toxicity coefficient (CTC)=[the theoretical toxicity index (TTI) of mixture actual measurement toxicity index (ATI)/mixture] × 100
Toxicity test the results are shown in Table 5.
Table 5 Shen piperazine mycin and the composite Toxicity Determination result to rice sheath blight disease of Enestroburin
Process | EC 50(μg/mL) | ATI | TTI | Co-toxicity coefficient CTC |
Shen piperazine mycin | 1.18 | 100.0 | / | / |
Enestroburin | 0.76 | 155.3 | / | / |
Shen piperazine mycin 50: Enestroburin 1 | 0.93 | 126.9 | 101.1 | 125.5 |
Shen piperazine mycin 30: Enestroburin 1 | 0.68 | 173.5 | 101.8 | 170.5 |
Shen piperazine mycin 20: Enestroburin 1 | 0.54 | 218.5 | 102.6 | 212.9 |
Shen piperazine mycin 10: Enestroburin 1 | 0.38 | 310.5 | 105.0 | 295.7 |
Shen piperazine mycin 1: Enestroburin 1 | 0.21 | 561.9 | 127.6 | 440.3 |
Shen piperazine mycin 1: Enestroburin 10 | 0.33 | 357.6 | 150.2 | 238.0 |
Shen piperazine mycin 1: Enestroburin 20 | 0.4 | 295.0 | 152.6 | 193.3 |
Shen piperazine mycin 1: Enestroburin 30 | 0.47 | 251.1 | 153.5 | 163.6 |
Shen piperazine mycin 1: Enestroburin 50 | 0.62 | 190.3 | 154.2 | 123.4 |
Biologicall test example 6: Shen piperazine mycin and the composite Toxicity Determination to rice sheath blight disease of alkene oxime amine
Subjects: rice sheath blight disease (Rhizoctonia solani), is gathered by field, through indoor separation and purification.
Test method: with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1156.5-2006 ", adopt Broad Bean Leaves method, test method and statistical method are with biologicall test example 1.
Toxicity test the results are shown in Table 6.
Table 6 Shen piperazine mycin and the composite Toxicity Determination result to rice sheath blight disease of alkene oxime amine
Process | EC 50(μg/mL) | ATI | TTI | Co-toxicity coefficient CTC |
Shen piperazine mycin | 1.22 | 100.0 | / | / |
Alkene oxime amine | 0.83 | 147.0 | / | / |
Shen piperazine mycin 50: alkene oxime amine 1 | 0.96 | 127.1 | 100.9 | 125.9 |
Shen piperazine mycin 30: alkene oxime amine 1 | 0.71 | 171.8 | 101.5 | 169.3 |
Shen piperazine mycin 20: alkene oxime amine 1 | 0.56 | 217.9 | 102.2 | 213.1 |
Shen piperazine mycin 10: alkene oxime amine 1 | 0.31 | 393.5 | 104.3 | 377.4 |
Shen piperazine mycin 1: alkene oxime amine 1 | 0.21 | 581.0 | 123.5 | 470.4 |
Shen piperazine mycin 1: alkene oxime amine 10 | 0.32 | 381.3 | 142.7 | 267.1 |
Shen piperazine mycin 1: alkene oxime amine 20 | 0.41 | 297.6 | 144.8 | 205.6 |
Shen piperazine mycin 1: alkene oxime amine 30 | 0.52 | 234.6 | 145.5 | 161.3 |
Shen piperazine mycin 1: alkene oxime amine 50 | 0.69 | 176.8 | 146.1 | 121.0 |
Biologicall test example 7: Shen piperazine mycin and the composite Toxicity Determination to watermelon blight of pyraclostrobin
Subjects: watermelon blight (Fusarium oxysporum f.sp.Niveum, FON), is gathered by field, through indoor separation and purification.
Test method: with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1156.2-2006 ", mycelial growth rate method.
Test method and statistical method, with biologicall test example 4, calculate concentration EC in suppression by method of least squares
50, then calculate co-toxicity coefficient (CTC) according to the abundant method of Sun Yun.As CTC < 80, then composition shows as antagonism, and as 80 < CTC < 120, then composition shows as summation action, work as CTC>120, then composition shows as synergistic effect.
Toxicity test the results are shown in Table 7.
Table 7 Shen piperazine mycin and the composite Toxicity Determination result to watermelon blight of pyraclostrobin
Table 1 is pointed out to table 7, and Shen piperazine mycin and methoxy acrylic ester compounds, at proportioning 50:1 ~ 1:50, have good synergistic effect, and especially between 30:1 ~ 1:30, embody more significant synergistic effect, co-toxicity coefficient is all more than 160.
Bactericidal composition of the present invention can be prepared into suspending agent, wetting powder, seed coat agent, aqueous emulsion, microemulsion, missible oil, granule, water dispersible granules by known method.Be described with specific embodiment below, in formula, percentage is mass percent.Active component Shen piperazine mycin and methoxy acrylic ester compounds compounded combination in varing proportions in present specification, methoxy acrylic ester compounds in single embodiment all can be substituted by other methoxy acrylic ester compounds or replace, and forms new embodiment.
Embodiment 1:51% Shen piperazine mycin 〃 kresoxim-methyl suspending agent
Shen piperazine mycin 50%, kresoxim-methyl 1%, methyl naphthalene sulfonate formaldehyde condensate 8%, sodium lignosulfonate 15%, xanthans 3%, silicone oil 5%, glycerine 8%, all the other water complement to 100%.Active component, dispersant and thickener are added in sand mill successively in the ratio of formula and processes, then send in mixer for well-distribution, even through shear agitation, obtained 51% Shen piperazine mycin 〃 kresoxim-methyl suspending agent.
This embodiment is applied to the water prevention rice sheath blight.By 51% Shen piperazine mycin 〃 kresoxim-methyl suspending agent, by active ingredient 200 grams/ha, (effective dose of Shen piperazine mycin is about 196 grams/ha, the effective dose of kresoxim-methyl is about 4 grams/ha) thin up spraying, every dispenser in 7 days once, continuous dispenser three times, control efficiency is respectively 96.1%.1% Shen piperazine mycin suspending agent, 30% kresoxim-methyl suspending agent respectively by active ingredient 300 grams/ha, 200 grams/ha process in the same way, the preventive effect after medicine is respectively 83.7%, 82.6%.Shen piperazine mycin and the composite rear synergistic effect of kresoxim-methyl are obvious, the consumption of the active ingredient in composition lower than the consumption of single dose, to the preventive effect of the rice sheath blight disease preventive effect significantly better than single dose.
Embodiment 2:62% Shen piperazine mycin 〃 Enestroburin wetting powder
Shen piperazine mycin 60%, Enestroburin 2%, pulls open powder 0.5%, lauryl sodium sulfate 2%, and white carbon 5%, attapulgite complements to 100%.The ratio of each components such as active component, dispersant, wetting agent in formula is mixed, after air-flow shatters, namely obtains 62% Shen piperazine mycin 〃 Enestroburin wetting powder.
This embodiment is applied to control capsicum epidemic disease.By 62% Shen piperazine mycin 〃 Enestroburin wetting powder, by active ingredient 250 grams/ha, (effective dose of Shen piperazine mycin is about 242 grams/ha, the effective dose of Enestroburin is about 8 grams/ha) thin up spraying, every dispenser in 7 days once, continuous dispenser three times, the control efficiency after medicine is 98.6%.1% Shen piperazine mycin suspending agent, 40% Enestroburin suspending agent respectively by active ingredient 300 grams/ha, 200 grams/ha in kind use, the preventive effect after medicine is respectively 74.1%, 81.2%.Shen piperazine mycin and the composite rear synergistic effect of Enestroburin are obvious, the effective ingredient consumption in composition lower than the consumption of single dose, to the preventive effect of the capsicum epidemic disease preventive effect significantly better than single dose.
Embodiment 3:42% Shen piperazine mycin 〃 alkene oxime amine seed coat agent
Shen piperazine mycin 40%, alkene oxime amine 2%, methyl naphthalene sulfonate formaldehyde condensate 8%, sodium lignosulfonate 10%, xanthans 3%, sodium carboxymethylcellulose 3%, glycerine 8%, polyvinylpyrrolidone 2%, acid scarlet 0.5%, all the other water complement to 100%.Active component, dispersant and thickener are added in sand mill successively in the ratio of formula and processes, then send in mixer for well-distribution, even through shear agitation, regulate pH value, obtained 42% Shen piperazine mycin 〃 alkene oxime amine seed coat agent.
This embodiment is applied to control Fusarium solani.42% Shen piperazine mycin 〃 alkene oxime amine seed coat agent dressed seed in the ratio of every double centner seed active ingredient 3 grams, the control efficiency after medicine is 97.5%.1% Shen piperazine mycin seed coat agent, 40% alkene oxime amine seed coat agent be every double centner seed active ingredient 4 grams, the ratio seed dressing of 2 grams respectively, and the preventive effect after medicine is respectively 76.2%, 71.8%.Shen piperazine mycin and the composite rear synergistic effect of alkene oxime amine are obvious, the consumption of the active ingredient in composition lower than the consumption of single dose, to the preventive effect of the Fusarium solani preventive effect significantly better than single dose.
Embodiment 4:11% Shen piperazine mycin 〃 trifloxystrobin water emulsion
Shen piperazine mycin 10%, oxime bacterium ester 1%, 1-METHYLPYRROLIDONE 10%, calcium dodecyl benzene sulfonate 5%, agriculture breast 600#5%, water complements to 100%.Former medicine, solvent, emulsifier are added together, make to be dissolved into homogeneous oil phase; By water-soluble component and the obtained aqueous phase of water mixing; Under high velocity agitation, oil phase is mixed with water, obtained 11% Shen piperazine mycin 〃 trifloxystrobin water emulsion.
This embodiment is applied to control alternaria leaf spot of apple.By 11% Shen piperazine mycin 〃 trifloxystrobin water emulsion, by active ingredient 200 grams/ha, (effective dose of Shen piperazine mycin is about 182 grams/ha, the effective dose of oxime bacterium ester is about 18 grams/ha) thin up spraying, every dispenser in 7 days once, continuous dispenser three times, the control efficiency after medicine is 98.2%.1% Shen piperazine mycin suspending agent, 50% oxime bacterium ester suspending agent are in kind used by 300 grams/ha, 300 grams/ha respectively, and the preventive effect after medicine is respectively 86.7%, 81.1%.Shen piperazine mycin and the composite rear synergistic effect of oxime bacterium ester are obvious, the consumption of the active ingredient in composition lower than the consumption of single dose, to the preventive effect of the alternaria leaf spot of apple preventive effect significantly better than single dose.
Embodiment 5:2% Shen piperazine mycin 〃 ZEN 90160 microemulsion
Shen piperazine mycin 1%, ZEN 90160 1%, 1-METHYLPYRROLIDONE 10%, isopropyl alcohol 10%, agriculture breast 500#5%, agriculture breast 1601#5%, water complements to 100%.Former medicine, solvent, emulsifier are added together, make to be dissolved into homogeneous oil phase; By water-soluble component and the obtained aqueous phase of water mixing; Under high velocity agitation, oil phase is mixed with water, obtained 2% Shen piperazine mycin 〃 ZEN 90160 microemulsion.
This embodiment is applied to prevents and treats potato black scurf.By 2% Shen piperazine mycin 〃 ZEN 90160 microemulsion, by active ingredient 300 grams/ha, (effective dose of Shen piperazine mycin is 150 grams/ha, the effective dose of ZEN 90160 is 150 grams/ha) thin up spraying, every dispenser in 7 days once, continuous dispenser three times, the control efficiency after medicine is 97.5%.1% Shen piperazine mycin suspending agent, 50% ZEN 90160 suspending agent are in kind used by 300 grams/ha, 250 grams/ha respectively, and the preventive effect after medicine is respectively 76.3%, 80.1%.Shen piperazine mycin and the composite rear synergistic effect of ZEN 90160 are obvious, the consumption of the active ingredient in composition lower than the consumption of single dose, to the preventive effect of the potato black scurf preventive effect significantly better than single dose.
Embodiment 6:22% Shen piperazine mycin 〃 Fluoxastrobin missible oil
Shen piperazine mycin 2%, Fluoxastrobin 20%, 1-METHYLPYRROLIDONE 8%, agriculture breast 1601#5%, agriculture breast 500#5%, dimethylbenzene complements to 100%.Active component, emulsifier and the auxiliary agent ratio in formula is added in mixing kettle successively, stirs, obtained 22% Shen piperazine mycin 〃 Fluoxastrobin missible oil.
This embodiment is applied to control cucumber blight dis-ease.By 22% Shen piperazine mycin 〃 Fluoxastrobin missible oil, by active ingredient 200 grams/ha, (effective dose of Shen piperazine mycin is about 18 grams/ha, the effective dose of Fluoxastrobin is about 182 grams/ha) thin up spraying, every dispenser in 7 days once, continuous dispenser three times, the control efficiency after medicine is 98.2%.1% Shen piperazine mycin suspending agent, 25% Fluoxastrobin suspending agent respectively by active ingredient 300 grams/ha, 200 grams/ha in kind use, the preventive effect after medicine is respectively 75.1%, 83.6%.After Shen piperazine mycin and azoxystrobin compound, synergistic effect is obvious, the consumption of the active ingredient in composition lower than the consumption of single dose, to the preventive effect of the cucumber blight dis-ease preventive effect significantly better than single dose.
Embodiment 7:2.1% Shen piperazine mycin 〃 pyraclostrobin aqueous emulsion
Shen piperazine mycin 0.1%, pyraclostrobin 2%, 1-METHYLPYRROLIDONE 3%, calcium dodecyl benzene sulfonate 5%, agriculture breast 600#3%, water complements to 100%.Former medicine, solvent, emulsifier are added together, make to be dissolved into homogeneous oil phase; By water-soluble component and the obtained aqueous phase of water mixing; Under high velocity agitation, oil phase is mixed with water, obtained 2.1% Shen piperazine mycin 〃 pyraclostrobin aqueous emulsion.
This embodiment is applied to lawn fusarium wilt.By 2.1% Shen piperazine mycin 〃 pyraclostrobin aqueous emulsion, by active ingredient 150 grams/ha, (effective dose of Shen piperazine mycin is about 7 grams/ha, the effective dose of pyraclostrobin is about 143 grams/ha) thin up spraying, every dispenser in 7 days once, continuous dispenser three times, the control efficiency after medicine is 98.4%.1% Shen piperazine mycin suspending agent, 30% pyraclostrobin suspending agent respectively by active ingredient 300 grams/ha, 200 grams/ha in kind use, the preventive effect after medicine is respectively 80.1%, 86.9%.Shen piperazine mycin and the composite rear synergistic effect of pyraclostrobin are obvious, the consumption of the active ingredient in composition lower than the consumption of single dose, to the preventive effect of the lawn fusarium wilt preventive effect significantly better than single dose.
Embodiment 8:3.1% Shen piperazine mycin 〃 Fluoxastrobin granule
Shen piperazine mycin 0.1%, Fluoxastrobin 3%, starch 3%, sodium lignin sulfonate 3%, ammonium lauryl sulfate 0.5%, supplies 100% with slag.Active component, auxiliary agent are mixed in the ratio of formula, mist projection granulating, with slag absorption, be drying to obtain 3.1% Shen piperazine mycin 〃 Fluoxastrobin granule.
This embodiment is applied to the watermelon blight in control seedling stage.By 3.1% Shen piperazine mycin 〃 Fluoxastrobin granule, by active ingredient 150 grams/ha, (effective dose of Shen piperazine mycin is about 5 grams/ha, the effective dose of Fluoxastrobin is about 145 grams/ha) spread fertilizer over the fields in plant root, every dispenser in 7 days once, continuous dispenser three times, control efficiency is respectively 98.6%.5% Shen piperazine mycin granule, 5% Fluoxastrobin granule in kind process by 300 grams/ha, 250 grams/ha respectively, and the preventive effect after medicine is respectively 76.2%, 83.5%.After Shen piperazine mycin and azoxystrobin compound, synergistic effect is obvious, the consumption of the active ingredient in composition lower than the consumption of single dose, to the preventive effect of the watermelon blight preventive effect significantly better than single dose.
Embodiment 9:51% Shen piperazine mycin water dispersion granules agent of Kresoxim
Shen piperazine mycin 1%, kresoxim-methyl 50%, sodium lignin sulfonate 6%, dodecyl sodium sulfate 1%, Magnesiumaluminumsilicate 3%, white carbon 3%, sodium alginate 1%, bentonite supplies 100%.The ratio of each components such as active component, dispersant, wetting agent in formula is mixed, through air-flow crushing, adds the water of 10 ~ 30%, then through kneading, granulation, dry obtained 51% Shen piperazine mycin water dispersion granules agent of Kresoxim.
This embodiment is applied to control wheat sharp eyespot.By 51% Shen piperazine mycin water dispersion granules agent of Kresoxim, (effective dose of Shen piperazine mycin is about 3 grams/ha by 150 grams/ha, the effective dose of kresoxim-methyl is about 147 grams/ha) thin up spraying, every dispenser in 7 days once, continuous dispenser three times, the control efficiency after medicine is 93.8%.1% Shen piperazine mycin suspending agent, 30% kresoxim-methyl suspending agent are in kind used by 300 grams/ha, 250 grams/ha respectively, and the preventive effect after medicine is respectively 81.7%, 81.3%.Shen piperazine mycin and the composite rear synergistic effect of kresoxim-methyl are obvious, the consumption of the active ingredient in composition lower than the consumption of single dose, to the preventive effect of the wheat sharp eyespot preventive effect significantly better than single dose.
Claims (5)
1. a bactericidal composition, active ingredient is the one of Shen piperazine mycin (A) and methoxy acrylic ester compounds (B), wherein active ingredient (A) is 50: 1 ~ 1: 50 with the mass ratio of (B), and described methoxy acrylic ester compounds is Fluoxastrobin.
2. bactericidal composition according to claim 1, is characterized in that active ingredient in composition (A) is 30: 1 ~ 1: 30 with the mass ratio of (B).
3. bactericidal composition according to claim 1, is characterized in that active ingredient in composition (A) is 20: 1 ~ 1: 20 with the mass ratio of (B).
4. the bactericidal composition according to any one of claims 1 to 3, is characterized in that active ingredient accounts for 1% ~ 90% of composition total weight.
5. bactericidal composition according to claim 4, is characterized in that said composition can be made into suspending agent, wetting powder, seed coat agent, aqueous emulsion, microemulsion, missible oil, granule, water dispersible granules.
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CN103271050A (en) * | 2013-06-19 | 2013-09-04 | 北京燕化永乐农药有限公司 | Compound bactericide |
CN103907644A (en) * | 2014-04-24 | 2014-07-09 | 北京燕化永乐生物科技股份有限公司 | Sterilization composite |
CN104957147B (en) * | 2015-01-08 | 2017-07-14 | 四川利尔作物科学有限公司 | Bactericidal composition and its application |
CN104823982B (en) * | 2015-01-08 | 2017-01-04 | 四川利尔作物科学有限公司 | Bactericidal composition and application thereof |
CN104839168B (en) * | 2015-01-12 | 2017-06-23 | 四川利尔作物科学有限公司 | Bactericidal composition and its application |
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CN106857546A (en) * | 2017-04-28 | 2017-06-20 | 佛山市瑞生通科技有限公司 | Bactericidal composition and its application containing trifloxystrobin and fen second mycin |
CN107691456B (en) * | 2017-09-15 | 2020-10-02 | 陕西大成作物保护有限公司 | Bactericidal composition containing fluoxastrobin and shenqinmycin |
CN107439548B (en) * | 2017-09-21 | 2020-05-29 | 安徽省农业科学院作物研究所 | Bactericidal composition containing orysastrobin and shenqinmycin |
CN108184862A (en) * | 2017-12-08 | 2018-06-22 | 甄金兰 | A kind of Synergistic bactericidal composition |
CN108294004B (en) * | 2018-02-13 | 2020-09-18 | 浙江永太科技股份有限公司 | Picoxystrobin-containing bactericidal composition |
CN109090128A (en) * | 2018-09-29 | 2018-12-28 | 武汉友芹种苗技术有限公司 | A kind of bactericidal composition for preventing and treating downy mildew of lettuce |
CN111248206A (en) * | 2020-02-27 | 2020-06-09 | 安徽省农业科学院植物保护与农产品质量安全研究所 | Bactericidal composition containing shenqinmycin and coumoxystrobin |
CN111937895B (en) * | 2020-08-19 | 2021-08-13 | 扬州大学 | Application of pyraclostrobin and composition containing pyraclostrobin in prevention and treatment of peach branch blight |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1155617A1 (en) * | 2000-05-17 | 2001-11-21 | Rockwool International A/S | Mineral wool plant substrate |
CN1802927A (en) * | 2006-01-19 | 2006-07-19 | 上海交通大学 | Method for preparing bactericidal agent using antagonizing bacteria M18 strain |
CN102249799A (en) * | 2011-04-27 | 2011-11-23 | 上海农安生物科技发展有限公司 | Method for controlling crop diseases with shenqinmycin and shenqinmycin preparation |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1141379C (en) * | 2000-08-31 | 2004-03-10 | 上海交通大学 | Growth-promoting antagonistic bacterium M18 for biologic agricultural chemical and its preparing process |
CN1369566A (en) * | 2002-02-08 | 2002-09-18 | 上海交通大学 | Culture medium of bacteria for producing phenazine-1-carboxylic acid and process for preparing phenazine-1-carboxylic acid |
US9216455B2 (en) * | 2010-05-10 | 2015-12-22 | Abdulaziz A. Alkhedhairy | Methods for producing silver nanoparticles |
CN101973946B (en) * | 2010-10-15 | 2012-12-12 | 上海交通大学 | Phenazine-1-carboxylic acids derivative and preparation method thereof |
-
2011
- 2011-12-18 CN CN201410193060.XA patent/CN103960244B/en active Active
- 2011-12-18 CN CN201110437597.2A patent/CN103155925B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1155617A1 (en) * | 2000-05-17 | 2001-11-21 | Rockwool International A/S | Mineral wool plant substrate |
CN1802927A (en) * | 2006-01-19 | 2006-07-19 | 上海交通大学 | Method for preparing bactericidal agent using antagonizing bacteria M18 strain |
CN102249799A (en) * | 2011-04-27 | 2011-11-23 | 上海农安生物科技发展有限公司 | Method for controlling crop diseases with shenqinmycin and shenqinmycin preparation |
Non-Patent Citations (1)
Title |
---|
不同杀菌剂对人参黑斑病菌的毒力测定及田间药效;王雪 等;《农药》;20111130;第50卷(第11期);第841-844页 * |
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