CN108294004B - Picoxystrobin-containing bactericidal composition - Google Patents

Picoxystrobin-containing bactericidal composition Download PDF

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CN108294004B
CN108294004B CN201810150378.8A CN201810150378A CN108294004B CN 108294004 B CN108294004 B CN 108294004B CN 201810150378 A CN201810150378 A CN 201810150378A CN 108294004 B CN108294004 B CN 108294004B
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picoxystrobin
mycin
bactericidal composition
triticum
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CN108294004A (en
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陈少亭
邵鸿鸣
李乙军
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Shanghai yongkuo Biomedical Technology Co.,Ltd.
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ZHEJIANG YONGTAI TECHNOLOGY CO LTD
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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Abstract

The invention relates to a bactericidal composition, and active ingredients of the composition comprise picoxystrobin and Changchuan mycin, wherein the weight ratio of picoxystrobin to Changchuan mycin is 1: 1-1: 100. The invention also relates to a method and application of the composition for preventing and treating agricultural fungal diseases.

Description

Picoxystrobin-containing bactericidal composition
Technical Field
The invention belongs to the field of agriculture, and particularly relates to a picoxystrobin-containing composition, a method for preventing and treating agricultural fungal diseases by using the picoxystrobin-containing composition and application of the picoxystrobin-containing composition.
Background
Picoxystrobin is a white powdery solid in a pure product, is insoluble in water and belongs to methoxyl acrylate. The action mechanism of the systemic broad-spectrum bactericide is the function of inhibiting mitochondrial respiration. The control target has broad spectrum, is mainly used for controlling leaf surface diseases of wheat, such as leaf blight, leaf rust, glume blight, brown spot, powdery mildew and the like, has special effect on diseases with low azoxystrobin control effect when being used for controlling barley and apple diseases, and can obtain grains with high yield, good quality and large and full grains after being treated by picoxystrobin on the grains.
The Changchuan mycin is white powder, is a biological bactericide developed by pesticide research institute in Shanghai, can be used for most organic solvents, such as methanol, acetone, acetonitrile, ethyl acetate and the like, and is slightly soluble in water. Can be used for preventing and treating gray mold of cucumber, tomato, strawberry and eggplant, and various fungal diseases such as corn small spot, sclerotinia rot and powdery mildew.
The Chinese patent application CN01126969.3 discloses an agricultural Changchuan mycin fungicide, which can be prepared into powder, wettable powder, granules, tablets, microcapsules and the like, and is used for preventing and treating various plant diseases such as gray mold, corn small spot, anthracnose wheat scab, cucumber downy mildew and the like.
Chinese patent application CN201610413420.1 discloses a bactericidal composition containing picoxystrobin and captan, which can be used for preventing and treating crop fungal diseases such as pear rust and has an obvious synergistic effect.
The long-term use of a large amount of single pesticides greatly increases the risk of drug resistance of the target, and further reduces the control effect and increases the dosage. In actual production, the objective requirement of the synergistic composition exists, and on one hand, the total application amount of pesticides can be reduced, the environmental pollution is reduced, and the cost is reduced; on the other hand, the pesticide effect can be improved, the drug resistance of the target can be delayed, and the long-term healthy development of agriculture is facilitated.
Disclosure of Invention
Aiming at the general requirements of the current environment, the inventor finds that the picoxystrobin and the Changchuan mycin can generate obvious synergistic action after combination for a long time so as to improve the pesticide effect and delay the development of the drug resistance of a target. Based on this, the present inventors have completed the present invention.
The invention relates to a bactericidal composition, which is characterized in that active ingredients of the composition comprise picoxystrobin and Changchun mycin, wherein the weight ratio of picoxystrobin to Changchun mycin is 1: 1-1: 100.
Preferably, the weight ratio of the picoxystrobin to the Changchun mycin is 1:5 to 1: 50.
More preferably, the weight ratio of picoxystrobin to changchin is 1:8 to 1: 32.
Further preferably, the weight ratio of picoxystrobin to changchin is 1:12 to 1:24, such as 1:12, 1:14, 1:16, 1:18, 1:20, 1:22, 1: 24.
In one embodiment of the present invention, it is preferable that the active ingredients of the composition consist only of picoxystrobin and Changchun mycin.
In one embodiment of the invention, the composition comprises, in addition to the active ingredient, agriculturally acceptable adjuvants and/or carriers formulated into agriculturally acceptable dosage forms.
Wherein, the weight percentage of the active ingredients in the composition is 1 to 60 percent, preferably 10 to 45 percent.
In one embodiment of the invention, the composition can be prepared into dosage forms of wettable powder, suspending agent and water dispersible granule.
During the preparation of the dosage forms of the present invention, agriculturally acceptable adjuvants and/or carriers are used including, but not limited to: dispersing agents, wetting agents, binders, disintegrating agents, thickening agents, anti-freezing agents, antifoaming agents, fillers and/or carriers, and the like.
Wherein the content of the first and second substances,
the dispersing agent can be selected from one or more of nonylphenol polyoxyethylene ether, naphthalene sulfonic acid formaldehyde condensate, sodium salt of naphthalene sulfonic acid formaldehyde condensate, ethoxylated nonylphenol phosphate ester, sodium lignosulfonate, calcium lignosulfonate, sodium p-hydroxyphenyl lignosulfonate, dodecyl trimethyl ammonium salt, glycerol fatty acid polyoxyethylene ether, polyoxyethylene alkylaryl ether, polyoxyethylene lanolin alcohol, fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether phosphate ester, polyoxyethylene glyceryl monofatty acid ester, sodium p-methoxyfatty amido benzene sulfonate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine and the like.
The wetting agent can be selected from one or more of calcium dodecyl benzene sulfonate, sodium lignosulfonate, isooctyl alcohol succinate sodium sulfonate, tristyrene phenol sulfate, polyoxyethylene lauryl ether sodium carboxylate, polyoxyethylene alkyl aryl ether phosphate ester salt, trisiloxane polyoxyethylene ether, tristyrene phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, dioctyl sulfosuccinate, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, dibutyl naphthalene sulfonate, dodecyl diphenyl ether sulfonate, isotridecyl sulfate and the like.
The binder may be selected from one or more of polyvinylpyrrolidone, carboxymethyl cellulose, starch, sucrose, dextrin, carboxyethyl cellulose, gelatin, gum arabic, xanthan gum, and the like.
The disintegrant may be selected from one or more of urea, sodium bicarbonate, sodium sulfate, calcium sulfate, magnesium chloride, ammonium sulfate, sodium chloride, and the like.
The thickener may be selected from one or more of xanthan gum, gelatin, polyvinyl alcohol, magnesium aluminum silicate, hydroxymethyl cellulose, hydroxyethyl cellulose, acacia, guar gum, sodium carboxymethylcellulose, etc.
The antifreeze can be one or more selected from glycerol, propylene glycol, ethylene glycol, polyethylene glycol or sorbitol.
The antifoaming agent may be selected from one or more of polysiloxane, butyl phosphate, n-octanol, isobutyl phosphate, and the like.
The filler and/or carrier may be selected from one or more of bentonite, montmorillonite, kaolin, attapulgite, clay, talc, diatomaceous earth, montmorillonite, pumice, and the like.
In a preferred embodiment of the present invention, the bactericidal composition of the present invention is prepared as a suspension concentrate, and the formulation thereof is as follows: 1-60% of active ingredient, 1-25% of dispersant, 1-25% of wetting agent, 0.5-5% of thickening agent, 0.5-8% of antifreezing agent, 0.1-5% of defoaming agent and water, and the balance is up to 100%. The preparation method comprises the following steps: the components are mixed with water, and a suspension system is formed after high-speed shearing dispersion and sanding by a sand mill to prepare the suspending agent.
More preferably, the bactericidal composition of the present invention is prepared into a suspending agent, and the formula of the bactericidal composition comprises: 10-30% of active ingredient, 4-12% of dispersing agent, 4-12% of wetting agent, 2-4% of thickening agent, 3-6% of antifreezing agent, 0.5-2% of defoaming agent and water, and the balance is made up to 100%.
In the suspension formulation of the present invention, the dispersant is preferably nonylphenol polyoxyethylene ether, polyoxyethylene lanolin alcohol, ethoxylated nonylphenol phosphate ester, or polyoxyethylene alkylaryl ether; the wetting agent is preferably calcium dodecylbenzene sulfonate, sodium dioctyl sulfosuccinate, sodium dodecyl diphenyl ether sulfonate or tristyrenated phenol sulfate.
More preferably, in the suspension formulation of the present invention, the dispersant is ethoxylated nonylphenol phosphate ester (beycostat a B09) and the wetting agent is dioctyl sodium sulfosuccinate. The compatibility of the dispersing agent and the wetting agent can obviously improve the suspension performance of picoxystrobin and Changchuan mycin.
Another aspect of the invention relates to a method for controlling an agricultural fungal disease by the fungicidal composition, wherein the fungicidal composition is contacted with an agricultural pathogenic fungus, for example, the fungicidal composition is applied to the locus of a crop disease, by any method known in the art, preferably by spraying. The specific application rate can be adjusted according to the disease condition of crops, and is for example 1-50 g/mu, preferably 4-20 g/mu.
Another aspect of the invention relates to the use of the fungicidal composition for the control of agricultural fungal diseases, wherein the fungicidal composition is contacted with an agricultural pathogenic fungus, e.g. the fungicidal composition is applied to the locus of a crop disease, by any method known in the art, preferably by spraying. The specific application rate can be adjusted according to the disease condition of crops, and is for example 1-50 g/mu, preferably 4-20 g/mu.
The fungicidal compositions of the present invention may be used in a variety of crops, including but not limited to: corn, rice, wheat, barley, sorghum, cotton, soybean, kidney bean, peanut, beet, rape, sunflower, sugarcane, tobacco, eggplant, tomato, potato, cucumber, pumpkin, watermelon, white gourd, cabbage, sweet potato, and the like.
The bactericidal composition provided by the invention can be used for controlling various diseases of the crops, including but not limited to: rice blast (Pyricularia grisea), sheath blight (Rhizoctonia solani), helminthosporium leaf spot (Cochliobolus miyabenus), bakanae disease (Gibberella fujikuroi), powdery mildew (Blumeria graminis), gibberellic disease (fusarium graminearum), rust disease (Puccinia striiformis), Puccinia striiformis (Puccinia graminis), Puccinia graminis (fusarium graminearum), rust disease (Puccinia striiformis), Puccinia graminis (p.graminis), Puccinia graminis (p.recandite), Puccinia graminis (p.hordei), Puccinia graminis (Septoria graminis), Puccinia dispersa (ussigo trichothecii), triticum graminis (triticum trichothecium), triticum reticulum (triticum) and sclerotiorum reticulatum), Pyricularia oryzae (sclerotium), Pyricularia reticulata (sclerotiorum reticulatum), Pyricularia oryzae (sclerotium reticulatum graminis (pecurospora), sclerotium graminis (sclerotium reticulatum graminearum), sclerotium graminearum (sclerotium triticum), sclerotium triticum reticulatum triticum) and triticum reticulatum graminearum triticum (triticum) rhizoctonum reticulatum), triticum solani (triticum solani), triticum solanum graminis (triticum solani), triticum graminearum graminis (triticum solani), sclerotium graminum graminis (triticum solanum graminis (triticum solani), sclerotium graminis (triticum solani), triticum graminis (triticum verticilli, Examples of diseases include, for example, southern corn (maize. umbilicalis maydis), leaf mold (Cladosporium fulvum), gray leaf spot (Stemphylium solani), tomato gray mold (Botrytis cinerea), cucumber downy mildew (Pseudoperonospora cubensis)), cucumber powdery mildew (Sphaerothecium monofilum), cucumber anthracnose (Cucumis sativus), cucumber anthracnose (Collybia cucurbitaceae), damping-off (Rhizoctonia solani), Rhizoctonia solani (Rhizoctonia solani), verticillium wilt (Verticillium wilt), Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), Phytophthora parasitica (Phytophthora nigra), soybean stem mold (Alternaria nigrospora nigra), Phytophthora infestans (Phytophthora nigrospora nigra), Phytophthora infestaphylum (Phytophthora nigra), Phytophthora infestaphylum (Phosphaera), and Phytophthora parasitica (Phosphaeromonas campestris), and Phytophthora parasitica (Phosphaerocola (Phosphaerophysalospora nigra), and Alternata), and sclerotium blight (Phosphaeria nikopsorales), and Alternata (Phosphaeria nikospora nikola) including Alchoora nikopsorales, Alchosis, Alchoma nikopsorales, Alchosis (Alcholla stem diseases (Alcholla) including Alcholla stem diseases (Alcholla) and Alcholla stem diseases (Alcholla typ, Late blight (Phytophthora infestans).
Preferably for the control of tomato gray mold (Botrytis cinerea).
Aiming at the general requirements of the current environment, the invention develops the synergistic combination of picoxystrobin and Changchuan mycin, which can reduce the total application amount of pesticides, reduce environmental pollution and reduce cost; on the other hand, the pesticide effect can be improved, the development of the drug resistance of the target can be delayed, and the long-term healthy development of agriculture is facilitated.
Detailed Description
The present invention will be further described with reference to the following examples and applications, wherein the percentages given in the following examples are by weight unless otherwise specified. However, the present invention is not limited to the following examples.
(I) laboratory biological experiments
The fungicidal compositions of the present invention were tested for their bacteriostatic effects against Botrytis cinerea (Botrytis cinerea).
Test pathogenic fungi: botrytis cinerea (Botrytis cinerea);
reagent to be tested: picoxystrobin and Changchuan mycin;
the test method comprises the following steps: the combined toxicity of the medicament is determined by a growth rate method. Preparing the medicament into 2000mg/L mother solution, mixing a proper amount of the mother solution according to the set proportion in the following table 1, preparing 6 concentration gradients by using 1% Tween 80 aqueous solution, adding the mixture into PDA culture medium at the temperature of about 50 ℃, quickly shaking up the mixture, pouring the mixture into a sterilized culture dish, and cooling the mixture to form the sterilized culture dishA nutrient plane. Pure PDA medium plates were used as blank control. Each concentration was repeated 3 times. Then, 0.5cm of Botrytis cinerea bacterium pieces are inoculated into a culture dish and cultured in an incubator at 25 ℃ and a humidity of 80% for 120 hours. Then, the petri dish was taken out, the colony diameter was measured, the growth inhibition rate against pathogenic bacteria by each drug treatment was calculated by the following formula, and the EC against pathogenic bacteria by each treatment was determined50
Figure BDA0001579865610000071
Then, the measured EC of each treatment was measured by the Sun cloud method50Conversion to Actual Toxicity Index (ATI); theoretical Toxicity Index (TTI) is calculated according to the mixture ratio of the mixture, and the co-toxicity coefficient (CTC) of the mixture is calculated according to the following formula, and the result is shown in the following table 1.
Figure BDA0001579865610000072
Figure BDA0001579865610000073
Theoretical (mix) virulence index (TTI) ═ a virulence index x a content (%) of a + B virulence index x B content (%) of B in the mix
Figure BDA0001579865610000074
If the co-toxicity coefficient is more than 120, the synergistic effect is shown; the co-toxicity coefficient is less than 80, which shows antagonism; the co-toxicity coefficient was between 100 and 120, indicating additive effect.
TABLE 1 Combined virulence assay results
Medicament EC50(mg/L) ATI TTI Co-toxicity coefficient CTC
Picoxystrobin (A) 12.80 100.00 / /
Changchuan mycin (B) 6.32 202.53 / /
A:B=1:8 5.20 246.15 191.14 128.78
A:B=1:12 4.65 275.27 194.64 141.42
A:B=1:16 3.22 397.52 196.50 202.30
A:B=1:20 3.61 354.57 197.65 179.39
A:B=1:24 3.98 321.61 198.43 162.08
A:B=1:28 4.31 296.98 199.00 149.24
A:B=1:32 4.73 270.61 199.42 135.70
As can be seen from table 1, the composition of picoxystrobin and changchin is in the range of 1:8 to 1:32, has obvious synergistic effect on botrytis cinerea.
(II) formulation examples
EXAMPLE 1 suspending agent
2% of picoxystrobin, 16% of Changchuan mycin, 6% of ethoxylated nonyl phenol phosphate, 6% of sodium lignosulfonate, 2% of polyvinyl alcohol, 5% of glycerol, 0.5% of polysiloxane and the balance of water to 100%.
The preparation method comprises the following steps: the components are mixed with water, and a suspension system is formed after high-speed shearing dispersion and sanding by a sand mill to prepare the suspending agent.
EXAMPLE 2 suspending agent
1% of picoxystrobin, 12% of Changchang mycin, 5% of nonylphenol polyoxyethylene ether, 6% of calcium dodecylbenzene sulfonate, 3% of magnesium aluminum silicate, 4% of propylene glycol, 0.8% of butyl phosphate and the balance of water to 100%.
The preparation method is the same as that of example 1.
EXAMPLE 3 suspending agent
1% of picoxystrobin, 16% of Changchuan mycin, 7% of ethoxylated nonyl phenol phosphate, 4% of dioctyl sodium sulfosuccinate, 4% of hydroxyethyl cellulose, 6% of glycerol, 0.8% of n-octanol and the balance of water to 100%.
The preparation method is the same as that of example 1.
EXAMPLE 4 suspending agent
0.5% of picoxystrobin, 10% of Changchuan mycin, 4% of calcium lignosulfonate, 4% of trisstyryl phenol sulfate, 2% of guar gum, 5% of propylene glycol, 0.5% of isobutyl phosphate and the balance of water to 100%.
The preparation method is the same as that of example 1.
EXAMPLE 5 suspending agent
1% of picoxystrobin, 24% of Changchuan mycin, 8% of fatty alcohol-polyoxyethylene ether phosphate, 7% of dioctyl sodium sulfosuccinate, 3% of sodium carboxymethylcellulose, 4% of glycerol, 0.7% of n-octanol, and the balance of water to 100%.
The preparation method is the same as that of example 1.
EXAMPLE 6 suspending agent
0.5% of picoxystrobin, 14% of Changchuan mycin, 5% of polyoxyethylene lanolin alcohol, 5% of trisiloxane polyoxyethylene ether, 4% of Arabic gum, 4% of propylene glycol, 1.2% of isobutyl phosphate and the balance of water to 100%.
The preparation method is the same as that of example 1.
EXAMPLE 7 suspending agent
0.5% of picoxystrobin, 16% of Changchuan mycin, 9% of p-methoxy fatty acid amido benzene sulfonic acid sodium, 4% of triphenylethyl phenol polyoxyethylene ether, 3% of magnesium aluminum silicate, 5% of glycerol, 0.7% of polysiloxane and the balance of water to 100%.
The preparation method is the same as that of example 1.
(III) determination of suspension Rate
The suspension percentage of the suspension formulated according to the invention was determined using the method described in GB/T14825-2006.
A sample 2g is taken and placed in a 250mL measuring cylinder, the sample is diluted to a scale with standard hard water, a plug is covered, the measuring cylinder is turned upside down for 30 times within l minutes by taking the middle part of the measuring cylinder as an axis, and then the sample is placed in a constant temperature water bath for 30 min. 225mL of the upper suspension were removed and the mass of active ingredient remaining in the 25mL of suspension at the bottom of the cylinder was determined. And the suspension ratio of the sample was calculated. The results are shown in Table 2 below.
TABLE 2 results of suspension ratio measurement
Test specimen Suspension rate
Example 1 90.4%
Example 2 86.9%
Example 3 95.2%
Example 4 88.7%
Example 5 91.6%
Example 6 89.2%
Example 7 88.1%
As can be seen from the results in Table 2, the suspending ratios of the suspending agents formulated in accordance with the present invention are all greater than 85%, and particularly greater than 95% for the formulation of example 3, which is preferred in accordance with the present invention.
(IV) field test
Test agents: the invention comprises 1 to 7 preparations, 22.5 percent of picoxystrobin suspending agent and 1 percent of Changchuan mycin emulsifiable concentrate
Test work: tomato
Control target: gray mold of tomato
The treatment of the test, control and blank control cells was performed in randomized block formation with a cell area of 50 square meters for 4 replicates. The results of the survey conducted 7 days after the application of the drug by random five-point sampling are shown in Table 3 below.
TABLE 3 field control results
Figure BDA0001579865610000111
As can be seen from the above table 3, the formulations of examples 1-7 of the present invention can significantly increase the field control effect on the tomato gray mold compared to 22.5% picoxystrobin suspending agent and 1% Changchuan mycin emulsifiable concentrate, and generate a synergistic effect.
The invention has been described with reference to specific embodiments. Those skilled in the art can make appropriate changes based on the contents of the present invention, and all changes that are relevant are considered to be included in the scope of the present invention when they do not depart from the contents of the present invention.

Claims (8)

1. The bactericidal composition is characterized in that active ingredients of the composition comprise picoxystrobin and Changchun mycin, wherein the weight ratio of picoxystrobin to Changchun mycin is 1: 8-1: 32.
2. The bactericidal composition of claim 1, wherein the active ingredients of the composition consist only of picoxystrobin and Changchun mycin.
3. The bactericidal composition of claim 1, further comprising an agriculturally acceptable adjuvant and/or carrier formulated into an agriculturally acceptable dosage form.
4. The bactericidal composition of claim 3, wherein the active ingredient is present in the composition in an amount ranging from 1% to 60% by weight.
5. The bactericidal composition of claim 4, wherein the active ingredients are present in the composition in an amount ranging from 10% to 45% by weight.
6. The bactericidal composition of claim 3, wherein the dosage form is wettable powder, suspending agent or water dispersible granule.
7. The germicidal composition of claim 6, wherein the dosage form is a suspension.
8. Use of the fungicidal composition according to claim 1 for controlling agricultural fungal diseases, characterized in that the fungicidal composition is mixed with botrytis cinerea (a)Botrytis cinerea) And (4) contacting.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1364414A (en) * 2001-10-08 2002-08-21 上海市农药研究所 Changchuan mycin agricultural bactericide and its preparing method and use
CN102204536A (en) * 2011-04-15 2011-10-05 陕西汤普森生物科技有限公司 Antibacterial composition containing picoxystrobin and antibiotic compound
CN103155925A (en) * 2011-12-18 2013-06-19 深圳诺普信农化股份有限公司 Sterilization composite containing phenazino-1-carboxylic acid
CN103843798A (en) * 2012-12-09 2014-06-11 青岛恒润源通果蔬专业合作社 Pesticide composition containing aureonucleomycin and strobilurin fungicide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1364414A (en) * 2001-10-08 2002-08-21 上海市农药研究所 Changchuan mycin agricultural bactericide and its preparing method and use
CN102204536A (en) * 2011-04-15 2011-10-05 陕西汤普森生物科技有限公司 Antibacterial composition containing picoxystrobin and antibiotic compound
CN103155925A (en) * 2011-12-18 2013-06-19 深圳诺普信农化股份有限公司 Sterilization composite containing phenazino-1-carboxylic acid
CN103843798A (en) * 2012-12-09 2014-06-11 青岛恒润源通果蔬专业合作社 Pesticide composition containing aureonucleomycin and strobilurin fungicide

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