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CN101664031B - Sterilizing composition containing kresoxim-methyl and kasugamycin - Google Patents

Sterilizing composition containing kresoxim-methyl and kasugamycin Download PDF

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Publication number
CN101664031B
CN101664031B CN200910114449A CN200910114449A CN101664031B CN 101664031 B CN101664031 B CN 101664031B CN 200910114449 A CN200910114449 A CN 200910114449A CN 200910114449 A CN200910114449 A CN 200910114449A CN 101664031 B CN101664031 B CN 101664031B
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methyl
kresoxim
mixture
kasugarnycin
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CN101664031A (en
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史万琪
王鲁
李婧婧
李琦
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Nanning Defengfu Chemical Co Ltd
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Nanning Defengfu Chemical Co Ltd
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Abstract

The invention discloses a sterilizing composition containing kresoxim-methyl and kasugamycin. The sterilizing agent contains the active components of kresoxim-methyl and kasugamycin which are at the weight ratio of 1:2-9, and the cumulative weight of the kresoxim-methyl and the kasugamycin accounts for 9-11 percent of the total weight of the sterilizing agent. The sterilizing composition has obvious synergistic action, long efficacy duration, high efficiency and low residual, takes effect quickly and can prolong the rice blast resistance to tricyclazole, protect the rice against the rice blast, improve the rice blast resistance of the diseased rice and treat and prevent the rice blast. The sterilizing composition complies with the current market demand and has wider market prospect.

Description

A kind of bactericidal composition that contains kresoxim-methyl and kasugarnycin
Technical field
The present invention relates to a kind of bactericide agricultural chemicals, specifically is a kind of bactericidal composition that contains kresoxim-methyl and kasugarnycin.
Background technology
Paddy rice is one of China's staple food crop, and cultivated area accounts for 1/4 of national arable area, and annual production accounts for 1/2 of national total grain output.Yet the harm of rice disease is having a strong impact on Rice Production always, and rice blast is that popularity is the most complicated in the paddy rice three big diseases; The disease that potential threat is maximum; 1975-1990 16 in the period of, the global grain loss that is caused by rice blast is up to 1.57 hundred million tons, annual is above 0.1 hundred million tons.This disease is by due to the fungal infection, and the harm region is extensive, strong wind blows under, can sweep across whole field at one time, the destruction paddy rice, even possibly cause that No kernels or seeds are gathered, as in a year of scarcity; Therefore the control of rice blast has just become a great problem of pendulum in face of vast paddy rice plantation family.
Kasugarnycin belongs to agricultural antibiotic class low toxicity bactericide, has stronger interior suction permeability, has prevention and therapeutic action simultaneously, and its therapeutic action is more remarkable.Its mechanism of action is to disturb the esterase system of the metabolism of amino acid of pathogen, destroys the biosynthesis of protein, suppresses the growth of mycelia and causes cell granulationsization, makes pathogen lose breeding and infection ability, thereby reaches the purpose that kill pathogenic bacteria is prevented and treated disease.Bacterium, yeast and plant epiphyte are all had activity, and especially spore germination, the growth of mattress silk and the spore to rice blast fungus all has the effect that amino acid synthesizes protein that suppresses in forming.Kasugarnycin is transmitted in the plant corpus through interior suction after being applied to crop such as paddy rice, suppresses the synthetic and even mycelial growth of rice blast protein significantly, makes peptide bond elongate the activity of peptide for inhibiting transferase.
Kresoxim-methyl is a kind of efficient, wide spectrum, new type bactericide.Kresoxim-methyl has good active to fungus-caused multiple diseases such as imperfect fungus, sac fungi, basidiomycetes, Oomycetes; As: diseases such as rice blast, grape powdery mildew, wheat rust, potato late blight, pumpkin eqpidemic disease, especially to rice blast, powdery mildew of cucumber, pear scab special efficacy.Kresoxim-methyl not only has the bactericidal activity of wide spectrum, simultaneously with excellent protection and therapeutic action.Kresoxim-methyl and other bactericide commonly used do not have cross resistance, and longer than the conventional sterilization agent lasting period, and have the selectivity of height, and be to crop, people and animals and beneficial organism safety, pollution-free basically to environment.
Actual agricultural chemicals field trial shows; Repeat and single-mindedly use a kind of reactive compound and prevent and treat the fast selective that harmful fungoid causes bacterial strain under many circumstances; Optionally dangerous for reducing resistant strain, normally used method is that the mixture that filters out the compound of different activities is prevented and treated harmful fungoid.And the reactive compound that how will have different effects mechanism makes up, and makes its ability delaying drug resistance, reduces amount of application, reduces the control cost, is the problems that people constantly study always.
Summary of the invention
Technical problem to be solved by this invention provides a kind of bactericidal composition that has synergistic function for the control rice blast pathogen.
The present invention solves the problems of the technologies described above with following technical scheme: bactericidal composition of the present invention is made up of following component: the conventional auxiliary agent of kasugarnycin and kresoxim-methyl and agricultural chemicals; Wherein kasugarnycin and kresoxim-methyl are as active component; Their weight ratio is 1: 2~9, is preferably 2: 8.
Kasugarnycin and kresoxim-methyl accumulating weight account for 9~11% of total formulation weight amount ratio.
The processing formulation of said bactericidal composition is a suspending agent, and account for the auxiliary agent of total formulation weight amount ratio below adding during preparation: wetting agent 1~3%, thickener 1~3%, antifoaming agent 1~3%, dispersant 3~5%, surplus are water.
Result of the test shows that product of the present invention has advantages such as synergistic effect is obvious, quick-acting good, the lasting period is long, highly-effective low-residue, can delay the resistance of rice blast to tricyclazole; Premorbid prevention rice blast protection paddy rice; Paddy disease-resistant power is improved in the morbidity back, and treatment rice blast has prevention and therapeutic action concurrently; Match with the current market demand, have very big market prospects.
Product of the present invention and other bactericide commonly used do not have cross resistance, and longer than the conventional sterilization agent lasting period.This medicine mainly disturbs amino acid whose metabolism esterase system, thereby influences the synthetic of protein, suppresses the mycelia elongation and causes cell granulationsization; But spore germination there is not influence; Have the selectivity of height, to crop, people and animals and beneficial organism safety, pollution-free basically to environment.
Embodiment
Active ingredient in the product of the present invention is kasugarnycin and kresoxim-methyl, and their title, structural formula and basic materialization parameter are following:
A) active ingredient I: kresoxim-methyl
ISO adopted name: kresoxim-methyl
CAS number: 143390-89-0
Chemical name: methyl (E)-2-methoxyimino-2-[2-(0-toloxyl) phenyl] acetate
Structural formula:
Figure G200910114449XD00021
Molecular formula: C 18H 19NO 4
Relative molecular mass (by international relative atomic mass of calendar year 2001): 313.35
Biologically active: sterilization
Proportion: 1.258;
Fusing point: 101 ℃;
Vapour pressure: 20 ℃ of time<1 * 10-5Pa.
B) active ingredient II: kasugarnycin
ISO adopted name: Kasugamycin
Chemical name: [5-amino-2-methyl-6-(2,3,4,5,6-carbonyl cyclohexyl oxo) pyrans-3-base amino-a-IMDA]
Structural formula:
Figure G200910114449XD00031
Molecular formula: C 14H 25N 3O 9
Relative molecular mass (by international relative atomic mass of calendar year 2001): 433.8
Biologically active: sterilization;
Fusing point: 202 ℃-204 ℃ (decomposition);
Vapour pressure (25 ℃):<13mPa;
Solubility property: exist with hydrochloride form, soluble in water, be slightly soluble in methyl alcohol, be insoluble to organic solvents such as ethanol, propyl alcohol, ester class (acetate), acetate, chloroform, benzene and benzinum.
Stability: stable at normal temperatures, stable under acid and neutrallty condition, under alkali condition, be prone to decompose.
Product of the present invention is to be dissolved in the suspension of processing in the The suitable solvent by standard compliant kasugarnycin and the former medicine of kresoxim-methyl and auxiliary agent.Long-term storage can have small amount of precipitate or layering, but places under the room temperature with hand moving should be able to the reinstatement.
The analytical method of active ingredient of the present invention is:
Kasugarnycin: bioassary method fluorescent agar diffusion method (NIHJ B-245);
Kresoxim-methyl: capillary gas chromatography.
Product of the present invention is mainly used in paddy rice, and controlling object is a rice blast, and the active ingredient amount of application is 250~330 gram/hectares, and method for using is spraying.
Below be the proportioning raw materials table of three embodiment A, B, C:
Figure G200910114449XD00041
The preparation technology of product of the present invention is: after former medicine of the kasugarnycin of buying and the former medicine incoming test of kresoxim-methyl active ingredient, through calculating, add and calculate required former medicine of kasugarnycin and the former medicine of kresoxim-methyl; Under continuous condition of stirring, add wetting agent, thickener and dispersant again and carry out abundant stirring and evenly mixing, the time is 45 minutes; After supplying water, put into antifoaming agent, after the laboratory sample analysis is qualified; Through liquid filling machine can finished product, be stained with qualified label, be packaged into finished product; After having the laboratory random sampling qualified again, warehouse-in dispatches from the factory.
Said wetting agent can be: polyethylene glycol, draw back powder, dodecyl sodium sulfate, lauryl sodium sulfate, the ninth of the ten Heavenly Stems (suffering) basic phenol polyethenoxy ether, sodium lignin sulfonate, neopelex, dioctyl succinate sodium sulfonate, cocoa butter N methyl taurine sodium, cetyl betain, dinonyl sodium phosphate, Tea Saponin, lauryl alcohol sodium sulphate and their compound.
Said dispersant can be: the di-2-ethylhexylphosphine oxide Sodium Toluene Sulphonate; The monoalkyl sodium naphthalene sulfonate; Two Negels; The naphthalene sulfonic acid-formaldehyde condensation product sodium salt; Alkyl or sweet-smelling alkyl sulfonic acid formaldehyde condensation products sodium salt; Naphtholsulfonic acid formaldehyde condensation products sodium salt; Petroleum sodium sulfonate; Alkyl benzene sulfonate calcium salt; N-methyl-fatty acyl group-taurate; Organophosphorus compounds; The APES formaldehyde condensation products; Lignosulfonates; The ninth of the ten Heavenly Stems (suffering) basic phenol polyethenoxy ether; Polyoxyethylene carboxylate; Alkylphenol-polyethenoxy polyethenoxy ether and their compound.
Said thickener can be: polyethylene glycol stearate diester, polyvinyl alcohol, gather the compound of hexylene glycol, polyacrylamide, bentonite, waterglass, xanthans, gelatin, gum Arabic, sodium alginate, sodium carboxymethylcellulose, sodium carboxymethyl starch and these kinds.
Said antifoaming agent can be an organosilicon, also can be the antifoaming agent of other kind.
The present invention enriches chemical industry Co., Ltd by the Nanning moral single agent of product of the present invention and kasugarnycin and kresoxim-methyl is carried out the indoor joint toxicity measuring of agricultural chemicals to the formulation screening test of product of the present invention when, and relevant data and result are following:
1 test basis: NY/T 1156.2-2006; Supply the examination target: the former bacterium of rice blast.
This test is gathered rice blast sample and separation and purification and is obtained the rice blast bacterial classification from the field; Adopt mycelial growth rate to suppress method; Carry out the joint toxicity measuring that kasugarnycin and kresoxim-methyl different proportion binary are mixed; Estimate its synergistic effect, and its virulence of analysis-by-synthesis, synergistic effect and production cost, confirm the best proportioning that these two kinds of medicaments are mixed.
2 experimental conditions
2.1 supply the examination target
Rice blast (Pyricularia oryzae), the Wuming County paddy field is gathered the rice blast sample from the Nanning city, and indoor separation and purification is identified and is cultivated, obtains the rice blast bacterial classification.
2.2 condition of culture
Bacterial classification is kept in 25 ℃ of illumination boxs.Inoculation is placed in the illumination box cultivates, 27 ± 1 ℃ of temperature,
Cultivate under relative moisture 85% left and right sides condition.
2.3 instrument and equipment
2.3.1 illumination box (Guangdong medical apparatus and instruments factory);
2.3.2 electronic balance (sensibility reciprocal 0.1mg);
2.3.3 card punch;
2.3.4 culture dish;
2.3.5 inoculator;
2.3.6 pipette
2.3.7 slide calliper rule etc.
3 experimental scheme
3.1 the examination material is prepared
The preparation of PDA medium (1000mL): potato 200g, glucose 17g, agar 17g.
Supply the rice blast fungi isolates of examination, on the PDA medium, place illumination box to cultivate earlier, 27 ± 1 ℃ of temperature are cultivated subsequent use under relative moisture 85% left and right sides condition.
3.2 reagent
3.2.1 test medicine
No. 1, mixture (kasugarnycin: kresoxim-methyl=3.0: 7.0, down with), mixture No. 2 (2.5: 7.5), mixture No. 3 (2.0: 8.0), mixture No. 4 (1.5: 8.5), No. 5, mixtures (1.0: 9.0).
3.2.2 contrast medicament
The former medicine of kresoxim-methyl (kresoxim-methyl), content 94%, German BASF European Co.,Ltd, commercial;
The former medicine of kasugarnycin (kasugamycin), content 65%, North China Pharmaceutical Group Preparation Co., Ltd., commercial.
3.2.3 other reagent
Acetone (analyzing pure);
0.05% Tween-80 distilled water solution.
3.3 dosage setting
3.3.1 dosage setting
According to the preliminary experiment result, it is following that specific concentration is set etc.:
Kasugarnycin is provided with that concentration of treatment is 80,40,20,10,5mg/L;
Kresoxim-methyl is provided with that concentration of treatment is 128,64,32,16,8mg/L;
Mixture is provided with that concentration of treatment is 64,32,16,8,4mg/L for No. 1;
Mixture is provided with that concentration of treatment is 64,32,16,8,4mg/L for No. 2;
Mixture is provided with that concentration of treatment is 64,32,16,8,4mg/L for No. 3;
Mixture is provided with that concentration of treatment is 64,32,16,8,4mg/L for No. 4;
Mixture is provided with that concentration of treatment is 64,32,16,8,4mg/L for No. 5.
3.4 the processing time
Measuring the date is on July 6th, 2009.
4 test procedures
4.1 medicament preparation
On the basis of preliminary experiment, accurately take by weighing the former medicine 1.0638g of 94% kresoxim-methyl, use acetone solution, in the volumetric flask of the 100ml that packs into, use the acetone constant volume, get 10gL -1Mother liquor; Accurately take by weighing the former medicine 1.5385g of 65% kasugarnycin, use acetone solution, in the volumetric flask of the 100ml that packs into, use the acetone constant volume, get 10gL -1Mother liquor; Take by weighing the kresoxim-methyl mother liquor respectively then, the kasugarnycin mother liquor is mixed in following ratio:
No. 1, mixture, kasugarnycin: kresoxim-methyl=3.0: 7.0;
No. 2, mixture, kasugarnycin: kresoxim-methyl=2.5: 7.5;
No. 3, mixture, kasugarnycin: kresoxim-methyl=2.0: 8.0;
No. 4, mixture, kasugarnycin: kresoxim-methyl=1.5: 8.5;
No. 5, mixture, kasugarnycin: kresoxim-methyl=1.0: 9.0;
Last again with the mixture mother liquor of two kinds of single agent and above-mentioned 5 kinds of different proportionings, become the soup of 5 concentration with 0.05% Tween-80 distilled water solution according to the geometric ratio gradient dilution respectively, the dosage setting is referring to 3.3.1.
4.2 chemicals treatment
Under aseptic condition; Quantitatively add the sterilising medium that melts in advance in the aseptic conical flask; From the low concentration to the high concentration, quantitatively draw equal volume (1ml) soup successively, add respectively in the above-mentioned conical flask, fully shake up; To pour 4 diameters into be in the culture dish of 9cm to equivalent then, and the pastille of processing respective concentration is dull and stereotyped.
Test is established the PDA flat board that does not add medicament and is treated to blank.
4.3 the transplanting of bacterium cake and cultivation
The aperture of using the bacterium of going out is selected uniform parts to beat as the card punch of 5mm on cultured bacterium colony and is got the bacterium cake; Be put on the PDA flat board that soup handled with sterilization tweezers gripping bacterium cake, mycelia faces down, and in 27 ℃ of constant incubators, cultivates 7d; Compare with blank, every processing repeats for 4 times.
5 data surveys and statistical analysis
5.1 investigation method
Look the growing state of bacterium in the blank culture dish, in incubator, cultivate about 7d, measure 2 times, respectively handle the diameter that increases of bacterium colony with its mean value representative with " ten " word interior extrapolation method.
5.2 computational methods
According to survey data, calculate preventive effect according to formula (1), unit is percentage (%), result of calculation keeps 2 significant digits.
P = D 0 - D 1 D 0 × 100 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ( 1 )
In the formula: P---control efficiency
D 0---the blank colony diameter
D 1---the chemicals treatment colony diameter
5.3 statistical analysis
Utilize DPS (data processing software) and Excel, set up the virulence regression equation of each medicament, calculate LC 50Value, LC 90With 95% confidence limit.
5.4 the mixed agent co-toxicity coefficient calculates and the synergistic effect evaluation
Adopt the abundant method of Sun Yun (1960) to estimate the mixture synergism effect.Calculate mixture actual measurement toxicity index according to formula.
ATI = S M × 100 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ( 3 )
In the formula: ATI---mixture actual measurement toxicity index;
S---the EC of standard medicament 50, unit is every liter (mg/L) of milligram;
The EC of M---mixture 50, unit is every liter (mg/L) of milligram.
Calculate the theoretical toxicity index of mixture according to formula
TTI=TI A×P A+TI B×P B……………………………………(4)
In the formula: TTI---the theoretical toxicity index of mixture;
TI A---A medicament toxicity index;
P A---the percentage composition of A medicament in mixture, unit are percentage (%);
TI B---B medicament toxicity index;
P B---the percentage composition of B medicament in mixture, unit are percentage (%).
Calculate the co-toxicity coefficient of mixture according to formula
CTC = ATI TTI × 100 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ( 5 )
In the formula: CTC---co-toxicity coefficient;
ATI---mixture actual measurement toxicity index;
The theoretical toxicity index of TTI---mixture.
Composite dose co-toxicity coefficient (CTC)>=120 shows as synergistic effect; CTC≤80 show as antagonism; 80<CTC<120 show as summation action.
6 result of the tests and analysis
6.1 single agent is to the toxicity test result of rice blast
Incidence and toxicity test result that bacterium colony is handled in single agent see attached list 1, and through statistical analysis, the virulence regression equation of single agent and assay see attached list 2.Find out that from subordinate list 2 kresoxim-methyl is to the EC of rice blast 50Be 23.72, EC 90Be 253.82; Kasugarnycin is to the EC of rice blast 50Be 21.14, EC 90Be 179.63.
6.2 mixture is to the toxicity test result of rice blast
Measured kasugarnycin and the kresoxim-methyl of 5 different proportionings virulence respectively to rice blast.The virulence of mixture is all apparently higher than kasugarnycin and kresoxim-methyl.Virulence height order is followed successively by: No. 1, No. 5>mixture of No. 2>mixture of No. 4>mixture of No. 3>mixture of mixture, No. 3, the highest mixture of virulence (is a kasugarnycin: kresoxim-methyl=2.0: 8.0) to the EC of rice blast 50Be 6.09, EC 90Be 174.54, No. 1, the minimum mixture of virulence (is a kasugarnycin: kresoxim-methyl=3.0: 7.0) to the EC of rice blast 50Be 19.78, EC 90Be 141.19.(seeing attached list 2)
6.3 mixture is to the co-toxicity coefficient of rice blast
Find out that from co-toxicity coefficient (seeing attached list 3) result of calculation the co-toxicity coefficient of each mixture is respectively: 122.53,139.41,165.21,145.53,131.36, all greater than 120; Show that these mixture synergism effects are obvious; No. 3, mixture (kasugarnycin kresoxim-methyl=2.0: 8.0) wherein, its co-toxicity coefficient is 165.21, synergy is the most obvious; Many-sided factor such as integrated cost, preventive effect, synergy situation considers that this proportioning is more reasonable.
7 conclusion (of pressure testing)s
7.1 this kasugarnycin of being measured of test and 5 proportioning mixtures of kresoxim-methyl to the co-toxicity coefficient (CTC) of rice blast all greater than 120; Show obvious synergistic effect; Explain that it is rationally feasible utilizing kasugarnycin and kresoxim-methyl to be mixed, and can significantly improve drug effect.
7.2 in 5 proportioning mixtures being measured, the co-toxicity coefficient of No. 3, mixture (be kasugarnycin kresoxim-methyl=2.0: 8.0) is greater than other mixtures.Take all factors into consideration synergistic effect, virulence and the economic performance etc. of mixture, think that the proportioning of No. 3, mixture is more reasonable.
Subordinate list 1 kasugarnycin, kresoxim-methyl and mixture thereof are to the toxicity test result of rice blast
Figure G200910114449XD00101
Subordinate list 2 supplies virulence regression equation and the assay of reagent agent to rice blast
Medicament Virulence regression equation Correlation coefficient EC 50And CL 95 (mg/L) EC 90And CL 95 (mg/L) SE(B)
The former medicine of kresoxim-methyl Y=1.3886X+3.0949 0.9938 23.72 (17.97-29.65) 253.82 (130.23-377.41) 0.1743
The former medicine of kasugarnycin Y=1.5356X+2.9816 0.9994 21.14 (16.66-25.62) 179.63 (97.73-261.54) 0.1774
No. 1, mixture Y=1.6534X+2.8782 0.9984 19.78 (15.76-23.80) 141.19 (77.26-205.12) 0.1818
No. 2, mixture Y=1.4071X+3.4061 0.9939 13.82 (10.60-17.03) 137.26 (71.98-202.54) 0.1740
No. 3, mixture Y=1.0314X+4.1893 0.9981 6.09 (3.38-8.80) 174.54 (62.30-286.78) 0.1711
No. 4, mixture Y=1.5718X+2.5918 0.9990 20.82 (16.35-25.30) 168.61 (85.62-251.60) 0.1794
No. 5, mixture Y=1.3795X+3.3943 0.9987 14.92 (11.42-18.41) 166.21 (78.66-253.75) 0.1730
Subordinate list 3 supplies the co-toxicity coefficient of reagent agent to rice blast
Medicament EC 50(mg/L) The actual measurement toxicity index Theoretical toxicity index Co-toxicity coefficient
The former medicine of kresoxim-methyl 23.72 137.36
The former medicine of kasugarnycin 21.14 100.00
No. 1, mixture 19.78 163.73 133.62 122.53
No. 2, mixture 13.82 183.67 131.75 139.41
No. 3, mixture 6.09 214.58 129.89 165.21
No. 4, mixture 20.82 186.31 128.02 145.53
No. 5, mixture 14.92 165.72 126.15 131.36
The applicant carries out field experiment in lichee village, Tao Xu town, Heng County, Guangxi to rice blast with product of the present invention in July, 2009, and its result sees table 4.
15 days test of pesticide effectiveness results behind the table 4 pair rice blast medicine
Figure G200910114449XD00111

Claims (2)

1. bactericidal composition that contains kresoxim-methyl and kasugarnycin; It is characterized in that containing in the bactericide that kasugarnycin and kresoxim-methyl process as active component; The weight ratio of kasugarnycin and kresoxim-methyl is 1: 2~9, and kasugarnycin and kresoxim-methyl accumulating weight account for 9~11% of total formulation weight amount.
2. according to the said bactericidal composition that contains kresoxim-methyl and kasugarnycin of claim 1, it is characterized in that: the weight ratio of kasugarnycin and kresoxim-methyl is 2: 8.
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CN101971837A (en) * 2010-10-27 2011-02-16 陕西韦尔奇作物保护有限公司 Antibacterial composition containing kasugamycin and mancozeb
CN101984813A (en) * 2010-12-14 2011-03-16 江苏省绿盾植保农药实验有限公司 Bactericide containing ZJ0712 and kasugamycin
CN106614627A (en) * 2016-12-07 2017-05-10 佛山市普尔玛农化有限公司 Bactericidal composition containing benzothiostrobin and kasugamycin
CN107183032A (en) * 2017-06-29 2017-09-22 天峨县平昌生态农业有限公司 A kind of bactericidal composition for being used to prevent and treat graw mold of tomato
CN108660463A (en) * 2018-06-29 2018-10-16 湖州织里宝丰铝业有限公司 Alkaline defatting agent for aluminium alloy extrusions

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