CN104351244A - Bactericidal composition containing oxalate diacetone ketone amine and amide bactericides - Google Patents
Bactericidal composition containing oxalate diacetone ketone amine and amide bactericides Download PDFInfo
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Abstract
The invention discloses a bactericidal composition containing oxalate diacetone ketone amine and amide bactericides. The bactericidal composition comprises a first active component and a second active component, wherein the weight ratio of the first active component to the second active component is (1 to 10) to (10 to 1); the first active component is oxalate diacetone ketone amine; the second active component is one of amide bactericides; the sum of the content of the first active component and the second active component is 5%-90% of the total weight of the bactericidal composition. The bactericidal composition can be prepared into water dispersible granules, wettable powder or oil-dispersible suspending agents which are allowable in agriculture, and has high effect of preventing cucumber downy mildew, cucumber powdery mildew, potato late blight, phyricularia oryzae and rice sheath blight disease. By virtue of the bactericidal composition, the problem of low prevention effect when only the oxalate diacetone ketone amine is used or only the amide bactericides are used can be effectively solved; when oxalate diacetone ketone amine and amide bactericides are compounded with each other, the bactericidal composition is remarkable in synergistic effect and high in safety to crops.
Description
Technical field
The invention belongs to technical field of compounded pesticide, relate to a kind of bactericidal composition, be specifically related to a kind of using oxalic acid copper diacetonamine as the first active component, the sterilization components such as the thifluzamide in acid amide fungicides, isotianil, isopyrazam are as the binary built bactericidal composition of the second active component.The invention still further relates to the preparation formulation of this bactericidal composition and it is in application agriculturally.
Background technology
Copper agent is one of the most ancient disinfectant use in agriculture type, has has a broad antifungal spectrum, not easily the advantage such as to develop immunity to drugs.Based on the use history of the Inorganic Copper preparation of Kocide SD, copper sulphate etc. more than 200 years, but because it is difficult to be biodegradable, long-term a large amount of use has caused the accumulation of copper in soil, can cause harmful effect to the normal growth of plant and soil function.At present, the exploitation of organic copper preparation, have become the hot topic that disinfectant use in agriculture is produced, and organic copper preparation is to crop safety, nuisanceless.
Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo for raw material, by its structural modification, synthesizes a kind of new compound with two acetone isolated in Qinling Mountains streptomycete zymotic fluid---oxalic acid copper diacetonamine.This is a kind of novel organocopper compound, toxicity shows that it shows good bacteriostatic activity to various agricultural pathogen, and field test results shows that it has good control efficiency to crop pests such as cucumber downy mildew, potato late blight, alternaria leaf spot of apple.Oxalic acid copper diacetonamine to crop based on protective effect, to the germ in invaded plants body almost without therapeutic activity.
Since first acid amide fungicides carboxin was successfully developed in 1966 by favourable incoming road company (existing Chemtura Corporation), this compounds uses the history of existing four more than ten years as bactericide, and have the kind of novel structure to report always, be the series bactericidal agent that new varieties is in recent years maximum.
Acid amide fungicides kind is a lot, commercial kind mainly contains thifluzamide at present, isotianil, isopyrazam, fluorine azoles bacterium acid amides, fluorine azoles bacterium aniline, Boscalid, fluopicolide, benzene metsulfovax, fluorine azoles ring bacterium amine, pyrrole metsulfovax, flusulfamide, first flusulfamide, fluopicolide, fenoxanil, Guardian, mandipropamid, cyflufenamid, Hexanaphthene flusulfamide, tiadinil, thiophene fluorine bacterium amine, zoxamide, ring propionyl bacterium amine, fenhexamid, Silthiopham, two chlorine zarilamid, fenfuram, flutolanil, carboxin, fluorine pyrrole bacterium acid amides, furametpyr, biphenyl pyrrole bacterium amine, mandipropamid, benalaxyl-M, mefenoxam etc.
Introduce the principal item of several acid amide fungicides below:
Silthiopham, other Chinese name: total eclipse is clean, english common name silthiopham, chemical name: N-pi-allyl-4,5-dimethyl-2-(TMS) thiophene-3-formamide.Silthiopham is inhibitor of energy, and have good prolection, the longevity of residure is long, uses, have strong inhibitory action to take-all mainly as wheat seed process.
Isotianil, the chloro-N-of English common name isotianil, chemical name: 3,4-bis-(2-cyano-phenyl)-5-isothiazole formamide is the isothiazole carboxamides that Bayer and Sumitomo Chemical are researched and developed jointly.Isotianil has very strong induced activity in plant corpus, has bactericidal activity simultaneously, is mainly used in the control of the Cereal diseases such as rice blast.
Isopyrazam, English common name isopyrazam, chemical name: 3-(methyl fluoride)-1-methyl-N-[1,2,3,4-tetrahydrochysene-9-isopropyl-Isosorbide-5-Nitrae-methylene-5-base]-pyrazole-4-carboxamide.Isopyrazam is mitochondrial respiratory inhibitor, has stronger inhibitory action, fungi is had to the effect suppressing mycelial growth and sporulation to Spores germination, the growth of germ tube and the formation of absorber.
Fluorine azoles bacterium acid amides, English common name fluxapyroxad, chemical name: 3-(difluoromethyl)-1-methyl-N-(3,4,5-trifluoro [the two benzene of 1,1-]-2-base))-1H-pyrazoles-4 formamide.Fluorine azoles bacterium acid amides is succinate dehydrogenase inhibitors, has potent selectivity bactericidal action to cereal, soybean, corn, oil crop and banana, tomato, grape.
Fluorine pyrrole bacterium acid amides, and English common name fluopyram, chemical name: 2-[the chloro-5-of 3-(trifluoromethyl)-2-pyridine radicals) ethyl] the fluoro-O-toluamide of-α, α, α-three.The mechanism of action of fluorine pyrrole bacterium acid amides suppresses mitochondrial respiratory by hindering the electro transfer of succinate dehydrogenase in respiratory chain, arrives the object controlling pathogen by suppressing the several stage in the growth of pathogenic bacteria cycle.
Thifluzamide, the bromo-2-methyl of English common name thifluzamide, chemical name: 2,6-bis--4-trifluoromethoxy-4-Trifluoromethyl-1,3-thiazole-5-carbonyl acyl is for aniline.Thifluzamide has stronger systemic action, and the lasting period is long, and Main Function suppresses the acidohydrogenase in disease fungus tricarbonic acid cycle, causes thalline dead.
Boscalid, the chloro-N-of English common name boscalid, chemical name: 2-(4 '-chlordiphenyl-2-base) vitamin PP.Boscalid is Novel tobacco acid amide fungicides, and fungicidal spectrum is comparatively wide, is mainly used in preventing and treating crop powdery mildew, gray mold, various rot, brown rot and root rot.
Fluorine azoles ring bacterium amine, English common name sedaxane, is succinate dehydrogenase inhibitors, mainly suppresses mitochondria, and to the Be very effective of rhizoctonia, the lasting period is long, other kind of biography and soil-borne disease is also had to the control of wide spectrum.
Fluorine azoles bacterium acid amides, English common name fluxapyroxad, chemical name: 3-(difluoromethyl)-1-methyl-N-(3,4,5-trifluoro [the two benzene of 1,1-]-2-base))-1H-pyrazoles-4 formamide.Fluorine azoles bacterium acid amides is succinate dehydrogenase inhibitors, has potent selectivity bactericidal action to cereal, soybean, corn, oil crop and banana, tomato, grape.
Fluorine azoles bacterium aniline, English common name penflufen, chemical name: 2 '-[(RS)-1,3 dimethylbutyl] fluoro-1, the 3-dimethyl pyrazole-4-formailide of-5-.Fluorine azoles bacterium aniline is a kind of amber dehydrogenase inhibitor, mainly acts on respiratory chain electron transmission Complex II, blocks energy metabolism.Basidiomycetes and the ascus fungus damage of kind of a biography, soil biography can be prevented.
Fluopicolide, the chloro-N of English common name flvopicolide, chemical name: 2,6-bis-[(the chloro-5-trifluoromethyl of 3--2-pyridine radicals) methyl] benzamide.This medicine protectiveness is good, permeability strong, has higher biologically active, has good control efficiency, can conduct from leaves of plants basal orientation blade tip direction Oomycete fungus diseases.
Cyflufenamid, English common name cyflufenamid, chemical name: (Z)-N-[α-(ring third methoxyimino)-2,3-bis-fluoro-6-(trifluoromethyl) benzyl]-2-phenyl acetamide.Cyflufenamid is the phenyl-acetamides series bactericidal agent developed by Tso Tat Co., Ltd., Japan, has excellent prevention effect and certain therapeutic activity, also has blade face infiltration and fumigation action, the feature of resistance of rainwater washing against and lasting period length, but interior absorption is poor.Cyflufenamid is mainly used in preventing and treating the powdery mildew in vegetables, fruit tree and various types of grain.
Numerous result of study shows, acid amide fungicides mainly by affecting the respiratory chain electron transport system of pathogen thus reaching the growth suppressing pathogen, finally causes it dead.It should be noted that this series bactericidal agent due to action site single, many pathogens produce resistance to it, therefore resistance risk bactericide in being classified as by international bactericide resistance Action Committee.Produce for reducing resistance risk and delaying drug resistance, being used by the rational mixture of acid amide fungicides and other class agricultural chemicals is one of effective method.
Inventor is found by a large amount of for a long time test, by oxalic acid copper diacetonamines different for the mechanism of action and acid amide fungicides composite, have significant synergies; treatment, the control efficiency of protection, minimizing dosage can be significantly improved; expanding prevention is composed, and reduces cost accounting, to crop safety.
Summary of the invention
The object of the present invention is to provide a kind of bactericidal composition containing oxalic acid copper diacetonamine and acid amide fungicides.This bactericidal composition can overcome alone oxalic acid copper diacetonamine to the germ in invaded plants body almost without the defect of therapeutic activity; Meanwhile, the pesticide resistance of multiple germ to multiple kinds of acid amide fungicides can also be delayed.
Second object of the present invention is to provide the preparation formulation of oxalic acid copper diacetonamine with wherein a kind of binary built bactericidal composition of acid amide fungicides.
3rd object of the present invention is to provide the application of above-mentioned bactericidal composition on control corps diseases.
In order to overcome the defect using unitary agent, and make oxalic acid copper diacetonamine and the wherein composite rationalization of a kind of acid amide fungicides, synergistic effect is remarkable, and bactericidal effect is good, and drug cost is low, not easily develops immunity to drugs, and this invention takes following technical scheme:
A kind of bactericidal composition containing oxalic acid copper diacetonamine and acid amide fungicides, comprise the first active component and the second active component, the weight ratio of the first active component and the second active component is 1:10 ~ 10:1, described first active component is oxalic acid copper diacetonamine, and described second active component is the one in acid amide fungicides.
Further, in bactericidal composition of the present invention, the content sum of described first active component and the second active component is 5% ~ 90% of described bactericidal composition gross weight.
Preferred as technical scheme, the second active component acid amide fungicides in bactericidal composition of the present invention is selected from thifluzamide, isotianil, isopyrazam, fluorine azoles bacterium acid amides, fluorine azoles bacterium aniline, Boscalid, fluopicolide, benzene metsulfovax, fluorine azoles ring bacterium amine, pyrrole metsulfovax, flusulfamide, first flusulfamide, fluopicolide, fenoxanil, Guardian, mandipropamid, cyflufenamid, Hexanaphthene flusulfamide, tiadinil, thiophene fluorine bacterium amine, zoxamide, ring propionyl bacterium amine, fenhexamid, Silthiopham, two chlorine zarilamid, fenfuram, flutolanil, carboxin, fluorine pyrrole bacterium acid amides, furametpyr, biphenyl pyrrole bacterium amine, mandipropamid, benalaxyl-M, one in mefenoxam.
Further, the described formulation containing the bactericidal composition of oxalic acid copper diacetonamine and acid amide fungicides is water dispersible granules, wetting powder or dispersibles oil-suspending agent.
Further, the described bactericidal composition containing oxalic acid copper diacetonamine and acid amide fungicides is preventing and treating the purposes on corps diseases.
Preferred as technical scheme, described corps diseases comprises cucumber downy mildew, powdery mildew of cucumber, potato late blight, rice blast, rice sheath blight disease.
Compared with single use oxalic acid copper diacetonamine respectively or acid amide fungicides, the beneficial effect that the present invention produces is mainly reflected in following aspect:
(1) oxalic acid copper diacetonamine is as a kind of new organic copper bactericide kind, its to the control of crop pest based on protective effect, but poor to the therapeutic activity of the germ in invaded plants body.Acid amide fungicides has protection and therapeutic activity preferably concurrently to the multiple pathogen of damage to crops or fungi, and to the multiple diseases Be very effective of various crop, but the resistance problem of chronic administration acid amide fungicides highlights day by day.One in oxalic acid copper diacetonamines different for the mechanism of action and acid amide fungicides is carried out binary built by the present invention, and the activity of this bactericidal composition and bactericidal effect are not the simple superposition of each composition activity, but has significant synergistic effect.In addition, the advantage of described bactericidal composition also shows that component is reasonable, and have treatment and protective effect concurrently, bactericidal effect is good, and drug cost is low, good to crop safety, the generation of delaying drug resistance.
(2) bactericidal composition of the present invention expands control spectrum, significantly improve the preventing effectiveness of the multiple diseases of multiple kinds of crops, especially better to the preventive effect of cucumber downy mildew, powdery mildew of cucumber, potato late blight, rice blast, rice sheath blight disease.
(3) bactericidal composition of the present invention can be prepared as water dispersible granules, wetting powder or dispersible the preparation of the different dosage forms such as oil-suspending agent, and each preparation is good to crop safety, meets the security requirement of pesticidal preparations.
Embodiment
In order to make object of the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.
(1) part prepared by preparation
Bactericidal composition containing oxalic acid copper diacetonamine and acid amide fungicides can be mixed with water dispersible granules, wetting powder or dispersible the formulations such as oil-suspending agent.When preparing above-mentioned different dosage form, to those skilled in the art, except needs use containing except fungicide active ingredient for the election, also need to select multiple auxiliary agent, can choice for use is different as required pesticidal preparations auxiliary element (auxiliary agent).Described auxiliary element can be one or more in dispersion medium, dispersant, emulsifier, wetting agent, thickener, defoamer, antifreezing agent, disintegrant, binding agent, filler etc.
For water dispersible granules, those skilled in the art are familiar with the corresponding auxiliary agent of use and complete the present invention very much.Dispersant to select in polycarboxylate (TERSPERSE2700, T36, GY-D06 etc.), lignosulfonates, alkylnaphthalene sulfonate one or more; One or more to be selected in alkyl sulfate, alkylsulfonate, naphthalene sulfonate by wetting agent; One or more to be selected in ammonium sulfate, sodium sulphate, polyvinylpyrrolidone, starch and derivative thereof, bentonite by disintegrant; Binding agent select in starch, glucose, polyvinyl alcohol, polyethylene glycol, sodium carboxymethylcellulose, sucrose one or more; Filler select diatomite, kaolin, white carbon, fine particle calcium carbonate, talcum powder, attapulgite, potter's clay one or more.
When preparing corresponding wetting powder, spendable auxiliary agent has: dispersant selects polycarboxylic acid salt (TERSPERSE 2700, T36, GY-D06 etc.), lignin sulfonate (Ufoxane3A, Borresperse NA, Borresperse CA-SA etc.), naphthalene and alkyl naphthalene formaldehyde condensate sulfonates class (NNO, MF, Morwet D-425, Tamol NN, TERSPERSE2020 etc.), Nekal BX (nekal), EO-PO block polyether class (polyoxyethylene polyoxypropylene block copolymer), alkylphenol-polyethenoxy base ether phosphate, in alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphate (SOPA) one or more, one or more to be selected in Sulfates (K-12), Sulfonates (ABS-Na, BX, Terwet 1004 etc.), compound wetting agent (Morwet EFW) by wetting agent, filler select in diatomite, kaolin, fine particle calcium carbonate, talcum powder, white carbon, attapulgite, potter's clay, ammonium sulfate, urea, sucrose, glucose, corn starch, sodium sulphate, sodium polyphosphate one or more.
When preparation dispersibles oil-suspending agent accordingly, spendable auxiliary agent has: the serial emulsifier (BY-110 of BY (castor oil polyoxyethylene ether) selected by emulsifier, BY-125, BY-140), calcium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, Nongru-700 # (common name: alkyl phenol formaldehyde resin polyoxyethylene ether), agriculture breast 2201, this dish-60# (common name: sorbitan monostearate), Tween-60 # (common name: sorbitan monostearate APEO), agriculture breast 1601# (common name: phenethyl phenol polyoxyethylene poly-oxygen propylene aether), one or more in TERSPERSE 4894 (Huntsman Corporation of U.S. product), dispersant select in polycarboxylate, lignosulfonates, EO-PO block copolymer (polyoxyethylene polyoxypropylene block copolymer), phosphate and its esters, Sulfonates, alkylnaphthalene sulfonate (dispersing agent NNO), TERSPERSE 2020 (Huntsman Corporation of the U.S. produces, alkyl naphthalene sulfonic acid salt) one or more, wetting agent select in alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphate, alkylphenol polyoxyethylene phosphate, phenethyl phenol polyethenoxy base ether phosphate, alkyl sulfate, alkylsulfonate, naphthalene sulfonate, TERSPERSE 2500 (Huntsman Corporation of U.S. product) one or more, thickener select in gas-phase silica, polyvinyl alcohol, organobentonite, attapulgite, aluminium-magnesium silicate one or more, stabilizing agent select in organic acid, organic base, ester class, alcohols, antioxidant, epoxychloropropane, tall oil one or more, dispersion medium selects soybean oil, rapeseed oil, cottonseed oil, corn oil, castor oil, palm oil, epoxidized soybean oil, methyl oleate and esterification oils, diesel oil, machine oil, mineral oil, and esters solvent as in repefral, dibutyl phthalate, ethyl acetate, methyl benzoate one or more.
Bactericidal composition of the present invention comprises the first active component and the second active component, and the first active component is oxalic acid copper diacetonamine, and the second active component is the one in acid amide fungicides.The weight ratio of the first active component and the second active component is 1:10 ~ 10:1, and the content sum of the first active component and the second active component is 5% ~ 90% of described bactericidal composition gross weight.Wherein, second active component acid amide fungicides is selected from thifluzamide, isotianil, isopyrazam, fluorine azoles bacterium acid amides, fluorine azoles bacterium aniline, Boscalid, fluopicolide, benzene metsulfovax, fluorine azoles ring bacterium amine, pyrrole metsulfovax, flusulfamide, first flusulfamide, fluopicolide, fenoxanil, Guardian, mandipropamid, cyflufenamid, Hexanaphthene flusulfamide, tiadinil, thiophene fluorine bacterium amine, zoxamide, ring propionyl bacterium amine, fenhexamid, Silthiopham, two chlorine zarilamid, fenfuram, flutolanil, carboxin, fluorine pyrrole bacterium acid amides, furametpyr, biphenyl pyrrole bacterium amine, mandipropamid, benalaxyl-M, one in mefenoxam.
It should be noted that, the active ingredient (or active component) in each example of formulations of subordinate is weight after folding hundred.In view of length, the present invention only have chosen several acid amide fungicides active component and is described.
Example of formulations 1
Take 300 grams of oxalic acid copper diacetonamines, 100 grams of Boscalids, 25 grams of TERSPERSE 2700 (polycarboxylates, Huntsman Corporation of the U.S. produces), 30 grams of sodium lignin sulfonates, 20 grams of Nekal BXs (nekal), 30 grams of K-12 (lauryl sodium sulfate), 20 grams of PVA (polyvinyl alcohol, molecular weight 2000), 20 grams of polyvinylpyrrolidones, kaolin supply 1000 grams.Namely the method for above-mentioned raw materials frequent regulation water intaking dispersible granule mixes, ultra micro air-flow crushing, mixing, granulation step, producing active constituent content is 40% oxalic acid copper diacetonamine Boscalid water dispersible granules.
Example of formulations 2
Take 100 grams of oxalic acid copper diacetonamines, 100 grams of tiadinils, 20 grams of T36 (polycarboxylate), 20 grams of dispersing agent NNOs (alkylnaphthalene sulfonate formaldehyde condensation products), 20 grams of Nekal BXs (nekal), 20 grams of K-12 (lauryl sodium sulfate), attapulgites add to 1000 grams.Namely the method for above-mentioned raw materials frequent regulation water intaking dispersible granule mixes, ultra micro air-flow crushing, mixing, granulation step, producing active constituent content is 20% oxalic acid copper diacetonamine tiadinil water dispersible granules.
Example of formulations 3
Take 100 grams of oxalic acid copper diacetonamines, 300 grams of cyflufenamids, 40 grams of TERSPERSE 2700 (polycarboxylate, Huntsman Corporation of the U.S. produces), 20 grams of dispersing agent NNOs (alkylnaphthalene sulfonate formaldehyde condensation products), 20 grams of Nekal BXs (nekal), 20 grams of K-12 (lauryl sodium sulfate), 30 grams of corn starchs, 50 grams of ammonium sulfate, attapulgites add to 1000 grams.Namely the method for above-mentioned raw materials frequent regulation water intaking dispersible granule mixes, ultra micro air-flow crushing, mixing, granulation step, producing active constituent content is 40% oxalic acid copper diacetonamine cyflufenamid water dispersible granules.
Example of formulations 4
Take 30 grams of oxalic acid copper diacetonamines, 300 grams of pyrrole metsulfovax, 40 grams of TERSPERSE, 2700,30 grams of alkylnaphthalene sulfonate formaldehyde condensation products (Tamol NN), 20 grams of lauryl sodium sulfate, attapulgites fill up to 1000 grams.Above-mentioned raw materials is through mixing, ultra micro air-flow crushing, hybrid technique step, and being prepared into active constituent content is 33% oxalic acid copper diacetonamine pyrrole metsulfovax wetting powder.
Example of formulations 5
Take 300 grams of oxalic acid copper diacetonamines, 60 grams of fluopicolides, 60 grams of calcium lignosulfonates, 40 grams of alkylnaphthalene sulfonate formaldehyde condensation products (Morwet D-425), 20 grams of lauryl sodium sulfate, white carbons fill up to 1000 grams.Above-mentioned raw materials is through mixing, ultra micro air-flow crushing, hybrid technique step, and being prepared into active constituent content is 36% oxalic acid copper diacetonamine fluopicolide wetting powder.
Example of formulations 6
Take 600 grams of oxalic acid copper diacetonamines, 300 grams of isotianils, 10 grams of calcium lignosulfonates, 10 grams of dispersing agent NNOs (alkylnaphthalene sulfonate formaldehyde condensation products), 10 grams of Nekal BXs (nekal), 10 grams of K-12 (lauryl sodium sulfate), attapulgites add to 1000 grams.Above-mentioned raw materials is through mixing, and after air-flow crushing, obtained active constituent content is 90% oxalic acid copper diacetonamine isotianil wetting powder.
Example of formulations 7
Take 200 grams of oxalic acid copper diacetonamines, 100 grams of fenoxanils, 30 grams of alkylphenol polyoxyethylene phosphates, 50 grams of polyoxyethylene polyoxypropylene block copolymers, 40 grams of calcium dodecyl benzene sulfonates, 30 grams of Nongru-700 #, 20 grams of castor oil polyoxyethylene ethers, 10 grams of gas-phase silicas, 10 grams of organobentonites, 20 grams of BHT (2,6-BHT, antioxidant), corn oil supplies 1000 grams.Above-mentioned raw materials is through mixing, and being less than 5um i.e. obtained active constituent content with sand mill sand milling to particle diameter is that 30% oxalic acid copper diacetonamine fenoxanil dispersibles oil-suspending agent.
Example of formulations 8
Take 200 grams of oxalic acid copper diacetonamines, 20 grams of mandipropamids, 30 grams of fatty alcohol-polyoxyethylene ether, 30 grams of dispersing agent NNOs, 60 grams of this dish-60#, 30 grams of agriculture breast 2201#, 30 grams of polyvinyl alcohol, 20 grams of epoxychloropropane, methyl oleate supplies 1000 grams.Above-mentioned raw materials is through mixing, and being less than 5um i.e. obtained active constituent content with sand mill sand milling to particle diameter is that 22% oxalic acid copper diacetonamine mandipropamid dispersibles oil-suspending agent.
Example of formulations 9
Take 40 grams of oxalic acid copper diacetonamines, 10 grams of zoxamides, 30 grams of alkylphenol polyoxyethylene phosphates, 50 grams of BY-125,40 grams of calcium dodecyl benzene sulfonates, 30 grams of TERSPERSE4894 (Huntsman Corporation of U.S. product), 20 grams of castor oil polyoxyethylene ethers, 10 grams of aluminium-magnesium silicates, 10 grams of organobentonites, 20 grams of BHT (2,6-BHT, antioxidant), epoxidized soybean oil supplies 1000 grams.Above-mentioned raw materials is through mixing, and being less than 5um i.e. obtained active constituent content with sand mill sand milling to particle diameter is that 5% oxalic acid copper diacetonamine zoxamide dispersibles oil-suspending agent.
(2) Biometric portion
1, indoor virulence experimental section
Choose on the crops such as cucumber, potato, paddy rice and serious, be difficult to control, representational disease occurs, carry out composite Toxicity Determination test with oxalic acid copper diacetonamine and acid amide fungicides part kind.
Toxicity Determination test 1: powdery mildew of cucumber Toxicity Determination
In order to prevent and treat the powdery mildew on vegetables in agricultural production, fruit tree, wheat, strawberry, flowers, carry out mutually composite synergy research with the fluorine pyrrole bacterium acid amides in oxalic acid copper diacetonamine and acid amide fungicides, isopyrazam, cyflufenamid, Boscalid respectively, concrete grammar is:
Subjects is cucumber powdery mildew's pathogen Sphaerotheca fuliginea.Former medicine is mixed with the test medicine of needs, test method is with reference to " People's Republic of China's agricultural industry criteria NY/T1156.11-2008 farm-chemical indoor determination test rule bactericide the 11st part: control cucurbits powdery mildew test pot-culture method ".
First single dose and each Mixed Pharmacy are arranged 5 variable concentrations gradients (preventive effect sets by geometric progression in the scope of 5% ~ 90%).With the pure water being added with a small amount of surfactant (Tween 80), wash the Fresh spores got and cover with on Powdery Mildew cucumber leaves, filter with double gauze, making spore concentration is 1 × 10
5the suspension of individual spore/milliliter, for subsequent use.Often process 3 basins, repeat for 4 times, and establish the process only containing solvent and surfactant not containing active ingredient to make blank.With spore suspension 24h inoculation before chemicals treatment, liquid is evenly sprayed in blade face to all wetting, for subsequent use after liquid natural air drying.Inoculation and chemicals treatment after potted plant cucumber natural air drying, then move to thermostatic chamber, under the condition of temperature 20 DEG C ~ 24 DEG C cultivation 7 days ~ 10 days.When the sick leaf rate of blank reaches more than 80%, classification investigation manages incidence everywhere, and often process and at least investigate 30 leaves, grade scale is:
0 grade: anosis;
1 grade: lesion area accounts for less than 5% of one-piece blade area;
3 grades: lesion area accounts for 6% ~ 15% of one-piece blade area;
5 grades: lesion area accounts for 16% ~ 25% of one-piece blade area;
7 grades: lesion area accounts for 26% ~ 50% of one-piece blade area;
9 grades: lesion area accounts for 50% ~ 75% of one-piece blade area;
11 grades: lesion area accounts for more than 75% of one-piece blade area.
Computational methods:
Disease index=[∑ (the sick number of sheets × relative level numerical value at different levels)/(investigation total leaf number × 11)] × 100
Control efficiency (%)=[(contrast disease index-process disease index)/contrast disease index] × 100
By the linear regression analysis between the probit value of preventive effect and the logarithm value of series concentration, obtain the EC of each medicament
50value, calculates the co-toxicity coefficient (CTC) of mixture, evaluates the activity of reagent agent to germ with this by the abundant method of Sun Yun.
The co-toxicity coefficient (CTC) >=120 of complex preparation shows as synergistic effect; CTC≤80 show as antagonism; 80 < CTC < 120 show as summation action.
Toxicity Determination test 1 (powdery mildew of cucumber Toxicity Determination) result of the test in Table 1-1 to showing 1-4.
Table 1-1 oxalic acid copper diacetonamine and fluorine pyrrole bacterium acid amides combine the Toxicity Determination to powdery mildew of cucumber
Table 1-2 oxalic acid copper diacetonamine and isopyrazam combine the Toxicity Determination to powdery mildew of cucumber
Table 1-3 oxalic acid copper diacetonamine and cyflufenamid combine the Toxicity Determination to powdery mildew of cucumber
Table 1-4 oxalic acid copper diacetonamine and Boscalid combine the Toxicity Determination to powdery mildew of cucumber
Toxicity Determination result (table 1-1 to showing 1-4) shows: oxalic acid copper diacetonamine respectively with fluorine pyrrole bacterium acid amides, isopyrazam, cyflufenamid, Boscalid, being that 1:10 ~ 10:1 is mixed with weight ratio has good virulence to cucumber powdery mildew's pathogen, all has significant synergistic effect.
Toxicity Determination test 2: cucumber downy mildew Toxicity Determination
Inventor carries out mutually composite synergy research with the fluopicolide in oxalic acid copper diacetonamine and acid amide fungicides, benzene metsulfovax, Hexanaphthene flusulfamide, Guardian, mandipropamid, and concrete grammar is:
Test adopts bacterium of downy mildew of cucumber (Pseudoperonospora cubensis) to be tested object.Former medicine is mixed with the test medicine of needs, and test method is with reference to " People's Republic of China's agricultural industry criteria NY/T1156.3-2006 ".
First single dose and each Mixed Pharmacy are arranged 5 variable concentrations gradients (on the basis of preliminary experiment result, different with proportioning according to different agents combination, concentration gradient arranges also different, and bacteriostasis rate sets by geometric progression in the scope of 5% ~ 90%).Test target bacterium is the bacterium of downy mildew of cucumber blade picking up from from up to down 4 leaf positions, leaf ~ 6, field, with the Pseudoperonospora cubensis sporangium at 4 DEG C of distillation washing lower blade back sides, be made into suspension (concentration controls at every milliliter of 1 × 105 ~ 1 × 107 sporangium), deposit for subsequent use at 4 DEG C; Liquid is evenly sprayed in the healthy leaves back side, after liquid natural air drying, each process blade and blade is gone up dorsad, is emitted in moisture preservation box by after marks for treatment.Test is established and is not made blank containing the process of medicament.Vacuum side of blade is inoculated in ready Fresh spores capsule suspension drop 10 μ L.Every blade inoculation 4, often process is no less than 5 leaves.24h inoculation before treatment.Ware lid on inoculation bonnet, is placed in climatic cabinate or has the humidistat of illumination, and alternately, temperature is 17 DEG C ~ 22 DEG C to the continuous illumination in every day/dark 12h, cultivates under the condition of relative moisture more than 90%.Measure depending on process and blank incidence and record lesion diameter, unit is millimeter (mm), calculates control efficiency.By the linear regression analysis between the probit value of control efficiency and the logarithm value of series concentration, obtain the EC of each medicament
50value, calculates the co-toxicity coefficient (CTC) of mixture, evaluates the activity of reagent agent to germ with this by the abundant method of Sun Yun.
The co-toxicity coefficient (CTC) >=120 of complex preparation shows as synergistic effect; CTC≤80 show as antagonism; 80 < CTC < 120 show as summation action.
Toxicity Determination test 2 result of the test in Table 2-1 to showing 2-5.
Table 2-1 oxalic acid copper diacetonamine and fluopicolide combine the Toxicity Determination to cucumber downy mildew
| Chemicals treatment | Virulence regression equation | Correlation coefficient | EC 50 | Co-toxicity coefficient |
| (r) | (mg/L) | (CTC) | ||
| Oxalic acid copper diacetonamine (A) | Y＝-5.7039+7.9169X | 0.9917 | 22.49 | - |
| Fluopicolide (B) | Y＝3.7837+3.7665X | 0.9959 | 2.10 | - |
| A:B＝1:10 | Y＝4.1695+3.4433X | 0.9850 | 1.74 | 131.5 |
| A:B＝1:5 | Y＝4.2999+2.7796X | 0.9959 | 1.79 | 138.7 |
| A:B＝1:3 | Y＝4.3267+2.6402X | 0.9925 | 1.80 | 151.2 |
| A:B＝1:1 | Y＝3.8636+2.9186X | 0.9981 | 2.45 | 156.9 |
| A:B＝3:1 | Y＝3.3341+2.4998X | 0.9943 | 4.64 | 141.6 |
| A:B＝5:1 | Y＝2.4061+3.2651X | 0.9988 | 6.23 | 138.1 |
| A:B＝10:1 | Y＝2.1496+2.9647X | 0.9940 | 9.15 | 130.7 |
Table 2-2 oxalic acid copper diacetonamine and benzene metsulfovax combine the Toxicity Determination to cucumber downy mildew
Table 2-3 oxalic acid copper diacetonamine and Hexanaphthene flusulfamide combine the Toxicity Determination to cucumber downy mildew
Table 2-4 oxalic acid copper diacetonamine and Guardian combine the Toxicity Determination to cucumber downy mildew
Table 2-5 oxalic acid copper diacetonamine and mandipropamid combine the Toxicity Determination to cucumber downy mildew
Toxicity Determination result (table 2-1 is to showing 2-5) shows: oxalic acid copper diacetonamine and fluopicolide, benzene metsulfovax, Hexanaphthene flusulfamide, Guardian, mandipropamid, being that 1:10 ~ 10:1 is mixed with weight ratio has good virulence to bacterium of downy mildew of cucumber, all has significant synergistic effect.
Toxicity Determination test 3: potato late blight Toxicity Determination
Toxicity Determination test 4: rice blast Toxicity Determination
Toxicity Determination test 5: rice sheath blight disease Toxicity Determination
In order to prevent and treat Major Diseases agricultural production endangering potato, paddy rice, carry out mutual composite synergy with oxalic acid copper diacetonamine and acid amide fungicides to study, the combination difference (see table 3-1 ~ table 5-3) that different tests object adopts, concrete grammar is:
Subjects is potato late blight (Potato Late Bright), rice blast fungus (Pyriculariagrisea), rice sheath blight disease (Rhizoctonia solani).Former medicine is mixed with the test medicine of needs, single dose and each Mixed Pharmacy is arranged 5 variable concentrations gradients (on the basis of preliminary experiment result, bacteriostasis rate sets by geometric progression in the scope of 5% ~ 90%).If clear water contrasts, repeat 3 times.Test adopts mycelial growth rate method, by cultured pathogen, be aseptically 5mm card punch with diameter, cut bacterium cake from colony edge, with transfer needle, bacterium cake is connected on the culture medium flat plate of different agents concentration, puts 28 DEG C, cultivate in saturated humidity incubator; When control group bacterium colony covers with, measure colony diameter, calculate each chemicals treatment and suppress the percentage of mycelial growth, by the linear regression analysis between the probit value of inhibiting rate and the logarithm value of series concentration, obtain the EC of each medicament
50value, calculates the co-toxicity coefficient (CTC) of mixture, evaluates the activity of reagent agent to germ with this by the abundant method of Sun Yun.
The co-toxicity coefficient (CTC) >=120 of complex preparation shows as synergistic effect; CTC≤80 show as antagonism; 80 < CTC < 120 show as summation action.
Table 3-1 oxalic acid copper diacetonamine and Boscalid combine the Toxicity Determination to potato late blight
Table 3-2 oxalic acid copper diacetonamine and fluopicolide combine the Toxicity Determination to potato late blight
Table 3-3 oxalic acid copper diacetonamine and pyrrole metsulfovax combine the Toxicity Determination to potato late blight
Table 3-4 oxalic acid copper diacetonamine and zoxamide combine the Toxicity Determination to potato late blight
Table 3-5 oxalic acid copper diacetonamine and first methuroxam combine the Toxicity Determination to potato late blight
Toxicity Determination result shows: oxalic acid copper diacetonamine respectively with Boscalid, fluopicolide, pyrrole metsulfovax, zoxamide, first methuroxam, being that 1:10 ~ 10:1 is mixed with weight ratio has good virulence to potato late blight, all has significant synergistic effect.
Table 4-1 oxalic acid copper diacetonamine and isotianil combine the Toxicity Determination to rice blast
Table 4-2 oxalic acid copper diacetonamine and fenoxanil combine the Toxicity Determination to rice blast
Table 4-3 oxalic acid copper diacetonamine and tiadinil combine the Toxicity Determination to rice blast
Toxicity Determination result shows: oxalic acid copper diacetonamine respectively with isotianil, fenoxanil, tiadinil, being that 1:10 ~ 10:1 is mixed with weight ratio has good virulence to rice blast, all has significant synergistic effect.
Table 5-1 oxalic acid copper diacetonamine and thifluzamide combine the Toxicity Determination to rice sheath blight disease
Table 5-2 oxalic acid copper diacetonamine and thiophene fluorine bacterium amine combine the Toxicity Determination to rice sheath blight disease
Table 5-3 oxalic acid copper diacetonamine and flutolanil combine the Toxicity Determination to rice sheath blight disease
Toxicity Determination result shows: oxalic acid copper diacetonamine respectively with thifluzamide, thiophene fluorine bacterium amine, flutolanil, being that 1:10 ~ 10:1 is mixed with weight ratio has good virulence to rice sheath blight disease, all has significant synergistic effect.
2. field trial part
Biological Examples 1: prevent and treat potato late blight field trial
Carry out example of formulations 1 (40% oxalic acid copper diacetonamine Boscalid water dispersible granules) in Fugu County of Shaanxi Province in 7 ~ August in 2014, example of formulations 5 (36% oxalic acid copper diacetonamine fluopicolide wetting powder) has prevented and treated potato late blight field trial.Test method is with reference to " pesticide field efficacy medicine test criterion (one) bactericidal agent for preventing and treating potato late blight GB/T 17980.34-2000 ".
The plot that test arrangement weighs in morbidity over the years, in July, 2014 starts to occur incidence of leaf, and test medicine and extension rate, in table 6, separately establish blank, often processes 4 times and repeats, every plot area 25m
2, Gong32Ge community, random district group arranges.Adopt conventional spray-on process, blade positive and negative evenly squirt, liquid consumption 50 liters/mu.First time dispenser is when blade begins to see, the dispenser of 14 days second time, is total to dispenser secondary.
Investigation and statistical method:
Within 14 days after second time dispenser, carry out disease index investigation, every community diagonal 5 sampling, often some investigation 2 ~ 3 strains, investigate whole blade, record total number of sheets, the sick number of sheets at different levels and sick progression, calculate disease index.
Grade scale is:
0 grade, without scab;
1 grade, lesion area accounts for less than 5% of whole leaf area;
3 grades, lesion area accounts for the 6%-10% of whole leaf area;
5 grades, lesion area accounts for the 11%-20% of whole leaf area;
7 grades, lesion area accounts for the 21%-50% of whole leaf area;
9 grades, lesion area accounts for more than 50% of whole leaf area.
Disease index and control efficiency computational methods:
Disease index=Σ (the sick number of sheets × relative level numerical value at different levels)/(investigating the total number of sheets × 9) × 100
Control efficiency (%)=[after (after the dispenser of blank district after disease index-chemicals treatment district dispenser disease index)/blank district dispenser disease index] × 100
Potato late blight field test results prevented and treated by table 6
Field test results (table 6) shows: 40% oxalic acid copper diacetonamine Boscalid water dispersible granules 1500 times, 2000 times, 36% oxalic acid copper diacetonamine fluopicolide wetting powder 3000 times, 3500 times, good preventive effect is had to potato late blight, obviously be better than 30% oxalic acid copper diacetonamine wetting powder 1000 times, 50% Boscalid water dispersible granules 2000 times, 10% fluopicolide suspending agent 3000 is doubly to the preventive effect of potato late blight, and preventive effect difference reaches pole significance level (referring to table 6).
To the security survey of potato, within some days, observe after the 1st day and medicine after each spray medicine, each chemicals treatment occurs without poisoning phenomenon potato.
Result of the test show oxalic acid copper diacetonamine respectively with Boscalid, fluopicolide mixture after, significantly improve the control efficiency to potato late blight, reducing dosage and drug cost, to potato growth safety, is the favourable agents preventing and treating potato late blight.
Biological Examples 2: control rice blast field trial
Within 2014, carry out example of formulations 2 (20% oxalic acid copper diacetonamine tiadinil water dispersible granules) at Shaanxi Province's Hanzhong City, example of formulations 7 (30% oxalic acid copper diacetonamine fenoxanil dispersibles oil-suspending agent) prevented and treated rice blast field trial, trial crops is paddy rice, and controlling object is rice blast (Pyricularia oryzae Cav.).Test is located at Hanzhong City Chenggu County, and test medicine and dosage refer to table 7.Separately establish contrast medicament and blank, often process 4 times and repeat, every plot area 30m
2, Gong32Ge community, random district group arranges.Adopt conventional spray-on process, mu dispenser liquid 50kg, evenly spray paddy rice complete stool.Altogether dispenser 2 times, in paddy rice booting latter stage and each dispenser of full heading time 1 time.
Investigation and statistical method:
Investigation in 14 days after 2nd dispenser, investigation method is the sampling of 5, every community, often some investigation 50 fringes, and grade scale is as follows:
0 grade: anosis;
1 grade: every fringe loss less than 5% (morbidity of indivedual branch stalk);
3 grades: every fringe loss 6%-20% (about 1/3 branch stalk morbidity);
5 grades: every fringe loss 21%-50% (fringe neck or main shaft morbidity, grain half is flat);
7 grades: every fringe loss 51%-70% (fringe neck is fallen ill, most of shrivelled kernel);
9 grades: every fringe loss 71%-100% (fringe neck is fallen ill, and causes dead ears).
Refer to calculate preventive effect according to disease.Some skies after 1st day and medicine after each spray medicine, observe medicament and respectively process impact on paddy rice.
Disease index=Σ (sick spike number × relative level numerical value at different levels)/(investigating total spike number × 9) × 100
Control efficiency (%)=[(contrast disease index-process disease index)/contrast disease index] × 100
Rice blast field test results prevented and treated by table 7
Field test results shows: 20% oxalic acid copper diacetonamine tiadinil water dispersible granules 1000 times, 1500 times, 30% oxalic acid copper diacetonamine fenoxanil dispersibles oil-suspending agent 1500 times, 2000 times, 92.21% is respectively to rice blast preventive effect of 14 days after second time medicine, 87.23%, 94.81%, 90.32%, obviously be better than 30% oxalic acid copper diacetonamine wetting powder 1000 times, 20% tiadinil water dispersible granules 1000 times, 30% fenoxanil suspending agent 1500 is doubly to the preventive effect of rice blast, preventive effect difference reaches pole significance level (referring to table 7), describe composite rear synergy remarkable.
To the security survey of paddy rice, within after spray medicine after the 1st day and medicine some days, observe, each test process occurs without poisoning phenomenon paddy rice.
Result of the test show oxalic acid copper diacetonamine respectively with tiadinil, fenoxanil mixture after, significantly improve the control efficiency to rice blast, reduce dosage and drug cost, to paddy growth safety, be control rice blast favourable agents.
In sum, composition of the present invention is two kinds of active component compound schemes of a kind of composition adopting oxalic acid copper diacetonamine and acid amide fungicides, its activity and bactericidal effect are not the simple superposition of each composition activity, compared with existing unitary agent, except there is significant bactericidal effect, and have significant synergistic effect, and good to crop safety, meet the security requirement of pesticidal preparations.
Claims (6)
1. one kind contains the bactericidal composition of oxalic acid copper diacetonamine and acid amide fungicides, it is characterized in that, comprise the first active component and the second active component, the weight ratio of the first active component and the second active component is 1:10 ~ 10:1, described first active component is oxalic acid copper diacetonamine, and described second active component is the one in acid amide fungicides.
2. the bactericidal composition containing oxalic acid copper diacetonamine and acid amide fungicides according to claim 1, it is characterized in that, the content sum of described first active component and the second active component is 5% ~ 90% of described bactericidal composition gross weight.
3. the bactericidal composition containing oxalic acid copper diacetonamine and acid amide fungicides according to claim 1 and 2, it is characterized in that, second active component acid amide fungicides is selected from thifluzamide, isotianil, isopyrazam, fluorine azoles bacterium acid amides, fluorine azoles bacterium aniline, Boscalid, fluopicolide, benzene metsulfovax, fluorine azoles ring bacterium amine, pyrrole metsulfovax, flusulfamide, first flusulfamide, fluopicolide, fenoxanil, Guardian, mandipropamid, cyflufenamid, Hexanaphthene flusulfamide, tiadinil, thiophene fluorine bacterium amine, zoxamide, ring propionyl bacterium amine, fenhexamid, Silthiopham, two chlorine zarilamid, fenfuram, flutolanil, carboxin, fluorine pyrrole bacterium acid amides, furametpyr, biphenyl pyrrole bacterium amine, mandipropamid, benalaxyl-M, one in mefenoxam.
4. the formulation containing the bactericidal composition of oxalic acid copper diacetonamine and acid amide fungicides according to claim 3 is water dispersible granules, wetting powder or dispersibles oil-suspending agent.
5. the bactericidal composition containing oxalic acid copper diacetonamine and acid amide fungicides according to claim 3 is preventing and treating the purposes on corps diseases.
6. the bactericidal composition containing oxalic acid copper diacetonamine and acid amide fungicides according to claim 5 is preventing and treating the purposes on corps diseases, it is characterized in that, described corps diseases comprises cucumber downy mildew, powdery mildew of cucumber, potato late blight, rice blast, rice sheath blight disease.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106031379A (en) * | 2015-03-10 | 2016-10-19 | 陕西美邦农药有限公司 | Pesticide composition containing sedaxane and copper preparation |
| CN106305778A (en) * | 2016-08-15 | 2017-01-11 | 青岛瀚生生物科技股份有限公司 | Agricultural compounded soil-borne-disease sterilization composition |
| CN108887269A (en) * | 2018-08-19 | 2018-11-27 | 安徽嘉联生物科技有限公司 | A kind of bactericidal composition containing fluorine azoles bacterium acyl azanol and tiger glue adipic acid copper |
| CN114946849A (en) * | 2022-05-27 | 2022-08-30 | 广西壮族自治区农业科学院 | Medicament for preventing and treating root rot of pachyrhizua angulatus stems |
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| CN101456873A (en) * | 2007-12-14 | 2009-06-17 | 西北农林科技大学农药研究所 | Agricultural bactericidal agent |
| CN101768175A (en) * | 2008-12-31 | 2010-07-07 | 西北农林科技大学农药研究所 | Agricultural fungicide of oxalic acid copper diacetonamine |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456873A (en) * | 2007-12-14 | 2009-06-17 | 西北农林科技大学农药研究所 | Agricultural bactericidal agent |
| CN101768175A (en) * | 2008-12-31 | 2010-07-07 | 西北农林科技大学农药研究所 | Agricultural fungicide of oxalic acid copper diacetonamine |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106031379A (en) * | 2015-03-10 | 2016-10-19 | 陕西美邦农药有限公司 | Pesticide composition containing sedaxane and copper preparation |
| CN106305778A (en) * | 2016-08-15 | 2017-01-11 | 青岛瀚生生物科技股份有限公司 | Agricultural compounded soil-borne-disease sterilization composition |
| CN108887269A (en) * | 2018-08-19 | 2018-11-27 | 安徽嘉联生物科技有限公司 | A kind of bactericidal composition containing fluorine azoles bacterium acyl azanol and tiger glue adipic acid copper |
| CN108887269B (en) * | 2018-08-19 | 2021-05-11 | 安徽省益农化工有限公司 | Sterilization composition containing fluconazole acyl hydroxylamine and copper succinate + glutarate |
| CN114946849A (en) * | 2022-05-27 | 2022-08-30 | 广西壮族自治区农业科学院 | Medicament for preventing and treating root rot of pachyrhizua angulatus stems |
| CN114946849B (en) * | 2022-05-27 | 2024-04-26 | 广西壮族自治区农业科学院 | Medicament for preventing and treating powder Ge Jingji rot |
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