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CN105815334A - Bactericidal composition containing diacetonamine oxalate-copper - Google Patents

Bactericidal composition containing diacetonamine oxalate-copper Download PDF

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Publication number
CN105815334A
CN105815334A CN201610015875.8A CN201610015875A CN105815334A CN 105815334 A CN105815334 A CN 105815334A CN 201610015875 A CN201610015875 A CN 201610015875A CN 105815334 A CN105815334 A CN 105815334A
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active component
oxalic acid
acid copper
grams
bactericidal composition
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Inventor
郑敬敏
马强
冯建雄
李明甫
张仙
张崇斌
乌小瑜
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Shaanxi Sunger Road Bio Science Co Ltd
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Shaanxi Sunger Road Bio Science 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
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
    • 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
    • A01N55/00Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/02Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
    • 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
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12Powders or granules
    • A01N25/14Powders or granules wettable
    • 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
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46N-acyl derivatives
    • 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
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/501,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/761,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products

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Abstract

The invention discloses a bactericidal composition containing diacetonamine oxalate-copper. The bactericidal composition comprises a first active component and a second active component, wherein a weight ratio of the first active component to the second active component is 1: 10 to 10: 1, the first active component is diacetonamine oxalate-copper, and the second active component is cyazofamid. The composition may be made into an agriculturally allowable water dispersible granule, wettable powder, suspending agent or dispersible oil suspending agent and exerts good prevention effect on cucumber downy mildew, potato late blight, tomato early blight and grape downy mildew. The composition effectively overcomes the problem of non-ideal prevention effect in single usage of diacetonamine oxalate-copper or the above-mentioned oomycete bactericide; and compounding of diacetonamine oxalate-copper and the oomycete bactericide produces substantial synergism and reduces the risks of resistance generation and bactericide application cost.

Description

A kind of bactericidal composition containing oxalic acid copper diacetonamine
Present patent application is the divisional application of patent CN104430491A.
Patent name: a kind of bactericidal composition containing oxalic acid copper diacetonamine
Number of patent application: 201410635827.X
Patent application day: on November 12nd, 2014
Technical field
The invention belongs to technical field of pesticide combination, relate to a kind of bactericidal composition, particularly to a kind of binary built bactericidal composition using oxalic acid copper diacetonamine as the first active component, its second active component is a kind of antibacterial preventing and treating oomycetes disease.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, is not likely to produce the advantages such as Drug resistance.Based on the use history of the Inorganic Copper preparation of Copper hydrate, copper sulfate etc. more than 200 years, but owing to it is difficult to be biodegradable, long-term a large amount of use has had resulted in copper accumulation in soil, can have undesirable effect the normal growth of plant and soil function.At present, the exploitation of organic copper preparation, it has also become the hot topic that disinfectant use in agriculture produces, organic copper preparation is to crop safety, nuisanceless.
Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo is with two acetone isolated in Qinling Mountains streptomycete fermentation liquid as raw material, by its structural modification, synthesis one new compound 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 prevention effect to crop pests such as cucumber downy mildew, the late blight of potato, alternaria leaf spot of apple.
Oomycete belongs to Mycophyta, and for a guiding principle of Mastigomycotina, Oomycete mainly has pythium spp, phytophthora, downy mildew etc., often results in the downy mildew of crop, epidemic disease, damping off etc..The medicament preventing and treating this kind of disease conventional mainly has dimethomorph, cyazofamid, phosethyl-Al pesticide and mixture thereof.
Be described below several preventing and treating crop Oomycete class disease main pesticide species:
Dimethomorph, has another name called peace gram, English common name dimethomorph, chemical name: (E, Z)-4-[3-(4-chlorphenyl) 3-(3,4-Dimethoxyphenyl) acryloyl] morpholine.Dimethomorph is an antibacterial specially killing Oomycete fungal, action character is the formation destroying cell envelope, each stage of oomycetes life cycle there is is effect, is widely used in the disease control that vegetable downy mildew, epidemic disease, seedling sudden fall ill, black shank etc. are caused by Mastigomycotina Oomycete fungal.Dimethomorph tool systemic activity, is used alone the resistance risk that comparison is high.
Flumorph, has another name called and goes out gram, English common name flumorph, chemical name: (E, 2) 4-[3-(3 ', 4 '-Dimethoxyphenyl)-3-(4-fluorophenyl) acryloyl] morpholine.Flumorph has efficiently, low toxicity, to features such as crop safeties, for preventing and treating the disease that Oomycete pathogen produces, such as crop downy mildew, late blight, frost epidemic disease etc..
Cyazofamid, English common name cyazofamid, chemical name: 4-chloro-2-cyano group-N, N-dimethyl-5-p-methylphenyl imidazoles-1-sulfonamide.Cyazofamid is sulphaguanidine azoles fungicide.Cyazofamid belongs to a kind of super protective fungicide, it may have certain interior suction and therapeutic activity, and the plasmodiophora brassica bacteria of Oomycete fungal such as downy mildew, Pseudo peronospara, phytophthora, pythium spp and Plasmodiophoromycetes is had the highest biological activity.Its controlling object is downy mildew, epidemic disease, such as cucumber downy mildew, downy mildew of garpe, tomato late blight, the late blight of potato etc..
Phosethyl-Al, has another name called that Yimeiling, the spirit of epidemic disease frost, fosetyl aluminium, mould epidemic disease be clean, Methylpartricin Sodium Laurylsulfate or mycete spirit, English common name phosethyl-Al, chemical name: three-(ethylphosphonic acid) aluminum.Phosethyl-Al is systemic fungicide, and disease caused by oomycetes is had specially good effect, can conduct up and down in plant, has protection and therapeutical effect.
Metalaxyl, other title: the spirit of Apron, conservation, ridomil, auspicious poison frost, first frost peace, the many Mils of thunder, English common name metalaxyl, chemical name: D, L-N-(2,6-3,5-dimethylphenyl)-N-(2 '-methoxyl group acetyl) methyl lactamine.Metalaxyl is acid amide fungicides, has interior absorption, has protection and therapeutical effect; can be absorbed by the root, stem and leaf of plant; having Bidirectional Conduction performance, the various crop downy mildew causing Pseudoperonospora cubensis, phytophthora pathogenic bacteria and rotten mildew fungus, the phytophthora root rot of gourd, fruit and vegetable class, the downy mildew of millet are effective.
Metalaxyl-M, English common name metalaxyl-M, chemical name: N-(2,6-xylyl)-N-(Methoxyacetyl)-D-alanine methyl ester.Metalaxyl-M is higher to crop pest activity than metalaxyl, excellent to crop pest preventive effects such as the vegetable caused by Pseudoperonospora cubensis, phytophthora pathogenic bacteria, rotten mildew fungus, fruit tree, Nicotiana tabacum L., oil plant, Cotton Gossypii, grains.
Cymoxanil, English common name cymoxanil, chemical name: 1-(2-cyano group-2-methoxyl group imido grpup)-3-ethyl carbamide.Cymoxanil is a kind of efficient, low toxicity antibacterial, belongs to Peronosporales fungus such as epidemic disease frost genus, Peronospora, single shaft frost effectively.Cymoxanil is how mixed with other protective fungicides, it is adaptable to the preventing and treating of the diseases such as the vegetables such as Fructus Cucumidis sativi, Fructus Vitis viniferae, Fructus Lycopersici esculenti, Fructus Litchi, fruit tree and Nicotiana tabacum L..
M 9834, English common name benalaxyl, chemical name: N-phenylacetyl group-N-2,6-xylyl-DL-Alanine methyl ester.M 9834 is systemic fungicide, is used for preventing and treating oomycetes diseases, such as the single shaft mycete of Fructus Vitis viniferae, Rhizoma Solani tuber osi, Fructus Fragariae Ananssae, the phytophthora of Fructus Lycopersici esculenti, Nicotiana tabacum L., Bulbus Allii Cepae, the downy mildew of Semen sojae atricolor, the false downy mildew etc. of Fructus Cucumidis sativi.
Propamocarb, have another name called general make every effort to overcome, amide, epidemic disease frost clean, English name propamocarb, chemical name: 3-(dimethylamino) propyl carbamic acid propyl ester.Propamocarb is a kind of systemic pesticide, and crops downy mildew, epidemic disease, late blight, damping off, black convulsive diseases are had excellent prevention effect.
Iprovalicarb, English common name iprovalicarb, chemical name: [two-methyl isophthalic acid-(4-tolyl) ethylaminocarbonyl]-propyl group]-carbamic acid isopropyl ester.Iprovalicarb is amino-acid ester analog derivative, has the brand-new biomimetic features of uniqueness so that it is the mechanism of action is different from other antibacterial preventing and treating Oomycete.Its mechanism of action is to act on the synthesis of fungal cell wall and protein, can suppress infecting and sprouting of spore, can suppress mycelial growth simultaneously, causes its deformation, death.For the fungus-caused disease of Peronosporaceae and Phytophthora, there is well treatment and eradicant action.
Frost spirit, has another name called Sandofan, English common name oxadixyl, chemical name: 2-methoxyl group-N-(2-oxo-1,3-oxazoles alkane-3-base) acetyl 2 ', 6 '-dimethylaniline.Frost spirit is disinfectant use in agriculture, has the highest preventive effect, protected and therapeutical effect to Peronosporales pathogen, and the lasting period is long.
Although oxalic acid copper diacetonamine has preferable preventive effect to Oomycete fungal disease, but its mechanism of action is single, there is resistance risk after listing, causes its preventive effect to reduce.The bactericide specially of the preventing and treating plant Oomycete guiding principle diseases such as above-mentioned phosethyl-Al, cymoxanil, frost spirit, pathogen produces the speed of resistance the most quickly to each kind, dosage is administered alone increasing, and conventional dose such as Mancozeb agriculture chemical compounding, use resistance to strengthen year by year for many years.
Oxalic acid copper diacetonamine as a kind of novel organic copper antibacterial, its to crop based on protective effect, to the pathogenic bacteria in invaded plants body almost without therapeutic activity.At present, the antibacterial of Oomycete class disease and the document report of oxalic acid copper diacetonamine mixture are not the most prevented and treated.
Inventor is found by experiment that, oxalic acid copper diacetonamines different for the mechanism of action and the Oomycete series bactericidal agent mixture of preventing and treating with therapeutic activity is used, can significantly improve the preventive effect to various crop disease, reduce cost accounting, high to crop safety.
Summary of the invention
In order to overcome the technological deficiency of the bactericide specially of single administration oxalic acid copper diacetonamine and preventing and treating plant Oomycete guiding principle disease, it is an object of the invention to provide a kind of compounding component reasonable, potentiation is notable, bactericidal effect is good, drug cost is low, is not likely to produce Drug resistance and the agricultural bactericidal composition to crop safety.
Second object of the present invention is to provide the preparation formulation of the binary built bactericidal composition containing oxalic acid copper diacetonamine.
Third object of the present invention is the application providing above-mentioned bactericidal composition on preventing and treating corps diseases.
For achieving the above object, this invention takes following technical scheme:
A kind of bactericidal composition containing oxalic acid copper diacetonamine, including 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, described second active component one in dimethomorph, flumorph, metalaxyl, Metalaxyl-M, phosethyl-Al, M 9834, frost spirit, cymoxanil, Propamocarb, cyazofamid, iprovalicarb.
Further, in the described bactericidal composition containing oxalic acid copper diacetonamine, the content sum of the first active component and the second active component is the 5%~85% of described bactericidal composition gross weight.
Further, the dosage form of the described bactericidal composition containing oxalic acid copper diacetonamine is water dispersible granules, wettable powder or dispersibles oil-suspending agent.
Further, the described bactericidal composition containing oxalic acid copper diacetonamine purposes on preventing and treating corps diseases.
Preferred, the described bactericidal composition containing oxalic acid copper diacetonamine as technical scheme, the purposes in preventing and treating cucumber downy mildew, the late blight of potato, early blight of tomato, downy mildew of garpe.
Compared with the most single use oxalic acid copper diacetonamine or above-mentioned oomycetes diseases antibacterial, what the present invention produced has the advantages that following aspect:
(1) oxalic acid copper diacetonamine is as a kind of new organic copper antibacterial kind, and Oomycete fungal disease shows preferably preventive effect, but its to the preventing and treating of crop pest based on protective effect, to the pathogenic bacteria in invaded plants body almost without therapeutic activity.In order to improve the preventive effect of oxalic acid copper diacetonamine further, reduce the risk producing resistance, it is contemplated that by its bactericide compounded with other.For the oomycetes diseases of serious harm crop, the present invention devises a kind of binary built bactericidal composition using oxalic acid copper diacetonamine as the first active component.Second active component (or second sterilization component) of this bactericidal composition one in dimethomorph, flumorph, metalaxyl, Metalaxyl-M, phosethyl-Al, M 9834, frost spirit, cymoxanil, Propamocarb, cyazofamid, iprovalicarb.Above-mentioned second active component be there is therapeutic activity prevent and treat Oomycete series bactericidal agent.Therefore, the binary built bactericidal composition component of the present invention is chosen rationally, effectively overcomes single administration oxalic acid copper diacetonamine or the preventive effect defect of above-mentioned oomycetes diseases antibacterial.
(2) being learnt by substantial amounts of indoor and field control effectiveness test, the activity of bactericidal composition of the present invention and bactericidal effect are not the simple superposition of each composition activity, but show significant potentiation.
(3) bactericidal composition of the present invention expands preventing and treating spectrum, bactericidal effect is good, significantly improve the preventing effectiveness of the multiple diseases of multiple kinds of crops, especially to cucumber downy mildew, the late blight of potato, early blight of tomato, downy mildew of garpe preventive effect preferable.
(4) bactericidal composition of the present invention can be prepared as water dispersible granules, wettable 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, is suitable for popularizing application.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.
(1) part prepared by preparation
The bactericidal composition containing oxalic acid copper diacetonamine of the present invention is binary built bactericidal composition, including the first active component and the second active component, first active component is oxalic acid copper diacetonamine, second active component one in dimethomorph, flumorph, metalaxyl, Metalaxyl-M, phosethyl-Al, M 9834, frost spirit, cymoxanil, Propamocarb, cyazofamid, iprovalicarb.Especially, the weight ratio of the first active component and the second active component is 1:10~10:1, and 5%~85% that the content sum of the first active component and the second active component is described bactericidal composition gross weight.
Above-mentioned bactericidal composition can be configured to water dispersible granules, wettable powder or dispersible the dosage forms such as oil-suspending agent.When preparing above-mentioned different dosage form, to those skilled in the art, in addition to needs use containing fungicide active ingredient for the election, in addition it is also necessary to select multiple auxiliary agent, can select as required to use different pesticidal preparations auxiliary elements (auxiliary agent).Described auxiliary element can be one or more in disperse medium, dispersant, emulsifying agent, wetting agent, thickening agent, defoamer, antifreezing agent, disintegrating agent, binding agent, filler etc..
For water dispersible granules, those skilled in the art are very familiar with using corresponding auxiliary agent to complete the present invention.Dispersant selects one or more in polycarboxylate (TERSPERSE2700, T36, GY-D06 etc.), lignosulfonates, alkylnaphthalene sulfonate;Wetting agent selects one or more in alkyl sulfate, alkylsulfonate, naphthalene sulfonate;One or more in ammonium sulfate, sodium sulfate, polyvinylpyrrolidone, starch and derivant, bentonite selected by disintegrating agent;One or more in starch, glucose, polyvinyl alcohol, Polyethylene Glycol, sodium carboxymethyl cellulose, sucrose selected by binding agent;Filler select kieselguhr, Kaolin, white carbon, fine particle calcium carbonate, Pulvis Talci, attapulgite, potter's clay one or more.
When preparing corresponding wettable powder, spendable auxiliary agent has: dispersant selects polycarboxylic acid salt (TERSPERSE2700, T36, GY-D06 etc.), lignin sulfonate (Ufoxane3A, BorresperseNA, BorresperseCA-SA etc.), naphthalene and alkyl naphthalene formaldehyde condensate sulfonates class (NNO, MF, MorwetD-425, TamolNN, 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 sulfate (SOPA) one or more;Wetting agent selects one or more in Sulfates (K-12), Sulfonates (ABS-Na, BX, Terwet1004 etc.), compound wetting agent (MorwetEFW);One or more in kieselguhr, Kaolin, fine particle calcium carbonate, Pulvis Talci, white carbon, attapulgite, potter's clay, ammonium sulfate, carbamide, sucrose, glucose, corn starch, sodium sulfate, sodium polyphosphate selected by filler.
When preparation dispersibles oil-suspending agent accordingly, spendable auxiliary agent has: BY (castor oil polyoxyethylene ether) series emulsifying agent (BY-110 selected by emulsifying agent, 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 polyoxyethylene ether), agriculture breast 1601# (common name: phenethyl phenol polyoxyethylene poly-oxygen propylene aether), one or more in TERSPERSE4894 (Huntsman Corporation of U.S. product);Dispersant selects one or more in polycarboxylate, lignosulfonates, EO-PO block copolymer (polyoxyethylene polyoxypropylene block copolymer), phosphate ester and its esters, Sulfonates, alkylnaphthalene sulfonate (dispersing agent NNO), TERSPERSE2020 (Huntsman Corporation of the U.S. produces, alkyl naphthalene sulfonic acid salt);Wetting agent selects one or more in alkylphenol-polyethenoxy base ether formaldehyde condensation products sulfate, alkylphenol polyoxyethylene phosphate ester, phenethyl phenol polyethenoxy base ether phosphate, alkyl sulfate, alkylsulfonate, naphthalene sulfonate, TERSPERSE2500 (Huntsman Corporation of U.S. product);Thickening agent selects one or more in gas-phase silica, polyvinyl alcohol, organobentonite, attapulgite, aluminium-magnesium silicate;One or more in organic acid, organic base, esters, alcohols, antioxidant, epoxychloropropane, tall oil selected by stabilizer;Disperse medium selects one or more in soybean oil, Oleum Brassicae campestris, Oleum Gossypii semen, Semen Maydis oil, Oleum Ricini, Petiolus Trachycarpi oil, epoxy soybean oil, methyl oleate and esterification oils, diesel oil, machine oil, mineral oil, and esters solvent such as dimethyl phthalate, dibutyl phthalate, ethyl acetate, essence of Niobe.
It should be noted that the effective ingredient (or active component) in each example of formulations of subordinate is weight after folding hundred.
Example of formulations 1
Weigh 300 grams of oxalic acid copper diacetonamines, 100 grams of Metalaxyl-Ms, 25 grams of TERSPERSE2700 (polycarboxylates, Huntsman Corporation of the U.S. produce), 30 grams of sodium lignin sulfonates, 20 grams of Nekal BXs (nekal), 30 grams of K-12 (sodium lauryl sulphate), 20 grams of PVA (polyvinyl alcohol, molecular weight 2000), 20 grams of polyvinylpyrrolidones, 30 grams of ammonium oxalate, Kaolin supply 1000 grams.The method of above-mentioned raw materials frequent regulation water intaking dispersible granule, i.e. it is 40% oxalic acid copper diacetonamine Metalaxyl-M water dispersible granules that active constituent content is produced in mixing, ultra micro comminution by gas stream, mixing, granulation step.
Example of formulations 2
Weigh 100 grams of oxalic acid copper diacetonamines, 100 grams of cyazofamids, 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 (sodium lauryl sulphate), 15 grams of ammonium oxalate, attapulgites add to 1000 grams.The method of above-mentioned raw materials frequent regulation water intaking dispersible granule, i.e. it is 20% oxalic acid copper diacetonamine cyazofamid water dispersible granules that active constituent content is produced in mixing, ultra micro comminution by gas stream, mixing, granulation step.
Example of formulations 3
Weigh 350 grams of oxalic acid copper diacetonamines, 500 grams of dimethomorphs, 20 grams of TERSPERSE2700 (polycarboxylate, Huntsman Corporation of the U.S. produces), 10 grams of dispersing agent NNOs (alkylnaphthalene sulfonate formaldehyde condensation products), 20 grams of Nekal BXs (nekal), 20 grams of K-12 (sodium lauryl sulphate), attapulgites add to 1000 grams.The method of above-mentioned raw materials frequent regulation water intaking dispersible granule, i.e. it is 85% oxalic acid copper diacetonamine dimethomorph water dispersion granula that active constituent content is produced in mixing, ultra micro comminution by gas stream, mixing, granulation step.
Example of formulations 4
Weigh 30 grams of oxalic acid copper diacetonamines, 300 grams of cymoxanil, 40 grams of TERSPERSE2700,30 grams of alkylnaphthalene sulfonate formaldehyde condensation products (TamolNN), 20 grams of sodium lauryl sulphates, attapulgites fill up to 1000 grams.Above-mentioned raw materials is blended, ultra micro comminution by gas stream, hybrid technique step, and being prepared into active constituent content is 33% oxalic acid copper diacetonamine cymoxanil wettable powder.
Example of formulations 5
Weigh 100 grams of oxalic acid copper diacetonamines, 300 grams of phosethyl-Als, 60 grams of calcium lignosulfonates, 40 grams of alkylnaphthalene sulfonate formaldehyde condensation products (MorwetD-425), 20 grams of sodium lauryl sulphates, 15 grams of ammonium oxalate, white carbons fill up to 1000 grams.Above-mentioned raw materials is blended, ultra micro comminution by gas stream, hybrid technique step, and being prepared into active constituent content is 40% oxalic acid copper diacetonamine phosethyl-Al wettable powder.
Example of formulations 6
Weigh 100 grams of oxalic acid copper diacetonamines, 200 grams of metalaxyls, 50 grams of calcium lignosulfonates, 30 grams of dispersing agent NNOs (alkylnaphthalene sulfonate formaldehyde condensation products), 30 grams of Nekal BXs (nekal), 20 grams of K-12 (sodium lauryl sulphate), 15 grams of ammonium oxalate, attapulgites add to 1000 grams.Above-mentioned raw materials is blended, and preparing active constituent content after comminution by gas stream is 30% oxalic acid copper diacetonamine metalaxyl wettable powder.
Example of formulations 7
Weigh 200 grams of oxalic acid copper diacetonamines, 100 grams of flumorphs, 30 grams of alkylphenol polyoxyethylene phosphate esters, 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-ditertbutylparacresol, antioxidant), 25 grams of ammonium oxalate, Semen Maydis oil supply 1000 grams.Above-mentioned raw materials is blended, and with sand mill sand milling to particle diameter less than 5um, i.e. preparing active constituent content is that 30% oxalic acid copper diacetonamine flumorph dispersibles oil-suspending agent.
Example of formulations 8
Weighing 400 grams of oxalic acid copper diacetonamines, 40 grams of iprovalicarbs, 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, 45 grams of ammonium oxalate, methyl oleate supplies 1000 grams.Above-mentioned raw materials is blended, and i.e. preparing active constituent content with sand mill sand milling to particle diameter less than 5um is that 44% oxalic acid copper diacetonamine iprovalicarb dispersibles oil-suspending agent.
Example of formulations 9
Weigh 30 grams of oxalic acid copper diacetonamines, 20 grams of M 9834s, 30 grams of alkylphenol polyoxyethylene phosphate esters, 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-ditertbutylparacresol, antioxidant), epoxy soybean oil supplies 1000 grams.Above-mentioned raw materials is blended, and i.e. preparing active constituent content with sand mill sand milling to particle diameter less than 5um is that 5% oxalic acid copper diacetonamine M 9834 dispersibles oil-suspending agent.
(2) Biometric portion
1, indoor virulence experimental section
Toxicity Determination test 1: cucumber downy mildew Toxicity Determination
Inventor has carried out the most compounding potentiation research with oxalic acid copper diacetonamine respectively with the dimethomorph prevented and treated in Oomycete series bactericidal agent, flumorph, metalaxyl, Metalaxyl-M, method particularly includes:
Test uses bacterium of downy mildew of cucumber (Pseudoperonosporacubensis) for test object.Former medicine is configured to the test medicine needed, and test method is with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1156.3 2006 ".
First single dose and each Mixed Pharmacy are arranged 5 variable concentrations gradients (on the basis of pilot study result, different with proportioning according to different agents combination, Concentraton gradient arranges the most different, and bacteriostasis rate is set by geometric progression in the range of 5%~90%).Test target bacterium is to pick up from field from up to down 4 leaves~the bacterium of downy mildew of cucumber blade of 6 leaf positions, Pseudoperonospora cubensis Sporangium with 4 DEG C of distillation washing lower blade back sides, it is made into suspension (concentration controls at 1 × 105 every milliliter~1 × 107 Sporangium), deposits standby at 4 DEG C;Medicinal liquid is uniformly sprayed in the healthy leaves back side, after medicinal liquid natural air drying, each process blade and blade is gone up dorsad, be emitted in moisture preservation box by after processing labelling.Test sets the process without medicament and makees blank.It is inoculated in vacuum side of blade with ready Fresh spores capsule suspension drop 10 μ L.Every blade inoculation 4, often processes no less than 5 leaves.24h inoculation before treatment.Ware lid on inoculation bonnet, is placed in growth cabinet or has the humidistat of illumination, and in continuous illumination every day/dark 12h alternately, temperature is 17 DEG C~22 DEG C, cultivates under conditions of relative humidity more than 90%.Measuring and record lesion diameter depending on process and blank incidence, unit is millimeter (mm), calculates prevention effect.By the linear regression analysis between probit value and the logarithm value of series concentration of prevention effect, obtain the EC of each medicament50Value, calculates the co-toxicity coefficient (CTC) of mixture, evaluates the reagent agent activity to pathogenic bacteria with this by the abundant method of Sun Yun.
The co-toxicity coefficient (CTC) >=120 of complex preparation shows as potentiation;CTC≤80 show as antagonism;80 < CTC < 120 show as summation action.
The result of the test of Toxicity Determination test 1 is shown in Table 1-1 to table 1-4.
Table 1-1 oxalic acid copper diacetonamine and the dimethomorph combination Toxicity Determination to cucumber downy mildew
Table 1-2 oxalic acid copper diacetonamine and the flumorph combination Toxicity Determination to cucumber downy mildew
Table 1-3 oxalic acid copper diacetonamine and the metalaxyl combination Toxicity Determination to cucumber downy mildew
Table 1-4 oxalic acid copper diacetonamine and the Metalaxyl-M combination Toxicity Determination to cucumber downy mildew
Toxicity Determination result (table 1-1 to table 1-4) draws: oxalic acid copper diacetonamine with prevent and treat Oomycete series bactericidal agent: the one in dimethomorph, flumorph, metalaxyl, Metalaxyl-M, with weight ratio as 1:10~10:1 is mixed that bacterium of downy mildew of cucumber is had preferable virulence, all there is significant potentiation.
Toxicity Determination test 2: late blight of potato Toxicity Determination
Inventor has carried out the most compounding potentiation research with oxalic acid copper diacetonamine respectively with the phosethyl-Al prevented and treated in Oomycete series bactericidal agent, M 9834, frost spirit, cymoxanil.The result of the test of Toxicity Determination test 2 is shown in Table 2-1 to table 2-4.
Toxicity Determination test 3: early blight of tomato Toxicity Determination
Inventor has carried out the most compounding potentiation with oxalic acid copper diacetonamine respectively with the Propamocarb prevented and treated in Oomycete series bactericidal agent, cyazofamid, iprovalicarb and has studied.The result of the test of Toxicity Determination test 3 is shown in Table 3-1 to table 3-3.
The test method that above-mentioned test 2 is the most identical with test 3 employing:
Subjects is the late blight of potato (Phytophthorainfestans), tomato early blight bacterium (Alternariasolani).Former medicine is configured to the test medicine needed, single dose and each Mixed Pharmacy are arranged 5 variable concentrations gradients (on the basis of pilot study result, bacteriostasis rate is set by geometric progression in the range of 5%~90%).If clear water compares, it is repeated 3 times.Test uses mycelial growth rate method, by cultured pathogen, aseptically with a diameter of 5mm card punch, cut bacterium cake from colony edge, with Inoculating needle, bacterium cake is connected on the culture medium flat plate of different agents concentration, puts 28 DEG C, saturated humidity incubator is cultivated;When matched group bacterium colony covers with, measure colony diameter, calculate the percentage rate of each chemicals treatment suppression mycelial growth, by the linear regression analysis between probit value and the logarithm value of series concentration of suppression ratio, obtain the EC of each medicament50Value, calculates the co-toxicity coefficient (CTC) of mixture, evaluates the reagent agent activity to pathogenic bacteria with this by the abundant method of Sun Yun.
The co-toxicity coefficient (CTC) >=120 of complex preparation shows as potentiation;CTC≤80 show as antagonism;80 < CTC < 120 show as summation action.
Table 2-1 oxalic acid copper diacetonamine and the phosethyl-Al combination Toxicity Determination to the late blight of potato
Table 2-2 oxalic acid copper diacetonamine and the M 9834 combination Toxicity Determination to the late blight of potato
Table 2-3 oxalic acid copper diacetonamine and the frost spirit combination Toxicity Determination to the late blight of potato
Table 2-4 oxalic acid copper diacetonamine and the cymoxanil combination Toxicity Determination to the late blight of potato
Toxicity Determination result (table 2-1 to 2-4) is learnt: oxalic acid copper diacetonamine with prevent and treat Oomycete series bactericidal agent: phosethyl-Al, M 9834, frost spirit, one in cymoxanil, with weight ratio as 1:10~10:1 is mixed that the late blight of potato is had preferable virulence, all there is significant potentiation.
Table 3-1 oxalic acid copper diacetonamine and the Propamocarb combination Toxicity Determination to early blight of tomato
Table 3-2 oxalic acid copper diacetonamine and the cyazofamid combination Toxicity Determination to early blight of tomato
Table 3-3 oxalic acid copper diacetonamine and the iprovalicarb combination Toxicity Determination to early blight of tomato
Can be seen that from above-mentioned Toxicity Determination result (table 3-1 to table 3-2), oxalic acid copper diacetonamine with prevent and treat Oomycete series bactericidal agent: the one in Propamocarb, cyazofamid, iprovalicarb, with weight ratio as 1:10~10:1 is mixed that early blight of tomato is had preferable virulence, all there is significant potentiation.
2, field test part
Biological Examples 1: prevent and treat late blight of potato field test
2014 7~carried out example of formulations 1 (40% oxalic acid copper diacetonamine Metalaxyl-M water dispersible granules) August in Fugu County of Shaanxi Province, example of formulations 7 (30% oxalic acid copper diacetonamine flumorph dispersibles oil-suspending agent) prevents and treats late blight of potato field test.
Test method is with reference to " pesticide field efficacy medicine test criterion (one) bactericidal agent for preventing and treating late blight of potato GB/T17980.34-2000 ".Test arrangement is shown in Table 4 at the plot of morbidity weight over the years, test medicine and extension rate, separately sets blank, often processes 4 times and repeat, every plot area 25, and Gong32Ge community, random district group arranges.Using conventional nebulization, blade positive and negative uniformly squirt, medicinal liquid consumption 50 liter/mu.Dispenser for the first time when blade begins to see, the dispenser of 14 days second time, altogether dispenser secondary.
Investigation and statistical method:
Within 14 days after second time dispenser, carry out disease index investigation, every community diagonal 5 sampling, every 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 the 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 the 50% of whole leaf area.
Disease index and prevention effect 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
Prevention effect (%)=[disease index after (disease index after disease index-chemicals treatment district dispenser after the dispenser of blank district)/blank district dispenser] × 100
Late blight of potato field test results prevented and treated by table 4
Field test results shows: 40% oxalic acid copper diacetonamine Metalaxyl-M water dispersible granules 2000 times, 2500 times, 30% oxalic acid copper diacetonamine flumorph dispersibles oil-suspending agent 1500 times, 2000 times, the preventive effect of the late blight of potato was respectively 96.83% in 14 days after second time dispenser, 91.00%, 95.20%, 91.60%, it is substantially better than 30% oxalic acid copper diacetonamine wettable powder 1000 times, 20% Metalaxyl-M water dispersible granules 1000 times, 20% flumorph wettable powder 1000 preventive effect to the late blight of potato again, preventive effect difference reaches pole significant level (referring to table 4).
Security survey to Rhizoma Solani tuber osi, observes after the 1st day and medicine after spray medicine for some days every time, and Rhizoma Solani tuber osi is occurred by each chemicals treatment without poisoning phenomenon.
After result of the test shows oxalic acid copper diacetonamine and Metalaxyl-M, flumorph mixture, hence it is evident that improve the prevention effect to the late blight of potato, reduce dosage and drug cost, to potato growth safety, be the favourable agents preventing and treating the late blight of potato.
Biological Examples 2: prevent and treat downy mildew of garpe field test
Downy mildew is one of important disease of Fructus Vitis viniferae, blade of mainly causing harm, also cause harm inflorescence and young fruit.Inventor has carried out example of formulations 2 (20% oxalic acid copper diacetonamine cyazofamid water dispersible granules) in 2014 in Yantai, Shandong, example of formulations 5 (40% oxalic acid copper diacetonamine phosethyl-Al wettable powder) prevents and treats downy mildew of garpe field test.
Test method is with reference to " GB/T17980.122-2004 pesticide field efficacy medicine test criterion (two) the bactericidal agent for preventing and treating downy mildew of garpe test of pesticide effectiveness ".Trial crops is Fructus Vitis viniferae, and controlling object is downy mildew of garpe (Plasmoparaviticola).Test kind is huge peak, and the age of tree 8 years grows fine.Being experimental field level land, fertility is preferable, experimental field cultivation condition uniformity.Test medicine and dosage refer to table 5.Separately setting blank, often process 4 times and repeat, 10, every community tree, Gong32Ge community, random district group arranges.Using aerosol apparatus even spraying, leave dual sides squirts as degree.The dispenser for the first time when blade begins to see morbidity, dispenser 1 time again every 10 days, altogether dispenser 2 times.
Investigation and statistical method:
After medicine 7 days for the second time, every community random searching 10 pumping then was the most climing, investigates whole blade from top to bottom, recorded the sick number of sheets at different levels and total number of sheets by following stage division.
Blade stage division:
0 grade: without scab;
1 grade: lesion area accounts for less than the 5% of whole leaf area;
3 grades: lesion area accounts for the 6%~25% of whole leaf area;
5 grades: lesion area accounts for the 26%~50% of whole leaf area
7 grades: lesion area accounts for the 51%~75% of whole leaf area;
9 grades: lesion area accounts for more than the 75% of whole leaf area.
Disease index and prevention effect computational methods:
Disease index=[∑ (the sick number of sheets × relative level numerical value at different levels)/(investigating the total number of sheets × 9)] × 100
Prevention effect (%)=[(comparison disease index-process disease index)/comparison disease index] × 100
Security survey and the impact on other biological: every time some skies after the 1st day and medicine after spray medicine, observe medicament and respectively process grape growth and the impact on other diseases.
Downy mildew of garpe field test results prevented and treated by table 5
Field test results (table 5) shows, 20% oxalic acid copper diacetonamine cyazofamid water dispersible granules 2500 times, 3000 times, 40% oxalic acid copper diacetonamine phosethyl-Al wettable powder 1000 times, 1500 times use nebulization to prevent and treat downy mildew of garpe, investigation in 7 days after second time dispenser, sick leaf rate comparison illumination is aobvious to be reduced, preventive effect is respectively 96.27%, 90.35%, 93.42%, 89.20%, it is substantially better than 30% oxalic acid copper diacetonamine wettable powder 1000 times, 10% cyazofamid suspending agent 2000 times, 40% phosethyl-Al wettable powder 300 preventive effect to downy mildew of garpe again, difference arrives pole significant level.
Observing during test, each chemicals treatment does not produces poisoning phenomenon to grape leaf, the tender tip.
After result of the test shows oxalic acid copper diacetonamine and cyazofamid, phosethyl-Al mixture, hence it is evident that improve the prevention effect to downy mildew of garpe, reduce dosage and drug cost, to grape growth safety, be the favourable agents preventing and treating downy mildew of garpe.
In sum, the compositions of the present invention is two kinds of active component compound schemes of a kind of composition using oxalic acid copper diacetonamine with preventing and treating Oomycete series bactericidal agent, its activity and bactericidal effect are not the simple superposition of each composition activity, compared with existing unitary agent, in addition to there is significant bactericidal effect, and have significant potentiation, and good to crop safety, meet the security requirement of pesticidal preparations.

Claims (5)

1. the bactericidal composition containing oxalic acid copper diacetonamine, it is characterised in that including 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;
Described second active component is selected from cyazofamid.
Bactericidal composition containing oxalic acid copper diacetonamine the most according to claim 1, it is characterised in that the content sum of described first active component and the second active component is the 5%~85% of described bactericidal composition gross weight.
The dosage form of the bactericidal composition containing oxalic acid copper diacetonamine the most according to claim 1 is water dispersible granules, wettable powder or dispersibles oil-suspending agent.
4. according to the bactericidal composition containing oxalic acid copper diacetonamine described in claim 1 or 2 or 3 in the purposes prevented and treated on corps diseases.
The bactericidal composition containing oxalic acid copper diacetonamine the most according to claim 4 purposes on preventing and treating corps diseases, it is characterised in that described corps diseases is cucumber downy mildew, the late blight of potato, early blight of tomato, downy mildew of garpe.
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CN101768175B (en) * 2008-12-31 2011-08-10 西北农林科技大学农药研究所 Agricultural fungicide of oxalic acid copper diacetonamine
CN101785464A (en) * 2010-03-25 2010-07-28 青岛瀚生生物科技股份有限公司 Oxine-copper composite bactericide
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CN105815331A (en) 2016-08-03
CN104430491A (en) 2015-03-25
CN105815335A (en) 2016-08-03
CN105815332A (en) 2016-08-03
CN105815333A (en) 2016-08-03
CN105815333B (en) 2017-11-17

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