CN104430491A - Sterilization composition containing diacetone amine copper oxalate - Google Patents

Sterilization composition containing diacetone amine copper oxalate Download PDF

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CN104430491A
CN104430491A CN201410635827.XA CN201410635827A CN104430491A CN 104430491 A CN104430491 A CN 104430491A CN 201410635827 A CN201410635827 A CN 201410635827A CN 104430491 A CN104430491 A CN 104430491A
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active component
oxalic acid
acid copper
grams
composition containing
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CN104430491B (en
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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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Priority to CN201610015394.7A priority Critical patent/CN105815332A/en
Priority to CN201610015169.3A priority patent/CN105815331A/en
Priority to CN201610015874.3A priority patent/CN105815333B/en
Priority to CN201410635827.XA priority patent/CN104430491B/en
Priority to CN201610015337.9A priority patent/CN105815335A/en
Priority to CN201610015875.8A priority patent/CN105815334A/en
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    • AHUMAN NECESSITIES
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    • 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
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, 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
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    • 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
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    • 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 sterilization composition containing diacetone amine copper oxalate. The sterilization composition containing the diacetone amine copper oxalate comprises a first active component and a second active component with the weight ratio of (1 to 10):(10 to1), wherein the first active component is the diacetone amine copper oxalate; the second active component is selected from one of dimethomorph, flumorph, metalaxyl, metalaxyl-M, fosetyl-Al, benalaxyl, oxadixyl, cymoxanil, propamocarb, cyazofamid and iprovalicarb. The composition can be prepared into a water dispersible granule, wettable powder or a dispersible oil suspending agent which are allowed to be used agriculturally, and has good control effects to cucumber downy mildew, potato late blight, tomato early blight and plasmopara viticola. According to the composite, the problem of non-ideal control effect by only utilizing diacetone amine copper oxalate or oomycetes fungicides is solved effectively; the compounding of diacetone amine copper oxalate and oomycetes fungicides has the obvious synergism, has the good crop safety, and can be used for reducing the risk of resistance production and drug delivery cost.

Description

A kind of bactericidal composition containing oxalic acid copper diacetonamine
Technical field
The invention belongs to technical field of pesticide combination, relate to a kind of bactericidal composition, particularly 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 bactericide 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, 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.
Oomycete belongs to Mycophyta, and be a guiding principle of Mastigomycotina, Oomycete mainly contains pythium spp, phytophthora, downy mildew etc., often causes the downy mildew of crop, epidemic disease, damping off etc.The medicament preventing and treating this kind of disease conventional mainly contains dimethomorph, cyazofamid, phosethyl-Al agricultural chemicals and mixture thereof.
Introduce the main pesticide species of several control crop Oomycete class disease below:
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 a bactericide specially killing Oomycete fungal, action character is the formation destroying cell envelope, there is effect to each stage of oomycetes history of life, be 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 higher resistance risk.
Flumorph, has another name called and to go 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 prevent and treat Oomycete pathogen produce disease, as crop downy mildew, late blight, white epidemic disease etc.
Cyazofamid, the chloro-2-cyano group of English common name cyazofamid, chemical name: 4--N, N-dimethyl-5-p-methylphenyl imidazoles-1-sulfonamide.Cyazofamid is sulphaguanidine azoles fungicide.Cyazofamid belongs to a kind of super protective fungicide, also has certain interior suction and therapeutic activity, has very high biologically active to the plasmodiophora brassica bacteria of Oomycete fungal as downy mildew, Pseudo peronospara, phytophthora, pythium spp and Plasmodiophoromycetes.Its controlling object is downy mildew, epidemic disease, as cucumber downy mildew, downy mildew of garpe, tomato late blight, potato late blight etc.
Phosethyl-Al, have another name called that Yimeiling, the spirit of epidemic disease frost, fosetyl aluminium, mould epidemic disease are clean, Methylpartricin Sodium Laurylsulfate or mould clever, English common name phosethyl-Al, chemical name: three-(ethylphosphonic acid) aluminium.Phosethyl-Al is systemic fungicide, has special efficacy, can conduct up and down in plant corpus disease caused by oomycetes, has protection and therapeutic action.
Metalaxyl, other title: the spirit of Apron, conservation, metalaxyl, auspicious poison frost, the white peace of first, 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 therapeutic action; can be absorbed by the root, stem and leaf of plant; have Bidirectional Conduction performance, to the various crop downy mildew that Pseudoperonospora cubensis, phytophthora root rot bacterium and rotten mildew fungus cause, phytophthora root rot, the millet downy mildew of gourd, fruit and vegetable class are effective.
Metalaxyl-M, English common name metalaxyl-M, chemical name: N-(2,6-xylyl)-N-(Methoxyacetyl)-D-alanine methyl esters.Metalaxyl-M is higher to crop pest activity than metalaxyl, excellent to the crop pest preventive effect such as vegetables, fruit tree, tobacco, oil plant, cotton, grain caused by Pseudoperonospora cubensis, phytophthora root rot bacterium, rotten mildew fungus.
Frost urea cyanogen, English common name cymoxanil, chemical name: 1-(2-cyano group-2-methoxyl group imido grpup)-3-ethyl carbamide.Frost urea cyanogen is a kind of efficient, low toxicity bactericide, to Peronosporales fungi as epidemic disease frost genus, Peronospora, single shaft frost belong to effectively.Frost urea cyanogen is how mixed with other protective fungicides, is applicable to the control of the diseases such as the vegetables such as cucumber, grape, tomato, lichee, fruit tree and tobacco.
M 9834, English common name benalaxyl, chemical name: N-phenylacetyl group-N-2,6-xylyl-DL-Alanine methyl esters.M 9834 is systemic fungicide, for preventing and treating oomycetes diseases, as the single shaft mould of grape, and the phytophthora of potato, strawberry, tomato, the downy mildew of tobacco, onion, soybean, the false downy mildew etc. of cucumber.
Propamocarb, has another name called Pu Like, acid amides, epidemic disease frost only, English name propamocarb, chemical name: 3-(dimethylamino) propyl carbamic acid propyl ester.Propamocarb is a kind of systemic pesticide, has excellent control efficiency to crops downy mildew, epidemic disease, late blight, damping off, black febrile disease with symptoms such as convulsion, opisthotonos, trismus, etc.
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 unique brand-new biomimetic features, its mechanism of action is different from bactericide that other prevent and treat Oomycete.Its mechanism of action is the synthesis acting on fungal cell wall and protein, can suppress infecting and sprouting of spore, can suppress mycelial growth simultaneously, causes its distortion, death.For Peronosporaceae and the fungus-caused disease of Phytophthora, there is well treatment and eradicant action.
The spirit of Evil frost, 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.The spirit of Evil frost is disinfectant use in agriculture, and have very high preventive effect to Peronosporales pathogen, have protection and therapeutic action, the lasting period is long.
Although oxalic acid copper diacetonamine has good preventive effect to Oomycete fungal disease, its mechanism of action is single, there is resistance risk after listing, causes its preventive effect to reduce.The bactericide specially of the control plant Oomycete guiding principle diseases such as above-mentioned phosethyl-Al, the spirit of white urea Qing, Evil frost, the speed that pathogen produces resistance to each kind is also very fast, use separately dosage increasing, and conventional dose is as mancozeb agriculture chemical compounding, uses resistance to strengthen year by year for many years.
Oxalic acid copper diacetonamine as a kind of novel organic copper bactericide, its to crop based on protective effect, to the germ in invaded plants body almost without therapeutic activity.At present, the bactericide of Oomycete class disease and the bibliographical information of oxalic acid copper diacetonamine mixture is not is not also prevented and treated.
Inventor is found by test, 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, reduces 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 control plant Oomycete guiding principle disease, the object of the present invention is to provide a kind of composite component reasonable, synergistic effect is remarkable, bactericidal effect is good, drug cost is low, not easily develops immunity to drugs and agricultural bactericidal composition to crop safety.
Second object of the present invention is the preparation formulation of the binary built bactericidal composition provided containing oxalic acid copper diacetonamine.
3rd object of the present invention is to provide the application of above-mentioned bactericidal composition on control corps diseases.
For achieving the above object, this invention takes following technical scheme:
A kind of bactericidal composition containing oxalic acid copper diacetonamine, 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 selected from the one in dimethomorph, flumorph, metalaxyl, Metalaxyl-M, phosethyl-Al, the spirit of M 9834, Evil frost, white urea cyanogen, Propamocarb, cyazofamid, iprovalicarb.
Further, contain in the bactericidal composition of oxalic acid copper diacetonamine described, the content sum of the first active component and the second active component is 5% ~ 85% of described bactericidal composition gross weight.
Further, the formulation of the described bactericidal composition containing oxalic acid copper diacetonamine is water dispersible granules, wetting powder or dispersibles oil-suspending agent.
Further, the purposes of the described bactericidal composition containing oxalic acid copper diacetonamine on control corps diseases.
Preferred as technical scheme, the described bactericidal composition containing oxalic acid copper diacetonamine, the purposes in control cucumber downy mildew, potato late blight, early blight of tomato, downy mildew of garpe.
Compared with single use oxalic acid copper diacetonamine respectively or above-mentioned oomycetes diseases bactericide, 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, shows preferably preventive effect to Oomycete fungal disease, but its to the control of crop pest based on protective effect, to the germ in invaded plants body almost without therapeutic activity.In order to improve the preventive effect of oxalic acid copper diacetonamine further, reducing and producing the risk of resistance, should consider by itself and other bactericide compounded.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 is selected from the one in dimethomorph, flumorph, metalaxyl, Metalaxyl-M, phosethyl-Al, the spirit of M 9834, Evil frost, white urea cyanogen, Propamocarb, cyazofamid, iprovalicarb.Above-mentioned second active component be there is therapeutic activity prevent and treat Oomycete series bactericidal agent.Therefore, binary built bactericidal composition component of the present invention is chosen rationally, effectively overcomes the preventive effect defect of single administration oxalic acid copper diacetonamine or above-mentioned oomycetes diseases bactericide.
(2) learnt by a large amount 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 synergistic effect.
(3) bactericidal composition of the present invention expands control spectrum, bactericidal effect is good, significantly improve the preventing effectiveness of the multiple diseases of multiple kinds of crops, especially better to the preventive effect of cucumber downy mildew, potato late blight, early blight of tomato, downy mildew of garpe.
(4) 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, is suitable for popularizing application.
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 of the present invention is binary built bactericidal composition, comprise the first active component and the second active component, first active component is oxalic acid copper diacetonamine, and the second active component is selected from the one in dimethomorph, flumorph, metalaxyl, Metalaxyl-M, phosethyl-Al, the spirit of M 9834, Evil frost, white urea cyanogen, Propamocarb, cyazofamid, iprovalicarb.Especially, 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% ~ 85% of described bactericidal composition gross weight.
Above-mentioned bactericidal composition 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 (TERSPERSE 2700, 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 (TERSPERSE2700, T36, GY-D06 etc.), lignin sulfonate (Ufoxane3A, Borresperse NA, BorresperseCA-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, Terwet1004 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.
It should be noted that, the active ingredient (or active component) in each example of formulations of subordinate is weight after folding hundred.
Example of formulations 1
Take 300 grams of oxalic acid copper diacetonamines, 100 grams of Metalaxyl-Ms, 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, 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 air-flow crushing, mixing, granulation step.
Example of formulations 2
Take 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 (lauryl sodium sulfate), 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 air-flow crushing, mixing, granulation step.
Example of formulations 3
Take 350 grams of oxalic acid copper diacetonamines, 500 grams of dimethomorphs, 20 grams of TERSPERSE 2700 (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 (lauryl sodium sulfate), 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 air-flow crushing, mixing, granulation step.
Example of formulations 4
Take 30 grams of oxalic acid copper diacetonamines, 300 grams of white urea cyanogen, 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 frost urea cyanogen wetting powder.
Example of formulations 5
Take 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 (Morwet D-425), 20 grams of lauryl sodium sulfate, 15 grams of ammonium oxalate, 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 40% oxalic acid copper diacetonamine phosethyl-Al wetting powder.
Example of formulations 6
Take 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 (lauryl sodium sulfate), 15 grams of ammonium oxalate, attapulgites add to 1000 grams.Above-mentioned raw materials is through mixing, and after air-flow crushing, obtained active constituent content is 30% oxalic acid copper diacetonamine metalaxyl wetting powder.
Example of formulations 7
Take 200 grams of oxalic acid copper diacetonamines, 100 grams of flumorphs, 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), 25 grams of ammonium oxalate, corn oils supply 1000 grams.Above-mentioned raw materials, through mixing, is less than 5um with sand mill sand milling to particle diameter, and namely obtained active constituent content is that 30% oxalic acid copper diacetonamine flumorph dispersibles oil-suspending agent.
Example of formulations 8
Take 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 through mixing, and being less than 5um i.e. obtained active constituent content with sand mill sand milling to particle diameter is that 44% oxalic acid copper diacetonamine iprovalicarb dispersibles oil-suspending agent.
Example of formulations 9
Take 30 grams of oxalic acid copper diacetonamines, 20 grams of M 9834s, 30 grams of alkylphenol polyoxyethylene phosphates, 50 grams of BY-125,40 grams of calcium dodecyl benzene sulfonates, 30 grams of TERSPERSE 4894 (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 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 mutual composite synergy respectively studied with oxalic acid copper diacetonamine and the dimethomorph prevented and treated in Oomycete series bactericidal agent, flumorph, metalaxyl, Metalaxyl-M, 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 1 result of the test in Table 1-1 to showing 1-4.
Table 1-1 oxalic acid copper diacetonamine and dimethomorph combine the Toxicity Determination to cucumber downy mildew
Table 1-2 oxalic acid copper diacetonamine and flumorph combine the Toxicity Determination to cucumber downy mildew
Table 1-3 oxalic acid copper diacetonamine and metalaxyl combine the Toxicity Determination to cucumber downy mildew
Table 1-4 oxalic acid copper diacetonamine and Metalaxyl-M combine the Toxicity Determination to cucumber downy mildew
Toxicity Determination result (table 1-1 to showing 1-4) draws: oxalic acid copper diacetonamine with prevent and treat Oomycete series bactericidal agent: the one in dimethomorph, flumorph, metalaxyl, Metalaxyl-M, 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 2: potato late blight Toxicity Determination
Inventor has carried out mutual composite synergy respectively studied with oxalic acid copper diacetonamine and the phosethyl-Al prevented and treated in Oomycete series bactericidal agent, the spirit of M 9834, Evil frost, white urea cyanogen.Toxicity Determination test 2 result of the test in Table 2-1 to showing 2-4.
Toxicity Determination test 3: early blight of tomato Toxicity Determination
Inventor has carried out mutual composite synergy respectively studied with oxalic acid copper diacetonamine and the Propamocarb prevented and treated in Oomycete series bactericidal agent, cyazofamid, iprovalicarb.Toxicity Determination test 3 result of the test in Table 3-1 to showing 3-3.
Above-mentioned test 2 adopts test method identical as follows with test 3:
Subjects is potato late blight (Phytophthora infestans), tomato early blight bacterium (Alternariasolani).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 2-1 oxalic acid copper diacetonamine and phosethyl-Al combine the Toxicity Determination to potato late blight
Table 2-2 oxalic acid copper diacetonamine and M 9834 combine the Toxicity Determination to potato late blight
Table 2-3 oxalic acid copper diacetonamine is Yu the Toxicity Determination to potato late blight is combined in the spirit of Evil frost
Table 2-4 oxalic acid copper diacetonamine and white urea cyanogen combine the Toxicity Determination to potato late blight
Toxicity Determination result (table 2-1 to 2-4) is learnt: oxalic acid copper diacetonamine with prevent and treat Oomycete series bactericidal agent: the one in the spirit of phosethyl-Al, M 9834, Evil frost, white urea cyanogen, being that 1:10 ~ 10:1 is mixed with weight ratio has good virulence to potato late blight, all has significant synergistic effect.
Table 3-1 oxalic acid copper diacetonamine and Propamocarb combine the Toxicity Determination to early blight of tomato
Table 3-2 oxalic acid copper diacetonamine and cyazofamid combine the Toxicity Determination to early blight of tomato
Table 3-3 oxalic acid copper diacetonamine and iprovalicarb combine the Toxicity Determination to early blight of tomato
As can be seen from above-mentioned Toxicity Determination result (table 3-1 is to showing 3-2), oxalic acid copper diacetonamine with prevent and treat Oomycete series bactericidal agent: the one in Propamocarb, cyazofamid, iprovalicarb, being that 1:10 ~ 10:1 is mixed with weight ratio has good virulence to early blight of tomato, 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 Metalaxyl-M water dispersible granules) in Fugu County of Shaanxi Province in 7 ~ August in 2014, example of formulations 7 (30% oxalic acid copper diacetonamine flumorph dispersibles oil-suspending agent) 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/T17980.34-2000 ".The plot that test arrangement weighs in morbidity over the years, test medicine and extension rate, in table 4, separately establish blank, and often process 4 times and repeat, every plot area 25 ㎡, 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 6% ~ 10% of whole leaf area;
5 grades, lesion area accounts for 11% ~ 20% of whole leaf area;
7 grades, lesion area accounts for 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 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, 96.83% was respectively to the preventive effect of potato late blight in 14 days after second time dispenser, 91.00%, 95.20%, 91.60%, obviously be better than 30% oxalic acid copper diacetonamine wetting powder 1000 times, 20% Metalaxyl-M water dispersible granules 1000 times, 20% flumorph wetting powder 1000 is doubly to the preventive effect of potato late blight, preventive effect difference reaches pole significance level (referring to table 4).
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.
After result of the test shows oxalic acid copper diacetonamine and Metalaxyl-M, flumorph mixture, significantly improving the control efficiency to potato late blight, reduce dosage and drug cost, to potato growth safety, is the favourable agents preventing and treating potato late blight.
Biological Examples 2: prevent and treat downy mildew of garpe field trial
Downy mildew is one of important disease of grape, 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 wetting powder) prevents and treats downy mildew of garpe field trial.
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 grape, and controlling object is downy mildew of garpe (Plasmopara viticola).Test kind is huge peak, and the age of tree 8 years, grows fine.Be experimental field level land, fertility is better, experimental field cultivation condition uniformity.Test medicine and dosage refer to table 5.Separately establish blank, often process 4 times and repeat, 10, every community tree, Gong32Ge community, random district group arranges.Use sprayer even spraying, leave dual sides squirts as degree.The first time dispenser when blade begins to see morbidity, the dispenser 1 time again every 10 days, dispenser 2 times altogether.
Investigation and statistical method:
After second time medicine 7 days, every community random searching 10 then pumping was newly climing, investigates whole blade from top to bottom, by the following stage division record sick number of sheets at different levels and total number of sheets.
Blade stage division:
0 grade: without scab;
1 grade: lesion area accounts for less than 5% of whole leaf area;
3 grades: lesion area accounts for 6% ~ 25% of whole leaf area;
5 grades: lesion area accounts for 26% ~ 50% of whole leaf area
7 grades: lesion area accounts for 51% ~ 75% of whole leaf area;
9 grades: lesion area accounts for more than 75% of whole leaf area.
Disease index and control efficiency computational methods:
Disease index=[∑ (the sick number of sheets × relative level numerical value at different levels)/(investigating the total number of sheets × 9)] × 100
Control efficiency (%)=[(contrast disease index-process disease index)/contrast disease index] × 100
Security survey and the impact on other biological: some skies after the 1st day and medicine after each 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 wetting powder 1000 times, 1500 times adopt spray-on process 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%, obviously be better than 30% oxalic acid copper diacetonamine wetting powder 1000 times, 10% cyazofamid suspending agent 2000 times, 40% phosethyl-Al wetting powder 300 is doubly to the preventive effect of downy mildew of garpe, difference arrives pole significance level.
Duration of test is observed, and each chemicals treatment does not produce poisoning phenomenon to grape leaf, the tender tip.
After result of the test shows oxalic acid copper diacetonamine and cyazofamid, phosethyl-Al mixture, significantly improving the control efficiency to downy mildew of garpe, reduce dosage and drug cost, to grape growth safety, is the favourable agents preventing and treating downy mildew of garpe.
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 prevent and treat Oomycete series bactericidal agent, 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 (5)

1. the bactericidal composition containing oxalic acid copper diacetonamine, 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;
Described second active component is selected from the one in dimethomorph, flumorph, metalaxyl, Metalaxyl-M, phosethyl-Al, the spirit of M 9834, Evil frost, white urea cyanogen, Propamocarb, cyazofamid, iprovalicarb.
2. the bactericidal composition containing oxalic acid copper diacetonamine according to claim 1, it is characterized in that, the content sum of described first active component and the second active component is 5% ~ 85% of described bactericidal composition gross weight.
3. the formulation of the bactericidal composition containing oxalic acid copper diacetonamine according to claim 1 is water dispersible granules, wetting powder or dispersibles oil-suspending agent.
4. the purposes of the bactericidal composition containing oxalic acid copper diacetonamine according to claim 1 or 2 or 3 on control corps diseases.
5. the purposes of the bactericidal composition containing oxalic acid copper diacetonamine according to claim 4 on control corps diseases, it is characterized in that, described corps diseases is cucumber downy mildew, potato late blight, early blight of tomato, downy mildew of garpe.
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