CN104351243A - Diacetone amine copper oxalate containing bactericidal composition - Google Patents
Diacetone amine copper oxalate containing bactericidal composition Download PDFInfo
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Abstract
The invention discloses a diacetone amine copper oxalate containing bactericidal composition. The diacetone amine copper oxalate containing bactericidal composition comprises a first active ingredient and a second active ingredient with a weight ratio of (1:15)-(10:1), wherein the first active ingredient is diacetone amine copper oxalate, and the second active ingredient is selected from one of self-protective fungicides such as zineb, mancozeb, trioneb, dithane stainless, propineb, thiram, ziram, chlorothalonil, sulfur and dimethachlon. The bactericidal composition can be prepared into water dispersible granules, wettable powder, suspending agents or dispersible oil suspending agents which are allowed to be used agriculturally, and has the relatively good prevention effect on apple altermaria leaf spot, apple brown spot, cucumber downy mildew, powdery mildew of cucumbers, and potato late blight. The diacetone amine copper oxalate containing bactericidal composition effectively solves the problem that a bactericidal composition adopting the diacetone amine copper oxalate or one of the protective fungicides singly has the poor prevention effect, and has the remarkable synergism due to compounding of the diacetone amine copper oxalate and one of the protective fungicides, and besides, the resistance generation can be delayed.
Description
Technical field
The invention belongs to technical field of compounded pesticide; relate to a kind of bactericidal composition; be specifically related to a kind of using oxalic acid copper diacetonamine as the first active component, the sterilization components such as protective fungicide zineb, mancozeb, Carbatene, ambam, Propineb, tmtd, ziram, tpn, sulphur, dimethachlon are as the binary built bactericidal composition of the second active component.The invention still further relates to the preparation formulation of this bactericidal composition and it is in application agriculturally.
Background technology
Copper agent is one of the most ancient disinfectant use in agriculture type, has has a broad antifungal spectrum, not easily the advantage such as to develop immunity to drugs.Based on the use history of the Inorganic Copper preparation of Kocide SD, copper sulphate etc. more than 200 years, but because it is difficult to be biodegradable, long-term a large amount of use has caused the accumulation of copper in soil, can cause harmful effect to the normal growth of plant and soil function.At present, the exploitation of organic copper preparation, have become the hot topic that disinfectant use in agriculture is produced, and organic copper preparation is to crop safety, nuisanceless.
Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo for raw material, by its structural modification, synthesizes a kind of new compound with two acetone isolated in Qinling Mountains streptomycete zymotic fluid---oxalic acid copper diacetonamine.This is a kind of novel organocopper compound, toxicity shows that it shows good bacteriostatic activity to various agricultural pathogen, and field test results shows that it has good control efficiency to crop pests such as cucumber downy mildew, potato late blight, alternaria leaf spot of apple.
Protective fungicide refers to before infection process crop, and first dispenser in crop surface, prevents germ from invading, play a protective role.After protective fungicide uses, can form that one deck is breathed freely, the compactness of permeable, printing opacity protection medicine film in crop surface, this layer of diaphragm can suppress sprouting and the invasion of germ spore, thus reaches the effect of sterilizing disease-preventing.This series bactericidal agent is very poor to the crop pest preventive effect infected and fall ill, and normal and systemic fungicide mixture uses and just can reach good preventive effect.Common protective fungicide has zineb, mancozeb, Carbatene, ambam, Propineb, tmtd, ziram, tpn, sulphur, dimethachlon etc.
Zineb, English common name zineb, chemical name is zinc ethylenebisdithiocarbamate, is broad spectrum activity, protective fungicide.The mechanism of action of zineb destroys coacetylase, thus affect the oxidation of fatty acid.Active ingredient chemical property is more active, different sulphur gas cyanogen compound is easily oxidized in water, enzyme cause of disease thalline being included to-SH base has stronger inhibitory action, and can directly kill germ spore, suppress the germination of spore, stop in germ invaded plants body, but less to the mycelial lethal effect of cause of disease in invaded plants body.Be mainly used in the multiple fungal disease preventing and treating the crops such as wheat class, vegetables, grape, fruit tree and tobacco, Chinese cabbage, cucumber downy mildew can be prevented and treated, anthracnose of tomato, potato late blight, fruit white rot of grape, black spot, apple, pear scab.
Mancozeb, English common name mancozeb, chemical name is the complex salt of the two dithiocarbamates formyl manganese of ethylene and zinc, is a kind of excellent protective fungicide, belongs to low-toxin farm chemicals.Its bactericidal range is wide, and not easily develop immunity to drugs, control efficiency is obviously better than other same series bactericidal agents.At present, domestic most composite bactericide is all formulated with mancozeb processing, manganese, zinc microelement have significantly short strong, production-increasing function to crop, to preventing and treating the Be very effective such as pear scab, alternaria leaf spot of apple, vegetable category epidemic disease, downy mildew, field crop rust, steady quality, reliable.
Carbatene; English common name metiram; chemical name is two (the two thiocarbamate esters) zinc (2+) of three [ammonia] ethene)] [tetrahydrochysene-1; 4; 7-bis-thiophene diazocine-3; 8-connects dithione], be a kind of polymer, belong to benzimidazole protective fungicide.Carbatene can stop the sprouting of germ spore, suppresses the elongation of germ germ tube, makes germ infect plant tissue, have good preventive effect to the various diseases that Oomycete fungal causes, be mainly used in preventing and treating vegetable downy mildew, anthracnose, brown spot etc.
Ambam, English common name amobam, chemical name is ethylene bisdithiocarbamic ammonium, organic sulfur preparation, and sterling is clear crystal, water soluble.Controlling disease mainly shields, and because liquid can infiltrate plant epidermis, has therapeutic action concurrently again.The mechanism of action forms chelation compound with the trace element (iron as contained in enzyme or coenzyme) needed for normal metabolic processes in somatic cells, makes metabolism not normal.Ambam belongs to low toxicity bactericide, effect is strong, working concentration is low, be made generally in 45% or 50% aqueous solution, fungicidal spectrum is wide, effective to various crop fungal disease, can supply seed treatment, foliar spray and soil disinfection, for various crop diseases such as the water prevention rice bacterial leaf blight, banded sclerotial blight, rice blast, cucumber downy mildew, powdery mildew, sweet potato black rot, cotton anthracnose, corn northern leaf blight and southern leaf blights, simultaneously can also Promoting plant growth.
Propineb, English common name propineb, chemical name is acrylic bisdithiocarbamic zinc, is the protective fungicide of the broad spectrum activity that Beyer Co., Ltd develops, and mechanism of action is the oxidation suppressing pyruvic acid in cause of disease thalline.Propineb all has excellent protective effect to the downy mildew of the crops such as vegetables, grape, tobacco and lupulus and tomato, the morning of potato, late blight, and also has certain inhibitory action to the disease of powdery mildew, rust and Botrytis.
Tmtd; English common name thiram; chemical name is tetramethyl thiuram disulfide; broad spectrum activity organic sulfur series bactericidal agent; there is good protective effect; be mainly used in seed and soil treatment, can be used for the seedling blight preventing and treating Cereal smut and various crop, also can be used for the disease of preventing and treating some fruit trees and vegetables.
Ziram; English common name ziram; chemical name is two-(dimethyl-thiocarbamic acid) zinc; it is a kind of efficient, bactericide that broad spectrum activity has protective effect; main mechanism is that the enzyme including-SH base with cause of disease thalline is had an effect; destroy normal metabolism, for fruit tree anthracnose, blossom rot, scab, brown rot, powdery mildew etc.Ziram belongs to low-toxin farm chemicals, to people and animals' low toxicity, to the high poison of fish, has spread effect to skin, eyes and the upper respiratory tract, to plant safety, pollution-free.
Tpn, English common name chlorothalonil, chemical name is daconil M (chloro-1, the 3-benzene dicarbonitrile of 2,4,5,6-tetra-), is a kind of low toxicity wide spectrum, protective fungicide.The mechanism of action of tpn is can have an effect with the glyceraldehyde 3-phosphate dehydrogenase in fungal cell, combines, thus destroys the activity of this enzyme, the metabolism of fungal cell is damaged and the power that loses one's life with the protein containing cysteine in this enzyme.Tpn does not have Uptake and translocation effect, and after being sprayed onto on plant corpus, can have good tackness on body surface, not easily be fallen by rain drop erosion, therefore the drug effect phase is longer.
Sulphur, English common name sulfur, non-internal-absorting protective fungicide, without result for the treatment of.The mechanism of action of sulphur is respiration inhibitor, acts on electron transfer process between germ helium reduction system cytochrome b and c, captures electronics, interference normal " oxidationreduction ".Sulphur can be used for wheat, beet, vegetables as cucumber, eggplant etc., fruit tree as apple, Lee, peach, grape, oranges and tangerines, the control of the crop pests such as matrimony vine.The controlling object of sulphur is wheat powdery mildew, rust, smut, head blight, cucurbits powdery mildew, apple, pears, peach scab, grape powdery mildew etc.Sulphur, except having bactericidal activity, also has acaricidal action, as preventing and treating phyllocoptruta oleivora etc.
Dimethachlon, English common name dimetachlone, chemical name is N-(3,5-dichlorophenyl) succimide, have eradicant fungicide, therapeutic action, the longevity of residure is long, starts to use the surrogate-data technique that carbendazim produces resistance area as sclerotinia rot of colza pathogen from 2002 in China, owing in recent years having found the phenomenon that sclerotinia rot of colza pathogen reduces dimethachlon susceptibility aborning, therefore preventing and treating sclerotinia rot of colza with it still exists larger risk separately.Therefore, this bactericide is carried out reasonably composite, significant to minimizing resistance risk.
Inventor is found by test; by composite for the one in oxalic acid copper diacetonamine and protective fungicide zineb, mancozeb, Carbatene, ambam, Propineb, tmtd, ziram, tpn, sulphur, dimethachlon; have significant synergies; control efficiency can be significantly improved; reduce dosage, expanding prevention is composed, and reduces cost accounting; delay drug-fast generation, to crop safety.
Summary of the invention
The object of the present invention is to provide a kind of composite component reasonable, synergistic effect is remarkable, and bactericidal effect is good, and 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 1:15 ~ 10:1; described first active component is oxalic acid copper diacetonamine, and described second active component is selected from the one in protective fungicide zineb, mancozeb, Carbatene, ambam, Propineb, tmtd, ziram, tpn, sulphur, dimethachlon.
Further, in bactericidal composition of the present invention, the content sum of the first active component and the second active component is 5% ~ 90% of described bactericidal composition gross weight.
Further, the formulation of the bactericidal composition containing oxalic acid copper diacetonamine is water dispersible granules, wetting powder, suspending agent or dispersibles oil-suspending agent.
Further, the purposes of the bactericidal composition containing oxalic acid copper diacetonamine on control corps diseases.
Preferred as technical scheme, described corps diseases is alternaria leaf spot of apple, apple marssonina leaf spot, apple mildew, cucumber downy mildew, powdery mildew of cucumber, potato late blight.
Compared with single use oxalic acid copper diacetonamine respectively or above-mentioned protective fungicide, the beneficial effect that the present invention produces is mainly reflected in following aspect:
(1) the second active component of bactericidal composition of the present invention selects the one in zineb, mancozeb, Carbatene, ambam, Propineb, tmtd, ziram, tpn, sulphur, dimethachlon.Use comparatively general in the control of these protective fungicides crop pest at home, and usage amount is larger.Use above-mentioned protective fungicide in a large number for a long time; multiple pathogen is to which creating stronger pesticide resistance; make the control efficiency of these protective fungicides of single administration poor; but this several bactericide belongs to the important kind in protective fungicide; also be difficult at short notice replace, therefore really should consider the resistance problems of above-mentioned bactericide.Oxalic acid copper diacetonamine as a kind of new organic copper bactericide kind, its to the control of crop pest based on protective effect.One in oxalic acid copper diacetonamines different for the mechanism of action and above-mentioned protective fungicide is carried out binary built by the present invention, and this is also continue play effect of above-mentioned bactericide and slow down the effective method of resistance.The activity of this bactericidal composition and bactericidal effect are not the simple superposition of each composition activity, but have significant synergistic effect.In addition, the advantage of described bactericidal composition also shows that component is reasonable, bactericidal effect is good, and drug cost is low, good to crop safety, the generation of delaying drug resistance.
(2) bactericidal composition of the present invention expands control spectrum, significantly improve the preventing effectiveness of the multiple diseases of multiple kinds of crops, especially to alternaria leaf spot of apple, apple marssonina leaf spot, apple mildew, cucumber downy mildew, powdery mildew of cucumber, the preventive effect of potato late blight is better.
(3) bactericidal composition of the present invention can be prepared as water dispersible granules, wetting powder, suspending agent or dispersible the preparation of the different dosage forms such as oil-suspending agent, and each preparation is good to crop safety, meets the security requirement of pesticidal preparations.
Embodiment
In order to make object of the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.
(1) part prepared by preparation
Bactericidal composition containing oxalic acid copper diacetonamine can be mixed with water dispersible granules, wetting powder, suspending agent or dispersible the formulations such as oil-suspending agent.When preparing above-mentioned different dosage form, to those skilled in the art, except needs use containing except fungicide active ingredient for the election, also need to select multiple auxiliary agent, can choice for use is different as required pesticidal preparations auxiliary element (auxiliary agent).Described auxiliary element can be one or more in dispersion medium, dispersant, emulsifier, wetting agent, thickener, defoamer, antifreezing agent, disintegrant, binding agent, filler etc.
For water dispersible granules, those skilled in the art are familiar with the corresponding auxiliary agent of use and complete the present invention very much.Dispersant to select in polycarboxylate (TERSPERSE2700, T36, GY-D06 etc.), lignosulfonates, alkylnaphthalene sulfonate one or more; One or more to be selected in alkyl sulfate, alkylsulfonate, naphthalene sulfonate by wetting agent; One or more to be selected in ammonium sulfate, sodium sulphate, polyvinylpyrrolidone, starch and derivative thereof, bentonite by disintegrant; Binding agent select in starch, glucose, polyvinyl alcohol, polyethylene glycol, sodium carboxymethylcellulose, sucrose one or more; Filler select diatomite, kaolin, white carbon, fine particle calcium carbonate, talcum powder, attapulgite, potter's clay one or more.
When preparing corresponding wetting powder, spendable auxiliary agent has: dispersant selects polycarboxylic acid salt (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 preparing corresponding suspending agent, spendable auxiliary agent has: dispersant as in polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate (dispersing agent NNO), TERSPERSE2020 (Huntsman Corporation of the U.S. produce, alkyl naphthalene sulfonic acid salt) one or more; Emulsifier is as one or more in Nongru-700 # (common name: alkyl phenol formaldehyde resin polyoxyethylene ether), agriculture breast 2201, this dish-60# (common name: Span60), Tween-60 # (common name: polyoxyethylene sorbitan stearate), agriculture breast 1601# (common name: triphenoethyl benzene phenol polyoxyethylene polyoxypropylene block polymer), TERSPERSE4894 (Huntsman Corporation of U.S. product); Wetting agent as in alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphate, alkylphenol-polyethenoxy base ether phosphate, phenethyl phenol polyethenoxy base ether phosphate, alkyl sulfate, alkylsulfonate, naphthalene sulfonate, TERSPERSE2500 (Huntsman Corporation of U.S. product) one or more; Thickener as in xanthans, polyvinyl alcohol, bentonite, aluminium-magnesium silicate one or more; Preservative as in formaldehyde, benzoic acid, Sodium Benzoate one or more; Stabilizing agent as in epoxidized soybean oil, epoxychloropropane, triphenyl phosphate one or more; Defoamer is as organic silicon defoamer; Antifreezing agent as ethylene glycol, propane diols, glycerine, urea, inorganic salts as in sodium chloride one or more; Water is deionized water.
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 TERSPERSE4894 (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), TERSPERSE2020 (Huntsman Corporation of the U.S. produce, 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, TERSPERSE2500 (Huntsman Corporation of U.S. product) one or more, thickener select in gas-phase silica, polyvinyl alcohol, organobentonite, attapulgite, aluminium-magnesium silicate one or more, stabilizing agent select in organic acid, organic base, ester class, alcohols, antioxidant, epoxychloropropane, tall oil one or more, dispersion medium selects soybean oil, rapeseed oil, cottonseed oil, corn oil, castor oil, palm oil, epoxidized soybean oil, methyl oleate and esterification oils, diesel oil, machine oil, mineral oil, and esters solvent as in repefral, dibutyl phthalate, ethyl acetate, methyl benzoate one or more.
Bactericidal composition of the present invention comprises the first active component and the second active component, and the first active component is oxalic acid copper diacetonamine, and the second active component is the one in protective fungicide.The weight ratio of the first active component and the second active component is 1:15 ~ 10:1, and the content sum of the first active component and the second active component is 5% ~ 90% of described bactericidal composition gross weight.As a preferred embodiment, the second active component protective fungicide is selected from the one in zineb, mancozeb, Carbatene, ambam, Propineb, tmtd, ziram, tpn, sulphur, dimethachlon.
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 30 grams of oxalic acid copper diacetonamines, 450 grams of zineb, 30 grams of GY-D06 (polycarboxylate), 25 grams of alkylnaphthalene sulfonates, 15 grams of Nekal BXs (nekal), 20 grams of K-12 (lauryl sodium sulfate), 25 grams of PVA (molecular weight 2000), 25 grams of sodium sulphate, attapulgites supply 1000 grams.Namely the method for above-mentioned raw materials frequent regulation water intaking dispersible granule mixes, ultra micro air-flow crushing, mixing, granulation step, producing active constituent content is 48% oxalic acid copper diacetonamine water dispersion granules agent of dithane.
Example of formulations 2
Take 50 grams of oxalic acid copper diacetonamines, 500 grams of mancozebs, 30 grams of TERSPERSE2700 (polycarboxylate, Huntsman Corporation of the U.S. produces), 25 grams of dispersing agent NNOs (alkylnaphthalene sulfonate formaldehyde condensation products), 20 grams of Nekal BXs (nekal), 20 grams of K-12 (lauryl sodium sulfate), kaolin add to 1000 grams.Namely the method for above-mentioned raw materials frequent regulation water intaking dispersible granule mixes, ultra micro air-flow crushing, mixing, granulation step, producing active constituent content is 55% oxalic acid copper diacetonamine mancozeb water dispersible granule.
Example of formulations 3
Take 100 grams of oxalic acid copper diacetonamines, 500 grams of Carbatenes, 40 grams of T36 (polycarboxylate), 20 grams of dispersing agent NNOs (alkylnaphthalene sulfonate formaldehyde condensation products), 30 grams of Nekal BXs (nekal), 20 grams of K-12 (lauryl sodium sulfate), 25 grams of sodium carboxymethylcelluloses, 60 grams of sodium sulphate, talcum powder add to 1000 grams.Namely the method for above-mentioned raw materials frequent regulation water intaking dispersible granule mixes, ultra micro air-flow crushing, mixing, granulation step, producing active constituent content is 60% oxalic acid copper diacetonamine Carbatene water dispersible granules.
Example of formulations 4
Take 100 grams of oxalic acid copper diacetonamines, 300 grams of ambam, 35 grams of GY-D06,35 grams of nekals, 30 grams of lauryl sodium sulfate, talcum powder 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 ambam wetting powder.
Example of formulations 5
Take 400 grams of oxalic acid copper diacetonamines, 500 grams of Propinebs, 10 grams of alkylphenol-polyethenoxy base ether phosphates, 10 grams of alkylnaphthalene sulfonate formaldehyde condensation products (TERSPERSE2020), 10 grams of lauryl sodium sulfate, corn starchs 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 90% oxalic acid copper diacetonamine Wettable propineb powder.
Agent embodiment 6
Take 250 grams of oxalic acid copper diacetonamines, 250 grams of tmtd, 20 grams of alkylphenol-polyethenoxy base ether phosphates, 15 grams of Tamol NN (alkylnaphthalene sulfonate formaldehyde condensation products), 15 grams of alkylphenol-polyethenoxy base ethers formaldehyde condensation products sulphate (SOPA), 20 grams of ABS-Na, sodium polyphosphates add to 1000 grams.Above-mentioned raw materials is through mixing, and after air-flow crushing, obtained active constituent content is 50% oxalic acid copper diacetonamine thiram wettable powder.
Example of formulations 7
Take 250 grams of oxalic acid copper diacetonamines, 200 grams of ziram, 40 grams of this dish-60#, 25 grams of alkylphenol-polyethenoxy base ether phosphates, 25 grams of dispersing agent NNOs, 15 grams of bentonites, 5 grams of polyvinyl alcohol, 45 grams of propane diols, 7 grams of benzoic acid, 10 grams of silicone defoaming agents (trade name: s-29 Nanjing "four news" (new ideas applied chemistry product Company), deionized waters add to 1000 grams.Above-mentioned raw materials is through mixing, and high speed shear dispersion 30min is 45% oxalic acid copper diacetonamine ziram suspending agent with active constituent content obtained after sand mill sand milling.
Example of formulations 8
Take 300 grams of oxalic acid copper diacetonamines, 100 grams of tpns, 30 grams of Tween-60 #, 20 grams of alkyl sulfates, 25 grams of lignosulfonates, 22 grams of aluminium-magnesium silicates, 5 grams of polyvinyl alcohol, 45 grams of glycerine, 8 grams of Sodium Benzoates, 7 grams of silicone defoaming agents (trade name: s-29 Nanjing "four news" (new ideas applied chemistry product Company), deionized waters add to 1000 grams.Above-mentioned raw materials is through mixing, and high speed shear dispersion 30min is 40% oxalic acid copper diacetonamine tpn suspending agent with active constituent content obtained after sand mill sand milling.
Example of formulations 9
Take 40 grams of oxalic acid copper diacetonamines, 10 grams of sulphur, 20 grams of alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphate, 40 grams of polyoxyethylene polyoxypropylene block copolymers, 50 grams of fatty alcohol-polyoxyethylene ether, 25 grams of Nongru-700 #, 25 grams of calcium dodecyl benzene sulfonates, 8 grams of attapulgites, 12 grams of aluminium-magnesium silicates, 15 grams of BHT (2,6-BHT, antioxidant), cottonseed 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 sulphur dispersibles oil-suspending agent.
Example of formulations 10
Take 500 grams of oxalic acid copper diacetonamines, 100 grams of dimethachlons, 40 grams of calcium dodecyl benzene sulfonates, (Huntsman Corporation of the U.S. produces 35 grams of TERSPERSE2020, alkyl naphthalene sulfonic acid salt), 50 grams of TERSPERSE4894 (Huntsman Corporation of U.S. product), 40 grams of Nongru-700 #, 25 grams of organobentonites, 25 grams of tall oils, 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 60% oxalic acid copper diacetonamine dimethachlon dispersibles oil-suspending agent.
Example of formulations 11
Take 350 grams of oxalic acid copper diacetonamines, 50 grams of zineb, 25 grams of this dish-60#, 55 grams of BY-140,35 grams of castor oil polyoxyethylene ethers, 40 grams of agriculture breast 1601#, 25 grams of TERSPERSE4894 (Huntsman Corporation of U.S. product), 10 grams of attapulgites, 15 grams of polyvinyl alcohol, 15 grams of BHT (BHTs, antioxidant), repefral 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 40% oxalic acid copper diacetonamine zineb dispersibles oil-suspending agent.
Example of formulations 12
Take 500 grams of oxalic acid copper diacetonamines, 50 grams of mancozebs, 35 grams of TERSPERSE2500 (Huntsman Corporation of U.S. product), 40 grams of BY-110,50 grams of sorbitan monostearates, 35 grams of phenethyl phenol polyoxyethylene poly-oxygen propylene aethers, 30 grams of fatty alcohol-polyoxyethylene ether, 15 grams of polyvinyl alcohol, 10 grams of attapulgites, 25 grams of epoxychloropropane, methyl benzoate 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 55% oxalic acid copper diacetonamine mancozeb dispersibles oil-suspending agent.
(2) Biometric portion
1, indoor virulence experimental section
Toxicity Determination test 1: powdery mildew of cucumber Toxicity Determination
In order to prevent and treat the powdery mildew on vegetables in agricultural production, fruit tree, wheat, strawberry, flowers, inventor has carried out mutual composite synergy with oxalic acid copper diacetonamine and protective fungicide zineb, tmtd, sulphur and has studied, and concrete grammar is:
Subjects is cucumber powdery mildew's pathogen (Sphaerotheca fuliginea).Former medicine is mixed with the test medicine of needs, test method is with reference to " People's Republic of China's agricultural industry criteria NY/T1156.11-2008 farm-chemical indoor determination test rule bactericide the 11st part: control cucurbits powdery mildew test pot-culture method ".
First single dose and each Mixed Pharmacy are arranged 5 variable concentrations gradients (preventive effect sets by geometric progression in the scope of 5% ~ 90%).With the pure water being added with a small amount of surfactant (Tween 80), wash the Fresh spores got and cover with on Powdery Mildew cucumber leaves, filter with double gauze, making spore concentration is 1 × 10
5the suspension of individual spore/milliliter, for subsequent use.Often process 3 basins, repeat for 4 times, and establish the process only containing solvent and surfactant not containing active ingredient to make blank.With spore suspension 24h inoculation before chemicals treatment, liquid is evenly sprayed in blade face to all wetting, for subsequent use after liquid natural air drying.Inoculation and chemicals treatment after potted plant cucumber natural air drying, then move to thermostatic chamber, under the condition of temperature 20 DEG C ~ 24 DEG C cultivation 7 days ~ 10 days.When the sick leaf rate of blank reaches more than 80%, classification investigation manages incidence everywhere, and often process and at least investigate 30 leaves, grade scale is:
0 grade: anosis;
1 grade: lesion area accounts for less than 5% of one-piece blade area;
3 grades: lesion area accounts for 6% ~ 15% of one-piece blade area;
5 grades: lesion area accounts for 16% ~ 25% of one-piece blade area;
7 grades: lesion area accounts for 26% ~ 50% of one-piece blade area;
9 grades: lesion area accounts for 50% ~ 75% of one-piece blade area;
11 grades: lesion area accounts for more than 75% of one-piece blade area.
Computational methods:
Disease index=∑ (the sick number of sheets × relative level numerical value at different levels)/(investigation total leaf number × 11) × 100
Control efficiency (%)=[(contrast disease index-process disease index)/contrast disease index] × 100
By the linear regression analysis between the probit value of preventive effect and the logarithm value of series concentration, obtain the EC of each medicament
50value, calculates the co-toxicity coefficient (CTC) of mixture, evaluates the activity of reagent agent to germ with this by the abundant method of Sun Yun.
The co-toxicity coefficient (CTC) >=120 of complex preparation shows as synergistic effect; CTC≤80 show as antagonism; 80 < CTC < 120 show as summation action.
Toxicity Determination test 1 (powdery mildew of cucumber Toxicity Determination) result of the test in Table 1-1 to showing 1-3.
Table 1-1 oxalic acid copper diacetonamine and zineb combine the Toxicity Determination to powdery mildew of cucumber
Table 1-2 oxalic acid copper diacetonamine and tmtd combine the Toxicity Determination to powdery mildew of cucumber
Table 1-3 oxalic acid copper diacetonamine and sulphur combine the Toxicity Determination to powdery mildew of cucumber
Toxicity Determination result (table 1-1 to showing 1-3) shows: oxalic acid copper diacetonamine respectively with the one in zineb, tmtd, sulphur, being that 1:15 ~ 10:1 is mixed with weight ratio has good virulence to cucumber powdery mildew's pathogen, all has significant synergistic effect.
Toxicity Determination test 2: alternaria leaf spot of apple Toxicity Determination
In order to prevent and treat the alternaria leaf spot of apple in agricultural production, inventor has carried out mutual composite synergy respectively with oxalic acid copper diacetonamine and has studied with Carbatene, tpn, dimethachlon, concrete grammar is:
Subjects is alternaria leaf spot of apple (Alternaria alternaria f.sp mali).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.
Alternaria leaf spot of apple Toxicity Determination the results are shown in Table 2-1 to showing 2-3.
Table 2-1 oxalic acid copper diacetonamine and Carbatene combine the Toxicity Determination to alternaria leaf spot of apple
Table 2-2 oxalic acid copper diacetonamine and tpn combine the Toxicity Determination to alternaria leaf spot of apple
Table 2-3 oxalic acid copper diacetonamine and dimethachlon combine the Toxicity Determination to alternaria leaf spot of apple
Toxicity Determination result (table 2-1 to showing 2-3) shows: oxalic acid copper diacetonamine respectively with the one in Carbatene, tpn, dimethachlon, being that 1:15 ~ 10:1 is mixed with weight ratio has good virulence to alternaria leaf spot of apple, all has significant synergistic effect.
Toxicity Determination test 3: cucumber downy mildew Toxicity Determination
In order to prevent and treat vegetables in agricultural production, fruit tree downy mildew, inventor has carried out mutual composite synergy with oxalic acid copper diacetonamine and mancozeb, ambam, Propineb and has studied, 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, 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, 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, and wash the Pseudoperonospora cubensis sporangium at the lower blade back sides with 4 DEG C of distillations, (concentration controls at every milliliter 1 × 10 to be made into suspension
5individual ~ 1 × 10
7individual 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.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.
Cucumber downy mildew Toxicity Determination the results are shown in Table 3-1 to showing 3-3.
Table 3-1 oxalic acid copper diacetonamine and mancozeb combine the Toxicity Determination to cucumber downy mildew
Table 3-2 oxalic acid copper diacetonamine and ambam combine the Toxicity Determination to cucumber downy mildew
Table 3-3 oxalic acid copper diacetonamine and Propineb combine the Toxicity Determination to cucumber downy mildew
Toxicity Determination result (table 3-1 to showing 3-3) shows: oxalic acid copper diacetonamine respectively with the one in mancozeb, ambam, Propineb, being that 1:15 ~ 10:1 is mixed with weight ratio has good virulence to cucumber downy mildew, all has significant synergistic effect.
2. field trial part
Biological Examples 1: control alternaria leaf spot of apple field trial
Within 2013, carry out example of formulations 3 (60% oxalic acid copper diacetonamine Carbatene water dispersible granules) at Shaanxi Province's Weinan City, example of formulations 8 (40% oxalic acid copper diacetonamine tpn suspending agent), example of formulations 10 (60% oxalic acid copper diacetonamine dimethachlon dispersibles oil-suspending agent) prevented and treated alternaria leaf spot of apple field trial.
Test method is with reference to " pesticide field efficacy medicine test criterion (two) bactericidal agent for preventing and treating alternaria leaf spot of apple test of pesticide effectiveness GB/T17980.124-2004 ".Test is located at Weinan City Fuping County, and soil is clay, and physical features is smooth, and soil fertility is even, pH value 7.1, fertility is better, experimental field cultivation condition uniformity, and apple variety is Fuji apple, the age of tree is 14 years, and distance between rows and hills is 5m × 6m, and this garden spot defoliation occurs heavier over the years.Test medicine and extension rate, in table 4, separately establish blank, and often process 4 times and repeat, every plot area 3 tree, Gong44Ge community, random district group arranges.Adopt conventional spray-on process, blade positive and negative evenly squirt.First time dispenser is when blade begins to see, the dispenser of 14 days second time, is total to dispenser twice.
Investigation and statistical method:
Within 14 days after second time dispenser, carry out disease index investigation, 2 strain trees are investigated in every community, and 2 young sprouts are fixed in every strain point east, south, west, north, middle different azimuth, investigate its 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 10% of whole leaf area;
3 grades, lesion area accounts for 11% ~ 25% of whole leaf area;
5 grades, lesion area accounts for 26% ~ 40% of whole leaf area;
7 grades, lesion area accounts for 41% ~ 65% of whole leaf area;
9 grades, lesion area accounts for more than 65% 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
Alternaria leaf spot of apple field test results prevented and treated by table 4
Field test results shows: 60% oxalic acid copper diacetonamine Carbatene water dispersible granules 1000 times, 1500 times, 40% oxalic acid copper diacetonamine tpn suspending agent 1500 times, 2000 times, 60% oxalic acid copper diacetonamine dimethachlon dispersibles oil-suspending agent 2500 times, 3000 times, good preventive effect is had to alternaria leaf spot of apple, obviously be better than 30% oxalic acid copper diacetonamine wetting powder 1000 times, 70% Carbatene water dispersible granules 700 times, 75% tpn wetting powder 500 times, 40% dimethachlon wetting powder 2000 is doubly to the preventive effect of alternaria leaf spot of apple, pole significance level (referring to table 4) is reached with the preventive effect difference of single dose.
To the security survey of apple tree, within some days, observe after the 1st day and medicine after each spray medicine, each chemicals treatment occurs without poisoning phenomenon apple tree.Test also finds, three kinds of Mixed Pharmacies also have good preventive effect to apple marssonina leaf spot, apple mildew.
After result of the test shows oxalic acid copper diacetonamine and Carbatene, tpn, dimethachlon mixture, significantly improve the control efficiency to alternaria leaf spot of apple, reduce dosage and drug cost, to Apple Growth safety, be control alternaria leaf spot of apple and apple marssonina leaf spot, apple mildew favourable agents.
Biological Examples 2: prevent and treat potato late blight field trial
Carry out example of formulations 1 (48% oxalic acid copper diacetonamine water dispersion granules agent of dithane) in Fugu County of Shaanxi Province in 7 ~ August in 2014, example of formulations 2 (55% oxalic acid copper diacetonamine mancozeb water dispersible granule), example of formulations 6 (50% oxalic acid copper diacetonamine thiram wettable powder) 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, in July, 2014 starts to occur incidence of leaf, and test medicine and extension rate, in table 5, separately establish blank, and often process 4 times and repeat, every plot area 25 ㎡, Gong44Ge 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 twice.
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 5
Field test results shows: 48% oxalic acid copper diacetonamine water dispersion granules agent of dithane 1500 times 2000 times, 55% oxalic acid copper diacetonamine mancozeb water dispersible granule 1000 times, 1500 times, 50% oxalic acid copper diacetonamine thiram wettable powder 2000 times, 2500 times, good preventive effect is had to potato late blight, obviously be better than 30% oxalic acid copper diacetonamine wetting powder 1000 times, 80% Zineb wettable powder 800 times, 80% mancozeb wettable powder 600 times, 25% thiram wettable powder 600 is doubly to the preventive effect of potato late blight, pole significance level (referring to table 5) is reached with the preventive effect difference of single dose.
To the security survey of potato, within some days, observe after the 1st day and medicine after each spray medicine, each chemicals treatment occurs without poisoning phenomenon potato.
Result of the test to show in oxalic acid copper diacetonamine and protective fungicide zineb, mancozeb, tmtd after a kind of mixture; significantly improve the control efficiency to potato late blight; reduce dosage and drug cost; to potato growth safety, it is the favourable agents preventing and treating potato late blight.
In sum; composition of the present invention is two kinds of active component compound schemes of a kind of composition adopted in oxalic acid copper diacetonamine and protective fungicide zineb, mancozeb, Carbatene, ambam, Propineb, tmtd, ziram, tpn, sulphur, dimethachlon; 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; 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 1:15 ~ 10:1; described first active component is oxalic acid copper diacetonamine, and described second active component is selected from the one in protective fungicide zineb, mancozeb, Carbatene, ambam, Propineb, tmtd, ziram, tpn, sulphur, dimethachlon.
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% ~ 90% of described bactericidal composition gross weight.
3. the formulation of the bactericidal composition containing oxalic acid copper diacetonamine according to claim 1 and 2 is water dispersible granules, wetting powder, suspending agent or dispersibles oil-suspending agent.
4. the purposes of the bactericidal composition containing oxalic acid copper diacetonamine according to claim 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 alternaria leaf spot of apple, apple marssonina leaf spot, apple mildew, cucumber downy mildew, powdery mildew of cucumber, potato late blight.
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| CN201510770958.3A CN105230650A (en) | 2014-11-06 | 2014-11-06 | Sterilizing composition containing oxalate diacetone amine copper |
| CN201410620595.0A CN104351243B (en) | 2014-11-06 | A kind of bactericidal composition containing oxalic acid copper diacetonamine | |
| CN201510770634.XA CN105284868B (en) | 2014-11-06 | 2014-11-06 | A kind of bactericidal composition containing oxalic acid copper diacetonamine |
| CN201510771308.0A CN105284888B (en) | 2014-11-06 | 2014-11-06 | A kind of bactericidal composition containing oxalic acid copper diacetonamine |
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| CN201410620595.0A CN104351243B (en) | 2014-11-06 | A kind of bactericidal composition containing oxalic acid copper diacetonamine |
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| CN201510770958.3A Division CN105230650A (en) | 2014-11-06 | 2014-11-06 | Sterilizing composition containing oxalate diacetone amine copper |
| CN201510770634.XA Division CN105284868B (en) | 2014-11-06 | 2014-11-06 | A kind of bactericidal composition containing oxalic acid copper diacetonamine |
| CN201510771308.0A Division CN105284888B (en) | 2014-11-06 | 2014-11-06 | A kind of bactericidal composition containing oxalic acid copper diacetonamine |
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| CN113207898A (en) * | 2020-01-08 | 2021-08-06 | 信阳农林学院 | Bactericide composition for preventing and treating wheat scab |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456873A (en) * | 2007-12-14 | 2009-06-17 | 西北农林科技大学农药研究所 | Agricultural bactericidal agent |
| CN101768175A (en) * | 2008-12-31 | 2010-07-07 | 西北农林科技大学农药研究所 | Agricultural fungicide of oxalic acid copper diacetonamine |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456873A (en) * | 2007-12-14 | 2009-06-17 | 西北农林科技大学农药研究所 | Agricultural bactericidal agent |
| CN101768175A (en) * | 2008-12-31 | 2010-07-07 | 西北农林科技大学农药研究所 | Agricultural fungicide of oxalic acid copper diacetonamine |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113207898A (en) * | 2020-01-08 | 2021-08-06 | 信阳农林学院 | Bactericide composition for preventing and treating wheat scab |
| CN113598170A (en) * | 2020-01-08 | 2021-11-05 | 信阳农林学院 | Medicament composition containing phenamacril and copper diacetonamine oxalate |
| CN113598174A (en) * | 2020-01-08 | 2021-11-05 | 信阳农林学院 | Pharmaceutical composition containing validamycin and copper diacetonamine oxalate |
| CN113598170B (en) * | 2020-01-08 | 2022-04-22 | 信阳农林学院 | Medicament composition containing phenamacril and copper diacetonamine oxalate |
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| Publication number | Publication date |
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| CN105284888A (en) | 2016-02-03 |
| CN105284868B (en) | 2017-10-10 |
| CN105284868A (en) | 2016-02-03 |
| CN105230650A (en) | 2016-01-13 |
| CN105284888B (en) | 2018-03-27 |
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