CN104798801A - Aqueous emulsion-fungicide composition containing pyraclostrobin and prochloraz and preparation method of aqueous emulsion-fungicide composition - Google Patents
Aqueous emulsion-fungicide composition containing pyraclostrobin and prochloraz and preparation method of aqueous emulsion-fungicide composition Download PDFInfo
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- CN104798801A CN104798801A CN201510192234.5A CN201510192234A CN104798801A CN 104798801 A CN104798801 A CN 104798801A CN 201510192234 A CN201510192234 A CN 201510192234A CN 104798801 A CN104798801 A CN 104798801A
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- prochloraz
- pyraclostrobin
- aqueous emulsion
- compositions
- microbicide compositions
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- 239000005869 Pyraclostrobin Substances 0.000 title claims abstract description 75
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000005820 Prochloraz Substances 0.000 title claims abstract description 70
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 57
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- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
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- -1 polyoxyethylene phosphonate Polymers 0.000 claims description 37
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- 230000008092 positive effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- WHHIPMZEDGBUCC-UHFFFAOYSA-N probenazole Chemical compound C1=CC=C2C(OCC=C)=NS(=O)(=O)C2=C1 WHHIPMZEDGBUCC-UHFFFAOYSA-N 0.000 description 1
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000009758 senescence Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000008223 sterile water Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- QGHREAKMXXNCOA-UHFFFAOYSA-N thiophanate-methyl Chemical compound COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC QGHREAKMXXNCOA-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides an aqueous emulsion-fungicide composition containing pyraclostrobin and prochloraz and a preparation method of the aqueous emulsion-fungicide composition. The aqueous emulsion-fungicide composition comprises the following raw materials by mass: 5 to 15 percent of pyraclostrobin, 10 to 30 percent of prochloraz, 5 to 10 percent of one or more emulsifiers, 10 to 20 percent of one or more solvents, 0.5 to 1 percent of one or more stabilizers, 0.01 to 0.5 percent of a foam killer, 3 to 5 parts of one or more antifreeze agents, and the balance of water. The aqueous emulsion-fungicide composition containing pyraclostrobin and prochloraz has the advantages that a new formula concept is introduced through research of functional mechanisms of fungicides, and the adopted emulsifiers are specific, so that the effective components are made into nanoscale particles of oil-in-water structures, the utilization ratio of a target is improved, and the synergia is obvious; the formula is unique in principle; the production and processing are complex; the physical and chemical properties are stable; fungal diseases of cash crops can be controlled; the activity is high; the soil residue is low; suitability for industrial production is realized.
Description
Technical field
The present invention relates to pesticide technology preparation field, aqueous emulsion microbicide compositions being specifically related to a kind of pyraclostrobin-containing and Prochloraz and preparation method thereof.
Background technology
Along with organic farming, the development of industrialized agriculture, the attention degree of people to food security is more and more higher, how to improve the service efficiency of agricultural chemicals, reduce the usage amount of agricultural chemicals, and then reduction agricultural chemicals is one of top priority of current pesticide technology worker the residual of agricultural product.In Environmental security, water baseization agricultural chemicals specifies that being subject to society strict today pays much attention to.In recent years; China's water baseization agricultural chemicals has had certain development; aqueous emulsion is a kind of O/w emulsion utilizing high molecular surfactant and a small amount of solvent to be formed under the effect of high-shear emulsion machine mechanical external force; active component is wrapped up by water; change that active substance easily volatilizees, the character such as inflammable, explosive completely; this technology is widely used in the fields such as household chemicals field, petroleum drilling fluid, agricultural chemicals; improving the safety of agricultural chemicals to crop, strengthening effect, reducing packing cost, cleaner production and aspect of preserving the ecological environment and serve positive effect.
8th phase " agricultural chemicals " in 2014 has delivered the paper formula of 30% pyraclostrobin suspending agent " orthogonal experiment preferably " of the people such as Wang Shunli, the document passes through wet type ultramicro grinding legal system for 30% pyraclostrobin suspending agent, and by flow point method and trial and error method Stepwise Screening dispersant, utilize orthogonal experiment optimization of C/C composites.The optimization formula of its result of study 30% pyraclostrobin suspending agent is pyraclostrobin 30% (mass fraction), non-ionic dispersing agent and anion humectant mixture (SC10) 3.5%, xanthans 0.14%, aluminium-magnesium silicate 1.5%, ethylene glycol 3.5%, water complements to 100%.Conclusion is said preparation after (54 ± 2) DEG C heat storage 14 d, and other indices all meet suspending agent relevant criterion.The paper " pyraclostrobin dimethomorph 18.7% water dispersible granules efficient liquid phase chromatographic analysis " that 12nd phase in 2008 " pesticide science and management " has delivered the people such as Zheng Yang there have been described herein employing high performance liquid chromatography, namely with first alcohol ︰ water=75 ︰ 25 (V/V) for mobile phase, the stainless steel column of C18 and diode array detector are with the pyraclostrobin in post separation determination pyraclostrobin dimethomorph 18.7% water dispersible granules and dimethomorph.Within 2010, o. 11th " Chinese agronomy circular " paper " 7 kinds of bactericide are to the Toxicity Determination of citrus anthracnose bacterium " the research structure result of having delivered the people such as Hu Xiurong shows: the virulence of 25% Prochloraz missible oil is the strongest, and EC50 is 0.0741mg/L; 25% pyraclostrobin missible oil, 30% likes that the virulence of seedling (15% propiconazole+15% Difenoconazole) missible oil, 10% difenoconazole water dispersible granule, 25% Fluoxastrobin suspending agent, 60,%00 Thailand (5% pyraclostrobin+55% Carbatene) dry suspending agent, 50% carbendazol wettable powder weakens successively.With regard to susceptibility, to 25% Prochloraz and 30%, citrus anthracnose bacterium likes that the susceptibility of seedling is apparently higher than other several medicaments.Thesis for the doctorate " Mango Fruit latent infection Botryodiplodia theobromae causes rotten mechanism and the basic research of the blossom-end rot Prevention Technique " conclusion of University Of Hainan Hu Meijiao is pointed out: analyzed by cross resistance, there is cross resistance between carbendazim, probenazole, thiophanate-methyl and olefin conversion 4 kinds of bactericide, and there is negative cross resistance between kresoxim-methyl and jinggangmeisu.Iprodione, Prochloraz and prochloraz iprodione 3 kinds of bactericide have good preventive effect to mango blossom-end rot, and prochloraz iprodione, the Prochloraz preventive effect to mango anthracnose reaches more than 93%.According to the overall merit to mango blossom-end rot and anthracnose control efficiency, prochloraz iprodione is best to the effect controlling mango postharvest disease, is secondly Prochloraz.
Open (bulletin) number 104365590A of document discloses " a kind of pyraclostrobin suspending agent preparation method of serialization " that Tang of Shandong United Pesticide Industry Co., Ltd. builds the people such as peak; mention a kind of preparation method of pyraclostrobin suspending agent of serialization, and its application in plant protection.Be dissolved in by pyraclostrobin in alcohol solution, alcohols solvent is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol; The part by weight of alcohol water is alcohol: water=100:1-10, the alcohol water yield added, all can dissolve pyraclostrobin at 40-64 DEG C, then cools to it and fully separates out, then intensification makes it be partly dissolved, each process need 1 ~ 12 hour, then through wet pulverizing to need particle diameter.Open (bulletin) number 102308823A discloses the technology of Shanxi Thompson Biological Technology Co., Ltd.'s " a kind of bactericidal composition containing pyraclostrobin ", be specifically related to a kind of bactericidal composition containing pyraclostrobin, its effective active composition contains (A) pyraclostrobin and the one in (B) Isoprothiolane or iprobenfos, wherein the weight ratio of A and B is 20: 1 ~ 1: 80, effective active composition adds auxiliary agent and excipients makes water dispersible granules, suspending agent etc., is mainly used in control rice blast, banded sclerotial blight, bakanae disease etc.The claimed pyraclostrobin of its claim 4 makes the technology of wetting powder, water dispersible granules, suspending agent, aqueous emulsion, microemulsion with, Isoprothiolane or iprobenfos bactericidal composition; Wherein Partial rights claimed range is wider, is technically difficult to realize.Open (bulletin) number 102696645A discloses the technology of " a kind of composition pesticide containing pyraclostrobin and Metalaxyl-M " of Guangdong Zhongxun Agricultural Technology Co., Ltd., and claim 1 is characterized in that active ingredient is pyraclostrobin and Metalaxyl-M.Claim 5 is characterized in that its formulation is suspending agent, water dispersible granules or wetting powder.Claim 6 is characterized in that phase composition is applied to control crops epidemic disease and downy mildew.
Pyraclostrobin is New-type wide-spectrum bactericide; mitochondrial respiratory inhibitor. there is protection, treatment, blade infiltration conduction, prevent and treat anthracnose, brown spot, powdery mildew and banded sclerotial blight etc. because the features such as low toxicity, efficient, safety are widely used in economic crops.Prochloraz is a kind of wide-spectrum bactericide, has obvious preventive effect to the disease that various crop is caused by sac fungi and imperfect fungus, also can be mixed with most of bactericide, bactericide, Insecticides (tech) & Herbicides (tech), all has good control efficiency.To the multiple diseases on field crop, fruit and vegetable, turf and ornamental plants, there is treatment and eradicant action.For efficient, wide spectrum, low-toxicity bactericide, have the multiple actions such as prevention & protection treatment, including Prochloraz is imidazoles wide-spectrum bactericide.Work by suppressing the biosynthesis of sterol, without systemic action, the multiple diseases preventive effect caused for sac fungi and imperfect fungus is splendid.Adopt gene induced technology, activated plant disease-resistant gene is expressed, and quick-acting is good, and the lasting period is long.Conventional use prevents and treats gourd, fruit and vegetable anthracnose, leaf spot, also can the water prevention rice bakanae disease, rice blast etc.Citrus anthracnose, blossom-end rot, penicilliosis, green mould, banana anthracnose, leaf spot, mango anthracnose, leaf spot of peanut, the vegetables anthracnose such as capsicum, eggplant, muskmelon, tomato, Strawberry anthracnose, bakanae disease of rice, rice blast, sclerotinia rot of colza, leaf spot, mushroom brown spot, apple anthracnose, pear scab etc., Prochloraz is also widely used in the fields such as crops seed soaking, fruit freshness preserving.The advantage of pyraclostrobin and Prochloraz combined, utilize and be added that synergy principle develops a kind of environmental friendliness, the Novel rural preparation of its technical characteristic marked improvement is used for preventing and treating corps diseases, the aqueous emulsion of the former medicine of solid and liquid former medicine preparation high-load still needs the technical problem solving some cores.
Current research and the product in market are generally aqueous emulsion, the missible oil of pyraclostrobin suspending agent, missible oil and Prochloraz, there is not yet correlative study and the report of the aqueous emulsion complex preparation of pyraclostrobin and Prochloraz.
Summary of the invention
According to the deficiencies in the prior art, the invention provides formula and the production technology thereof of a kind of pyraclostrobin-containing and prochloraz aqueous emulsion.Technology of the present invention add man-hour by temperature of charge keep 35 ~ 40 DEG C improve the solvability of pyraclostrobin in Conventional solvents, be unlikely to again to increase too much heat energy and organic solvent, Prochloraz fusing point is 46.5-49.3 DEG C simultaneously, be added in quantitative solvent after Prochloraz must being heated in advance to dissolve, under the condition of insulation, can be that the mixture material of pyraclostrobin and Prochloraz fully dissolves and keeps liquid, when being conducive to high shear, form the emulsion of O/W.This technical matters effectively overcomes public technology pyraclostrobin can only cook missible oil and suspending agent; Prochloraz can only do the problem of aqueous emulsion and missible oil, achieves synergistic effect during material stability and the control corps diseases of pyraclostrobin and prochloraz aqueous emulsion.
The present invention is by the following technical solutions: the aqueous emulsion microbicide compositions of a kind of pyraclostrobin-containing and Prochloraz, it is characterized in that: described microbicide compositions, by mass percentage, comprise following component: 5 ~ 15% pyraclostrobins, 10 ~ 30% Prochlorazs, 5 ~ 10% emulsifier, 10 ~ 20% organic solvents, 0.5 ~ 1% stabilizing agent, 0.01 ~ 0.5% defoamer, 3 ~ 5% antifreezes, surplus is water.
Described a kind of pyraclostrobin-containing and the aqueous emulsion microbicide compositions of Prochloraz, described emulsifier is perfluorinated sulfonate, multi-styrene phenol polyoxyethylene phosphonate organic amine salt, Rf-(CH2CH2O) nPO4, alkanolamide polyoxyethylene ether phosphate organic amine salt, one or several compositions in anhydrous sorbitol acid anhydrides.
Described a kind of pyraclostrobin-containing and the aqueous emulsion microbicide compositions of Prochloraz, described antifreeze is one or several compositions in glycerine, ethylene glycol, propane diols.
Described a kind of pyraclostrobin-containing and the aqueous emulsion microbicide compositions of Prochloraz, described organic solvent is one or several compositions in methyl oleate, soybean oil, turpentine oil, palm oil, cottonseed oil, dimethylbenzene, aromatic solvent naphtha, alkane solvent oil.
Described a kind of pyraclostrobin-containing and the aqueous emulsion microbicide compositions of Prochloraz, described stabilizing agent is one or several compositions in ethyl acetate, sodium citrate, EDTA-2Na, sodium lactate, sodium acetate, urea.
The preparation method of the aqueous emulsion microbicide compositions of a kind of pyraclostrobin-containing and Prochloraz, described preparation method comprises the following steps: after former for described microbicide compositions medicine is added reactor, open heater, 30min at temperature of charge keeps 35 ~ 40 DEG C, material is dissolved completely transparent, then open high-shear emulsifying agent device, slowly add water, shear 60min, form the aqueous emulsion microbicide compositions of O/W.
The mechanism of action of microbicide compositions Prochloraz+pyraclostrobin of the present invention is that Prochloraz can the mitochondrial respiration of T suppression cell and premature senescence resistance, there is volume increase effect, the synthesis of pyraclostrobin energy T suppression cell film and cell wall, so the combination of Prochloraz and pyraclostrobin has obvious synergistic effect.It has protection and therapeutic activity concurrently, and is very suitable for resistance management and the disease comprehensive regulation.This invention composition fungicidal spectrum is wide, to the microbial disease of sac fungi, basidiomycetes, imperfect fungus and ovum as powdery mildew, downy mildew, leaf mold, rust, epidemic disease, rice blast, smut, leaf spot and root, stem disease evil all have good effect.It is a kind of curative fungicide agent of wide spectrum.This product purpose is wide, and safety is good.The control of the various fungal diseases such as the blight dis-ease of the various crop such as watermelon, grape, vegetables, flowers, anthracnose, powdery mildew, downy mildew, epidemic disease can be widely used in, and have obvious trophism, can also increase production.
pyraclostrobin:chemical name: methyl (N)-[[[1-(4-chlorobenzene) pyrazoles-3 base)-oxygen]-0-methoxyl group]-N-methoxymethyl carbamate
pyraclostrobin chemical structural formula
physicochemical property:outward appearance: pyraclostrobin sterling is that white is to the tasteless crystalline solid of oldlace.
Fusing point 63.7 ~ 65.2 DEG C:
Vapour pressure (20-25 DEG C): 2.6 × 10-8Pa;
Solvability (20 DEG C, g/100mL): water (distilled water) 0.00019, normal heptane 0.37, methyl alcohol 10, acetonitrile >=50, toluene, carrene >=57, acetone, ethyl acetate >=65. n-octyl alcohol 2.4, DMF; 43; N-Octanol/Water Partition: logPow4.18 (pH6.5);
Stability: sterling is Photolysis Half 0.06d (1.44h) in aqueous; Preparation storage at normal temperature: stablize for when 20 degrees Celsius 2 years.
The mechanism of action: pyraclostrobin is New-type wide-spectrum bactericide.The mechanism of action: be mitochondrial respiratory inhibitor. namely by stoping electro transfer in cytochrome synthesis.There is protection, treatment, blade infiltration conduction.Pyraclostrobin missible oil shows there is good control efficiency to powdery mildew of cucumber, downy mildew and banana freckle, leaf spot, stalk break etc. through field control effectiveness test result.
prochloraz: Chinese: Prochloraz; Chemical name: N-propyl group-N-[α-(2,4,6-Trichlorophenoxy)-1H-imidazoles-1-formamide; The mode of action: protect, root out
Physicochemical character: clear crystal, former medicine is golden yellow liquid, low temperature is tending towards solidifying, fusing point 46.5 ~ 49.3 DEG C (>99% purity), boiling point 208 ~ 210 DEG C/0.2mmHg (decomposition), vapour pressure 150 μ Pa (25 DEG C), 90 μ Pa (20 DEG C), density 1.42 (20 DEG C), solvability 34.4mg/L when 25 DEG C, be dissolved in organic solvent, wide range, as chloroform, ether, toluene 2.5, acetone 3.5, hexane 7.5 × 10
-3(kg/L), at pH7, stable in 20 DEG C of Water Unders, decompose in concentrated acid and concentrated base medium, light and long term high temperature heating (200 DEG C) decompose.
Acceptable daily intake: 0 ~ 0.01mg/kg bw
Acute oral LD50:1600mg/kg
Acute through skin LD50:>3000mg/kg
Action character: azole broad-spectrum germicide.The various crop disease caused for sac fungi and imperfect fungus has special efficacy.Effect is caused by suppressing the biosynthesis of sterol.Although do not have a systemic action, it has certain conductive performance.
Aquatile: LC50 (96 hours mg/L) rainbow trout 1, blue gill sunfish 2.2
Honeybee: nontoxic, LD50 (locally) 50 μ g/ honeybee, (per os) 60 μ g/ honeybee
Natural enemy: acute oral LD50 wild duck 3132mg/kg is nontoxic to beneficial insect
Water and soil conservation: half life period (field) 5-37 days, KD152 (sandy loam) in soil, 256 (grey matter clay loams).
The invention has the beneficial effects as follows: aqueous emulsion microbicide compositions that the invention provides a kind of pyraclostrobin-containing and Prochloraz and preparation method thereof, its antimicrobial combination coefficient of synergism is up to 2.4, belong to extremely significantly synergy, selected by its pyraclostrobin and Prochloraz composition, formulation is aqueous emulsion, belong to the one of environment protection water-based agent type, automatically disperse in water, emulsion particle particle diameter is between 0.5 ~ 1um, be far smaller than suspending agent 2 ~ 10um, be conducive to control target absorb and improve preventive effect, pesticide activity component is wrapped to form O/W emulsion by water completely; There is flash-point high, nonflammable, consumption of organic solvent significantly reduces than missible oil, the process technology technique improved is different from conventional art route, and it is very low that energy consumption cost increase accounts for cost ratio, and the selection of that adapt with its formula, appropriate surfactant is conducive to the physical stability of product.
Embodiment
below in conjunction with specific embodiment, the present invention is described in further detail.
Aqueous emulsion microbicide compositions of a kind of pyraclostrobin-containing and Prochloraz and preparation method thereof, specifically comprises following component (by mass percentage)
Example 1
5% pyraclostrobin, 30% Prochloraz, 3% multi-styrene phenol polyoxyethylene phosphonate organic amine salt, 3% alkanolamide polyoxyethylene ether phosphate organic amine salt, 4% anhydrous sorbitol acid anhydrides methyl oleate, 15% solvent naphtha, 0.1% urea, 0.5% defoamer, 5% ethylene glycol, surplus is water.
Example 2
10% pyraclostrobin, 30% Prochloraz, 3% multi-styrene phenol polyoxyethylene phosphonate organic amine salt, 3% alkanolamide polyoxyethylene ether phosphate organic amine salt, 4% anhydrous sorbitol acid anhydrides methyl oleate, 15% dimethylbenzene, 0.1% urea, 0.5% defoamer, 5% ethylene glycol, surplus is water.
Example 3
10% pyraclostrobin, 10% Prochloraz, 3% multi-styrene phenol polyoxyethylene phosphonate organic amine salt, 3% alkanolamide polyoxyethylene ether phosphate organic amine salt, 4% anhydrous sorbitol acid anhydrides methyl oleate, 10% methyl oleate, 0.1% urea, 0.5% defoamer, 5% ethylene glycol, surplus is water.
Example 4
15% pyraclostrobin, 10% Prochloraz, 3% multi-styrene phenol polyoxyethylene phosphonate organic amine salt, 3% alkanolamide polyoxyethylene ether phosphate organic amine salt, 4% anhydrous sorbitol acid anhydrides methyl oleate, 10% methyl oleate, 0.1% ethyl acetate, 0.5% defoamer, 5% ethylene glycol, surplus is water.
Example 5
15% pyraclostrobin, 20% Prochloraz, 1% multi-styrene phenol polyoxyethylene phosphonate organic amine salt, 1% alkanolamide polyoxyethylene ether phosphate organic amine salt, 3% anhydrous sorbitol acid anhydrides methyl oleate, 20% methyl oleate, 0.1% ethyl acetate, 0.5% defoamer, 5% ethylene glycol, surplus is water.
Example 6
15% pyraclostrobin, 25% Prochloraz, 1% multi-styrene phenol polyoxyethylene phosphonate organic amine salt, 1% alkanolamide polyoxyethylene ether phosphate organic amine salt, 3% anhydrous sorbitol acid anhydrides methyl oleate, 20% dimethylbenzene, 0.1% ethyl acetate, 0.5% defoamer, 3% ethylene glycol, surplus is water.
Example 7
15% pyraclostrobin, 30% Prochloraz, 2% multi-styrene phenol polyoxyethylene phosphonate organic amine salt, 2% alkanolamide polyoxyethylene ether phosphate organic amine salt, 4% anhydrous sorbitol acid anhydrides methyl oleate, 20% dimethylbenzene, 0.1% ethyl acetate, 0.5% defoamer, 3% ethylene glycol, surplus is water.
Example 8
10% pyraclostrobin, 20% Prochloraz, 2% multi-styrene phenol polyoxyethylene phosphonate organic amine salt, 2% alkanolamide polyoxyethylene ether phosphate organic amine salt, 4% anhydrous sorbitol acid anhydrides methyl oleate, 20% palm oil, 0.3% sodium acetate, 0.5% defoamer, 3% ethylene glycol, surplus is water.
Example 9
10% pyraclostrobin, 30% Prochloraz, 2% Rf-(CH2CH2O) nPO4,2% alkanolamide polyoxyethylene ether phosphate organic amine salt, 4% anhydrous sorbitol acid anhydrides methyl oleate, 20% palm oil, 0.3% sodium acetate, 0.5% defoamer, 3% ethylene glycol, surplus is water.
Example 10
10% pyraclostrobin, 30% Prochloraz, 2% Rf-(CH2CH2O) nPO4,2% alkanolamide polyoxyethylene ether phosphate organic amine salt, 4% anhydrous sorbitol acid anhydrides methyl oleate, 20% aromatic solvent naphtha, 0.3% sodium acetate, 0.5% defoamer, 3% ethylene glycol, surplus is water.
Example 11
10% pyraclostrobin, 30% Prochloraz, 2% Rf-(CH2CH2O) nPO4,2% alkanolamide polyoxyethylene ether phosphate organic amine salt, 4% anhydrous sorbitol acid anhydrides methyl oleate, 20% turpentine oil, 0.3% sodium acetate, 0.5% defoamer, 3% ethylene glycol, surplus is water.
test of pesticide effectiveness part:
Example of the present invention is the method adopting Toxicity Determination and field trial to combine.First pass through Toxicity Determination, synergy ratio (SR) after clear and definite two kinds of medicaments are composite according to a certain percentage, the antagonism of SR < 0.5,0.5≤SR≤1.5 are summation action, SR > 1.5 is synergistic effect, again on this basis, then carry out field control effectiveness test.
, Toxicity Determination
Test method: after the effective inhibition concentration scope of each medicament is determined in indication, medicament sets 5 dosage process according to active constituent content, if clear water contrast.Carry out with reference to " farm-chemical indoor determination experiment criterion bactericide ", adopt mycelial growth rate method to measure medicament to the virulence of crop pathogens.Measure colony diameter by right-angled intersection method after 72h, calculate each process net growth, mycelial growth inhibition rate.
Through amount of growth (mm)=measurement colony diameter-5
Mycelial growth inhibition rate is converted into probability to (y), liquor strength (ug/ml) is converted to logarithm value (x), try to achieve virulence regression equation (y=a+bx) with method of least squares, and calculate the EC of often kind of medicament thus
50value.Calculate two kinds of medicament different ratio synergies ratio (SR) according to Wadley method, SR < 0.5 is antagonism, and 0.5≤SR≤1.5 are summation action simultaneously, and SR > 1.5 is synergistic effect, and computing formula is as follows:
Wherein: a, b are respectively active matter A and B ratio shared in component;
A is pyraclostrobin, and B is Prochloraz;
Toxicity test result of the present invention:
table 1 microbicide compositions of the present invention prevents and treats powdery mildew of cucumber toxicity test result
As shown in Table 1, pyraclostrobin and Prochloraz complex preparation show, when pyraclostrobin in control cucumber downy mildew toxicity test data: during Prochloraz=1:3, its virulence coefficient is the highest.The synergy ratio SR of example 2,9,10,11 is all greater than 2.1, and illustrating that this is combined in aforementioned proportion combination is all show as synergy, and the composition synergic ratio of this invention obvious high market same type of composition preparation.
According to " farm-chemical indoor determination experiment criterion bactericide ", the a small amount of organic solvent dissolution of active substance of indoor biometrics, add the result that mother liquor that the sterile water containing Tween80 prepares carries out testing, not relating to the result that in formula composition, formulation, synergist, solvent difference produce.
, field control effectiveness test
1 test objective
By field control effectiveness test, verify and prepare 40% pyrazoles prochloraz aqueous emulsion to the control efficiency of powdery mildew of cucumber through the most obvious example 2 of indoor biometrics synergy, determine its field using dosage and using method, and observe whether have poisoning to cucumber.
2 experimental conditions
The selection of 2.1 subjects, crop and kind
Powdery mildew of cucumber
Cucumber, kind is 9618
2.2 crop geneticss and environmental condition
Test site is prosperous village, Xia Gaokan town, Dongling District, Shenyang City, and soil types is sandy loam, can irrigate.Planting density every mu 4000 strain, on January 6th, 2011 transplants, in July ,-2011 in January, 2011 breeding time.
3 experimental scheme and arrangement
3.1 medicament
3.1.1 test medicine
Medicament title: 40% pyrazoles Prochloraz EW; Manufacturer: Pucheng, Shaanxi Province Mei Er orchard workerization Co., Ltd.
3.1.2 medicament is contrasted
Medicament title: 30% pyraclostrobin SC; Manufacturer: Shenzhen Nuo Puxin agrochemical Co., Ltd.
450g/L Prochloraz EW, is divided into 40% Prochloraz EW according to density conversion quality, manufacturer: Shenzhen Nuo Puxin agrochemical Co., Ltd.
3.1.3 dosing is numbered with process
table 2 reagent agent experimental scheme
The only preventive effect contrast under crop equal conditions of above-mentioned test dose, does not represent the optimal dose promoted the use of.
3.2 communities arrange
3.2.1 community arrangement
3.2.2 plot area and repetition
Plot area (or plant number): in greenhouse, every plot area is 22.4m
2
number of repetition: repeat 4 times
3.3 application method
3.3.1 using method
Adopt foliar spray method
3.3.2 spraying equipment
Workers and peasants' 16 types-manual sprayer
3.3.3 spraying time and number of times
First time dispenser: on June 5th, 2011
Second time dispenser: on June 13rd, 2011
Third time dispenser: on June 18th, 2011
Crop growing stage: cucumber result mid-term
The target organisms emergence period: powdery mildew of cucumber starts the phase
3.3.4 capacity is used
Per hectare amount of liquid medicine 900 liters
3.3.5 the medicament data of other damage by disease and insect is prevented and treated
Duration of test is not prevented and treated other damage by disease and insect
4 investigation, record and measuring method
4.1 meteorological and soil informations
4.1.1 meteorological data
Dispenser (June 5) weather is fine for the first time, the maximum air temperature 31.1 DEG C, the minimum air temperature 16.6 DEG C; Second time dispenser (June 13) weather is fine, the maximum air temperature 29.5 DEG C, the minimum air temperature 15.4 DEG C; Third time dispenser (June 18) is cloudy, the maximum air temperature 28.2 DEG C, the minimum air temperature 16.6 DEG C.Duration of test June 8, June 14, June 17, June 22 shower; June 11, June 12, June 15, June 16 light rain, June 23 moderate rain, duration of test does not meet other diastrous weather.
4.1.2 soil information
Soil types is sandy loam, the content of organic matter 2.5%, pH 6.0, and duration of test fills with 1 water.
4.2 investigation methods, time and number of times
4.2.1 control time and number of times
Investigation basic diseases radix before dispenser, 7 days investigation prevention results after last dispenser, investigate 2 times altogether.
First time investigation: on June 5th, 2011
Second time investigation: on June 25th, 2011
4.2.2 investigation method
Get 4 points at random according to the every community of pesticide field efficacy medicine test criterion (-) bactericidal agent for preventing and treating cucumber, whole blades of often some investigation 2 strains, every sheet leaf accounts for the percentage classification record of leaf area by scab, and stage division is as follows:
0 grade: without scab;
1 grade: lesion area accounts for whole leaf area less than 5%;
3 grades: lesion area accounts for whole leaf area 6%-10%;
5 grades: lesion area accounts for whole leaf area 11%-20%;
7 grades: lesion area accounts for whole leaf area 21%-40%;
9 grades: lesion area accounts for whole leaf area more than 40%.
4.2.3 drug effect computational methods
Calculate by following formula:
Disease index=
Control efficiency (%)=
CK
0disease index before the dispenser of-blank district
CK
1disease index after the dispenser of-blank district
PT
0disease index before the dispenser of-chemicals treatment district
PT
1disease index after the dispenser of-chemicals treatment district
4.3 direct impacts on crop
All process communities all do not produce any poisoning to cucumber, to the growth indifference compared with the control of cucumber.
The seed output and quality of 4.4 products
Each process community, to the quality of cucumber indifference compared with the control, is not carried out survey and is produced.
4.5 to other biotic influence
4.5.1 on the impact of other damage by disease and insect
Each process is on the impact of other damage by disease and insect indifference compared with the control
4.5.2 on the impact of other non-target organism
Each process is on the impact of other non-target organism indifference compared with the control
5 results and analysis
the analysis of table 3 field test data
table 3 40% pyrazoles.
prochloraz aqueous emulsion prevents and treats powdery mildew of cucumber field control effectiveness test result
Biometric analysis method: adopt DPS software application Duncan duncan's new multiple range method to carry out statistical analysis to data.
Evaluating drug: it can be seen from the table, the average preventive effect of last dispenser test medicine 40% pyrazoles prochloraz aqueous emulsion per hectare effective ingredient consumption 90 grams, 120 grams, 150 grams after 7 days is respectively 83.24%, 86.20% and 91.46%; The average preventive effect of contrast medicament 30% pyraclostrobin suspending agent per hectare effective ingredient consumption 135 grams is 79.65%, the average preventive effect of 450g/L prochloraz aqueous emulsion hectare effective ingredient consumption 300 grams is 81.04%, process difference between D, E remarkable, process C is significantly higher than process A and B.
Tentatively clear and definite by the above results, 40% pyrazoles prochloraz aqueous emulsion of the present invention effectively can control powdery mildew of cucumber.
Technical essential: adopt foliar spray, interval 6-7d, continuous use three times, per hectare effective ingredient consumption 120 grams-150 grams, to the preventive effect of powdery mildew of cucumber between 86.58%-91.47%, recommends effective ingredient consumption to be 120 grams/ha-150 grams/ha.
, conclusion
Along with a large amount of exploitation and the use of various pharmaceutical preparations, the susceptibility decline problem of phytopathogen to bactericide is also more and more outstanding, main cause has: use single medicament in the long-term continuous several times of the same area, improving constantly of same medicament working concentration, accelerates the drug-fast generation of germ.Under action of agricultural chemicals of the same race, pathogen can be induced on the one hand to produce variation, occur new resistance types; On the other hand, because the selection pressure of agricultural chemicals, the pesticide resistance originally existed in Pathogen population will accumulate gradually, causes anti-pharmacopoeia group to become the dominant population of whole colony; Moreover Traditional Agricultural pharmaceutically dosage form due to through water dilution rear suspension liquid in trace bigger than normal, adhesivity on target is bad, the availability of pesticide active ingredient only has about 20%, thus affect the result of use of bactericide, a scientific and reasonable formulation is very beneficial for the availability improving pesticide activity thing, thus reduces the usage amount of agricultural chemicals.The explanation of above-mentioned indoor and outdoors field control effectiveness test data, pyraclostrobin-containing of the present invention and prochloraz aqueous emulsion, use safety, poisoning can not be caused by controlling object, its drug effect is obviously higher than the pyraclostrobin of identical component, Prochloraz single dose preventive effect, and experiment proves that formulation principle of the present invention is unique, and synergy is obvious, production and processing technology is simple simultaneously, has obvious economical, societal benefits.
Claims (6)
1. the aqueous emulsion microbicide compositions of a pyraclostrobin-containing and Prochloraz, it is characterized in that: described microbicide compositions, by mass percentage, comprise following component: 5 ~ 15% pyraclostrobins, 10 ~ 30% Prochlorazs, 5 ~ 10% emulsifier, 10 ~ 20% solvents, 0.5 ~ 1% stabilizing agent, 0.01 ~ 0.5% defoamer, 3 ~ 5% antifreezes, surplus is water.
2. the aqueous emulsion microbicide compositions of a kind of pyraclostrobin-containing according to claim 1 and Prochloraz, it is characterized in that, described emulsifier is perfluorinated sulfonate, multi-styrene phenol polyoxyethylene phosphonate organic amine salt, Rf-(CH2CH2O) nPO4, alkanolamide polyoxyethylene ether phosphate organic amine salt, one or several compositions in anhydrous sorbitol acid anhydrides.
3. the aqueous emulsion microbicide compositions of a kind of pyraclostrobin-containing according to claim 1 and Prochloraz, is characterized in that, described antifreeze is one or several compositions in glycerine, ethylene glycol, propane diols.
4. the aqueous emulsion microbicide compositions of a kind of pyraclostrobin-containing according to claim 1 and Prochloraz, it is characterized in that, described solvent is one or several compositions in methyl oleate, soybean oil, turpentine oil, palm oil, cottonseed oil, dimethylbenzene, aromatic solvent naphtha, alkane solvent oil.
5. the aqueous emulsion microbicide compositions of a kind of pyraclostrobin-containing according to claim 1 and Prochloraz, it is characterized in that, described stabilizing agent is one or several compositions in ethyl acetate, sodium citrate, EDTA-2Na, sodium lactate, sodium acetate, urea.
6. the preparation method of the aqueous emulsion microbicide compositions of a pyraclostrobin-containing according to claim 1 and Prochloraz, it is characterized in that, described preparation method comprises the following steps: after former for described microbicide compositions medicine is added reactor, open heater, 30min at temperature of charge keeps 35 ~ 40 DEG C, makes material dissolve completely transparent, then high-shear emulsifying agent device is opened, slowly add water, shear 60min, form the aqueous emulsion microbicide compositions of O/W.
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| CN119032956A (en) * | 2023-12-26 | 2024-11-29 | 河北省农林科学院植物保护研究所 | Sterilization composition for preventing and treating cucumber target spot disease and application thereof |
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