CN103461383A - Bactericide composition and production process thereof - Google Patents

Bactericide composition and production process thereof Download PDF

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CN103461383A
CN103461383A CN2013104115635A CN201310411563A CN103461383A CN 103461383 A CN103461383 A CN 103461383A CN 2013104115635 A CN2013104115635 A CN 2013104115635A CN 201310411563 A CN201310411563 A CN 201310411563A CN 103461383 A CN103461383 A CN 103461383A
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microbicide compositions
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proteolytic enzyme
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CN103461383B (en
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张强
秦广俊
吴治国
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SHAANXI PUCHENG MEIERGUO AGROCHEMICAL CO Ltd
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Abstract

The invention provides a bactericide composition and a production process thereof. The bactericide composition comprises the following components according to mass percent: 10-40% of difenoconazole, 10-40% of azoxystrobin, 1-6% of dispersant, 1-3% of wetting agent, 0.5-2% of chelating agent, 1-5% of texturing agent, 3-5% of humectant, 0.05-0.1% of proteolytic enzyme and the balance of fillers. According to the bactericide composition provided by the invention, a new formula concept is introduced by researching the mechanism of action of the bactericide, the special texturing agent, the chelating agent and the proteolytic enzyme are screened to form a polymer membrane on a target surface, and active molecules are embedded in the polymer membrane, so that the active molecules are controlled to be slowly released so as to avoid phytotoxicity caused by excessive penetration; a proper amount of selective proteolytic enzyme damages plant pathogenic bacteria to facilitate the absorption of bactericidal active ingredients; the principle of the formula is unique, and meanwhile, the production and processing steps are simple and the properties are stable, so that the bactericide composition is suitable for industrial production.

Description

A kind of microbicide compositions and production technology thereof
Technical field
The present invention relates to a kind of safe microbicide compositions, be specifically related to a kind of microbicide compositions and production technology thereof.
Background technology
Along with organic farming, the development of industrialized agriculture, people are more and more higher to the attention degree of food security, how to improve the service efficiency of agricultural chemicals, reduce the usage amount of agricultural chemicals, and then to reduce agricultural chemicals be one of top priority of current pesticide technology worker agricultural product residual.Water base property water dispersible granules is stipulated to be subject to society in Environmental security and is paid much attention to strict today.In recent years, water baseization of China agricultural chemicals has had certain development.Existing market is generally the aqueous suspension of Difenoconazole and Fluoxastrobin, yet Fluoxastrobin can not with insecticide emulsifiable concentrate, especially organic phosphates missible oil is mixed, can not be mixed with silicone based safener, its reason is that organic solvent can dissolve the part Fluoxastrobin, organosilicon and other synergist permeability and plate-out ability are excessively strong, cause crop to absorb molecular state Fluoxastrobin medicament excessive, thereby cause poisoning, this certainly will cause the contradiction on crop pest management of product: in order to strengthen control efficiency, just need to strengthen the absorption of pathogene to medicament, can cause poisoning to crop again but the medicament absorption is excessive.In order to improve safety, the enhancing bactericidal effect to crop, reduce packing cost, by studying the mechanism of action of its combination, the invention provides a kind of formulation principle and explained hereafter microbicide compositions.
difenoconazole:adopted name: Difenoconazole (Difenoconazole), Difenoconazole; Chemical name: suitable, the chloro-4-[4-methyl-2-1H-1 of trans-3-, 2,4-triazol-1-yl methyl)-1, the mute pentane of 3-bis--2-yl) phenyl 4-chlorphenyl ether (suitable, inverse proportion is about 45:55)
Figure 848548DEST_PATH_IMAGE001
Physicochemical property: these product are colorless solid, 76 ℃ of fusing points, 220 ℃/4Pa of boiling point, vapour pressure 120nPa(20 ℃).Dissolubility (20 ℃): water 3.3 mg/litre are soluble in organic solvent.K (ow) 20000(is by anti-phase TLC).≤ 300 ℃ stable, and in soil, mobility is little, slow degradation.
Toxicity: rat acute LD50 of passing through mouth 1453 mg/kg, rabbit is acute is greater than 2010 mg/kg through skin LD50.Rabbit skin and eyes are had to spread effect, to cavy without allergic.Rat acute sucks LC50(4 hour) be greater than 0.045 mg/litre air, wild duck acute oral LD50 is greater than 2150 mg/kg.(fish work) trout LC50(96 hour) 0.8 mg/litre.Nontoxic to honeybee.
The mode of action: interior absorption sterilization, tool protection and therapeutic action.
Products characteristics: Difenoconazole is that in triazole bactericidal agent, safety is higher, is widely used in the crops such as fruit tree, vegetables, effectively prevents and treats scab, anthrachose of grape, white rot, spot defoliation, powdery mildew, brown spot, rust, yellow rust, head blight etc.
Prevent and kill off object: fungicidal spectrum is wide, and leaf surface treatment or seed treatment can improve output and the guaranteed quality of crop.To Ascomycetes, Basidiomycetes and comprise Alternaria, Ascochyta, the mould genus of tail spore, Colletotrichum, ball Cuo Pseudomonas, Phoma, Ramularia, Septoria, Venturia partly know disease, Erysiphaceae, Uredinales and some Seedborne pathogen have lasting protection and therapeutic action.Also fine to bitter rot or anthracnose of grape, white rot effect.
The mechanism of action: Difenoconazole has protection, treatment and systemic activity, is sterol demethylation inhibitor, suppresses the biosynthesis of cell wall sterol, stops the growth of fungi.
fluoxastrobin: chemical name (E)-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-the 3-methoxy-methyl acrylate; Amici reaches; (E)-2-{2-[6 (2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl }-the 3-methoxy-methyl acrylate.
English name: Azoxystrobin
CAS:131860-33-8, molecular formula: C22H17N3O5 molecular weight: 403.3875
Physicochemical property: relative density: 1.34g/cm3, dissolubility: 20 ℃ of 6mg/L at, vapour pressure 1.1 * 10 -7mPa(20 ℃), sterling is white crystalline solid, solubility: be slightly soluble in hexane, n-octyl alcohol, be dissolved in methyl alcohol, toluene, acetone, be soluble in ethyl acetate, acetonitrile, carrene, boiling point: 581.3 ℃, in the aqueous solution, Photolysis Half is 2 weeks, to hydrolysis-stable.Former medicine is off-white color to yellow solid (content is higher, fineness better, color more shallow).
Purposes: this product is methoxy acrylate (Strobilurin) series bactericidal agent, efficiently, wide spectrum, nearly all mycota (Ascomycotina, Basidiomycotina, Mastigomycotina and Deuteromycotina) disease is all had to good activity as powdery mildew, rust, glume blight, net blotch, downy mildew, rice blast etc.Can be used for cauline leaf spraying, seed treatment, also can carry out soil treatment, be mainly used in cereal, paddy rice, peanut, grape, potato, fruit tree, vegetables, coffee, lawn etc.
Summary of the invention
Should increase the absorption of strong pathogene to medicament in order to solve existing bactericide, prevent that again medicament from absorbing the excessive deficiency that crop is caused to poisoning., the invention provides its production technology of a kind of microbicide compositions.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A kind of microbicide compositions, it is characterized in that: described microbicide compositions by mass percentage, comprises following component: 10~40% Difenoconazoles, 10~40% Fluoxastrobins, 1~6% dispersant, 1~3% wetting agent, 0.5~2% chelating agent, 1~5% structural agent, 3~5% humectant, 0.05~0.1% proteolytic enzyme, surplus is filler.
Described microbicide compositions is characterized in that: described proteolytic enzyme is the optional water proteolytic enzyme, is specially serine protease.
Described microbicide compositions is characterized in that: described chelating agent is one or several compositions in ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, sodium pyrophosphate and sodium phosphate trimer.
Described microbicide compositions is characterized in that: one or several compositions that described structural agent is fatty alcohol, corn starch, sucrose, ethylene glycol monobutyl ether.
Described microbicide compositions is characterized in that: described humectant is one or several compositions in glycerine, ethylene glycol, propane diols.
Described microbicide compositions is characterized in that: described dispersant is not one or several compositions in quality sodium sulfonate, naphthalene sulfonate, di-2-ethylhexylphosphine oxide bitter edible plant sodium sulfonate, modified polycarboxylic acid salt, polycarboxylate of Tea Saponin, desugar.
Described microbicide compositions is characterized in that: described wetting agent is lauryl sodium sulfate, sodium hexadecyl sulfate, neopelex, polyethylene glycol, fatty alcohol-polyoxyethylene ether, a kind of or several middle composition in alkylphenol polyoxyethylene.
Described microbicide compositions is characterized in that: described filler is white carbon, water-washed kaoline, winnofil, one or more compositions in sericite.
A kind of production technology of described microbicide compositions is characterized in that: weighing 10~40% Difenoconazoles in proportion, 10~40% Fluoxastrobins, 1~6% dispersant, 1~3% wetting agent, 0.5~2% chelating agent, 1~5% structural agent, 3~5% humectant, 0.05~0.1% proteolytic enzyme, surplus is that filler makes it to mix, air-flow crushing to 20~30 micron, the water that adds again total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.And the bake out temperature in Granulation Equipments is less than 60 ℃, avoid the serine stretch protein enzyme deactivation.
Advantage of the present invention is: the present invention introduces new formula theory by the mechanism of action of research bactericide, special structural agent, chelating agent and proteolytic enzyme have been screened, form polymeric membrane on the target surface, the active matter molecule is embedded in polymeric membrane, control its slow release, avoid causing by force poisoning owing to penetrating; Optionally proteolytic enzyme causes damage to phytopathogen in right amount, is conducive to the absorption of fungicide active ingredient, this formulation principle uniqueness, and production and processing simultaneously is simple, and stable in properties is applicable to suitability for industrialized production production.
embodiment:
Example 1
Weighing 10% Difenoconazole in proportion, 10% Fluoxastrobin, 6% LAB-3 type modified polycarboxylic acid salt, 2% lauryl sodium sulfate, 0.5% ethylenediamine tetra-acetic acid, 2% C10 alcohol, 3% glycerine, 0.05% serine protease, 10% white carbon, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, the water that adds again total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 2
Weighing 10% Difenoconazole in proportion, 40% Fluoxastrobin, 1% T36 type modified polycarboxylic acid salt, 2% neopelex, 1% ethylenediamine tetra-acetic acid, 2% C15 alcohol, 3% glycerine, 0.05% serine protease, 10% white carbon, 5% winnofil, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, then add the water of total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 3
Weighing 20% Difenoconazole in proportion, 40% Fluoxastrobin, 6% Tea Saponin, 3% sodium hexadecyl sulfate, 1% disodium ethylene diamine tetraacetate, 2% C15 alcohol, 3% ethylene glycol, 0.1% serine protease, 5% white carbon, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, the water that adds again total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 4
Weighing 20% Difenoconazole in proportion, 40% Fluoxastrobin, 3% T36 modified polycarboxylic acid salt, 3% polyethylene glycol, 1% disodium ethylene diamine tetraacetate, 2% C15 alcohol, 3% ethylene glycol, 0.1% serine protease, 5% white carbon, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, the water that adds again total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 5
Weighing 40% Difenoconazole in proportion, 40% Fluoxastrobin, 6% LAB-3 type modified polycarboxylic acid salt, 2% AEO5 type fatty alcohol-polyoxyethylene ether, 1% disodium ethylene diamine tetraacetate, 5% corn starch, 5% propane diols, 0.1% serine protease, 0.5% white carbon, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, the water that adds again total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 6
Weighing 30% Difenoconazole in proportion, 40% Fluoxastrobin, 5% R85A type desugar is the quality sodium sulfonate not, 2% sodium hexadecyl sulfate, 1% disodium ethylene diamine tetraacetate, 5% corn starch, 5% propane diols, 0.1% serine protease, 5% white carbon, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, the water that adds again total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 7
Weighing 20% Difenoconazole in proportion, 40% Fluoxastrobin, 4%T2700 type modified polycarboxylic acid salt, 2% lauryl sodium sulfate, 2% disodium ethylene diamine tetraacetate, 1% sodium pyrophosphate, 5% corn starch, 4% glycerine, 0.06% serine protease, 5% sericite, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, the water that adds again total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 8
Weighing 25% Difenoconazole in proportion, 40% Fluoxastrobin, 6% D500 type naphthalene sulfonate, 2% NP8.5 type alkylphenol polyoxyethylene, 1% tetrasodium ethylenediamine tetraacetate, 1% sodium pyrophosphate, 3% sucrose, 3% glycerine, 0.08% serine protease, 3% white carbon, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, then add the water of total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 9
Weighing 25% Difenoconazole in proportion, 40% Fluoxastrobin, 6% di-2-ethylhexylphosphine oxide bitter edible plant sodium sulfonate, 2% lauryl sodium sulfate, 1% tetrasodium ethylenediamine tetraacetate, 1% sodium pyrophosphate, 3% sucrose, 3% glycerine, 0.08% serine protease, 3% white carbon, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, then add the water of total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 10
Weighing 15% Difenoconazole in proportion, 40% Fluoxastrobin, 2%SC213,3% lauryl sodium sulfate, 1% sodium pyrophosphate, 3% ethylene glycol monobutyl ether, 3% glycerine, 0.08% serine protease, 3% white carbon, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, the water that adds again total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 11
Weighing 40% Difenoconazole in proportion, 25% Fluoxastrobin, 6%T2700,2% lauryl sodium sulfate, 1% sodium phosphate trimer, 3% ethylene glycol monobutyl ether, 3% glycerine, 0.08% serine protease, 3% white carbon, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, the water that adds again total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 12
Weighing 40% Difenoconazole in proportion, 20% Fluoxastrobin, 6%T36,1% lauryl sodium sulfate, 1% disodium ethylene diamine tetraacetate, 3% ethylene glycol monobutyl ether, 3% glycerine, 0.05% serine protease, 3% white carbon, surplus is that water-washed kaoline makes it to mix, air-flow crushing to 20~30 micron, then add the water of total amount 15~18%, select conventional Granulation Equipments to make described microbicide compositions.
test of pesticide effectiveness part:
Example of the present invention is the method that adopts Toxicity Determination and field trial to combine.First by Toxicity Determination, the 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 be summation action, SR>1.5 be synergistic effect, then this basic going up, then carry out field control effectiveness test.
, Toxicity Determination
Test method: after indicating definite effective inhibition concentration scope of each medicament, medicament is set 5 dosage according to active constituent content and is processed, and establishes the clear water contrast.Carry out with reference to " farm-chemical indoor determination experiment criterion bactericide ", adopt the mycelial growth rate method to measure the virulence of medicament to crop pathogens.Measure colony diameter by the right-angled intersection method after 72h, calculate and respectively process net growth, mycelial growth inhibition rate.
Through amount of growth (mm)=measurement colony diameter-5
Figure 218742DEST_PATH_IMAGE002
Mycelial growth inhibition rate is converted into to probability to (y), and liquor strength (ug/ml) is converted to logarithm value (x), with method of least squares, tries to achieve virulence regression equation (y=a+bx), and calculates thus the EC of every kind of medicament 50value.Calculate the different proportioning synergy ratio (SR) of two kinds of medicaments according to the Wadley method, SR<0.5 is antagonism simultaneously, and 0.5≤SR≤1.5 are summation action, and SR>1.5 are synergistic effect, and computing formula is as follows:
Figure 114017DEST_PATH_IMAGE003
Figure 257554DEST_PATH_IMAGE004
?
Figure 889261DEST_PATH_IMAGE004
Wherein: a, b are respectively active matter A and B shared ratio in component;
A is Difenoconazole, and B is Fluoxastrobin;
Toxicity test result of the present invention:
Figure 344087DEST_PATH_IMAGE006
As shown in Table 1, Difenoconazole and azoxystrobin compound preparation show in control cucumber downy mildew toxicity test data, and when Difenoconazole: during Fluoxastrobin=2:1, its virulence coefficient is the highest.The synergy ratio SR of example 2,5,6,8,9,11,12 all is greater than 1.5, illustrates that this is combined in the aforementioned proportion combination is all to show as synergy, and the similar composite preparation in the obvious high market of the composition synergic ratio of this invention.
, field control effectiveness test
The pilot survey method: according to test number, totally 14 process, each processes 2 repetitions, and the Gong28Ge community and is observed after dispenser for the second time.
2.1 in experiment, the example medicament all has the applicant to research and develop, contrast medicament 37% Difenoconazole WDG(Gansu China real agricultural science and technology Co., Ltd), 250 grams per liter Fluoxastrobin SC(Hunan Dafang Nonghua Co., Ltd produce), 125g/L Difenoconazole+200g/L Fluoxastrobin SC (Zhejiang Boshida Crop Technology Co., Ltd.).Application example Difenoconazole and the azoxystrobin water dispersible granule control watermelon anthrax test of pesticide effectiveness.
This experimental establishment, in Pu Shi village, Weinan City Pucheng County Long Yang town, Shaanxi Province, is investigated the watermelon anthrax state of an illness before medicine, with the first phase dispenser of state of an illness initial stage, once, dispenser is 2 times altogether in dispenser in every 10 days.Within the 7th day, 14 days, 15 days after dispenser for the second time, investigate respectively disease index and calculate imitation.Result of the test is in Table 2.
Figure 494576DEST_PATH_IMAGE007
As can be seen from Table 2, after Difenoconazole and azoxystrobin compound, can effectively prevent and treat watermelon anthrax, watermelon blight, watermelon powdery mildew also be had to good preventive effect simultaneously, control efficiency all is better than the preventive effect of single dose, and the preventive effect phase is long.In the test scope of medication, the target crop is had no adverse effects.
2.2 in experiment, the example medicament all has the applicant to research and develop, contrast medicament 37% Difenoconazole WDG(Gansu China real agricultural science and technology Co., Ltd), 250 grams per liter Fluoxastrobin SC(Hunan Dafang Nonghua Co., Ltd produce), 125g/L Difenoconazole+200g/L Fluoxastrobin SC (Zhejiang Boshida Crop Technology Co., Ltd.).Application example Difenoconazole and azoxystrobin water dispersible granule are prevented and treated the downy mildew of garpe test of pesticide effectiveness.
This experimental establishment, in the Weinan City Pucheng County halogen Yanghu Lake, Shaanxi Province, is investigated the downy mildew of garpe state of an illness before medicine, with the first phase dispenser of state of an illness initial stage, once, dispenser is 2 times altogether in dispenser in every 10 days.Within the 7th day, 14 days, 15 days after dispenser for the second time, investigate respectively disease index and calculate imitation.Result of the test is in Table 3
Figure 777528DEST_PATH_IMAGE008
3, conclusion
A large amount of exploitations and use along with various pharmaceutical preparations, phytopathogen is also more and more outstanding to the susceptibility decline problem of bactericide, main cause has: use single medicament in the long-term continuous several times of the same area, improving constantly of same medicament working concentration, accelerated the drug-fast generation of germ.Under action of agricultural chemicals of the same race, can induce on the one hand pathogen to produce variation, new anti-medicine type appears; 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, thereby affects the result of use of bactericide.Above-mentioned indoor and outdoors field control effectiveness test data declaration, the Difenoconazole of pbz polymer film forming agent of the present invention and serine protease and Fluoxastrobin water dispersion granule, use safety, can not cause poisoning by controlling object, in drug effect than the Difenoconazole of identical component, Fluoxastrobin single dose, Difenoconazole and Fluoxastrobin SC complex preparation virulence coefficient and preventive effect obviously will be got well, experimental results show that formulation principle uniqueness of the present invention, combination rationally, production and processing technology is simple simultaneously, has obvious economical, societal benefits.

Claims (9)

1. a microbicide compositions, it is characterized in that: described microbicide compositions by mass percentage, comprises following component: 10~40% Difenoconazoles, 10~40% Fluoxastrobins, 1~6% dispersant, 1~3% wetting agent, 0.5~2% chelating agent, 1~5% structural agent, 3~5% humectant, 0.05~0.1% proteolytic enzyme, surplus is filler.
2. microbicide compositions according to claim 1, it is characterized in that: described proteolytic enzyme is the optional water proteolytic enzyme.
3. microbicide compositions according to claim 1, it is characterized in that: described chelating agent is one or several compositions in ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, sodium pyrophosphate and sodium phosphate trimer.
4. microbicide compositions according to claim 1, is characterized in that: one or several compositions that described structural agent is fatty alcohol, corn starch, sucrose, ethylene glycol monobutyl ether.
5. microbicide compositions according to claim 1, it is characterized in that: described humectant is one or several compositions in glycerine, ethylene glycol, propane diols.
6. microbicide compositions according to claim 1 is characterized in that: described dispersant is not one or several compositions in quality sodium sulfonate, naphthalene sulfonate, di-2-ethylhexylphosphine oxide bitter edible plant sodium sulfonate, modified polycarboxylic acid salt, polycarboxylate of Tea Saponin, desugar.
7. microbicide compositions according to claim 1, it is characterized in that: described wetting agent is lauryl sodium sulfate, sodium hexadecyl sulfate, neopelex, polyethylene glycol, fatty alcohol-polyoxyethylene ether, a kind of or several middle composition in alkylphenol polyoxyethylene.
8. microbicide compositions according to claim 1, it is characterized in that: described filler is white carbon, water-washed kaoline, winnofil, one or more compositions in sericite.
9. the production technology of a microbicide compositions according to claim 1, it is characterized in that: weighing 10~40% Difenoconazoles in proportion, 10~40% Fluoxastrobins, 1~6% dispersant, 1~3% wetting agent, 0.5~2% chelating agent, 1~5% structural agent, 3~5% humectant, 0.05~0.1% proteolytic enzyme, surplus is that filler makes it to mix, air-flow crushing to 20~30 micron, the water that adds again total amount 15~18%, select Granulation Equipments to make described microbicide compositions, and the bake out temperature in Granulation Equipments is less than 60 ℃.
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WO2016000671A1 (en) 2014-07-03 2016-01-07 Biopract Gmbh Method for prophylaxis of infections in crops and ornamentals, preferably in viticulture, and in woody plants
AU2015283359B2 (en) * 2014-07-03 2019-07-04 Biopract Gmbh Method for prophylaxis of infections in crops and ornamentals, preferably in viticulture, and in woody plants
US10426171B2 (en) 2014-07-03 2019-10-01 Biopract Gmbh Methods for prophylaxis of infections in crops and ornamentals, preferably in viticulture, and in woody plants
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US12004513B2 (en) 2014-07-03 2024-06-11 Biopract Gmbh Method for prophylaxis of infections in crops and ornamentals, preferably in viticulture, and in woody plants
CN105746513A (en) * 2016-03-24 2016-07-13 朱永明 Compound for killing harmful underwater organisms and preparation method of compound
CN105746513B (en) * 2016-03-24 2018-06-19 朱永明 It is a kind of for compound of dissipation bottom harmful organism and preparation method thereof
CN107027768A (en) * 2017-04-28 2017-08-11 山东沃森农业科技有限公司 A kind of bactericide for being used to prevent and treat dendrobium candidum southern blight
CN111771877A (en) * 2020-07-16 2020-10-16 山西珍草康生物科技有限公司 Quick-acting environment-friendly agricultural insecticide and acaricide for killing high-resistance pests and application thereof
CN114831128A (en) * 2022-04-06 2022-08-02 安徽华辰检测技术研究院有限公司 Pesticide preparation containing difenoconazole and azoxystrobin
CN114831128B (en) * 2022-04-06 2024-06-07 安徽华辰检测技术研究院有限公司 Pesticide preparation containing difenoconazole and azoxystrobin

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