CN103461383B - Bactericide composition and production process thereof - Google Patents
Bactericide composition and production process thereof Download PDFInfo
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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
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, 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 base property water dispersible granules 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.Existing market is generally the aqueous suspension of Difenoconazole and Fluoxastrobin, but Fluoxastrobin can not with insecticide emulsifiable concentrate, especially organic phosphates missible oil is used with, can not be mixed with silicone based safener, its reason is that organic solvent can dissolve part Fluoxastrobin, organosilicon and other synergist permeability and plate-out ability excessively strong, crop is caused to absorb molecular state Fluoxastrobin medicament excessive, thus cause poisoning, this certainly will cause the contradiction on product crop pest management: in order to strengthen control efficiency, just need to strengthen pathogene to the absorption of medicament, but medicament absorption is excessive can cause poisoning to crop again.In order to improve safety to crop, strengthen bactericidal effect, reducing 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, and the chloro-4-of trans-3-[4-methyl-2-1H-1,2,4-triazol-1-yl methyl)-1,3-bis-mute pentane-2-base) phenyl 4-chlorphenyl ether (suitable, inverse proportion is about 45:55)
Physicochemical property: these product are colorless solid, fusing point 76 DEG C, boiling point 220 DEG C/4Pa, vapour pressure 120nPa(20 DEG C).Dissolubility (20 DEG C): water 3.3 mg/litre, is soluble in organic solvent.K (ow) 20000(is by anti-phase TLC).Stablize for≤300 DEG C, in soil, mobility is little, slowly degrades.
Toxicity: rat acute LD50 of passing through mouth 1453 mg/kg, rabbit is acute is greater than 2010 mg/kg through skin LD50.Spread effect is had, to cavy without allergic to rabbit skin and eyes.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 crop 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 inhibitors, the biosynthesis of T suppression cell wall sterol stops the growth of fungi.
fluoxastrobin: chemical name (E)-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate; Amici reaches; (E)-2-{2-[6 (2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl }-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: 6mg/L at 20 DEG C, vapour pressure 1.1 × 10
-7mPa(20 DEG C), 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 DEG C, 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, all have good activity to nearly all mycota (Ascomycotina, Basidiomycotina, Mastigomycotina and Deuteromycotina) disease such 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
The absorption of strong pathogene to medicament should be increased in order to solve existing bactericide, preventing medicament from absorbing excessive deficiency crop being caused to poisoning again., 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, comprise 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 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: described structural agent is one or several compositions of 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 Tea Saponin, desugar one or several compositions not in quality sodium sulfonate, naphthalene sulfonate, di-2-ethylhexylphosphine oxide bitter edible plant sodium sulfonate, modified polycarboxylic acid salt, polycarboxylate.
Described microbicide compositions, is characterized in that: described wetting agent is lauryl sodium sulfate, sodium hexadecyl sulfate, neopelex, polyethylene glycol, fatty alcohol-polyoxyethylene ether, the one in alkylphenol polyoxyethylene or several middle composition.
Described microbicide compositions, is characterized in that: described filler is white carbon, water-washed kaoline, winnofil, one or more compositions in sericite.
A production technology for described microbicide compositions, is characterized in that: weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, add the water of total amount 15 ~ 18% again, select conventional Granulation Equipments to make described microbicide compositions.And the bake out temperature in Granulation Equipments is less than 60 DEG C, avoid serine stretch protein enzyme deactivation.
Advantage of the present invention is: the present invention introduces new formula theory by the mechanism of action studying bactericide, special structural agent, chelating agent and proteolytic enzyme are screened, polymeric membrane is formed at target surface, active matter molecule is embedded in polymeric membrane, control its slow releasing, avoid causing poisoning by force owing to penetrating; Appropriate optionally proteolytic enzyme causes damage to phytopathogen, is conducive to the absorption of fungicide active ingredient, and this formulation principle is unique, and production and processing is simultaneously simple, stable in properties, is applicable to suitability for industrialized production and produces.
embodiment:
Example 1
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, add the water of total amount 15 ~ 18% again, select conventional Granulation Equipments to make described microbicide compositions.
Example 2
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, then the water adding total amount 15 ~ 18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 3
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, add the water of total amount 15 ~ 18% again, select conventional Granulation Equipments to make described microbicide compositions.
Example 4
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, add the water of total amount 15 ~ 18% again, select conventional Granulation Equipments to make described microbicide compositions.
Example 5
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, add the water of total amount 15 ~ 18% again, select conventional Granulation Equipments to make described microbicide compositions.
Example 6
Weigh 30% Difenoconazole in proportion, 40% Fluoxastrobin, 5% R85A type desugar not quality sodium sulfonate, 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 mixing, air-flow crushing to 20 ~ 30 micron, add the water of total amount 15 ~ 18% again, select conventional Granulation Equipments to make described microbicide compositions.
Example 7
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, add the water of total amount 15 ~ 18% again, select conventional Granulation Equipments to make described microbicide compositions.
Example 8
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, then the water adding total amount 15 ~ 18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 9
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, then the water adding total amount 15 ~ 18%, select conventional Granulation Equipments to make described microbicide compositions.
Example 10
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, add the water of total amount 15 ~ 18% again, select conventional Granulation Equipments to make described microbicide compositions.
Example 11
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, add the water of total amount 15 ~ 18% again, select conventional Granulation Equipments to make described microbicide compositions.
Example 12
Weigh 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 mixing, air-flow crushing to 20 ~ 30 micron, then the water adding 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 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 Difenoconazole, and B is Fluoxastrobin;
Toxicity test result of the present invention:
As shown in Table 1, Difenoconazole and azoxystrobin compound preparation show, when Difenoconazole in control cucumber downy mildew toxicity test data: during Fluoxastrobin=2:1, its virulence coefficient is the highest.The synergy ratio SR of example 2,5,6,8,9,11,12 is all greater than 1.5, 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.
, field control effectiveness test
Pilot survey method: according to test number totally 14 process, each process 2 repetition, Gong28Ge community, executes observation post administration with second time.
In 2.1 experiments, example medicament all has applicant to research and develop, contrast medicament 37% Difenoconazole WDG(Gansu Hua Shi 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 is in Pu Shi village, Weinan City Pucheng County Long Yang town, Shaanxi Province, and the investigation watermelon anthrax state of an illness before medicine, with the first phase dispenser of state of an illness initial stage, dispenser in every 10 days once, is total to dispenser 2 times.Within the 7th day, 14 days, 15 days after second time dispenser, investigate disease index respectively and calculate imitation.Result of the test is in table 2.
As can be seen from Table 2, effectively can prevent and treat watermelon anthrax after Difenoconazole and azoxystrobin compound, also have good preventive effect to watermelon blight, watermelon powdery mildew, control efficiency is all better than the preventive effect of single dose simultaneously, and the preventive effect phase is long.In test scope of medication, target crop is had no adverse effects.
In 2.2 experiments, example medicament all has applicant to research and develop, contrast medicament 37% Difenoconazole WDG(Gansu Hua Shi 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 prevent and treat the downy mildew of garpe test of pesticide effectiveness.
This experimental establishment is in the Weinan City Pucheng County halogen Yanghu Lake, Shaanxi Province, and the investigation downy mildew of garpe state of an illness before medicine, with the first phase dispenser of state of an illness initial stage, dispenser in every 10 days once, is total to dispenser 2 times.Within the 7th day, 14 days, 15 days after second time dispenser, investigate disease index respectively and calculate imitation.Result of the test is in table 3
3, 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, thus affects the result of use of bactericide.The explanation of above-mentioned indoor and outdoors field control effectiveness test data, the Difenoconazole of pbz polymer film forming agent of the present invention and serine protease and Fluoxastrobin water dispersion granule, use safety, poisoning can not be caused by controlling object, in Difenoconazole, the Fluoxastrobin single dose of drug effect than identical component, Difenoconazole and Fluoxastrobin SC complex preparation virulence coefficient and preventive effect obviously will be got well, experiment proves that formulation principle of the present invention is unique, combination rationally, production and processing technology is simple simultaneously, has obvious economical, societal benefits.
Claims (8)
1. a microbicide compositions, it is characterized in that: described microbicide compositions, by mass percentage, comprise following component: 10 ~ 40% Difenoconazoles, 10 ~ 40% Fluoxastrobins, 1 ~ 6% dispersant, 1 ~ 3% wetting agent, 0.5 ~ 2% chelating agent, 1 ~ 5% structural agent, 35% humectant, 0.05 ~ 0.1% serine protease, surplus is filler.
2. microbicide compositions according to claim 1, 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.
3. microbicide compositions according to claim 1, is characterized in that: described structural agent is one or several compositions of fatty alcohol, corn starch, sucrose, ethylene glycol monobutyl ether.
4. microbicide compositions according to claim 1, is characterized in that: described humectant is one or several compositions in glycerine, ethylene glycol, propane diols.
5. microbicide compositions according to claim 1, is characterized in that: described dispersant is one or several compositions in Tea Saponin, desugar sodium lignin sulfonate, naphthalene sulfonate, modified polycarboxylic acid salt, polycarboxylate.
6. microbicide compositions according to claim 1, is characterized in that: described wetting agent is lauryl sodium sulfate, sodium hexadecyl sulfate, neopelex, polyethylene glycol, fatty alcohol-polyoxyethylene ether, the one in alkylphenol polyoxyethylene or several middle composition.
7. microbicide compositions according to claim 1, is characterized in that: described filler is white carbon, water-washed kaoline, winnofil, one or more compositions in sericite.
8. the production technology of a microbicide compositions according to claim 1, it is characterized in that: weigh 10 ~ 40% Difenoconazoles in proportion, 10 ~ 40% Fluoxastrobins, 1 ~ 6% dispersant, 1 ~ 3% wetting agent, 0.5 ~ 2% chelating agent, 1 ~ 5% structural agent, 35% humectant, 0.05 ~ 0.1% serine protease, surplus is that filler makes it mixing, air-flow crushing to 20 ~ 30 micron, add the water of 15 ~ 18%, select Granulation Equipments to make described microbicide compositions, and the bake out temperature in Granulation Equipments is less than 60 DEG C.
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| 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 |
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Free format text: CORRECT: INVENTOR; FROM: ZHANG QIANG QIN GUANGJUN WU ZHIGUO TO: ZHANG QIANG LIU JIE WU ZHIGUO QIN GUANGJUN SHU JUAN |
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| C53 | Correction of patent for invention or patent application | ||
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Address after: 715500, Weinan County, Shaanxi City, Pucheng province Chen Zhen East Village (Agricultural Chemical Industry Park) Applicant after: Shaanxi Pucheng Meierguo Agrochemical Co.,Ltd. Address before: Weinan City, Shaanxi Province town of 715500 Dong Xiang, Pucheng County, No. 3 Applicant before: Shaanxi Pucheng Meierguo Agrochemical Co.,Ltd. |
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| C14 | Grant of patent or utility model | ||
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