CN105284828A - Copper abietate and zinc thiazole-containing bactericidal composition - Google Patents
Copper abietate and zinc thiazole-containing bactericidal composition Download PDFInfo
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Abstract
The invention discloses a copper abietate and zinc thiazole-containing bactericidal composition. Effective components, namely copper abietate and zinc thiazole, of the bactericidal composition are compounded, and the rest comprises auxiliary components, wherein the mass ratio of the effective components, namely copper abietate to zinc thiazole, in the pesticide composition is (1-50): (50-1); the mass percentage of the effective components, namely copper abietate and zinc thiazole, in the preparation is 1 to 80 percent, and the rest comprises pesticidally available and acceptable auxiliary components. The dosage form of the pesticide composition can be missible oil, a suspending agent, wettable powder, water dispersible granules, emulsion in water, granules and microcapsules, and the pesticide composition is mainly used for preventing and controlling rot of fruit trees, alternaria leaf spot, rice blast, soybean root rot, cucurbits fusarium wilt, cotton verticillium wilt, jujube rust, grapevine white rot, panaxpseudoginseng black spot, tea leaf tea gall, forest rot, citrus canker, bleeding disease, leaf cast, forest seedling blight, erwinia aroideae, pseudomonas lachrymans, bacterial rice leaf blight, apple ring spot viruses, fusarium asiaticum and the like.
Description
Technical field
The present invention relates to technical field of pesticide combination, particularly relate to a kind of bactericidal composition containing copper rosinate and zinc thiazole.
Background technology
Copper rosinate is a kind of new copper preparation sterilization pesticide of high-efficiency low-toxicity wide spectrum; there is lasting period length, new feature easy to use; overcome many shortcomings of former bordeaux mixture; it is the desirable bactericide replacing bordeaux mixture; and there are prevention & protection and treatment double action, can be used for the frequently seen plants disease of preventing and treating caused by multiple fungus and bacterium, have obvious stimulating growth effect to vegetables; can replace with other bactericide, spray effect is good.For preventing and treating the various vegetables diseases such as downy mildew of cucurbits, epidemic disease, scab, anthracnose, bacterial angular leaf spot, eggplant damping off, tomato late blight.
The structure of zinc thiazole is made up of two groups, and one is thiazolyl group, outer to bacterium unrestraint power at plant corpus, but be efficient therapeutic agent in plant corpus, medicament is in the pitted vessel of plant, and bacterium is subject to grievous injury, its cell wall is thinning disintegrates then, causes the death of bacterium.Two is zinc ions, has not only antifungal but also Bactericidal effect.Cation (H+, K+ etc.) on zinc ion in medicament and pathogen surface of cell membrane exchanges, and causes the protein coagulating on germ cell membrane to kill germ; Part zinc ion penetrates in pathogen cell, is combined with some enzyme, affects its activity, causes dysfunction, and germ thus exhaustion is dead.Under the acting in conjunction of two groups, kill germ more thorough, control efficiency is better, and controlling object is more extensive.
In the real process of agricultural production, using chemical agent is the most effective means of control plant pest, but is the generation of disease drug resistance by the problem that chemical control disease the most easily produces.In the chemical control of bacteriosis, years of researches are carried out both at home and abroad, although some antibacterium medicaments have started to enter practical stage, but the medicament of chemosynthesis has cycle long, the shortcoming such as cost is high, toxicity is large, environmental pollution is serious, can not meet the requirement of agricultural sustainable development far away.And long-term use single pesticidal preparations continuously high dose, easily cause the problems such as the remaining of medicament, environmental pollution and resistance to pesticide resistance fungi development.And by contrast, exploitation is efficient with research, low toxicity, low-residual composite and mixture has small investment, the lead time is short and be subject to domestic and international attention, numerous and confused increasing develops dynamics.We are on the basis of lab screening and field trial, filter out copper rosinate and zinc thiazole carries out composite, have obvious synergistic effect.And about copper rosinate and zinc thiazole composite composition pesticide and apply and there is no people at present and reported.
Summary of the invention
Based on above situation, the object of the invention is to provide a kind of new and effective composition pesticide, is mainly used in preventing and treating fruit tree putrefaction disease; Spot defoliation; Rice blast; Root rot; Cucurbits fusarium wilt; Cotton verticillium wilt; Jujube tree rust; Fruit white rot of grape; Panax pseudoginseng black spot; Tealeaves tea gall, forest rot, canker, gummosis, defoliation, woods seedling blight, dish Bacteria erwinia, avenae subsp.citrull, Xanthomonas oryzae, ring rot of apple germ, fusarium graminearum etc.
Technical scheme of the present invention is realized by following measures:
Contain a bactericidal composition for copper rosinate and zinc thiazole, active ingredient copper rosinate and the zinc thiazole two yuan of this composition pesticide are composite, and all the other are auxiliary element.In wherein said composition pesticide, the mass ratio of active ingredient copper rosinate and zinc thiazole is 1 ~ 50: 50 ~ 1, described composition pesticide of the present invention is through toxicity test experimental verification, when the mass ratio of copper rosinate and zinc thiazole is 1 ~ 20: 20 ~ 1, synergistic effect is better.
The formulations of pesticide that described composition pesticide of the present invention can be prepared are missible oil, suspending agent, wetting powder, water dispersible granules, aqueous emulsion, microemulsion, granule, microcapsule formulations.Wherein active ingredient copper rosinate and zinc thiazole gross mass in the formulation accounts for 1% ~ 80% of the whole quality of the pharmaceutical preparations, and when wherein accounting for 1%-20%, toxicity reaches good balance with residual, and cost is also lower.
The specific embodiments of the formulations of pesticide that composition pesticide of the present invention is mixed with is as follows:
Described bactericidal composition is cream preparation, and the mass fraction of component is: copper rosinate 1 ~ 20 part; Zinc thiazole 1 ~ 20 part; Conventional emulsifier 10 ~ 30 parts; Conventional solvents 20 ~ 50 parts; Conventional synergist 1 ~ 5 part.The concrete production stage of this cream preparation be first active ingredient copper rosinate and zinc thiazole are added dissolve completely in solvent after add emulsifier again, synergist becomes transparent and homogeneous oily liquids after stirring, filling, namely can be made into the cream preparation of the present composition.
Described bactericidal composition is suspending agent, and the mass fraction of component is: copper rosinate 1 ~ 20 part; Zinc thiazole 1 ~ 20 part; Dispersant 5 ~ 20 parts; Antifreezing agent 1 ~ 5 part; Thickener 0.1 ~ 2 part; Defoamer 0.1 ~ 0.8 part; Penetrating agent 0 ~ 10 part; PH value regulator 0.1 ~ 5 part; Water, surplus.The concrete production stage of this suspending agent is for first to mix other auxiliary agents, mix through high speed shear, add active ingredient copper rosinate and zinc thiazole, abrading-ball 2 ~ 3 hours in ball crusher, make a diameter all at below 5mm, namely can be made into the aqueous suspension formulations of the present composition.
Described bactericidal composition is wetting powder, and the mass fraction of component is: copper rosinate 1 ~ 20 part; Zinc thiazole 1 ~ 20 part; Dispersant 3 ~ 10 parts; Wetting agent 1 ~ 5 part; Filler, surplus.The concrete production stage of this wetting powder is: mixed with zinc thiazole and dispersant, wetting agent and filler by active ingredient copper rosinate by above-mentioned formula, uniform stirring in stirred tank, mixing after airslide disintegrating mill, namely can be made into the wetting powder of the present composition.
Described bactericidal composition is water dispersible granules, and the mass fraction of component is: copper rosinate 1 ~ 20 part; Zinc thiazole 1 ~ 20 part; Dispersant 3 ~ 10 parts; Wetting agent 1 ~ 10 part; Disintegrant 1 ~ 5 part; Filler, surplus.The concrete production stage of this water dispersible granules is: mixed with zinc thiazole and dispersant, wetting agent, disintegrant and filler by active ingredient copper rosinate by above-mentioned formula, pulverize with micro jet, through mediating, then add in fluidized-bed granulation dryer and to carry out after granulation, drying, screening, through sample analysis, namely can be made into the water dispersible granules of the present composition.
Described bactericidal composition is aqueous emulsion, and the mass fraction of component is: copper rosinate 1 ~ 20 part; Zinc thiazole 1 ~ 20 part; Emulsifier 3 ~ 30 parts; Solvent 5 ~ 15 parts; Stabilizing agent 2 ~ 15 parts; Antifreezing agent 1 ~ 5 part; Defoamer 0.1 ~ 8 part; Thickener 0.2 ~ 2 part; Water, surplus.The concrete production stage of this aqueous emulsion is: first copper rosinate and zinc thiazole, solvent and emulsifier, cosolvent are added together, and makes to be dissolved into uniform oil phase; By part water, antifreeze, other the insecticides adjuvant such as antimicrobial mixes uniformly aqueous phase; While high-speed stirred, oil phase is added aqueous phase in a kettle., slowly add water until reach phase inversion point, open clipper and carry out high speed shear, and add remaining water, shear about half an hour, form the aqueous emulsion of oil-in-water type, namely can be made into the aqueous emulsion of the present composition.
Described bactericidal composition is microemulsion, and the mass fraction of component is: copper rosinate 1 ~ 20 part, zinc thiazole 1 ~ 20 part, emulsifier 10 ~ 30 parts, antifreezing agent 1 ~ 8 part, stabilizing agent 0.5 ~ 10 part, Conventional solvents cosolvent 20 ~ 50 parts.Copper rosinate and zinc thiazole cosolvent are dissolved completely, then add other compositions such as emulsifier, antifreezing agent stabilizing agent, Homogeneous phase mixing, finally adds water, can be made into microemulsion after fully stirring.
Described bactericidal composition is granule, and the mass fraction of component is:: copper rosinate 1 ~ 20 part, zinc thiazole 1 ~ 20 part, wetting dispersing agent 1 ~ 10 part; Thickener 0.1 ~ 5 part; Defoamer 0.1 ~ 5 part; Castor oil, surplus is supplied.Each components such as active ingredient copper rosinate and zinc thiazole, dispersant, stabilizing agent, defoamer and solvent are mixed in the ratio of filling a prescription, after putting into the grinding of sand milling still, sends into mixing in mixer for well-distribution and get product.
Described bactericidal composition is microcapsule formulations, and the mass fraction of component is:: copper rosinate 1 ~ 20 part, zinc thiazole 1 ~ 20 part, 5 ~ 20 parts, urea; 5 ~ 20 parts, formaldehyde; Emulsifying dispersant 5 ~ 20 parts; Antifreezing agent 1 ~ 5 part; Thickener 0.1 ~ 2 part; Defoamer 0.1 ~ 0.8 part; Water, surplus.Urea and formaldehyde (amount of substance ratio is about l:1.5 ~ 2.0) is added in the there-necked flask that agitating device is housed, regulate the pH value of solution to about 8 ~ 9 with sodium hydroxide solution, then be warming up to 70 ~ 80 DEG C, be obtained by reacting stable urea resin prepolymer.The former medicine getting a certain amount of copper rosinate and zinc thiazole is dissolved in cyclohexane, and adds emulsifying dispersant in the solution, with vigorous stirring, and the O/W type stable emulsion that to be made into the aqueous solution containing emulsifying dispersant be aqueous phase.Above-mentioned urea resin prepolymer is added in emulsion, adjust ph, polymerization reaction take place under acid catalysed conditions, oil phase substance is wrapped, form microcapsule granule.Slow intensification, solidification, temperature controls at 40 ~ 50 DEG C, hardening time 1h.Select to add appropriate auxiliary agent, stable microcapsule suspending agent.
Wherein above-described emulsifier is selected from calcium dodecyl benzene sulfonate and aliphatic acid polyethenoxy ether, alkylphenol polyoxyethylene sulfosuccinate, styrylphenol polyoxyethylene ether, polyoxyethylene nonylphenol ether, castor oil polyoxyethylene ether, aliphatic acid polyethenoxy base ester, any one in polyoxyethylene aliphatic alcohol ether or more than one any mixtures than composition.
Described solvent is dimethylbenzene or biodiesel, toluene, diesel oil, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, turpentine-based vegetable oil code name is ND-45, solvent naphtha, dimethyl formamide, dimethyl sulfoxide (DMSO), one or more in water equal solvent are arbitrarily than the mixture of composition.
It is LG-3, GY-D1252, GY-D1256, SNWGF-01 that described dispersant is selected from polycarboxylate code name, lignosulfonates code name is 201107,201108, alkylphenol polyoxyethylene methyl ether condensate sulfate, alkylsulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, aliphatic amine polyoxyethylene ether, one or more in fatty acid glyceride APEO.
Described wetting agent is selected from lauryl sodium sulfate, calcium dodecyl benzene sulfonate, Nekal BX, moistening bleeding agent F, alkylbenzenesulfonate polyoxyethylene triphen phosphenylic acid salt dimly, spaonin powder, silkworm excrement, one or more in soapberry powder.
Described disintegrant is selected from bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, one or more in sodium bicarbonate.
Described thickener is selected from xanthans, carboxymethyl cellulose, carboxyethyl cellulose, methylcellulose, Magnesiumaluminumsilicate, in polyvinyl alcohol one or more.
Described stabilizing agent is selected from sodium citrate, the one in resorcinol.
Described antifreezing agent is selected from ethylene glycol, propane diols, one or more in glycerine.
Described defoamer is selected from silicone oil, silicone compound, C
10-20saturated fat acid compounds, C
8-10one or more of fatty alcohol.
Described filler is selected from kaolin, diatomite, bentonite, attapulgite, white carbon, starch, one or more in precipitated calcium carbonate.
The composite bactericide that the present invention is active ingredient with copper rosinate and zinc thiazole has obvious synergistic effect, delays the drug-fast generation in key, and reduces into product cost and use cost, can be used for the improvement of resistance disease.Be mainly used in preventing and treating fruit tree putrefaction disease; Spot defoliation; Rice blast; Root rot; Cucurbits fusarium wilt; Cotton verticillium wilt; Jujube tree rust; Fruit white rot of grape; Panax pseudoginseng black spot; Tealeaves tea gall, forest rot, canker, gummosis, defoliation, woods seedling blight, dish Bacteria erwinia, avenae subsp.citrull, Xanthomonas oryzae, ring rot of apple germ, fusarium graminearum etc.
Embodiment
For making technical scheme of the present invention, object and advantage are clearly understood, the following specific embodiment of the present invention is described, but the present invention is not limited to these examples.The mode that effect experimental of the present invention adopts indoor biometrics and field trial to combine, if no special instructions, the ratio below mentioned is all ratio of quality and the number of copies.
Embodiment: copper rosinate and zinc thiazole different ratio co-toxicity are tested.
1.1 test targets
Cucumber bacterial angular leaf spot bacterium (germ bacterial classification picks up from Jimo Yi Feng town, Qingdao of Shandong province cucumber booth, obtains through the Sheng Ce laboratory separation and purification of research and development centre of Hailir Pharmaceutical Group Co., Ltd.).
1.2 test method
The female medicine of 35% copper rosinate, the female medicine of 97% zinc thiazole, is provided by Chemical Co., Ltd. Shandong Hailier.Add aqua sterilisa by purified slant tube bacterial classification, be made into former bacteria suspension, then be diluted to 107/rise bacteria suspension, for subsequent use.First be made into 1000mg/L mother liquor by after copper rosinate and the water-soluble solution of the female medicinal sterile of zinc thiazole, dilute with sterile water again during use.(unit: mg/litre)
Copper rosinate is mixed with zinc thiazole sets 5 assembly ratios altogether, and on the basis of preliminary experiment, each single dose and each proportioning establish 5 concentration process respectively, not contain the system of liquid for blank (maximum concentration with reference to chemicals treatment dilutes).Each concentration process repeats 4 times, under aseptic technique, each concentration gradient medicament is drawn 4ml successively respectively from low concentration to high concentration, add in the aseptic conical flask melted in advance containing 36ml sterilising medium, fully shake up, then pour into immediately in the culture dish of diameter 9cm, make corresponding pastille dull and stereotyped.Every ware add 107/rise bacterial suspension 200 μ l, then with after sterilizing triangular glass rod bacteria suspension in ware is pushed away even, be placed in 28 DEG C of insulating boxs and cultivate.Separately establish the process not containing medicament as blank.Each process repetition 4 times.
1.3 investigation method
Cultivate after 48 hours and culture dish is taken out, according to blank, observe bacteria colony count in each ware of each concentration.
Relative inhibition is calculated according to each process bacteria colony count:
1.4 synegism evaluation
The synergistic effect of pharmacy mix is evaluated according to the co-toxicity coefficient method (CTC) of Sun & Johnson (1960), namely CTC≤80 are antagonism, 80 < CTC < 120 are summation action, and CTC >=120 are synergistic effect.
Actual measurement toxicity index (ATI)=standard agent EC
50/ reagent agent EC
50* 100
In toxicity index * 100 mixture of theoretical toxicity index (the TTI)=medicament A of mixture the percentage composition+medicament B of A medicament toxicity index * 100 mixture in the percentage composition of B medicament
The theoretical toxicity index (TTI) * 100 of co-toxicity coefficient (CTC)=mixture actual measurement toxicity index (ATI)/mixture.
2.1 toxicity test results
Table 1 copper rosinate and zinc thiazole are to the toxicity test of cucumber bacterial angular leaf spot bacterium
As can be seen from the table, the result of the test of different proportion proportioning shows, dilute respectively in active ingredient ratio and all show stronger synergistic effect, wherein with copper rosinate: time zinc thiazole is 1:20 ~ 20:1, synergistic effect is best, suggestion carries out further field control effectiveness test to suitable proportion about 1:20 ~ 20:1 mixture preparation, to evaluate its field practical application effect.
The experimental result of the 3 field trial water prevention rice bacterial leaf blight, cucumber bacterial angular leaf spot
3, the field trial water prevention rice bacterial leaf blight
3.1.1 test method
Test is at Jimo Yi Feng town, Qingdao of Shandong province paddy base, and test kind is hybrid rice variety, and often process 4 times and repeat, every community double diagonal line investigates 5 points, five strains whole blade during investigation, and a situation arises for statistics disease.
Record occurring degree by staging, grade scale is as follows:
0 grade: anosis;
1 grade: scab heap area accounts for less than 5% of whole leaf area;
3 grades: scab heap area accounts for below the 6%-10% of whole leaf area;
5 grades: scab heap area accounts for below the 11%-20% of whole leaf area;
7 grades: scab heap area accounts for below the 21%-50% of whole leaf area;
9 grades: scab heap area accounts for more than 50% of whole leaf area.
3.1.2 control time and method
Test is investigated 4 times altogether, i.e. disease index investigation before medicine, preventive effect investigation in 7 days after the 1st medicine, 7 days and preventive effect investigation in 15 days after 2 medicines.
3.1.3 drug effect computational methods
Sick leaf rate (%)=sick number of sheets/investigate the total number of sheets × 100
Disease index=∑ (the sick number of sheets × relative level numerical value at different levels)/(investigating the total number of sheets × 9) × 100
Control efficiency (%)=(1-(before blank district medicine after disease index × treatment region medicine disease index)/(after blank district medicine before disease index × treatment region medicine disease index)) × 100.
3.1.3 poisoning investigation method
Whether after dispenser, continuous 7d estimates medicament has poisoning to crop.
3.2 result of the tests and analysis
Copper rosinate and zinc thiazole control successful higher than copper rosinate and zinc thiazole single dose with 5:1 ratio composite bactericide for bacterial blight of rice as shown in Table 2, and bactericidal effect increases progressively with the increase of dosage.According to field range estimation, within the scope of test dose, plant growth is normal, and the poisoning phenomenon to paddy rice does not all appear in each treatment agent, illustrates that it is safe to paddy rice, significant for agricultural produce, is worthy to be popularized.
3.2 field trial control cucumber bacterial angular leaf spots
3.2.1 test method
Test on Shandong Pingdu City cucumber ground, test kind is middle peasant No. 8, and often process 4 times and repeat, every community double diagonal line investigates 5 points, often some investigation 3 strain cucumber, and record occurring degree by staging, grade scale is as follows:
0 grade: anosis;
1 grade: scab heap area accounts for less than 5% of whole leaf area;
3 grades: scab heap area accounts for below the 6%-10% of whole leaf area;
5 grades: scab heap area accounts for below the 11%-20% of whole leaf area;
7 grades: scab heap area accounts for below the 21%-50% of whole leaf area;
9 grades: scab heap area accounts for more than 50% of whole leaf area.
3.2.2 control time and number of times
Test altogether investigate 4 times, before medicine radix investigation, first time medicine after 7 days, second time 7 days and medicine after within 15 days, investigate.
3.2.3 drug effect computational methods
Sick leaf rate (%)=sick number of sheets/investigate the total number of sheets × 100
Disease index=∑ (the sick number of sheets × relative level numerical value at different levels)/(investigating the total number of sheets × 9) × 100
Control efficiency (%)=(1-(before blank district medicine after disease index × treatment region medicine disease index)/(after blank district medicine before disease index × treatment region medicine disease index)) × 100.
3.2.4 poisoning investigation method
Whether after dispenser, continuous 15d estimates medicament has poisoning to crop.
3.2.5 result of the test and analysis
Table 3 different disposal prevents and treats measurement result to cucumber bacterial angular leaf spot
Shown by above field experiment, copper rosinate and zinc thiazole complex preparation are obviously better than single dose for the preventive effect of cucumber bacterial angular leaf spot, and bactericidal effect increases progressively with the increase of dosage.According to field range estimation, within the scope of test dose, plant growth is normal, occurs without poisoning situation, significant for agricultural produce, is worthy to be popularized.
In sum, the present invention contains the bactericidal composition of copper rosinate and zinc thiazole, has good control efficiency to bacterial blight of rice and cucumber bacterial angular leaf spot, and it is to Target crops safety.Complex preparation not only increases preventive effect, and expands the control to bacterium, so this compounded combination tool in production practices is of great significance.
Claims (4)
1. one kind contains the bactericidal composition of copper rosinate and zinc thiazole, it is characterized in that: the active ingredient of this composition pesticide is copper rosinate and zinc thiazole binary built, all the other are auxiliary element, and wherein the mass ratio of active ingredient copper rosinate and zinc thiazole is 1 ~ 50: 50 ~ 1.
2. composition pesticide according to claim 1, is characterized in that: copper rosinate and zinc thiazole gross weight in the formulation accounts for 1% ~ 80% of the whole quality of the pharmaceutical preparations.
3. composition pesticide according to claim 2, is characterized in that: copper rosinate and zinc thiazole gross weight in the formulation accounts for 1% ~ 50% of the whole quality of the pharmaceutical preparations.
4. the composition pesticide according to claim 1 or 2 or 3, is characterized in that: the formulation of this composition pesticide is missible oil, suspending agent, wetting powder, water dispersible granules, aqueous emulsion, microemulsion, microcapsule formulations, granule.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108184513A (en) * | 2018-03-22 | 2018-06-22 | 曾彦粤 | A kind of Citrus Huanglongbing pathogen control method |
| CN108739832A (en) * | 2018-06-22 | 2018-11-06 | 浙江新农化工股份有限公司 | Composition and its preparation containing zinc thiazole and organic copper fungicide and application |
| CN109006866A (en) * | 2018-08-09 | 2018-12-18 | 浙江新农化工股份有限公司 | Composition and its preparation and application containing zinc thiazole and Cupravit |
| CN109221178A (en) * | 2018-10-08 | 2019-01-18 | 江苏省农业科学院 | A kind of dissolving method of zinc thiazole raw medicine and application |
-
2015
- 2015-10-31 CN CN201510731310.5A patent/CN105284828A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108184513A (en) * | 2018-03-22 | 2018-06-22 | 曾彦粤 | A kind of Citrus Huanglongbing pathogen control method |
| CN108739832A (en) * | 2018-06-22 | 2018-11-06 | 浙江新农化工股份有限公司 | Composition and its preparation containing zinc thiazole and organic copper fungicide and application |
| CN109006866A (en) * | 2018-08-09 | 2018-12-18 | 浙江新农化工股份有限公司 | Composition and its preparation and application containing zinc thiazole and Cupravit |
| CN109006866B (en) * | 2018-08-09 | 2021-02-23 | 浙江新农化工股份有限公司 | Composition containing zinc thiazole and copper oxychloride as well as preparation and application thereof |
| CN109221178A (en) * | 2018-10-08 | 2019-01-18 | 江苏省农业科学院 | A kind of dissolving method of zinc thiazole raw medicine and application |
| CN109221178B (en) * | 2018-10-08 | 2021-01-26 | 江苏省农业科学院 | Dissolving method and application of zinc thiazole raw medicine |
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Application publication date: 20160203 |