CN102293200A - Sterilization composition containing zoxamide and copper pimaric acid - Google Patents
Sterilization composition containing zoxamide and copper pimaric acid Download PDFInfo
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- CN102293200A CN102293200A CN201110177966A CN201110177966A CN102293200A CN 102293200 A CN102293200 A CN 102293200A CN 201110177966 A CN201110177966 A CN 201110177966A CN 201110177966 A CN201110177966 A CN 201110177966A CN 102293200 A CN102293200 A CN 102293200A
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- zoxamide
- bactericidal composition
- copper rosinate
- copper
- sterilization composition
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Abstract
The invention relates to a sterilization composition belonging to the field of pesticide complex formulation. The sterilization composition is a complex formulation of active ingredients of zoxamide and copper pimaric acid in a weight ratio of 80:1-1-80, and a preferably weight ratio is 45:1-1:40. A total weight percentage of the active ingredients in the sterilization composition is 1-90%, preferably 1-55%, and the balance is agrochemically allowed and accepted auxiliary components. The sterilization composition can be prepared into a wettable pulvis, a suspending agent, a soluble liquid formulation, a micron emulsion, an emulsion in water and water dispersible granule according to a known method. The sterilization composition of the invention is mainly used in control of fungus diseases in vegetable, fruit tree and corn, etc.
Description
Technical field
The present invention relates to the agriculture chemical compounding technical field, be specifically related to a kind of zoxamide and composite bactericidal composition of copper rosinate of containing.
Background technology
The mechanism of action of zoxamide is relatively unique in the Oomycete bactericide, and it suppresses the sclerotium division by the combination and the breaking of microtubule cytoskeleton of tubulin β-subunit.Zoxamide do not influence move about spore in move about, sporangiocyst forms or sprout.Be accompanied by first circulation of sclerotium division, the elongation of germ tube is suppressed, thereby stops the disease mattress to penetrate host plant.The crop of suitable control is potato, grape, cucumber, capsicum, spinach etc.; by the microbial disease of Oomycete cause of disease such as cucumber downy mildew, downy mildew of garpe, potato and tomato late blight etc.; other disease such as gray mold etc. also there is certain activity; be mainly used in cauline leaf and handle, the Oomycete disease is had good protection activity.Its structural formula is:
Copper rosinate is a kind of novel, efficient, broad-spectrum germicide, multiple fungi and bacteriosis to make inroads on crop have good control efficiency, the copper rosinate medicine liquid spray is when crop surface, can form good " the medicine film " of one deck adhesion rapidly, copper ion on the film can be killed the pathogen of dropping on the medicine film effectively, thereby stops germ to be invaded.Copper rosinate has very strong adhesivity, spread and permeability, thereby lasting medicine, and than resistance of rainwater washing against; Even meet rain after the dispenser in half an hour, to drug effect also not obviously influence.It also has acaricidal action in addition, uses with miticide to have the notable synergistic effect,, noresidue low to the person poultry toxicity; To crop safety, be difficult for producing poisoning, be a kind of new and effective bactericide that application value is arranged very much.Can be used for preventing and treating tens kinds of diseases such as downy mildew, eqpidemic disease, anthracnose, fusarium wilt, leaf spot, angular leaf spot of infringement fruit tree, vegetables, cotton and grain and oil crop.
No matter be zoxamide, copper rosinate or other efficient germicides, long-term use separately all makes disease develop immunity to drugs easily, causes the problem that dosage strengthens, preventive effect reduces, the lasting period shortens, and is unfavorable for environment sustainable development.The active ingredient of the different mechanisms of action is carried out composite, is to delay the disease method commonly used that develops immunity to drugs, and according to the effect in the production application, judge this composite be synergistic effect or antagonism.Complex role is more significantly filled a prescription, and can obviously improve preventive effect, reduces the dosage of agricultural chemicals greatly, also can enlarge fungicidal spectrum, improves germicidal efficiency.Zoxamide is different with the copper rosinate mechanism of action, and mutually composite have good synergistic effect within the specific limits.And composite about zoxamide and copper rosinate do not see relevant report at present at home and abroad as yet.
Summary of the invention
I research staff of company is devoted for years in the research in the composite field of agriculture chemicals fungicide, through a large amount of experiment sievings, a kind of new and effective bactericidal composition has been proposed finally, bactericidal composition of the present invention is to be that the binary that active ingredient is carried out is mixed with zoxamide and copper rosinate, be used to prevent and treat the fungal disease of agriculture vegetables, fruit tree, seeding corn and other crops, especially outstanding to the downy mildew control efficiency, and can delay the drug-fast generation of germ, can enlarge fungicidal spectrum and reduce drug cost, improve actual preventive effect.
Specifically, the present invention for a kind of be the bactericidal composition preparation that two yuan of active ingredients are mixed with zoxamide and copper rosinate, the percentage by weight of active ingredient zoxamide and copper rosinate is 80: 1～1: 80 in the bactericidal composition wherein of the present invention, on some concrete experiment basis, the percentage by weight of active ingredient zoxamide and copper rosinate can be preferably 45: 1～1: 40.
Pesticide sterilizing composite of the present invention is wetting powder, suspending agent, soluble liquid, microemulsion, missible oil, aqueous emulsion and water dispersible granules with the formulations of pesticide that the method in pesticidal preparations field can be prepared into, the gross mass percentage composition of active ingredient is 1%～90% in the preparation, be preferably 1%～55%, all the other are usual auxiliaries in the agricultural chemicals.
Pesticide sterilizing composite of the present invention all has the better prevention effect to the fungal disease of vegetables, fruit tree, seeding corn and other crops, for example prevents and treats early blight and late blight, alternaria leaf spot of apple, pear scab, wheat rust, melon anthracnose and downy mildew, rice sheath blight disease and the rice blast etc. of the early blight of downy mildew of garpe, tomato and late blight, potato.Especially outstanding to the downy mildew control efficiency.
Bactericidal composition of the present invention is compared similar medicament many advantages, first, can improve preventive effect greatly to controlling fungal diseases of crop, especially downy mildew there is special efficacy, the second, drug effect is more lasting, and be difficult for by rain drop erosion, quick-acting is compared single agent also very big raising, and the 3rd, delayed drug-fast generation greatly, agricultural chemicals access times have repeatedly been reduced, reduce the agricultural chemicals usage amount, reduce peasant's use cost, the 4th, low-residual, lasting period easily decomposes later, and consumption is few, and is friendly more to environment.
Embodiment:
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention describes with following specific embodiment, but the present invention only limits to these examples absolutely not.The method that the present invention adopts indoor bioassay and field trial to combine.If no special instructions, the ratio of below mentioning (comprising percentage) all is a mass ratio.Should be pointed out that all any modifications of being made within the spirit and principles in the present invention, be equal to replacement and improvement etc., all should be included within protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Wherein necessary component and the easy manufacture implementation method about the formulations of pesticide is as follows:
One of technical scheme of the present invention, described bactericidal composition are wetting powder, and the percentage by weight of component is:
The concrete procedure of processing of this bactericidal composition wetting powder is: press above-mentioned prescription with zoxamide and copper rosinate and dispersant, wetting agent and filler mixing, in stirred tank, evenly stir, behind airslide disintegrating mill, mixing, promptly can be made into the wetting powder of the present composition.
Two of technical scheme of the present invention, described bactericidal composition are suspending agent, and the percentage by weight of component is:
The concrete production stage of this suspending agent is earlier other auxiliary agents to be mixed, mix through high speed shear, add zoxamide and copper rosinate, abrading-ball is 2～3 hours in ball crusher, make a diameter all below 5mm, make the suspending agent preparation that contains the bactericidal composition of zoxamide and copper rosinate of the present invention.
Three of technical scheme of the present invention, described bactericidal composition are aqueous emulsion, and the percentage by weight of component is:
The concrete production stage of this aqueous emulsion is: at first former medicine zoxamide is added with copper rosinate, solvent and emulsifier, cosolvent and be in the same place, make and be dissolved into uniform oil phase; With part water, antifreeze, other insecticides adjuvant such as antimicrobial mixes into uniform water; When the reactor high speed stirs, oil phase is added water, slowly add water, open clipper and carry out high speed shear, and add remaining water, shear half an hour approximately, form the aqueous emulsion of oil-in-water type until reaching the phase inversion point.Promptly make the aqueous emulsion of the bactericidal composition that contains zoxamide and copper rosinate.
Four of technical scheme of the present invention, described bactericidal composition are water dispersible granules, and the percentage by weight of component is:
The concrete procedure of processing of this bactericidal composition water dispersible granules is: by above-mentioned prescription zoxamide, copper rosinate and dispersant, wetting agent, disintegrant and filler are mixed, pulverize with micro jet, through mediating, add then and carry out granulation, drying, screening in the fluidized bed prilling dryer after sample analysis makes the water dispersible granules that contains the bactericidal composition of zoxamide and copper rosinate of the present invention.
Described emulsifier is selected from any one or more mixtures formed with arbitrary proportion in calcium dodecyl benzene sulfonate and aliphatic acid polyethenoxy ether, alkylphenol polyoxyethylene sulfosuccinate, styryl phenol APEO, polyoxyethylene nonylphenol ether, castor oil polyoxyethylene ether, aliphatic acid polyethenoxy base ester, the polyoxyethylene aliphatic alcohol ether.
Described solvent is any one or more mixed solvents formed with arbitrary proportion in dimethylbenzene or biodiesel, toluene, diesel oil, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, turpentine oil, solvent naphtha, dimethyl formamide, dimethyl sulfoxide (DMSO), the water equal solvent.
Described dispersant is selected from one or more in polycarboxylate, lignosulfonates, alkylphenol polyoxyethylene formaldehyde condensation products sulphate, alkyl benzene sulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, alkylphenol polyoxyethylene, aliphatic amine polyoxyethylene ether, polyoxyethylene carboxylate, the fatty acid glyceride APEO.
Described wetting agent is selected from: lauryl sodium sulfate, calcium dodecyl benzene sulfonate, draw back in powder copper rosinate X., wetting and penetrating agent F, alkylnaphthalene sulfonate, polyoxyethylene triphenylethylene phosphenylic acid salt, spaonin powder, silkworm excrement, the soapberry powder one or more.
Described disintegrant is selected from: one or more in bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, the sodium bicarbonate.
Described thickener is selected from: one or more in xanthans, CMC, hydroxyethylcellulose, methylcellulose, Magnesiumaluminumsilicate, the polyvinyl alcohol.
Described stabilizing agent is selected from: a kind of in sodium citrate, the resorcinol.
Described antifreezing agent is selected from: one or more in ethylene glycol, propane diols, the glycerine.
Described defoamer is selected from: silicone oil, silicone compound, C
10-20Saturated fat acid compounds, C
8-10In the aliphatic alcohols compound one or more.
Described filler is selected from: one or more in kaolin, diatomite, bentonite, attapulgite, white carbon, starch, the precipitated calcium carbonate.
Indoor virulence and field experiment
The synergy test that zoxamide and copper rosinate are composite.It is tested object that bacterium of downy mildew of cucumber is adopted in test.
Concrete grammar is:
(1) test medicine
The former medicine of 95% zoxamide, 35% copper rosinate is provided by extra large rel research and development centre.
Zoxamide and copper rosinate dissolve with proper amount of acetone, are made into the mother liquor of 10000 μ g/ml, preserve in 4 ℃ of following low temperature, and be stand-by, is diluted to a series of concentration with sterile water before the test.
(2) subjects
The cucumber downy mildew germ, separation and purification gained from the cucumber roc incidence of leaf of Shouguang, Shandong is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
PDA medium: potato 200g, glucose 20g, agar 20g, water 1000ml
AEA medium: dusty yeast 5g/L, glycerine 20mL/L, MgSO
40.25g/L, NaNO
36g/L, KCL0.5g/L, KH
2PO
41.5g/L, agar powder 20g/L, deionized water 1L.
(3) test method
Bacterium of downy mildew of cucumber after pre-cultivation the on the AEA medium, is inoculated in the bacterium dish of diameter 5mm respectively on the AEA flat board that contains the variable concentrations gradient, cultivates down in 25 ℃ of dark conditions.Every processing repeats 3 times.When control strain colony diameter length is above to 6.5cm, adopt " right-angled intersection method " to measure.According to the linear regression analysis between the logarithm value of the probit value of inhibiting rate and medicine series concentration, obtain the EC that two kinds of single agent suppress mycelial growths
50Value, correlation coefficient and virulence regression equation.
On the basis of preliminary experiment, respectively single agent zoxamide and copper rosinate are carried out toxicity test in order to last method, the two EC
50Value is respectively 6.2mg/L and 7.3mg/L.
Test was respectively 3: 13,5: 11,7: 9,9: 7,11: 5 totally 5 combinations that are mixed with 16% zoxamide copper rosinate mass ratio.
(4) data statistics and analysis
Carry out the toxicity test of mixture according to mixed ratio with single agent toxicity test method.
EC that each that will measure according to the abundant method of Sun Yun handled
50Value is converted into the actual toxicity index (ATI) of using with; According to the proportioning of mixture, obtain theory and use toxicity index (TTI) with, calculate the co-toxicity coefficient (CTC) of mixture by following formula.
Single agent toxicity index=(standard medicament EC
50/ reagent agent EC
50) * 100
ATI=(standard medicament EC
50/ reagent agent (using with) EC
50) * 100
The content (%) of toxicity index * B in using with of content (the %)+B of toxicity index * A of TII=A in using with
CTC＝(ATI/TTI)×100
If co-toxicity coefficient is big by 120, showing has synergistic effect; If be starkly lower than 100 (below 80), be indicated as antagonism; Between 100～120, be indicated as summation action.
(5) toxicity test result and analysis
The composite virulence of table 1 zoxamide and copper rosinate to bacterium of downy mildew of cucumber
The composite co-toxicity of table 2 zoxamide and copper rosinate to bacterium of downy mildew of cucumber
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| Zoxamide | 1∶0 | 100.00 | 100.00 | / | / |
| Copper rosinate | 0∶1 | 84.93 | 84.93 | / | / |
| Zoxamide+copper rosinate | 3∶13 | 114.65 | 87.76 | 130.65 | Synergy |
| Zoxamide+copper rosinate | 5∶11 | 123.95 | 89.64 | 138.27 | Synergy |
| Zoxamide+copper rosinate | 7∶9 | 128.26 | 91.52 | 140.14 | Synergy |
| Zoxamide+copper rosinate | 9∶7 | 125.32 | 93.41 | 134.17 | Synergy |
| Zoxamide+copper rosinate | 11∶5 | 122.57 | 95.29 | 128.63 | Synergy |
According to bactericide joint toxicity measuring result, zoxamide and copper rosinate mass ratio are that 3: 13,5: 11,7: 9,9: 7,11: 5 o'clock co-toxicity coefficient is all obviously big by 120, all show as synergistic effect, especially co-toxicity coefficient is the highest when zoxamide and copper rosinate mass ratio are 7: 9, and we think that its synergistic effect is best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 7: 9 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
Test example 1: field trial is measured the control efficiency to cucumber downy mildew
(1) test method
Test dispenser twice altogether, check plot spray equivalent clear water.When making up a prescription, after with low amounts of water medicament fully being dissolved earlier, add suitable quantity of water again and carry out complete stool spraying processing, even spraying.All adopting power driven sprayer, operating pressure during the spray medicine is 0.3～0.4MPa, shower nozzle aperture 1.3mm.The sub-district spouting liquid is 40～50kg/667m
2, dispenser twice continuously, sprays application to the crop complete stool uniformly with soup at 10 days intervals.
(2) investigation method
Experimental field be located at Shouguang, Shandong, publish the medium cucumber field of course of disease degree for experimental field, soil fertility is medium, and irrigation and drainage are convenient.Adopt the bilinear sampling method, 5 points are got in every sub-district, look into 5 caves at every, and 2 blades in the fixing middle part of every strain fix a point to check during investigation.
Come classification according to the cucumber downy mildew grade scale, write down total strain number, diseased plant number, degree of being in a bad way, calculate diseased plant rate, disease index and preventive effect.
The cucumber downy mildew grade scale is
0 grade: no scab;
1 grade: lesion area accounts for below 5% of whole leaf area;
3 grades: lesion area accounts for 6%～10% of whole leaf area;
5 grades: lesion area accounts for 11%～25% of whole leaf area;
7 grades: lesion area accounts for 26%～50% of whole leaf area;
9 grades: lesion area accounts for more than 50% of whole leaf area.
Test is investigated 4 times altogether, i.e. disease index investigation before the medicine, preventive effect investigation in 10 days behind the 1st medicine, 10 days and preventive effect investigation in 20 days behind 2 medicines.
(3) poisoning investigation
Whether continuous 7d range estimation medicament has poisoning to crop after the dispenser.
(4) drug effect computational methods
Sick leaf rate (the %)=sick number of sheets/investigate total number of sheets * 100
Disease index=∑ (the sick numbers of sheets at different levels * relative level numerical value)/(investigating total number of sheets * 9) * 100
Control efficiency (%)=(1-(disease index behind disease index before the blank district medicine * treatment region medicine)/(disease index before disease index behind the blank district medicine * treatment region medicine)) * 100
(5) field control effectiveness test result of the test
The effect of each test medicine control cucumber downy mildew of table 3
As shown in Table 3,16% zoxamide and copper rosinate are that 7: 9 the effect of the combination control cucumber downy mildew that is mixed is more remarkable, spray for the first time that 10 days best preventive effects are 90.03% behind the medicine, spray for the second time that 10 days best preventive effects are 92.08% behind the medicine, best preventive effect after 20 days is 90.24%, and the effect of complex preparation significantly is better than two kinds of single agent, has not only significantly improved the control efficiency for downy mildew, and further prolonged its lasting period, and no poisoning produces under continuous 7 days poisoning is observed.Simultaneously, under same dosage, the single agent of 24% zoxamide SC is better than 12% copper rosinate EC for the effect of downy mildew.The field experiment that can further do other proportionings is to estimate its actual preventive effect.
To sum up test described, of the present invention is the composite bactericidal composition preparation of active ingredient with zoxamide and copper rosinate, aspect the fungal disease of control vegetables, fruit tree, seeding corn and other crops the better prevention effect is being arranged all, especially the control efficiency to downy mildew is outstanding, simultaneously to crop safety, to the disease control of field crops such as vast vegetables, fruit tree, corn, reduce the peasant drug cost, increasing both production and income is significant, and suggestion is promoted the use of.
Claims (7)
1. pesticide sterilizing composite is characterized in that: this bactericidal composition is to be two yuan of preparations that are mixed that active ingredient is carried out with zoxamide and copper rosinate, and all the other are usual auxiliaries in the agricultural chemicals.
2. bactericidal composition according to claim 1 is characterized in that: the percentage by weight of active ingredient zoxamide and copper rosinate is 80: 1～1: 80 in this bactericidal composition.
3. bactericidal composition according to claim 1 is characterized in that: the percentage by weight of active ingredient zoxamide and copper rosinate is 45: 1～1: 40 in this bactericidal composition.
4. bactericidal composition according to claim 1 is characterized in that: to account for the percentage of gross weight in the preparation be 1%～90% for active ingredient zoxamide and copper rosinate total content in this bactericidal composition.
5. bactericidal composition according to claim 4 is characterized in that: active ingredient zoxamide and the copper rosinate gross weight percentage composition in preparation is preferably 1%～55%.
6. bactericidal composition according to claim 1 is characterized in that: the formulation that bactericidal composition of the present invention can be mixed with is wetting powder, suspending agent, soluble liquid, microemulsion, missible oil, aqueous emulsion and water dispersible granules.
7. bactericidal composition according to claim 1 is characterized in that: bactericidal composition of the present invention is mainly used in the fungal disease of control to vegetables, fruit tree, seeding corn and other crops.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110177966 CN102293200B (en) | 2011-06-20 | 2011-06-20 | Sterilization composition containing zoxamide and copper pimaric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110177966 CN102293200B (en) | 2011-06-20 | 2011-06-20 | Sterilization composition containing zoxamide and copper pimaric acid |
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| CN102293200B CN102293200B (en) | 2013-06-12 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103210913A (en) * | 2013-03-24 | 2013-07-24 | 广东中迅农科股份有限公司 | Zoxamide water dispersible granule and preparation method thereof |
| CN113647402A (en) * | 2021-08-13 | 2021-11-16 | 天津市汉邦植物保护剂有限责任公司 | Sterilization composition containing benthiavalicarb isopropyl and copper abietate and application thereof |
| EP4238418A1 (en) * | 2022-03-04 | 2023-09-06 | UPL Corporation Limited | Fungicide composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061799A (en) * | 2006-04-28 | 2007-10-31 | 湖南万家丰科技有限公司 | Sterilization combination containing difenoconazole and copper rosinate |
| CN101647433A (en) * | 2009-07-21 | 2010-02-17 | 深圳诺普信农化股份有限公司 | Sterilization composition based on zoxamide |
| WO2010046389A2 (en) * | 2008-10-21 | 2010-04-29 | Basf Se | Use of oomycetes fungicide on cultivated plants |
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2011
- 2011-06-20 CN CN 201110177966 patent/CN102293200B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061799A (en) * | 2006-04-28 | 2007-10-31 | 湖南万家丰科技有限公司 | Sterilization combination containing difenoconazole and copper rosinate |
| WO2010046389A2 (en) * | 2008-10-21 | 2010-04-29 | Basf Se | Use of oomycetes fungicide on cultivated plants |
| CN101647433A (en) * | 2009-07-21 | 2010-02-17 | 深圳诺普信农化股份有限公司 | Sterilization composition based on zoxamide |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103210913A (en) * | 2013-03-24 | 2013-07-24 | 广东中迅农科股份有限公司 | Zoxamide water dispersible granule and preparation method thereof |
| CN103210913B (en) * | 2013-03-24 | 2015-11-18 | 广东中迅农科股份有限公司 | Zoxamide water dispersible granule and preparation method thereof |
| CN113647402A (en) * | 2021-08-13 | 2021-11-16 | 天津市汉邦植物保护剂有限责任公司 | Sterilization composition containing benthiavalicarb isopropyl and copper abietate and application thereof |
| EP4238418A1 (en) * | 2022-03-04 | 2023-09-06 | UPL Corporation Limited | Fungicide composition |
| WO2023166298A1 (en) * | 2022-03-04 | 2023-09-07 | UPL Corporation Limited | Fungicide composition |
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|---|---|
| CN102293200B (en) | 2013-06-12 |
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