CN105454250B - The composition of 2 mercaptobenzothiazole zincs and mitochondrial cytochrome enzyme inhibitor series bactericidal agent - Google Patents
The composition of 2 mercaptobenzothiazole zincs and mitochondrial cytochrome enzyme inhibitor series bactericidal agent Download PDFInfo
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Abstract
The present invention relates to Fungicidal active compound composition, more particularly to the composition comprising 2 mercaptobenzothiazole zincs and mitochondrial cytochrome enzyme inhibitor class (QoIs) bactericide and its preparation and application.A kind of bactericidal composition, said composition includes Fungicidal active compound I and Fungicidal active compound II, Fungicidal active compound I is 2 mercaptobenzothiazole zincs, and Fungicidal active compound II is at least one Fluoxastrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin, Enestroburin, pyraoxystrobin, alkene oxime amine and cyazofamid selected from mitochondrial cytochrome series bactericidal agent.The resistance to the action of a drug that Fungicidal active compound composition of the present invention can effectively slow down disease produces, and substantially reduces QoIs bactericide and the resistance risk brought is used alone in 2 mercaptobenzothiazole zincs；Invention can also give full play to the prophylactic-therapeutic effect of QoIs bactericide and 2 mercaptobenzothiazole zincs to the disease such as fungoid, bacillary, and its good protective value.
Description
Technical field
The invention belongs to agriculture field, is related to Fungicidal active compound composition, more particularly to include 2- sulfydryl benzo thiophenes
Composition and its preparation and application of the azoles zinc with mitochondrial cytochrome enzyme inhibitor series bactericidal agent.
Background technology
2-mercaptobenzothiazole salt is mainly used as thiofide, and United States Patent (USP) (US004012332) discloses one
Vulcanizer of the kind containing 2-mercaptobenzothiazole copper, Chinese patent (CN101463018A) disclose one kind with 2- sulfydryl benzene
And thiazole sodium is the method that raw material prepares rubber vulcanization accelerator dibenzothiazyl disulfide.Except being widely used in the vulcanization of rubber
Beyond field, 2-mercaptobenzothiazole salt can be additionally used in disinfectant use in agriculture, and Chinese patent (CN101514210B) discloses one kind
Copper -2-mercaptobenzothiazole with specific crystal formation and its purposes in agricultural plant disease is prevented and treated.
2-mercaptobenzothiazole zinc (Zinc 2-mercaptobenzothiazole) is mainly used as vulcanization at a high speed and promoted at present
Enter agent, for manufacturing the general industry product such as tire, sebific duct, rubber overshoes, adhesive plaster, its active compound is buff powder, micro- to have bitter taste, nothing
Poison, relative density 1.70 (25 DEG C), 300 DEG C of decomposition temperature, dissolves in chloroform, acetone, is partially soluble in benzene and ethanol, four chlorinations
Carbon, insoluble in gasoline, water and ethyl acetate, storage is stable, meets strong acid or strong base solution decomposes, concrete structure formula such as following formula institute
Show：
2-mercaptobenzothiazole zinc as disinfectant use in agriculture purposes by the Chinese invention patent application (Shen of the applicant
Please be number 201210293110.2) open.Although the compound shows very high bioactivity to most of bacterium, true to part
Bacterium also has excellent inhibitory action, but under many circumstances, still can not fully meet prevented and treated in agricultural production it is a variety of thin
Bacterium and the simultaneous requirement of fungi.
The mechanism of action of mitochondrial cytochrome enzyme inhibitor series bactericidal agent is that the breathing for suppressing fungal cell's mitochondria is made
With being combined by Qo the or Qi sites with pathogen mitochondrial cytochrome b, block the electronics between cytochrome b and c1 to pass
Pass, so as to suppress the synthesis of energy in its mitochondrial respiratory, reach the effect for suppressing fungi growth or being killed.Mitochondria is thin
Born of the same parents' pigment enzyme inhibitor series bactericidal agent have efficiently and wide spectrum characteristic, be widely used in the anti-of four big Gammaproteobacteria diseases on many crops
Control.Encoded yet with its target cyt b protein by mitochondrial DNA, the frequency of mutation is higher than core DNA about 10 times, target site
Mutations result in amino acid displacement be that germ produces rapidly the reason for high anti-to mitochondrial cytochrome enzyme inhibitor series bactericidal agent.
Its resistance development is classified as " excessive risk " by bactericide resistance Action Committee (FRAC).To extend the lasting period to reduce medication time
Number, controlling object is delayed to produce resistance to mitochondrial cytochrome enzyme inhibitor series bactericidal agent, it is necessary to by mitochondrial cytochrome
Enzyme inhibitor series bactericidal agent is processed into mixture use with other reactive compounds.
Therefore, selection 2-mercaptobenzothiazole zinc combines to form compounding with mitochondrial cytochrome enzyme inhibitor series bactericidal agent
Agent, to meeting requirement that a medicine in agricultural production controls more, reducing dosage, delay germ is drug-fast to produce, extend medicament
Service life etc. is respectively provided with important realistic meaning.
The content of the invention
Multiple diseases, and mitochondrial cytochrome enzyme inhibitor can not be prevented and treated simultaneously in order to solve 2-mercaptobenzothiazole zinc
Series bactericidal agent is also easy to produce the problem of resistance, and of the invention first purpose is to provide a kind of bactericidal composition, the bactericidal composition
With synergistic effect, delay the resistance to the action of a drug, improvement and the compatibility of plant, so as to meet the needs of agricultural production.The of the present invention
Two purposes are to provide the preparation of above-mentioned bactericidal composition.Third object of the present invention is to provide above-mentioned bactericidal composition
With the application of preparation.
In order to realize first above-mentioned purpose, present invention employs following technical scheme：
A kind of bactericidal composition, said composition include Fungicidal active compound I and Fungicidal active compound II, the sterilization
Reactive compound I is 2-mercaptobenzothiazole zinc, Fungicidal active compound II be selected from：
Fluoxastrobin (azoxystrobin) (being known in EP 0382375),
Kresoxim-methyl (kresoxim-methyl) (being known in EP 0253213),
Trifloxystrobin (trifloxystrobin) (being known in EP 0460575),
Pyraclostrobin (pyraclostrobin) (being known in DE 4423612),
Enestroburin (enestroburin) (being known in EP 936213),
Pyraoxystrobin (Pyraoxystrobin) (being known in DE4423612),
Alkene oxime amine (SYP-1620) (being known in CN03134025),
At least one mitochondrial cytochrome enzyme inhibitor class of cyazofamid (cyazofamid) (being known in EP 298196)
Bactericide.
Mitochondrial cytochrome enzyme inhibitor series bactericidal agent provided by the present invention and 2-mercaptobenzothiazole Zn composition
Conven-tional adjuvants and additive and/or diluent can also be contained.
Component I of the present invention and component II mass ratio is 100: 1~1: 100.Preferably, I: II mass ratio is 1:
10~80: 1, most preferably mass ratio is 1: 3~8: 1.
In order to realize second above-mentioned purpose, present invention employs following technical scheme：
A kind of bactericidal composition preparation, said preparation include the bactericidal composition and system described in any one above-mentioned technical scheme
Agent auxiliary material, bactericidal composition described by percentage to the quality account for the 1~90% of total amount；It is preferred that described bactericidal composition
Account for the 20~60% of total amount.
The present composition can be prepared into agriculturally acceptable solid-like or liquid preparation.This kind of preparation can lead to
Mixing active component I and II is crossed to prepare with method known to suitable auxiliary element use.Solid-like form includes the wettable of powdery
Property pulvis, pulvis, seed treatment dry powder doses, seed treatment dispersible pulvis, water dispersible granules, granule, liquid preparation bag
Include suspending agent, suspension emulsion, microcapsule suspending agent, seed treatment suspending agent, seed treatment microcapsule suspending agent, suspension seed-coating agent.
Auxiliary element described in the present composition includes wetting agent, dispersant, thickener, antifreezing agent, preservative, stably
Agent, film forming agent, into wafer, pH acid-base modifiers, defoamer, colouring agent, filler etc. and other active ingredients that are beneficial in preparation
The known substance that middle stabilization or reactive compound play, all it is to commonly use in preparing or agriculturally allow the various composition used, and
It is not particularly limited, specific composition and dosage determine as desired by experiment.
Described wetting agent is selected from EO/PO block polyethers, AEO, tallow ethyoxyl ammonium salt, alkyl
One or more in naphthalene sulfonate, fatty alcohol polyoxyethylene ether sulfate and acyl group glutamate；
The dispersant is selected from naphthalene sulfonic acid condensate sodium salt, phenolsulfonic acid condensation product sodium salt, the contracting of methyl naphthalene sulfonic acid sodium formaldehyde
Compound, sodium lignin sulfonate, sodium metnylene bis-naphthalene sulfonate, acrylate homopolymer sodium salt, polymeric polycarboxylic acid salt, dioctyl sulfo group
One or more in butanedioic acid sodium salt, EO/PO block polyethers and maleic acid-acrylic acid copolymer sodium salt；
The thickener is selected from xanthans, Magnesiumaluminumsilicate, sodium carboxymethylcellulose, starch phosphate sodium, octenyl succinic
One or more in acid-starch sodium and polyvinyl alcohol；
One or more of the solvent in dimethylbenzene, turpentine-based vegetable oil, methyl oleate and heavy aromatic solvent oil；
One or more of the antifreezing agent in ethylene glycol, propane diols, glycerine, isopropanol and urea；
The film forming agent is selected from polyvinyl alcohol, polyvinyl acetate, polyethylene glycol, polymethylacrylic acid ethylene glycol
Ester, carboxymethyl cellulose, gum arabic, xanthans and starch etc. have in the high molecular polymer of caking property and film forming
It is one or more；
The cyst material is carbamide resin；It is that interfacial polymerization is passed through by isocyanate-monomer and polyalcohol or polyamine
React and be made；Isocyanates includes toluene di-isocyanate(TDI), 4,4- methyl diphenylene diisocyanates, the multiple methylene of more phenyl
Quito isocyanates, polyphenyl polymethylene polyisocyanates etc..
The pH acid-base modifiers are in citric acid, glacial acetic acid, hydrochloric acid, ammoniacal liquor, triethanolamine and diethylenetriamine
It is one or more；Institute's expense is to adjust the pH value of final products to being advisable in stability range；
One or more of the disintegrant in sodium chloride, ammonium sulfate, sodium sulphate and soluble starch；
The one kind of the preservative in Kathon CG, formaldehyde, phenyl salicylate, butyl p-hydroxybenzoate and potassium sorbate
It is or a variety of；
The stabilizer is selected from epoxidized soybean oil, epoxychloropropane, triphenyl phosphite, glycidol ether and pentaerythrite
In one or more；
The defoamer is selected from organic silicon defoamer and/or polyether antifoam agent；
One or more of the colouring agent in iron oxide, titanium oxide and azo dyes；
One or more of the filler in kaolin, diatomite, talcum powder, precipitated calcium carbonate and white carbon；
The water is deionized water or distilled water.
Preparation described in the invention can be prepared with universal method.Therefore, present invention additionally comprises above-mentioned composition preparation
Preparation method.
In order to realize the 3rd above-mentioned purpose, present invention employs following technical scheme：
Above-mentioned bactericidal composition or the purposes of bactericidal composition preparation, the bactericidal composition or bactericidal composition preparation are used
In preventing and treating crop pathogenetic bacteria, oomycetes and fungal disease.
The bactericidal composition or bactericidal composition preparation of the present invention has extraordinary bactericidal activity, to pathogenetic bacteria, oomycetes
It is highly effective with fungi, such as preventing and treating following germ：Xanthomonas (Xanthomonas), false list in pathogenetic bacteria
Born of the same parents Pseudomonas (Pseudomonas), erwinia category (Erwinia), Lao Ershi Bacillus (Ralstonia), clavibacter category
(Clavibacter)；
Sac fungus in disease fungus：Venturia (Venturia), powdery mildew (Erysiphales), Gibberella
(Gibberella), Sclerotinia (Sclerotinia)；
Basidiomycetes (Basidiomycetes) in disease fungus：Ustilago (Ustilago), rest fungus
(Uredinales)；
Downy mildew (Peronosporales) in oomycetes：Phytophthora (Phytophthora), pythium (Pythium),
Plasmopara (Plasmopara)；
Fungi Imperfecti (Deuteromyces) in disease fungus：Rhizoctonia (Rhizoctonia), Fusarium
(Fusarium), Botrytis (Botrytis), Pyricularia Sacc. (Pyricularia), Cercospora (Cercospora), bipolaris
(Bipolaris), colletotrichum (Colletotrichum).
Within the scope of the present invention, the preferably following species of signified crop disclosed herein：Cereal wheat, barley, rice, height
Fine strain of millet；Fruit tree kind apple, pears, peach, citrus, grape, lichee, banana, longan, mango, loquat；Greengrocery cucumber, watermelon, potyvirus,
Sponge gourd, muskmelon, spinach, celery, tomato, capsicum, eggplant, ginger, green onion, garlic, leek, wild cabbage, Chinese cabbage, strawberry, asparagus lettuce, Kidney bean,
Cowpea, broad bean, radish, carrot, potato, Chinese yam, taro, lotus rhizome, water chestnut, wild rice stem, sweet potato；Sugar plant class beet, sugarcane；Oil
Material makees species soybean, peanut, rape, sesame, sunflower；Or such as tobacco, tea.This enumerate is not offered as having any limit
System.
The present composition is especially effective to following crop disease：
Cucumber bacterial angular leaf spot, wildfire, Solanaceae green grass or young crops are withered caused by pseudomonas (Pseudomonas) strain
Disease etc.；
Bacterial blight of rice, bacterial leaf streak of rice, cucumber are thin caused by xanthomonas (Xanthomonas) strain
Bacterium property leaf blight, cabbage black rot, citrus bacterial canker disease etc.；
Soft rot of Chinese cabbage, fire blight of pear etc. caused by erwinia category (Erwinia) strain；
Tomato, bacterial wilt of peanut etc. caused by Lao Ershi Bacillus (Ralstonia) strain；
Canker of tomato caused by clavibacter category (Clavibacter) strain；
Epidemic disease of potato, tomato etc. caused by Phytophthora (Pyhtophthora) strain；
Downy mildew of garpe etc. caused by downy mildew (Peronosporales)；
Tobacco caused by powdery mildew (Erysiphales), sesame, sunflower and the powdery mildew such as melon etc.；
A variety of grass head blight such as Wheat And Barley and corn, rice caused by Gibberella (Gibberella) strain
Bakanae disease；
Scab of apple etc. caused by Venturia (Venturia) strain；
Various plants sclerotiniose caused by Sclerotinia (Sclerotinia) strain；
Wheat loose smut etc. caused by Ustilago (Ustilago) strain；
Gray mold of various plants etc. caused by Botrytis (Botrytis) strain；
Rice blast caused by Pyricularia Sacc. (Pyricularia) strain；
Beet cercospora leaf spot, the cercospora brown spot of peanut caused by Cercospora (Cercospora) strain；
Corn southern leaf blight, water rice brown spot caused by bipolaris (Bipolaris) strain；
Cotton seedling blight and rice sheath blight disease caused by Rhizoctonia (Rhizoctonia) strain；
Apple, pears, cotton, grape, wax gourd, cucumber, capsicum, eggplant caused by colletotrichum (Colletotrichum) strain
More planting fruit-trees such as son and the anthracnose of vegetables.
The method that uses of bactericidal composition of the present invention include to plant to be processed or its grow place or seed or
Other propagating materials, the Formulas I comprising effective active bactericidal amount and Formula II reactive compound are applied with mixing.Can be in fungal infection material
Applied before or after material, plant or seed.
Terms used herein " growth place " includes growth process plant or sows the field of cultivated plant seed, or kind
Son is embedded in the place in soil.
The bactericidal composition of the present invention can use with itself concentration form or with general conventional formulations, root
According to the property of target disease it is different using pouring, spraying, atomizing, dress seed, spread fertilizer over the fields or smearing method, it applies total effective active agent
Amount changes with weather condition, crop condition or application process.
Compared to the prior art Fungicidal active compound composition of the present invention has the advantages of very prominent：
1. being made up of the active ingredient of different mechanism of action, the resistance to the action of a drug that can effectively slow down disease produces, and substantially reduces line
The resistance risk brought is used alone in mitochondrial cytochrome enzyme inhibitor series bactericidal agent and 2-mercaptobenzothiazole zinc；
2. synergy is obvious, mitochondrial cytochrome enzyme inhibitor series bactericidal agent and 2-mercaptobenzothiazole zinc can be given full play to
To the prophylactic-therapeutic effect of the disease such as fungoid, bacillary, and its good protective value；
3. not only increasing antibacterial or antibacterial effect, fungicidal spectrum is have also been enlarged, crop can be occurred simultaneously bacillary
Disease and some fungi venereal disease evil play prevention or therapeutic effect well, times for spraying are reduced, so as to play integrated control
Effect；
4. the usage amount of medicament can be reduced by compounding, mitigate pressure of the agricultural chemicals to environment, while reduce cost；
5. the tolerance of crop can be significantly improved, it is higher to the security of crop；
6. can be by microelement-supplementing, so as to promote plant growth, improve resistance and disease resistance.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, present invention specific examples below
Illustrated with example, described embodiment is to preferably explain the present invention, rather than the limit to the scope of the present invention
System, it is all based on any modification and variation made in basic thought of the present invention and principle, it is claimed to belong to the present invention
Scope.
Prepare embodiment：
Following term illustrates in embodiments of the invention, reactive compound I (2-mercaptobenzothiazole zinc) and bactericidal activity
Compound II is with the composition of specific blend composition of proportions.
First, the preparation of suspending agent
Embodiment 1：
By 40% reactive compound (35.0%2- mercaptobenzothiazole zincs and 5.0% pyraclostrobin composition), fat
It is alcohol APEO 2.0%, maleic-acrylic acid homopolymer sodium salt 3.0%, xanthans 0.05%, Magnesiumaluminumsilicate 0.6%, pungent
Starch alkenyl succinate sodium 1.0%, glycerine 2.0%, phenyl salicylate 0.4%, organic silicon defoamer 0.1%, deionized water
Mend to 100%, put into high shear homogeneous emulsifying machine high speed and shear 20 minutes, then transport in sand mill, circulation sand milling 1-3 times
Produce 40% content reactive compound suspending agent.
Embodiment 2：
By 30% reactive compound (20.0%2- mercaptobenzothiazole zincs and 10.0% azoxystrobin composite), poly alkyl alcohol
Oxygen ethene ether sulfate 1.0%, phenolsulfonic acid condensation product sodium salt 1.0%, polymeric polycarboxylic acid salt 2.0%, ocentyl succinic
Sodium starch 2.0%, glycerine 2.0%, organic silicon defoamer 0.1%, Kathon CG 0.2%, deionized water are mended to 100%, are put into
High shear homogeneous emulsifying machine high speed is sheared 25 minutes, then pump is sanded 90 minutes into sand mill, and 35% activity is produced after filtering
Compound suspending agent.
2nd, microcapsule suspending agent
Embodiment 3：
25% reactive compound (10.0%2- mercaptobenzothiazole zincs and 15.0% trifloxystrobin composition) microcapsule suspending agent
Preparation method：By 2-mercaptobenzothiazole zinc 10.0%, trifloxystrobin 15.0%, alkylnaphthalene sulfonate 1.0%, acyl group glutamate
2.0%th, organic silicon defoamer 0.1%, polyphenyl polymethylene polyisocyanates PAPI 3% and diphenylmethane diisocyanate
Ester MDI 2%, Arabic gum (5%) aqueous solution 10%, deionized water 40.46% is sufficiently mixed, then puts into sand in sand mill
Mill, it is 3-5 microns to be sanded to D90 particle diameters.Stirring (maintaining 700 turns/min) is opened, is then warming up to the suspension being sanded
60 DEG C, while triethanolamine 0.04% is slowly added to, maintain the cyst material solidification temperature of stabilization 8 hours, add fatty alcohol afterwards
Polyoxyethylene ether sulfate 1.0%, methyl naphthalene sulfonate formaldehyde condensate 1.0%, urea 2.0%, glycerine 2.0%, silicic acid
Magnalium (2%) aqueous solution 10%, appropriate diluted hydrochloric acid aqueous solution adjust pH value to 6.5 or so, preservative formaldehyde 0.1%, organosilicon
Defoamer 0.3%, stirs, that is, 25% reactive compound microcapsule suspending agent is made.
3rd, the preparation of water dispersible granules
Method one：After agricultural chemicals, dispersant, disintegrant, wetting agent, binding agent etc. are well mixed, by air-flow crushing, make
Grain shaping.
Embodiment 4：
60% reactive compound (40.0%2- mercaptobenzothiazole zincs and 20.0% Enestroburin composition), EO/PO are embedding
Section polyethers 4.0%, lignosulfonates 3.0%, soluble starch 5.0%, polyvinyl alcohol 2.0%, precipitated calcium carbonate 3.0%,
Diatomite 23.0% is sufficiently mixed, then obtains water dispersible granules by air-flow crushing, granulating and forming.Contain in water dispersible granules containing 60%
Reactive compound is measured, product cut size is 80-120 mesh.
Method two：Agricultural chemicals and various auxiliary agents are ground in water, granulating and drying obtains after being deployed into slurry.
Embodiment 5：
By 55% reactive compound (40.0%2- mercaptobenzothiazole zincs and 15.0% kresoxim-methyl composition), poly alkyl alcohol
Oxygen ethene ether sulfate 2.0%, naphthalene sulfonate 5.0%, soluble starch 5.0%, xanthans 1.0%, diatomite 32.0% fill
Divide mixing, then put into high shear homogenized milk agent high speed shearing corase grind and homogeneous, then pump is sanded into sand mill, is sanded extremely
Certain particle diameter, then granulating and forming obtain water dispersible granules.Contain 55% content reactive compound in water dispersible granules, product cut size is
80-120 mesh.
4th, the preparation of wettable powder
By recipe requirements, active compound, various auxiliary agents and filler etc. are sufficiently mixed in the ratio of formula, through ultrafine crusher powder
It is i.e. available after broken.
Embodiment 6：
By 70% reactive compound (45.0%2- mercaptobenzothiazole zincs, 25.0% pyraclostrobin composition), wooden
Plain sodium sulfonate 2.0%, polymeric polycarboxylic acid salt 3.0%, white carbon 3.0%, precipitated calcium carbonate 5.0%, kaolin 17.0% fill
Divide mixing, then wettable powder is obtained to certain particle diameter by ultra-fine grinding.Contain 70% content active ingredient in wettable powder
Thing.
5th, the preparation of suspension seed-coating agent
By recipe requirements, active compound, auxiliary agent and inserts, film forming agent etc. are sufficiently mixed, put into high shear emulsifying
Agent high speed is sheared, then pump is sanded into sand mill, and suspension seed-coating agent is produced after filtering.
Embodiment 7：
By 30% reactive compound (18.0%2- mercaptobenzothiazole zincs and 12.0% pyraoxystrobin composition), alkylnaphthalene sulphur
Hydrochlorate 1.0%, AEO 2.0%, methyl naphthalene sulfonate formaldehyde condensate 2.0%, gum arabic 2.0%,
Glycerine 3.0%, xanthans 0.2%, iron oxide 0.2%, organic silicon defoamer 0.1%, deionized water 59.5% are sufficiently mixed,
High shear homogenized milk agent high speed shearing corase grind and homogeneous are put into again, then pump is sanded into sand mill, is sanded to certain grain
Footpath, suspension seed-coating agent is produced after refiltering.Contain 30% content reactive compound, D in suspension seed-coating agent90Particle diameter is 3-5 microns.
6th, seed treatment dry powder doses
Embodiment 8：
40% reactive compound (20.0%2- mercaptobenzothiazole zincs and 20.0% azoxystrobin composite), naphthalene sulfonic acids are contracted
Compound sodium salt 4.0%, talcum powder 2.0%, precipitated calcium carbonate 5.0%, diatomite 49.0% are sufficiently mixed, then pass through ultra-fine grinding
To certain particle diameter, dry powder doses are obtained.Contain 40% content reactive compound in dry powder doses.
7th, the preparation of suspension emulsion
Embodiment 9：
40% reactive compound (25.0%2- mercaptobenzothiazole zincs and 15.0% alkene oxime amine composition) suspension emulsion system
Preparation Method：By 2-mercaptobenzothiazole zinc 50.0%, EO/PO block polyethers 2.0%, methyl naphthalene sulfonate formaldehyde condensate
3.0%th, acrylate homopolymer sodium salt 1.0%, glycerine 2.0%, xanthans 0.3%, potassium sorbate 0.1%, polyether antifoam agent
0.1%th, deionized water 41.5% is sufficiently mixed, then puts into high shear homogenized milk agent high speed shearing corase grind and homogeneous, then
Pump is sanded into sand mill, is sanded to certain particle diameter, and suspending agent is produced after refiltering.The benzo of sulfydryl containing 50.0%2- in suspending agent
Zinc thiazole, D90 particle diameters are 3-5 microns.Again by 50.0% 50.0%2- mercaptobenzothiazole zincs suspending agent, alkene oxime amine
15.0%th, turpentine-based vegetable oil 15.0%, AEO 3.0%, fat alcohol ethoxyl compound 4.0%, the third three
Alcohol 3.0%, sodium carboxymethylcellulose 0.3%, polyether antifoam agent 0.1%, deionized water 9.6% are sufficiently mixed, high speed shear,
Suspension emulsion is made in matter emulsification, filtering, and suspension emulsion contains the reactive compound of 40% content.
Assays Example
Compound in Fungicidal active compound II has same or analogous characteristic, same class compound each component
Biological test experiment shows same or analogous effect, and therefore, only amount of activated compound is entered in Assays Example
Row citing proves its effect, does not represent other compositions in same class compound and does not have this bioassay results.
Biologicall test example 1：
Tomato early blight bacterium (Alternaria solani) activity test
Test method：Reference《People's Republic of China (PRC) agricultural industry criteria NY/T 1156.1-2006》Spore germination method.
EC is calculated using DPS data handling systems50, synergy ratio SR is calculated according to Wadley methods, evaluates synergy.SR is more than 1.5
For synergistic effect, SR is summation action between 0.5~1.5, and SR is antagonism less than 0.5.
(DPS in this example is used to calculate EC in following instance50With the synergy of Wadley methods evaluation mixture)
Result of the test shows：2-mercaptobenzothiazole zinc substantially carries with Fluoxastrobin mixture to the activity of tomato early blight bacterium
Height, there is synergistic effect, without antagonism, synergy when especially 2-mercaptobenzothiazole zinc and Fluoxastrobin proportioning are 1: 3~8: 1
Substantially, 2-mercaptobenzothiazole zinc and Fluoxastrobin mixture, can reduce the dosage of Fluoxastrobin, delay the resistance of Fluoxastrobin to produce, carry
High using effect (being shown in Table 1).
Table 1,2-mercaptobenzothiazole zinc and Fluoxastrobin mixture are to tomato early blight bacterium virulence
Biologicall test example 2：
Powdery mildew of cucumber (Sphaerotheca aphanis) activity test
Test method：Reference《People's Republic of China (PRC) agricultural industry criteria NY/T 1156.11-2008》Pot-culture method.
Result of the test shows：The activity of 2-mercaptobenzothiazole zinc and kresoxim-methyl or pyraoxystrobin mixture to cucumber powdery mildew's pathogen
Significantly improve, there is synergistic function, without antagonism, especially 2-mercaptobenzothiazole zinc is matched somebody with somebody with kresoxim-methyl or pyraoxystrobin
Than for 1: 3~8: 1 when synergy it is obvious, 2-mercaptobenzothiazole zinc and kresoxim-methyl or pyraoxystrobin mixture can reduce kresoxim-methyl or azoles
The dosage of bacterium ester, delay the resistance of kresoxim-methyl and pyraoxystrobin to produce, improve using effect (being shown in Table 2,3).
Table 2,2-mercaptobenzothiazole zinc and kresoxim-methyl mixture are to cucumber powdery mildew's pathogen virulence
Table 3,2-mercaptobenzothiazole zinc and pyraoxystrobin mixture are to cucumber powdery mildew's pathogen virulence
Biologicall test example 3：
Cucumber downy mildew (Pseudoperonospora cubensis) activity test
Test method：Reference《People's Republic of China (PRC) agricultural industry criteria NY/T 1156.7-2006》Pot-culture method.
Result of the test shows：The activity of 2-mercaptobenzothiazole zinc and Enestroburin or cyazofamid mixture to cucumber downy mildew
Significantly improve, there is synergistic function, especially proportioning be 1: 5~8: 1 when synergy it is the most obvious, 2-mercaptobenzothiazole zinc with
Enestroburin or cyazofamid mixture, the dosage of Enestroburin and cyazofamid can be reduced, delay the resistance of Enestroburin and cyazofamid
Produce, improve using effect (being shown in Table 4,5).
Table 4,2-mercaptobenzothiazole zinc and Enestroburin mixture are to bacterium of downy mildew of cucumber virulence
Table 5,2-mercaptobenzothiazole zinc and cyazofamid mixture are to bacterium of downy mildew of cucumber virulence
Biologicall test example 4：
Rice blast (Pyricularia oryzae Cav.) activity test
Test method：Reference《People's Republic of China (PRC) agricultural industry criteria NY/T 1156.8-2007》Pot-culture method.
Result of the test shows：2-mercaptobenzothiazole zinc significantly improves with trifloxystrobin mixture to the activity of rice blast,
With synergistic function, synergy is obvious when especially 2-mercaptobenzothiazole zinc and trifloxystrobin proportioning are 1: 3~8: 1,2- sulfydryls
Benzopyrene zinc and trifloxystrobin mixture, can reduce the dosage of trifloxystrobin, delay the resistance of trifloxystrobin to produce, and improve using effect
(being shown in Table 6).
Table 6,2-mercaptobenzothiazole zinc and trifloxystrobin mixture are to rice blast fungus virulence
Biologicall test example 5：
Watermelon anthrax bacteria (Colletotrichum orbiculare) activity test
Test method：Reference《People's Republic of China (PRC) agricultural industry criteria NY/T 1156.11-2008》Pot-culture method.
Result of the test shows：2-mercaptobenzothiazole zinc substantially carries with pyraclostrobin mixture to the activity of watermelon anthrax
Height, there is synergistic function, synergy is obvious when especially 2-mercaptobenzothiazole zinc and pyraclostrobin proportioning are 1: 3~8: 1,
2-mercaptobenzothiazole zinc and pyraclostrobin mixture, the dosage of pyraclostrobin can be reduced, delay the resistance of pyraclostrobin
Produce, improve using effect (being shown in Table 7).
Table 7,2-mercaptobenzothiazole zinc and pyraclostrobin mixture are to watermelon anthrax bacteria virulence
Field test embodiment
2-mercaptobenzothiazole zinc can prepare a variety of formulations, and following field test embodiment uses 20% suspending agent
(SC) bulk testing is carried out.
Every a kind of compound in Fungicidal active compound II has same or analogous characteristic, same class compound each group
Divide variable rate technology to go out same or analogous effect, therefore, only amount of activated compound is illustrated in field test embodiment
Its effect is proved, other compositions in same class compound is not represented and does not have this field test effect.
1st, 25% Fluoxastrobin SC+20%2- mercaptobenzothiazole zincs SC：
Prevent and treat cucumber bacterial angular leaf spot, downy mildew
Test method：Prevent and treat cucumber bacterial angular leaf spot reference《National Standard of the People's Republic of China GB/
T17980.110-2004》Carry out field control effectiveness test；Prevent and treat cucumber downy mildew reference《National Standard of the People's Republic of China GB/
T17980.26-2000》Carry out field control effectiveness test.
2nd, 50% kresoxim-methyl WG+20%2- mercaptobenzothiazole zincs SC：
Prevent and treat cucumber bacterial angular leaf spot, downy mildew
Test method：Prevent and treat cucumber bacterial angular leaf spot reference《National Standard of the People's Republic of China GB/
T17980.110-2004》Carry out field control effectiveness test；Prevent and treat cucumber downy mildew reference《National Standard of the People's Republic of China GB/
T17980.26-2000》Carry out field control effectiveness test.
3rd, 25% pyraclostrobin EC+20%2- mercaptobenzothiazole zincs SC：
Prevent and treat cucumber Bacterial Leaf Blight, downy mildew
Test method：Prevent and treat cucumber Bacterial Leaf Blight reference《National Standard of the People's Republic of China GB/
T17980.110-2004》Carry out field control effectiveness test；Prevent and treat cucumber downy mildew reference《National Standard of the People's Republic of China GB/
T17980.26-2000》Carry out field control effectiveness test.
4th, 25% alkene oxime amine SC+20%2- mercaptobenzothiazole zincs SC：
Prevent and treat cucumber bacterial angular leaf spot, downy mildew
Test method：Prevent and treat cucumber bacterial angular leaf spot reference《National Standard of the People's Republic of China GB/
T17980.110-2004》Carry out field control effectiveness test；Prevent and treat cucumber downy mildew reference《National Standard of the People's Republic of China GB/
T17980.26-2000》Carry out field control effectiveness test.
5th, 20% pyraoxystrobin SC+20%2- mercaptobenzothiazole zincs SC：
Control of plant bacterial wilt, late blight
Test method：Control of plant bacterial wilt reference《People's Republic of China (PRC) agricultural industry criteria NY/T 1464.32-
2010》Carry out field control effectiveness test；Prevent and treat tomato late blight reference《National Standard of the People's Republic of China GB/T 17980.31-
2000》Carry out field control effectiveness test.
17th, 100 g/l of cyazofamid SC+20%2- mercaptobenzothiazole zincs SC：
Prevent and treat fruit white rot of grape, downy mildew
Test method：Prevent and treat fruit white rot of grape reference《National Standard of the People's Republic of China GB/T 17980.121-
2004》Carry out field control effectiveness test；Prevent and treat downy mildew of garpe reference《National Standard of the People's Republic of China GB/T
17980.122-2004》Carry out field control effectiveness test.
Applicant is carried out using the mode of two kinds of components " bucket mixes " in above-mentioned field test, why using this side
Formula, reason are being to find with 2-mercaptobenzothiazole zinc to have in magnanimity Fungicidal active compound in these test objectives
The component of cooperative synergism effect, and be completed in before the application complex composition preparation embodiment, those skilled in the art manage
Solution " bucket mixes " is that the clear and definite technology for preparing complex composition is guided, and applicant is exactly to realize this hair under the guide of such technology
Bright technical scheme, desired technique effect is reached, the complex composition finally prepared not only has unitary agent
Stability, and with the outstanding bactericidal property shown by above-mentioned data.
Although reactive compound I 2-mercaptobenzothiazoles zinc and selected from mitochondrial cytochrome enzyme level in the present invention
The reactive compound II of agent series bactericidal agent is known compound, and the bactericidal property of each component and fungicidal spectrum are by this area
Technical staff's basic understanding, but above-mentioned reactive compound is compounded and effectively delays mitochondrial cytochrome enzyme inhibitor to realize
The resistance and energy notable synergistic of series bactericidal agent, ensure the effect that a medicine is controlled more, are then non-aobvious and easy for those skilled in the art
See.Applicant has paid substantial amounts of creative work during the experiment for suitably compounding component is sought, and have passed through many times
Biology test and the test of pesticide effectiveness, the result of the test of bactericidal composition defined herein it is encouraging.
Claims (15)
1. a kind of bactericidal composition, said composition includes Fungicidal active compound I and Fungicidal active compound II, and its feature exists
In：The Fungicidal active compound I is 2-mercaptobenzothiazole zinc, and the Fungicidal active compound II is selected from line at least one
Fluoxastrobin, kresoxim-methyl in mitochondrial cytochrome enzyme inhibitor series bactericidal agent, trifloxystrobin, pyraclostrobin, Enestroburin, azoles bacterium
Ester and cyazofamid, wherein I: II mass ratio are 1: 10 ~ 80: 1.
2. bactericidal composition according to claim 1, it is characterised in that I：II mass ratio is 1: 3 ~ 8: 1.
A kind of 3. bactericidal composition preparation, it is characterised in that：Said preparation include claim 1 or 2 described in bactericidal composition and
Preparation auxiliary material, bactericidal composition described by percentage to the quality account for the 1 ~ 90% of total amount.
4. bactericidal composition preparation according to claim 3, it is characterised in that described bactericidal composition account for total amount 20 ~
60%。
5. bactericidal composition preparation according to claim 3, it is characterised in that：Preparation auxiliary material includes wetting agent, disperseed
One kind in agent, thickener, antifreezing agent, preservative, disintegrant, stabilizer, film forming agent, defoamer, colouring agent, filler and water or
It is a variety of.
6. bactericidal composition preparation according to claim 5, it is characterised in that：
Described wetting agent is selected from EO/PO block polyethers, AEO, tallow ethyoxyl ammonium salt, alkylnaphthalene sulphur
One or more in hydrochlorate, fatty alcohol polyoxyethylene ether sulfate and acyl group glutamate；
The dispersant be selected from naphthalene sulfonic acid condensate sodium salt, phenolsulfonic acid condensation product sodium salt, methyl naphthalene sulfonate formaldehyde condensate,
Sodium lignin sulfonate, sodium metnylene bis-naphthalene sulfonate, acrylate homopolymer sodium salt, polymeric polycarboxylic acid salt, dioctyl sodium sulfosuccinates
One or more in acid sodium-salt, EO/PO block polyethers and maleic acid-acrylic acid copolymer sodium salt；
The thickener is selected from xanthans, Magnesiumaluminumsilicate, sodium carboxymethylcellulose, starch phosphate sodium, ocentyl succinic and formed sediment
One or more in powder sodium and polyvinyl alcohol；
One or more of the antifreezing agent in ethylene glycol, propane diols, glycerine, isopropanol and urea；
The film forming agent is selected from polyvinyl alcohol, polyvinyl acetate, polyethylene glycol, polymethylacrylic acid glycol ester, carboxylic
One or more in methylcellulose, gum arabic, xanthans and starch；
One or more of the disintegrant in sodium chloride, ammonium sulfate, sodium sulphate and soluble starch；
The one kind or more of the preservative in Kathon CG, formaldehyde, phenyl salicylate, butyl p-hydroxybenzoate and potassium sorbate
Kind；
The stabilizer is in epoxidized soybean oil, epoxychloropropane, triphenyl phosphite, glycidol ether and pentaerythrite
It is one or more；
The defoamer is selected from organic silicon defoamer and/or polyether antifoam agent；
One or more of the colouring agent in iron oxide, titanium oxide and azo dyes；
One or more of the filler in kaolin, diatomite, talcum powder, precipitated calcium carbonate and white carbon；
The water is deionized water or distilled water.
7. according to the bactericidal composition preparation described in claim 3 ~ 6 any one claim, it is characterised in that：The preparation
Formulation for wettable powder, pulvis, seed treatment dry powder doses, seed treatment dispersible pulvis, water dispersible granules, granule,
Suspending agent, suspension emulsion, microcapsule suspending agent, seed treatment suspending agent, seed treatment microcapsule suspending agent or suspension seed-coating agent.
8. the purposes of the bactericidal composition described in claim 1 or 2, it is characterised in that：The bactericidal composition is used to prevent and treat crop
Pathogenetic bacteria, oomycetes and fungal disease.
9. the purposes of the bactericidal composition preparation described in claim 3 ~ 7 any one claim, it is characterised in that：The sterilization
Composite preparation is used to prevent and treat crop pathogenetic bacteria, oomycetes and fungal disease.
10. purposes according to claim 8, it is characterised in that described crop pathogenetic bacteria, oomycetes and fungi include with
Under one or more：
1）Xanthomonas (Xanthomonas), pseudomonas (Pseudomonas) in pathogenetic bacteria, erwinia category
(Erwinia), Lao Ershi Bacillus（Ralstonia）, clavibacter category（Clavibacter)；
2）Sac fungus in disease fungus：Venturia（Venturia）, powdery mildew (Erysiphales), Gibberella
(Gibberella), Sclerotinia (Sclerotinia)；
3）Basidiomycetes (Basidiomycetes) in disease fungus：Ustilago (Ustilago), rest fungus
（Uredinales)；
4）Downy mildew (Peronosporales) in oomycetes：Phytophthora (Phytophthora), pythium（Pythium it is), single
The mould category (Plasmopara) of axle；
5）Fungi Imperfecti in disease fungus（Deuteromyces）：Rhizoctonia (Rhizoctonia), Fusarium
(Fusarium), Botrytis (Botrytis), Pyricularia Sacc. (Pyricularia), Cercospora (Cercospora), bipolaris
(Bipolaris), colletotrichum (Colletotrichum).
11. purposes according to claim 8, it is characterised in that described crop includes：
1）Cereal：Wheat, barley, rice, sorghum；
2）Fruit tree kind：Apple, pears, peach, citrus, grape, lichee, banana, longan, mango, loquat；
3）Greengrocery：Cucumber, watermelon, potyvirus, sponge gourd, muskmelon, spinach, celery, tomato, capsicum, eggplant, ginger, green onion, garlic, leek,
Wild cabbage, Chinese cabbage, strawberry, asparagus lettuce, Kidney bean, cowpea, broad bean, radish, carrot, potato, Chinese yam, taro, lotus rhizome, water chestnut, wild rice stem,
Sweet potato；
4）Sugar plant class：Beet, sugarcane；
5）Oil crops class：Soybean, peanut, rape, sesame, sunflower；
6）Or tobacco, tea.
12. purposes according to claim 8, it is characterised in that crop pathogenetic bacteria and fungal disease include：
1）Cucumber bacterial angular leaf spot, wildfire or Solanaceae bacterial wilt caused by pseudomonas strain；
2）Bacterial blight of rice, bacterial leaf streak of rice, cucumber Bacterial Leaf Blight, wild cabbage caused by xanthomonas strain
Black rot or citrus bacterial canker disease；
3）Soft rot of Chinese cabbage or fire blight of pear caused by erwinia category strain；
4）Tomato or bacterial wilt of peanut caused by Lao Ershi Bacillus species；
5）Canker of tomato caused by clavibacter category strain；
6）The epidemic disease of potato or tomato, late blight caused by Phytophthora strain；
7）Downy mildew of garpe caused by downy mildew；
8）Tobacco, sesame, sunflower and melon powdery mildew caused by powdery mildew；
9）Wheat And Barley caused by Gibberella strain or a variety of grass head blight of corn, bakanae disease of rice；
10）The scab of apple caused by Venturia strain；
11）Various plants sclerotiniose caused by Sclerotinia strain；
12）Wheat loose smut caused by Ustilago strain；
13）The gray mold of various plants caused by Botrytis strain；
14）Rice blast caused by Pyricularia Sacc. strain；
15）Beet cercospora leaf spot or the cercospora brown spot of peanut caused by Cercospora strain；
16）Corn southern leaf blight caused by bipolaris strain or water rice brown spot；
17）Cotton seedling blight or rice sheath blight disease caused by Rhizoctonia strain；
18）Apple caused by colletotrichum strain, pears, cotton, grape, wax gourd, cucumber, the anthracnose of capsicum or eggplant.
13. purposes according to claim 9, it is characterised in that described crop pathogenetic bacteria, oomycetes and fungi include with
Under one or more：
1）Xanthomonas (Xanthomonas), pseudomonas (Pseudomonas) in pathogenetic bacteria, erwinia category
(Erwinia), Lao Ershi Bacillus（Ralstonia）, clavibacter category（Clavibacter)；
2）Sac fungus in disease fungus：Venturia（Venturia）, powdery mildew (Erysiphales), Gibberella
(Gibberella), Sclerotinia (Sclerotinia)；
3）Basidiomycetes (Basidiomycetes) in disease fungus：Ustilago (Ustilago), rest fungus
（Uredinales)；
4）Downy mildew (Peronosporales) in oomycetes：Phytophthora (Phytophthora), pythium（Pythium it is), single
The mould category (Plasmopara) of axle；
5）Fungi Imperfecti in disease fungus（Deuteromyces）：Rhizoctonia (Rhizoctonia), Fusarium
(Fusarium), Botrytis (Botrytis), Pyricularia Sacc. (Pyricularia), Cercospora (Cercospora), bipolaris
(Bipolaris), colletotrichum (Colletotrichum).
14. purposes according to claim 9, it is characterised in that described crop includes：
1）Cereal：Wheat, barley, rice, sorghum；
2）Fruit tree kind：Apple, pears, peach, citrus, grape, lichee, banana, longan, mango, loquat；
3）Greengrocery：Cucumber, watermelon, potyvirus, sponge gourd, muskmelon, spinach, celery, tomato, capsicum, eggplant, ginger, green onion, garlic, leek,
Wild cabbage, Chinese cabbage, strawberry, asparagus lettuce, Kidney bean, cowpea, broad bean, radish, carrot, potato, Chinese yam, taro, lotus rhizome, water chestnut, wild rice stem,
Sweet potato；
4）Sugar plant class：Beet, sugarcane；
5）Oil crops class：Soybean, peanut, rape, sesame, sunflower；
6）Or tobacco, tea.
15. purposes according to claim 9, it is characterised in that crop pathogenetic bacteria and fungal disease include：
1）Cucumber bacterial angular leaf spot, wildfire or Solanaceae bacterial wilt caused by pseudomonas strain；
2）Bacterial blight of rice, bacterial leaf streak of rice, cucumber Bacterial Leaf Blight, wild cabbage caused by xanthomonas strain
Black rot or citrus bacterial canker disease；
3）Soft rot of Chinese cabbage or fire blight of pear caused by erwinia category strain；
4）Tomato or bacterial wilt of peanut caused by Lao Ershi Bacillus species；
5）Canker of tomato caused by clavibacter category strain；
6）The epidemic disease of potato or tomato, late blight caused by Phytophthora strain；
7）Downy mildew of garpe caused by downy mildew；
8）Tobacco, sesame, sunflower and melon powdery mildew caused by powdery mildew；
9）Wheat And Barley caused by Gibberella strain or a variety of grass head blight of corn, bakanae disease of rice；
10）The scab of apple caused by Venturia strain；
11）Various plants sclerotiniose caused by Sclerotinia strain；
12）Wheat loose smut caused by Ustilago strain；
13）The gray mold of various plants caused by Botrytis strain；
14）Rice blast caused by Pyricularia Sacc. strain；
15）Beet cercospora leaf spot or the cercospora brown spot of peanut caused by Cercospora strain；
16）Corn southern leaf blight caused by bipolaris strain or water rice brown spot；
17）Cotton seedling blight or rice sheath blight disease caused by Rhizoctonia strain；
18）Apple caused by colletotrichum strain, pears, cotton, grape, wax gourd, cucumber, the anthracnose of capsicum or eggplant.
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| WO1998056959A1 (en) * | 1997-06-13 | 1998-12-17 | Bayer Aktiengesellschaft | Use of 2-mercapto-pyridine-n-oxide |
| CN102977052A (en) * | 2012-12-19 | 2013-03-20 | 河南省新乡市农业科学院 | 2-mercaptobenzothiazole manganese zinc as well as preparation method and application of 2-mercaptobenzothiazole manganese zinc |
| CN103461348A (en) * | 2012-08-16 | 2013-12-25 | 浙江新农化工股份有限公司 | Use of 2-mercaptobenzothiazole metal salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998056959A1 (en) * | 1997-06-13 | 1998-12-17 | Bayer Aktiengesellschaft | Use of 2-mercapto-pyridine-n-oxide |
| CN103461348A (en) * | 2012-08-16 | 2013-12-25 | 浙江新农化工股份有限公司 | Use of 2-mercaptobenzothiazole metal salt |
| CN102977052A (en) * | 2012-12-19 | 2013-03-20 | 河南省新乡市农业科学院 | 2-mercaptobenzothiazole manganese zinc as well as preparation method and application of 2-mercaptobenzothiazole manganese zinc |
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