CN103719125A - Bactericide composition and application thereof - Google Patents

Bactericide composition and application thereof Download PDF

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CN103719125A
CN103719125A CN201310726065.XA CN201310726065A CN103719125A CN 103719125 A CN103719125 A CN 103719125A CN 201310726065 A CN201310726065 A CN 201310726065A CN 103719125 A CN103719125 A CN 103719125A
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methyl
thiophanate
microbicide compositions
oxime amine
alkene oxime
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罗昌炎
詹姆斯·T·布里斯托
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Jiangsu Rotam Chemical Co Ltd
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Jiangsu Rotam Chemical Co Ltd
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Abstract

The invention provides a bactericide composition and an application thereof, and relates to a bactericide composition containing N-methyl 2-{2-((((4-(2,6 dichloro-phenyl)-3-butenylidene-2-yl)amino)xy)methyl)-phenyl}-2-methoxyiminoacetamide and thiophanate-methyl and application thereof. The bactericide composition contains active ingredients, namely, the N-methyl 2-{2-((((4-(2,6 dichloro-phenyl)-3-butenylidene-2-yl)amino)xy)methyl)-phenyl}-2-methoxyiminoacetamide and the thiophanate-methyl at weight ratio of (1:100)-(100:1). The bactericide composition has the synergy of bacterium-killing effects through the binary compounding of the N-methyl 2-{2-((((4-(2,6 dichloro-phenyl)-3-butenylidene-2-yl)amino)xy)methyl)-phenyl}-2-methoxyiminoacetamide and the thiophanate-methyl. The bactericide composition has an obvious effect for preventing and treating banded sclerotial blight, rice blast, false smut and gibberellic diseases on wheat, rice, fruit trees, vegetables, flowers and plants. Meanwhile, the result finds that the content of chlorophylls in crops can be improved through the combination of the N-methyl 2-{2-((((4-(2,6 dichloro-phenyl)-3-butenylidene-2-yl)amino)xy)methyl)-phenyl}-2-methoxyiminoacetamide and the thiophanate-methyl.

Description

A kind of microbicide compositions and uses thereof
Technical field
A kind of microbicide compositions of the present invention and uses thereof relates to a kind of microbicide compositions that contains alkene oxime amine and thiophanate-methyl and uses thereof.
Background technology
In horticultural crop and dry-land crop production, crop can run into multiple fungi or infecting of bacterium and various diseases, also often because of in soil multiple cause a disease or saprophytic fungi (as mould in corruption, epidemic disease is mould, Rhizoctonia solani Kuhn, sickle-like bacteria, botrytis cinerea etc.) and bacterium (soft-rot fungi etc.) infect harm, cause rotten kind, rotten, seedling extremely.
In horticultural crop and dry-land crop production, crop can run into multiple fungi or infecting of bacterium and various diseases, also often because of in soil multiple cause a disease or saprophytic fungi (as mould in corruption, epidemic disease is mould, Rhizoctonia solani Kuhn, sickle-like bacteria, botrytis cinerea etc.) and bacterium (soft-rot fungi etc.) infect harm, cause rotten kind, rotten, seedling extremely.
Fungicide is natural or the compound in synthetic source, it is not caused by fungi infringement for the protection of plant.Current agricultural methods depend critically upon use fungicide.In fact, some crops can not growth effectively in the situation that not using fungicide.Use fungicide to allow that grower increases the quality of output and crop, and increase thus the value of crop.In most cases, the value added that crop is worth is to use at least three times of cost of fungicide.
But there is no a kind of fungicide is all useful in all cases, and reuses single fungicide of planting and usually cause this kind or relevant fungicide to produce drug resistance.Therefore, researching and producing more safely, having better performance, needing lower dosage, easily using and fungicide that expense is lower and the composition of fungicide.
When exceeding independent use, the activity of two kinds or more compounds just there is synergistic function during compound active.
The object of the invention is for providing, harmful fungoid and bacterium to be had good effect and solved depressant dose rate and/or agricultural methods and the composition of the problem of enhanced activity spectrum and/or drug resistance management.
Alkene oxime amine (SYP-1620) is found by Shenyang Chemical Engineering Inst, is under the jurisdiction of methoxy acrylic bactericide for 1999.Molecular formula: C21H20CI2N3O3, chemical name: (E, E, E)-N-methyl-2-[((((1-methyl-3-(2,, 6 ,-dichlorophenyl)-2-acrylic) imino group) oxygen base) methyl) phenyl]-2-methoxyimino acetic amide; Structural formula is
Figure 201310726065X100002DEST_PATH_IMAGE002A
Alkene oxime amine obtains Chinese invention patent mandate, the patent No.: ZL00110143.9 for 2003.Alkene oxime amine acts on the mitochondrial respiratory of fungi, medicament by with mitochondria electron transport chain in the combination of compound III (Cyt bc1 compound), blocking-up electronics is by Cyt bc1 complex logistics to Cyt c, and the ATP that destroys fungi is synthetic, thereby plays the effect of inhibition or kill fungi.Alkene oxime amine fungicidal spectrum is wide, activity is high, have prevention and therapeutic action, there is good compatibility with environmental organism, the plurality of plant diseases being caused by mastigomycetes, zygomycete, sac fungi, basidiomycetes and imperfect fungus is had to good control efficiency, to powdery mildew, rust control efficiency brilliance.Can be used for preventing and treating the plurality of plant diseases such as wheat rust, wheat powdery mildew, rice sheath blight disease, false smut, powdery mildew of cucumber, cucumber downy mildew, downy mildew of garpe, alternaria leaf spot of apple, apple mildew, sigatoka, early blight of tomato, pear scab, powdery mildew of strawberry, rust of sunflower., plant growth proterties and quality are improved significantly meanwhile, and can improve output.
Thiophanate-methyl is in a kind of broad spectrum activity, to inhale low toxicity bactericide, has interior suction, preventive and therapeutic action, can effectively prevent and treat the disease of various crop.Thiophanate-methyl has to top property conduction function, and multiple diseases is had to preventive and therapeutic action.Tetranychid and pathogenic nematode are had to inhibitory action.Multiple diseases on Cereal, greengrocery, fruit tree is had to good preventive and therapeutic effect.Thiophanate-methyl can be used for preventing and treating the control of vegetable disease, as gray mold, anthracnose, stalk breaks such as powdery mildew of cucumber, anthracnose, eggplant, onion, celery, tomato, Kidney beans; Thiophanate-methyl has certain preventive effect to dahlia blossom rot, Chinese rose brown spot, Malus spectabilis graywall, kaffir lily leaf spot; Thiophanate-methyl can be used for preventing and treating ring rot of apple, anthracnose, brown spot of grape, anthracnose, gray mold, peach brown rot etc.; The processing that thiophanate-methyl is also applied to after oranges and tangerines, banana and other fruit harvests is rotted to control to store.The Thiophanate-Methyl general by name of thiophanate-methyl, this compound can be expressed from the next
Figure DEST_PATH_IMAGE004A
Because the environmental requirement to bactericide and economic requirement continue to improve now, the for example requirement to activity profile, toxicity, selectivity, rate of application, residue composition and favourable preparation feasibility, in addition due to aspect drug resistance for example, the healthy aspect of crop may have problems, therefore the new bactericide that, exploitation is better than existing bactericide is in some aspects lasting task.
Summary of the invention
The present invention seeks to provides a kind of microbicide compositions and uses thereof for above-mentioned weak point.
Found that described new microbicide compositions has good antifungal and bacterium performance, said composition comprises alkene oxime amine and thiophanate-methyl.
Astoundingly, the bactericidal activity of microbicide compositions of the present invention is than active the adding with obviously higher of single reactive compound.In other words, there is synergistic effect unpredictable, necessary being, and be not only active augmenting.
When reactive compound is present in microbicide compositions of the present invention with specific weight ratio, synergistic effect is obvious especially.But the weight ratio of the reactive compound in microbicide compositions can change within the specific limits.
A kind of microbicide compositions of the present invention and uses thereof is to take following technical scheme to realize:
A kind of microbicide compositions of the present invention, it is characterized in that: comprise active component alkene oxime amine and thiophanate-methyl, the wherein weight proportion 1:100-100:1 of active component alkene oxime amine and thiophanate-methyl, preferably 1:50-50:1, more preferably 1:25-25:1, more preferably 1:10-10:1.
Prepare a method for microbicide compositions, the active component in described microbicide compositions is mixed with filler and/or surfactant.
The formulation of described microbicide compositions is suspending agent, seed coat agent, wetting powder, water dispersible granules, microcapsule suspending agent, coated granule, extrudes granule, missible oil, microemulsion, aqueous emulsion, effervescent tablet.
Described microbicide compositions, wherein the content of active component alkene oxime amine and thiophanate-methyl accounts for the 5%-90% of microbicide compositions.
Described microbicide compositions, wherein the content of active component alkene oxime amine and thiophanate-methyl accounts for the 10%-80% of microbicide compositions.
Described microbicide compositions, wherein the content of active component alkene oxime amine and thiophanate-methyl accounts for the 20%-60% of microbicide compositions.
Prevent and treat a method for plant pathogen, described microbicide compositions is acted on to pathogenic bacteria and/or its environment, or in plant, plant parts, seed, soil, region, material or space.
Prevent and treat a method for plant pathogen, alkene oxime amine and thiophanate-methyl compound are used simultaneously or used respectively or sequential application.
The purposes of described microbicide compositions for preventing and treating fungus and bacterium.
The purposes of described microbicide compositions for preventing and treating cereal, fruit, vegetables fungus and bacterium.
Described microbicide compositions is for improving the purposes of crop chlorophyll content.
Microbicide compositions of the present invention has extraordinary fungicide performance, and can be used to prevent and treat phytopathogenic fungi, as Plasmodiophoromycetes, Oomycete, Chytridiomycetes, connect and Gammaproteobacteria, Ascomycetes, Basidiomycetes, deuteromycetes etc.
Microbicide compositions of the present invention has the extraordinary bacterium performance of killing, and can be used to prevent and treat plant malignant bacteria.As pseudomonadaceae, Rhizobiaceae, enterobacteriaceae, excellent Bacteriaceae and Streptomycetaceae.
The Fungicidal composition that contains alkene oxime amine and thiophanate-methyl can be used as blade face bactericide in crop protection, as fungicide, is used for seed dressing and is used as soil fungicide.
Fungicidal mixture of the present invention is particularly suited for preventing and treating following plant disease:
Chain lattice spore (AIternaria) on-vegetables, oilseed rape, sugar beet and fruit and rice belongs to,
Silk capsule mould (Aphanomyces) on-sugar beet and vegetables belongs to,
Bipolaris (Bipolaris) in-corn, Cereal, rice and lawn belongs to and interior navel is wriggled, and spore (Drechslera) belongs to,
Standing grain powdery mildew (Blumeria graminis) (powdery mildew) on-Cereal,
Botrytis cinerea (Botrytis cinerea) (gray mold) on-strawberry, vegetables, flowers and grape vine,
Lettuce dish stalk mould (Bremia lactucae) on-lettuce,
Tail spore (Cercospora) on corn, soybean, rice and sugar beet belongs to,
Cochliobolus (Cochliobolus) on-corn, Cereal, rice belongs to (for example standing grain cochliobolus on Cereal (Cochliobolus sativus), palace portion cochliobolus (Cochliobolusmiyabeanus) on rice)
Thorn dish spore (Colletotricum) on-soybean and cotton belongs to,
Interior navel on-Cereal and corn wriggle spore (Drechslera) belong to,
Prominent navel on-corn wriggle spore (Exserohilum) belong to,
Two spore powdery mildews (Erysiphe cichoracearum) on-cucumber and monofilament shell powdery mildew (Sphaerotheca fuliginea),
Fusarium (Fusarium) on-each Plants belongs to and wheel branch spore (Verticillium) belongs to,
Gaeumannomyce (Gaeumanomyces graminis) on-Cereal belongs to,
Red mould (Gibberella) on-Cereal and rice belongs to (for example gibberella fujikuroi on rice (Gibberellafujikuroi)),
Gram’s staining complex (Grain staining complex) on-rice,
Length on-corn and rice wriggle spore (Helminthosporium) belong to,
Michrodochium nivale on-Cereal,
Ball chamber bacterium (Mycosphaerella) on-Cereal, banana and peanut belongs to,
Yam bean layer rest fungus (Phakopsora pachyrhizi) on-soybean and mountain horse sulphur layer rest fungus (Phakopsara meibomiae),
Phomopsis (Phomopsis) on-soybean and sunflower belongs to,
Phytophthora infestans (Phytophthora infestans) on-potato and tomato,
The raw single shaft of grape mould (Plasmopara viticola) on-grape vine,
Apple mildew bacterium (Podosphaera leucotricha) on-apple,
Wheat-based maize ear rot bacterium (Pseudocercosporella herpotrichoides) on-Cereal,
False downy mildew (Pseudoperonospora) on-lupulus and cucurbit belongs to,
Handle rest fungus (Puccinia) on-Cereal and corn belongs to,
Nuclear cavity bacteria (Pyrenophora) on-Cereal belongs to,
Pyricularia oryzae (Pyricularia 0 η zae), Bamboo grass wood photovoltaicing leather bacteria (Corticium sasakii), broom on-rice
Stalk Cylindrocarpon (Sarocladium oryzae), sheath rot of rice plant (S.attenuatum), rice leaf are black
Powder bacterium (Entyloma oryzae),
Piricularia oryzae (Pyricularia grisea) on-lawn and Cereal,
-lawn, rice, corn, cotton, oilseed rape, sunflower, sugar beet, vegetables and other are planted
Corruption mould (Pythium) on thing belongs to,
-cotton, rice, potato, lawn, corn, oilseed rape, potato, sugar beet, vegetables and its
Rhizoctonia (Rhizoctonia) on his plant belongs to,
Sclerotinite (Sclerotinia) on-oilseed rape and sunflower belongs to,
Wheat septoria (Septoria tritici) and the many spores of clever withered shell (Stagonosporanodorum) on-wheat,
Grape snag shell (Erysiphe) on-grape vine,
Setospaeria on-corn and lawn belongs to,
Silk axle smut (Sphacelotheca reilinia) on-corn,
Thielaviopsis sp (Thievaliopsis) on-soybean and cotton belongs to,
Tilletia foetida (Tilletia) on-Cereal belongs to,
Smut (Ustilago) on-Cereal, corn and sugar beet belongs to,
Black star bacterium (Venturia) on-apple and pears belongs to (scab).
Microbicide compositions of the present invention is particularly suitable for preventing and treating following disease: rice blast (Pyricularia oryzae); Rice green smut (Ustilagrnoidea virens (Cke) Tak); Stripe rust of wheat (Puccinia striiformis), leaf rust (Puccinia recondite) and other rust; Large wheat yellow rust (Puccinia striiformis), leaf rust (Puccinia recondite) and other rust; Barley and wheat powdery mildew, powdery mildew of cucumber, apple mildew and grape powdery mildew; Wheat sharp eyespot (Rhizotonia cerealis van der Hoeven apud.Boerema & Verhoeven and glume blight (Septoria nodorum).Length on cereal wriggle spore, mouth spore is mould, Septoria is sick, caryosphere shell Pseudomonas disease, Psedocercosporella herpotrichoides and Gaeumannomyces graminis.Peanut Cercospora arachidicola and Cerosporidium personata; The mould genus of other tail spore on beet, soybean and paddy is sick.Tomato, cucumber, grape grey mould (Botrytic cinerea).It is sick that hinge spore on vegetables belongs to.Anthracnose on cucumber, apple scab, cucumber downy mildew, downy mildew of garpe, the epidemic disease on potato and tomato is mould, and the Thanatephorus cucumeris on paddy and other host are as other rhizoctonia on Wheat and barley, vegetables; All fruit diseases are as scab, mildew disease, leaf spot, rust, anthracnose, downy mildew, brown rot etc.
Microbicide compositions of the present invention also demonstrates has very strong incentive action to plant.Therefore, they are applicable to mobilize the inside of plant to defend to resist harmful microbe attack.
In this article, plant excitation (induction of resistance) compound can be understood to such material, and system of defense that can stimulating plant, makes when inoculating harmful microorganism afterwards, can demonstrate the significant resistance to these microorganisms when processed plant.
In the present invention, harmful microorganism should be understood to the fungus and bacterium that plant is pathogenic.Therefore, compound of the present invention is used in and has carried out for protective plant in certain hour after the processing of mentioned pathogen attack.A period of time that this protection reaches is generally from 1 to 10 day that uses reactive compound processing to start to calculate, preferably 1 to 7 day.
Active compound combinations has good plant tolerance under controlling plant diseases desired concn, and this makes to process the acrial part of plant, in-vitro propagate strain, seed and soil.Active compound combinations of the present invention can also foliage applying or for seed dressing.
Unexpectedly, use microbicide compositions of the present invention for seedling post processing, to significantly improve the content of plant corpus inner chlorophyll.
All plants and plant parts all can be processed according to the present invention.The implication of plant of the present invention should be understood to all plant and plant population, wild plant that for example need and unwanted or crop plants (comprising the crop plants that nature exists).Crop plants can be by conventional breeding or optimum seeking method or by biotechnology and genetic engineering method or the plant that obtains by the combination of described method; comprise genetically modified plants, also comprise the plant cultivars that is subject to the protection of plant seedling power or is not subject to its protection.The implication of plant parts should be understood to ground and underground position and the organ that plant is all, for example bud, leaf, Hua Hegen, and specifiable example has leaf, needle, stem, dry, flower, fruit body, fruit, seed, root, stem tuber and rhizome.Plant parts also comprises harvested material, and asexual and sexual propagation thing, for example rice shoot, stem tuber, rhizome, cutting and seed.
The processing that reactive compound used according to the invention carries out plant and plant parts, by conventional method, directly carry out, or realize by acting on its environment of living in, habitat or storage area, the for example immersion liquid of described conventional treatment method, spraying, evaporation, atomizing, broadcast sowing or smear, and, to breeding thing, especially seed, can also smear one or more layers.
Active compound combinations of the present invention can be converted into conventional formulation, for example suspending agent, seed coat agent, wetting powder, water dispersible granules, microcapsule suspending agent, coated granule, extrudes granule, missible oil, microemulsion, aqueous emulsion, effervescent tablet, microcapsule suspension-suspending agent.
The reactive compound that a kind of microbicide compositions of the present invention comprises alkene oxime amine and thiophanate-methyl.In described microbicide compositions, alkene oxime amine and thiophanate-methyl reactive compound mix with filler and/or surfactant.
According to the present invention, term " filler " refers to can be combined with reactive compound or for example combine, so that it is easier to be administered to the natural or synthetic organic or inorganic compound of object (plant, crop or careless class).Therefore, described filler is preferably inertia, at least should be agricultural acceptable.Described filler can be solid or liquid.
In the present invention, operable nonactive medium can be both that solid can be also liquid, can be used as for example having of solid media material use: phyteral powdery type (for example particle of soybean meal, starch, grain dust, wood powder, bark powder, sawdust, walnut shell powder, wheat bran, cellulose powder, coconut husk, corncob and tobacco stem, extract residue after plant essence etc.), paper, sawdust, pulverize synthesized polymer body, clay class (such as kaolin, bentonite, acid china clay etc.), the talcum powder class of synthetic resin etc.Silica (for example diatomite, silica sand, mica, moisture silicic acid, calcium silicates), chemical fertilizer, the clay fertilizer of active carbon, natural mineral matter class (float stone, attapulgite and zeolite etc.), the inorganic mineral powder of firing diatomite, sand, plastics medium etc. (such as polyethylene, polypropylene, polyvinylidene chloride etc.), potassium chloride, calcium carbonate, calcium phosphate etc., ammonium sulfate, ammonium phosphate, urea, greening ammonium etc., these materials can be used separately or two or more is mixed.
Can be used as can selecting of liquid media materials'use in following material, for example water, alcohol type (for example methyl alcohol, ethanol, isopropyl alcohol, butanols, ethylene glycol etc.), ketone (for example acetone, methyl ethyl ketone, isobutyrone, cyclohexanone etc.), ethers (for example ether, dioxanes, methylcellulose, oxolane etc.), aliphatic hydrocarbon class (for example kerosene, mineral wet goods), aromatic hydrocarbons class (for example benzene, toluene, dimethylbenzene, solvent naphtha, Fluhyzon, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbon, chlorobenzene, Deng), halogenated hydrocarbon class, amide-type, sulfone class, dimethyl sulfoxide (DMSO), mineral and vegetable oil, animal wet goods.
For making the emulsification of active ingredient compound, disperse, solubilization, and/or wetting can use surfactant for example can enumerate fatty alcohol-polyoxyethylene ether, polyoxyethylene alkylaryl ether, polyoxyethylene high-grade aliphatic ester, the phosphate of polyoxyethylene alcohol or phenol, the fatty acid ester of polyalcohol, alkane aromatic sulfonic acid, naphthalene sulfonic acids polymer, lignosulfonates, a shape copolymer of macromolecule comb shape, butyl naphthalene sulfonate, alkylaryl sulfonates, alkyl sodium sulfosuccinate, grease, fatty alcohol and ethylene oxide condensate, the polyacrylates such as alkyltaurate, protein hydrolysate.Suitable oligosaccharide thing or polymer, the combination of for example vinyl monomer based on independent, acrylic acid, EO and/or PO or itself and for example (polynary) alcohol or (polynary) amine.
For making active ingredient compound decentralized stabilization, adhering to and/or combination, can use the adjuvants such as such as xanthans, aluminium-magnesium silicate, gelatin, starch, methyl cellulose, polyvinyl alcohol, polyvinyl acetate and natural phospholipid (as cephalin and lecithin) and synthetic phospholipid, bentonite, sodium lignin sulfonate.
The wherein optional spent glycol of antifreezing agent, propane diols, glycerine, sorbierite.As the deflocculant of suspension product, can use the such as adjuvant of naphthalene sulfonic acids polymer, polymeric phosphate etc.
As defoamer, can use silicone defoaming agent.
Operable colouring agent, for example inorganic pigment, as iron oxide, titanium oxide and Prussian blue; And organic pigment/dyestuff: alizarin dyes, azo dyes and metal phthalocyanine dyestuff; And trace element, for example molysite, manganese salt, boron salt, mantoquita, cobalt salt, molybdenum salt and zinc salt.
Optionally, also can comprise other annexing ingredient, for example protecting colloid, adhesive, thickener, thixotropic agent, bleeding agent, stabilizing agent, screening agent.
Described preparation of the present invention can be mixed described reactive compound to prepare with conventional additives by known way.Described conventional additives is as conventional extender and solvent or thinner, emulsifier, dispersant and/or adhesive or fixative, wetting agent, waterproofing agent, if need, can also comprise drier and colouring agent, stabilizing agent, pigment, defoamer, preservative, thickener, water and other processing aid.
These compositions not only comprise and can be applicable to immediately pending object as spraying or dusting equipment by suitable equipment, but also be included in to be applied to, need the concentrated business composition that dilutes before object.
Microbicide compositions containing alkene oxime amine and thiophanate-methyl of the present invention can also be co-administered with other active component, for example, for expanding activity profile or preventing from forming resistance.Described other active component such as fungicide, bactericide, attractant, insecticide, miticide, nematocide, growth regulator, weed killer herbicide, safener, fertilizer or semiochemical etc.
As a further improvement on the present invention, the application of described microbicide compositions fungus and bacterium disease on control crop.
Reactive compound alkene oxime amine and thiophanate-methyl can be used simultaneously, or use respectively, or sequential application, and order during separate administration is on the nothing impact conventionally of the result of control.
Microbicide compositions of the present invention can be used it by conventional methods, for example water, spraying, atomizing, broadcast sowing, dust, and as processing the powder, dry mixing powder of dry seed, moist seed dressing, wet-mixing kind, slurries seed dressing, process seed solution, process seed water solube powder, process the water solube powder of earth, or by formation shell etc.
When using microbicide compositions of the present invention,
-while conventionally processing plant parts, the rate of application of active compound combinations is generally 0.1 to 10000g/ha, is preferably 10 to 1000g/ha;
During seed dressing, the rate of application of active compound combinations is 0.001 to 50g/kg seed, is preferably 0.01 to 10g/kg seed;
-for soil treatment: the rate of application of active compound combinations is generally 0.1-10000 g/ha, preferably 1-5000 g/ha.
Above-mentioned dosage is only general exemplary dose, and during actual using, those skilled in the art can, according to actual conditions and needs, especially adjust rate of application according to the seriousness of the character of pending plant or crop and germ.
A kind of microbicide compositions and uses thereof has following distinguishing feature:
This bright microbicide compositions has good antifungal and bacterium performance, and said composition comprises alkene oxime amine and thiophanate-methyl.
The bactericidal activity of microbicide compositions of the present invention is than active the adding with obviously higher of single reactive compound.In other words, there is synergistic effect unpredictable, necessary being, and be not only active augmenting.
When reactive compound is present in microbicide compositions of the present invention with specific weight ratio, synergistic effect is obvious especially.But the weight ratio of the reactive compound in microbicide compositions can change within the specific limits.
 
The present invention is by carrying out binary built by alkene oxime amine and thiophanate-methyl, make the present invention on bactericidal effect, obtain the effect of cooperative gain, especially the control efficiency of the banded sclerotial blight on wheat, paddy rice, fruit tree, vegetables and flowers class crop, rice blast, false smut, head blight is given prominence to.Also find, the combination of alkene oxime amine and thiophanate-methyl is for improving crop chlorophyll content simultaneously.
Embodiment
 
Example of formulations
Embodiment 1 2% alkene oxime amine+3% thiophanate-methyl suspending agent
Figure 591564DEST_PATH_IMAGE006
Each components such as active component, dispersant, wetting agent and water are mixed according to the ratio of formula, after grinding and/or high speed shear, obtain 2% alkene oxime amine+3% thiophanate-methyl suspending agent.
 
Embodiment 2 10% alkene oxime amine+10% thiophanate-methyl wetting powders
Active component, various auxiliary agent and filler etc. are mixed in the ratio composition of formula, after ultra-fine pulverizer disintegrating, obtain 10% alkene oxime amine+10% thiophanate-methyl wetting powder
Embodiment 3 10% alkene oxime amine+0.1% thiophanate-methyl aqueous emulsions
Former medicine, solvent, emulsifier are added together, make to be dissolved into even oil phase; Water-soluble component and water mixing are made to water; Under high-speed stirred, oil phase is mixed with water, make 10% alkene oxime amine+0.1% thiophanate-methyl aqueous emulsion.
 
Embodiment 4 50% alkene oxime amine+10% thiophanate-methyl water dispersible granules
Active component, dispersant, wetting agent, disintegrant and filler are mixed in the ratio of formula, through air-flow crushing, become wetting powder, then add a certain amount of water mixing extruder grain.After drying screening, obtain 50% alkene oxime amine+10% thiophanate-methyl water dispersible granules.
 
Embodiment 5 10% alkene oxime amine+50% thiophanate-methyl suspending agents
Figure 435707DEST_PATH_IMAGE014
Each components such as active component, dispersant, wetting agent and water are mixed according to the ratio of formula, after grinding and/or high speed shear, obtain 10% alkene oxime amine+50% thiophanate-methyl suspending agent.
 
Embodiment 6 50% alkene oxime amine+1% thiophanate-methyl wetting powders
Active component, various auxiliary agent and filler etc. are mixed in the ratio composition of formula, after ultra-fine pulverizer disintegrating, obtain 50% alkene oxime amine+1% thiophanate-methyl wetting powder.
Embodiment 7 2% alkene oxime amine+50% thiophanate-methyl suspending agents
Figure 902033DEST_PATH_IMAGE018
Above-mentioned each component is mixed in proportion, and through sand milling, be prepared into suspending agent.
 
Embodiment 8 1% alkene oxime amine+10% thiophanate-methyl aqueous emulsions
Oil phase:
Figure 100934DEST_PATH_IMAGE020
Water:
Figure 582862DEST_PATH_IMAGE022
Alkene oxime amine and thiophanate-methyl are dissolved in methyl oleate, add polystyrene to obtain oil phase; According to the component in formula, mix and obtain water; Under agitation add water to obtain aqueous emulsion oil phase.
 
Embodiment 9 50% alkene oxime amine+40% thiophanate-methyl wetting powders
Figure 638542DEST_PATH_IMAGE024
Combinations thereof is mixed in proportion, and grind, pulverize, be prepared into wetting powder.
 
Embodiment 10 50% alkene oxime amine+30% thiophanate-methyl coated granules
Figure 704456DEST_PATH_IMAGE026
In blender, levigate active component is evenly applied on the carrier being soaked by polyethylene glycol.Can obtain in this way dustless coated granule.
 
Embodiment 11 5% alkene oxime amine+25% thiophanate-methyl wetting powders
Said components is mixed in proportion, and grind, pulverize, be prepared into wetting powder.
 
Embodiment 12 1% alkene oxime amine+50% thiophanate-methyls are extruded granule
Figure 840219DEST_PATH_IMAGE030
Active component is mixed with auxiliary agent and grind, mixture water is moistening.This mixture is extruded, then dry in air stream.
Embodiment 13 50% alkene oxime amine+1% thiophanate-methyl suspending agents
Figure 332381DEST_PATH_IMAGE032
Above-mentioned each component is mixed in proportion, and through sand milling, be prepared into suspending agent.
 
Embodiment 14 20% alkene oxime amine+40% thiophanate-methyl suspending agents
Figure 574006DEST_PATH_IMAGE034
Above-mentioned each component is mixed in proportion, and through sand milling, be prepared into suspending agent.
 
Embodiment 15 50% alkene oxime amine+2% thiophanate-methyl suspension emulsions
Figure 175363DEST_PATH_IMAGE036
Thiophanate-methyl is dissolved in Solvesso200, adds ethoxylated castor oil, obtain methyl sulfur bacterium missible oil; By alkene oxime amine, fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium, MODIFIED LIGNOSULPHONATE, xanthans, bentonite, glycerine, above-mentioned each component such as water mixes in proportion, and through sand milling, is prepared into suspending agent.
The oil phase of thiophanate-methyl is joined in the suspending agent containing alkene oxime amine, obtain suspended emulsion.
 
Embodiment 16 5% alkene oxime amine+15% methyl sulfur bacterium missible oils
Figure 881150DEST_PATH_IMAGE038
Said components is mixed to the liquid of transparent and homogeneous, obtain 5% alkene oxime amine+15% methyl sulfur bacterium missible oil.
 
Embodiment 17 2% alkene oxime amine+50% thiophanate-methyl microcapsule suspension-suspending agents
Figure 29366DEST_PATH_IMAGE040
By PAPI, the oil phase that alkene oxime amine and Solvesso 200 form adds in the aqueous solution containing Atlox4913, forms emulsion.Then heat and be incubated 50 ounder C, add catalyst reaction 2 hours.After cooling, obtain the microcapsules of alkene oxime amine.
Atlox 4913, dispersant LFH, defoamer, urea, thiophanate-methyl and water mix in proportion, and through sand milling, are prepared into suspending agent.
The microcapsules of the alkene oxime amine obtaining is added in the aqueous suspension agent of thiophanate-methyl, stir and obtain 2% alkene oxime amine+50% thiophanate-methyl microcapsule suspension-suspending agent.
 
Embodiment 18 0.1% alkene oxime amine+10% thiophanate-methyl suspension seed-coating agents
Figure 820605DEST_PATH_IMAGE042
Above-mentioned each component is mixed in proportion, and through sand milling, be prepared into suspension seed-coating agent.
 
Embodiment 19 5% alkene oxime amine+5% thiophanate-methyl aerosols
First by antifreezing agent propane diols, thinner SOLVESSO 100 mixes, and adds alkene oxime amine and thiophanate-methyl under stirring; Surfactant is added wherein, under agitation by a breaking plant colloid mill, pulverize, by the suspension passing through after colloid mill, then through a micronizer.Move in circles to till the particle diameter≤2um of solids.
 
Embodiment 20 50% alkene oxime amine+5% thiophanate-methyl wetting powders
Figure 708981DEST_PATH_IMAGE046
Active component, various auxiliary agent and filler etc. are mixed in the ratio composition of formula, after ultra-fine pulverizer disintegrating, obtain 50% alkene oxime amine+5% thiophanate-methyl wetting powder.
Embodiment 21 20% alkene oxime amine+80% thiophanate-methyls
Figure 542945DEST_PATH_IMAGE048
In above embodiment, proportioning is weight per distribution ratio.
 
Biological test example
The combination of active principles of different agricultural chemicals is made to agricultural chemicals, is effectively and the efficiently mode of one of the upper resistance germ of current development novel pesticide and control agricultural.Effectively and efficiently mode of the one of resistance germ.The agricultural chemicals of different cultivars shows three kinds of type of action: summation action, synergistic effect and antagonism after mixing conventionally.But be specially which kind of effect, unpredictable, only have by great many of experiments and just can know.Compound synergic is well filled a prescription, and owing to obviously having improved actual control efficiency, has reduced the usage amount of agricultural chemicals, thereby has delayed widely the drug-fast generation speed of germ, is the important means of integrated control disease.
The mode that adopts Toxicity Determination and bactericidal assay to combine in embodiment of the present invention, first pass through Toxicity Determination, co-toxicity coefficient (CTC) after clear and definite two kinds of medicaments are composite by a certain percentage, CTC<80 is anti-effect short of money, 80≤CTC≤120 are summation action, CTC > 120 is synergistic effect, carries out on this basis bactericidal assay again.
 
Test one
Subjects: rice sheath blight disease
Test method: test is with reference to < < pesticide bioassay technology > > (old spring chief editor, publishing house of Beijing Agricultural University publishes), and < < farm-chemical indoor determination test rule NY/T1156.2-2006 and 1156.6-2006 > >, this test adopts growth rate method (Plating).On the basis of preliminary experiment, on aseptic operating platform, according to test, process the sterilising medium melting in advance is quantitatively placed in aseptic conical flask, from low concentration to high concentration, getting successively 5ml liquid joins respectively the hot medium of 45ml (PDA medium is housed, 45-50 ℃) conical flask in, after shaking up, pour rapidly diameter 90mm glass culture dish into, each culture dish is poured band medicine medium 10ml into.Level is standing, makes flat board after cooling.Five repetitions of each concentration.With the processing that does not contain medicament effective ingredient, make blank.
By cultured pathogen, under aseptic condition, with the sterilizing card punch of diameter 4mm, from colony edge, cut bacterium cake, with inoculator by pure culture biscuits involvng inoculation in the dull and stereotyped central authorities of pastille, by facing down and medium laminating of having mycelia, cover ware lid.Above all operations all carries out sterile working at superclean bench.After processing, be placed in the constant temperature aseptic culture case of 26 ± 0.5 ℃ and cultivate, after 5d, take out.Adopt right-angled intersection method to measure respectively the colony diameter (take millimeter as unit) of each processing, calculate the mean value of colony diameter.
The logarithm value of processing effective ingredient concentration (μ g/ml) take each is as independent variable X, and the probit value that inhibiting rate changes into is dependent variable Y, with method of least squares, calculates concentration EC in virulence equation and inhibition 50, according to toxicity index and the co-toxicity coefficient (CTC) of the abundant method calculating of Sun Yun medicament.
Actual measurement toxicity index (ATI)=(standard medicament EC 50/ reagent agent EC 50) * 100
The percentage composition of B in percentage composition+B medicament toxicity index * mixture of A in theoretical toxicity index (TTI)=A medicament toxicity index * mixture
Co-toxicity coefficient (CTC)=[theoretical toxicity index of mixture actual measurement toxicity index (ATI)/mixture (TTI)] * 100
When CTC≤80, composition performance is for antagonism, and as 80 < CTC < 120, composition performance is for summation action, and when CTC >=120, composition performance is synergistic effect.
Table 1
Figure 306633DEST_PATH_IMAGE050
As known from Table 1, alkene oxime amine and thiophanate-methyl are in the scope of proportioning 1:100-100:1 of control Rhizoctonia solani Kuhn time, co-toxicity coefficient is all greater than 120, illustrate that both all show as gain effect at the mixture within the scope of this, especially work as both ratios at 1:5, gain effect is particularly outstanding.
 
Test two
Subjects: fusarium graminearum
Test method: adopt growth rate method to carry out the toxicity test of fusarium graminearum to medicament of the present invention, preculture fusarium graminearum on PDA flat board, cultivates after 4d for 25 ℃, breaks into the bacterium sheet of 5.0mm in colony edge.Bacterium sheet is inoculated on the PDA flat board that contains respective concentration medicament, each processing repeats 3 times, separately establishes blank sterilising medium for contrast.Cultivate after 4d for 25 ℃, when contrast bacterium cake diameter exceedes 5.0mm, by right-angled intersection method, measure colony diameter, calculate mycelial growth inhibition rate.
Mycelial growth inhibition rate=(contrast colony growth diameter-processing colony growth diameter)/contrast colony growth diameter
Mycelial growth inhibition rate is converted into probability value (y), and liquor strength (μ g/ml) converts logarithm value (x) to, with method of least squares, calculates concentration EC in virulence equation and inhibition 50, according to toxicity index and the co-toxicity coefficient (CTC) of the abundant method calculating of Sun Yun medicament, toxicity test result is as shown in table 2.
Table 2
Figure 251455DEST_PATH_IMAGE052
As known from Table 2, alkene oxime amine and thiophanate-methyl are in the scope of proportioning 1:100-100:1 of control fusarium graminearum time, co-toxicity coefficient is all greater than 120, illustrate that both all show as gain effect at the mixture within the scope of this, especially work as both ratios at 1:1, gain effect is particularly outstanding.
 
Test three
Subjects: rice green smut
Test method: adopt growth rate method to carry out: the toxicity test of Ustilaginoidea virens to medicament of the present invention, preculture Ustilaginoidea virens on PDA flat board, cultivates after 4d for 25 ℃, breaks into the bacterium sheet of 5.0mm in colony edge.Bacterium sheet is inoculated on the PDA flat board that contains respective concentration medicament, each processing repeats 3 times, separately establishes blank sterilising medium for contrast.Cultivate after 4d for 25 ℃, when contrast bacterium cake diameter exceedes 5.0mm, by right-angled intersection method, measure colony diameter, calculate mycelial growth inhibition rate.
Mycelial growth inhibition rate=(contrast colony growth diameter-processing colony growth diameter)/contrast colony growth diameter
Mycelial growth inhibition rate is converted into probability value (y), and liquor strength (μ g/ml) converts logarithm value (x) to, with method of least squares, calculates concentration EC in virulence equation and inhibition 50, according to toxicity index and the co-toxicity coefficient (CTC) of the abundant method calculating of Sun Yun medicament, toxicity test result is as shown in table 3.
Table 3
Figure 918453DEST_PATH_IMAGE054
As known from Table 3, alkene oxime amine and thiophanate-methyl are in the scope of proportioning 1:100-100:1 of control Ustilaginoidea virens time, co-toxicity coefficient is all greater than 120, illustrate that both all show as gain effect at the mixture within the scope of this, especially work as both ratios at 1:5, gain effect is particularly outstanding.
 
Test four
Subjects: rice blast
Test method: adopt growth rate method to carry out the toxicity test of rice blast fungus to medicament of the present invention, preculture rice blast fungus on PDA flat board, cultivates after 4d for 25 ℃, breaks into the bacterium sheet of 5.0mm in colony edge.Bacterium sheet is inoculated on the PDA flat board that contains respective concentration medicament, each processing repeats 3 times, separately establishes blank sterilising medium for contrast.Cultivate after 4d for 25 ℃, when contrast bacterium cake diameter exceedes 5.0mm, by right-angled intersection method, measure colony diameter, calculate mycelial growth inhibition rate.
Mycelial growth inhibition rate=(contrast colony growth diameter-processing colony growth diameter)/contrast colony growth diameter
Mycelial growth inhibition rate is converted into probability value (y), and liquor strength (μ g/ml) converts logarithm value (x) to, with method of least squares, calculates concentration EC in virulence equation and inhibition 50, according to toxicity index and the co-toxicity coefficient (CTC) of the abundant method calculating of Sun Yun medicament, toxicity test result is as shown in table 4.
 
Table 4
Figure 923318DEST_PATH_IMAGE056
As known from Table 4, alkene oxime amine and thiophanate-methyl are in the scope of proportioning 1:100-100:1 of control rice blast time, and co-toxicity coefficient is all greater than 120, illustrates that both all show as gain effect at the mixture within the scope of this, especially work as both ratios at 1:10, gain effect is particularly outstanding.
 
Preventive effect test
When the effect of active compound combinations exceedes the summation of the effect when each reactive compound is used separately, there is synergistic function.The predictive role of the particular combination of two kinds of reactive compounds can be used so-called " Colby formula " (referring to S.R. Colby, " Calculating Synergistic and Antagonistic Responses of Herbicide Combinations ", Weeds 1967,15,20-22) calculate as follows: if
X is the activity when using consumption for mg/ha or the concentration reactive compound A that is mppm;
Y is the activity when using consumption for ng/ha or the concentration reactive compound B that is nppm, is expressed as the percentage that accounts for untreated control;
E is the activity when using consumption for m and n g/ha or the concentration reactive compound A that is m and n ppm and B,
So
Figure DEST_PATH_IMAGE058A
If the activity of actual observation (O) is greater than expection active (E), so said composition super add and, there is synergistic effect.
Following biological test example is in order to illustrate the present invention.But the present invention is not limited to these embodiment.
 
The preventive effect of five pairs of rice sheath blight diseases of experiment
Test adopts greenhouse seedling potted plant determination method, trial crops at greenhouse pot culture to the 2-3 leaf phase.By design dosage, on crops sprayer, carry out foliar spray processing, 24 hours inoculation test pathogens after chemicals treatment, postvaccinal test material is middle moisturizing cultivation in the controlled environment chamber all, when the blank of not dispenser is fully fallen ill, carry out result investigation, disease scale, preventive effect computational methods are all with reference to State Standard of the People's Republic of China [pesticide field efficacy medicine test criterion].
To the preventive effect of rice sheath blight disease
Test six wheat scabs
Test adopts greenhouse seedling potted plant determination method, trial crops at greenhouse pot culture to the 2-3 leaf phase.By design dosage, on crops sprayer, carry out foliar spray processing, 24 hours inoculation test pathogens after chemicals treatment, postvaccinal test material is middle moisturizing cultivation in the controlled environment chamber all, when the blank of not dispenser is fully fallen ill, carry out result investigation, disease scale, preventive effect computational methods are all with reference to State Standard of the People's Republic of China [pesticide field efficacy medicine test criterion].
To the preventive effect of wheat scab
Figure 968820DEST_PATH_IMAGE062
The preventive effect of seven pairs of rice green smuts of experiment
Test adopts greenhouse seedling potted plant determination method, trial crops at greenhouse pot culture to the 2-3 leaf phase.By design dosage, on crops sprayer, carry out foliar spray processing, 24 hours inoculation test pathogens after chemicals treatment, postvaccinal test material is middle moisturizing cultivation in the controlled environment chamber all, when the blank of not dispenser is fully fallen ill, carry out result investigation, disease scale, preventive effect computational methods are all with reference to State Standard of the People's Republic of China [pesticide field efficacy medicine test criterion].
To the preventive effect of rice green smut
Figure DEST_PATH_IMAGE064
The preventive effect of eight pairs of rice blasts of experiment
Test adopts greenhouse seedling potted plant determination method, trial crops at greenhouse pot culture to the 2-3 leaf phase.By design dosage, on crops sprayer, carry out foliar spray processing, 24 hours inoculation test pathogens after chemicals treatment, postvaccinal test material is middle moisturizing cultivation in the controlled environment chamber all, when the blank of not dispenser is fully fallen ill, carry out result investigation, disease scale, preventive effect computational methods are all with reference to State Standard of the People's Republic of China [pesticide field efficacy medicine test criterion].
To the preventive effect of rice blast
Figure DEST_PATH_IMAGE066
The mensuration of test nine on the impact of cucumber chlorophyll content
Test method: accurately take the cucumber leaves 0.5g that cleans and blot surface moisture, put into mortar after shredding.Add 5ml 80% acetone, the CaCO of a little 3powder is ground to organize completely and bleaches, and finally together with residue, pours in the lump in the filter paper of funnel, draws 80% ketone oil filter paper wash-out pigment around with 1ml liquid-transfering gun, until after filter paper and residue bleach completely, stop filtering, is settled to scale with 80% acetone.Pigment extract is poured in the cuvette that thickness is 1cm, and wavelength is adjusted to respectively 663nm and 645nm, with 80% acetone zeroing.Measure the optical density value of each processing sample under two wavelength.According to gained optical density value, calculate chlorophyll content.
Figure DEST_PATH_IMAGE068
The combination that alkene oxime amine and thiophanate-methyl are described has remarkable effect for improving cucumber chlorophyll content content.

Claims (16)

1. a microbicide compositions, is characterized in that: contain active component alkene oxime amine and thiophanate-methyl, the weight ratio of described active component alkene oxime amine and thiophanate-methyl is 1:100-100:1.
2. microbicide compositions according to claim 1, is characterized in that: the weight ratio of described active component alkene oxime amine and thiophanate-methyl is 1:50-50:1.
3. microbicide compositions according to claim 1, is characterized in that: the weight ratio of described active component alkene oxime amine and thiophanate-methyl is 1:25-25:1.
4. microbicide compositions according to claim 1, is characterized in that: the weight ratio of described active component alkene oxime amine and thiophanate-methyl is 1:10-10:1.
5. microbicide compositions according to claim 1, is characterized in that: the weight ratio of described active component alkene oxime amine and thiophanate-methyl is 1:5-5:1.
6. microbicide compositions according to claim 1, is characterized in that: the weight percentage that described active component alkene oxime amine and thiophanate-methyl account for described composition is 5%-90%.
7. microbicide compositions according to claim 1, is characterized in that: the weight percentage that described active component alkene oxime amine and thiophanate-methyl account for described composition is 10%-80%.
8. microbicide compositions according to claim 1, is characterized in that: the weight percentage that described active component alkene oxime amine and thiophanate-methyl account for described composition is 20%-60%.
9. microbicide compositions according to claim 1, is characterized in that: described active component alkene oxime amine and thiophanate-methyl mix with filler and/or surfactant.
10. microbicide compositions according to claim 1, is characterized in that: the formulation of described microbicide compositions is suspending agent, seed coat agent, wetting powder, water dispersible granules, microcapsule suspending agent, coated granule, extrudes granule, missible oil, microemulsion, aqueous emulsion, effervescent tablet, microcapsule suspension-suspending agent, ultra low volume liquids.
Prevent and treat the method for plant pathogen for 11. 1 kinds, microbicide compositions claimed in claim 1 is acted on to pathogenic bacteria and/or its environment, or in plant, plant parts, seed, soil, region, material or space.
12. according to the method for claim 11, by active component alkene oxime amine and thiophanate-methyl is used simultaneously or is used respectively or sequential application in pathogenic bacteria and/or its environment, or in plant, plant parts, seed, soil, region, material or space.
13. according to the method for claim 11, and described pathogenic bacteria are selected from swollen Gammaproteobacteria, Oomycete, Chytridiomycetes, connect and Gammaproteobacteria, Ascomycetes, Basidiomycetes, deuteromycetes.
The purposes of 14. microbicide compositions claimed in claim 1 for preventing and treating cereal, fruit, vegetables fungus and bacterium.
15. microbicide compositions claimed in claim 1 are in the purposes of preventing and treating banded sclerotial blight, rice blast, false smut, head blight.
16. microbicide compositions claimed in claim 1 are for improving the purposes of crop chlorophyll content.
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