Summary of the invention
The object of the present invention is to provide a kind of mixed ratio reasonable, control efficiency is good, the Synergistic bactericidal composition that drug cost is low.
Another object of the present invention is to provide by formulations such as the formulated missible oil of this bactericidal composition, microemulsion, aqueous emulsion, suspending agent, wetting powder, water dispersible granules, granules.
Another object of the present invention is to provide the purposes that bactericidal composition is used for downy mildew that control causes by the Oomycete disease fungus, epidemic disease, late blight.
Technical scheme of the present invention is as described below:
A kind of bactericidal composition, the arbitrary fungicide active ingredient that it is characterized in that containing the flumorph of synergy effective dose and be selected from thiophanate-methyl, benomyl, Propineb, cyazofamid, iprovalicarb.
Wherein, flumorph can change in very wide scope with the weight ratio that is selected from arbitrary fungicide active ingredient of thiophanate-methyl, benomyl, Propineb, cyazofamid, iprovalicarb, be preferably 40: 1~1: 40, more preferably 10: 1~1: 15, further be preferably 5: 1~1: 12.
And, the weight ratio of flumorph and thiophanate-methyl more preferably 1: 1~1: 12, the weight ratio of flumorph and benomyl or Propineb more preferably 1: 1~1: 10, the weight ratio of flumorph and cyazofamid or iprovalicarb more preferably 5: 1~1: 5.
Further, the weight ratio of flumorph and thiophanate-methyl is more preferably 1: 8~1: 12; The weight ratio of flumorph and benomyl or Propineb more preferably 1: 4~1: 10; The weight ratio of flumorph and cyazofamid or iprovalicarb more preferably 5: 1~1: 1.
Active component is 0.5% to 95% of gross weight in the composition of the present invention.
Except the fungicidal activity composition, also can comprise functional aid in the bactericidal composition of the present invention.That is to say, the present composition can add other components such as functional aid, is mixed with the preparation of missible oil, aqueous emulsion, microemulsion, suspending agent, wetting powder, water dispersible granules or other formulations.
In these preparations, except active component, all contain surfactant, and also can contain the thinners such as organic solvent or cosolvent, carrier (filler) or water according to different dosage form, add in case of necessity other functional aids such as antifreeze, thickener, stabilizing agent, defoamer, disintegrant.Surfactant can be emulsifier, dispersant, wetting agent or bleeding agent.Surfactant can be nonionic with ionic, also can be two or more compound uses.
Described emulsifier comprises alkylphenol-polyethenoxy (polyoxypropylene) ether, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol polyethenoxy ether, fatty alcohol-polyoxyethylene ether, polyoxyethylene carboxylate, phenethyl phenol polyethenoxy polyethenoxy ether, castor oil ethylene oxide adduct, alkylphenol polyoxyethylene formaldehyde condensation products, and the phosphate of these compounds, alkyl benzene sulphonate (calcium salt or sodium salt) or directly use commercially available emulsifier monomer and composite product.Concrete example is such as farming breast 500
#Series, 600
#Series, 1600
#Series, NP is serial, OP is serial, AEO is serial, 700
#, 400
#Serial and composite kind 2201,0203B, 2021B, 4103 etc., these all are emulsifier productions well known in the art, market is on sale.
Described dispersant; wetting agent; bleeding agent comprises lignosulfonates (sodium salt or calcium salt); Negel; condensation compound of methyl naphthalene sulfonic acid and formaldehyde sulphate; naphthalene sulfonic acid-formaldehyde condensation product; methanonaphthalene sodium sulfonate dibutyl naphthalene sulfonic acid-formaldehyde condensation product; N-methyl fatty acyl group sodium taurocholate; alkylphenol polyoxyethylene formaldehyde condensation products sulphate; polymerization of carboxylic acid sodium; the alkylphenol polyoxyethylene phosphate; the withered powder of tea; saponin; lignosulfite; aliphatic alcohol sulfate; dodecyl sodium sulfate; alkylbenzenesulfonate; penetrant t; bleeding agent OT; fatty acid amide-N methyl taurine sodium salt; sodium sulfate of polyethenoxy ether of fatty alcohol; pull open powder; JFC; can use separately, but also compound use.Above-mentioned surfactant all is materials well known in the art, can obtain by various commercial channel.
Described solvent, cosolvent comprise toluene, dimethylbenzene, chlorobenzene, solvent naphtha, alpha-methyl-naphthalene, turpentine oil, carrene, chloroform, methyl alcohol, ethanol, isopropyl alcohol, butanols, isoamyl alcohol, cyclohexanone, isophorone, acetophenone, ethyl acetate, butyl acetate, N.N-dimethyl formamide, dimethyl sulfoxide (DMSO), methyl cellosolve, ethyl cellosolve etc.
Described antifreeze comprises ethylene glycol, glycerine, propane diols, urea, glycerine, ether diglycol, polyethylene glycol, isopropyl alcohol etc.
Described carrier, filler comprise white carbon, precipitated calcium carbonate, potter's clay, attapulgite, kaolin, diatomite, bentonite, sepiolite, zeolite, quartz sand, talcum powder, can use separately, also can two kinds or above mixing use.
Described disintegrant has sodium alginate, sodium carboxymethyl starch, sulfuric acid amine, bentonite, urea, calcium chloride.
Described defoamer has bubble enemy, silicone, C
8-10Fatty alcohol, C
10-20Saturated fat acids (such as capric acid, stearic acid etc.) and amide-type.
Described binding agent comprises starch, dextrin, gum Arabic, soybean protein, gelatine, sodium sulphate, gypsum, polyvinyl alcohol, polyethylene glycol, rosin, paraffin, CMC, sodium silicate.Can use separately, also can two or morely use with.
Can contain toner in the preparation, inorganic pigment iron oxide for example, titanium oxide or Prussian blue; Organic dyestuff is such as A Lizhalin, azo dyes, metal phthalocyanine or kiton colors.In water-base preparation, for preventing moldy metamorphism, need to add a certain amount of preservative, described preservative has Sodium Benzoate, polyformaldehyde, sorbitol, formalin, citric acid, to the yl benzoic acid methyl esters, face phenyl phenol sodium, 1,2-benzisothiazole-3-ketone (code name BIT) etc.
The product that the present invention describes can be the finished product preparation form to be provided, and namely each material mixes in the composition, but the composition of composition also can provide with independent preparation directly mixing in bucket (tank) before using.Concentrate of the present invention usually and water be mixed to get the concentration of required active substance.
Composition of the present invention can be used for various plants, such as Chinese cabbage, wild cabbage, cauliflower, wax gourd, cucumber, tomato, lichee, grape, wheat, rape, potato, tobacco and flowers etc.The place of using of the product that composition of the present invention and carrier are made is farmland, orchard or warehouse etc.
Composition of the present invention also can with other compound with weeding, desinsection or bactericidal property particularly the protective fungicide agent composition use, also can use with nematocide, protective agent, growth regulator, nutrient for plants or soil conditioner mixture.Composition of the present invention can be used by common method, such as cast, injection, spraying.Amount of application of the present invention is with weather condition or crop state variation, and time of application can be before or after crop be susceptible.The duration of protective effect is usually relevant with the content of individualized compound in the composition, also relevant with extraneous factor, weather for example, but by using suitable formulation can slow down climatic influences.
The remarkable advantage of composition of the present invention: the one, composition shows extremely strong synergistic effect in certain ratio range, the bactericidal effect of mixed composition is significantly improved than its single dose, thereby reduced using dosage, when reducing peasant's drug cost, reduced influence degree.The 2nd, interracial structure differs larger, and the resistance that the application of said composition can delay single dose occurs and development.
Embodiment:
The present invention is elaborated with following specific embodiment, so that advantage of the present invention is more obvious, but the present invention is limited to absolutely not these examples.Percentage all is weight percentage in the prescription of all preparations, and the processing of biologically-active moiety is effective content.
Formulation Example:
1, the preparation of missible oil
By the prescription requirement, add respectively solvent, former medicine, emulsifier, mix, use in case of necessity the hot bath heating for dissolving, namely obtain transparence missible oil.Such as embodiment 1~3 prescription.
Embodiment 1 (55% missible oil)
Flumorph 5%, thiophanate-methyl 50%, farming breast 500
#7.5%, agricultural newborn 600-2
#4.5%, methyl alcohol 8%, dimethylbenzene complements to 100%.
Embodiment 2 (25% missible oil)
Flumorph 3%, benomyl 22%, farming breast 507
#10%, agricultural newborn OX-653 3%, methyl alcohol 10%, dimethylbenzene complements to 100%.
Embodiment 3 (10% missible oil)
Flumorph 6%, iprovalicarb 4%, farming breast 500
#10%, agricultural newborn OX-635 5%, methyl alcohol 10%, dimethylbenzene complements to 100%.
2, the preparation of wetting powder
By the prescription requirement, former medicine, various auxiliary agent and filler etc. are fully mixed, behind ultra-fine pulverizer disintegrating, namely obtain converted products.Such as embodiment 4~10 prescriptions.
Embodiment 4 (55% wetting powder)
Flumorph 5%, thiophanate-methyl 50%, lauryl sodium sulfate 1.5%, carboxymethyl cellulose 1%, sodium lignin sulfonate 10%, precipitated calcium carbonate complements to 100%.
Embodiment 5 (40% wetting powder)
Flumorph 5%, benomyl 35%, lauryl sodium sulfate 1.5%, carboxymethyl cellulose 1%, sodium lignin sulfonate 10%, precipitated calcium carbonate complements to 100%.
Embodiment 6 (40% wetting powder)
Flumorph 5%, Propineb 35%, neopelex 1%, white carbon 10%, sodium lignin sulfonate 10%, precipitated calcium carbonate complements to 100%.
Embodiment 7 (10% wetting powder)
Flumorph 6%, cyazofamid 4%, neopelex 1%, white carbon 10%, sodium lignin sulfonate 10%, precipitated calcium carbonate complements to 100%.
Embodiment 8 (10% wetting powder)
Flumorph 6%, iprovalicarb 4%, alkyl amide taurate 2%, Fluhyzon formaldehyde condensation 5%, alkylphenol-polyethenoxy phosphate 5%, precipitated calcium carbonate complements to 100%.
3, the preparation of aqueous emulsion
Former medicine, solvent, emulsifier and co-emulsifier are added together, make dissolving be even oil phase.Water, antifreeze etc. is mixed, becomes the homogeneous water.Under high-speed stirred, water is joined oil phase or oil phase is joined water, form the aqueous emulsion of favorable dispersibility.Such as embodiment 10~13 prescriptions.
Embodiment 11 (35% aqueous emulsion)
Flumorph 3%, thiophanate-methyl 32%, polyvinyl alcohol 0.8%, in triphenylethylene phenol+oxirane, phosphorylation, the triethanolamine and 8.5%, alkyl-diethylene glycol ether-sodium sulfonate 2.5%, farming breast 2,201 13%, dimethyl formamide 8%, ethylene glycol 5%, water complements to 100%.
Embodiment 12 (10% aqueous emulsion)
Flumorph 6%, cyazofamid 4%, polyvinyl alcohol 0.9%, alkylaryl polyoxyethylene propylene ether 8.5%, farming breast 2,201 15%, dimethyl formamide 12%, ethylene glycol 5%, water complements to 100%.
Embodiment 13 (10% aqueous emulsion)
Flumorph 6%, iprovalicarb 4%, polyvinyl alcohol 1.5%, alkylaryl polyoxyethylene propylene ether 10%, farming breast 2,201 15%, dimethyl formamide 15%, ethylene glycol 5%, water complements to 100%.
4, the preparation of water-dispersible granules
Former medicine and powder carrier, wet spreading agent and binding agent etc. are carried out co-grinding, after adding again water and mediating, add in the comminutor that the certain specification screen cloth is housed and carry out granulation.And then drying, screening (by the screen cloth scope) namely gets granular product.Such as embodiment 14~15 prescriptions.
Embodiment 14 (40% water-dispersible granules)
Flumorph 5%, Propineb 35%, methyl naphthalene sulfonate formaldehyde condensate 12%, epoxidized polyether 5%, soluble starch 15%, gypsum complements to 100%.
Embodiment 15 (15% water-dispersible granules)
Flumorph 10%, iprovalicarb 5%, methanonaphthalene sodium sulfonate 5%, epoxidized polyether 5%, sodium sulphate, gypsum complements to 100%.
5, the preparation of suspending agent
By the prescription requirement, take water as medium, former medicine, dispersant, suspending agent and antifreezing agent etc. are added in the sand milling still, carry out porphyrize, make suspending agent.Such as embodiment 16~18 prescriptions.
Embodiment 16 (55% suspending agent)
Flumorph 5%, thiophanate-methyl 50%, methyl naphthalene sulfonate formaldehyde condensate 5.5%, white carbon 0.2%, aluminium-magnesium silicate 0.18%, ethylene glycol 4%, silicone a little, water complements to 100%.
Embodiment 17 (40% suspending agent)
Flumorph 5%, Propineb 35%, calcium lignosulfonate 5%, white carbon 0.3%, ethylene glycol 4%, silicone a little, water complements to 100%.
Embodiment 18 (10% suspending agent)
Flumorph 6%, cyazofamid 4%, methyl naphthalene sulfonic acid naphthaldehyde condensation compound 2.5%, bentonite 1.0%, farming breast 1,601 3%, glycerine 4%, silicone a little, water complements to 100%.
6, the preparation of microemulsion
Former medicine, solvent, emulsifier and co-emulsifier are added together, make dissolving be even oil phase.Water, antifreeze etc. is mixed, becomes the homogeneous water.Under high-speed stirred, water is joined oil phase or oil phase is joined water, form the microemulsion of favorable dispersibility.Such as embodiment 19~21 prescriptions.
Embodiment 19 (35% microemulsion)
Flumorph 3%, thiophanate-methyl 32%, propyl alcohol 7%, phenethyl phenol polyethenoxy ether 10%, carrene 10%, glycerine 5%, water complements to 100%.
Embodiment 20 (25% microemulsion)
Flumorph 3%, benomyl 22%, dimethylbenzene 12%, phenyl xenol polyvinylether 15%, ring ethanol 8%, ethylene glycol 8%, water complements to 100%.
Embodiment 21 (10% microemulsion)
Flumorph 6%, iprovalicarb 4%, ethanol 6%, sodium alkyl benzene sulfonate 8%, the third hexanone 8%, propane diols 6%, water complements to 100%.
7, the present invention illustrates the synergistic effect that the present invention makes up with following biologically active embodiment.
The joint toxicity measuring of test example 1 flumorph and thiophanate-methyl
For the examination bacterium
Cucumber downy mildew (Psenudoperonos pora.Cubensis)
For the examination cucumber variety
" the close thorn in Shandong ", cucumber is potted plant to be cultured to two open and flat phases of few leaf in the greenhouse.
The experimental concentration design
The experimental concentration of combination medicament and flumorph single dose is five concentration of 32,16,8,4,2 μ g/ml, and the thiophanate-methyl concentration for the treatment of is 80,40,20,10,5 μ g/ml, and other establishes the blank of not dosing, and each is processed 4 times and repeats.
Test method
Select second true leaf of the potted plant cucumber of growth neat and consistent, put to culture dish at petiole place humidification cotton balls after cutting, by top set concentration in the crops sprayer processing of spraying, after the blade liquid dries, in second day inoculation cucumber downy mildew germ, then place in the crop cultivation case and cultivate.
Condition of culture
Cultivation temperature: 28 ℃ of daytimes, 23 ℃ of nights.Incubation time: 6 days.
Investigation and method of counting
6 days " Invest, Then Investigate " control efficiency are cultivated in moisturizing in incubator, by the grade scale classification record of medicine inspecting institute of the Ministry of Agriculture " agricultural chemicals field trial criterion ", calculate control efficiency with disease index, and obtain virulence regression equation and EC
50, according to Wadley fungicide in mixture synergy evaluation assessment, calculate interactional ratio behind two single dose mixtures (be that SR<0.5 is antagonism, 0.5≤SR≤1.5 are summation action, and SR>1.5 are synergistic effect).
Result of the test sees the following form 1.
The joint toxicity measuring result of table 1 flumorph and thiophanate-methyl
Result of the test shows: flumorph and thiophanate-methyl weight ratio are 1: 10 o'clock, and its interaction ratio is respectively 2.22, and the bactericide interaction theory according to GiSi (1985) proposes has the notable synergistic effect.
The joint toxicity measuring of test example 2 flumorphs and benomyl
For the examination bacterium
Cucumber downy mildew (Psenudoperonos pora.Cubensis)
For the examination cucumber variety
" the close thorn in Shandong ", cucumber is potted plant to be cultured to two open and flat phases of few leaf in the greenhouse.
The experimental concentration design
The experimental concentration of combination medicament and flumorph single dose is five concentration of 32,16,8,4,2 μ g/ml, and the benomyl concentration for the treatment of is 80,40,20,10,5 μ g/ml, and other establishes the blank of not dosing, and each is processed 4 times and repeats.
Test method
Select second true leaf of the potted plant cucumber of growth neat and consistent, put to culture dish at petiole place humidification cotton balls after cutting, by top set concentration in the crops sprayer processing of spraying, after the blade liquid dries, in second day inoculation cucumber downy mildew germ, then place in the crop cultivation case and cultivate.
Condition of culture
Cultivation temperature: 28 ℃ of daytimes, 23 ℃ of nights.Incubation time: 6 days.
Investigation and method of counting
6 days " Invest, Then Investigate " control efficiency are cultivated in moisturizing in incubator, by the grade scale classification record of medicine inspecting institute of the Ministry of Agriculture " agricultural chemicals field trial criterion ", calculate control efficiency with disease index, and obtain virulence regression equation and EC
50, according to Wadley fungicide in mixture synergy evaluation assessment, calculate interactional ratio behind two single dose mixtures (be that SR<0.5 is antagonism, 0.5≤SR≤1.5 are summation action, and SR>1.5 are synergistic effect).
Result of the test sees the following form 2.
The joint toxicity measuring result of table 2 flumorph and benomyl
Result of the test shows: flumorph and benomyl weight ratio are 1: 7 o'clock, and its interaction ratio is respectively 1.92, and the bactericide interaction theory according to GiSi (1985) proposes has the notable synergistic effect.
The joint toxicity measuring of test example 3 flumorphs and Propineb
For the examination bacterium
Tomato late blight (Phytophthora infestans)
For the examination tomato variety
" Fu Dan ", tomato is potted plant to be cultured to two open and flat phases of few leaf in the greenhouse.
The experimental concentration design
The experimental concentration of combination medicament is five concentration of 120,60,30,15,7.5 μ g/ml, the flumorph concentration for the treatment of is 40,20,10,5,2.5 μ g/ml, the Propineb concentration for the treatment of is 800,400,200,100,50 μ g/ml, and other establishes the blank of not dosing, and each is processed 4 times and repeats.
Test method
Select second true leaf of the potted tomato of growth neat and consistent, put to culture dish at petiole place humidification cotton balls after cutting, by top set concentration in the crops sprayer processing of spraying, after the blade liquid dries, in second day inoculating tomato late blight germ, then place in the crop cultivation case and cultivate.
Condition of culture
Cultivation temperature: 28 ℃ of daytimes, 23 ℃ of nights.Incubation time: 6 days.
Investigation and method of counting
6 days " Invest, Then Investigate " control efficiency are cultivated in moisturizing in incubator, by the grade scale classification record of medicine inspecting institute of the Ministry of Agriculture " agricultural chemicals field trial criterion ", calculate control efficiency with disease index, and obtain virulence regression equation and EC
50, according to Wadley fungicide in mixture synergy evaluation assessment, calculate interactional ratio behind two single dose mixtures (be that SR<0.5 is antagonism, 0.5≤SR≤1.5 are summation action, and SR>1.5 are synergistic effect).
Result of the test sees the following form 3.
The joint toxicity measuring result of table 3 flumorph and Propineb
Result of the test shows: flumorph and Propineb weight ratio are 1: 7 o'clock, and its interaction ratio is respectively 2.05, and the bactericide interaction theory according to GiSi (1985) proposes has the notable synergistic effect.
The joint toxicity measuring of test example 4 flumorphs and cyazofamid
For the examination bacterium
Downy mildew of garpe (Plasmopara viticola)
For the examination grape variety
" huge peak ", grape is potted plant to be cultured to two open and flat phases of few leaf in the greenhouse.
The experimental concentration design
The experimental concentration of combination medicament and cyazofamid single dose is five concentration of 32,16,8,4,2 μ g/ml, and the flumorph concentration for the treatment of is 40,20,10,5,2.5 μ g/ml, and other establishes the blank of not dosing, and each is processed 4 times and repeats.
Test method
Select second true leaf of the grape pot of growth neat and consistent, put to culture dish at petiole place humidification cotton balls after cutting, by top set concentration in the crops sprayer processing of spraying, after the blade liquid dries, in second day inoculation downy mildew of garpe germ, then place in the crop cultivation case and cultivate.
Condition of culture
Cultivation temperature: 28 ℃ of daytimes, 23 ℃ of nights.Incubation time: 6 days.
Investigation and method of counting
6 days " Invest, Then Investigate " control efficiency are cultivated in moisturizing in incubator, by the grade scale classification record of medicine inspecting institute of the Ministry of Agriculture " agricultural chemicals field trial criterion ", calculate control efficiency with disease index, and obtain virulence regression equation and EC
50, according to Wadley fungicide in mixture synergy evaluation assessment, calculate interactional ratio behind two single dose mixtures (be that SR<0.5 is antagonism, 0.5≤SR≤1.5 are summation action, and SR>1.5 are synergistic effect).
Result of the test sees the following form 4.
The joint toxicity measuring result of table 4 flumorph and cyazofamid
Result of the test shows; Flumorph and cyazofamid weight ratio are 2: 1 o'clock, and its interaction ratio is respectively 1.91, and the bactericide interaction theory according to GiSi (1985) proposes has the notable synergistic effect.
The joint toxicity measuring of test example 5 flumorphs and iprovalicarb
For the examination bacterium
Cucumber downy mildew (Psenudoperonos pora.Cubensis)
For the examination cucumber variety
" the close thorn in Shandong ", cucumber is potted plant to be cultured to two open and flat phases of few leaf in the greenhouse.
The experimental concentration design
The experimental concentration of combination medicament is five concentration of 16,8,4,2,1 μ g/ml, and flumorph and iprovalicarb concentration for the treatment of are 32,16,8,4,2 μ g/ml, and other establishes the blank of not dosing, and each is processed 4 times and repeats.
Test method
Select second true leaf of the potted plant cucumber of growth neat and consistent, put to culture dish at petiole place humidification cotton balls after cutting, by top set concentration in the crops sprayer processing of spraying, after the blade liquid dries, in second day inoculation cucumber downy mildew germ, then place in the crop cultivation case and cultivate.
Condition of culture
Cultivation temperature: 28 ℃ of daytimes, 23 ℃ of nights.Incubation time: 6 days.
Investigation and method of counting
6 days " Invest, Then Investigate " control efficiency are cultivated in moisturizing in incubator, by the grade scale classification record of medicine inspecting institute of the Ministry of Agriculture " agricultural chemicals field trial criterion ", calculate control efficiency with disease index, and obtain virulence regression equation and EC
50, according to Wadley fungicide in mixture synergy evaluation assessment, calculate interactional ratio behind two single dose mixtures (be that SR<0.5 is antagonism, 0.5≤SR≤1.5 are summation action, and SR>1.5 are synergistic effect).
Result of the test sees the following form 5.
The joint toxicity measuring result of table 5 flumorph and iprovalicarb
Result of the test shows: flumorph and iprovalicarb weight ratio are 2: 1 o'clock, and its interaction ratio is respectively 2.18, and the bactericide interaction theory according to GiSi (1985) proposes has the notable synergistic effect.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.