CN102204546B - Bactericidal composition containing thifluzamide and triazole compounds - Google Patents
Bactericidal composition containing thifluzamide and triazole compounds Download PDFInfo
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Abstract
The invention relates to a bactericidal composition containing thifluzamide and triazole compounds. The bactericidal composition comprises an active component A and an active component B, wherein the active component A is selected from thifluzamide, and the active component B is selected from one of metconazole, triticonazole, imibenconazole or fenbuconazole; the weight proportion of the effective active component A to the effective active component B is (1-80 percent): (1-80 percent); and an accessory ingredient and an excipient are added into the effective active components to prepare wettable powder, water dispersible granules, a suspending agent, suspended emulsion or a suspension seed coating agent. The bactericidal composition provided by the invention is used for preventing and curing rice blast, banded sclerotial blight, septoria nodorum, a rust disease, powdery mildew, anthracnose, botrytis, downy mildew, alternaria mali Roberts, a rot disease, a tan disease, cladosporium cucumerinum, leaf spot, an epidemic disease, a black rot disease, a brown spot disease, a scab disease and leaf blight and has the effects of less dosage, rain washing resistance and obvious synergia.
Description
Technical field
The invention belongs to technical field of pesticide, relate to the application of a kind of bactericidal composition containing thifluzamide and triazole class compounds in crop pest.
Technical background
Thifluzamide, English name: thifluzamide, molecular formula: C
13h
6br
2f
6n
2o
2s, the bromo-2-methyl-4-of chemical name: 2,6-bis-trifluoromethoxy-4-Trifluoromethyl-1,3-thiazole-5-carbonyl acyl is for aniline, structural formula:
Thifluzamide belongs to thiazole amide bactericide, has strong interior conductivity and the long lasting effect of inhaling.Thifluzamide is succinate dehydrogenase inhibitor, and Main Function is the acidohydrogenase suppressing in disease fungus tricarbonic acid cycle, causes thalline dead.Due to fluorine-containing, its its competitiveness in biochemical pathway is very strong, once be combined with substrate or enzyme, is just difficult for recovering.Thifluzamide all has activity to pathomycetes such as Rhizoctonia, Puccinia, Ustilago, Tilletia, corticium, nuclear cavity Pseudomonas, especially the fungus-caused disease of Basidiomycetes is had to special efficacy as banded sclerotial blight, damping off etc.
Metconazole (metconazole), molecular formula: C
17h
22clN
3o, chemical name: (1RS, 5RS; 1RS, 5SR)-5-(4-chlorphenyl)-2,2-dimethyl-1-(1-hydrogen-1,2,4-triazole-1-methyl) cyclopentanol, C-14 demethylation enzyme inhibitor in ergosterol biosynthesis.Although the mechanism of action is the same with other triazole bactericidal agents, activity profile difference is larger.Two kinds of isomer have bactericidal activity, but cis activity is higher than trans.The antifungal spectrum of metconazole is very extensive, and active splendid.Metconazole field is used and cereal septoria musiva, fusarium and handle rest fungus are planted to disease is had remarkable effect.Metconazole is compared with traditional biocide agent, and dosage is extremely low and prevent and treat cereal to plant disease scope very wide.
Triticonazole (triticonazole), molecular formula: C
17h
20clN
3o, chemical name: (±)-(E)-5-(4-benzyl chloride thiazolinyl)-2,2-dimethyl-1-(1H-1,2,4-triazol-1-yl methyl) cyclopentanol, C-14 demethylation enzyme inhibitor in sterol biosynthesis.Main as seed treatment.
Glyoxalin (imibenconazole), molecular formula: C
17h
13cl
3n
4s, chemical name: 4-chlorobenzyl N-(2,4-dichlorophenyl)-2 (1H-1,2,4-triazol-1-yl) thioacetamide ester, glyoxalin belongs to broad spectrum activity triazole bactericidal agent.Be mainly the biosynthesis that destroys and stop the cell membrane important component part ergosterol of germ, thereby destroyed the formation of cell membrane, cause germ dead.
RH-7592 (fenbuconazole), molecular formula: C
19h
17clN
4, chemical name: 4-(4-chlorphenyl)-2-phenyl-2 (1H-1,2,4-triazol-1-yl methyl) butyronitrile, belongs to ergosterol biosynthesis inhibitor (EBI).Have protection concurrently, cure the disease and the interior absorption spectrum bactericide of killing action.
In the real process of agricultural production, preventing and treating the problem that disease the most easily produces is the drug-fast generation of germ.Different cultivars composition carries out composite, is to prevent and treat the very common method of resistance germ.Heterogeneity is carried out composite, according to practical application effect, judge certain composite be synergy, add and or antagonism.In most cases, the composite effect of agricultural chemicals is all additive effect, really has the seldom composite of synergistic effect, especially synergistic effect very obviously, synergy ratio very high composite just still less.Through inventor's research, discovery is mutually composite by thifluzamide and effective active composition B, there is within the specific limits good synergistic effect, and relevant composite about thifluzamide and metconazole, triticonazole, glyoxalin, RH-7592, there is not yet at present relevant report at home and abroad.
Summary of the invention
The object of the invention is to propose a kind of have synergistic function, use cost is low, preventive effect the is good bactericidal composition containing thifluzamide and triazole class compounds.
The present invention is achieved through the following technical solutions:
Containing the bactericidal composition of thifluzamide, it is characterized in that: the percentage by weight of A, two kinds of active components of B is 1～80%: 1～80%, and described A component is thifluzamide, B component is selected from a kind of in metconazole, triticonazole, glyoxalin or RH-7592.
The described bactericidal composition containing thifluzamide, is characterized in that: wherein the percentage by weight of thifluzamide and effective active composition B is 2～60%: 2～60%.
The described bactericidal composition containing thifluzamide, is characterized in that: the percentage by weight of thifluzamide and metconazole is 5～40%: 5～40%.
The described bactericidal composition containing thifluzamide, is characterized in that: the percentage by weight of thifluzamide and triticonazole is 5～40%: 5～40%.
The described bactericidal composition containing thifluzamide, is characterized in that: the percentage by weight of thifluzamide and glyoxalin is 5～40%: 5～50%.
The described bactericidal composition containing thifluzamide, is characterized in that: the percentage by weight of thifluzamide and RH-7592 is 5～40%: 5～40%.
The described bactericidal composition containing thifluzamide, wherein effective active component content accounts for 1～90% of gross weight, is preferably 5～80%.
The described bactericidal composition containing thifluzamide is made wetting powder, water dispersible granules, suspending agent, suspension emulsion or suspension seed-coating agent.
Described bactericidal composition is mainly used in preventing and treating the plant diseases such as rice blast, banded sclerotial blight, glume blight, rust, powdery mildew, anthracnose, spot defoliation, rot, brown spot, scab, leaf spot, leaf blight, gray mold, downy mildew, epidemic disease, black spot, brown spot, shot hole.
The amount of application when content of active component depends on independent use in the present composition, also depends on mixed ratio and the synergistic effect degree of a kind of compound and another kind of compound, and the while is also relevant with target fungi.Conventionally in composition, active weight percentage is gross weight 1～90%, is preferably 5%～80%.According to different preparation types, active component content scope is different.Conventionally, liquid preparation contains 1～60% active substance by weight, is preferably 5～50%; Solid pharmaceutical preparation contains 5～85% active substance by weight, is preferably 10～80%.
In bactericidal composition of the present invention, at least contain a kind of surfactant, the dispersion of active component in water while being beneficial to use.Surface-active contents is 5～30% of total formulation weight amount, and surplus is solid or liquid diluent.
The selected surfactant of bactericidal composition of the present invention is known in those skilled in the art: can be selected from one or more in dispersant, wetting agent, thickener or defoamer.According to different dosage form, in preparation, can also contain stabilizing agent known in those skilled in the art, antifreeze etc.
Bactericidal composition of the present invention, can be processed into acceptable formulation on any agricultural chemicals on demand.Wherein preferred dosage form is wetting powder, water dispersible granules, suspending agent, suspension emulsion, suspension seed-coating agent.
When making wetting powder, composition comprises following constituent content: thifluzamide 1～80%, active component B1～80%, dispersant 5～10%, wetting agent 2～10%, filler 8～91%.
The former medicine of thifluzamide, the former medicine of active component B, dispersant, wetting agent, filler are mixed, in mixed cylinder, mix, after airslide disintegrating mill is pulverized, mix again, can be made into the wetting powder product of the present composition.
When making water dispersible granules, composition comprises following constituent content: thifluzamide 1～80%, active component B1～80%, dispersant 3～12%, wetting agent 1～8%, disintegrant 1～10%, binding agent 1～8%, filler 10～92%.
The former medicine of thifluzamide, the former medicine of active component B, dispersant, wetting agent, disintegrant, filler etc. are obtained to the particle diameter needing through air-flow crushing together, then add other auxiliary agents such as binding agent, obtain preparation materials.By item quantitatively send in fluidized bed granulation dryer through granulation and dry after, make the water dispersible granules product of the present composition.
When making suspending agent, composition comprises following constituent content: thifluzamide 1～50%, active component B1～50%, dispersant 2～10%, wetting agent 2～10%, defoamer 0.1～1%, thickener 0.1～2%, antifreeze 0.1～8%, stabilizing agent 0.05～3%, deionized water adds to 100%.
Dispersant, wetting agent, defoamer, thickener, antifreeze in above-mentioned formula are mixed through high speed shear, add the former medicine of thifluzamide, the former medicine of active component B, in ball mill, ball milling is 2～3 hours, make diameter of particle all below 5 μ m, make the suspending agent product of the present composition.
When making suspension emulsion, composition comprises following constituent content: thifluzamide 1～50%, active component B1～50%, emulsifier 2～10%, dispersant 2～10%, defoamer 0.1～2%, thickener 0.1～2%, antifreeze 0.1～8%, stabilizing agent 0.05～3%, water add to 100%.
Dispersant, defoamer, thickener, antifreeze, stabilizing agent in above-mentioned formula are mixed through high speed shear, add the former medicine of active component B, in ball mill, ball milling is 2～3 hours, make diameter of particle all below 5 μ m, make active component B suspending agent, then by the former medicine of thifluzamide, emulsifier and various auxiliary agent with the direct emulsification of high speed agitator in suspending agent, make the suspension emulsion product of the present composition.
When making suspension seed-coating agent, composition comprises following constituent content: thifluzamide 1～40%, active component B1～40%, film forming agent 3～6%, binding agent 2～5%, dispersant 2～10%, wetting agent 2～5%, antifreeze 0.1～8%, defoamer 0.1～2%, thickener 0.1～2%, filler 10～92%.
The former medicine of thifluzamide, active ingredient B in above-mentioned formula are mixed, carry out high-speed wet type pulverizing, frosted, then add dispersant, binding agent, film forming agent, wetting agent, antifreeze, filler etc., through modulation kettle, mix, make present composition suspension seed-coating agent product.
Beneficial effect of the present invention: (1) present composition effective active composition thifluzamide and effective active composition B belong to the bactericide of two kinds of different mechanisms of action, and both are mutually mixed and can produce conflict; (2) present composition has good synergistic effect within the specific limits, and preventive effect is higher than single dose, and dosage is little; (3) the present invention not with an organic solvent, is difficult for producing poisoning, is convenient to transportation and storage; (4) present composition has expanded fungicidal spectrum, and crop rice blast, banded sclerotial blight, glume blight, rust, powdery mildew, anthracnose, spot defoliation, rot, brown spot, scab, leaf spot, leaf blight, gray mold, downy mildew, epidemic disease, black spot, brown spot, shot hole are all had to special efficacy.
Embodiment
Below in conjunction with embodiment, to further instruction of the present invention, the percentage in embodiment is all weight percentage, but the present invention is not limited thereto.
The embodiment of the present invention is the method that adopts Toxicity Determination and field trial to combine.
Application Example one
Example 1 80% thifluzamide metconazole wetting powder
Thifluzamide 78%, metconazole 2%, aryl phenol polyoxyethylene succinate sulfonate 6%, silkworm excrement 5%, attapulgite add to 100%, and mixture carries out air-flow crushing, make 80% thifluzamide metconazole wetting powder.
Example 2 65% thifluzamide metconazole wetting powders
Thifluzamide 60%, metconazole 5%, two (alkyl) naphthalenesulfonate formaldehyde condensation compound 5%, spaonin powder 3%, diatomite add to 100%, and mixture carries out air-flow crushing, make 65% thifluzamide metconazole wetting powder.
Example 3 64% thifluzamide metconazole water dispersible granules
Thifluzamide 60%, metconazole 4%, polycarboxylate 8%, lauryl sodium sulfate 5%, ammonium sulfate 2%, diatomite add to 100%, mix and make 64% thifluzamide metconazole water dispersible granules.
Example 4 70% thifluzamide metconazole water dispersible granules
Thifluzamide 40%, metconazole 30%, lignosulfonates 7%, neopelex 5%, bentonite add to 100%, mix and make 70% thifluzamide metconazole water dispersible granules.
Example 5 35% thifluzamide metconazole suspending agents
Thifluzamide 15%, metconazole 20%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 6%, silkworm excrement 5%, C10～20 saturated fat acids 1.2%, xanthans 1.5%, propane diols 3%, deionized water add to 100%, mix and make 35% thifluzamide metconazole suspending agent.
Example 6 40% thifluzamide metconazole suspending agents
Thifluzamide 30%, metconazole 10%, the phonetic formaldehyde condensation products sulphate 8% of alkylphenol-polyethenoxy, lauryl sodium sulfate 4%, silicone compound 1.5%, gum Arabic 2.5%, ethylene glycol 3%, deionized water add to 100%, mix and make 40% thifluzamide metconazole suspending agent.
Example 7 45% thifluzamide metconazole suspension emulsions
Thifluzamide 40%, metconazole 5%, naphthalene sulfonic acid-formaldehyde condensation product 6.5%, Nekal BX 6%, silicone compound 1.8%, triphenyl phosphite 2%, polyvinylpyrrolidone 2.2%, Nongru-700 #7%, ethylene glycol 1.5%, water add to 100%, aforementioned formula material is mixed, make 45% thifluzamide metconazole suspension emulsion.
Example 8 38% thifluzamide metconazole suspension emulsions
Thifluzamide 18%, metconazole 20%, alkylphenol-polyethenoxy are phonetic 4.5%, neopelex 3.5%, silicone oil 0.8%, polyvinylpyrrolidone 1.3%, tween 6%, polyethylene glycol 3%, water add to 100%, aforementioned formula material is mixed, make 38% thifluzamide metconazole suspension emulsion.
Example 9 25% thifluzamide metconazole suspension seed-coating agents
Thifluzamide 20%, metconazole 5%, fatty alcohol-polyoxyethylene ether 5%, naphthalenesulfonateformaldehyde formaldehyde carboxylic compound 3.5%, polyvinyl acetate 2%, ethylene glycol 5%, dextrin 1.3%, C10～20 saturated fat acids 0.7%, naphthenate 16%, bentonite add to 100%, through mixing, make 25% thifluzamide metconazole suspension seed-coating agent.
Example 10 15% thifluzamide metconazole suspension seed-coating agents
Thifluzamide 5%, metconazole 10%, Sodium Polyacrylate 3%, sodium alginate 4.5%, calcium chloride 2%, humus 15%, glycerine 2%, silicone 1.2%, polyvinyl acetate 1.3%, white carbon 10%, kaolin adds to 100%, through mixing, makes 15% thifluzamide metconazole suspension seed-coating agent.
Example 11 56% thifluzamide triticonazole wetting powders
Thifluzamide 6%, triticonazole 50%, naphthalene sulfonic acid-formaldehyde condensation product 6%, silkworm excrement 5%, starch add to 100%, and mixture carries out air-flow crushing, make 56% thifluzamide triticonazole wetting powder.
Example 12 78% thifluzamide triticonazole wetting powders
Thifluzamide 70%, triticonazole 8%, polycarboxylate 7%, soapberry powder 4%, attapulgite add to 100%, and mixture carries out air-flow crushing, make 78% thifluzamide triticonazole wetting powder.
Example 13 48% thifluzamide triticonazole water dispersible granules
Thifluzamide 40%, triticonazole 8%, lignosulfonates 7%, lauryl sodium sulfate 6%, sodium bicarbonate 1.5%, kaolin add to 100%, mix and make 48% thifluzamide triticonazole water dispersible granules.
Example 14 65% thifluzamide triticonazole water dispersible granules
Thifluzamide 55%, triticonazole 10%, polyoxyethylene carboxylate 8%, neopelex 5%, bentonite add to 100%, mix and make 65% thifluzamide triticonazole water dispersible granules.
Example 15 25% thifluzamide triticonazole suspending agents
Thifluzamide 15%, triticonazole 10%, aryl phenol polyoxyethylene succinate sulfonate 7%, lauryl sodium sulfate 6%, silicone compound 0.6%, polyvinylpyrrolidone 1.5%, polyethylene glycol 1.2%, deionized water adds to 100%, mixes and makes 25% thifluzamide triticonazole suspending agent.
Example 16 40% thifluzamide triticonazole suspending agents
Thifluzamide 10%, triticonazole 30%, polycarboxylate 6%, lauryl sodium sulfate 5%, silicone oil 0.4%, gum Arabic 1%, glycerine 1.6%, deionized water adds to 100%, mixes and makes 40% thifluzamide triticonazole suspending agent.
Example 17 30% thifluzamide triticonazole suspension emulsions
Thifluzamide 20%, triticonazole 10%, polyoxyethylene carboxylate 6%, lauryl sodium sulfate 5%, polyvinylpyrrolidone 1.4%, polyethylene glycol 2%, C10～20 saturated fat acids 0.3%, agriculture breast 600#7%, water add to 100%, mix and make 30% thifluzamide triticonazole suspension emulsion.
Example 18 20% thifluzamide triticonazole suspension emulsions
Thifluzamide 15%, triticonazole 5%, aryl phenol polyoxyethylene succinate sulfonate 7%, soapberry powder 5%, sodium phosphate trimer 1.2%, ethylene glycol 1.3%, C
10～20saturated fat acids 0.6%, OP series 6%, water add to 100%, mix and make 20% thifluzamide triticonazole suspension emulsion.
Example 19 10% thifluzamide triticonazole suspension seed-coating agents
Thifluzamide 8%, triticonazole 2%, fatty alcohol-polyoxyethylene ether 5%, naphthalenesulfonateformaldehyde formaldehyde carboxylic compound 3%, polyvinyl acetate 2%, ethylene glycol 5%, dextrin 2.4%, C10～20 saturated fat acids 1.6%, naphthenate 18%, bentonite add to 100%, through mixing, make 10% thifluzamide triticonazole suspension seed-coating agent.
Example 20 30% thifluzamide triticonazole suspension seed-coating agents
Thifluzamide 25%, triticonazole 5%, Sodium Polyacrylate 3%, sodium alginate 4.4%, calcium chloride 2%, humus 15%, glycerine 2%, silicone 1.2%, polyvinyl acetate 2.6%, white carbon 10%, kaolin adds to 100%, through mixing, makes 30% thifluzamide triticonazole suspension seed-coating agent.
Example 21 58% thifluzamide glyoxalin wetting powders
Thifluzamide 26%, glyoxalin 32%, aryl phenol polyoxyethylene succinate sulfonate 6%, Nekal BX 6%, kaolin add to 100%, and mixture carries out air-flow crushing, make 58% thifluzamide glyoxalin wetting powder.
Example 22 70% thifluzamide glyoxalin wetting powders
Thifluzamide 60%, glyoxalin 10%, naphthalene sulfonic acid-formaldehyde condensation product 8%, lauryl sodium sulfate 6%, diatomite add to 100%, and mixture carries out air-flow crushing, make 70% thifluzamide glyoxalin wetting powder.
Example 23 56% thifluzamide Imibenconazole water dispersible granules
Thifluzamide 50%, glyoxalin 6%, lignosulfonates 7%, neopelex 6%, urea 1%, attapulgite add to 100%, mix and make 56% thifluzamide Imibenconazole water dispersible granule.
Example 24 72% thifluzamide Imibenconazole water dispersible granules
Thifluzamide 22%, glyoxalin 50%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 6%, lauryl sodium sulfate 5%, bentonite add to 100%, mix and make 72% thifluzamide Imibenconazole water dispersible granule.
Example 25 25% thifluzamide glyoxalin suspending agents
Thifluzamide 20%, glyoxalin 5%, the phonetic formaldehyde condensation products sulphate 7% of alkylphenol-polyethenoxy, lauryl sodium sulfate 4%, silicone compound 0.4%, polyvinylpyrrolidone 1.6%, ethylene glycol 1.5%, deionized water add to 100%, mix and make 25% thifluzamide glyoxalin suspending agent.
Example 26 36% thifluzamide glyoxalin suspending agents
Thifluzamide 6%, glyoxalin 30%, polycarboxylate 6%, soapberry powder 5%, silicone oil 0.3%, gum Arabic 1.2%, glycerine 1.8%, deionized water add to 100%, mix and make 36% thifluzamide glyoxalin suspending agent.
Example 27 24% thifluzamide glyoxalin suspension emulsions
Thifluzamide 18%, glyoxalin 6%, lignosulfonates 6%, lauryl sodium sulfate 5%, C
10～20saturated fat acids 0.6%, gum Arabic 1.2%, agriculture breast 600#5%, polyethylene glycol 3%, water add to 100%, and aforementioned formula material is mixed, and make 24% thifluzamide glyoxalin suspension emulsion.
Example 28 38% thifluzamide glyoxalin suspension emulsions
Thifluzamide 30%, glyoxalin 8%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 7%, soapberry powder 4%, silicone compound 0.5%, sodium phosphate trimer 1.5%, 600# phosphate 6%, propane diols 2%, water add to 100%, aforementioned formula material is mixed, make 38% thifluzamide glyoxalin suspension emulsion.
Example 29 20% thifluzamide glyoxalin suspension seed-coating agents
Thifluzamide 18%, metconazole 2%, fatty alcohol-polyoxyethylene ether 5%, naphthalenesulfonateformaldehyde formaldehyde carboxylic compound 4%, polyvinyl acetate 2%, ethylene glycol 3%, dextrin 1.2%, C10～20 saturated fat acids 0.8%, naphthenate 22%, bentonite add to 100%, through mixing, make 20% thifluzamide glyoxalin suspension seed-coating agent.
Example 30 10% thifluzamide glyoxalin suspension seed-coating agents
Thifluzamide 5%, glyoxalin 5%, Sodium Polyacrylate 3%, sodium alginate 4.2%, calcium chloride 2%, humus 20%, glycerine 2%, silicone 2.2%, polyvinyl acetate 3.6%, white carbon 10%, kaolin adds to 100%, through mixing, makes 10% thifluzamide glyoxalin suspension seed-coating agent.
Example 31 50% thifluzamide RH-7592 wetting powders
Thifluzamide 5%, RH-7592 45%, naphthalene sulfonic acid-formaldehyde condensation product 6%, soapberry powder 5%, diatomite add to 100%, and mixture carries out air-flow crushing, make 50% thifluzamide RH-7592 wetting powder.
Example 32 70% thifluzamide RH-7592 wetting powders
Thifluzamide 10%, RH-7592 60%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 7%, Nekal BX 4%, kaolin add to 100%, and mixture carries out air-flow crushing, make 70% thifluzamide RH-7592 wetting powder.
Example 33 56% thifluzamide RH-7592 water dispersible granules
Thifluzamide 50%, RH-7592 6%, lauryl sodium sulfate 5%, lignosulfonates 5%, ammonium sulfate 1.5%, kaolin add to 100%, mix and make 56% thifluzamide RH-7592 water dispersible granules.
Example 34 67% thifluzamide RH-7592 water dispersible granules
Thifluzamide 45%, RH-7592 22%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 5%, soapberry powder 6%, bentonite add to 100%, mix and make 67% thifluzamide RH-7592 water dispersible granules.
Example 35 27% thifluzamide RH-7592 suspending agents
Thifluzamide 18%, RH-7592 9%, polycarboxylate 6%, spaonin powder 4%, silicone oil 0.2%, xanthans 1.2%, ethylene glycol 1.8%, deionized water add to 100%, mix and make 27% thifluzamide RH-7592 suspending agent.
Example 36 45% thifluzamide RH-7592 suspending agents
Thifluzamide 30%, RH-7592 15%, naphthalene sulfonic acid-formaldehyde condensation product 6%, lauryl sodium sulfate 5%, C
10～20saturated fat acids 0.2%, sodium phosphate trimer 1.4%, glycerine 2%, deionized water add to 100%, mix and make 45% thifluzamide RH-7592 suspending agent.
Example 37 30% thifluzamide RH-7592 suspension emulsions
Thifluzamide 20%, RH-7592 10%, lignosulfonates 5%, lauryl sodium sulfate 5%, silicone compound 0.4%, polyvinylpyrrolidone 1.6%, 600# phosphate 6%, polyethylene glycol 3%, water add to 100%, aforementioned formula material is mixed, make 30% thifluzamide RH-7592 suspension emulsion.
Example 38 48% thifluzamide RH-7592 suspension emulsions
Thifluzamide 40%, RH-7592 8%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 6%, soapberry powder 6%, silicone compound 0.2%, gum Arabic 1.5%, OP series 6%, ethylene glycol 2%, water add to 100%, aforementioned formula material is mixed, make 48% thifluzamide RH-7592 suspension emulsion.
Example 39 20% thifluzamide RH-7592 suspension seed-coating agents
Thifluzamide 10%, RH-7592 10%, fatty alcohol-polyoxyethylene ether 5%, naphthalenesulfonateformaldehyde formaldehyde carboxylic compound 4.4%, polyvinyl acetate 2%, ethylene glycol 3%, dextrin 2.6%, C10～20 saturated fat acids 1.5%, naphthenate 27%, bentonite add to 100%, through mixing, make 20% thifluzamide RH-7592 suspension seed-coating agent.
Example 40 10% thifluzamide RH-7592 suspension seed-coating agents
Thifluzamide 5%, RH-7592 5%, Sodium Polyacrylate 3%, sodium alginate 3.2%, calcium chloride 2.2%, humus 12%, glycerine 2%, silicone 1.6%, polyvinyl acetate 3.6%, white carbon 10%, kaolin adds to 100%, through mixing, makes 10% thifluzamide RH-7592 suspension seed-coating agent.
Wetting powder the key technical indexes of the present invention:
Water dispersible granules the key technical indexes of the present invention:
Suspending agent the key technical indexes of the present invention:
Suspension emulsion the key technical indexes of the present invention:
Suspension seed-coating agent the key technical indexes of the present invention:
The embodiment of the present invention is the method that adopts Toxicity Determination and field trial to combine.First pass through Toxicity Determination, synergy ratio (SR) after clear and definite two kinds of medicaments are composite by a certain percentage, SR < 0.5 is antagonism, 0.5≤SR≤1.5 are summation action, SR > 1.5 is synergistic effect, on this basis, then carry out field trial.
Thifluzamide and active component B (B be selected from metconazole, triticonazole, glyoxalin, RH-7592 a kind of) are composite to crop pest Toxicity Determination.
After the effective inhibition concentration scope of each medicament is determined in prerun, each medicament is established respectively 5 dosage by active constituent content and is processed, and establishes clear water contrast.With reference to < < farm-chemical indoor determination test rule bactericide > >, carry out, adopt mycelial growth rate method to measure the virulence of medicament to crop germ.After 72h, by right-angled intersection method, measure colony diameter, calculate and respectively process net growth, mycelial growth inhibition rate.
Net growth (mm)=measurement colony diameter-5
Mycelial growth inhibition rate is converted into probit value (y), and liquor strength (μ g/mL) converts logarithm value (x) to, with method of least squares, tries to achieve virulence regression equation (y=a+bx), and calculates thus the EC of every kind of medicament
50value.According to Wadley method, calculate the different proportioning synergy ratio (SR) of two medicaments, SR < 0.5 is antagonism simultaneously, and 0.5≤SR≤1.5 are summation action, and SR > 1.5 is synergistic effect.Computing formula is as follows:
Wherein: a, b are respectively active component thifluzamide and active component B (metconazole, triticonazole, glyoxalin, RH-7592) shared ratio in combination;
A is thifluzamide;
B is a kind of in metconazole, triticonazole, glyoxalin, RH-7592.
Implementation of an application example two:
Thifluzamide and metconazole are composite to wheat powdery mildew Toxicity Determination.
Test medicine provides by Shanxi Thompson Biological Technology Co., Ltd..
Experimental scheme: effective inhibition concentration scope of determining thifluzamide, the former medicine of metconazole and the two different proportioning mixture through preliminary experiment.
Toxicity test result
Table 1 thifluzamide, metconazole and the composite toxicity test analysis of results table to wheat powdery mildew thereof
As shown in Table 1, thifluzamide, the EC of metconazole to wheat powdery mildew
50be respectively 0.88mg/L and 0.75mg/L.Thifluzamide and metconazole proportioning were at 80: 1 to 1: 80 o'clock, synergy ratio SR is all greater than 1.5, illustrate that thifluzamide and metconazole were mixed in scope and all show synergistic effect at 80: 1 to 1: 80, wherein when thifluzamide and metconazole proportioning are 20: 1 to 1: 20, synergistic effect is the most remarkable, especially when the proportioning of thifluzamide and metconazole is during at 4: 1 to 1: 4, synergy ratio SR is maximum, and synergistic effect is the most obvious.
Implementation of an application example three
Thifluzamide and triticonazole are composite to cucumber anthracnose Toxicity Determination.
Test medicine provides by Shanxi Thompson Biological Technology Co., Ltd..
Experimental scheme: effective inhibition concentration scope of determining thifluzamide, the former medicine of triticonazole and the two different proportioning mixture through preliminary experiment.
Toxicity test result
Table 2 thifluzamide, triticonazole and the composite toxicity test analysis of results table to bitter rot or anthracnose of grape thereof
As shown in Table 2, thifluzamide, the EC of triticonazole to cucumber anthracnose
50be respectively 0.89mg/L and 0.76mg/L.Thifluzamide and triticonazole proportioning were at 80: 1 to 1: 80 o'clock, synergy ratio SR is all greater than 1.5, illustrate that thifluzamide and triticonazole were mixed in scope and all show synergistic effect at 80: 1 to 1: 80, wherein when thifluzamide and triticonazole proportioning are 20: 1 to 1: 20, synergistic effect is the most remarkable, especially when the proportioning of thifluzamide and triticonazole is during at 4: 1 to 1: 4, synergy ratio SR is maximum, and synergistic effect is the most obvious.
Implementation of an application example four
Thifluzamide and glyoxalin are composite to rice sheath blight disease Toxicity Determination.
Test medicine provides by Shanxi Thompson Biological Technology Co., Ltd..
Experimental scheme: effective inhibition concentration scope of determining thifluzamide, the former medicine of glyoxalin and the two different proportioning mixture through preliminary experiment.
Toxicity test result
Table 3 thifluzamide, glyoxalin and the composite toxicity test analysis of results table to pear scab thereof
As shown in Table 3, thifluzamide, the EC of glyoxalin to pear scab
50be respectively 0.66mg/L and 0.85mg/L.Thifluzamide and glyoxalin proportioning were at 80: 1 to 1: 80 o'clock, synergy ratio SR is all greater than 1.5, illustrate that thifluzamide and glyoxalin were mixed in scope and all show synergistic effect at 80: 1 to 1: 80, wherein when thifluzamide and glyoxalin proportioning are 20: 1 to 1: 20, synergistic effect is the most remarkable, especially when the proportioning of thifluzamide and glyoxalin is during at 4: 1 to 1: 4, synergy ratio SR is maximum, and synergistic effect is the most obvious.
Implementation of an application example five
Thifluzamide and RH-7592 are composite to rice sheath blight disease Toxicity Determination.
Test medicine provides by Shanxi Thompson Biological Technology Co., Ltd..
Experimental scheme: effective inhibition concentration scope of determining thifluzamide, the former medicine of RH-7592 and the two different proportioning mixture through preliminary experiment.
Toxicity test result
Table 4 thifluzamide, RH-7592 and the composite toxicity test analysis of results table to rice sheath blight disease thereof
As shown in Table 4, thifluzamide, the EC of RH-7592 to rice sheath blight disease
50be respectively 0.69mg/L and 0.76mg/L.Thifluzamide and RH-7592 proportioning were at 80: 1 to 1: 80 o'clock, synergy ratio SR is all greater than 1.5, illustrate that thifluzamide and RH-7592 were mixed in scope and all show synergistic effect at 80: 1 to 1: 80, wherein when thifluzamide and RH-7592 proportioning are 20: 1 to 1: 20, synergistic effect is the most remarkable, especially when the proportioning of thifluzamide and RH-7592 is during at 4: 1 to 1: 4, synergy ratio SR is maximum, and synergistic effect is the most obvious.
The composite seed dressing control of Application Example six thifluzamides and the triazole class compounds wheat diseases test of pesticide effectiveness
This experimental establishment is in suburb, Xinxiang City, Henan Province, test medicine is researched and developed, is provided by Shanxi Thompson Biological Technology Co., Ltd., contrast medicament 240g/L thifluzamide suspending agent (commercial), 5% metconazole seed treatment emulsion (commercial), 25 grams per liter triticonazole suspension seed-coating agents (commercial), 25 grams per liter glyoxalin suspension seed-coating agents (commercial), 5% RH-7592 seed dressing (commercial).
The local wheat state of an illness of investigation is mixed 1 minute by seed dressing with seed jolting before sowing in closed container before medicine, then by planting seed to experimental field, and in one day laggard row man-made irrigation.Within after dispenser 30 days, 50 days, investigate respectively disease index and calculate preventive effect.
Experimental result is as follows:
The composite seed dressing control of table 5 thifluzamide and the triazole class compounds wheat diseases test of pesticide effectiveness
As can be seen from Table 5, after thifluzamide and triazole class compounds are composite, can effectively prevent and treat wheat diseases, control efficiency is all better than the preventive effect of single dose, and the preventive effect phase reaches more than 50 days.In test scope of medication, target crop is had no adverse effects.
Application Example seven thifluzamides and metconazole and the composite control wheat powdery mildew test of pesticide effectiveness thereof
This experimental establishment is in Deyang City suburb, Sichuan Province, and test medicine is researched and developed, provided by Shanxi Thompson Biological Technology Co., Ltd., contrast medicament 240g/L thifluzamide suspending agent (commercial), 60 grams per liter metconazole aqueous emulsions (commercial).
The investigation wheat powdery mildew state of an illness before medicine, in the dispenser for the first time of state of an illness initial stage, once, dispenser is 2 times altogether in dispenser in every 7 days.Within after dispenser 3 days, 14 days, 30 days for the second time, investigate respectively disease index and calculate preventive effect.Experimental result is as follows:
Table 6 thifluzamide, metconazole and the composite control wheat powdery mildew test of pesticide effectiveness thereof
As can be seen from Table 6, after thifluzamide and metconazole are composite, can effectively prevent and treat wheat powdery mildew, control efficiency is all better than the preventive effect of single dose, and the preventive effect phase is long.In test scope of medication, target crop is had no adverse effects.
The sick test of pesticide effectiveness of Application Example eight thifluzamides and triticonazole and composite control alternaria leaf spot of apple thereof
This experimental establishment is in suburb, Liquan County, Shaanxi Province, and test medicine is researched and developed, provided by Shanxi Thompson Biological Technology Co., Ltd., contrast medicament 240g/L thifluzamide suspending agent (commercial), 25 grams per liter triticonazole suspending agents (commercial).
The sick disease index of investigation alternaria leaf spot of apple before medicine, in their early stage dispenser, every dispenser on the 7th once, dispenser is 3 times altogether, within after dispenser 3 days, 14 days, 30 days for the second time, investigates disease indexs and calculates preventive effect.Experimental result is as follows:
Table 7 thifluzamide, the sick test of pesticide effectiveness of the composite control alternaria leaf spot of apple of triticonazole
As can be seen from Table 7, after thifluzamide and triticonazole are composite, can effectively prevent and treat alternaria leaf spot of apple disease, control efficiency is all better than the preventive effect of single dose, and the preventive effect phase is long.In test scope of medication, target crop is had no adverse effects.
Application Example nine thifluzamides and glyoxalin and the composite rice sheath blight disease effect of preventing and treating thereof are tested
This experimental establishment is in the suburb of Liuzhou City, Guangxi province, and test medicine is researched and developed, provided by Shanxi Thompson Biological Technology Co., Ltd., contrast medicament 240g/L thifluzamide suspending agent (commercial), 10% glyoxalin suspending agent (commercial).
Investigation rice sheath blight disease disease index before medicine, in their early stage dispenser, dispenser for the second time after 7 days, dispenser is 2 times altogether, within after dispenser 3 days, 14 days, 30 days for the second time, investigates disease indexs and calculates preventive effect.Experimental result is as follows:
Table 8 thifluzamide, glyoxalin and the composite rice sheath blight disease test of pesticide effectiveness of preventing and treating thereof
As can be seen from Table 8, after thifluzamide and glyoxalin are composite, can effectively prevent and treat rice sheath blight disease, control efficiency is all better than the preventive effect of single dose, and the preventive effect phase is long.In test scope of medication, target crop is had no adverse effects.
Application Example ten thifluzamides and RH-7592 and the composite sigatoka test of pesticide effectiveness of preventing and treating thereof
This experimental establishment is in Hekou County, Yunnan Province, and test medicine is researched and developed, provided by Shanxi Thompson Biological Technology Co., Ltd., contrast medicament 240g/L thifluzamide suspending agent (commercial), 24% RH-7592 missible oil (commercial).
The investigation sigatoka state of an illness before medicine, in the dispenser for the first time of state of an illness initial stage, once, dispenser is 3 times altogether in dispenser in every 7 days.Within after dispenser 3 days, 14 days, 30 days for the second time, investigate respectively disease index and calculate preventive effect.Experimental result is as follows:
Table 9 thifluzamide, RH-7592 and the composite sigatoka test of pesticide effectiveness of preventing and treating thereof
As can be seen from Table 9, after thifluzamide and RH-7592 are composite, can effectively prevent and treat sigatoka, control efficiency is all better than the preventive effect of single dose, and the preventive effect phase is long.In test scope of medication, target crop is had no adverse effects.
Claims (6)
1. containing a bactericidal composition for thifluzamide and triazole class compounds, it is characterized in that: active component is comprised of thifluzamide and glyoxalin, wherein the percentage by weight of thifluzamide and glyoxalin is 1～80% ︰ 1～80%.
2. bactericidal composition according to claim 1, is characterized in that: the percentage by weight of thifluzamide and glyoxalin is 2～60% ︰ 2～60%.
3. bactericidal composition according to claim 2, is characterized in that: the percentage by weight of thifluzamide and glyoxalin is 5～40% ︰ 5～50%.
4. bactericidal composition according to claim 1, is characterized in that: bactericidal composition is made wetting powder, water dispersible granules, suspending agent, suspension emulsion or suspension seed-coating agent.
5. bactericidal composition according to claim 1 is for preventing and treating the purposes of disease on grass family class crop, vegetables, ornamental flower and fruit tree.
6. purposes according to claim 5, is characterized in that: described disease is rice blast, banded sclerotial blight, glume blight, rust, powdery mildew, anthracnose, spot defoliation, rot, brown spot, scab, leaf spot, leaf blight, gray mold, downy mildew, epidemic disease, black spot or shot hole.
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102379293B (en) * | 2011-10-26 | 2013-05-08 | 广东中迅农科股份有限公司 | Bactericidal composition |
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| CN102613206A (en) * | 2012-03-19 | 2012-08-01 | 王春水 | Agricultural bactericide containing thifluzamide and application of agricultural bactericide |
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| CN103563921B (en) * | 2012-08-04 | 2015-11-18 | 南京华洲药业有限公司 | A kind of bactericidal composition and application thereof containing thifluzamide and Flutriafol |
| CN103563919A (en) * | 2012-08-04 | 2014-02-12 | 南京华洲药业有限公司 | Bactericidal composition containing thifluzamide and triadimefon and application thereof |
| CN103563913B (en) * | 2012-08-04 | 2015-11-04 | 南京华洲药业有限公司 | A kind of bactericidal composition and application thereof containing thifluzamide and prothioconazoles |
| CN103004810A (en) * | 2012-12-11 | 2013-04-03 | 青岛东生药业有限公司 | Seed treatment dispersible powder and preparing method thereof |
| CN103004806A (en) * | 2012-12-11 | 2013-04-03 | 青岛东生药业有限公司 | Seed treating agent and preparing method thereof |
| CN103392711A (en) * | 2013-08-21 | 2013-11-20 | 陕西康禾立丰生物科技药业有限公司 | Thifluzamide composition for preventing and treating rice diseases, and preparation of thifluzamide composition |
| CN114391547B (en) * | 2022-01-19 | 2024-04-09 | 安徽省农业科学院植物保护与农产品质量安全研究所 | Seed coating formulation for preventing and controlling soybean southern blight and bacterial wilt |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002000608A2 (en) * | 2000-06-12 | 2002-01-03 | Basf Aktiengesellschaft | A process for the preparation of 2,2-dimethyl-5-(4-chlorobenzyl) cyclopentanone and an intermediate useful therefor |
| CN101828559A (en) * | 2010-06-02 | 2010-09-15 | 陕西上格之路生物科学有限公司 | Agricultural sterilizing composite containing thifluzamide |
| CN101878765A (en) * | 2010-07-02 | 2010-11-10 | 惠州市中迅化工有限公司 | Pesticide composition containing thifluzamide and difenoconazole and application thereof |
-
2011
- 2011-04-16 CN CN201110095714.1A patent/CN102204546B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002000608A2 (en) * | 2000-06-12 | 2002-01-03 | Basf Aktiengesellschaft | A process for the preparation of 2,2-dimethyl-5-(4-chlorobenzyl) cyclopentanone and an intermediate useful therefor |
| CN101828559A (en) * | 2010-06-02 | 2010-09-15 | 陕西上格之路生物科学有限公司 | Agricultural sterilizing composite containing thifluzamide |
| CN101878765A (en) * | 2010-07-02 | 2010-11-10 | 惠州市中迅化工有限公司 | Pesticide composition containing thifluzamide and difenoconazole and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| "24%满穗等几种新型杀菌剂防治水稻纹枯病对比试验";汤峰;《现代农业科技》;20071210(第23期);第85页 * |
| 汤峰."24%满穗等几种新型杀菌剂防治水稻纹枯病对比试验".《现代农业科技》.2007,(第23期),第85页. |
| 陈明亮."24%噻呋酰胺悬浮剂（满穗）防治水稻纹枯病的田间效果".《大麦与谷类科学》.2009,(第2期),第52-53页. |
| 陈明亮."24%噻呋酰胺悬浮剂(满穗)防治水稻纹枯病的田间效果".《大麦与谷类科学》.2009,(第2期),第52-53页. * |
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