Background technology
Cyazofamid (cyazofamid), molecular formula C13H13ClN4O2S, chemical name are：4- chloro- 2- cyano group-N, N- bis-Methyl -5- p-methylphenyl imidazoles -1- sulfonamide, is a kind of sulphaguanidine azoles fungicide, to Oomycete fungal such as phytophthora, downy mildewBacterium, Pseudo peronospara, the plasmodiophora brassica bacteria of pythium spp and Plasmodiophoromycetes have very high bioactivity.Mechanism of action is to block ovumMitochondrial cytochrome b c in Gammaproteobacteria germ body1The electron transmission of complex carrys out the supply of interfering energy, its binding site is enzymeQ1Center, with other fungicide without cross tolerance.Its high selection activity to pathogen is probably since target enzymes are to medicamentSensitivity difference caused by.Field information has late blight and downy mildew high prevention effect, and dosage is than otherFungicide is 2~38 times low, such as has prominent prevention effect, and medication with the concentration processing late blight of potato of 50~100mg/LPhase is flexible, lasting period length.The downy mildew of grape, cucumber, muskmelon is handled with same concentration, also there is fabulous prevention effect.The medicineAgent can extend the plant growth time, and make increasing both production and income.The effect of quality is improved for tomato.
But cyazofamid single dose long-time service, easily makes disease develop immunity to drugs, dosage is caused to increase, preventive effect is reduced, heldThe problem of effect phase shortens, is unfavorable for environment sustainable development.Active ingredient without same-action mechanism is compounded, and is to delay diseaseThe harmful common method that develops immunity to drugs, can significantly improve preventive effect, substantially reduce the dosage of pesticide, can also expand fungicidal spectrum,Improve germicidal efficiency.
CN102027957A discloses a kind of bactericidal composition containing cyazofamid, including effective active components A with effectivelyActive ingredient B, wherein effective active composition A are cyazofamid, and effective active composition B is in carbendazim, S-Ethyl ethylthio sulfonate, iprodioneOne kind, the cyazofamid bactericidal composition are used to preventing downy mildew, epidemic disease, spot defoliation, anthracnose, scab, gray mold, whitePowder disease, leaf spot multiple diseases, and with notable synergistic effect.CN101700015A discloses a kind of mould containing cyazofamid and spring thunderThe bactericidal composition of element, synergistic effect is played by compounding, applied widely, cost is low, effect is good, can be used to prevent PhycomycetesThe diseases such as the downy mildew that is produced Deng fungi in the various crops such as grape, cucumber, tomato, potato, epidemic disease, and simultaneous can control thinFungal disease such as cucumber bacterial angular leaf spot etc., has a good prevention effect, at the same to delay the resistance to the action of a drug of pathogen have compared withGood effect.
Research currently for cyazofamid compound medicine composition is less, and since fungus breeding is fast, generation overlap phenomenonSeriously, easily develop immunity to drugs to fungicide, therefore, there is still a need for developing efficient, low toxicity, low-residual, the different mechanisms of action, at the same timeThe complex preparation of synergistic function again.
The content of the invention
The present invention is directed to above-mentioned problem of the prior art, proposes a kind of pharmaceutical composition of controlling plant diseases, by cyanogen frostAzoles is compounded with fluorine bacterium azoles, it has unexpectedly been found that the composition of compounding can be remarkably reinforced the activity of cyazofamid and fluorine bacterium azoles.
First purpose of the present invention is to provide a kind of pharmaceutical composition of controlling plant diseases, by cyazofamid and fluorine bacterium azolesCompounding, to improve the prevention effect to plant disease.
To achieve the above object, the present invention provides a kind of pharmaceutical composition of controlling plant diseases, including cyazofamid withFluorine bacterium azoles, and cyazofamid and the mass ratio of fluorine bacterium azoles are 60: 1-1: 60 in described pharmaceutical composition.
In the pharmaceutical composition of controlling plant diseases of the present invention, can contain other controlling plant diseases activity intoPoint, or preferably, in the pharmaceutical composition of controlling plant diseases of the present invention, planted using cyazofamid and fluorine bacterium azoles as preventionThe active ingredient of thing disease（I.e.：The active ingredient of other controlling plant diseases is not contained）.
Preferably, described pharmaceutical composition is made of cyazofamid, fluorine bacterium azoles, auxiliary agent and carrier.
Wherein, the auxiliary agent is wetting agent, dispersant, emulsifying agent, suspending agent, bonding agent, antifreeze, thickener, pH tuneSave the one or more in agent.
Preferably, the formulation of described pharmaceutical composition for wettable powder, water dispersible granules, aqueous dispersion tablets, suspending agent,One or more in microemulsion, oil suspending agent, missible oil or aqueous emulsion etc..
A kind of preferred embodiment of the pharmaceutical composition of controlling plant diseases according to the present invention, by weight percentageThan meter, component includes：
Cyazofamid and fluorine bacterium azoles 15-45%；
Dispersant 6-10%
Wetting agent 7-11%；
Antifreeze 0.1-1%
Thickener 3-7%；
PH adjusting agent 0.01-01%；
And carrier, it is preferably that remainder is carrier；
Wherein, cyazofamid and the mass ratio of fluorine bacterium azoles are 60: 1-1: 60.
A kind of preferred embodiment of the pharmaceutical composition of controlling plant diseases according to the present invention, by weight percentageThan meter, component includes：
Cyazofamid and fluorine bacterium azoles 15-45%；
Wetting agent 7-11%；
PH adjusting agent 0.01-01%；
Suspending agent 7-13%；
And carrier, it is preferably that remainder is carrier；
Wherein, cyazofamid and the mass ratio of fluorine bacterium azoles are 60: 1-1: 60.
A kind of preferred embodiment of the pharmaceutical composition of controlling plant diseases according to the present invention, by weight percentageThan meter, component includes：
Cyazofamid and fluorine bacterium azoles 15-45%；
Emulsifying agent 2-8%；
Wetting agent 2-8%；
Suspending agent 2-8%；
And carrier, it is preferably that remainder is carrier；
Wherein, cyazofamid and the mass ratio of fluorine bacterium azoles are 60: 1-1: 60.
Preferably, cyazofamid and the mass ratio of fluorine bacterium azoles are 8: 1-1: 60 in described pharmaceutical composition, more preferably 8:1-1: 8, more preferably 4: 1-1: 4, more preferably 1: 2.
Preferably, cyazofamid and the mass ratio of fluorine bacterium azoles are 8: 1-1: 60 in described pharmaceutical composition, more preferably 4:1-1: 20 more preferably 1: 1-1: 4, more preferably 1: 2.
Preferably, cyazofamid and the mass ratio of fluorine bacterium azoles are 8: 1-1: 40 in described pharmaceutical composition, more preferably 4:1-1: 20, more preferably 4: 1-1: 8, more preferably 2: 1-1: 8, more preferably 2: 1-1: 4, more preferably 1: 1-1: 2,More preferably 1: 1.
Preferably, cyazofamid and the mass ratio of fluorine bacterium azoles are 60: 1-1: 20 in described pharmaceutical composition, more preferably 20:1-1: 8, more preferably 8: 1-1: 8, more preferably 4: 1-1: 4, more preferably 4: 1-1: 2, more preferably 4: 1-1: 1, morePreferably 2: 1-1: 1, more preferably 1: 1.
Wetting agent is also known as bleeding agent, and main function is to make solid material in composition be more easy to be soaked in water.Carried in the present inventionIn the composition of confession, sodium butylnaphthalenesulfonate, lauryl sodium sulfate, neopelex, lignin can be selected in wetting agentOne or more in sulfonate, isopropyl naphthalene sulfonate, sodium alklyarylsulfonate etc..
Dispersant be for reducing in composition dispersion system solid or liquid particle aggregation, prepare wettable powder,When water dispersible granules, aqueous dispersion tablets, suspending agent, oil suspending agent, add dispersant and be easily formed dispersion liquid and suspension, and protectHold the metastable function of dispersion.In composition provided by the invention, dispersant can be selected phosphate, Sulfonates,Alkylnaphthalene sulfonate condensation polymer, carboxylic acid salt high-molecular, polycarboxylate polymeric modified resin, alkyl sulfate, modified alkyl sulphurHydrochlorate, alkyl naphthalene sulfonic acid condensation polymer sodium salt, naphthalene sulfonate（Condensation polymer）Class, polycarboxylate polymeric dispersant, multi-styrene benzeneEther phosphate dispersant, naphthalenesulfonate formaldehyde condensation compound, APES formaldehyde condensation product sulfonate, lignin sulfonic acidOne or more in salt, maleic acid-acrylic acid copolymer sodium salt, alkyl sulfo succinate etc..
Emulsifying agent can promote the liquid that two kinds immiscible in composition to form stabilized emulsion, while be also emulsionStabilizer.In composition provided by the invention, calcium dodecyl benzene sulfonate, triphenoethyl benzene phenol polyethenoxy can be selected in emulsifying agentEther, alkyl phenol formaldehyde resin polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, castor oil polyoxyethyleneEther, nonylphenol polyoxyethylene ether, octyl phenol polyoxyethylene ether, Fatty alcohol polyoxyethylene polyoxypropylene ether, aliphatic alcohol polyethenoxyEther modifier, aliphatic amine polyoxyethylene ether, alkylaryl polyoxyethylene poly-oxygen propylene aether, EO-PO（Epoxy ethane-epoxy propane）One or more in block polyether, oleic acid polyoxyethylene, phenethyl phenol polyoxyethylene ether, nonyl phenol phosphate etc..
Suspending agent is used for increasing the viscosity of decentralized medium in composition, to reduce the sinking speed of particulate or increase particulate parentIt is water-based.In composition provided by the invention, phosphate, Sulfonates, alkylnaphthalene sulfonate condensation polymer, carboxylic acid can be selected in suspending agentSalt high-molecular, polycarboxylate polymeric modified resin, alkyl sulfate, modified alkyl sulfonate, alkyl naphthalene sulfonic acid condensation polymer sodiumSalt, naphthalene sulfonate（Condensation polymer）Class, polycarboxylate polymeric dispersant, multi-styrene phenylate phosphate dispersant, naphthalene sulfonateFormaldehyde condensation products, APES formaldehyde condensation product sulfonate, lignosulfonates, organobentonite, white carbon, siliconOne or more in sour magnalium etc..
Binding agent is for the material by homogeneity in composition or heterogeneous body surface bonding connection together.The present invention carriesIn the composition of confession, sodium carboxymethylcellulose, polyvinylpyrrolidone, starch, polyvinyl alcohol, Methyl cellulose can be selected in binding agentOne or more in element, fructose etc..
Antifreeze is the material for reducing the freezing point of composition liquid, improving freezing tolerance.Combination provided by the inventionIn thing, the one or more in the optional spent glycol of antifreeze, propane diols, glycerine, urea etc..
Thickener is the viscosity for increasing decentralized medium in composition, to reduce the sinking speed of particulate, improves combinationThe layering of thing liquid body.In composition provided by the invention, xanthans, polyethylene glycol can be selected in thickener（As Macrogol 4000,Macrogol 6000）, aluminium-magnesium silicate, gum arabic, the one or more in gelatin etc..
PH adjusting agent is the acid-base value for regulation composition.In composition provided by the invention, pH adjusting agent can be selectedOne or more in citric acid, sodium acid carbonate, diethylamine, triisopropanolamine, phosphoric acid, glacial acetic acid.
The carrier can be solid carrier, such as white carbon, diatomite, kaolin；Can also be liquid flux or pointDispersion media, such as water, organic solvent.
Second aspect of the present invention is to provide a kind of pharmaceutical composition of any one above-mentioned controlling plant diseases anti-Control the application in plant disease.
Wherein, the plant is preferably crops（Including cereal, veterinary antibiotics etc.）, gardening, fruit tree and forest plants,Preferably cereal, vegetable crop, such as rice, wheat, corn, Chinese cabbage, cucumber.
The plant disease is infectious disease caused by pathogen, wherein, pathogen can be fungi, bacterium, virusWith nematode etc..
Wherein, the plant disease can be downy mildew, it is epidemic disease, spot defoliation, anthracnose, scab, gray mold, whitePowder disease, smut, leaf spot, clubroot, samping off, brown rot etc..
Pharmaceutical composition provided by the invention containing controlling plant diseases is compounded by cyazofamid and fluorine bacterium azoles, is had brightAobvious synergistic effect, can substantially reduce EC50, the dosage of pesticide can be reduced, has the advantages that high-efficiency low-toxicity, cost accounting are low etc..
Embodiment 1
Cyazofamid is mixed with fluorine bacterium azoles according to 60: 1-1: 60 weight proportions, carries out powdery mildew of cucumber and cucumber downy mildewPrevention experiment.Experimental result is shown in Tables 1 and 2.
Prevention effect of 1 cyazofamid of table with fluorine bacterium azoles Pesticidal combination to powdery mildew of cucumber
From table 1 it follows that cyazofamid or fluorine bacterium azoles, the half effective concentration EC of powdery mildew of cucumber is used alone50PointNot Wei 0.7251ppm and 0.5354ppm, in the present embodiment cyazofamid and fluorine bacterium azoles according to 1: 60-60: 1 weight proportion in the range ofWhat compounding obtained wants compositions：
1）Survey toxicity index（ATI）It is above theoretical toxicity index（TTI）, especially in cyazofamid and fluorine bacterium azoles weightMatch as in the range of 8: 1-1: 60, ATI is apparently higher than TTI.
2）Co-toxicity coefficient（CTC）100 are above, does not produce antagonism, cyazofamid and fluorine bacterium azoles weight proportion are 8:In the range of 1-1: 8, CTC is higher than 120, has a synergistic effect, and cyazofamid and fluorine bacterium azoles weight proportion be in the range of 4: 1-1: 4,CTC is higher than 150, can reach 170.42, illustrates that cyazofamid and fluorine bacterium azoles pharmaceutical composition have obvious in the present embodimentSynergistic effect.
The above results show, are 8 in cyazofamid and fluorine bacterium azoles weight proportion:1—1:60（Especially 8:1-1:8）WeightUnder proportioning, pesticide concentration can be reduced, improves the safety in utilization of pharmaceutical composition.
3）EC50It is decreased obviously, in the case that cyazofamid and the weight proportion of fluorine bacterium azoles are 8: 1-1: 60, EC50SubstantiallyEC during less than exclusive use fluorine bacterium azoles50Value（0.5354）, LC during cyazofamid is significantly lower than used alone50Value（0.7251）, safety in utilization improves, and the dosage of cyazofamid and fluorine bacterium azoles significantly reduces, and cost is greatly reduced.
Prevention effect of 2 cyazofamid of table with fluorine bacterium azoles Pesticidal combination to cucumber downy mildew
From table 1 it follows that cyazofamid or fluorine bacterium azoles, the half effective concentration EC of cucumber downy mildew is used alone50PointNot Wei 0.9435ppm and 2.3549ppm, in the present embodiment cyazofamid and fluorine bacterium azoles according to 1: 60-60: 1 weight proportion in the range ofWhat compounding obtained wants compositions：
1）Survey toxicity index（ATI）It is above theoretical toxicity index（TTI）, especially in cyazofamid and fluorine bacterium azoles weightMatch as in the range of 8: 1-1: 40, ATI is apparently higher than TTI.
2）Co-toxicity coefficient（CTC）100 are above, does not produce antagonism, cyazofamid and fluorine bacterium azoles weight proportion are 8:In the range of 1-1: 40, CTC is higher than 130, has synergistic effect, cyazofamid and fluorine bacterium azoles weight proportion are 4: 1-1: 20 scopesInterior, CTC is higher than 200, can reach 344.64, illustrates that cyazofamid and fluorine bacterium azoles pharmaceutical composition have obvious in the present embodimentSynergistic effect.
The above results show, are 8: 1-1: 40 in cyazofamid and fluorine bacterium azoles weight proportion（Especially 4: 1-1: 20）WeightUnder amount proportioning, pesticide concentration can be reduced, improves the safety in utilization of pharmaceutical composition.
3）EC50It is decreased obviously, in the case that cyazofamid and the weight proportion of fluorine bacterium azoles are 60: 1-1: 20, EC50SubstantiallyEC during less than exclusive use cyazofamid50Value（0.9435）, LC during fluorine bacterium azoles is significantly lower than used alone50Value（2.3549）, safety in utilization improves, and the dosage of cyazofamid and fluorine bacterium azoles significantly reduces, and cost is greatly reduced.