CN104904721A - Fungicide composition, preparation of fungicide composition and application of preparation - Google Patents
Fungicide composition, preparation of fungicide composition and application of preparation Download PDFInfo
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- CN104904721A CN104904721A CN201510311690.7A CN201510311690A CN104904721A CN 104904721 A CN104904721 A CN 104904721A CN 201510311690 A CN201510311690 A CN 201510311690A CN 104904721 A CN104904721 A CN 104904721A
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Abstract
The invention relates to the field of agricultural fungicide, discloses a fungicide composition, a preparation of the fungicide composition and application of the preparation, and in particular relates to a fungicide composition for preventing gray mold, a preparation of the fungicide composition and application of the preparation. The fungicide composition contains fludioxonil and pyrazolecarboxamide compounds, which have the weight ratio of 1:1000-1000:1. The pesticide preparation prepared from the fungicide composition is used for preventing gray mold, has treatment and protection functions, has good synergism, has good fungicidal effect, and is safe to crops, and the application frequency of the pesticide preparation can be reduced.
Description
Technical field
The present invention relates to disinfectant use in agriculture field, specifically, relate to a kind of microbicide compositions and preparation and application thereof, particularly relating to a kind of bactericidal composition for preventing and treating gray mold and preparation and application thereof.
Background technology
Gray mold is the common and a kind of fungal disease of more difficult control of open country, protecting field crop, and belong to low temperature and high relative humidity type disease, growth of pathogenic bacteria temperature is 2 ~ 30 DEG C, is the disease high-incidence season when temperature 20 ~ 25 DEG C, humidity continue more than 90%.Gray mold, caused by the pathogen of Botrytis cinerea infects, belongs to fungal disease, and flower, really, leaf, stem all can fall ill.Botrytis cinerea (Botrytis cinerea) is a kind of wide host's property, can causes the gray mold of more than 200 kind of known plants (as fruit, vegetables and flowers), can not only field crops be infected, bring about great losses can to equally the after-stage of adopting of plant.
Fludioxonil (fludioxonil); chemical name is 4-(2; 2-bis-fluoro-1; 3-benzo dioxy-4-base) pyrroles-3-nitrile; the contact bactericide of new pyrrole class; its mechanism of action is the transfer by suppressing glucose phosphorylated relevant, and the mycelial growth of Antifungi, finally cause germ dead.With existing bactericide without cross resistance, belong to the wide-spectrum bactericide of non-internal-absorting.Namely also seed treatment can be can be used as cauline leaf inorganic agent, as seed treatment be mainly used in control kind pass and soil-borne disease bacterium as Alternaria, Ascochyta, aspergillus, Fusarium, Helminthosporium, Rhizoctonia and Penicillium bacterium etc., but single use easily make pathogen generation resistance.
Pyrazol acid amide compounds is the created compound I with the novel structure of independent intellectual property right and the Compound II per (structure is shown in compound shown in following formula (I) and formula (II)) of Central China Normal University's exploitation, early-stage Study shows that these 2 compound fungicidal spectrums are wide, and has certain Uptake and translocation.
Report is there is no for preventing and treating gray mold about pyrazol acid amide compounds I and Compound II per and the composite of fludioxonil.
Summary of the invention
The object of the present invention is to provide a kind of microbicide compositions to control of plant disease Be very effective, particularly provide a kind of to the significant microbicide compositions of gray mold control efficiency.
The present inventor finds through deep research, by the pyrazol acid amide compounds of following ad hoc structure and the composite use of fludioxonil, not only do not offset pyrazol acid amide compounds and fludioxonil drug effect separately, on the contrary, also there is obviously synergistic effect, the control efficiency of fungus-caused plant disease is significantly improved, particularly the control efficiency of gray mold is significantly improved, this completes the present invention.
Also be, to achieve these goals, according to a first aspect of the invention, the invention provides a kind of microbicide compositions, wherein, the active component of this microbicide compositions comprises fludioxonil and pyrazol acid amide compounds, and described pyrazol acid amide compounds is compound shown in following formula (I) and/or the shown compound of formula (II)
According to a second aspect of the invention, the invention provides above-mentioned microbicide compositions and prevent and treat the application in gray mold.
According to a third aspect of the invention we, the invention provides a kind of preparation had prepared by above-mentioned microbicide compositions, wherein, the formulation of described preparation is missible oil, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension agent, suspension emulsion, ultra low volume spraying agent, oil-suspending agent, microcapsule suspending agent, water surface film-spreading oil solution, wetting powder, water dispersible granules, dry suspending agent, soluble powder or soluble granula, can emulsified powder, can emulsified particles agent, granule, solid microcapsule formulation, effervescent tablet, effervescent, the floating dispersible granule of water or seed coat agent.
According to a forth aspect of the invention, the invention provides above-mentioned preparation and prevent and treat the application in gray mold.
According to microbicide compositions provided by the invention, it has obvious synergistic function, and bactericidal effect is good, and drug cost is low, not easily produces resistance, good to crop safety.Particularly the control efficiency of microbicide compositions provided by the invention to gray mold is remarkable.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The active component of microbicide compositions provided by the invention comprises fludioxonil and pyrazol acid amide compounds, and described pyrazol acid amide compounds is compound shown in following formula (I) and/or the shown compound of formula (II)
Pyrazol acid amide compounds shown in Chinese style of the present invention (I) can adopt the synthetic route shown in following synthetic route (1) to synthesize:
Pyrazol acid amide compounds shown in Chinese style of the present invention (II) can adopt the synthetic route shown in following synthetic route (2) to synthesize:
In addition, fludioxonil can synthesize and obtains, and also by commercially available, such as, can be purchased from Shangyu Nutrichem Co., Ltd.
In the present invention, described active component comprises fludioxonil and described pyrazol acid amide compounds, the weight ratio of fludioxonil and described pyrazol acid amide compounds can in very large range change, particularly, such as, the weight ratio of fludioxonil and described pyrazol acid amide compounds is 1:1000 ~ 1000:1.Although in the present invention, as long as described active component comprises described fludioxonil and described pyrazol acid amide compounds can demonstrate significant synergistic function, but consider from improving this synergistic function aspect further, the weight ratio of preferred fludioxonil and described pyrazol acid amide compounds is 1:60 ~ 60:1; More preferably the weight ratio of fludioxonil and described pyrazol acid amide compounds is 1:20 ~ 20:1; More preferably the weight ratio of fludioxonil and described pyrazol acid amide compounds is 1:10 ~ 10:1; More preferably the weight ratio of fludioxonil and described pyrazol acid amide compounds is 1:5 ~ 5:1.
In microbicide compositions of the present invention, the content of described active component in microbicide compositions can in very large range change, and particularly, this active component content is in the composition 1 ~ 95 % by weight, is preferably 5-80 % by weight.
In microbicide compositions of the present invention, in addition to the active ingredient (s, microbicide compositions is usually also containing various surfactant conventional on agricultural chemicals and carrier.
Above-mentioned surfactant can be the known various surfactants in formulations of pesticide field, the present invention be preferably in emulsifier, dispersant and wetting agent one or more.
Other carrier except above-mentioned surfactant can be the known various carriers in formulations of pesticide field, comprises various silicates, carbonate, Sulfates, oxide-based, phosphoric acid salt, plant vector class, synthetic vectors class.Particularly, such as: white carbon, kaolin, diatomite, clay, talcum, organobentonite, float stone, titanium dioxide, dextrin, cellulose powder, precipitated calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine are fertile, one or more in the mixture of urea and amine fertilizer, glucose, maltose, sucrose, Anhydrous potassium carbonate, natrium carbonicum calcinatum, Carbon Dioxide hydrogen potassium, anhydrous sodium bicarbonate, attapulgite, Anhydrous potassium carbonate and the mixture of Carbon Dioxide hydrogen potassium and the mixture of natrium carbonicum calcinatum and anhydrous sodium bicarbonate.
Mentioned emulsifier can be the known various emulsifier in formulations of pesticide field, particularly, this emulsifier can be calcium dodecyl benzene sulfonate, triphen ethyl phenol polyoxyethylene ether phosphate, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, alkylphenol-polyethenoxy polyethenoxy ether, fatty amine, the ethylene oxide adduct of fatty acid amide, polyoxyethylene carboxylate, rosin acid ethylene oxide adduct, polyol fatty acid ester and ethylene oxide adduct thereof, styryl phenyl APEO, alkyl phenol formaldehyde resin polyoxyethylene ether, terminal hydroxy group polyoxyethylene poly-oxygen propylene aether, styrylphenol formaldehyde resin polyoxyethylene poly-oxygen propylene aether, one or more combinations in castor oil polyoxyethylene ether.
Above-mentioned dispersant can be the known various dispersants in formulations of pesticide field, particularly, this dispersant is acrylate homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, rosin segmented APEO polyoxypropylene ether sulfonate, terminal hydroxy group polyoxyethylene poly-oxygen propylene aether block copolymer, triphen ethyl phenol polyoxyethylene ether phosphate, aliphatic alcohol polyoxyvinethene phosphate, to one or more combinations in hydroxyphenyl lignin sulfonic acid sodium salt.
Above-mentioned wetting agent can be the known various wetting agents in formulations of pesticide field, particularly, this wetting agent can be one or more in lauryl sodium sulfate, Teepol, neopelex, fatty alcohol-polyoxyethylene ether, alkylnaphthalene sulfonate, alkyl phenol resin polyoxyethylene ether sulfate.
Microbicide compositions of the present invention; this microbicide compositions can also containing formulations of pesticide field the various preparation used additives commonly used; particularly, said preparation used additives can be one or more in solvent, cosolvent, thickener, antifreezing agent, capsule material, protectant, defoamer, disintegrant, stabilizing agent, preservative and binding agent.
Above-mentioned solvent can be the known various solvents in formulations of pesticide field, and particularly, this solvent can be one or more in organic solvent, vegetable oil, mineral oil, solvent naphtha and water.
Wherein, described organic solvent comprises 1-METHYLPYRROLIDONE, oxolane, dimethyl sulfoxide (DMSO), N, N-dimethyldecamide, N, dinethylformamide, trimethylbenzene, durene, dimethylbenzene, toluene, octane, heptane, methyl alcohol, one or more in isopropyl alcohol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, Isosorbide-5-Nitrae-dioxane and cyclohexanone.
Described vegetable oil comprises methylated vegetable oils, turpentine-based vegetable oil, turpentine oil, one or more in epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine-seed oil.
Described mineral oil comprise in liquid wax, machine oil, kerosene and lubricating oil one or more.
Meanwhile, above-mentioned solvent also can use as cosolvent.
Above-mentioned antifreezing agent can be the known various antifreezing agents in formulations of pesticide field, the present invention be preferably in ethylene glycol, propane diols, glycerine and urea one or more.
Above-mentioned thickener can be the known various thickeners in formulations of pesticide field, particularly, this thickener can be one or more in xanthans, polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyethylene glycol, white carbon, diatomite, kaolin, clay, sodium alginate, Magnesiumaluminumsilicate, lagoriolite, carboxymethyl cellulose, HPMC and organobentonite.
Above-mentioned capsule material can be the known each seed capsules material in formulations of pesticide field, and the present invention is preferably polyurethane, polyureas or Lauxite.
Above-mentioned protectant can be the known various protectants in formulations of pesticide field, and the present invention is preferably polyvinyl alcohol and/or polyethylene glycol.
Above-mentioned defoamer can be the known various defoamers in formulations of pesticide field, the present invention be preferably in organosiloxane, tributyl phosphate and silicone one or more.
Aforementioned stable agent is selected from triphenyl phosphite, epoxychloropropane, aceticanhydride.Foregoing preservatives is selected from benzoic acid, Sodium Benzoate, BIT (be called for short BIT), one or more in Kathon CG and potassium sorbate.
The present invention also provides above-mentioned microbicide compositions to be belonged to application in the disease caused by Botrytis cinerea in control.
The present invention also provides a kind of preparation prepared by above-mentioned microbicide compositions, the formulation of described preparation be missible oil, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension agent, suspension emulsion, ultra low volume spraying agent, oil-suspending agent, microcapsule suspending agent, water surface film-spreading oil solution, wetting powder, water dispersible granules, dry suspending agent, soluble powder or soluble granula, can emulsified powder, can emulsified particles agent, granule, solid microcapsule formulation, effervescent tablet, effervescent, the floating dispersible granule of water or seed coat agent.
The formulation of microbicide compositions of the present invention can be the known various formulations in formulations of pesticide field, particularly, can be missible oil, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension agent, suspension emulsion, ultra low volume spraying agent, oil-suspending agent, microcapsule suspending agent, water surface film-spreading oil solution, wetting powder, water dispersible granules, dry suspending agent, soluble powder or soluble granula, can emulsified powder, can emulsified particles agent, granule, solid microcapsule formulation, effervescent tablet, effervescent, the floating dispersible granule of water or seed coat agent, above-mentioned formulation all can be prepared by the conventional method of this area.
Under preferable case, described cream preparation by weight percentage consist of active component 1 ~ 95%, cosolvent 0-20%, emulsifier 1 ~ 30%, solvent complement to 100%.
The preparation method of above-mentioned cream preparation such as can comprise makes it form homogeneous transparent oil phase each active component, solvent, cosolvent and emulsifier mix and blend, can obtain cream preparation.
Under preferable case, described cream preparation by weight percentage consist of active component 1 ~ 95%, cosolvent 0-20%, emulsifier 1 ~ 30%, solvent complement to 100%.
The preparation method of above-mentioned cream preparation such as can comprise makes it form homogeneous transparent oil phase each active component, solvent, cosolvent and emulsifier mix and blend, can obtain cream preparation.
Under preferable case, described aqueous emulsion or microemulsion by weight percentage consist of active component 1 ~ 95%, emulsifier 1 ~ 30%, cosolvent 0 ~ 30%, solvent 1 ~ 30%, antifreezing agent 0 ~ 10%, thickener 0 ~ 10%, water complements to 100%.
Under preferable case, described method for producing aqueous emulsion such as can comprise active component, emulsifier, cosolvent and solvent, becomes homogeneous oil phase; By mixing such as water, thickener, antifreezing agents, it is made to become homogeneous aqueous phase.Under high speed shear, aqueous phase joined oil phase or oil phase is joined aqueous phase, forming the aqueous emulsion of favorable dispersibility.
Under preferable case, the preparation method of described microemulsion is by active component, emulsifier, and solvent stirs into the oil phase of transparent and homogeneous.Under the condition stirred.Gradually add water, make it form the microemulsion of transparent and homogeneous.
Under preferable case, described aqueous suspension agent by weight percentage consist of active component 1 ~ 95%, surfactant 1 ~ 30%, antifreezing agent 1 ~ 10%, thickener 0.1 ~ 5%, water complements to 100%.
Under preferable case, described oil-suspending agent by weight percentage consist of active component 1 ~ 95%, emulsifier 1 ~ 30%, dispersant 0.1% ~ 10%, thickener 0.1 ~ 5%, oil complements to 100%.
The preparation method of water/oil-suspending agent: with water or oil for medium, by active component, surfactant, etc. auxiliary agent add in sand milling still, after carrying out being ground to certain particle diameter, filter.Joined in ground mother liquor by the thickener measured, shearing is uniformly dispersed again.Make oil-suspending agent or aqueous suspension agent.
Under preferable case, described soluble granula, soluble powder, water dispersible granules or wetting powder by weight percentage consist of active component 1 ~ 95%, surfactant 1 ~ 30%, other carriers complement to 100%.
Wherein, the preparation method of water-dispersible granules and soluble granula is: by each active component, dispersant, wetting agent.Carriers etc. mix, then by air-flow crushing to certain particle diameter, then add water and mediate, finally add in comminutor and carry out granulation, after drying, water-dispersible granules or soluble granula can be obtained.
The preparation method of soluble powder and wetting powder is: fully mixed by the fillers such as each active component, various auxiliary agent and other carriers, use ultra-fine pulverizer disintegrating.
Under preferable case; above-mentioned microcapsule suspending agent by weight percentage consist of active component 1 ~ 95%, solvent 1 ~ 30%, protectant 0.1 ~ 5.0%, defoamer 0.05 ~ 1.0%, capsule material 1 ~ 30%, dispersant 1 ~ 30%, wetting agent 0 ~ 30%, antifreezing agent 0 ~ 10%, thickener 0.1 ~ 5%, water complement to 100%.
Preparation method: by solvent, the mixing of capsule material, then add active component; Added emulsification in the mixture be made up of protectant, antifreezing agent, defoamer and water again, stirred until polymerisation completes; Add thickener, dispersant and wetting agent again, obtain stable microcapsule suspending agent.
Present invention also offers above-mentioned preparation and prevent and treat the application in gray mold.
Microbicide compositions of the present invention can provide with finished product preparation form, and namely in composition, each material mixes; Also can provide with independent dosage form, mix voluntarily in bucket or tank before using, and optionally mix with water according to the concentration of required active substance and carry out diluting.
Composition of the present invention also can have sterilization with other, the compound of desinsection or herbicidal performance uses, also can be used in combination with nematocide, protective agent, growth regulator, nutrient for plants or soil conditioner.
The using method of microbicide compositions of the present invention is simple, before plant disease is sprouted or after sprouting, place to crop and plant growth is used according to a conventional method, as mixed soil, spraying, injection, cast etc., its amount of application is determined according to weather conditions or crop condition, generally use 1-100g for every mu, be diluted to 1-2000mg/L and use.Thinner is preferably water.
Microbicide compositions of the present invention, its bactericidal effect usually with extraneous factor as weather is relevant, but can climatic influences be slowed down by the suitable formulation of use.
Below by way of specific embodiment, the present invention is further detailed, but the present invention is not limited in following embodiment.
In following test case and preparation example, fludioxonil is purchased from Shangyu Nutrichem Co., Ltd's (purity is 98 % by weight).
In following preparation example, in all preparation proportionings, percentage composition is all weight percentage.
In following test case and preparation example, synthesizing according to foregoing synthetic route (1) and synthetic route (2) of compound (also the compound shown in formula (I) and formula (II) being called Y12196 and Y13149 below) shown in formula (I) and formula (II), its concrete synthetic method is as follows.
1, the synthesis of 2,4-bis-chloro-1-(2-nitro-phenoxy) benzene
By 2.82g (20mmol) 2-fluoronitrobenzene and 4.89g (30mmol) 2,4-chlorophenesic acid, 4.15g (30mmol) K
2cO
3add in the mono-neck bottle of 100ml with 50ml DMF, after adding hot reflux 5h, decompression removing DMF, washes three times with the 10%NaOH aqueous solution, is extracted with ethyl acetate, anhydrous Na
2sO
4precipitation after dry, obtains the chloro-1-of 2,4-bis-(2-nitro-phenoxy) benzene 5.50g, yield 97%.
2, the synthesis of 2-(2,4-dichlorophenoxy) aniline
By 5.50g (19.36mmol) 2, the chloro-1-of 4-bis-(2-nitro-phenoxy) benzene 100ml ethanol dissolves, add 1.04g (19.36mmol) ammonium chloride and 10ml water, 3.24g (58.08mmol) iron powder is in three batches added after adding hot reflux, after reaction 6h, reaction system is used silica gel suction filtration, revolve ethanol, add 100ml ethyl acetate, with 60ml × 3 time saturated common salt washing, precipitation after dry, obtain 2-(2,4-dichlorophenoxy) aniline 4.50g, yield 91%.
3, the synthesis of 2-(2-chloro-trifluoromethyl phenoxy) aniline
By 5.00g (45.82mmol) Ortho-Aminophenol and the chloro-4-fluoride trifluoro toluene of 9.10g (45.82mmol) 3-, 9.50g (68.73mmol) K
2cO
3add in the mono-neck bottle of 250ml with 100ml DMF, after adding hot reflux 5h, decompression removing DMF, washes three times with the 10%NaOH aqueous solution, is extracted with ethyl acetate, anhydrous Na
2sO
4precipitation after dry, obtains 2-(2-chloro-trifluoromethyl phenoxy) aniline 9.53g, yield 72%.
4, the synthesis of the compound shown in formula (I)
By 0.50g (1.97mmol) 2-(2,4-dichlorophenoxy) aniline is dissolved in 20ml carrene, add 0.30g (2.95mmol) triethylamine, more slowly drip 3-difluoromethyl-1-methyl isophthalic acid H-pyrazoles-4-formyl chloride 0.46g (2.36mmol) under condition of ice bath.To add 30ml carrene in system after TLC monitoring reacts completely, the washing of 50ml × 3 time saturated common salt, anhydrous sodium sulfate drying, column chromatography is purified to obtain Compound I 0.70g, yield 86%.
5, the synthesis of the compound shown in formula (II)
0.57g (1.97mmol) 2-(2-chloro-trifluoromethyl phenoxy) aniline is dissolved in 20ml carrene, add 0.30g (2.95mmol) triethylamine, more slowly drip 3-difluoromethyl-1-methyl isophthalic acid H-pyrazoles-4-formyl chloride 0.46g (2.36mmol) under condition of ice bath.To add 30ml carrene in system after TLC monitoring reacts completely, the washing of 50ml × 3 time saturated common salt, anhydrous sodium sulfate drying, column chromatography is purified to obtain Compound I 0.75g, yield 85%.
Obtained formula (I) and the relevant nuclear magnetic data of the compound shown in formula (II) as follows:
Compound shown in formula (I):
1h NMR (600MHz, CDCl
3) δ 8.67 (s, 1H), 8.55 (d, J=8.4Hz, 1H), 7.99 (s, 1H), 7.48 (t, J=8.4Hz, 1H), 7.21 (m, 2H), 7.04 (s, 1H), 6.92 (t, J=48.6Hz, 1H), 6.74 (d, J=13.8Hz, 1H), 3.95 (s, 3H) .MS:m/z=411.29 (M+) .mp:102.5-103.6 DEG C.
Compound shown in formula (II):
1h NMR (600MHz, CDCl
3) δ 8.62 (s, 1H), 8.58 (d, J=8.4Hz, 1H), 7.99 (s, 1H), 7.75 (s, 1H), 7.46 (d, J=9Hz, 1H), 7.24 (d, J=7.8Hz, 1H), 7.11 (t, J=7.8Hz, 1H), 6.99 (d, J=9Hz, 1H), 6.87 (t, J=53.4Hz, 1H), 6.86 (s, 1H), 3.92 (s, 3H) .MS:m/z=445.15 (M+) .mp:114.3-115.4 DEG C.
Test case 1
This test case is for illustration of fludioxonil and the composite Toxicity Determination to gray mold of cucumber of pyrazol acid amide compounds
Subjects: botrytis cinerea pers (Botrytis cinerea)
Test method: with reference to " People's Republic of China (PRC) agricultural industry criteria NY/T 1156.2-2006 " mycelial growth rate method.Each medicament establishes 5 dosage process respectively by active constituent content, by above-mentioned each pathogen PDA medium culture, when bacterium colony just covers with culture dish, bacterium block is broken at colony edge with the card punch of diameter 5mm, with transfer needle, bacterium block is moved to the toxic PDA medium central authorities be mixed with in advance, then be placed in 25 DEG C of incubators and cultivate, often process repetition 4 times.Depending on CK colony growth situation, adopt right-angled intersection method slide calliper rule to measure each process colony diameter cm, obtain correction inhibition percentage.By the linear regression analysis between the probit value of inhibiting rate and the logarithm value of series concentration, obtain the EC of each medicament
50value, then calculate co-toxicity coefficient (CTC) according to the abundant method of Sun Yun.
Drug effect calculates: two diameters are surveyed in each bacterium colony right-angled intersection, represent bacterium colony size with its mean.Colony growth inhibiting rate is obtained: colony growth inhibiting rate %=(blank bacterium colony increases diameter-chemicals treatment bacterium colony and increases diameter) × 100/ blank bacterium colony increases diameter by following formula.
3.11 professional versions of result DPS carry out data analysis statistical, obtain regression line, EC
50, correlation coefficient.According to the EC of Sun Yunpei (Y-P Sun) method by each process of mensuration
50be converted into actual poison exponent (ATI); According to the proportioning of mixture, obtain theoretical toxicity index (TTI), by the co-toxicity coefficient (CTC) of following formulae discovery mixture.
Co-toxicity coefficient (CTC)=[the theoretical toxicity index (TTI) of the actual toxicity index of mixture (ATI)/mixture] × 100
The actual toxicity index of mixture (ATI)=(EC of standard agent
50the EC of/mixture
50) × 100
The content of B in the TI × mixture active ingredient of the content+B agent of A in the TI × mixture active ingredient of theoretical toxicity index (the TTI)=A agent of mixture
Toxicity index (TI)=(EC of standard agent
50the EC of/reagent agent
50) × 100 (using the one in A agent, B agent as standard agent)
A agent, B agent are respectively two kinds of active components mixed mutually, and mixture is the mixture after A agent mixes mutually with B agent.
Evaluation criterion: when CTC >=120, shows as synergistic effect; When CTC≤80, show as antagonism; 80 < CTC < 120, show as summation action.
Its result is as shown in table 1.
Table 1
| Medicament | EC 50(μg/mL) | ATI | TTI | Co-toxicity coefficient CTC |
| Fludioxonil (A) | 0.06235 | 100.00 | ||
| Y12196(B1) | 2.08570 | 2.99 | ||
| Y13149(B2) | 1.53012 | 4.07 | ||
| A+B1(60：1) (1) | 0.0442 | 141.16 | 98.41 | 143.44 |
| A+B1(40：1) | 0.0405 | 153.95 | 97.63 | 157.68 |
| A+B1(20：1) | 0.0462 | 134.96 | 95.38 | 141.49 |
| A+B1(12：1) | 0.0326 | 191.55 | 92.54 | 207.00 |
| A+B1(8：1) | 0.0334 | 186.68 | 89.22 | 209.23 |
| A+B1(4：1) | 0.0357 | 174.65 | 80.60 | 216.69 |
| A+B1(2：1) | 0.0326 | 191.55 | 67.66 | 283.09 |
| A+B1(1：1) | 0.0327 | 190.73 | 51.50 | 370.39 |
| A+B1(1：2) | 0.0377 | 165.43 | 35.33 | 468.28 |
| A+B1(1：4) | 0.0563 | 110.79 | 22.39 | 494.75 |
| A+B1(1：8) | 0.1325 | 47.06 | 13.77 | 341.76 |
| A+B1(1：12) | 0.2758 | 22.61 | 10.45 | 216.29 |
| A+B1(1：20) | 0.3849 | 16.20 | 7.61 | 212.88 |
| A+B1(1：40) | 0.5982 | 10.42 | 5.36 | 194.60 |
| A+B1(1：60) | 0.7084 | 8.80 | 4.58 | 192.16 |
| A+B2(60：1) | 0.0399 | 156.27 | 98.43 | 158.76 |
| A+B2(40：1) | 0.0401 | 155.49 | 97.66 | 159.21 |
| A+B2(20：1) | 0.0396 | 157.45 | 95.43 | 164.99 |
| A+B2(12：1) | 0.0319 | 195.45 | 92.62 | 211.03 |
| A+B2(8：1) | 0.0286 | 218.01 | 89.34 | 244.02 |
| A+B2(4：1) | 0.0287 | 217.25 | 80.81 | 268.82 |
| A+B2(2：1) | 0.0312 | 199.84 | 68.02 | 293.78 |
| A+B2(1：1) | 0.0322 | 193.63 | 52.04 | 372.12 |
| A+B2(1：2) | 0.0354 | 176.13 | 36.05 | 488.62 |
| A+B2(1：4) | 0.0508 | 122.74 | 23.26 | 527.76 |
| A+B2(1：8) | 0.1298 | 48.04 | 14.73 | 326.13 |
| A+B2(1：12) | 0.2687 | 23.20 | 11.45 | 202.67 |
| A+B2(1：20) | 0.3809 | 16.37 | 8.64 | 189.50 |
| A+B2(1：40) | 0.5786 | 10.78 | 6.41 | 168.12 |
| A+B2(1：60) | 0.6999 | 8.91 | 5.64 | 157.88 |
Remarks:
(1)numeric ratio in the bracket represented is the weight proportion of two kinds of medicaments.
Preparation example 1
This preparation example is for illustration of the preparation of suspending agent
Take 10% fludioxonil, 20%Y13149,2%TERSPERSE 2500 (is purchased from Hensel Man, identical below), 3%TERSPERSE 4896 (is purchased from Hensel Man, identical below), 0.2% xanthans, 3% white carbon, 5% ethylene glycol, 0.3% benzoic acid, 0.5% silicone defoaming agent (trade name: s-29 Nanjing "four news" (new ideas applied chemistry product Company), deionized water adds to 100%.
Preparation method: by active ingredient, wetting agent, dispersant, antifreezing agent etc. mix, and add in sand mill after being ground to certain particle diameter, filter.Add again the xanthans prepared be stirred to evenly 30% fludioxonil-Y13149 suspending agent Y1.
Preparation example 2
This preparation example is for illustration of the preparation of suspending agent
Take 25% fludioxonil, 25%Y12196,2%NNO (be purchased from Shanghai Tiantan Accessory Ingredient Co., Ltd, identical below), 2%TERSPERSE 2500,0.1% xanthans, 3% white carbon, 5% propane diols, 0.5% Sodium Benzoate, 0.5% silicone defoaming agent, deionized water adds to 100%.
Preparation method: by active ingredient, wetting agent, dispersant, antifreezing agent etc. mix, and add in sand mill after being ground to certain particle diameter, filter.Add again the xanthans prepared be stirred to evenly 50% fludioxonil-Y12196 suspending agent Y2.
Preparation example 3
This preparation example is for illustration of the preparation of wetting powder
Take 30% fludioxonil, 30%Y12196,5% calcium lignosulfonate, 2% Nekal BX (being purchased from Shanghai Tiantan Accessory Ingredient Co., Ltd, identical below), 1% lauryl sodium sulfate, 5% white carbon, kaolin add to 100%.
Preparation method: by above-mentioned raw materials obtained 60% fludioxonil-Y12196 wetting powder Y3 after mixing, air-flow crushing.
Preparation example 4
This preparation example is for illustration of the preparation of wetting powder
Take 12% fludioxonil, 48%Y13149,4% calcium lignosulfonate, 3%TERSPERSE 2700,2% Nekal BX, 2% lauryl sodium sulfate, 5% white carbon, fine particle calcium carbonate add to 100%.
Preparation method: by above-mentioned raw materials obtained 60% fludioxonil-Y13149 wetting powder Y4 after mixing, air-flow crushing.
Preparation example 5
This preparation example is for illustration of the preparation of microemulsion
Take 5% fludioxonil, 10%Y12196, 4%TX-10 (is purchased from Xingtai blue star auxiliary agent company, identical below), 5% Nongru-700 # (is purchased from Nanjing Teva-Chem. Co., Ltd., identical below), 6% agriculture breast 500# (is purchased from Nanjing Teva-Chem. Co., Ltd., identical below), 4% agriculture breast 1601# (is purchased from Nanjing Teva-Chem. Co., Ltd., identical below), 15% cyclohexanone, 5%N-methyl pyrrolidone, 5% n-butanol, 1% epoxychloropropane, through dissolving completely and mixing, deionized water adds to 100%, obtained 15% fludioxonil-Y12196 microemulsion Y5 after stirring.
Preparation example 6
This preparation example is for illustration of the preparation of microemulsion
Take 10% fludioxonil, 10%Y13149,5% agriculture breast 400#, 4% agriculture breast 500#, 6% agriculture breast 1601#, 25% cyclohexanone, 10% trimethylbenzene, 5% isopropyl alcohol, 3% calcium dodecyl benzene sulfonate, through dissolving completely and mixing, deionized water adds to 100%, obtained 20% fludioxonil-Y13149 microemulsion Y6 after stirring.
Preparation example 7
This preparation example is for illustration of the preparation of aqueous emulsion
Take 5% fludioxonil, 5%Y12196, 3% agriculture breast 2201# (is purchased from Nanjing Teva-Chem. Co., Ltd., identical below), 1.5% Nonyl pheno (EO=10) ether phosphate (is purchased from Nanjing Teva-Chem. Co., Ltd., identical below), 2.5% triphenoethyl benzene phenol polyethenoxy ether phosphate (agriculture breast 600# acid phosphatide, be purchased from Nanjing Teva-Chem. Co., Ltd.), 2%Span-60# (is purchased from Xingtai blue star auxiliary agent company, identical below), 1% epoxychloropropane, 20% dimethylbenzene, 10% cyclohexanone, 0.1% xanthans, 0.5% benzoic acid, deionized water adds to 100%.
Preparation method: by above-mentioned active ingredient, emulsifier, after dispersant dissolution with solvents, under the condition of high shear, joins in aqueous phase, then adds xanthans and to stir obtained 10% fludioxonil-Y12196 aqueous emulsion Y7.
Preparation example 8
This preparation example is for illustration of the preparation of aqueous emulsion
Take 6% fludioxonil, 6%Y13149,2% agriculture breast 2201#, 10% Nonyl pheno (EO=10) ether phosphate, 2%Span-60#, 2% emulsifier T-60 (being purchased from Xingtai blue star auxiliary agent company), 1% triphenyl phosphite, 15% trimethylbenzene, 10% cyclohexanone, 0.3% xanthans, 0.5% benzoic acid, deionized water adds to 100%.
Preparation method: by above-mentioned active ingredient, emulsifier, after dispersant dissolution with solvents, under the condition of high shear, joins in aqueous phase, then adds xanthans and to stir obtained 12% fludioxonil-Y13149 aqueous emulsion Y8.
Preparation example 9
This preparation example is for illustration of the preparation of water dispersible granules
Take 35% fludioxonil, 35%Y13149,3%TERSPERSE 2700,2% dispersing agent NNO (alkylnaphthalene sulfonate formaldehyde condensation products), 3% Nekal BX (nekal), 4%K-12 (lauryl sodium sulfate), 3% diatomite, 5% glucose, kaolin adds to 100%.
By formula rate, namely the method for the frequent regulation water intaking dispersible granule such as former medicine and dispersant, wetting agent, binding agent is mixed, ultra micro air-flow crushing, add certain specification screen cloth is housed comminutor in carry out granulation.And then namely drying, screening obtain the obtained 70% fludioxonil-Y13149 water dispersible granules Y9 of granular product.
Preparation example 10
This preparation example is for illustration of the preparation of water dispersible granules
Take 40% fludioxonil, 20%Y12196,3%TERSPERSE 2700,2% dispersing agent NNO (alkylnaphthalene sulfonate formaldehyde condensation products), 3% Nekal BX (nekal), 4%K-12 (lauryl sodium sulfate), 3% diatomite, 5% glucose, kaolin adds to 100%.
By formula rate, namely the method for the frequent regulation water intaking dispersible granule such as former medicine and dispersant, wetting agent, binding agent is mixed, ultra micro air-flow crushing, add certain specification screen cloth is housed comminutor in carry out granulation.And then namely drying, screening obtain the obtained 60% fludioxonil-Y12196 water dispersible granules Y10 of granular product.
Contrast preparation example 1
Take 24%Y12196,2%TERSPERSE 2500,3%TERSPERSE 2425,0.2% xanthans, 3% white carbon, 5% ethylene glycol, 0.3% benzoic acid, 0.5% silicone defoaming agent (trade name: s-29 Nanjing "four news" (new ideas applied chemistry product Company), deionized water adds to 100%.
Preparation method: by active ingredient, wetting agent, dispersant, antifreezing agent etc. mix, and add in sand mill after being ground to certain particle diameter, filter.Add the xanthans prepared again to be stirred to and evenly can to obtain 24%Y12196 suspending agent.
Contrast preparation example 2
Take 24%Y13149,2%TERSPERSE 2500,3%TERSPERSE 2425,0.2% xanthans, 3% white carbon, 5% ethylene glycol, 0.3% benzoic acid, 0.5% silicone defoaming agent (trade name: s-29 Nanjing "four news" (new ideas applied chemistry product Company), deionized water adds to 100%.
Preparation method: by active ingredient, wetting agent, dispersant, antifreezing agent etc. mix, and add in sand mill after being ground to certain particle diameter, filter.Add the xanthans prepared again to be stirred to and evenly can to obtain 24%Y13149 suspending agent.
Contrast preparation example 3
Take 2.5% fludioxonil, 30%N-methyl pyrrolidone, 5%505#, 7%602#, trimethylbenzene add to 100%.
Preparation method: by active ingredient, emulsifier, cosolvent etc. mix to and evenly can obtain 2.5% fludioxonil missible oil.
Test case 2
This test case is for illustration of control gray mold of cucumber field control effectiveness test
Field information example 1, control gray mold of cucumber field control effectiveness test
Control gray mold of cucumber field control effectiveness test carries out field control effectiveness test with reference to medicine inspecting institute of the Ministry of Agriculture " pesticide field efficacy medicine test criterion (one) GB/T17980.28-2000 bactericidal agent for preventing and treating eliminating vegetable botrytis ".Experimental field is positioned at ShaoXing,ZheJiang academy of agricultural sciences.The community process of test medicine, contrast medicament and blank adopts the group arrangement of random district, plot area 15m
2, repeat for 4 times, investigation state of an illness radix before dispenser, dispenser 2 times altogether.Every community adopts 5 samplings, often some investigation 2 strains, investigates whole blade of every strain and whole fruit.
Leaf diseases grade scale is as follows:
0 grade: anosis;
1 grade: single blade has scab 3;
3 grades: single blade has scab 4 ~ 6;
5 grades: single blade has scab 7 ~ 10;
7 grades: single blade has scab 11 ~ 20, and part is in flakes intensive;
9 grades: single blade has that scab is intensive accounts for leaf area more than 1/4th.
Fruit disease grade scale is as follows:
0 grade: anosis;
1 grade: residual flower morbidity;
3 grades: fall ill in areola portion;
5 grades: scab length accounts for fruit less than 10%;
7 grades: scab length accounts for fruit 11% ~ 25%;
9 grades: scab length accounts for more than 26% of fruit.
Drug effect computational methods:
According to investigation result, (1), (2) formulae discovery disease index and preventive effect according to below.Test data adopts Deng Kenshi duncan's new multiple range method (DMRT) to carry out statistical analysis.
In formula: CK
0, CK
1be respectively the disease index that the dispenser of blank district is forward and backward; PT
0, PT
1be respectively the disease index that chemicals treatment district medicine is forward and backward.
In addition, dispenser medicine, active ingredient amount and test result are as shown in table 2
Table 2
As can be seen from above effect data; bactericidal composition provided by the invention can be used for preventing and treating gray mold special efficacy, and component is reasonable, and treatment adds protective effect; bactericidal effect is good; reduce times for spraying, drug cost is low, and its activity and bactericidal effect are not the simple superposition of each composition activity; but have significant synergistic effect; slow down the generation of resistance, to crop safety, meet the security requirement of pesticidal preparations.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. a microbicide compositions, it is characterized in that, the active component of this microbicide compositions comprises fludioxonil and pyrazol acid amide compounds, and described pyrazol acid amide compounds is compound shown in following formula (I) and/or the shown compound of formula (II)
2. microbicide compositions according to claim 1, wherein, the content of described active component in microbicide compositions is 1-95 % by weight.
3. microbicide compositions according to claim 2, wherein, the content of described active component in microbicide compositions is 5-80 % by weight.
4. according to the microbicide compositions in claim 1-3 described in any one, wherein, the weight ratio of described fludioxonil and described pyrazol acid amide compounds is 1:1000 ~ 1000:1.
5. microbicide compositions according to claim 4, wherein, the weight ratio of described fludioxonil and described pyrazol acid amide compounds is 1:60 ~ 60:1.
6. microbicide compositions according to claim 5, wherein, the weight ratio of described fludioxonil and described pyrazol acid amide compounds is 1:20 ~ 20:1.
7. the microbicide compositions described in claim 1-6 any one is preventing and treating the application in gray mold.
8. the preparation prepared by the microbicide compositions described in claim 1-6 any one, wherein, the formulation of described preparation be missible oil, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension agent, suspension emulsion, ultra low volume spraying agent, oil-suspending agent, microcapsule suspending agent, water surface film-spreading oil solution, wetting powder, water dispersible granules, dry suspending agent, soluble powder or soluble granula, can emulsified powder, can emulsified particles agent, granule, solid microcapsule formulation, effervescent tablet, effervescent, the floating dispersible granule of water or seed coat agent.
9. the application in gray mold prevented and treated by preparation described in claim 8.
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