CN102318626A - Germicidal composition containing bupirimate and EBDC compounds - Google Patents
Germicidal composition containing bupirimate and EBDC compounds Download PDFInfo
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Abstract
The invention relates to a germicidal composition in the field of pesticide complex formulation; the active components are blended binarily by any two of bupirimate, dithane, metiram, mancozeb, thiram, and chlorothalonil; the mass ratio of the two active components is 90:1-1:95, and the preferable mass ratio is 70-5:7-80; the total mass percent of the active components in the germicidal composition is 1%-90%, and preferably 5%-70%; the residues are auxiliary components which are allowable and acceptable in pesticides; the composition can be prepared into wettable powder, suspensions, smoke agents, and water dispersible granules by known methods; the germicidal composition of the invention is mainly used to control diseases caused by powdery mildew, pucciniaceae, rhynchosporium, pyrenophora, and septoria.
Description
Technical field
The present invention relates to the agriculture chemical compounding technical field, be specifically related to a kind of with one of any in bupirimate and compound zineb, Propineb, Carbatene, mancozeb, tmtd, the tpn be two yuan of composite bactericidal compositions of active ingredient.
Background technology
Bupirimate belongs to the miazines systemic fungicide, has protection and therapeutic action.Can be absorbed rapidly by plant roots, stem, leaf, and in plant corpus, run to each position, so resistance of rainwater washing against.Have that consumption is few, efficient, low toxicity, powdery mildew had advantage such as special efficacy, therefore replaced agricultural chemicals such as phonetic phenol of second and dimethirimol.Be suitable for ornamental plants, field crops such as fruit tree, vegetables, flowers.The various powdery mildews of controlling object like apple, grape, cucumber, strawberry, rose, sweet Lay powdery mildew, have poisoning to some kinds such as strawberry, apple, roses.Its chemical structural formula is:
Zineb is the protectiveness organophosphorus fungicide; The formal name used at school zinc ethylene bisdithiocarbamate; Be mainly used in the blade face protection, can prevent and treat multiple fungus-caused disease, be broad-spectrum germicide; Can prevent and treat the multiple diseases of paddy rice, fruit tree, vegetables and tobacco, like tomato blight, anthracnose, ring spot; Brassicaceous vegetable and beans soft rot, anthracnose, soybean rust; The scab of pears, apple; Anthracnose of tobacco, rust; Wheat rust; Rice sheath blight disease etc.
Propineb is a kind of wide spectrum, quick-acting protective fungicide; Be applicable to Chinese cabbage downy mildew, cucumber downy mildew, the tomato sick control such as late blight, mango anthracnose early of tomato, Chinese cabbage, cucumber, mango and flowers and other crops; Downy mildew of crops such as vegetables, tobacco, lupulus and morning, the late blight of tomato and potato all there are good protective action, and the germ disease of powdery mildew, rust and Botrytis is also had certain inhibitory action.
Carbatene (metiram) chemical name: the co-ordination complex of two two sulphur deoxidation base formic acid manganese of ethylene and zinc ion, molecular formula: (C
4H
6N
2S
4Zn) x is protective fungicide, and the fungus-caused various diseases of Oomycete are had good preventive effect.
Mancozeb (mancozeb) molecular formula: C
4H
6N
2S
4The MnZn chemical name: the complex salt of two two thiocarbamoyl manganese of ethylene and zinc is the complex that maneb and zinc are formed, and belongs to the wider protective fungicide of fungicidal spectrum.It mainly is the oxidation that suppresses pyruvic acid in the thalline.Effective to multiple diseases such as the anthracnose on fruit tree, the vegetables, early blight, simultaneously its normal and systemic fungicide is mixed, and is used for the generation of delaying drug resistance.
The tmtd chemical name is a tetramethyl thiuram disulfide, belongs to the dithiocarbamate bactericide, and protective effect is strong; Has a broad antifungal spectrum; Because the disease to seed transmission and soil infection in seedling stage has good control efficiency, in very long one section, is mainly used in seed treatment and soil treatment, also has been widely used in foliage-spray at present; Another important use be as systemic fungicide composite mix medicine, and can be composite with other protective fungicides.
Tpn, chemical name 2,4,5,6-tetrachloro-1, the 3-benzene dinitrile is a kind of non-internal-absorting wide spectrum organochlorine bactericide of efficient, low toxicity, is mainly used in crop pests such as control vegetables, melon and fruit, peanut, paddy rice, wheat.Tpn is as disinfectant use in agriculture; Control downy mildew of cucurbits, powdery mildew, anthracnose, gray mold, black spot; Tomato late blight, gray mold, ring spot, eggplant cotton disease, early blight, bacterial blight, pepper anthracnose, eqpidemic disease; Potato cinerea, eqpidemic disease, tens kinds of vegetable diseases such as Chinese cabbage downy mildew, black spot.
More than several kinds of bactericide are long-term uses separately, preventive effect has begun to descend, and has produced pesticide resistance to a certain degree, and residual quantity is high, the repeated drug taking number of times is too much, causes the degraded difficulty, causes environmental pollution.Tpn for example, the degraded of the tpn in the soil are mainly accomplished through action of microorganisms (Motonaga et al, 1996); Singh etc. have studied 4 kinds of medicines such as tpn in degradation in soil; Although the result shows that the ratio that tpn disappears is very fast in soil, the repeated use of tpn greatly reduces it in degradation in soil speed, and 1 time is used the degradation half life of back tpn is 8.6d; After using for 2 times is 13.6d; After using for 3 times is 21.5d, this shows, the repeated use of tpn produces certain inhibitory action to the degraded of tpn.Other several kinds of agricultural chemicals also can slow down degradation rate behind the repeated drug taking again.
Summary of the invention
Based on above background context, studying a kind of bactericidal composition efficient, easy degraded just becomes an important directions, especially the agriculture chemical compounding field of pesticide field, and the R&D cycle is short, cost is low, achievement is remarkable.I research staff of company discovers through a series of, and two yuan of arbitrary fungicide active ingredients are composite in bupirimate and compound zineb, Propineb, Carbatene, mancozeb, tmtd, the tpn all has extremely strong synergistic effect to the target bacterium, has improved bactericidal activity greatly; Delayed the drug-fast generation of germ; Reduce the access times repeatedly of agricultural chemicals, reduced agricultural cost, and be prone to degraded after the lasting period; Environmentally friendly, thus the present invention accomplished.And about bupirimate and be selected from the two yuan of composite researchs of arbitrary fungicide active ingredient in compound zineb, Propineb, Carbatene, mancozeb, tmtd, the tpn, do not see relevant report at present at home and abroad as yet through retrieval.
The purpose of this invention is to provide the low bactericidal composition of a kind of efficient, low toxicity, use cost to satisfy the needs of agricultural production.Two kinds of active component combination backs produce synergistic effect, when improving preventive effect, can also avoid the drug-fast generation of germ and delay the drug-fast generation speed of germ.The objective of the invention is to realize through following concrete measure:
A kind of bactericidal composition based on bupirimate; It is characterized in that bactericidal composition of the present invention is is that two yuan of carrying out of fungicide active ingredient are composite with one of any (representing with B) in bupirimate (representing with A) and compound zineb, Propineb, Carbatene, mancozeb, tmtd, the tpn, wherein the mass percent of two kinds of effective constituents A and B is 90～1: 1～95.
On the basis of some specific aim proportioning tests; Any one or two yuan of composite bactericidal composition in A bupirimate of the present invention and B compound zineb, Propineb, Carbatene, mancozeb, tmtd, the tpn, the mass percent of two kinds of effective active composition A and B can be preferably 70～5: 7～80.But also can be equal to other compound proportions does not just have synergistic effect, does not do formulation screening test, and just synergistic effect is more obvious in this preferable range, and emphasis has added some detailed inquiry experiments.
As another important technology characteristics of the present invention; Described is two yuan of composite bactericidal compositions of active ingredient with arbitrary compound in (A) bupirimate and (B) zineb, Propineb, Carbatene, mancozeb, tmtd, the tpn; The formulations of pesticide that can be prepared into are wetting powder, suspending agent, fumicants and water dispersible granules; The quality percentage composition of active ingredient is 1%～90% in the preparation, is preferably 5%～70%, and all the other are usual auxiliaries in the agricultural chemicals.
The formulation embodiment of the invention described above bactericidal composition is following:
One of technical scheme of the present invention, described bactericidal composition are wetting powder, and the percentage by weight of component is:
The concrete procedure of processing of this bactericidal composition wetting powder is: press above-mentioned prescription with A and B and dispersant, wetting agent and filler mixing; In stirred tank, evenly stir; Behind airslide disintegrating mill, mixing, promptly can be made into the wetting powder of the present composition.
Two of technical scheme of the present invention, described bactericidal composition are suspending agent, and the percentage by weight of component is:
The concrete production stage of this suspending agent is earlier other auxiliary agents to be mixed; Mix through high speed shear, add A and B, abrading-ball is 2～3 hours in ball crusher; Make a diameter all below 5mm, make the suspending agent preparation of the bactericidal composition of A of containing of the present invention and B.
Three of technical scheme of the present invention, described bactericidal composition are water dispersible granules, and the percentage by weight of component is:
The concrete procedure of processing of this bactericidal composition water dispersible granules is: by above-mentioned prescription A, B and dispersant, wetting agent, disintegrant and filler are mixed; Pulverize with micro jet; Through mediating; Add then and carry out granulation, drying, screening in the fluidized bed prilling dryer after sample analysis, make the water dispersible granules of the bactericidal composition of A of containing of the present invention and B.
Four of technical scheme of the present invention, described bactericidal composition are fumicants, and the mass percent of component is:
The procedure of processing of above-mentioned fumicants is: sieve and handle various raw material foreign material, especially remove metal sundries, various raw materials are pulverized separately; Raw material to pulverizing is dried; Remove moisture, mix after the metering respectively in proportion, promptly process present composition fumicants after the check qualified products.
Above-mentioned fuel is selected from one or more in corncob, cow dung end, stalk, the bagasse.Adjuvant is selected from one or more in land plaster, kaolin, bentonite, the diatomite.
Described emulsifier is selected from any one or more mixtures formed with arbitrary proportion in calcium dodecyl benzene sulfonate and aliphatic acid polyethenoxy ether, APES sulfosuccinate, styryl phenol APEO, NPE, castor oil polyoxyethylene ether, aliphatic acid polyethenoxy base ester, the polyoxyethylene aliphatic alcohol ether.
Said solvent is any one or more mixed solvents formed with arbitrary proportion in xylol or biodiesel, toluene, diesel oil, methyl alcohol, ethanol, n-butanol, isopropyl alcohol, turpentine oil, solvent naphtha, dimethyl formamide, dimethyl sulfoxide (DMSO), the water equal solvent.
Described dispersant is selected from one or more in polycarboxylate, lignosulfonates, APES formaldehyde condensation products sulphate, alkyl benzene sulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, APES, aliphatic amine polyoxyethylene ether, polyoxyethylene carboxylate, the fatty acid glyceride APEO.
Described wetting agent is selected from: lauryl sodium sulfate, calcium dodecyl benzene sulfonate, Nekal BX., among the wetting and penetrating agent F, alkylnaphthalene sulfonate, polyoxyethylene triphenylethylene phosphenylic acid salt, spaonin powder, silkworm excrement, soapberry powder one or more.
Described disintegrant is selected from: one or more in bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, the sodium bicarbonate.
Described thickener is selected from: one or more in xanthans, CMC, hydroxyethylcellulose, methylcellulose, Magnesiumaluminumsilicate, the polyvinyl alcohol.
Described stabilizing agent is selected from: a kind of in sodium citrate, the resorcinol.
Described antifreezing agent is selected from: one or more in ethylene glycol, propane diols, the glycerine.
Described antifoaming agent is selected from: silicone oil, silicone compound, C
10-20Saturated fat acid compounds, C
8-10In the aliphatic alcohols compound one or more.
Described filler is selected from: one or more of pottery powder in kaolin, diatomite, bentonite, attapulgite, white carbon, starch, the precipitated calcium carbonate.
Pesticide sterilizing composite of the present invention all has the better prevention effect to the diseases such as leaf spot, powdery mildew, rust, downy mildew, scab, eqpidemic disease, anthracnose and rice blast of various crop; For example prevent and treat scab, the grey scab of early blight and late blight, the melon and fruit class of downy mildew of garpe, powdery mildew of cucumber, tomato, early blight and late blight, powdery mildew of wheat and barley, rust, melon anthracnose and downy mildew, rice sheath blight disease and the rice blast etc. of potato, excellent preventive effect is all arranged.Bactericidal composition of the present invention all has the certain activity effect to fungal disease, and some bacterial diseases are also had effect, more than is typical several classification and disease, is not limited in and enumerates disease.
In addition, other medicaments that bactericidal composition of the present invention is compared the same-action field have a lot of obviously advantages, at first can improve the preventive effect to corps diseases greatly, and quick-acting is compared single agent and improved a lot, and drug effect is also more lasting; Secondly delay the drug-fast generation of crop greatly, reduced the resistance of crop, reduce the access times repeatedly of agricultural chemicals, reduce the usage amount of agricultural chemicals, reduce peasant's use cost agricultural chemicals; The residual quantity of this bactericidal composition is lower at last, and the lasting period, later than being easier to degraded, the usage amount of agricultural chemicals was also less relatively, to environment also close friend more, the increasing both production and income of agricultural region is had bigger meaning.
Embodiment:
In order to make the object of the invention, technical scheme and advantage clearer, the present invention describes with following specific embodiment, but the present invention only limits to these examples absolutely not.The method that the present invention adopts indoor bioassay and field trial to combine.If no special instructions, the ratio of below mentioning (comprising percentage) all is a mass ratio.Should be pointed out that all any modifications of within spirit of the present invention and principle, being made, be equal to replacement and improvement etc., all should be included within protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with accompanying claims.
The formulation embodiment:
Instance 1:
Bupirimate 35g, tpn 65g, ammonium nitrate 100g, corncob 100g, bentonite is supplied 500g, preparation technology: 1. every kind of raw material is sieved respectively, remove wherein foreign material; 2. adopt comminution by gas stream and supporting mixing apparatus, respectively various raw materials are pulverized; 3. in the special fireproof drying room, the raw material of pulverizing is dried, to removing moisture; 4. after various raw materials being measured respectively, put into the high efficient mixed machine and mix; 5. product is through after the assay was approved, and the paper bag of packing into reinstalls the polyethylene film packaging bag, seals.
Instance 2:
Bupirimate 40g, tmtd 85g, Nekal BX 40g, spaonin powder 20g; Lignosulfonates 20g, pottery powder 310g mixes each component by above-mentioned prescription; In stirred tank, evenly stir, behind airslide disintegrating mill, mixing, promptly can be made into the wetting powder of the present composition.
Instance 3:
With the former powder 48g of bupirimate, the former powder 120g of Propineb, acrylic copolymer sodium salt 20g; Naphthalene sulfonic acid-formaldehyde condensation product sodium salt 35g, alkylsurfuric acid sodium salt 25g, ammonium sulfate 35g; Filler corn starch, fine particle calcium carbonate are supplied 500 grams, put in the cone-type mixer, mix 30 minutes; Carry out comminution by gas stream, make its fineness can reach 800 orders; The material of pulverizing is added water mediate, amount of water carries out extruder grain with the material of having mediated, and through the fluid bed dryer oven dry, obtains finished product through screening more again.
Instance 4:
Bupirimate 21g, mancozeb 48g, wetting agent 2.7g, dispersant 24g, antifreezing agent 0.6g, thickener 0.9g, antifoaming agent 0.15g, PH conditioning agent 0.6g, stabilizing agent 6g, filler is supplied 300g.Dispersant, wetting agent, antifoaming agent, thickener, antifreeze, emulsifier in the above-mentioned formulation material are mixed through high speed shear; Add bupirimate, mancozeb; Ball milling is 2～3 hours in ball mill; Make diameter of particle all below 5um, make said composition suspending agent product.
Indoor bioassay:
Biologicall test instance 1:
(1) experimental subjects:
The cucumber anthracnose germ, separation and purification gained from the cucumber anthracnose incidence of leaf of Shouguang, Shandong cucumber booth is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
Supply the examination medium:
PDA medium: potato 200g, glucose 20g, agar 20g, water 1000ml.
AEA medium: dusty yeast 5g/L, glycerine 20mL/L, MgSO
40.25g/L, NaNO
36g/L, KCL0.5g/L, KH
2PO
41.5g/L, agar powder 20g/L, deionized water 1L.
(2) experimental pharmacy:
The former medicine of 95% bupirimate, synthetic institute of sea, Qingdao rel research and development centre provides the former medicine of 96% mancozeb, Limin Chemical Co., Ltd..
Combination setting is mixed:
23% bupirimate mancozeb percentage composition was respectively 5: 18,7: 16,9: 14,11: 12,13: 10, i.e. 5%+18%, 7%+16%, 9%+14%, 11%+12%, 13%+10% totally 5 combinations that are mixed.
(3) test method:
Single agent is to the toxicity test of cucumber anthracnose germ:
Bupirimate and mancozeb dissolve with an amount of trichloroethanes, are made into the mother liquor of 10000 μ g/ml, preserve in 4 ℃ of following low temperature, and be for use, is diluted to a series of concentration with sterile water before the test.
The cucumber anthracnose germ after cultivating in advance on the AEA medium, is inoculated in the bacterium dish of diameter 5mm respectively on the AEA flat board that contains the variable concentrations gradient, cultivates down in 25 ℃ of dark conditions.Every processing repetition 3 times.When control strain colony diameter length is above to 6.5cm, adopt " right-angled intersection method " to measure.According to the linear regression analysis between the logarithm value of the probit value of inhibiting rate and medicine series concentration, obtain the EC that two kinds of single agent suppress mycelial growths
50Value, correlation coefficient and virulence regression equation.
On the basis of preliminary experiment, respectively single agent bupirimate and mancozeb are carried out toxicity test, EC in order to last method
50Value is followed successively by 4.28mg/l and 7.96mg/l.
The mixture toxicity test:
Carry out the toxicity test of mixture according to mixed ratio with single agent toxicity test method.
EC that each that will measure according to the abundant method of Sun Yun handled
50Value is converted into the actual toxicity index (ATI) of using with; According to the proportioning of mixture, obtain theory and use toxicity index (TTI) with, calculate the co-toxicity coefficient (CTC) of mixture by following formula.
Single agent toxicity index=(standard medicament EC
50/ confession reagent agent EC
50) * 100
ATI=(standard medicament EC
50/ confession reagent agent (using with) EC
50) * 100
The content (%) of toxicity index * B in using with of content (the %)+B of toxicity index * A of TTI=A in using with
CTC＝(ATI/TTI)×100
If co-toxicity coefficient is big by 120, showing has synergistic effect; If be starkly lower than 100 (below 80), be indicated as antagonism; Between 100～120, be indicated as summation action.
(4) result and analysis:
The composite co-toxicity test of table 1 bupirimate and mancozeb to the cucumber anthracnose germ
| The pharmacy quality ratio | Virulence regression equation | Correlation coefficient (r) | EC 50(mg/L) |
| Bupirimate (A) | Y＝2.6741X+3.3114 | 0.9882 | 4.28 |
| Mancozeb (B) | Y＝2.5923X+2.6645 | 0.9816 | 7.96 |
| A: B is 5: 18 | Y＝2.4982X+3.4934 | 0.9835 | 4.01 |
| A: B is 7: 16 | Y＝2.7105X+3.5433 | 0.9799 | 3.45 |
| A: B is 9: 14 | Y＝2.6188X+3.5979 | 0.9874 | 3.43 |
| A: B is 11: 12 | Y＝2.7004X+3.5002 | 0.9912 | 3.59 |
| A: B is 13: 10 | Y＝2.5833X+3.5356 | 0.9801 | 3.69 |
The composite co-toxicity of table 2 bupirimate and mancozeb to the cucumber anthracnose germ
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| Bupirimate (A) | 1∶0 | 100.00 | 100.00 | / | / |
| Mancozeb (B) | 0∶1 | 106.75 | 63.82 | / | / |
| A∶B | 5∶18 | 124.17 | 67.84 | 167.27 | Synergy |
| A∶B | 7∶16 | 124.76 | 71.86 | 183.04 | Synergy |
| A∶B | 9∶14 | 119.15 | 75.88 | 173.62 | Synergy |
| A∶B | 11∶12 | 116.04 | 79.90 | 157.02 | Synergy |
| A∶B | 13∶10 | 106.75 | 63.82 | 145.23 | Synergy |
Measuring the result according to above indoor virulence test shows; Bupirimate and mancozeb all have synergistic effect preferably by the percentage composition of experiment; Wherein with bupirimate: mancozeb is that 7: 16 o'clock co-toxicity coefficient is up to 183.04; Think that bupirimate and mancozeb percentage composition are that 7: 16 o'clock synergistic effects are best, the percentage composition of bupirimate and mancozeb is 9: 14 o'clock in addition, and good synergistic effect is also arranged.Suggestion is to suitable proportion 5: 18-9: the mixture preparation of 14 left and right sides scopes carries out further field control effectiveness test, to estimate its field practical application effect.
Biologicall test instance 2: the composite Toxicity Determination of bupirimate and tmtd to wheat powdery mildew.
The former medicine of 95% tmtd, Jiangsu Province Nantong Baoye Chemicals Co., Ltd..
The wheat powdery mildew germ, separation and purification gained from the wheat paddock powdery mildew incidence of leaf is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
Single agent bupirimate and tmtd are carried out toxicity test, EC
50Value is followed successively by 4.57mg/l and 8.42mg/l.
Combination setting is mixed:
25% bupirimate tmtd percentage composition was respectively 5: 20,7: 18,9: 16,11: 14,13: 12, i.e. 5%+20%, 7%+18%, 9%+16%, 11%+14%, 13%+12% totally 5 combinations that are mixed.
Test method is similar with biologicall test embodiment 1
Experimental result and analysis:
The composite virulence experiment of table 3 bupirimate and tmtd to the wheat powdery mildew germ
| The pharmacy quality ratio | Virulence regression equation | Correlation coefficient (r) | EC 50(mg/L) |
| Bupirimate (A) | Y＝2.1432X+3.5856 | 0.9825 | 4.57 |
| Tmtd (B) | Y＝2.2405X+2.9268 | 0.9756 | 8.42 |
| A: B is 5: 20 | Y＝2.3515X+3.3532 | 0.9803 | 5.02 |
| A: B is 7: 18 | Y＝2.4218X+3.4168 | 0.9634 | 4.51 |
| A: B is 9: 16 | Y＝2.2354X+3.6694 | 0.9125 | 3.94 |
| A: B is 11: 14 | Y＝2.2785X+3.6501 | 0.9227 | 3.91 |
| A: B is 13: 12 | Y＝2.4323X+3.4674 | 0.9415 | 4.27 |
The composite co-toxicity of table 4 bupirimate and tmtd to the wheat powdery mildew germ
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| Bupirimate (A) | 1∶0 | 100.00 | 100.00 | / | / |
| Tmtd (B) | 0∶1 | 54.28 | 54.28 | / | |
| A∶B | 5∶20 | 91.12 | 63.42 | 143.68 | Synergy |
| A∶B | 7∶18 | 101.44 | 67.08 | 151.22 | Synergy |
| A∶B | 9∶16 | 116.06 | 70.74 | 164.08 | Synergy |
| A∶B | 11∶14 | 116.81 | 74.39 | 157.02 | Synergy |
| A∶B | 13∶12 | 107.11 | 78.05 | 137.23 | Synergy |
Measuring the result according to above indoor virulence test shows; The used bupirimate and the percentage composition of tmtd all have synergistic effect in the experiment; Wherein the co-toxicity coefficient when the percentage composition of bupirimate and tmtd is 9: 16 is 164.08 to the maximum, thinks that promptly 9: 16 o'clock synergistic effects of bupirimate and tmtd percentage composition are best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 9: 16 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
Biologicall test instance 3: bupirimate and chlorothalonil compound are to the Toxicity Determination of powdery mildew of cucumber.
The former medicine of 98% tpn, Limin Chemical Co., Ltd..
The powdery mildew of cucumber germ, separation and purification gained from the powdery mildew of cucumber incidence of leaf of Shouguang, Shandong cucumber booth is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
Single agent bupirimate and tpn are carried out toxicity test, EC
50Value is followed successively by 4.53mg/l and 8.03mg/l.
Combination setting is mixed:
The percentage composition of 25% bupirimate tpn was respectively 5: 20,8: 17,11: 14,14: 11,17: 8, i.e. 5%+20%, 8%+17%, 11%+14%, 14%+11%, 17%+8% totally 5 combinations that are mixed.
Test method is similar with biologicall test embodiment 1
Result and analysis:
Table 5 bupirimate and chlorothalonil compound are to the co-toxicity of powdery mildew of cucumber germ
| The pharmacy quality ratio | Virulence regression equation | Correlation coefficient (r) | EC 50(mg/L) |
| Bupirimate (A) | Y＝2.8485X+3.1311 | 0.9688 | 4.53 |
| Tpn (B) | Y＝2.4916X+2.7458 | 0.9711 | 8.03 |
| A: B is 5: 20 | Y＝2.9556X+3.1445 | 0.9804 | 4.24 |
| A: B is 8: 17 | Y＝2.8671X+3.3720 | 0.9674 | 3.70 |
| A: B is 11: 14 | Y＝2.6469X+3.5313 | 0.9599 | 3.59 |
| A: B is 14: 11 | Y＝2.6554X+3.5275 | 0.9645 | 3.59 |
| A: B is 17: 8 | Y＝2.1669X+3.679 | 0.9564 | 3.49 |
Table 6 bupirimate and chlorothalonil compound are to the co-toxicity of powdery mildew of cucumber germ
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| Bupirimate (A) | 1∶0 | 100.00 | 100.00 | / | / |
| Tpn (B) | 0∶1 | 56.41 | 56.41 | / | / |
| A∶B | 5∶20 | 106.74 | 65.13 | 163.88 | Synergy |
| A∶B | 8∶17 | 122.54 | 70.36 | 174.16 | Synergy |
| A∶B | 11∶14 | 126.25 | 75.59 | 167.02 | Synergy |
| A∶B | 14∶11 | 126.36 | 80.82 | 156.34 | Synergy |
| A∶B | 17∶8 | 129.72 | 86.05 | 150.74 | Synergy |
Mensuration result according to above bactericide co-toxicity test; When bupirimate and tpn percentage composition are above experiment ratio; Result of the test shows all has synergistic effect; And the co-toxicity coefficient when ratio is 8: 17 is 174.16 to the maximum, and we can think that the percentage composition of bupirimate and tpn is at 8: 17 o'clock, and synergistic effect is best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 8: 17 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
Biologicall test instance 4: the composite Toxicity Determination of bupirimate and Propineb to the cucumber downy mildew germ.
The cucumber downy mildew germ, separation and purification gained from the cucumber plastic tent cucumber downy mildew incidence of leaf of Shouguang, Shandong is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
Single agent bupirimate and Propineb are carried out toxicity test, EC
50Value is followed successively by 5.13mg/l and 8.46mg/l.
Combination setting is mixed:
26% bupirimate Propineb percentage composition was respectively 5: 21,8: 18,11: 15,14: 12,17: 9, i.e. 5%+21%, 8%+18%, 11%+15%, 14%+12%, 17%+9% totally 5 combinations that are mixed.
Test method is similar with biologicall test embodiment 1
Result and analysis:
The composite co-toxicity of table 7 bupirimate and Propineb to the cucumber downy mildew germ
| The pharmacy quality ratio | Virulence regression equation | Correlation coefficient (r) | EC 50(mg/L) |
| Bupirimate (A) | Y＝3.4125X+2.5767 | ?0.9744 | 5.13 |
| Propineb (B) | Y＝3.5126X+1.7425 | ?0.9867 | 8.46 |
| A: B is 5: 21 | Y＝3.5752X+2.6067 | ?0.9918 | 4.67 |
| A: B is 8: 18 | Y＝3.6004X+2.8956 | 0.9943 | 3.84 |
| A: B is 11: 15 | Y＝3.4982X+2.9719 | 0.9806 | 3.80 |
| A: B is 14: 12 | Y＝3.7013X+2.7790 | 0.9746 | 3.98 |
| A: B is 17: 9 | Y＝3.5465X+2.9273 | 0.9834 | 3.84 |
The composite co-toxicity of table 8 bupirimate and Propineb to the cucumber downy mildew germ
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| Bupirimate (A) | 1∶0 | 100.00 | 100.00 | / | / |
| Propineb (B) | 0∶1 | 60.64 | 60.64 | / | / |
| A∶B | 5∶21 | 109.83 | 68.21 | 161.02 | Synergy |
| A∶B | 8∶18 | 133.55 | 72.75 | 183.57 | Synergy |
| A∶B | 11∶15 | 135.01 | 77.29 | 174.68 | Synergy |
| A∶B | 14∶12 | 128.85 | 81.83 | 157.45 | Synergy |
| A∶B | 17∶9 | 133.56 | 86.37 | 154.63 | Synergy |
Show according to above bactericide co-toxicity test determination result; Bupirimate and Propineb percentage composition are that 8: 18 o'clock co-toxicity coefficient is 183.57 to the maximum, and we think that bupirimate and Propineb percentage composition are that 8: 18 o'clock synergistic effects are best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 8: 18 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
Biologicall test instance 5: the composite Toxicity Determination of bupirimate and zineb to cucumber downy mildew.
The former medicine of 90% zineb, Sichuan richness reach agricultural chemical industry Co., Ltd.
The cucumber downy mildew germ, separation and purification gained from the cucumber downy mildew incidence of leaf of Shouguang, Shandong cucumber booth is cultivated in 4 ℃ of refrigerators on the PDA inclined-plane and is preserved.
Single agent bupirimate and zineb are carried out toxicity test, EC
50Value is followed successively by 5.33mg/l and 8.87mg/l.
Combination setting is mixed:
The percentage composition of 25% bupirimate zineb was respectively 5: 20,8: 17,11: 14,14: 11,17: 8, i.e. 5%+20%, 8%+17%, 11%+14%, 14%+11%, 17%+8% totally 5 combinations that are mixed.
Test method is similar with biologicall test embodiment 1
Result and analysis:
The composite co-toxicity of table 9 bupirimate and zineb to the cucumber downy mildew germ
| The pharmacy quality ratio | Virulence regression equation | Correlation coefficient (r) | EC 50(mg/L) |
| Bupirimate (A) | Y＝2.7321X+3.0145 | 0.9745 | 5.33 |
| Zineb (B) | Y＝2.614X+2.5221 | 0.9813 | 8.87 |
| A: B is 5: 20 | Y＝2.4538X+3.2644 | 0.9716 | 5.10 |
| A: B is 8: 17 | Y＝2.7426X+3.2508 | 0.9694 | 4.34 |
| A: B is 11: 14 | Y＝2.8314X+3.3474 | 0.9803 | 3.83 |
| A: B is 14: 11 | Y＝2.6552X+3.4253 | 0.9594 | 3.92 |
| A: B is 17: 8 | Y＝2.4583X+2.8710 | 0.9779 | 3.98 |
The composite co-toxicity of table 10 bupirimate and zineb to the cucumber downy mildew germ
| Test medicine | Mass ratio | The actual measurement poison refers to | Theoretical poison refers to | Co-toxicity coefficient | Conclusion |
| Bupirimate (A) | 1∶0 | 100.00 | 100.00 | / | / |
| Zineb (B) | 0∶1 | 60.09 | 60.09 | / | / |
| A∶B | 5∶20 | 104.58 | 68.07 | 153.63 | Synergy |
| A∶B | 8∶17 | 122.73 | 72.86 | 168.44 | Synergy |
| A∶B | 11∶14 | 139.02 | 77.65 | 179.03 | Synergy |
| A∶B | 14∶11 | 136.05 | 82.44 | 165.03 | Synergy |
| A∶B | 17∶8 | 133.79 | 87.23 | 153.38 | Synergy |
Mensuration result according to above bactericide co-toxicity test; When bupirimate and zineb percentage composition are above experiment ratio; Result of the test shows all has synergistic effect; And the co-toxicity coefficient when ratio is 11: 14 is 179.03 to the maximum, and we can think that the percentage composition of bupirimate and zineb is at 11: 14 o'clock, and synergistic effect is best.Suggestion is carried out further field control effectiveness test to the mixture preparation of 11: 14 left and right sides scopes of suitable proportion, to estimate its field practical application effect.
Field trial 1: to the preventive effect of wheat powdery mildew
(1) basic condition experimental field:
Experimental field be located at Henan, publish the medium wheat paddock of course of disease degree for experimental field, soil fertility is medium, and irrigation and drainage are convenient.Dispenser weather in March on the same day 31 is clear to cloudy, 11 ℃ of mean temperature of air, relative moisture 81%, 2～3 grades of southerlies; April 7 was fine, 18.2 ℃ of mean temperature of air, relative moisture 60%, 2～3 grades of southerlies.
(2) spraying time and method
At the 1st medicine of wheat powdery mildew their early stage (March 31) spray, (April 10) spray medicine second time sprays 2 times altogether behind the 10d.(operating pressure 0.2～0.3MPa), 750L carries out foliar spray according to the per hectare amount of liquid medicine to adopt the 3WBS-16 knapsack sprayer.
(3) pilot survey and data
Investigation state of an illness radix before the medicine, test is investigated 3 times altogether, i.e. disease index investigation before the medicine, preventive effect investigation in 10 days behind the 1st medicine, 10 days and preventive effect investigation in 20 days behind 2 medicines.
(4) drug effect computational methods
Sick leaf rate (the %)=sick number of sheets/investigate total number of sheets * 100
Disease index=∑ (the sick numbers of sheets at different levels * relative level numerical value)/(investigating total number of sheets * 9) * 100
Control efficiency (%)=(1-(disease index behind disease index before the blank district medicine * treatment region medicine)/(disease index before disease index behind the blank district medicine * treatment region medicine)) * 100
(5) poisoning investigation method
Whether continuous 7d range estimation medicament has poisoning to crop after the dispenser.
(6) experimental result and analysis
Table 11 is respectively organized the test effect that test medicine is handled the control wheat powdery mildew
Interpretation of result:
Can know by table 11; The effect of the combination control wheat powdery mildew that is mixed of 9% bupirimate+16% tmtd is more remarkable, and behind the medicine 10 days for the first time, 10 days and 20 days preventive effects 90.76%, 93.31% and 90.85% the highest behind the medicine for the second time; 10 days preventive effects the highest are 85.11% behind the 25% bupirimate SC medicine second time; 10 days preventive effect is up to 83.45% behind the 50% tmtd WP medicine second time, and dosage is all greater than complex preparation, and the effect of complex preparation significantly is superior to two kinds of single agent; Not only significantly improved effect, and further prolonged its lasting period for wheat powdery mildew.
Field trial 2: to the preventive effect of cucumber downy mildew
(1) investigation method
Experimental field be located at Shouguang, Shandong, publish the medium cucumber field of course of disease degree for experimental field, soil fertility is medium, and irrigation and drainage are convenient.Adopt the bilinear sampling method, 5 points are got in every sub-district, look into 5 caves at every, and 2 blades in the fixing middle part of every strain fix a point to check during investigation.
Come classification according to the cucumber downy mildew grade scale, write down total strain number, diseased plant number, degree of being in a bad way, calculate diseased plant rate, disease index and preventive effect.The cucumber downy mildew grade scale is:
0 grade: no scab;
1 grade: lesion area accounts for below 5% of whole leaf area;
3 grades: lesion area accounts for 6%～10% of whole leaf area;
5 grades: lesion area accounts for 11%～25% of whole leaf area;
7 grades: lesion area accounts for 26%～50% of whole leaf area;
9 grades: lesion area accounts for more than 50% of whole leaf area.
Test is investigated 3 times altogether, i.e. disease index investigation before the medicine, preventive effect investigation in 10 days behind the 1st medicine, 10 days and preventive effect investigation in 20 days behind the 2nd medicine.
(2) control time and number of times
Test is investigated 3 times altogether, i.e. disease index investigation before the medicine, preventive effect investigation in 10 days behind the 1st medicine, 10 days and preventive effect investigation in 20 days behind the 2nd medicine.
(3) drug effect computational methods
Sick leaf rate (the %)=sick number of sheets/investigate total number of sheets * 100
Disease index=∑ (the sick numbers of sheets at different levels * relative level numerical value)/(investigating total number of sheets * 9) * 100
Control efficiency (%)=(1-(disease index behind disease index before the blank district medicine * treatment region medicine)/(disease index before disease index behind the blank district medicine * treatment region medicine)) * 100
(4) poisoning investigation method
Whether continuous 7d range estimation medicament has poisoning to crop after the dispenser.
(5) experimental result and analysis
Table 12 is respectively organized the test effect that test medicine is handled the control cucumber downy mildew
Interpretation of result:
Can know that by table 12 effect that 8: 18 the combination that is mixed of 26% bupirimate Propineb prevents and treats powdery mildew of cucumber is very remarkable.Under same 10 milliliters every mu consumption, the effect of complex preparation significantly is superior to two kinds of single agent, and its quick-acting and lasting effect are all relatively good, and is the most outstanding with lasting effect especially.Complex preparation significantly is superior to the effect under the low concentration consumption in control efficiency under the consumption of high concentration.10 days control efficiency reaches 91.32% and 94.49% respectively behind the 1st, 2 medicine; 20 days preventive effects reach 90.76% behind the 2nd medicine; And single agent 25% bupirimate SC the highest preventive effect of 10 days behind the 2nd medicine is 84.06%, and 20 days preventive effects are 82.24% behind the 2nd medicine of single agent 70% Propineb WP, and the effect of complex preparation significantly is superior to two kinds of single agent; Not only significantly improved effect, and further prolonged its lasting period for the powdery mildew of cucumber germ.
Comprehensive above model experiment is said; To be two yuan of composite bactericidal composition preparations of active ingredient all have the better prevention effect to diseases such as the leaf spot of various crop, powdery mildew, rust, downy mildew, eqpidemic disease, anthracnose with one of any in new type bactericide bupirimate and several kinds of compound tmtd, Propineb, tpn, mancozeb, zineb, the Carbatene; Can effectively suppress further developing of disease; Simultaneously to crop safety; Suggestion is promoted the use of, and in use should be used alternatingly with other different mechanisms medicines, to delay the pesticide resistance of plant.
Claims (5)
1. pesticide sterilizing composite preparation; It is characterized in that: this bactericidal composition preparation is to be the preparation that active ingredient is carried out two yuan of composite bactericidal compositions with one of any (representing with B) in bupirimate (representing with A) and zineb, Propineb, Carbatene, mancozeb, tmtd, the tpn; All the other components are agricultural chemicals used additives and formulation preparation complementary component in the preparation, and wherein the mass percent of two kinds of effective constituents A and B is 90～1:1～95 in this bactericidal composition preparation.
2. bactericidal composition preparation according to claim 1 is characterized in that: on some specific aim ratio formulation screening test bases, the mass percent of effective constituents A and B is preferably 70～5 in this bactericidal composition preparation: 7～80.
3. bactericidal composition preparation according to claim 1 and 2; It is characterized in that: in this bactericidal composition preparation in two kinds of active ingredient bupirimates and zineb, Propineb, Carbatene, mancozeb, tmtd, the tpn one of any gross mass account for 1%～90% of total formulation gross mass, all the other are agricultural chemicals used additives and the required complementary component of formulation preparation.
4. bactericidal composition preparation according to claim 3 is characterized in that: the percentage that one of any gross mass accounts for the total formulation gross mass in two kinds of active ingredient bupirimates and zineb, Propineb, Carbatene, mancozeb, tmtd, the tpn in this bactericidal composition preparation is preferably 5%～70%.
5. according to the described bactericidal composition preparation of claim 1 to 4, it is characterized in that: the pesticidal preparations formulation that bactericidal composition preparation of the present invention can be mixed with is wetting powder, suspending agent, fumicants and water dispersible granules.
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| CN104488928A (en) * | 2014-12-18 | 2015-04-08 | 广西田园生化股份有限公司 | Compound composition containing methylsulfonylconazole and dithiocarbamate fungicide and preparation |
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| CN103408378B (en) * | 2013-08-27 | 2015-02-18 | 安徽农业大学 | Special smoke agent for preventing low-temperature freeze injury of wheat and preparation method thereof |
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