Summary of the invention
The object of the present invention is to provide a kind of component reasonable, bactericidal effect is good, and drug cost is low, and bactericidal composition that is difficult for developing immunity to drugs and bactericide can be used in control fruit tree, eliminating vegetable botrytis.
For achieving the above object, the invention provides a kind of agricultural bactericidal composition, said agricultural bactericidal composition contains two azoles of phenylate and the cyprodinil that weight ratio is 1: 100 ~ 100:1.
Preferably, the weight ratio of two azoles of said phenylate and cyprodinil is 1:20 ~ 20:1; Especially preferably, the weight ratio of two azoles of said phenylate and cyprodinil is 1:20 ~ 10:1.
The present invention also provides a kind of disinfectant use in agriculture, and said disinfectant use in agriculture contains percentage by weight 0.1% ~ 90% above-mentioned agricultural bactericidal composition, and all the other are acceptable carrier and auxiliary agent in the agricultural chemicals.The above-mentioned agricultural bactericidal composition that preferably contains percentage by weight 10% ~ 80%, all the other are acceptable carrier and auxiliary agent in the agricultural chemicals.
According to method known in those skilled in the art, bactericidal composition of the present invention can be mixed with the formulation that allows on the agricultural when practical application, and formulation is suspending agent, aqueous emulsion, microemulsion, wetting powder or water dispersible granules preferably.
To suspending agent, spendable auxiliary agent has: dispersant is selected from polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate, TERSPERSE 2425 (U.S. Huntsman Corporation produces, the alkyl naphthalene sulfonic acid salt); Wetting agent is selected from alkylphenol-polyethenoxy and gathers basic ether formaldehyde condensation products sulphate, alkylphenol-polyethenoxy base ether phosphate, phenethyl phenol polyethenoxy base ether phosphate, alkyl sulfate, alkylsulfonate, naphthalene sulfonate, TERSPERSE 2500 (U.S. Huntsman Corporation product); Thickener is selected from xanthans, aluminium-magnesium silicate, bentonite; Preservative is selected from benzoic acid, Sodium Benzoate, BIT (1, the 2-benzisothiazole-3-ketone); Antifoaming agent is silicone based antifoaming agent; Antifreezing agent is selected from ethylene glycol, propane diols, glycerine, urea, inorganic salts such as sodium chloride.
To aqueous emulsion, spendable auxiliary agent has: emulsifier is selected from Nonyl pheno (EO=10) ether phosphate, triphen ethyl-phenol polyoxyethylene ether phosphate (agricultural newborn 600# phosphate), Nongru-700 #, agricultural newborn 2201#, Span-60#, emulsifier T-60, TX-10, agricultural newborn 1601#, agricultural newborn 600#, agricultural newborn 400#; Solvent is selected from xylol, toluene, cyclohexanone, solvent naphtha (trade mark: S-150, S-180, S-200); Stabilizing agent is selected from triphenyl phosphite, epoxychloropropane; Antifreezing agent is selected from ethylene glycol, propane diols, glycerine, urea, inorganic salts such as sodium chloride; Thickener is selected from xanthans, bentonite, aluminium-magnesium silicate; Preservative is selected from BIT (1, the 2-benzisothiazole-3-ketone), benzoic acid, Sodium Benzoate.
To microemulsion, spendable auxiliary agent has: emulsifier is selected from calcium dodecyl benzene sulfonate (agricultural newborn 500#), Nongru-700 #, agricultural newborn 2201#, this dish-60#, Tween-80, TX-10, farming breast 1601, agricultural newborn 600#, agricultural newborn 400#; Cosolvent is selected from methyl alcohol, isopropyl alcohol, n-butanol, ethanol; Solvent is selected from cyclohexanone, N-Methyl pyrrolidone, xylol, toluene, solvent naphtha (trade mark: S-150, S-180, S-200); Stabilizing agent is selected from triphenyl phosphite, epoxychloropropane.
To wetting powder, spendable auxiliary agent has: dispersant is selected from polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate; Wetting agent is selected from alkyl sulfate, alkylsulfonate, naphthalene sulfonate; Filler is selected from diatomite, kaolin, white carbon, fine particle calcium carbonate, talcum powder, attapulgite, potter's clay etc.
For water dispersible granules, those skilled in the art are familiar with the use corresponding adjuvants and accomplish the present invention very much.Dispersant is selected for use from polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate; Wetting agent is selected from polyoxyethylene alcohol, alkyl sulfate, alkylsulfonate, naphthalene sulfonate; Disintegrant is selected from ammonium sulfate, urea, sucrose, glucose, citric acid, succinic acid, sodium bicarbonate; Binding agent is selected from diatomite, corn starch, PVA, carboxymethyl (ethyl) cellulose family and microcrystalline cellulose class; Filler is selected from diatomite, kaolin, white carbon, fine particle calcium carbonate, sepiolite, talcum powder, attapulgite, potter's clay etc.
The present invention also provides above-mentioned agricultural bactericidal composition or disinfectant use in agriculture in the purposes of preventing and treating fruit tree gray mold and eliminating vegetable botrytis.
Bactericidal composition of the present invention can provide with the finished product preparation form, and promptly each material mixes in the composition; Also can provide, in bucket (jar), directly mix before using with single agent formulation.Concentrate of the present invention mixes the concentration that obtains required active substance usually with water.
Compared with prior art, the beneficial effect of the present invention's generation is:
(1) compare with single agent, bactericidal composition according to the invention has significant synergistic effect to disease, has improved bactericidal effect;
(2) reduce the medication number of times, reduce drug cost, reduce environmental pollution and residue of pesticide;
(3) composition is made up of the active ingredient of different effects mechanism, and the action site increase helps overcoming and delays the drug-fast generation of germ.
Embodiment
Come the present invention is further specified below in conjunction with specific embodiment, but do not limit the invention to these embodiments.One skilled in the art would recognize that the present invention contained in claims scope all alternatives, improvement project and the equivalents that possibly comprise.
Among the present invention in the proportioning of all preparations percentage all be weight percentage, " active ingredient than " or " proportioning " all refers to the ratio of two azoles of phenylate and cyprodinil.
One, biologicall test
Instance 1: two azoles of phenylate and the composite Toxicity Determination of cyprodinil to ash arrhizus bacteria
Test target pathogen is ash arrhizus bacteria (Botrytis cinerea), and this bacterial classification is preserved by the laboratory.Adopt the blade bacterination process.Select the consistent potted plant cucumber seedling of two leaf period growing ways, subsequent use.Two azoles of phenylate and cyprodinil are dissolved with DMF respectively, be mixed with the soup of series concentration again with 0.1% Tween-80 aqueous solution dilution, the more two azoles of phenylate are processed preset series concentration compound solution with cyprodinil respectively by different proportionings.To the cucumber seedling processing of spraying, after 24 hours, the ash arrhizus bacteria that will cultivate about 3 days with card punch breaks into diameter 5mm bacterium cake along the edge with the different series concentration liquid, with tweezers the bacterium cake is had the one side of mycelia to connect to be affixed on and respectively handles blade central authorities.25 ℃ of half-lights are preserved moisture behind the 24h, about about 3 days of restore nature illumination cultivation, every processing repetition 3 times.Wait to contrast abundant morbidity back with each inoculation point scab diameter of slide calliper rule metering, calculate preventive effect.With each inoculation point scab diameter of slide calliper rule metering, represent the scab size with its mean.Obtain by following formula and respectively to handle preventive effect: control efficiency %=(contrast scab average diameter-processings scab average diameter) * 100/ contrasts the scab average diameter
On the basis of chemical control efficient, carry out the data analysis statistics with " DPS data handling system ", obtain EC
50EC that each that will measure according to the abundant method of Sun Yun handled
50Be converted into actual poison exponent (ATI); According to the proportioning of mixture, obtain theoretical poison exponent (TTI), calculate the co-toxicity coefficient (CTC) of mixture by following formula.
Theory is used the content (%) of toxicity index * B in using with of content (the %)+B of toxicity index * A in using with of toxicity index (TTI)=A with
If co-toxicity coefficient is greater than 120, showing has synergistic effect; If be starkly lower than 100, be indicated as antagonism; Between 100~120, be indicated as summation action.
Two azoles of table 1 phenylate and the composite Toxicity Determination result of cyprodinil to gray mold of cucumber
Can find out that from above-mentioned Toxicity Determination result two azoles of phenylate and cyprodinil are mixed, and in weight is the scope of 100:1~1:100, botrytis cinerea pers are all shown as synergistic effect.Wherein mass ratio is that synergistic effect is the most obvious in the scope of 10:1~1:20.
Instance 2: two azoles of phenylate and the composite Toxicity Determination of cyprodinil to the grape grey mould bacterium
Test target pathogen is ash arrhizus bacteria (Botrytis cinerea), and this bacterial classification is preserved by the laboratory.Adopt the blade bacterination process.Select the consistent grape pot seedling of two leaf period growing ways, subsequent use.Two azoles of phenylate and cyprodinil are dissolved with DMF respectively, be mixed with the soup of series concentration again with 0.1% Tween-80 aqueous solution dilution, the more two azoles of phenylate are processed preset series concentration compound solution with cyprodinil respectively by different proportionings.To the grape seedlings processing of spraying, after 24 hours, the ash arrhizus bacteria that will cultivate about 3 days with card punch breaks into diameter 5mm bacterium cake along the edge with the different series concentration liquid, with tweezers the bacterium cake is had the one side of mycelia to connect to be affixed on and respectively handles blade central authorities.25 ℃ of half-lights are preserved moisture behind the 24h, about about 3 days of restore nature illumination cultivation, every processing repetition 3 times.Wait to contrast abundant morbidity back with each inoculation point scab diameter of slide calliper rule metering, calculate preventive effect.With each inoculation point scab diameter of slide calliper rule metering, represent the scab size with its mean.Obtain by following formula and respectively to handle preventive effect: control efficiency %=(contrast scab average diameter-processings scab average diameter) * 100/ contrasts the scab average diameter
On the basis of chemical control efficient, carry out the data analysis statistics with " DPS data handling system ", obtain EC
50EC that each that will measure according to the abundant method of Sun Yun handled
50Be converted into actual poison exponent (ATI); According to the proportioning of mixture, obtain theoretical poison exponent (TTI), calculate the co-toxicity coefficient (CTC) of mixture by following formula.
Theory is used the content (%) of toxicity index * B in using with of content (the %)+B of toxicity index * A in using with of toxicity index (TTI)=A with
If co-toxicity coefficient is greater than 120, showing has synergistic effect; If be starkly lower than 100, be indicated as antagonism; Between 100~120, be indicated as summation action.
Two azoles of table 1 phenylate and the composite Toxicity Determination result of cyprodinil to grape grey mould
Can find out that from above-mentioned Toxicity Determination result two azoles of phenylate and cyprodinil are mixed, and in weight is the scope of 100:1~1:100, the grape grey mould bacterium are all shown as synergistic effect.Wherein mass ratio is that synergistic effect is the most obvious in the scope of 10:1~1:20.
The result shows, two azoles of phenylate and cyprodinil are mixed and prevent and treat gray mold and have reasonability and feasibility.
Two, preparation preparation
Percentage composition is mass percent in all preparation proportionings.
1, water dispersible granules
Press formula rate, former medicine and dispersant, wetting agent, binding agent, filler etc. are mixed, behind comminution by gas stream, obtain pulvis, add a certain amount of water and mix, in comminutor, carry out granulation, dry then, screening promptly gets granular product.
The two azoles cyprodinil water dispersible granules (active ingredient is than 1:1) of embodiment 1:50% phenylate
Take by weighing the two former medicines of azoles of 25% phenylate, the former medicine of 25% cyprodinil, 4% NNO (alkylnaphthalene sulfonate formaldehyde condensation products), 1% Nekal BX (nekal), 4%K-12 (lauryl sodium sulfate), 5% carboxymethyl (ethyl) cellulose, 3% diatomite, 5% glucose, kaolin and add to 100%.Mix, behind comminution by gas stream, granulate.
The two azoles cyprodinil water dispersible granules (active ingredient is than 5:1) of embodiment 2:48% phenylate
Take by weighing the two former medicines of azoles of 40% phenylate, the former medicine of 8% cyprodinil, 4% NNO (alkylnaphthalene sulfonate formaldehyde condensation products), 1% Nekal BX (nekal), 4%K-12 (lauryl sodium sulfate), 5% carboxymethyl (ethyl) cellulose, 3% diatomite, 5% glucose, kaolin and add to 100%.Mix, behind comminution by gas stream, granulate.
2, suspending agent
Pressing formula rate, is medium with water, former medicine, dispersant, suspending agent and antifreezing agent etc. is joined shear 30min in the high-shear emulsion machine, use the sand mill sand milling again after, obtain suspending agent.
The two azoles cyprodinil suspending agents (active ingredient is than 1:5) of embodiment 3:30% phenylate
Take by weighing the two former medicines of azoles of 5% phenylate, the former medicine of 25% cyprodinil, 3% FS3000 (phosphate type anion surfactant), 0.5% SXC (sulfonic acid type anion surfactant), 0.1% xanthans, 1% aluminium-magnesium silicate, 5% ethylene glycol, 0.15%BIT (1; The 2-benzisothiazole-3-ketone), 0.3% organically-modified silicone antifoam agent, deionized water adds to 100%.Process slurry, carry out sand milling, obtain product.
The two azoles cyprodinil suspending agents (active ingredient is than 1:10) of embodiment 4:44% phenylate
Take by weighing the two former medicines of azoles of 4% phenylate, the former medicine of 40% cyprodinil, 3% FS3000 (phosphate type anion surfactant), 0.5% SXC (sulfonic acid type anion surfactant), 0.1% xanthans, 1% aluminium-magnesium silicate, 5% ethylene glycol, 0.15%BIT (1; The 2-benzisothiazole-3-ketone), 0.3% organically-modified silicone antifoam agent, deionized water adds to 100%.Process slurry, carry out sand milling, obtain product.
The two azoles cyprodinil suspending agents (active ingredient is than 1.25:1) of embodiment 5:45% phenylate
Take by weighing the two former medicines of azoles of 25% phenylate, the former medicine of 20% cyprodinil, 4% FS3000,1% SXC, 0.1% xanthans, 1% aluminium-magnesium silicate, 5% ethylene glycol, 0.15%BIT, 0.3% organically-modified silicone antifoam agent, deionized water adds to 100%.Process slurry, carry out sand milling, obtain product.
The two azoles cyprodinil suspending agents (active ingredient is than 10:1) of embodiment 6:55% phenylate
Take by weighing the two former medicines of azoles of 50% phenylate, the former medicine of 5% cyprodinil, 4% FS3000,1% SXC, 0.1% xanthans, 1% aluminium-magnesium silicate, 5% ethylene glycol, 0.15%BIT, 0.3% organically-modified silicone antifoam agent, deionized water adds to 100%.Process slurry, carry out sand milling, obtain product.
3, wetting powder
By the prescription requirement, various auxiliary agents, filler, former medicine are mixed after after the Roughpulverizer pulverizing, get into airslide disintegrating mill and fully pulverize the mixed wetting powder that gets.
The two azoles cyprodinil wetting powders (active ingredient is than 1:1) of embodiment 7:80% phenylate
Take by weighing the two former medicines of azoles of 40% phenylate, the former medicine of 40% cyprodinil, 5% calcium lignosulfonate, 2% Nekal BX, 1%K-12, kaolin and add to 100%.Mix, obtain product after the pulverizing.
The two azoles cyprodinil wetting powders (active ingredient is than 20:1) of embodiment 8:63% phenylate
Take by weighing the two former medicines of azoles of 60% phenylate, the former medicine of 3% cyprodinil, 5% calcium lignosulfonate, 2% Nekal BX, 1%K-12, kaolin and add to 100%.Mix, obtain product after the pulverizing.
The two azoles cyprodinil wetting powders (active ingredient is than 50:1) of embodiment 9:51% phenylate
Take by weighing the two former medicines of azoles of 50% phenylate, the former medicine of 4% cyprodinil, 5% calcium lignosulfonate, 2% Nekal BX, 1%K-12, kaolin and add to 100%.Mix, obtain product after the pulverizing.
4, microemulsion
The two azoles cyprodinil microemulsions (active ingredient is than 1:1.5) of embodiment 10:25% phenylate
Take by weighing the two former medicines of azoles of 10% phenylate, the former medicine of 15% cyprodinil, 5% Nongru-700 #, 5% agricultural newborn 500#, 6% agricultural newborn 1601#, 15% cyclohexanone, 5%N-methyl pyrrolidone, 5% n-butanol, through dissolving fully and mixing, deionized water adds to 100%.After stirring, obtain product.
The two azoles cyprodinil microemulsions (active ingredient is than 100:1) of embodiment 11:30.3% phenylate
Take by weighing the two former medicines of azoles of 30% phenylate, the former medicine of 0.3% cyprodinil, 5% Nongru-700 #, 5% agricultural newborn 500#, 6% agricultural newborn 1601#, 15% cyclohexanone, 5%N-methyl pyrrolidone, 5% n-butanol, through dissolving fully and mixing, deionized water adds to 100%.After stirring, obtain product.
5, aqueous emulsion
The two azoles aqueous emulsions (active ingredient is than 1:1) of embodiment 12:10% cyprodinil phenylate
Take by weighing the former medicine of 5% cyprodinil, the two former medicines of azoles of 5% phenylate, 4% agricultural newborn 2201#, 2% Nonyl pheno (EO=10) ether phosphate, 2.5% agricultural newborn 600# acid phosphatide, 20% cyclohexanone, 10% solvent naphtha S150, mixed dissolution obtains oil phase.With 5% ethylene glycol, 0.3% xanthans, 0.5% benzoic acid, deionized water adds to 100%, is made into water.Oil phase adds aqueous phase and fully mixes, and behind high-shear emulsifying, obtains product.
The two azoles aqueous emulsions (active ingredient is than 1:100) of embodiment 13:10.1% cyprodinil phenylate
Take by weighing the former medicine of 0.1% cyprodinil, the two former medicines of azoles of 10% phenylate, 4% agricultural newborn 2201#, 2% Nonyl pheno (EO=10) ether phosphate, 2.5% agricultural newborn 600# acid phosphatide, 20% cyclohexanone, 10% solvent naphtha S150, mixed dissolution obtains oil phase.With 5% ethylene glycol, 0.3% xanthans, 0.5% benzoic acid, deionized water adds to 100%, is made into water.Oil phase adds aqueous phase and fully mixes, and behind high-shear emulsifying, obtains product.
Three, field application test
Application examples 1: control gray mold of cucumber field control effectiveness test
Regulation with reference to medicine inspecting institute of the Ministry of Agriculture " GB/T 17980.28-2000 pesticide field efficacy medicine test criterion ()---bactericidal agent for preventing and treating eliminating vegetable botrytis "; The sub-district of test medicine, contrast medicament and blank is handled and is adopted district's group arrangement at random, sub-district area 15m
2, 4 repetitions, this test amounts to twice of dispenser.Be in their early stage during dispenser for the first time, execute medicine for the second time after the week.This test is investigated 2 times altogether, and 5 samplings are adopted in every experimental plot, investigates 2 strains at every, investigates whole blades of every strain, record disease grade.
The disease grade scale is following:
0 grade: no scab;
1 grade: single blade has 3 of scabs;
3 grades: single blade has 4 ~ 6 of scabs;
5 grades: single blade has 7 ~ 10 of scabs;
7 grades: single blade has 11 ~ 20 of scabs, and part is intensive in flakes;
9 grades: single blade has the intensive leaf area that accounts for of scab more than 1/4th.
The drug effect computational methods:
According to investigation result, calculate disease index and preventive effect according to following (1), (2) formula.
In the formula: CK
0, CK
1Be respectively the forward and backward disease index of blank district dispenser; PT
0, PT
1Be respectively the forward and backward disease index of chemicals treatment district medicine.
Table 3 control gray mold of cucumber field control effectiveness test result
Application examples 2: control grape grey mould field control effectiveness test
Regulation with reference to medicine inspecting institute of the Ministry of Agriculture " GB/T 17980.28-2000 pesticide field efficacy medicine test criterion ()---bactericidal agent for preventing and treating eliminating vegetable botrytis "; The sub-district of test medicine, contrast medicament and blank is handled and is adopted district's group arrangement at random, sub-district area 20m
2, 4 repetitions, this test amounts to dispenser three times.For the first time be administered to grape and bloomed preceding 6 days, fruit phase, each dispenser of fruiting period just 1 time, 7 ~ 10 days at interval.5 samplings are adopted in every experimental plot, every some investigation 2 strains.The sick progression of investigation fruit ear number, morbidity fruit ear number and fruit ear calculates disease index.
The disease grade scale is following:
0 grade: full fruit (fringe) is anosis;
1 grade: fruit grain (fringe) below 1/4 rots;
2 grades: 1/4~1/2 fruit grain (fringe) rots;
3 grades: 1/2~3/4 fruit grain (fringe) rots;
4 grades: fruit grain (fringe) rots more than 3/4.
The drug effect computational methods:
According to investigation result, calculate disease index and preventive effect according to following (1), (2) formula.
In the formula: CK
0, CK
1Be respectively the forward and backward disease index of blank district dispenser; PT
0, PT
1Be respectively the forward and backward disease index of chemicals treatment district medicine.
Table 4 control grape grey mould field control effectiveness test result
Comprehensive above-mentioned indoor biometrics and field control effectiveness test result show that the beneficial effect that bactericidal composition according to the invention produces is:
(1) compare with single agent, this bactericidal composition has significant synergistic effect to disease, has improved bactericidal effect;
(2) reduce the medication number of times, lower drug cost, reduce environmental pollution and residue of pesticide;
(3) composition is made up of the active ingredient of different effects mechanism, and the action site increase helps overcoming and delays the drug-fast generation of germ.The present composition does not all have obvious harmful effect to trial crops, and leaf look, growing way etc. are all normal, and safety is good, meets the security requirement of pesticidal preparations.
Bactericidal composition according to the invention has good preventive effect to fruit tree and eliminating vegetable botrytis.