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 the bactericidal composition that is difficult for developing immunity to drugs can be used in the control of cereal crop disease such as rice seedling blight, wheat powdery mildew.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of bactericidal composition for control cereal crop damping off and powdery mildew, described bactericidal composition contain in the two azoles of the phenylate of 1: 100 ~ 100:1 of weight ratio and fluorine ring azoles.
Preferably, the weight ratio of the two azoles of phenylate and fluorine ring azoles is 1:20 ~ 20:1, more preferably 1:10 ~ 10:1.
The present invention also provides a kind of bactericide, contains the above-mentioned bactericidal composition based on active component 0.1% ~ 90% percentage by weight, and all the other are acceptable carrier and auxiliary agent on the agricultural chemicals.More preferably contain the above-mentioned bactericidal composition based on active component 10% ~ 70% percentage by weight.
According to method known in those skilled in the art, bactericidal composition of the present invention can be mixed with the formulation that agricultural allows when practical application, and formulation is suspending agent, aqueous emulsion, microemulsion, wetting powder or water dispersible granules preferably.
For water dispersible granules, those skilled in the art are familiar with the corresponding auxiliary agent of use and finish 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.
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.
To suspending agent, spendable auxiliary agent has: dispersant is selected from polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate, TERSPERSE 2425(U.S. Huntsman Corporation product, alkyl naphthalene sulfonic acid salt); Wetting agent is selected from the poly-basic ether formaldehyde condensation products sulphate of alkylphenol-polyethenoxy, 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); Defoamer is silicone based defoamer; Antifreezing agent is selected from ethylene glycol, propane diols, glycerine, urea, inorganic salts such as sodium chloride.
To suspension emulsion, spendable auxiliary agent has: dispersant is selected from polycarboxylate, lignosulfonates, alkylnaphthalene sulfonate, TERSPERSE 2425; Wetting agent is selected from the poly-basic ether formaldehyde condensation products sulphate of alkylphenol-polyethenoxy, alkylphenol-polyethenoxy base ether phosphate, phenethyl phenol polyethenoxy base ether phosphate, alkyl sulfate, alkylsulfonate, naphthalene sulfonate, TERSPERSE 2500; 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 dimethylbenzene, toluene, cyclohexanone, solvent naphtha (trade mark: S-150, S-180, S-200); Thickener is selected from xanthans, aluminium-magnesium silicate, bentonite; Preservative is selected from benzoic acid, Sodium Benzoate, BIT(1, the 2-benzisothiazole-3-ketone); Defoamer is silicone based defoamer; 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 dimethylbenzene, 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, dimethylbenzene, toluene, solvent naphtha (trade mark: S-150, S-180, S-200); Stabilizing agent is selected from triphenyl phosphite, epoxychloropropane.
The invention still further relates to above-mentioned bactericidal composition or the bactericide purposes in control cereal crop damping off, powdery mildew, particularly in the purposes of preventing and treating rice seedling blight and wheat powdery mildew.
Bactericidal composition of the present invention can provide with the finished product preparation form, and namely each material mixes in the composition; Also can provide with single agent formulation, in bucket (jar), directly mix before using.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 of the present invention has significant synergistic effect to disease, has improved bactericidal effect;
(2) reduce drug cost, reduce environmental pollution and residue of pesticide;
(3) composition is made up of the active ingredient of different mechanism of action, and action site increases, and is conducive to overcome 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 may comprise.In the present invention, if no special instructions, the ratio in the prescription is weight ratio, belongs to the weight ratio that " active ingredient ratio " all refers to the two azoles of phenylate and fluorine ring azoles.
One, biologicall test
Example 1: the two azoles of phenylate and the composite Toxicity Determination to rice seedling blight of fluorine ring azoles
Test target rice seedling blight (Rhizoctonia solani) is cultivated by the long-term live body of this laboratory, select two leaves wholeheartedly, the potted plant rice seedling of growing way unanimity, spraying is handled the back and is dried naturally, inoculate about 24h, spraying a banded sclerotial blight mycelia of the every basin rice seedling base portion central authorities' clamping connection piece of medicine, the bacterium piece does not contact with basin soil and water layer.Postvaccinal examination material moves in the humidistat to be cultivated, 26 ℃ of temperature, and humidity 80 ~ 90% is observed the rice growth situation every day, investigation prevention effect when blank is fully fallen ill after 5 days.
Investigation method and grade scale are as follows:
0 grade: do not fall ill;
1 grade: the morbidity of first leaf sheath;
3 grades: first blade and the morbidity of second leaf sheath;
5 grades: second blade and the morbidity of the 3rd leaf sheath;
7 grades: whole strain morbidity.
Calculate each with disease index and handle control efficiency, carry out the data analysis statistics with " DPS data handling system " 3.11 professional versions, obtain regression line, EC
50, correlation coefficient.EC that each that will measure according to Sun Yunpei (Y-P Sun) method 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.
The two azoles of table 1 phenylate and the composite Toxicity Determination result to rice seedling blight of fluorine ring azoles
Example 2: the two azoles of phenylate and the composite Toxicity Determination to wheat powdery mildew of fluorine ring azoles
Test target wheat powdery mildew (Blumeria graminis) is cultivated by the long-term live body of this laboratory and is selected for use susceptible variety (raising wheat No. 6) potted plant, treat that seedling grows to 2 leaves~3 leaf phases, spraying is handled the back and is dried naturally, and the fresh spore of white powder germ that the wheat leaf blade of falling ill was produced in last 24 hour is evenly shaken off to be inoculated on the potted plant wheat seedling of 2~3 leaf phases that chemicals treatment crosses.Postvaccinal examination material moves to 20 ℃, relative moisture 80% left and right sides controllable greenhouse glass room is interior cultivates.Note keeping basin soil moistening every day, investigate according to the classification of blank incidence about 7 days.
The investigation grade scale:
0 grade: anosis;
1 grade: lesion area accounts for below 5% of one-piece blade area;
3 grades: lesion area accounts for 6% ~ 15% of one-piece blade area;
5 grades: lesion area accounts for 16% ~ 25% of one-piece blade area;
7 grades: lesion area accounts for 26% ~ 50% of one-piece blade area;
9 grades: lesion area accounts for more than 50% of one-piece blade area.
The preventive effect computational methods:
Co-toxicity coefficient computational methods: EC that each that will measure according to Sun Yunpei (Y-P Sun) method 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.
The two azoles of table 2 phenylate and the composite Toxicity Determination result to wheat powdery mildew of fluorine ring azoles
From The above results as can be seen, the two azoles of phenylate and fluorine ring azoles are mixed, and in weight ratio is the scope of 1:100~100:1, rice seedling blight and wheat powdery mildew are all shown as synergistic effect.Wherein synergistic effect is the most obvious in the scope of 1:10~10:1.The result shows, the two azoles of phenylate and fluorine ring azoles are mixed and prevent and treat the cereal crop damping off and powdery mildew has reasonability and feasibility.
Two, preparation preparation
Percentage composition is mass percent in all preparation proportionings.
1, 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 epoxiconazole suspension concentrates (active ingredient is than 5:1) of embodiment 1:30% phenylate
Take by weighing the two former medicines of azoles of 25% phenylate, 5% epoxiconazole raw drug, 4%FS3000(phosphate anion surfactant), the 1%SXC(sulfonate anionic surfactant), 0.1% xanthans, 1% aluminium-magnesium silicate, 5% ethylene glycol, 0.2%BIT(1, the 2-benzisothiazole-3-ketone), 0.3% organically-modified silicone antifoam agent, deionized water adds to 100%.Make slurry, carry out sand milling, obtain product.
The two azoles epoxiconazole suspension concentrates (active ingredient is than 10:1) of embodiment 2:33% phenylate
Take by weighing the two former medicines of azoles of 30% phenylate, 3% epoxiconazole raw drug, 4%FS3000(phosphate anion surfactant), the 1%SXC(sulfonate anionic surfactant), 0.1% xanthans, 1% aluminium-magnesium silicate, 5% ethylene glycol, 0.2%BIT(1, the 2-benzisothiazole-3-ketone), 0.3% organically-modified silicone antifoam agent, deionized water adds to 100%.Make slurry, carry out sand milling, obtain product.
2, suspension emulsion
Press formula rate, former medicine and dispersant, wetting agent, defoamer, water etc. are mixed, obtain the suspension mother liquor through the sand mill sand milling; Again another former medicine, solvent, emulsifier etc. are mixed, obtain the homogeneous oil phase, according to metering proportion, under high shear conditions, oil phase and excess water joined to mix in the suspension mother liquor shear evenly.Adding thickener and preservative again stirs and obtains required product.
The two azoles fluorine ring azoles suspension emulsions (active ingredient is than 1.5:1) of embodiment 3:25% phenylate
The two former medicines of azoles of 15% phenylate, 10% epoxiconazole raw drug, 3%FS3000,1%SXC(sulfonic acid type anion surfactant), 30% solvent naphtha S150,5% farming breast 500,1%NS-500LQ, 0.1% xanthans, 5% ethylene glycol, 0.03%BIT, 0.3% organically-modified silicone antifoam agent, deionized water adds to 100%.Earlier the two former medicines of azoles of phenylate, FS3000, SXC, ethylene glycol, defoamer, part deionized water are mixed, obtain the two azoles suspension mother liquors of phenylate in the sand mill sand milling.Again epoxiconazole raw drug, solvent naphtha, emulsifiers dissolve are mixed and obtain the homogeneous oil phase, according to metering proportion, under high shear conditions, oil phase and excess water joined to mix in the suspension mother liquor shear evenly.Adding thickener xanthans and preservative BIT again mixes and obtains required product.
The two azoles fluorine ring azoles suspension emulsions (active ingredient is than 20:1) of embodiment 4:42% phenylate
The two former medicines of azoles of 40% phenylate, 2% epoxiconazole raw drug, 3%FS3000,1%SXC(sulfonic acid type anion surfactant), 30% solvent naphtha S150,5% farming breast 500,1%NS-500LQ, 0.1% xanthans, 5% ethylene glycol, 0.03%BIT, 0.3% organically-modified silicone antifoam agent, deionized water adds to 100%.Earlier the two former medicines of azoles of phenylate, FS3000, SXC, ethylene glycol, defoamer, part deionized water are mixed, obtain the two azoles suspension mother liquors of phenylate in the sand mill sand milling.Again epoxiconazole raw drug, solvent naphtha, emulsifiers dissolve are mixed and obtain the homogeneous oil phase, according to metering proportion, under high shear conditions, oil phase and excess water joined to mix in the suspension mother liquor shear evenly.Adding thickener xanthans and preservative BIT again mixes and obtains required product.
3, water dispersible granules
Press formula rate, former medicine and dispersant, wetting agent, binding agent, filler etc. are mixed, obtain pulvis after air-flow is pulverized, add a certain amount of water and mix, carry out granulation in comminutor, dry, screening namely gets granular product then.
The two azoles epoxiconazole water dispersants (active ingredient is than 1:2) of embodiment 5:45% phenylate
Take by weighing the two former medicines of azoles of 15% phenylate, 30% epoxiconazole raw drug, 4%NNO(alkylnaphthalene sulfonate formaldehyde condensation products), 2% Nekal BX (nekal), 3%K-12(lauryl sodium sulfate), 5% carboxymethyl (ethyl) cellulose, 3% diatomite, 5% glucose, kaolin add to 100%.Mix, after air-flow is pulverized, granulate.
The two azoles epoxiconazole water dispersants (active ingredient is than 1:20) of embodiment 6:31.5% phenylate
Take by weighing the two former medicines of azoles of 1.5% phenylate, 30% epoxiconazole raw drug, 4%NNO(alkylnaphthalene sulfonate formaldehyde condensation products), 2% Nekal BX (nekal), 3%K-12(lauryl sodium sulfate), 5% carboxymethyl (ethyl) cellulose, 3% diatomite, 5% glucose, kaolin add to 100%.Mix, after air-flow is pulverized, granulate.
The two azoles epoxiconazole water dispersants (active ingredient is than 1:10) of embodiment 7:44% phenylate
Take by weighing the two former medicines of azoles of 4% phenylate, 40% epoxiconazole raw drug, 4%NNO(alkylnaphthalene sulfonate formaldehyde condensation products), 2% Nekal BX (nekal), 3%K-12(lauryl sodium sulfate), 5% carboxymethyl (ethyl) cellulose, 3% diatomite, 5% glucose, kaolin add to 100%.Mix, after air-flow is pulverized, granulate.
4, wetting powder
By the prescription requirement, with various auxiliary agents, filler, former medicine mix pulverize by Roughpulverizer after, enter airslide disintegrating mill and fully be pulverized and mixed and make wetting powder.
The two azoles fluorine ring azoles wetting powders (active ingredient is than 1:1) of embodiment 8:50% phenylate
Take by weighing the two former medicines of azoles of 25% phenylate, 25% epoxiconazole raw drug, 4%NNO, 2% Nekal BX, 5% white carbon, fine particle calcium carbonate and add to 100%.Mix, obtain product after the pulverizing.
The two azoles fluorine ring azoles wetting powders (active ingredient is than 100:1) of embodiment 8:80.8% phenylate
Take by weighing the two former medicines of azoles of 80% phenylate, 0.8% epoxiconazole raw drug, 4%NNO, 2% Nekal BX, 5% white carbon, fine particle calcium carbonate and add to 100%.Mix, obtain product after the pulverizing.
The two azoles fluorine ring azoles wetting powders (active ingredient is than 2.5:1) of embodiment 9:70% phenylate
Take by weighing the two former medicines of azoles of 50% phenylate, 20% epoxiconazole raw drug, 5% calcium lignosulfonate, 3% Nekal BX, 3%K-12, kaolin and add to 100%.Mix, obtain product after the pulverizing.
The two azoles fluorine ring azoles wetting powders (active ingredient is than 1:100) of embodiment 10:50.5% phenylate
Take by weighing the two former medicines of azoles of 0.5% phenylate, 50% epoxiconazole raw drug, 5% calcium lignosulfonate, 3% Nekal BX, 3%K-12, kaolin and add to 100%.Mix, obtain product after the pulverizing.
5, microemulsion
The two azoles fluorine ring azoles microemulsions (active ingredient is than 2:1) of embodiment 11:15% phenylate
Take by weighing the two former medicines of azoles of 10% phenylate, 5% epoxiconazole raw drug, 8% Nongru-700 #, 5% agricultural newborn 500#, 5% agricultural newborn 1601#, 20% 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 fluorine ring azoles microemulsions (active ingredient is than 1:5) of embodiment 12:18% phenylate
Take by weighing the two former medicines of azoles of 3% phenylate, 15% epoxiconazole raw drug, 8% Nongru-700 #, 5% agricultural newborn 500#, 5% agricultural newborn 1601#, 20% cyclohexanone, 5%N-methyl pyrrolidone, 5% n-butanol, through dissolving fully and mixing, deionized water adds to 100%.After stirring, obtain product.
6, aqueous emulsion
The two azoles aqueous emulsions (active ingredient is than 1:1) of embodiment 13:10% fluorine ring azoles phenylate
Take by weighing 5% epoxiconazole raw drug, the two former medicines of azoles of 5% phenylate, 5% agricultural newborn 2201#, 2% Nonyl pheno (EO=10) ether phosphate, 3% 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 rice seedling blight field control effectiveness test
According to the regulation of medicine inspecting institute of the Ministry of Agriculture " pesticide field efficacy medicine test criterion (three)---bactericidal agent for preventing and treating rice seedling blight ", the residential quarter of test medicine, contrast medicament and blank is handled and is adopted district's group arrangement at random, residential quarter area 15m
2, 4 repetitions, seedbed medication.The 10th day and investigation in 20 days after emerging, 5 samplings of every experimental plot diagonal, every continuous 5 strains of investigation, record disease grade.
The disease grade scale is as follows:
0 grade: complete stool is anosis;
1 grade: the slight browning of basal part of stem, rice growth is normal substantially;
3 grades: the obvious browning of basal part of stem, rot with softening and slight;
5 grades: the obvious browning of basal part of stem and rotten, young leaves wither to hang down and crispatura;
7 grades: the basal part of stem browning rots, and complete stool green grass or young crops is withered or yellowish-brown is withered.
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 rice seedling blight field control effectiveness test result
Application examples 2, control wheat powdery mildew field control effectiveness test
The residential quarter of test medicine, contrast medicament and blank is handled and is adopted district's group arrangement at random, residential quarter area 20 square meters, 4 repetitions, each spraying control of booting stage and flowering initial stage 1 time.Five point samplings are at random adopted in investigation in 15 days after the dispenser for the second time, get 20 strains at every, investigate last 3 leaves (having boot leaf then to comprise boot leaf) of every strain.
The disease grade scale is as follows:
0 grade: no scab;
1 grade: lesion area accounts for whole below 5% of leaf area;
3 grades: lesion area accounts for 6% ~ 15% of whole leaf area;
5 grades: lesion area accounts for 16% ~ 25% of whole leaf area;
7 grades: lesion area accounts for 26% ~ 50% of whole leaf area;
9 grades: lesion area accounts for whole more than 51% of leaf area.
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 wheat powdery mildew field control effectiveness test result
Comprehensive above-mentioned indoor biometrics and field control effectiveness test, the result shows that the beneficial effect that bactericidal composition of the present 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) 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 of the present invention has good preventive effect to cereal crop disease such as rice seedling blight and wheat powdery mildew etc.