CN106212479B - A kind of microbicide compositions - Google Patents

A kind of microbicide compositions Download PDF

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Publication number
CN106212479B
CN106212479B CN201610637533.XA CN201610637533A CN106212479B CN 106212479 B CN106212479 B CN 106212479B CN 201610637533 A CN201610637533 A CN 201610637533A CN 106212479 B CN106212479 B CN 106212479B
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bacterium azoles
nitrile bacterium
active component
microbicide compositions
composition
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CN106212479A (en
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季红进
仲汉根
花伟
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Andao maihuifeng (Jiangsu) Co.,Ltd.
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Jiangsu Huifeng Agrochemical Co Ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647Triazoles; Hydrogenated triazoles
    • A01N43/6531,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Abstract

The present invention provides a kind of microbicide compositions, the composition includes two kinds of effective constituents As and B, and active component A is the structural compounds with formula (I), and active component B is nitrile bacterium azoles, and the weight ratio between two components is 1:40~40:1.The present invention also provides the Preparation method and uses of the composition.Test result shows that above-mentioned bactericidal composition synergy provided by the invention is apparent, it is often more important that amount of application is reduced, and use cost reduces.The bactericidal composition can effectively prevent certain specific fungal diseases of crop.By compounding the fungicide of different role mechanism and the mode of action, the amount of application of each single dose is effectively reduced, there is good effect for expand fungicidal spectrum and delay fungi, fungus resistant and improve control effect etc..

Description

A kind of microbicide compositions
Technical field
The invention belongs to agriculture plant protection fields, more particularly to a kind of bactericidal composition for having and improving performance, tool Say to body it is to be related to a kind of bactericidal composition including benzoisothiazolinone class and nitrile bacterium azoles.
Background technology
Benzoisothiazolinone class compound is a kind of novel, wide-spectrum bactericide, is mainly used for preventing and treating Cereal The various bacterias such as crop, veterinary antibiotics, fungal disease.Its bactericidal effect mechanism, main includes destroying germ cell core knot Structure makes it lose the metabolism of cardia and failure death and interference germ cell, makes its physiologic derangement, eventually leads to dead Die two aspects.It is not infected in the early stages of disease by pathogen using can effectively protect plant, disease takes the circumstances into consideration to increase after occurring Dosage can obviously control the sprawling of germ, to the double action for reaching protection and rooting out.
Nitrile bacterium azoles are a kind of efficient, and low toxicity belongs to broad spectrum activity triazole bactericidal agent, mainly to the ergosterol of pathogen Biosynthesis plays inhibiting effect, and preferable control effect is all had to sac fungus, basidiomycetes.The agent lasting period is long, pacifies to crop Entirely, certain stimulating growth acts on.Simultaneously to table angle sterol biosynthesis inhibitor.It is high with strong absorbability, drug effect, to making Object safety, lasting period long feature have preventive and therapeutic action.This product can also be used for seed treatment, can prevent wheat and dissipate dust-brand Germ, net fungus tilletia etc..
Actual pesticide experience have shown that, repeat and a kind of reactive compound of single-minded application prevent harmful fungoid very The fast selective that will lead to fungal bacterial strain in the case of more, to reduce the danger of refractory fungal bacterial strain selectivity, at present usually Harmful fungoid is prevented using the mixture of different activities compound.By will have the reactive compound of different role mechanism into Row combination, can delaying drug resistance generate, reduce amount of application, reduce cost accounting.
Invention content
The purpose of the present invention is being directed to fungicide resistance and pedo relict problem in practical applications, filters out difference and kill The fungicide of bacterium principle is compounded, and a kind of new microbicide compositions are obtained, to improve bactericidal agent for preventing and treating effect, delaying drug resistance It generates, reduces amount of application, reduce cost accounting.
It is a further object to provide the preparation method comprising two kinds of effective constituents As and B bactericidal compositions and Agriculture field prevents the application of corps diseases.
The purpose of the present invention can be achieved by the following measures:
A kind of microbicide compositions with synergistic effect, the composition includes two kinds of active components of A and B, wherein activity Component A is the structural compounds with formula (I), and active component B is nitrile bacterium azoles.
In formula (I), R is selected from H or C1~C8Alkyl.
C in the present invention1~C8Alkyl refers to the linear or branched alkyl group containing 1 to 8 carbon atom, it includes C1Alkyl (such as methyl), C2Alkyl (such as ethyl), C3Alkyl (such as n-propyl, isopropyl), C4Alkyl (such as normal-butyl, isobutyl group, tertiary butyl, Sec-butyl), C5Alkyl (such as n-pentyl), C6Alkyl, C7Alkyl, C8Alkyl.It includes but not limited to C1~C6Alkyl, C1~C5 Alkyl, C1~C4Alkyl etc..
In a kind of preferred embodiment, R is selected from H or C1~C4Alkyl.
In a kind of preferred scheme, R is selected from H ,-CH3Or-C4H9
In formula (I), when R is H, A is 1,2-benzisothiazolin-3-one (abbreviation BIT in specification).
In formula (I), when R is CH3When, A is 2- methyl-1s, 2- benzisothiazole-3-ketones (abbreviation MBIT in specification).
In formula (I), when R is C4H9When, A is 2- normal-butyls -1,2-benzisothiazolin-3-one, and " butyl " in the formula is Normal-butyl (abbreviation BBIT in specification).
Inventor is found by experiment that composition of the invention is for preventing crops bacterium or fungal disease prevention Synergy is apparent, it is often more important that amount of application is reduced, and reduces use cost.Compound structure type containing component A and component B is not Together, mechanism of action is different, and the two compounding can expand fungicidal spectrum, and can delay the production of pathogen resistance to a certain extent Raw and development speed, and no interactions resistance between component A and component B.
The weight ratio between two components in microbicide compositions of the present invention is 1:40~40:1, for the medicine for making between two components Effect synergistic effect is more notable, and the weight ratio between two component of weight of component A and component B can be advanced optimized to 1:40~ 30:1, further it is optimized to 1:40~20:1.
In some embodiments, two kinds of active component As and B can be selected 40:1、39:1、38:1、37:1、36:1、 35:1、34:1、33:1、32:1、31:1、30:1、29:1、28:1、27:1、26:1、25:1、24:1、23:1、22:1、21:1、 20:1、19:1、18:1、17:1、16:1、15:1、14:1、13:1、12:1、11:1、10:1、9:1、8:1、7:1、6:1、5:1、4: 1、3:1、2:1、1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9、1:10、1:11、1:12、1:13、1:14、1:15、 1:16、1:17、1:18、1:19、1:20、1:21、1:22、1:23、1:24、1:25、1:26、1:27、1:28、1:29、1:30、1: 31、1:32、1:33、1:34、1:35、1:36、1:37、1:38、1:39、1:40 equal more specifically proportionings, can also be to take up an official post Two proportionings of meaning are selected in the range of forming.
The dosage form allowed on pesticide can be made by active constituent and insecticides adjuvant or auxiliary material in the composition of the present invention.Into one Step, the composition is made of the active component of 2~95% parts by weight and the insecticides adjuvant of 98~5% parts by weight to be allowed on pesticide Dosage form.
The present invention provides the bactericidal compositions comprising component A and component B in terms of agriculture field prevents corps diseases Purposes, the especially purposes in terms of the fungi or bacterium for preventing certain crops.
Above-mentioned composition specifically may include insecticides adjuvant or auxiliary material, such as carrier, solvent, dispersant, wetting agent, gluing One or more of agent, thickener, adhesive, surfactant or fertilizer etc..It can be mixed during application common Auxiliary agent.
Suitable auxiliary agent or auxiliary material can be solid or liquid, they are typically common substance during formulation, Such as natural or regenerated minerals, solvent, dispersant, wetting agent, adhesive, thickener, adhesive.
The method of administration of the present composition includes that the composition of the present invention is used for the aerial part of plant growth, especially It is leaf portion or blade face.It can select to soak seed or be applied to controlling object surface.The frequency and amount of application of application depend on pathogen Biology and weather life condition.The growth place of plant, such as rice field can be soaked with the liquid preparation of composition, or Composition is applied in soil by person in solid form, and such as in granular form (soil application), composition can be by soil through planting Object root enters in plant (systemic action).
The composition of the present invention can be prepared into various dosage forms pesticide-acceptable, including but not limited to missible oil, suspension Agent, wettable powder, water dispersible granules, pulvis, granula, aqua, aqueous emulsion, microemulsion, poison bait, mother liquor, female powder etc., in one kind In preferred embodiment, dosage form of the invention uses wettable powder, suspending agent, water dispersible granules, aqueous emulsion or microemulsion.According to this Property and application composition the institute purpose to be achieved and ambient conditions of a little compositions, can select composition to spray, Atomizing dusts, broadcasts sowing or sprinkles the method application poured or the like.
Can by known method can by the present invention composition be prepared into various dosage forms, can by active ingredient with help Agent can uniformly mix together with surfactant when needing, grind, be prepared into required dose such as solvent, solid carrier Type.
Above-mentioned solvent can be selected from aromatic hydrocarbon, preferably contain 8-12 carbon atom, such as xylene mixture or substituted benzene, phthalein Esters of gallic acid, if Dibutyl phthalate or phthalandione two are sad, fat hydrocarbon, such as thiacyclohexane or paraffin, the ether of alcohol and ethylene glycol and they And ester, such as ethyl alcohol, ethylene glycol, ethylene glycol monomethyl;Ketone, such as cyclohexanone, highly polar solvent, such as N- methyl -2- pyrrolidines Ketone, dimethyl sulfoxide (DMSO) or dimethylformamide and vegetable oil or vegetable oil, such as soybean oil.
Above-mentioned solid carrier, such as pulvis and dispersible dose of typically natural mineral fillers, such as talcum, kaolinite Soil, montmorillonite or atlapulgite.In order to manage the physical property of composition, polymolecularity silicic acid or polymolecularity can also be added Adsorpting polymerization object carrier, such as granulated adsorptive carriers or non-adsorbed carrier, suitable granulated adsorptive carriers are porous types, it is such as floating Stone, bentonite or bentonite;Suitable non-adsorbed carrier such as calcite or sand.Further, it is possible to use a large amount of inorganic in nature or having The prefabricated material to granulate of machine property is as carrier, especially dolomite.
The chemical property of active ingredient in composition according to the present invention, suitable surfactant are sulfomethylated lignin Acid, naphthalene sulfonic acids, phenolsulfonic acid, alkali salt or amine salt, alkylaryl sulfonates, alkyl sulfate, alkylsulfonate, fat Alcohol sulfate, aliphatic acid and sulphated fatty alcohol glycol ether, the also condensation product of sulfonated naphthalene and naphthalene derivatives and formaldehyde, naphthalene or The condensation product of naphthalene sulfonic acids and phenol and formaldehyde, NONIN HS 240, ethoxylated isooctyl-phenol, octyl phenol, nonyl phenol, Alkylaryl polyglycol ether, tributyl benzene polyglycol ether, three stearyl phenyl polyglycol ethers, alkyl aryl polyether alcohol, Ethoxylated castor oil, polyoxyethylene alkyl ether, ethylene oxide condensation product, ethoxylation polyoxypropylene, bay acid polyethylene glycol Ether acetal, sorbitol ester, lignin sulfite waste liquor and methylcellulose.
When preparing liquid dosage form, can active component A be first dissolved in alkaline matter, form benzisothiazole metal Salt, suitable alkaline matter include:Alkali carbonate, alkali metal hydroxide (such as sodium hydroxide, potassium hydroxide), alkali metal Alkoxy carbonate, alkali metal alcoholates or magnesium methoxide.
Two kinds of active ingredients show as synergistic effect in the composition of the present invention, and the activity of the composition is than using individualized The independent activity of the expected summation of activity and single compound of closing object is more notable.Synergistic effect shows as allowing amount of application Reduction, broader antifungal control spectrum, quick, more longlasting control effect, by a small number of applying only once or several times more Good control plant pest fungi and broaden the possible administration interval time.These characteristics are plant epiphyte control practices It especially needs in the process.
In terms of the microbicide compositions of the present invention can be applied to agriculture field prevention corps diseases, targeted specific disease Disease includes but not limited to that rice sheath blight disease, cucumber bacterial angular leaf spot, cucumber downy mildew, bacterial leaf streak of rice, watermelon are withered Wither disease, downy mildew of garpe, bacterial wilt of tomato, eggplant bacterial wilt, rice green smut, bacterial leaf streak of rice, pepper anthracnose, The red star of bitter rot or anthracnose of grape, tobacco bacterial wilt, tobacco, cucumber anthracnose, celery septoria disease, lotus rhizome damping-off, powdery mildew of strawberry, lettuce Lettuce downy mildew, celery gray mold, apricot Bacterial septicaemia syndrome, Peach canker disease, downy mildew, wheat powdery mildew, gibberella saubinetii Disease, jujube tree rust, apple spot fallen leaves etc..
The other features of the bactericidal composition of the present invention shown are mainly shown as:1, composition mixture of the invention tool There is apparent synergistic effect;2, since two single dose chemical constitutions of this composition are widely different, the mechanism of action is entirely different, no There are cross resistances, can delay two single doses that generated resistance problem is used alone;3, composition of the invention to crop safety, Preventive effect is good.Tests prove that microbicide compositions chemical property of the present invention is stablized, synergy is notable, is shown to controlling object bright Aobvious synergy and complementation.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, is not used to limit The fixed present invention, any modifications, equivalent replacements and improvementsmade within the spirit and principles of the invention, etc. should be included in Within protection scope of the present invention.
Percentage is weight percentage in all formulas of following embodiment.The processing work of the various preparations of the present composition Skill is the prior art, can be varied from according to different situations.
One, dosage form prepares embodiment
(1) processing of wettable powder and embodiment
Active components A and B activity ingredient and various auxiliary agents and filler etc. are sufficiently mixed in proportion, through ultrafine crusher powder Obtained wettable powder after broken.
1, active component A (BIT) prepares wettable powder with active component B
Embodiment 1:21%BIT nitrile bacterium azoles wettable powders
BIT 1%, nitrile bacterium azoles 20%, pull open powder 2%, bentonite 1.5%, alkyl polyoxyethanyl ether sulfonate 1%, hard charcoal Black 2%, diatomite complements to 100%.
Embodiment 2:30%BIT nitrile bacterium azoles wettable powders
BIT 15%, nitrile bacterium azoles 15%, sodium lignin sulfonate 6%, alkylsulfonate 7%, white carbon 10%, kaolin are mended Enough to 100%.
Embodiment 3:15.5%BIT nitrile bacterium azoles wettable powders
BIT 15%, nitrile bacterium azoles 0.5%, sodium lignin sulfonate 6%, alkylsulfonate 7%, white carbon 10%, kaolin Complement to 100%.
2, active component A (MBIT) prepares suspending agent with active component B
Embodiment 4:21%MBIT nitrile bacterium azoles wettable powders
MBIT 1%, nitrile bacterium azoles 20%, remaining component are prepared according to the method for embodiment 1.
Embodiment 5:30%MBIT nitrile bacterium azoles wettable powders
MBIT 15%, nitrile bacterium azoles 15%, remaining component are prepared according to the method for embodiment 2.
Embodiment 6:15.5%MBIT nitrile bacterium azoles wettable powders
MBIT 15%, nitrile bacterium azoles 0.5%, remaining component are prepared according to the method for embodiment 3.
3, active component A (BBIT) prepares wettable powder with active component B
Embodiment 7:21%BBIT nitrile bacterium azoles wettable powders
BBIT 1%, nitrile bacterium azoles 20%, remaining component are prepared according to the method for embodiment 1.
Embodiment 8:30%BBIT nitrile bacterium azoles wettable powders
BBIT 15%, nitrile bacterium azoles 15%, remaining component are prepared according to the method for embodiment 2.
Embodiment 9:15.5%BBIT nitrile bacterium azoles wettable powders
BBIT 15%, nitrile bacterium azoles 0.5%, remaining component are prepared according to the method for embodiment 3.
(2) processing of suspending agent and embodiment
By active constituent activity grouping A and active component B, with each components such as dispersant, wetting agent, thickener and water by matching The ratio of side is uniformly mixed, and after sand milling and/or high speed shear, obtains semi-finished product, is mended after analysis and is mixed with water filtering i.e. Obtain finished product.
1, active component A (BIT) prepares suspending agent with active component B
Embodiment 10:20.5%BIT nitrile bacterium azoles suspending agents
BIT 0.5%, nitrile bacterium azoles 20%, bentonite 4%, glycerine 3%, methyl naphthalene sulfonate formaldehyde condensate 5%, water Complement to 100%.
11 5.5%BIT nitrile bacterium azoles suspending agents of embodiment
BIT 5%, nitrile bacterium azoles 0.5%, white carbon 3%, glycerine 6%, sodium benzoate 2%, fatty alcohol polyoxyethylene ether Phosphate 7%, water complements to 100%.
Embodiment 12:10.5%BIT nitrile bacterium azoles suspending agents
BIT 10%, nitrile bacterium azoles 0.5%, white carbon 4%, ethylene glycol 5%, sodium lignin sulfonate 7%, xanthans 2%, water Complement to 100%.
2, active component A (MBIT) prepares suspending agent with active component B
Embodiment 13:20.5%MBIT nitrile bacterium azoles suspending agents
MBIT 0.5%, nitrile bacterium azoles 20%, remaining component are prepared according to the method for embodiment 10.
Embodiment 14:5.5%MBIT nitrile bacterium azoles suspending agents
MBIT 5%, nitrile bacterium azoles 0.5%, remaining component are prepared according to the method for embodiment 11.
Embodiment 15:10.5%MBIT nitrile bacterium azoles suspending agents
MBIT 10%, nitrile bacterium azoles 0.5%, remaining component are prepared according to the method for embodiment 12.
3, active component A (BBIT) prepares suspending agent with active component B
Embodiment 16:20.5%BBIT nitrile bacterium azoles suspending agents
BBIT 0.5%, nitrile bacterium azoles 20%, remaining component are prepared according to the method for embodiment 10.
Embodiment 17:5.5%BBIT nitrile bacterium azoles suspending agents
BBIT 5%, nitrile bacterium azoles 0.5%, remaining component are prepared according to the method for embodiment 11.
Embodiment 18:10.5%BBIT nitrile bacterium azoles suspending agents
BBIT 10%, nitrile bacterium azoles 0.5%, remaining component are prepared according to the method for embodiment 12.
(3) processing of aqua and embodiment
Active ingredient is added in a kettle and auxiliary agent, surplus are supplied with water, and stirs evenly, you can obtains aqua.
1, active component A (BIT) prepares aqua with active component B
Embodiment 19:15.5%BIT nitrile bacterium azoles aquas
BIT 0.5%, nitrile bacterium azoles 15%, fatty alcohol polyoxyethylene ether 10%, ethyl alcohol 5%, surplus is supplied with water.
Embodiment 20:11%BIT nitrile bacterium azoles aquas
BIT 1%, nitrile bacterium azoles 10%, dimethyl sulfoxide (DMSO) 5%, ethyl alcohol 5%, alkylol sodium sulphate 8%, surplus is mended with water Foot.
Embodiment 21:4.1%BIT nitrile bacterium azoles aquas
BIT 4%, nitrile bacterium azoles 0.1%, isopropanol 15%, ethylene glycol 5%, alkylol sodium sulphate 8%, surplus is mended with water Foot.
2, active component A (MBIT) prepares aqua with active component B
Embodiment 22:15.5%MBIT nitrile bacterium azoles aquas
MBIT 0.5%, nitrile bacterium azoles 15%, remaining component are prepared according to the method for embodiment 19.
Embodiment 23:11%MBIT nitrile bacterium azoles aquas
MBIT 1%, nitrile bacterium azoles 10%, remaining component are prepared according to the method for embodiment 20.
Embodiment 24:4.1%MBIT nitrile bacterium azoles aquas
MBIT 4%, nitrile bacterium azoles 0.1%, remaining component are prepared according to the method for embodiment 21.
3, active component A (BBIT) prepares aqua with active component B
Embodiment 25:15.5%BBIT nitrile bacterium azoles aquas
BBIT 0.5%, nitrile bacterium azoles 15%, remaining component are prepared according to the method for embodiment 19.
Embodiment 26:11%BBIT nitrile bacterium azoles aquas
BBIT 1%, nitrile bacterium azoles 10%, remaining component are prepared according to the method for embodiment 20.
Embodiment 27:4.1%BBIT nitrile bacterium azoles aquas
BBIT 4%, nitrile bacterium azoles 0.1%, remaining component are prepared according to the method for embodiment 21.
Two, drug effect verification test
(1) Assays Example
The incidence that whole strain blade is investigated according to experiment grade scale, calculates disease index and control effect.
Control effect is converted into niqueMin (y), liquid does height (μ g/ml) and is converted into logarithm (x), with least square Concentration EC50 during method calculates virulence equation and inhibits, the toxicity index grade co-toxicity coefficient (CTC) of medicament is calculated according to Sun Yunpei's Method.
Survey toxicity index (ATI)=(standard agent EC50/ reagent agent EC50) * 100
Percentage composition+B medicament toxicity index * the mixtures of A in theoretical toxicity index (TTI)=A medicament toxicity index * mixtures The percentage composition of middle B
Co-toxicity coefficient (CTC)=[mixture surveys toxicity index (ATI)/mixtures theoretical toxicity index (TTI)] * 100
CTC≤80, composition show as antagonism, 80 < CTC < 120, and composition shows as summation action, and CTC >= 120, composition shows as synergistic effect.
1, BIT and myclobutanil compositional test toxicity test
Table 1.BIT is with myclobutanil compositional to tomato late blight toxicity test interpretation of result