CN105230635B - Bactericidal composition and its application - Google Patents
Bactericidal composition and its application Download PDFInfo
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- CN105230635B CN105230635B CN201410242395.6A CN201410242395A CN105230635B CN 105230635 B CN105230635 B CN 105230635B CN 201410242395 A CN201410242395 A CN 201410242395A CN 105230635 B CN105230635 B CN 105230635B
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Abstract
The invention discloses a kind of bactericidal composition and its application, belong to pesticide field, the bactericidal composition active ingredient is that first thiophene lures amine (A) and imidazoles series bactericidal agent (B), and (A) is 1 with (B) weight ratio：40~40：1, preferable ratio is 1:20~20:1, more preferable ratio is 1：10~10：1.Imidazoles series bactericidal agent (B) can select cyazofamid, Fenamidone etc..Said composition, which can be added, allows the auxiliary element used to be processed into the formulations such as suspending agent, water dispersible granules, wettable powder, dry suspending agent in other agricultural chemicals.The bactericidal composition can effectively prevent and treat crucifer clubroot, prevention effect is apparently higher than A and B single doses, by by the bactericide compounded of different mechanism of action and the mode of action, effectively reduce the amount of application of each single dose, to expanding fungicidal spectrum and delaying the plant resistance to the action of a drug to have preferable effect, the lasting period can also be extended, with obvious promotional value.
Description
Technical field
Lure amine as the first active component the present invention relates to a kind of microbicide compositions, particularly first thiophene, selected from cyazofamid,
The imidazoles such as Fenamidone series bactericidal agent belongs to technical field of compounded pesticide as the microbicide compositions of the second active component.
Background technology
In agricultural production, crops can healthy growth, in addition to being influenceed by worm, crop smothering, the preventing and treating to disease is also very heavy
Will.Reinforcement and sustainable development implementation with environmental protection ideas, efficient, low toxicity, high activity, low-residual have turned into agricultural chemicals and sent out
The inexorable trend of exhibition.However, even efficient germicide, long-term exclusive use, also easily makes disease develop immunity to drugs, causes to use
The problems such as dose is increased, preventive effect is reduced, the lasting period shortens, is unfavorable for environment sustainable development.Therefore, how Scientific Usage of Drugs, drop
The consumption of low chemical pesticide, improves drug effect, the problem for being badly in need of solving as plant protection art.
First thiophene lures amine to be a kind of thiadiazole plant disease-proof activator, the general entitled N- of chemistry (5- methyl isophthalic acids, 3- thiazoles-
2- yls) -4- methyl isophthalic acids, 2,3- thiadiazoles -5- formamides, its structural formula is such as shown in (I).Current result of study shows, the change
Compound has induction disease resisting effect well to virus disease, and mechanism of action is induction plant generation system, the disease-resistant work of wide spectrum
Property.Plant disease-proof activator is the novel agricultural chemicals of the class received much concern in recent years, itself has no obvious bactericidal activity, but
Can as plant immunoactivator, inducer of systemic acquired resistance, so as to reach the purpose of defending and fighting against diseases.Wherein, BTH
(diazosulfide, the production of Syngenta Co., Ltd of Switzerland) and TDL (tiadinil, Nihon Nihyaku Co., Ltd's production) are such medicament
Representative Cultivars, widely applied in agricultural production at present.
Cyazofamid, its structural formula is such as shown in (II).It is a kind of novel low-toxicity bactericide, with good protection activity and one
Fixed interior suction therapeutic activity, the lasting period is long, resistance of rainwater washing against, using conveniently, safely.The medicine belongs to mitochondrial respiratory inhibitor, its
Bactericidal mechanism is, by suppressing the Qi in germ metabolic process in cytochrome b cl, and to cause germ dead, different from methoxyl group
Esters of acrylic acid medicament (being QO inhibitor in cytochrome b cl).There is effect to all growth phases of oomycetes.It is used alone
Have the resistance risk that comparison is high, thus often with protective fungicide compounding use, with the generation of delaying drug resistance.
Fenamidone, its structural formula is such as shown in (III).It is by rhone-poulenc agro companies (existing Bayer Crop
Science companies) the bactericide of imidazolines of exploitation thinks that its mechanism of action is to act on Intramitochondrial electron transmission system
Unite, hinder the phosphorylation aoxidized from ADP to ATP to play sterilization by hindering pathogen to produce the necessary energy of breeding
Effect.
Clubroot is to infect caused worldwide ten by rape plasmodiophora brassicae Plasmodiophora brassicae Woron
Serious plant disease on Zi Hua sections crop.It is 4,000,000 hm in the long-term hazard area of China2, account for crop in cruciferae cultivated area
More than 1/3, the time hazard area that is very popular is up to 9,000,000 hm2, average product loss is up to 20%~30%, and serious field reaches
More than 60%, or even total crop failure.The disease has turned into crop in cruciferae and has produced one of upper significant problem urgently to be resolved hurrily.Cruciferae
Crop is the important vegetables and oil crops of China, brassicaceous vegetable mainly include cabbage (Chinese cabbage, pakchoi, cabbage heart,
Purple tsai-tai and purple flowering stalk), wild cabbage class (cabbage, cauliflower, cabbage mustard, broccoli, kohlrabi), mustard (leaf mustard, stem mustard
Dish, root mustard, hot pickled mustard tube) radish kind and aquatic vegetable etc., its cultivated area, the 40%~50% of yield Jun Zhan China vegetables total amount.
Rape is the important oil crops of China, and China's rapeseed cultivation area in 2012 is 7,000,000 hm2, 13,000,000 tons of yield.Can from above
See that crop in cruciferae production, either as vegetables, or as oil crops, is respectively provided with highly important meaning.
The content of the invention
For above-mentioned situation, the present invention provides a kind of component rationally, and significantly, bactericidal effect is good, drug cost for synergistic effect
It is low, the resistance to the action of a drug, the agricultural bactericidal composition to crop safety are not likely to produce, the need for meeting agricultural production, institute in composition
Comprising active component there is synergistic effect to improve preventive effect and being beneficial to mutually to delay the drug-fast generation of germ.
In order to overcome the defect of existing unitary agent, the present invention is achieved through the following technical solutions：
The bactericidal composition of the present invention, its active ingredient is that first thiophene lures amine and imidazoles series bactericidal agent, and first thiophene lures amine and imidazoles
The weight ratio of series bactericidal agent is 1：40~40：1, preferably weight ratio is 1：20~20：1, more preferably weight ratio is 1：10~
10：1.
The imidazoles series bactericidal agent, can be cyazofamid, Fenamidone, IMAZALIL, sulfuric acid IMAZALIL, pefurazoate, the third chlorine
Any of spirit, fluorine bacterium azoles etc..In the present invention according to experiment effect, preferably cyazofamid, Fenamidone are compounded.
Pesticidal preparations auxiliary element can also be contained in the bactericidal composition, so that the agent for being adapted to agriculturally use is made
Type.The pesticidal preparations auxiliary element is one kind or several in solvent, emulsifying agent, dispersant, stabilizer, antifreezing agent or wetting agent
Kind.
First thiophene of the present invention lures amine with imidazoles microbicide compositions according to well known to those skilled in the art of the present technique
The preparation formulation that method can be prepared is dry suspending agent (DF), wettable powder (WP), water dispersible granules (WDG), suspending agent
(SC) etc..
A. wettable powder (WP), be can be dispersed in water solid powder preparation.Wettable powder of the present invention is removed
Into active compound plus outside such as white carbon, precipitated calcium carbonate, clay, diatomite, attapulgite diluent or inert substance, also
Ionic or nonionic surface active agent (wetting agent, dispersant), wetting agent is for example, alkylbenzenesulfonate (DBS-Na), alkane
Base naphthalene sulfonate (pull open powder), alkylphenol-polyethenoxy base ether sulfate, alkylphenol-polyethenoxy base ether formaldehyde condensation products sulfuric acid
Salt, aliphatic alcohol sulfate, fatty alcohol ethylene oxide adduct sulfonate, alkyl amide taurate, aliphatic alcohol polyethenoxy base
Ether (JFC), content 0.1~30%；Dispersant such as naphthalene sulfonate, naphthalene or alkyl naphthalene formaldehyde condensate sulfonates (NO, NN0, MF),
Lignin and its derivative sulfonate (M-9, POLYFON etc.), polyoxyethylene poly-oxygen propylene aether block copolymer, alkyl phenol polyoxy
Vinyl ethers formaldehyde condensation products sulfate (SOPA), PVA, CMC content 0.1~30%；Also contain penetrating agent JFC, azone, thiophene
One or more materials among ketone, penetrant t, content 0.3~30%；Stabilizer, foam inhibitor, anticaking agent can also be contained
Etc. other auxiliary agents.
B. water dispersible granules (WDG), be can be comparatively fast disintegrated in water, the scattered granule for forming higher suspension dispersion.
By active component, the key element such as the auxiliary agent such as wetting agent, dispersant, interleaving agent, disintegrant, stabilizer, adhesive and carrier composition.Its
Auxiliary agent and carrier, and the compound method of precursor (preformed objects before granulation) are analogous to wettable powder and suspending agent substantially.
C. suspending agent (SC), is the not dispersion of water soluble solid agricultural chemicals or immiscible liquids agricultural chemicals in water or oil.By living
Property composition, auxiliary agent (wetting dispersing agent, thickener, stabilizer, pH adjusting agent, defoamer, antifreezing agent) are through soybean dietary fiber system
.Wetting dispersing agent can be naphthalene or alkyl naphthalene formaldehyde condensate sulfonates (NO, NN0, MF), lignin and its derivative sulfonic acid
Salt (M-9, POLYFON etc.), alkylphenol-polyethenoxy base ether sulfonate, polyoxyethylene polyoxypropylene base ether block copolymers, alkane
Base phenol polyethenoxy base phosphate, carboxymethyl cellulose (CMC), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), condensation
One or more in phosphate etc., content 0.1~12%；Thickener and stabilizer can be xanthan gum (XG), polyethylene
One or more in alcohol (PVA), Magnesiumaluminumsilicate etc., content 0.05~0.5%；PH adjusting agent and defoamer can be optionally appropriate
Addition.
D. dry suspending agent (Dry Flowable, abbreviation DF), be can be comparatively fast disintegrated in water, the scattered higher suspension that formed disperses
The granule of system.Preparation method：The preparation obtained by the dehydration of suspending agent.Its auxiliary agent and carrier, and precursor (are dehydrated
Preceding preformed objects) compound method it is consistent with suspending agent.
Bactericidal composition of the present invention goes for preparing the pesticidal preparations of controlling plant diseases, is particularly suitable for use in
Prepare the pesticidal preparations of preventing and treating crucifer clubroot.
Rationally, bactericidal effect is good for instant component, and its activity and bactericidal effect are not the simple superposition of each component activity,
But have significant synergistic effect, and it is good to crop safety, meet the security requirement of pesticidal preparations.The present invention is to Cruciferae
There is preferable prevention effect in terms of plant clubroot.
Embodiment
To make embodiments of the invention technical problem, technical scheme and the advantage to be solved clearer, below by apparatus
Body embodiment is described in detail, but the present invention is limited to absolutely not these examples.As described below is only the present invention preferably embodiment,
Only to explain the present invention, the limitation to the scope of the claims of the present invention therefore can not be interpreted as.It should be pointed out that it is all
Any modifications, equivalent substitutions and improvements done within the spirit and principles in the present invention etc., should be included in the protection of the present invention
Within the scope of.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Agricultural chemicals is made in the combination of active principles of different agricultural chemicals, is current exploitation and develops novel pesticide and prevent and treat agriculturally
A kind of effective and quick way of resistance germ.After the pestsides synthesis of different cultivars, a large amount of three kinds of effects classes are typically exhibited
Type：Summation action, synergistic effect and antagonism.Compound synergic is formulated well, can significantly improve actual prevention effect, drop
The usage amount of low agricultural chemicals, is the important means of integrated control disease so as to help to delay the drug-fast generation speed of germ.
In order to prevent and treat the vegetables clubroot in agricultural production, inventor lures amine and imidazoles series bactericidal agent (such as with first thiophene：Cyanogen frost
Azoles, Fenamidone) the synergy research of mutual compounding has been carried out, specific method is：Experiment uses clubroot for test object.By original
Medicine is configured to the test medicine needed, test method reference《People's Republic of China's agricultural industry criteria》.First by single dose and
Each Mixed Pharmacy sets 5 various concentrations gradients (on the basis of pilot study result, to be combined and matched not according to different agents
Together, concentration sets also different, and bacteriostasis rate is set in the range of 5%~90%).If blank control, it is repeated 3 times.Using
Method is tried in field, the pakchoi that the field plantation frequently occurred in clubroot is dressed seed by each processing, in 5~6 leaf of pakchoi, is pulled out
Go out root, be classified by inquiry, check incidence, calculate the percentage that each processing suppresses pathogen growth, pass through inhibiting rate
Linear regression analysis between probit value and the logarithm value of series concentration, obtains the EC50 values of each medicament, uses co-toxicity coefficient meter
The co-toxicity coefficient (CTC) of mixture is calculated, activity of the reagent agent to germ is evaluated with this.
The co-toxicity coefficient (CTC) >=120 of complex preparation shows as synergistic effect；CTC≤80 show as antagonism；80 ﹤
CTC ﹤ 120 show as summation action.
The first thiophene of table 1 lures amine to compound the field toxicity test to pakchoi clubroot with cyazofamid
| Chemicals treatment | Virulence regression equation | EC50(mg/L) | Co-toxicity coefficient (CTC) |
| First thiophene lures amine (A) | Y=2.0195+1.3693X | 150.1973 | —— |
| Cyazofamid (B) | Y=1.8758+1.4519X | 141.8236 | —— |
| A：B=1:40 | Y=1.3681+1.9326X | 75.7401 | 187.51 |
| A：B=1:20 | Y=1.4385+1.9299X | 70.0478 | 203.01 |
| A：B=1:10 | Y=1.4434+1.9533X | 66.1993 | 215.33 |
| A：B=1:1 | Y=1.4802+1.9791X | 60.0444 | 242.97 |
| A：B=10:1 | Y=1.4477+1.9613X | 64.7389 | 230.76 |
| A：B=20:1 | Y=1.4569+1.9314X | 68.3106 | 219.26 |
| A：B=40:1 | Y=1.4162+1.9261X | 72.5482 | 206.73 |
The first thiophene of table 2 lures amine to compound the field toxicity test to pakchoi clubroot with Fenamidone
| Chemicals treatment | Virulence regression equation | EC50(mg/L) | Co-toxicity coefficient (CTC) |
| First thiophene lures amine (A) | Y=2.0195+1.3693X | 150.1973 | —— |
| Imidazoles bacterium copper (C) | Y=1.9311+1.4018X | 154.5833 | —— |
| A：C=1:40 | Y=1.4350+1.8755X | 79.5911 | 194.08 |
| A：C=1:20 | Y=1.3551+1.9638X | 71.7868 | 215.04 |
| A：C=1:10 | Y=1.4149+1.9670X | 66.4749 | 231.93 |
| A：C=1:1 | Y=1.4287+1.9925X | 61.9950 | 245.76 |
| A：C=10:1 | Y=1.4114+1.9826X | 64.5703 | 233.21 |
| A：C=20:1 | Y=1.3484+1.9510X | 74.4072 | 202.13 |
| A：C=40:1 | Y=1.4080+1.8813X | 81.1500 | 185.21 |
Field toxicity test result shows that first thiophene lures amine and cyazofamid compounding, first thiophene to lure amine and Fenamidone to compound to small
Cabbage clubroot has obvious synergistic effect, and prevention effect is better than single dose kind.Inventor has found that first thiophene lures amine by test
Compounded with other imidazoles series bactericidal agents (such as IMAZALIL, sulfuric acid IMAZALIL, pefurazoate, Prochloraz, fluorine bacterium azoles), to pakchoi root
Swollen disease also has similar Complex synergism.
Present invention is described further with reference to embodiment.
Embodiment 1：42% first thiophene lures amine cyazofamid suspending agent
Weigh 2% first thiophene and lure amine, 40% cyazofamid, 5% polycarboxylic acids sodium, 2% neopelex, 6% ethylene glycol,
0.25%XG, 0.6% organic silicon defoamer, 0.4% sodium benzoate, deionized water adds to 100% parts by weight.Preparation method：Will
Active compound, auxiliary agent are sheared by high shear dispersion machine and mixed after 30min, are sanded through sand mill and are reached 1-4 microns of fineness, you can be made
42% first thiophene lures amine cyazofamid suspending agent.
Embodiment 2：30% first thiophene lures amine cyazofamid suspending agent
Weigh 15% first thiophene and lure amine, 15% cyazofamid, 3% phosphoric acid ester APEO, 4% NPE,
6% ethylene glycol, 0.25%XG, 0.6% organic silicon defoamer, 0.4% sodium benzoate, deionized water adds to 100% parts by weight.System
Preparation Method：Active compound, auxiliary agent are sheared by high shear dispersion machine and mixed after 30min, is sanded through sand mill and reaches that fineness 1-4 is micro-
Rice, you can 30% first thiophene is made and lures amine cyazofamid suspending agent.
Embodiment 3：22% first thiophene lures amine cyazofamid water dispersible granules
Weigh 20% first thiophene and lure amine, 2% cyazofamid, 4% lauryl sodium sulfate, 3% dodecyl sodium sulfate, 3% wood
Quality, kaolin complements to 100% parts by weight, and each component is mixed, through mechanical crushing, then through air-flow crushing, is well mixed, then
Through wet granulation and dry, you can 22% first thiophene is made and lures amine cyazofamid water dispersible granules.
Embodiment 4：33% first thiophene lures amine Fenamidone water dispersible granules
Weigh 3% first thiophene and lure amine, 30% Fenamidone, 5% polycarboxylic acids sodium, 6% sodium lignin sulfonate, 2% dodecyl
Sodium sulphate, talcum powder complements to 100% parts by weight, and each component is mixed, through mechanical crushing, then through air-flow crushing, is well mixed,
Through wet granulation and dry again, you can 33% first thiophene is made and lures amine Fenamidone water dispersible granules.
Embodiment 5：31.5% first thiophene lures amine Fenamidone wettable powder
Weigh 30% first thiophene and lure amine, 1.5% Fenamidone, 4% neopelex, 5% dodecyl naphthalene sulfonic acids
Sodium, 3% white carbon, kaolin complements to 100% parts by weight, and each component is mixed, through mechanical crushing, then through air-flow crushing, mixes
Close uniform, you can 31.5% first thiophene is made and lures amine Fenamidone wettable powder.
Embodiment 6：30% first thiophene lures amine Fenamidone dry suspending agent
Weigh 15% first thiophene and lure amine, 15% Fenamidone, 3% lauryl sodium sulfate, 4% dodecyl sodium sulfate, 2%
Polycarboxylic acids sodium, kaolin complements to 100% parts by weight.Preparation method：Each component is well mixed, the water of weight equivalents is added,
Sheared and mixed after 30min by high shear dispersion machine, be sanded through sand mill and reach 1-4 microns of fineness, after spray drying, you can system
Obtain 30% first thiophene and lure amine Fenamidone dry suspending agent.
Embodiment 7：41% first thiophene lures amine cyazofamid wettable powder
Weigh 1% first thiophene and lure amine, 40% cyazofamid, 5% neopelex, 5% dodecyl sodium naphthalene sulfonate,
3% white carbon, kaolin complements to 100% parts by weight, and each component is mixed, through mechanical crushing, then through air-flow crushing, mixing is equal
It is even, you can 41% first thiophene is made and lures amine cyazofamid wettable powder.
Embodiment 8：41% first thiophene lures amine Fenamidone suspending agent
Weigh 40% first thiophene and lure amine, 1% Fenamidone, 5% polycarboxylic acids sodium, 2% neopelex, 6% second two
Alcohol, 0.25%XG, 0.6% organic silicon defoamer, 0.4% sodium benzoate, deionized water adds to 100% parts by weight.Preparation method：
Active compound, auxiliary agent are sheared by high shear dispersion machine and mixed after 30min, is sanded through sand mill and reaches 1-4 microns of fineness, you can system
Obtain 41% first thiophene and lure amine Fenamidone suspending agent.
Tested with pesticidal preparations preventing and treating violet clubroot made from above-described embodiment
1st, test process：Experiment is carried out with reference to People's Republic of China's standard (pesticide field efficacy medicine test criterion).This examination
Test dosing and three concentration for the treatment of are set according to the difference of each composition respectively.Comparison medicament is the commercially available first thiophene of agricultural chemicals 25% respectively
Lure amine and 100 g/l of cyazofamid SC and blank clean water experiment.
2nd, test method：The field that clubroot occurs throughout the year is chosen, each plot area is 50m2, it is repeated 4 times, planting season
Between carry out pouring root with different disposal, check that drug effect method is：Adult plant is uprooped according to People's Republic of China's standard (agricultural chemicals
Field control effectiveness test criterion) investigated, per the 5 points of samplings of cell diagonal, every is extracted 10 plants of investigation.Result of the test see the table below
3：
The first thiophene of table 3 lures amine and cyazofamid to compound the prevention effect to violet clubroot
Field efficacy result shows, it is excellent anti-that first thiophene lures amine and cyazofamid complex composition to have violet clubroot
Effect is controlled, prevention effect is better than single dose kind.Inventor has found that first thiophene lures amine and other imidazoles series bactericidal agents (such as by test
Fenamidone, IMAZALIL, sulfuric acid IMAZALIL, pefurazoate, Prochloraz, fluorine bacterium azoles etc.) compounding, have similar to violet clubroot
Effect.
Rapeseed clubroot experiment is prevented and treated with pesticidal preparations made from above-described embodiment.
1st, test process：Experiment is carried out with reference to People's Republic of China's standard (pesticide field efficacy medicine test criterion).This examination
Test dosing and three concentration for the treatment of are set according to the difference of each composition respectively.Comparison medicament is the commercially available first thiophene of agricultural chemicals 25% respectively
Lure amine and 45% Fenamidone SC and blank clean water experiment.
2nd, test method：The field that clubroot occurs throughout the year is chosen, each plot area is 50m2, it is repeated 4 times, after slow seedling
Pouring root is carried out with different processing, checks that drug effect method is：5~6 leaf phases were uprooped according to People's Republic of China's standard (agriculture
Medicine field control effectiveness test criterion) investigated, per the 5 points of samplings of cell diagonal, every is extracted 10 plants of investigation, and result of the test is seen below
Table 4：
The first thiophene of table 4 lures amine and Fenamidone to compound the prevention effect to rapeseed clubroot
Field efficacy result shows that it is excellent that first thiophene lures amine and Fenamidone complex composition also to have rapeseed clubroot
Prevention effect, prevention effect is better than single dose kind.Inventor has found that first thiophene lures amine and other imidazoles series bactericidal agents by test
(such as cyazofamid, IMAZALIL, sulfuric acid IMAZALIL, pefurazoate, Prochloraz, fluorine bacterium azoles etc.) are compounded, and have similar to rapeseed clubroot
Effect.
Claims (7)
1. a kind of bactericidal composition, it is characterised in that：Active ingredient is that first thiophene lures amine and imidazoles series bactericidal agent, and the first thiophene lures amine
Weight ratio with imidazoles series bactericidal agent is 1：40~40：1, the imidazoles series bactericidal agent is cyazofamid or Fenamidone.
2. bactericidal composition according to claim 1, it is characterised in that：The first thiophene lures the weight of amine and imidazoles series bactericidal agent
Amount is than being 1：20~20：1.
3. bactericidal composition according to claim 2, it is characterised in that：The first thiophene lures the weight of amine and imidazoles series bactericidal agent
Amount is than being 1：10~10：1.
4. according to any described bactericidal composition in claims 1 to 3, it is characterised in that：Also contain in the bactericidal composition
There is pesticidal preparations auxiliary element, so that the formulation for being adapted to agriculturally use is made.
5. bactericidal composition according to claim 4, it is characterised in that：The pesticidal preparations auxiliary element is solvent, breast
One or more in agent, dispersant, stabilizer, antifreezing agent or wetting agent.
6. bactericidal composition according to claim 5, it is characterised in that：The formulation of the bactericidal composition be suspending agent,
Water dispersible granules, wettable powder or dry suspending agent.
7. application of the bactericidal composition in the pesticidal preparations for preparing controlling plant diseases described in claim 1, its feature exists
In the plant disease is crucifer clubroot.
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