CN106070233B - A kind of difenoconazole dispersible oil-suspending agent and its preparation method and application - Google Patents
A kind of difenoconazole dispersible oil-suspending agent and its preparation method and application Download PDFInfo
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- CN106070233B CN106070233B CN201610404844.1A CN201610404844A CN106070233B CN 106070233 B CN106070233 B CN 106070233B CN 201610404844 A CN201610404844 A CN 201610404844A CN 106070233 B CN106070233 B CN 106070233B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
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- Wood Science & Technology (AREA)
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Abstract
The present invention relates to a kind of difenoconazole dispersible oil-suspending agents and its preparation method and application, its raw material composition contains difenoconazole, nonionic surfactant, anion surfactant, cosurfactant, stabilizer and decentralized medium, the nonionic surfactant is the mixture of dibenzyl xenyl polyoxyethylene ether, styryl phenyl polyoxyethylene ether and triphenoethyl benzene phenol polyoxyethylene polyoxypropylene block polymer, and the anion surfactant is alkyl sulfate and the mixture of phosphoric acid ester.Preparation method is simple, and the period is short, is mainly used in vegetables, fruit tree, prevents fungal disease on grape.The characteristics of product of the present invention has suspensibility high, and strong adhesive force, ability to resist splash erosion is strong, and pesticide utilization rate is high, and stability is good and low environment pollutes.
Description
Technical field
The invention belongs to pesticide formulation process technology regions, and in particular to a kind of difenoconazole dispersible oil-suspending agent and
Preparation method and application.
Background technology
With the raising of global ecological environment and health perception, the formulations of pesticide are developed just towards efficient, less toxic, low-residual
Direction is developed.Under the situation of current novel agrochemical compound initiative more difficult, improved by advanced formulation method
The performance of pesticide, the bioactivity and efficiency for giving full play to active ingredient have become and improve pesticide control effect, reduce
Residual contamination, the important channel for saving dispenser cost.The dosage form registered at present mainly has missible oil, wettable powder, suspending agent, water
Dispersible granule.These conventional dosage forms in use exist to water liquid to Target crops wetting with deposition properties it is poor, be lost in seriously,
On the one hand a large amount of medicaments are wasted, in addition also results in the series of problems such as environmental pollution, be to restrict its efficient, safety and scientifical use
Key technical problem.
CN101785455A discloses a kind of pesticide oil suspension agent, includes pesticide activity component, emulsifier, antifoaming agent and dispersion
Medium, and the preparation method of the pesticide oil suspension agent is disclosed, but the invention fails to embody deposition of the pesticide active ingredient to target
There is the problem of higher effective rate of utilization with withholding efficiency.
CN101984809A discloses a kind of oil using turpentine-based vegetable oil as carrier and hangs preparation and preparation method thereof, with pine
Aliphatic radical vegetable oil for carrier oil hang preparation raw material composition and its in terms of quality percentage containing the clean property ingredient 1% of pesticide~
50%th, emulsifier 1%~10%, wetting dispersing agent 2%~8%, suspension stabilizer 0~5%, organic silicon defoamer 0~
0.2%, remaining is turpentine-based vegetable oil.But fail to obtain effect well in terms of product ability to resist splash erosion and drug effect, it should
It is relatively narrow with range, need further to improve production technology so as to improve product characteristic.
Difenoconazole is a kind of fungicide of broad-spectrum high efficacy, the main biosynthesis for inhibiting germ cell ergosterol,
So as to destroy membrane structure and function, it is mainly used for the crops such as fruit tree, vegetables, wheat, potato, beans, melon, to vegetables
There is protection and therapeutic effect well with a variety of fungal diseases such as melon and fruit.Difenoconazole belongs to high activity, is insoluble in water
Organic compound, it is necessary to add the auxiliary elements such as carrier, filler, emulsifier and dispersant, be configured to various types of preparations
Field could be convenient for apply.Water is replaced as decentralized medium, addition difference by the use of turpentine-based vegetable oil or methylated vegetable oil
Emulsifier, dispersant, stabilizer, the auxiliary agents such as antifoaming agent by pesticide processing into dispersible oil-suspending agent dosage form, improve product and hang
Floating rate and bin stability.On the one hand it can preferably solve in pesticide active ingredient processing and storage to unstability such as water decompositions
Problem, on the other hand due to vegetable oil in itself have to target good adhesion and adhesion properties, can improve pesticide effectively into
Divide to the deposition of target with withholding efficiency, so as to improve pesticide efficacy.
Invention content
It is an object of the invention to release a kind of to can be applied to vegetables, fruit tree, the effective profit for preventing fungal disease on grape
With rate it is high, be lost in low novel agrochemical dosage form, so as to improve pesticidal preparations quality level, reduce loss pollution to environment and suitable
It loses, realizes the sustainable development of the formulations of pesticide.
In order to achieve the above object, the present invention provides a kind of difenoconazole dispersible oil-suspending agent, raw material composition contains benzene
Ether methyl cyclic-azole, nonionic surfactant, anion surfactant, cosurfactant, stabilizer and decentralized medium, wherein
Difenoconazole, nonionic surfactant, anion surfactant, cosurfactant, stabilizer and decentralized medium
Weight ratio is (5~35)：(3~10)：(3~10)：(1~10)：(1~10)：(20~90).
The nonionic surfactant for dibenzyl xenyl polyoxyethylene ether, styryl phenyl polyoxyethylene ether and
The mixture of triphenoethyl benzene phenol polyoxyethylene polyoxypropylene block polymer, the anion surfactant are alkylsurfuric acid
The mixture of salt and phosphoric acid ester.
Preferably, the dibenzyl xenyl polyoxyethylene ether, styryl phenyl polyoxyethylene ether and triphenoethyl benzene
The weight ratio of phenol polyoxyethylene polyoxypropylene block polymer is 5：4：4.
Preferably, the weight ratio of the alkyl sulfate and phosphoric acid ester is 1：1.
The cosurfactant be isopropanol, butanol and octanol in one kind or the mixture of isopropanol and octanol, institute
Stabilizer is stated as one in gas-phase silica and diatomite or gas-phase silica and diatomaceous mixture, the decentralized medium
For one kind in turpentine-based vegetable oil and methylated vegetable oil or the mixture of turpentine-based vegetable oil and methylated vegetable oil.
Preferably, the weight ratio of the isopropanol and octanol is 2：1.
Preferably, the gas-phase silica and diatomaceous weight ratio are 1：3.
Preferably, the weight ratio of the turpentine-based vegetable oil and methylated vegetable oil is 2：1.
The present invention also provides a kind of preparation methods of above-mentioned difenoconazole dispersible oil-suspending agent, and dispersion is situated between first
Matter, nonionic surfactant, anion surfactant, cosurfactant are accurately weighed by formula rate, add in mixing
The difenoconazole technical material and stabilizer for uniformly, then adding formula ratio are sufficiently mixed in device, at a high speed (6000-
8000r/min) shear-mixed 5min carries out wet grinding into horizontal sand mill, and it is qualified products to reach regulation technical indicator.
The present invention also provides a kind of applications of above-mentioned difenoconazole dispersible oil-suspending agent, and main application is in vegetable
Dish, fruit tree prevent fungal disease on grape.
Compared with traditional oil suspending agent, the present invention has at least the following advantages or advantageous effect：
(1) raw material and decentralized medium price used is low, derives from a wealth of sources, production cost is relatively low.
(2) product of the present invention has preferable viscosity and dispersibility, has higher suspensibility, up to more than 95%, medicine
Object can be utilized efficiently.
(3) product of the present invention is to adhesion work of the target with bigger and drop expanding area and with stronger anti-rain
Water scouring capability can improve pesticide active ingredient to the deposition of target with withholding efficiency, be efficiently used so as to improve pesticide
Rate, the loss of less pesticide, less environmental pollution.
(4) for gas-phase silica and diatomite, product of the present invention has the stabilizer used under low temperature and hot environment
Preferable stability is not susceptible to deposit, and resolution ratio is low.
(5) product synthesis technology of the present invention is simple, and the period is short, and investment is small, and toxicity is low.
(6) products application range of the present invention is wide, can be applied on the crops and industrial crops such as vegetables, fruit tree, cereal
Fungal disease has preferable control effect.
Specific embodiment
It in order to which the present invention is better described, is further described below by embodiment, but the application not merely limits
It is scheduled on the range of following embodiments.
Embodiment 1
In 1500 milliliters of glass burn wide-mouth bottle, 777.4 grams of loose turpentine-based vegetable oils and methylated vegetable oil 2 are added in：1 is mixed
Close object, dibenzyl xenyl polyoxyethylene ether+styryl phenyl polyoxyethylene ether+triphenoethyl benzene phenol polyoxypropylene polyoxy second
Alkene block polymer 5：4：4 50 grams of mixtures, alkyl sulfate and phosphoric acid ester 1：1 10 grams of mixture, 40 grams of isopropanol, stirring
It is uniformly mixed；Purity is added as 52.9 grams of 95% difenoconazole technical material, 80 grams of gas-phase silica, after being stirred at a high speed
(6000-8000r/min) is sheared 5 minutes, is ground subsequently into sand mill, after the key technical indexes reaches standard requirement to obtain the final product
5% difenoconazole dispersible oil-suspending agent.
Embodiment 2
In 1500 milliliters of glass burn wide-mouth bottle, 662.1 grams of turpentine-based vegetable oils, dibenzyl xenyl polyoxyethylene are added in
Ether+styryl phenyl polyoxyethylene ether+triphenoethyl benzene phenol polyoxyethylene polyoxypropylene block polymer 5：4：4 mixtures 70
Gram, alkyl sulfate and phosphoric acid ester 1：1 20 grams of mixture, 30 grams of octanol, are uniformly mixed；Purity is added as 95% benzene
157.9 grams of ether methyl cyclic-azole active compound, 60 grams of diatomite, (6000-8000r/min) is sheared 5 minutes at a high speed after being stirred, Ran Houjin
Enter sand mill grinding, up to 15% difenoconazole dispersible oil-suspending agent after the key technical indexes reaches standard requirement.
Embodiment 3
In 1500 milliliters of glass burn wide-mouth bottle, 609.5 grams of turpentine-based vegetable oils and methylated vegetable oil 2 are added in：1 mixing
Object, dibenzyl xenyl polyoxyethylene ether+styryl phenyl polyoxyethylene ether+triphenoethyl benzene phenol polyoxyethylene polyoxypropylene
Block polymer 5：4：4 70 grams of mixtures, alkyl sulfate and phosphoric acid ester 1：1 30 grams of mixture, isopropanol and octanol 2：1 is mixed
40 grams of object is closed, is uniformly mixed；Purity is added as 210.5 grams of 95% difenoconazole technical material, gas-phase silica and diatom
Soil 1：3 40 grams of mixtures, (6000-8000r/min) is sheared 5 minutes at a high speed after being stirred, and is ground subsequently into sand mill, when
The key technical indexes reaches after standard requires up to 20% difenoconazole dispersible oil-suspending agent.
Embodiment 4
In 1500 milliliters of glass burn wide-mouth bottle, 524.2 grams of turpentine-based vegetable oils, dibenzyl xenyl polyoxyethylene are added in
Ether+styryl phenyl polyoxyethylene ether+triphenoethyl benzene phenol polyoxyethylene polyoxypropylene block polymer 5：4：4 mixtures 70
Gram, alkyl sulfate and phosphoric acid ester 1：1 30 grams of mixture, isopropanol and octanol 2：1 40 grams of mixture, is uniformly mixed；
Purity is added as 315.8 grams of 95% difenoconazole technical material, gas-phase silica and diatomite 1：3 20 grams of mixtures, stirring are mixed
(6000-8000r/min) is sheared 5 minutes at a high speed after conjunction, is ground subsequently into sand mill, is wanted when the key technical indexes reaches standard
Up to 30% difenoconazole dispersible oil-suspending agent after asking.
Embodiment 5
In 1500 milliliters of glass burn wide-mouth bottle, 471.6 grams of turpentine-based vegetable oils and methylated vegetable oil 2 are added in：1 mixing
Object, dibenzyl xenyl polyoxyethylene ether+styryl phenyl polyoxyethylene ether+triphenoethyl benzene phenol polyoxyethylene polyoxypropylene
Block polymer 5：4：4 70 grams of mixtures, alkyl sulfate and phosphoric acid ester 1：1 30 grams of mixture, isopropanol and octanol 2：1 is mixed
40 grams of object is closed, is uniformly mixed；Purity is added as 368.4 grams of 95% difenoconazole technical material, 20 grams of gas-phase silica, is stirred
High speed (6000-8000r/min) is sheared 5 minutes after mixing mixing, is ground subsequently into sand mill, when the key technical indexes reaches mark
Up to 35% difenoconazole dispersible oil-suspending agent after alignment request.
Comparative example 1
It is a kind of using turpentine-based vegetable oil as the oil suspending agent of carrier, preparation method is as follows：
471.6 grams of turpentine-based vegetable oils, T-80+polyoxyethylene polyoxypropylene block
70 grams of copolymer mixture, 30 grams of polycarboxylate, 40 grams of polysiloxanes, purity for 368.4 grams of 95% difenoconazole technical material and
20 grams of concavo-convex rod soil after mixing, is placed in high speed shear ball-grinding machine, and the grain size that high speed shear is milled to 90% is less than 4 μ
M forms the oil-suspending agent using turpentine-based vegetable oil as carrier.
Comparative example 2
A kind of pesticide oil suspension agent, preparation method are as follows：
70 grams of nonylphenol polyoxyethylene ether+castor oil ethylene oxide adduct is added in 1500 milliliters of glass burn wide-mouth bottle
+ polyglycerol fatty acid fat+JFC (fatty alcohol polyoxyethylene ether), 471.6 grams of turpentine-based vegetable oils.After mixing, emulsifying, then add
Enter the difenoconazole technical material, 40 grams of organic silicon defoamers, 20 grams of profit scholars that splash of 351 grams of contents 95%, stirring makes material in beaker
Into uniform slurry object, this slurry object is sanded, is continuously sanded 1~1.5 hour, obtains oil suspending agent sample.
According to China's correlation pesticide national standard or professional standard (the agricultural-chemical suspension rate assay methods of GB/T14825-2006,
The pesticide heat storage stability assay methods of GB/T19136-2003, the pesticide low-temperature stability assay methods of GB/T19137-2003,
The agricultural chemicals suspension agent product standards of HG/T2467.5-2003 write specification) regulation, to the difenoconazole dispersible oil of the present invention
Suspending agent the key technical indexes is measured, and the results are shown in Table 1：
1 difenoconazole dispersible oil-suspending agent of table and comparative example the key technical indexes measurement result table
The test result of table 1 shows, the difenoconazole dispersible oil-suspending agent of different effective contents prepared by the present invention
Dispersibility and stability are good, have preferable stability under low temperature and hot environment, are not susceptible to deposit, resolution ratio
It is low, show that there is good effect to the stability of product of the present invention as stabilizer using gas-phase silica and diatomite, together
When product of the present invention there is high suspensibility, compared with oil-suspending agent prepared by comparative example, there is prominent dispersion effect.
Difenoconazole dispersible oil-suspending agent Efficiency assessment embodiment：
The assay method of every evaluation index：
1) adhesion work (W)
Surface tension (Υ), the measure of medical liquid surface tension use platinum plate method.The surface tension of liquid is less than target
During surface free energy, liquid is possible to soak and sprawl in target surface.
Dynamic contact angle (θ), dynamic contact angle is measured using OCA20 contact angle measurements, using video method.Dynamic Contact
The small liquid in angle is strong to wetting ability on selected target.
The measure of adhesion work uses calculating method, W=Υ (cos θ+1) (Υ is surface tension in formula, and θ is contact angle).
Under the conditions of isothermal and isobaric, the maximum work that when liquid level and Solid Surface Adhesion of unit area is externally made is known as adhesion work, it is
Can liquid soak a kind of measurement of solid.Adhesion work is bigger, and liquid more can soak solid, and liquid-solid combination must be more firm.
2) drop expanding area (S)
The measure of drop expanding area uses integration method.Drop expanding area directly represents expansion of the liquid in target surface
Exhibition ability, drop expanding area is big, shows that formulation spreads are good.
3) ability to resist splash erosion
Appropriate Leaf of banana is taken, suspending agent, is diluted to the dilution containing principal component 1%, at every piece by number label respectively
0.5g dilutions are dropped evenly on Leaf of banana, it is allowed to be dried at room temperature for.No. 1 Leaf of banana keeps dry as control, remains
Remaining Leaf of banana is dried again after rinsing (n=2) with deionized water, then is carried with 90% isopropanol water solution elution and ultrasound
Remaining principal component on Leaf of banana is taken, measures the principal component content in extracting solution, calculates recovery percentage F.F=Mi/Mo its
In：F is recovery percentage；Mi is the principal component content in the extracting solution of the i-th Leaf of banana；Mo is not to be rinsed in Banana Leaf
The principal component content theoretical value of on piece.
Difenoconazole dispersible oil-suspending agent Efficiency assessment：
2 difenoconazole dispersible oil-suspending agent of table and comparative example the effect of property measurement result table
The difenoconazole dispersible oil-suspending agent of the present invention is can be seen that from above measurement result and prepared by comparative example
Oil-suspending agent pesticide compare adhesion work with bigger and drop expanding area and with stronger anti-rain drop erosion energy
Power.Adhesion work is bigger, and adhesion strength is stronger, and liquid more can soak solid, and liquid-solid combination must be more firm, i.e. difenoconazole dispersible
Oil-suspending agent can have and Leaf of banana firm connection；Drop expanding area is big, shows that formulation spreads are good, i.e., difenoconazole can
Disperseing oil-suspending agent has better plate-out ability；From experimental data it is found that difenoconazole dispersible oil-suspending agent also has more
Strong ability to resist splash erosion can improve pesticide active ingredient to the deposition of target with withholding efficiency, so as to improve pesticide
Effective rate of utilization, the loss of less pesticide, less environmental pollution.
The effect of difenoconazole dispersible oil-suspending agent in practical applications for the verification present invention, 2012 in Beijing
(difenoconazole is effective for the difenoconazole dispersible oil-suspending agent that the rich test site of southern exposure agriculture is carried out prepared by a 1-5
Content is on the basis of 35% × 25ml/75L) pear scab field control effectiveness test is prevented, result of the test is as shown in table 3.It tries in field
Test the result shows that, show preferable preventive effect in field control pear scab practical application；Under Isodose, preventive effect is slightly higher
In comparison medicament, preferable preventive effect is shown in field control pear scab practical application, it is suitable with comparison medicament, to making
Object safety.
3 difenoconazole of table prevention pear scab result of the test (2012, the rich test site of Beijing southern exposure agriculture)
Shown by table 3, under Isodose, as the difenoconazole dispersible oil-suspending agent prepared by embodiment 1-5 with it is right
Ratio preparation is compared, and preferable preventive effect is respectively provided with to pear scab, is again demonstrated difenoconazole dispersible oil of the present invention and is hanged
Floating agent has good adherence, plate-out ability and ability to resist splash erosion.It can be seen that the present invention is adding in new non-ionic table
The performance of the dispersible oil-suspending agent of p-phenylene's methyl cyclic-azole has obtained very big after bright activating agent, anion surfactant and stabilizer
Improvement, i.e., difenoconazole dispersible oil-suspending agent dispersibility and suspensibility be improved, in low temperature and high temperature ring
Under border there is preferable stability, be not susceptible to deposit, resolution ratio is low, and product of the present invention has a wide range of applications, due to having
Good adherence, plate-out ability and ability to resist splash erosion, product of the present invention can be applied to the fields such as vegetables, fruit tree, cereal
Fungal disease is prevented.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, the invention is not limited in specific embodiment disclosed and described above, to the one of invention
A little modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, it although is used in this specification
Some specific terms, but these terms are merely for convenience of description, do not limit the present invention in any way.
Claims (6)
1. a kind of difenoconazole dispersible oil-suspending agent, it is characterised in that its raw material composition contains difenoconazole, nonionic
Surfactant, anion surfactant, cosurfactant, stabilizer and decentralized medium, wherein difenoconazole, it is non-from
Sub- surfactant, anion surfactant, cosurfactant, stabilizer and decentralized medium weight ratio be (5~35)：
(3~10)：(3~10)：(1~10)：(1~10)：(20~90), the nonionic surfactant gather for dibenzyl xenyl
The mixing of ethylene oxide ether, styryl phenyl polyoxyethylene ether and triphenoethyl benzene phenol polyoxyethylene polyoxypropylene block polymer
Object, dibenzyl xenyl polyoxyethylene ether, styryl phenyl polyoxyethylene ether and triphenoethyl benzene phenol polyoxypropylene polyoxy second
The weight ratio of alkene block polymer is 5：4：4, mixing of the anion surfactant for alkyl sulfate and phosphoric acid ester
The weight ratio of object, alkyl sulfate and phosphoric acid ester is 1：1, the cosurfactant is in isopropanol, butanol and octanol
The mixture of a kind of or isopropanol and octanol, the stabilizer are one or gas-phase silica in gas-phase silica and diatomite
With diatomaceous mixture, the decentralized medium is one kind or rosin-based plant in turpentine-based vegetable oil and methylated vegetable oil
The mixture of oil and methylated vegetable oil.
2. difenoconazole dispersible oil-suspending agent according to claim 1, it is characterised in that the isopropanol and octanol
Weight ratio be 2：1.
3. difenoconazole dispersible oil-suspending agent according to claim 1, it is characterised in that the gas-phase silica with
Diatomaceous weight ratio is 1：3.
4. difenoconazole dispersible oil-suspending agent according to claim 1, it is characterised in that the turpentine-based vegetable oil
Weight ratio with methylated vegetable oil is 2：1.
5. a kind of preparation method of difenoconazole dispersible oil-suspending agent as described in claim 1, it is characterized in that first point
Dispersion media, nonionic surfactant, anion surfactant, cosurfactant are accurately weighed by formula rate, are added in
The difenoconazole technical material and stabilizer for uniformly, then adding formula ratio are sufficiently mixed in mixer, high speed shear is mixed
5min is closed, carries out wet grinding into horizontal sand mill, it is qualified products to reach regulation technical indicator.
6. a kind of application of difenoconazole dispersible oil-suspending agent as described in claim 1, it is characterized in that it is in vegetables, fruit
Fungal disease is prevented on tree, grape.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785444A (en) * | 2010-03-09 | 2010-07-28 | 上海市环境科学研究院 | High-yield culture method of Thai Bink No.3 earthworm |
| WO2012146888A1 (en) * | 2011-04-26 | 2012-11-01 | Syngenta Limited | Formulation component |
| CN103141476A (en) * | 2013-01-15 | 2013-06-12 | 中国农业科学院植物保护研究所 | Difenoconazole dispersible oil suspending agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785444A (en) * | 2010-03-09 | 2010-07-28 | 上海市环境科学研究院 | High-yield culture method of Thai Bink No.3 earthworm |
| WO2012146888A1 (en) * | 2011-04-26 | 2012-11-01 | Syngenta Limited | Formulation component |
| CN103141476A (en) * | 2013-01-15 | 2013-06-12 | 中国农业科学院植物保护研究所 | Difenoconazole dispersible oil suspending agent |
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