CN104829856A - Method for coating surfaces of microspheres with epoxy resin layer by virtue of supercritical carbon dioxide - Google Patents
Method for coating surfaces of microspheres with epoxy resin layer by virtue of supercritical carbon dioxide Download PDFInfo
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- CN104829856A CN104829856A CN201510244936.3A CN201510244936A CN104829856A CN 104829856 A CN104829856 A CN 104829856A CN 201510244936 A CN201510244936 A CN 201510244936A CN 104829856 A CN104829856 A CN 104829856A
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- epoxy resin
- microballoon
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- microspheres
- wraps
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention provides a method for coating the surfaces of microspheres with an epoxy resin layer by virtue of supercritical carbon dioxide. According to the method, based on the characteristics of supercritical carbon dioxide which is an all-purpose solvent, the surfaces of PS microspheres are coated with an epoxy resin layer; the, a solvent in epoxy resin is extracted out by using supercritical carbon dioxide so as to form an adhesive layer on the surfaces of the PS microspheres; moreover, when gas is released, the microspheres are suspended and roll continuously in a gas flow so that the epoxy resin uniformly coats the surfaces of the microspheres; after gas is completely released, the microspheres are collected to obtain microspheres well coated with the epoxy resin; after being treated, the PS microspheres have smooth surfaces and fixed particle diameter just like original spheres; when an edge sealing adhesive is cured, the microspheres are synchronously cured and adhered to a glass plate or PET, thus achieving the aim of fixing the microspheres; the phenomenon of image instability because of spacing deviation caused when an external force acts between two plates of an LCD can be reduced and the quality of the LCD can be improved. The method is simple, easy to implement, low in cost and good in use effect.
Description
Technical field
The present invention relates to materials science field, especially a kind of critical carbon dioxide wraps the method for epoxy resin layer at microsphere surface.
Background technology
When available liquid crystal indicating meter makes by two sheet glass or be coated with ITO(indium tin oxide target) PET plate between inject its surrounding of liquid crystal and scribble PET glue and the two mutually bonding centres of plate are coated with determine that the PS microballoon of particle diameter is as interval insulant, particularly flexible liquid crystal screen PET adopts same method to make, and the microballoon between them easily slides, piles up.When injecting, between two plates, spacing need be consistent.The distance that the PS microballoon of same particle size controls between two plates is adopted when usually preparing liquid-crystal display.Currently used PS ball surface free crosses process one deck PS microsphere features smooth surface, and the effect being subject to external force when microballoon is applied between sheet glass is easily slided, and can cause the deviation of sheet glass spacing after microballoon olistostrome.Once deviation appears in two distances between plates, liquid crystal molecule can not turn direction by galvanic element can cause the phenomenons such as a series of images distortion such as Hua Ping.Particularly more easily there is this problem in flexible PET plate, need ensure that microballoon is close to upper and lower surface plate and is not slided when external force is easily slided therefore applied on liquid crystal display by PS microballoon as microballoon.When prepared by liquid-crystal display by spraying coating process by PS microballoon even spread on transparent panel, frame adhesive sealing is adopted in the surrounding of plate, again frame adhesive is heating and curing, its condition of cure is: temperature 150-180 DEG C, evenly be subject to gasbag pressure 1.5kg between two plates during solidification, the time is 1.5-2 hour.This technique ensure that to only have a PS microballoon in the vertical direction between upper and lower two sheet glass, and two sheet glass spacing are also the spacing of microballoon.
Summary of the invention
The object of the invention is: a kind of loop chain Isaria and products thereof and preparation method and using method are provided, PS microballoon is the same with protocorm at normal temperatures after treatment has smooth surface and fixing particle diameter, when edge sealing adhesive solidifies, microballoon synchronously solidifies and bonds on sheet glass or PET, reaches the effect of fixing microballoon.
The present invention is achieved in that supercritical co wraps the method for epoxy resin layer at microsphere surface, comprises the steps:
(1) microsphere surface process: PS microballoon is carried out sulfonation process, obtains the PS microballoon of sulfonating surface process;
(2) configure epoxy resin: be dissolved in solvent by epoxy resin, then add latent curing agent and stir;
(3) surface wraps resin: joined by the PS microballoon of sulfonating surface process in the solid epoxy solution configured, carry out supersound process under agitation, to stir after 30min by microballoon suction filtration out, the epoxy resin making PS microsphere surface wrap up one deck to contain solvent;
(4) first supercritical processing: the microballoon gone out by suction filtration is placed in supercritical co reactor, after passing into supercritical co, make the dissolution with solvents of epoxy resin in supercritical co, then solvent is together discharged with carbonic acid gas, obtain the microballoon that surface wraps epoxy resin layer.
Microsphere surface process described in step (1) is, PS microballoon is placed in the sulfuric acid that mass percent concentration is 50%, solid-liquid ratio is 1:5, unit is g/mL, after stirring 30min, repeatedly clean through ultrasonic wave with distilled water afterwards, until sulfuric acid cleans up also suction filtration, oven dry completely, obtain the PS microballoon through sulfonation process.
Latent curing agent described in step (2) is modified imidazole, Dyhard RU 100 or cationic solidifying agent.
Surface described in step (3) wraps resin and is specially, and pours in epoxy resin by PS microballoon, under the condition of 200r/min, stir 30min, make epoxy resin on PS microballoon complete wetting, then by microballoon suction filtration out, the coated thickness of the epoxy resin on microballoon is 0.5-1 μm.
First supercritical processing described in step (4) is that the microballoon gone out by suction filtration is placed in supercritical co reactor, after passing into supercritical co, under 200r/min, stirs 15min, makes the dissolution with solvents of epoxy resin in supercritical co; After stirring completes, open the air outlet valve of supercritical co reactor, solvent is together discharged with carbonic acid gas, obtain the microballoon that surface wraps epoxy resin layer.
Supercutical fluid has the dissolving power of similar Diffusion of gas stream and liquid, there is low-viscosity simultaneously, the characteristic of low surface tension, supercutical fluid can enter in microporous substances by rapid permeability, therefore efficient as the material of solvent compared with liquid time for extracting, especially solubility with temperature, pressure and polarity and change.Supercritical fluid extraction sepn process utilizes postcritical dissolving power and its density relationship, namely the impact of pressure and temperature on supercutical fluid dissolving power is utilized to carry out, the density that the single phase of its characteristic between fluid and liquid is close with liquid when material is in supercritical state, though viscosity is higher than gas but be starkly lower than liquid, spread coefficient is that the 10-100 of liquid doubly can by some constituents extraction in material out, then to reduce pressure intensification, be extracted material and then automatically separate out completely.Carbon dioxide chemistry stable in properties colorless and odorless is nontoxic, and security is good, and price comparatively other other gases is cheap, the advantage easily obtained.After it is separated with extraction component, there is no dissolvent residual completely, extraction and fractionation can be united two into one, when the CO 2 supercritical of saturated solute is through splitter because pressure drop makes carbonic acid gas and extract reply rapidly to become and be separated two-phase.Utilize this characteristic of carbonic acid gas to use and the dissolution with solvents of dissolved solids epoxy resin can prepare solidifying agent and solidifying agent and the auxiliary agent that solids epoxy carbonic acid gas liquid under supercritical co state out leaves the solvent extraction in epoxy resin solid-state epoxy resin and solid sent out by other auxiliary agents, these all can not be dissolved in supercritical co.
Owing to have employed above technical scheme, the present invention adopts the feature of the menstruum universale of supercritical co, at PS microsphere surface parcel epoxy resin, recycling supercritical co by the solvent extraction in epoxy resin out, one deck glue paste is formed at PS microsphere surface, and, constantly roll in the gas flow because microballoon during release gas is in suspended state, therefore epoxy resin evenly can be wrapped microsphere surface, namely after air release is complete, collect microballoon is the microballoon having wrapped epoxy resin, PS microballoon is the same with protocorm at normal temperatures after treatment has smooth surface and fixing particle diameter, when edge sealing adhesive solidifies, microballoon synchronously solidifies and bonds on sheet glass or PET, reach the effect of fixing microballoon, decrease the judder phenomenon that the spacing deviation because producing by External Force Acting between LCD two plate brings, the quality of LCD can be improved.The inventive method is simple, and easy to implement, with low cost, result of use is good.
Embodiment
Embodiments of the invention 1: supercritical co wraps the method for epoxy resin layer at PS microsphere surface,
(1) surface treatment: it is in the sulphuric acid soln of 50% that the PS microballoon microballoon of 10 μm is taken 10g and 50ml mass percent, sulfuric acid and PS microballoon to be joined in there-necked flask simultaneously and to stir 30min with agitator, repeatedly clean in ultrasonic wave 5 times with distilled water until the complete washes clean of sulfuric acid after stirring, last suction filtration, oven dry obtain the PS microballoon of sulfonating surface process;
(2) configure epoxy resin: take 25g E20 epoxy resin and be dissolved in butanone completely, then add Dyhard RU 100 1g and methylimidazole 0.1g stirs;
(3) surface wraps resin: joined by the PS microballoon of sulfonating surface process in the solid epoxy solution configured, in there-necked flask, supersound process while stirring under the condition of 200r/min, to stir after 30min by microballoon suction filtration out, now microsphere surface has wrapped up one deck and has contained solvent epoxy resin;
(4) first supercritical processing: the microballoon gone out by suction filtration is placed in supercritical co reactor, off-response still and lower the temperature, pressurizeing passes in reactor by liquid carbon dioxide, setting operating pressure 20mpa, temperature of reaction 40 DEG C, rotating speed 200r/min, turn on agitator is opened air outlet valve after stirring 15min and is discharged by carbonic acid gas, namely after air release is complete, collect microballoon is the PS microballoon having wrapped epoxy resin, and the thickness of epoxy resin is 1 μm.
The PS microballoon prepared by the method is applied in LED screen preparation, to eliminate because PS microballoon slides the Huaping phenomenon that causes and manifests bad phenomenon, prepared LED screen product qualification rate reaching more than 99%.
Embodiments of the invention 2: supercritical co wraps the method for epoxy resin layer on silicon dioxide microsphere surface,
(1) surface treatment: it is in the sulphuric acid soln of 50% that the silicon dioxide microsphere microballoon of 8 μm is taken 10g and 50ml mass percent, sulfuric acid and silicon dioxide microsphere to be joined in there-necked flask simultaneously and to stir 30min with agitator, repeatedly clean in ultrasonic wave 5 times with distilled water until the complete washes clean of sulfuric acid after stirring, last suction filtration, oven dry obtain the silicon dioxide microsphere of sulfonating surface process;
(2) epoxy resin is configured: take 12.5g E44 epoxy resin and be dissolved in completely in butanone and add positively charged ion hexafluoro antimonate again and stir;
(3) surface wraps resin: joined by the silicon dioxide microsphere of sulfonating surface process in the solid epoxy solution configured, in there-necked flask, supersound process while stirring under the condition of 200r/min, to stir after 30min by microballoon suction filtration out, now microsphere surface has wrapped up one deck and has contained solvent epoxy resin;
(4) first supercritical processing: the microballoon gone out by suction filtration is placed in supercritical co reactor, off-response still and lower the temperature, pressurizeing passes in reactor by liquid carbon dioxide, setting operating pressure 20mpa, temperature of reaction 40 DEG C, rotating speed 200r/min, turn on agitator is opened air outlet valve after stirring 15min and is discharged by carbonic acid gas, namely after air release is complete, collect microballoon is the silicon dioxide microsphere having wrapped epoxy resin, and the thickness of epoxy resin is 0.5 μm.
The silicon dioxide microsphere prepared by the method is applied in LED screen preparation, to eliminate because silicon dioxide microsphere slides the Huaping phenomenon that causes and manifests bad phenomenon, prepared LED screen product qualification rate reaching more than 99%.
Of the present inventionly be not limited to the embodiment described in embodiment, those skilled in the art's technical scheme according to the present invention draws and other embodiment belongs to technological innovation scope of the present invention equally.Obvious those skilled in the art can carry out various change and modification to the present invention and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (5)
1. supercritical co wraps a method for epoxy resin layer at microsphere surface, it is characterized in that: comprise the steps:
(1) microsphere surface process: microballoon is carried out sulfonation process, obtains the PS microballoon of sulfonating surface process;
(2) configure epoxy resin: be dissolved in solvent by epoxy resin, then add latent curing agent and stir;
(3) surface wraps resin: joined by the microballoon of sulfonating surface process in the solid epoxy solution configured, carry out supersound process under agitation, to stir after 30min by microballoon suction filtration out, the epoxy resin making microsphere surface wrap up one deck to contain solvent;
(4) first supercritical processing: the microballoon gone out by suction filtration is placed in supercritical co reactor, after passing into supercritical co, make the dissolution with solvents of epoxy resin in supercritical co, then solvent is together discharged with carbonic acid gas, obtain the microballoon that surface wraps epoxy resin layer.
2. supercritical co according to claim 1 wraps the method for epoxy resin layer at microsphere surface, it is characterized in that: the microsphere surface process described in step (1) is, PS microballoon is placed in the sulfuric acid that mass percent concentration is 50%, solid-liquid ratio is 1:5, unit is g/mL, and after stirring 30min, rear distilled water cleans repeatedly through ultrasonic wave, until sulfuric acid cleans up also suction filtration, oven dry completely, obtain the microballoon through sulfonation process.
3. supercritical co according to claim 1 wraps the method for epoxy resin layer at microsphere surface, it is characterized in that: the latent curing agent described in step (2) is modified imidazole, Dyhard RU 100 or cationic solidifying agent.
4. supercritical co according to claim 1 wraps the method for epoxy resin layer at microsphere surface, it is characterized in that: the surface described in step (3) wraps resin and is specially, PS microballoon is poured in epoxy resin, under the condition of 200r/min, stir 30min, make epoxy resin on PS microballoon complete wetting, then by microballoon suction filtration out, the coated thickness of the epoxy resin on microballoon is 0.5-1 μm.
5. supercritical co according to claim 1 wraps the method for epoxy resin layer at microsphere surface, it is characterized in that: the first supercritical processing described in step (4) is, the microballoon gone out by suction filtration is placed in supercritical co reactor, after passing into supercritical co, under 200r/min, stir 15min, make the dissolution with solvents of epoxy resin in supercritical co; After stirring completes, open the air outlet valve of supercritical co reactor, solvent is together discharged with carbonic acid gas, obtain the microballoon that surface wraps epoxy resin layer.
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| CN201510244936.3A CN104829856B (en) | 2015-05-14 | 2015-05-14 | The method that critical carbon dioxide wraps epoxy resin layer in microsphere surface |
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| CN201510244936.3A CN104829856B (en) | 2015-05-14 | 2015-05-14 | The method that critical carbon dioxide wraps epoxy resin layer in microsphere surface |
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| CN104829856A true CN104829856A (en) | 2015-08-12 |
| CN104829856B CN104829856B (en) | 2018-03-27 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6270836B1 (en) * | 1998-07-27 | 2001-08-07 | Frisby Technologies, Inc. | Gel-coated microcapsules |
| CN101585744A (en) * | 2009-06-23 | 2009-11-25 | 中北大学 | Supercritical fluid technology coating modifying technique of ammonium nitrate |
| CN101972212A (en) * | 2010-10-29 | 2011-02-16 | 华侨大学 | Method for preparing core-shell type composite microspheres by supercritical fluid technology |
| CN102167309A (en) * | 2011-03-04 | 2011-08-31 | 北京化工大学 | Preparation method of shape-controllable hollow carbon microsphere |
| CN103709281A (en) * | 2013-11-29 | 2014-04-09 | 中科院广州化学有限公司 | Fluorine-containing nano-microsphere/fluorine-containing epoxy resin hybrid, preparation method and application thereof |
-
2015
- 2015-05-14 CN CN201510244936.3A patent/CN104829856B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6270836B1 (en) * | 1998-07-27 | 2001-08-07 | Frisby Technologies, Inc. | Gel-coated microcapsules |
| CN101585744A (en) * | 2009-06-23 | 2009-11-25 | 中北大学 | Supercritical fluid technology coating modifying technique of ammonium nitrate |
| CN101972212A (en) * | 2010-10-29 | 2011-02-16 | 华侨大学 | Method for preparing core-shell type composite microspheres by supercritical fluid technology |
| CN102167309A (en) * | 2011-03-04 | 2011-08-31 | 北京化工大学 | Preparation method of shape-controllable hollow carbon microsphere |
| CN103709281A (en) * | 2013-11-29 | 2014-04-09 | 中科院广州化学有限公司 | Fluorine-containing nano-microsphere/fluorine-containing epoxy resin hybrid, preparation method and application thereof |
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| CN104829856B (en) | 2018-03-27 |
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