CN1506415A - Prepn of field electronic ink - Google Patents
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- CN1506415A CN1506415A CNA02139590XA CN02139590A CN1506415A CN 1506415 A CN1506415 A CN 1506415A CN A02139590X A CNA02139590X A CN A02139590XA CN 02139590 A CN02139590 A CN 02139590A CN 1506415 A CN1506415 A CN 1506415A
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Abstract
The field electronic ink is prepared through dispersing electrophoresis display fluid in polymer precursor via stirring, applying electric field to the system to make the electrophoresis display fluid drops arranged regularly, and initiating polymerization to form resin to coat the electrophoresis display fluid regularly. Applying electric field can make the electrophoresis display fluid display electrophoretically in the pores. The said technology has the advantages of microcapsule electrophoresis display technology and simple technological process. The field electronic ink includes through parts of electrophoresis grain, suspension liquid and dispersing matrix, and the polymer may be water soluble polymer, thermosetting polymer, thermoplastic polymer, polyurea, polyamine, etc.
Description
Technical field the present invention relates to a kind of preparation method of electronic ink material, be particularly related to and a kind of the electrophoresis showed fluid be dispersed in the polymer precursor, and it is applied electric field to impel its regular arrangement, initiated polymerization is to obtain the preparation method of electronic ink material then.
The background technology electronic ink display technology have contrast gradient greatly, with great visual angle, high show lightness, low price, good stability, easily realize big plane, can realize advantage such as flexible demonstration.But its traditional preparation method carries out micro encapsulation to the electrophoresis showed fluid, and then microcapsule are arranged on the matrix with the preparation display unit.Usually the method for micro encapsulation has mechanical process, chemical method, physico-chemical processes etc., no matter which kind of method all has complex process, cost is higher, is unfavorable for the shortcoming of producing in enormous quantities.And being the electrophoresis disclosing solution that directly will include particulate and dye solution, more easy settling mode is dispersed in the transparent polymer precursor, initiated polymerization then, then the electrophoresis showed fluid, is only needed can make the electric ink display material once going on foot by dispersed encapsulated in transparent fluoropolymer resin.This technical matters is simple, and its shortcoming is that electrophoretic fluid size in polymkeric substance is uneven, arranges in a jumble, has influenced image quality.
Summary of the invention the purpose of this invention is to provide that a kind of to utilize electric field that the electrophoresis showed fluid is disperseed regular to prepare the method for electronic ink material in transparent fluoropolymer resin.Its basic way is electrophoretic fluid to be evenly dispersed in constitute two phase systems in the polymer precursor, the electric charge that can take place at the interface of the polymer precursor of the electrophoresis showed fluid of oiliness in this system (water-based) and water-based (oiliness) is given and accepted, thereby makes the electrophoretic fluid liquid droplet charged.When system was applied electric field, charged electrophoretic fluid drop can produce induced dipole moment under effect of electric field, if the applied field size to fit, the electrophoresis showed fluid drop will be regularly arranged under effect of electric field.Initiated polymerization thing presoma reaction then, the electrophoresis showed fluid just by even regular ground dispersed encapsulated therein after resin formation.
The field-causing electron ink material is made up of electrophoresis base fluid, electrophoretic particles, dyestuff, disperse matrix.The electrophoretic particles of selecting for use can be single-phase pigment and composite pigment (inorganic/inorganic compounding, organic/inorganic is compound, inorganic/polymkeric substance is compound, organic/polymer composite particles) etc. with regard to its chemical constitution; With regard to its optical property can be scattered light particle, absorb light particle, reflective particles, electro-luminescent particles, photoluminescence particle etc.The also electrophoretic particles that can make with the granules of pigments of 10～100nm parcel superpolymer or make black pigment particles with coated porous superpolymer such as perosmic anhydride or ruthenium tetroxides.When selecting the bigger inorganic particle of density, can reduce particulate density at the polymkeric substance (as polyethylene) of its surface parcel layer of transparent.Inorganic pigment granules commonly used has titanium dioxide, silicon oxide, chrome yellow, ultramarine, carbon black, manganese violet, iron oxide red, cadmium red etc.; Organic pigment particle has red, toluidine red, phthalocyanine blue, quinacridone etc.
Organic solvent can be selected one or more solvent complex, to satisfy the performance requriements that electric ink shows.Operable organic solvent comprises epoxy compounds, aromatic hydrocarbons, halohydrocarbon, aliphatic hydrocarbon, siloxanes etc.Can use sec-butylbenzene and the composite dispersion medium of zellon, perhaps by zellon and the composite dispersion medium of normal hexane.Organic solvent dyeing, operable dyestuff have azo class, anthraquinone class, triphenylmethane class, disperse class and reduction class dyestuff,, Sudan red red as oil soluble, solvent blue, the blue RR of Macrolex, Hytherm indigo plant, EX-SF DISPERSE BLUE EX-SF 300, vat blue etc.
Polymkeric substance as disperse matrix can be any and the immiscible polymkeric substance of electrophoretic fluid, as water-soluble polymers, thermosetting polymer, thermal plastic polymer, polyureas, polyamine, urea-formaldehyde resin, Mierocrystalline cellulose and derivative thereof, polyvinyl alcohol, polymethylmethacrylate etc.
Embodiment at first with the reprecipitation method at particle surface parcel polyethylene and polyvinyl alcohol: low molecular weight polyethylene is dissolved in the hexanaphthene in 80 ℃, adds electrophoretic particles, stir it is uniformly dispersed, at this moment polyethylene just is adsorbed on particle surface.Use ethanol D-loop hexane then,, will be wrapped on the particle and be precipitated out again because polyethylene is insoluble to ethanol; Perhaps electrophoretic particles is dispersed in the polyvinyl alcohol water solution, stirs certain hour, use the ethanol replacing water then as mentioned above,, can obtain wrapping up the particle of polyvinyl alcohol again with zellon displacement alcohol.If selected particle is metal oxide then can wraps up polymethylmethacrylate with emulsion polymerization: metal oxide particle such as titanium dioxide are dispersed in the water, be warming up to 60～90 ℃, add methyl methacrylate, methacrylic acid as reaction monomers, sodium bisulfite or Sodium Persulfate be as initiator, reacts to add a small amount of sodium bisulfite after 2 hours again and be warming up to 70～100 ℃ to keep 1 hour so that react completely.Naturally cool to room temperature then, again 50 ℃ of following forced air dryings 4 hours, grinding gets final product a little.Or wrap up urea-formaldehyde resin: particles dispersed in water, is added the urea-formaldehyde resin performed polymer of preparation in addition in the entry, regulate pH value with acetic acid and dilute hydrochloric acid and be 2～4,40～60 ℃ and reacted 3 hours down that taking-up is dried to grind and got final product with situ aggregation method.
The electrophoretic particles that has wrapped up polymkeric substance is added in the electrophoretic fluid base fluid, in order to make particle good dispersion in oil phase, can add oil soluble surfactant such as SPAN80, cetyl trimethylammonium bromide or the like helps its dispersion, has so just made electrophoretic fluid.
The electrophoresis showed fluid is distributed in polymer precursor or its solution, and stirring makes it be separated into emulsion, can add some tensio-active agents in order to make emulsion keep stable in polymer precursor.Emulsion can smear, spray or spray ink Printing on rigid planar such as metal sheet, sheet glass, use emulsion to be applied to be parallel to emulsion place planar electrostatic field perpendicular to this planar plate electrode, field intensity remains on about 5V/mm substantially.Keep this electric field, the reaction of initiated polymerization thing presoma, resin solidification just can obtain electronic ink material later.
Embodiment one: 10～30 gram titanium dioxide are dispersed in the 150ml water, be warming up to 70 ℃, add 10～20ml methyl methacrylate, 0.5～2ml methacrylic acid, 1～4 restrains sodium bisulfite or Sodium Persulfate, reacts to add a small amount of sodium bisulfite after 2 hours again and be warming up to 80 ℃ to keep 1 hour so that react completely.Naturally cool to room temperature then, 50 ℃ of following forced air dryings 4 hours, grind stand-by a little again.Other gets 6g urea, 15ml 37% formalin, add trolamine and regulate ph=9.3,80 ℃ down reaction made performed polymer in one hour, add acetic acid and regulate PH=3.5,75～85 ℃ of reactions 25～35 minutes make the lower molecular weight urea-formaldehyde resin.Get aforementioned titanium dioxide 100mg and the 18mg cetyl trimethylammonium bromide that has wrapped up polymethylmethacrylate and add 3ml with in the painted zellon of EX-SF DISPERSE BLUE EX-SF 300, pour in the lower molecular weight urea-formaldehyde resin after one hour in ultrasonic dispersion down, stir and make it be separated into homogeneous latex emulsion 30 seconds, emulsion is spread upon on the flat board, it is applied the electric field of 4～5V/mm, keep being heated to 60 ℃ then more than 10 minutes, keep this temperature vacuum-drying to get final product in 1 hour.
Embodiment two: 10～50mg titanium dioxide is dispersed in 10 ml waters, adds water-soluble blue dyes and OP-10 emulsifying agent, make the electrophoresis showed fluid.Other gets 100 gram methyl methacrylates, adds 0.06～0.30 gram Diisopropyl azodicarboxylate, 1～3 gram methacrylic acid, 0.1～0.4 gram stearic acid, 0.5～0.75 gram dibutyl phthalate.React under 85 ℃ to viscosity and be about 2000 centipoises, because methyl methacrylate polymerization is polyaddition reaction, speed of response is very fast, and the wayward intermediate that obtains the viscosity that requires can add Resorcinol (stopper) in system.The heavy-gravity intermediate that reaction is obtained is cooled to 20 ℃ rapidly, again the electrophoretic fluid that makes is dispersed in the polymethylmethacrylate intermediate, be coated on the sheet glass after stirring, it is applied be parallel to the electric field that sheet glass place planar field intensity is about 4～5V/mm, keep more than 10 minutes.Use the initiation reaction of uviolizing reaction system then, continue reaction down at 40 ℃ and obtained transparent firm in one hour
With the synthetic glass is the field-causing electron ink material of base material.
Embodiment three: the 0.72g gelatin is dissolved under 40 ℃ in the 6ml distilled water, adds the electrophoresis showed fluid described in the embodiment one, stirring makes it be dispersed to required particle diameter; Simultaneously, the 0.72g gum arabic is dissolved under 40 ℃ in the 6ml distilled water, mixes with above-mentioned emulsion; Make pH value greater than 5 with the 10%NaOH adjusting, stir adding 15ml distilled water down, regulate PH=4.5 with Glacial acetic acid again, gelatin and gum arabic are condensed, and be wrapped in around the capsule heart solution; Inclining the upper strata stillness of night, adds the urea formaldehyde polycondensate described in 3ml such as the embodiment one, after stirring, be coated on the glass basis, apply and be parallel to the electric field that sheet glass place planar field intensity is about 2～6V/mm, keep more than 10 minutes, be warming up to 60 ℃ and keep down getting final product in 2 hours.
Claims (4)
1. field-causing electron ink material preparation method, it is characterized in that: electrophoretic fluid is dispersed in the polymer precursor, apply electric field and make its arrangement regular, cause the presoma polymerization, reaction finish the rear electrophoresis fluid just by even regular ground dispersed encapsulated in fluoropolymer resin.
2. according to the described field-causing electron ink material of claim 1 preparation method, it is characterized in that: the electrophoresis showed fluid is distributed in polymer precursor or its solution, stirring makes it be separated into emulsion, can add some tensio-active agents in order to make emulsion keep stable in polymer precursor.Then emulsion is coated on flat board or the film, it is applied electric field, keep just can making the regular arrangement of drop, again the control condition initiated polymerization more than 15 minutes.
3. according to the described electric field of claim 2, it is characterized in that: that uses that plate electrode applies is parallel to emulsion place planar electric field, and strength of electric field is 15V/mm～50V/mm.
4. according to the described polymer precursor of claim 2, it is characterized in that: be in a liquid state before the reaction or the solubleness in solvent is very big and do not dissolve each other with the oil phase capsule-core.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02139590 CN1239643C (en) | 2002-12-09 | 2002-12-09 | Prepn of field electronic ink |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02139590 CN1239643C (en) | 2002-12-09 | 2002-12-09 | Prepn of field electronic ink |
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| Publication Number | Publication Date |
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| CN1506415A true CN1506415A (en) | 2004-06-23 |
| CN1239643C CN1239643C (en) | 2006-02-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 02139590 Expired - Fee Related CN1239643C (en) | 2002-12-09 | 2002-12-09 | Prepn of field electronic ink |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299816C (en) * | 2005-08-02 | 2007-02-14 | 天津大学 | Yellow electronic ink microcapsule preparation method |
| CN100397228C (en) * | 2005-12-01 | 2008-06-25 | 北京化工大学 | Method for preparing black-white electrophoresis display liquid used for electronic ink |
| CN102888599A (en) * | 2012-11-01 | 2013-01-23 | 哈尔滨工业大学 | Method for preparing high-density metal oxide membrane on porous base material |
-
2002
- 2002-12-09 CN CN 02139590 patent/CN1239643C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299816C (en) * | 2005-08-02 | 2007-02-14 | 天津大学 | Yellow electronic ink microcapsule preparation method |
| CN100397228C (en) * | 2005-12-01 | 2008-06-25 | 北京化工大学 | Method for preparing black-white electrophoresis display liquid used for electronic ink |
| CN102888599A (en) * | 2012-11-01 | 2013-01-23 | 哈尔滨工业大学 | Method for preparing high-density metal oxide membrane on porous base material |
| CN102888599B (en) * | 2012-11-01 | 2014-06-11 | 哈尔滨工业大学 | Method for preparing high-density metal oxide membrane on porous base material |
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| CN1239643C (en) | 2006-02-01 |
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