CN1796469A - Method for preparing Nano capsule of electronic ink - Google Patents
Method for preparing Nano capsule of electronic ink Download PDFInfo
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- CN1796469A CN1796469A CN 200410073521 CN200410073521A CN1796469A CN 1796469 A CN1796469 A CN 1796469A CN 200410073521 CN200410073521 CN 200410073521 CN 200410073521 A CN200410073521 A CN 200410073521A CN 1796469 A CN1796469 A CN 1796469A
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Abstract
This invention involves a process for preparing electronic ink nanocapsules. The diameters of the traditional electronic ink microcapsules are so large (30-300mu m) that largely restrict the response speed of the electronic ink display. This invention adopts in situ fine emulsion polymerization to prepare electronic ink nanocapsules (200-800nm) with controllable diameters. The electrophoresis displaying liquid is an organic sol composed of inorganic oxide nanoparticles and a low dielectric constant, low viscosity, high boiling point liquid organic compound. The process of this invention endows the electrophoresis particles in the electronic ink nanocapsules with good reversible mobility in the electrical field, and largely increases the response speed of the electronic ink, which makes the video displaying of the electronic ink display a possibility.
Description
Technical field the present invention relates to the preparation method of Nano capsule of electronic ink, being particularly related to the organosol is electrophoresis disclosing solution liquid, and polymkeric substance such as ethene base system, acrylic acid series, metha crylic and isocyanic ester and multipolymer thereof are the preparation of the electric ink Na capsule of capsule wall material.
The background technology electric ink is that the electrophoresis disclosing solution that will include particulate and electrophoresis base fluid is wrapped in the microcapsule, because the special stability of microscale suspension system, when micro-capsule is applied electric field, in micro-capsule, realize electrophoresis showed, and can get back to original equilibrium state after discharging electric field.Utilize the demonstration equipment of this fabrication techniques have contrast gradient greatly, with great visual angle, high display brightness, low price, easily realize big plane, high definition, low power consumption, can not power consumption keep that image, thickness are minimum, electromagnetic-radiation-free, can realize advantage such as flexible demonstration.Yet the internal diameter of the electric ink capsule of micro-meter scale (30-300 μ m) is big, shows that under electric field action the time spent when particle moves between the capsule internal surface is long, and it is the major cause of restriction display speed.Therefore dwindle capsule grain diameter and very big benefit is arranged improving the corresponding speed that shows.It is encapsulated that we adopt the original position fine emulsion polymerization that electrophoresis disclosing solution is realized, special tensio-active agent (or carry out two kinds of tensio-active agents and carry out composite) by selecting different HLB values as emulsifying agent with the Nano capsule of acquisition particle diameter between 100-800nm.Electrophoresis disclosing solution is a kind of organosol, and it is the stable sol system of nano-metal-oxide particles dispersed in organic phase, and the preparation method adopts high-temperature-hot-water solution in the organic phase.But having technology Nano capsule of electronic ink simple, with low cost, preparation, present method can realize advantages such as quick reverse response to electric field.
Summary of the invention the purpose of this invention is to provide a kind of preparation method of Nano capsule of electronic ink, its electrophoresis disclosing solution is a kind of organosol, it is the stable sol system that nano-metal-oxide particle (3-80nm) is dispersed in organic phase, and the preparation method adopts high-temperature-hot-water solution in the organic phase.The size of Nano capsule with select to have the yin, yang ionic surface active agent of different HLB values (8～40) or by they and neutral surface active agent composite (composite HLB=8～40) to control the miniemulsion size between 800-100nm; Adopt the original position fine emulsion polymerization, cause with azo-initiator, it is encapsulated to be with vinyl monomer, acrylic monomer, metha crylic monomer and isocyanate-monomer that monomer carries out electrophoresis disclosing solution, obtains the Nano capsule of electronic ink that median size is 100～800nm.
The wall material of the Nano capsule of electronic ink described in the present invention, selection has good light transmittance, certain mechanical strength, certain Young's modulus and be insoluble to the ethene base system of electrophoresis disclosing solution, acrylic acid series, polymkeric substance such as metha crylic and isocyanic ester or their multipolymer, selectable monomer is a vinyl monomer, acrylic monomer, metha crylic monomer and isocyanate-monomer, can select vinylbenzene for use, vinyl acetate, vinyl cyanide, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid, methacrylic acid, methyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, N hydroxymethyl acrylamide, tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, poly methylene poly phenyl poly isocyanate, hexamethylene vulcabond etc.Use wherein one or more monomer to carry out polyreaction, form capsular cyst wall.
Initiator is an azo-initiator, optional nitrogen bis-isobutyronitrile, the 2,2'-Azobis(2,4-dimethylvaleronitrile) etc. of choosing spouse.
The emulsifying agent that is fit to is cationic emulsifier and anionic emulsifier or carries out composite emulsifying agent by them and nonionic emulsifying agent; Cationic emulsifier can be selected quaternary ammonium salt emulsifying agent such as cetyl trimethylammonium bromide etc. for use; Anionic emulsifier can be selected sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, calcium dodecylbenzene sulphonate etc. for use; Nonionic emulsifying agent can be selected tween, this dish, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether etc. for use; For controlling the capsule median size in 100～800 nanometers, the HLB value of emulsifying agent needs to select or be composite is between 40～8, and its total consumption is 0.01～5% of a water, preferred 0.05～3%.
Electronic ink display solution is the stable organosol system that metal oxide nanoparticles and liquid organic compound are formed.In principle, having the muriate of stable existence and can hydrolysis produce the oxide compound of the element of oxide compound can be selected, first-selected ZnO, TiO
2Deng.Liquid organic compound is low-k, low viscosity, high boiling liquid organic compound.Specifiable these materials can be alkanes such as nonane, certain herbaceous plants with big flowers alkane, toluene, dimethylbenzene etc., halogenated hydrocarbon such as zellon, tetrafluoroethylene etc., ethers such as hexyl ether, isoamyl oxide, butyl ether etc., ketone such as sym.-diisopropylideneacetone, isophorone etc., ester class such as butyl formate, and other liquid state organics such as low viscosity transformer oil, silicone oil, high point petroleum ether etc., it can be one or more combination, but must consideration can not dissolve selected wall material, preferred transformer oil, high boiling sherwood oil or silicone oil etc.Organosol adopts the pyrohydrolytic method preparation of metal-salt hydrochlorate in organic phase.Its preparation process is: after a certain amount of metal-salt hydrochlorate grinds in mortar, it is some to add liquid organic compound, add a small amount of surface-modifying agent stearic acid, stirring and dissolving is heated to 80～130 ℃, add water 0.5mL, reflux under agitation slow hydrolysis 6～72 hours, cool to room temperature, filter, filtrate is the organosol of inorganic, metal oxide granules of pigments.
Embodiment
1. the preparation of organosol electrophoresis disclosing solution: after a certain amount of metal-salt hydrochlorate grinds in mortar, it is some to add sherwood oil (or transformer oil), add a small amount of surface-modifying agent stearic acid, stirring and dissolving is heated to 80 ℃ (using transformer oil to be heated to 120 ℃), adds water 0.5mL, reflux, under agitation slow hydrolysis 24 hours, cool to room temperature obtains the organosol electrophoresis disclosing solution.
2. the preparation of blue Nano capsule of electronic ink: take by weighing a certain amount of initiators for polymerization and mix with an amount of monomer (or mix monomer), ultrasonic dissolution in ice bath, it is some to add electrophoresis disclosing solution again, and stirring and evenly mixing is made oil phase.Add a certain amount of emulsifying agent in the suitable quantity of water, stirring and dissolving is made water.Oil phase is mixed with water, placed the ice bath stirring and emulsifying 0.5～2 hour, make the micron order white emulsion, ultra-sonic dispersion is 1～10 minute in being placed on ice bath, make the nano level miniemulsion, it is transferred in the there-necked flask, heating in water bath to 50～80 ℃, stirring velocity 400-500 rev/min rotating speed reacted 6～12 hours down, promptly got Nano capsule of electronic ink.
The present invention illustrates by the following example.
Embodiment one: it is in the Erlenmeyer flask of 90/120 sherwood oil that the 0.2g stearic acid is dissolved in the boiling point that contains 30mL, adds the ZnCl of 0.5g porphyrize again
2.2H
2O loads onto reflux, 100 ℃ and stir under reaction, add 0.5mL distilled water, solution becomes red-brown after 24 hours, filters, filtrate is zinc-oxide nano organosol electrophoresis disclosing solution.
6mL vinylbenzene, 50mg Diisopropyl azodicarboxylate initiator and 0.5mL zinc-oxide nano organosol electrophoresis disclosing solution made initiator dissolve the system oil phase fully in ultrasonic 5 minutes in ice bath after mixing.The anionic of 12mg is dissolved in the 20mL distilled water and makes water.Oil phase is mixed with water in the there-necked flask of 100mL, speed with 1000 rev/mins in ice bath stirs the white emulsion that obtained micro-meter scale in 1 hour, be placed in the Ultrasonic Cleaners that the 250W frequency is 180KHz ultra-sonic dispersion again 120 seconds, and obtained the nanometer miniemulsion.The there-necked flask that fills this miniemulsion placed be warmed up to 68 ℃ water-bath in advance, under 400-500 rev/min the stirring velocity, polyreaction 12 hours, the median size of system are the Nano capsule of electronic ink emulsion of 130nm.
Embodiment two: the 0.15g stearic acid is dissolved in the Erlenmeyer flask of the transformer oil that contains 50mL, adds 0.3mLTiCl again
4, load onto reflux, 100 ℃ and stir under reaction, add 0.5mL distilled water, solution becomes oyster white after 24 hours, filters, filtrate is TiOx nano organosol electrophoresis disclosing solution.
After 6mL methyl methacrylate, 60mg Diisopropyl azodicarboxylate initiator and 0.5mL TiOx nano organosol electrophoresis liquid are mixed, in ice bath, initiator was dissolved fully in ultrasonic 5 minutes and make oil phase.Anionic and tween-80 (carrying out composite according to the amount shown in the table 1) are dissolved in the 20mL distilled water makes water.Oil phase is mixed with water in the there-necked flask of 100mL, in ice bath, stir the white emulsion that obtained micro-meter scale in 1 hour with 1000 rev/mins speed, be placed in the Ultrasonic Cleaners ultra-sonic dispersion again 180 seconds, obtain the nanometer miniemulsion.The there-necked flask that fills this miniemulsion placed be warmed up to 60 ℃ water-bath in advance, 400-500 rev/min stirring velocity, polyreaction 12 hours, the Nano capsule of electronic ink emulsion (as shown in table 1) of the different median sizes of system.
The compound surfactant of the different HLB values of table 1 is to the influence of capsule grain diameter
| Numbering | Sodium lauryl sulphate/mg | Tween-80/μ L | The HLB calculated value | Na capsule median size/nm |
| 1 2 3 4 5 | 20.0 16.0 14.0 10.0 5.0 | 10 4 6 10 15 | 27.1 33.3 29.1 21.0 11.2 | 230 130 210 360 475 |
Embodiment three: the preparation of zinc-oxide nano organosol electrophoresis disclosing solution is with embodiment one.10mL vinylbenzene, 60mg Diisopropyl azodicarboxylate initiator and 1.0mL zinc-oxide nano organosol electrophoresis disclosing solution made initiator dissolve the system oil phase fully in ultrasonic 3 minutes in ice bath after mixing.The cats product cetyl trimethylammonium bromide of 20mg is dissolved in the 30mL distilled water makes water.Oil phase is mixed with water in the there-necked flask of 150mL, speed with 1000 rev/mins in ice bath stirs the white emulsion that obtained micro-meter scale in 1 hour, be placed in the Ultrasonic Cleaners that the 250W frequency is 180KHz ultra-sonic dispersion again 120 seconds, and obtained the nanometer miniemulsion.The there-necked flask that fills this miniemulsion placed be warmed up to 65 ℃ water-bath in advance, under 400-500 rev/min the stirring velocity, polyreaction 8 hours, the median size of system are the Nano capsule of electronic ink of 830nm.
Claims (6)
1. the preparation method of Nano capsule of electronic ink, employed monomer is vinyl monomer, acrylic monomer, metha crylic monomer and isocyanate-monomer; Initiator is an azo-initiator; Electrophoresis disclosing solution is a metal-oxide organosol; Its principal character is: the oil phase that the mixed solution of monomer, initiator and electrophoresis disclosing solution is formed is dispersed in aqueous phase by emulsifying agent, adopts the original position fine emulsion polymerization to form polymer wall electrophoresis disclosing solution is wrapped up.
2. according to the preparation method of the described Nano capsule of electronic ink of claim 1, it is characterized in that organosol is that metal oxide nanoparticles and liquid organic compound are formed first-selected ZnO, TiO
2With transformer oil, silicone oil or high point petroleum ether, mass ratio is 1: 10～10000.
3. according to the preparation method of the described Nano capsule of electronic ink of claim 1, it is characterized in that electrophoresis liquid and monomeric mass ratio are 1: 1～100, initiator is 0.05～2% of a monomer consumption, emulsifying agent is single the moon or cats product or carries out composite (HLB=8～40) by them and nonionogenic tenside that its total consumption is 0.01～5% of a water.
4. according to the preparation method of the described Nano capsule of electronic ink of claim 1, the HLB that it is characterized in that emulsifying agent (comprising composite) changes to 8 from 40, and the median size of prepared Nano capsule of electronic ink is become about 800nm by 100nm.
5. according to the preparation method of the described Nano capsule of electronic ink of claim 1, the chemical heat hydrolysis method in the oil phase is adopted in the preparation that it is characterized in that organosol, and the median size of metal oxide particle is 3～80nm.
6. according to the preparation method of the described Nano capsule of electronic ink of claim 1, it is characterized in that comprising the steps:
(1) monomer, initiator and electrophoresis disclosing solution are made oil phase at 0～10 ℃ of mixed dissolution;
(2) adopt methods such as stirring, heating will show emulsifiers dissolve and in distilled water, make water;
(3) oil phase is mixed with water, under 0～10 ℃ of vigorous stirring, form microemulsion, again the microemulsion ultra-sonic dispersion that forms was formed 100～800nm miniemulsion in 1～10 minute, wherein the mass ratio of oil phase and water is 1: 1～10;
(4) emulsion is heated to 50～80 ℃, stirring reaction 1～12 hour, forming median size is the Nano capsule of 100～800nm;
(5) cooling discharge.
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| CN 200410073521 CN100500774C (en) | 2004-12-29 | 2004-12-29 | Method for preparing Nano capsule of electronic ink |
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| CN 200410073521 CN100500774C (en) | 2004-12-29 | 2004-12-29 | Method for preparing Nano capsule of electronic ink |
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| CN1796469A true CN1796469A (en) | 2006-07-05 |
| CN100500774C CN100500774C (en) | 2009-06-17 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649035A (en) * | 2012-02-06 | 2012-08-29 | 京东方科技集团股份有限公司 | Electrophoresis particle, manufacture method of electrophoresis particles and electrophoresis microcapsule |
| CN102719145A (en) * | 2012-06-29 | 2012-10-10 | 广州大学 | Disperse dye nanocapsule for thermal sublimation digital printing ink-jet ink and preparation method of disperse dye nanocapsule |
| CN102757681A (en) * | 2012-06-21 | 2012-10-31 | 京东方科技集团股份有限公司 | Electronic ink and preparation method thereof |
| WO2015090025A1 (en) * | 2013-12-19 | 2015-06-25 | 京东方科技集团股份有限公司 | Electronic ink, electronic paper and preparation method of electronic ink |
| CN105334643A (en) * | 2015-11-17 | 2016-02-17 | 深圳市国华光电科技有限公司 | Intelligent glass |
| CN113662247A (en) * | 2021-09-08 | 2021-11-19 | 湖北中烟工业有限责任公司 | Water-exploded bead core liquid and preparation method thereof |
-
2004
- 2004-12-29 CN CN 200410073521 patent/CN100500774C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649035A (en) * | 2012-02-06 | 2012-08-29 | 京东方科技集团股份有限公司 | Electrophoresis particle, manufacture method of electrophoresis particles and electrophoresis microcapsule |
| CN102757681A (en) * | 2012-06-21 | 2012-10-31 | 京东方科技集团股份有限公司 | Electronic ink and preparation method thereof |
| CN102719145A (en) * | 2012-06-29 | 2012-10-10 | 广州大学 | Disperse dye nanocapsule for thermal sublimation digital printing ink-jet ink and preparation method of disperse dye nanocapsule |
| CN102719145B (en) * | 2012-06-29 | 2014-03-26 | 广州大学 | Disperse dye nanocapsule for thermal sublimation digital printing ink-jet ink and preparation method of disperse dye nanocapsule |
| WO2015090025A1 (en) * | 2013-12-19 | 2015-06-25 | 京东方科技集团股份有限公司 | Electronic ink, electronic paper and preparation method of electronic ink |
| US9632388B2 (en) | 2013-12-19 | 2017-04-25 | Boe Technology Group Co., Ltd. | Electronic ink, electronic paper and method for preparing electronic ink |
| CN105334643A (en) * | 2015-11-17 | 2016-02-17 | 深圳市国华光电科技有限公司 | Intelligent glass |
| CN113662247A (en) * | 2021-09-08 | 2021-11-19 | 湖北中烟工业有限责任公司 | Water-exploded bead core liquid and preparation method thereof |
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| CN100500774C (en) | 2009-06-17 |
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