CN1216948C - Red electronic ink display material and its preparing technology - Google Patents
Red electronic ink display material and its preparing technology Download PDFInfo
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- CN1216948C CN1216948C CN 02139477 CN02139477A CN1216948C CN 1216948 C CN1216948 C CN 1216948C CN 02139477 CN02139477 CN 02139477 CN 02139477 A CN02139477 A CN 02139477A CN 1216948 C CN1216948 C CN 1216948C
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- red
- microcapsule
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- electronic ink
- zellon
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- Inks, Pencil-Leads, Or Crayons (AREA)
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Abstract
The present invention relates to a red display material of electronic ink and a preparation technique thereof, particularly to a red display material of electronic ink using nanometer red powder (phenylazo-2-hydroxy-3-neper formanilide) as pigment grains and a preparation technique thereof. The electronic ink is the electrophoresis display material of microcapsule, namely that fine grains of the pigment and a dye solution are wrapped in a microcapsule; an electrophoresis display principle is utilized to realize electrophoresis display in the microcapsule. The present invention has the advantages of strong visibility, low power consumption, portability, low manufacture cost, no electromagnetic radiation, etc. The present invention uses a heavy precipitation method to wrap a polyethylene film on the surface of nanometer red powder, uses tetrachloroethylene as a dispersion medium and uses Span-80 as a surface active agent, and a capsule core solution is obtained by ultrasonic dispersion; thiourea and a formalin are used as a wall material, an in-situ polymerization method is adopted to prepare the transparent and firm microcapsule of urea-formaldehyde resin, and the red display material of electronic ink is obtained. The grain size of the microcapsule prepared by the method is no larger than 100 microns, and the resolution of a display of electronic ink can be further improved.
Description
Technical field the present invention relates to a kind of red electric ink display material and technology of preparing thereof, is the red electric ink of granules of pigments with nanometer phenylazo-2-hydroxyl-3-naphthanilide (being commonly called as red) particularly.
The background technology electric ink is the micro encapsulation electrophoretic display technology, it is meant pigment particle and dye solution is wrapped in the microcapsule, utilize the electrophoresis showed principle, in micro-capsule, realize electrophoresis showed, thereby suppressed the electrophoresis micelle greater than shortcomings such as the reunion in the capsule range scale, depositions, improve its stability, increase the service life.Electric ink is a kind of suspended substance of ink shape, under External Electrical Field, can realize reversible, bistable state, the flexible demonstration, be a kind of flexible display material and technology, have good visuality, reduce power consumption, information and be written into strong, easy to carry, the advantages such as manufacturing process is cheap, electromagnetic-radiation-free of ability.Electric ink can only show the black and white color at present, and the demonstration of other any double-colored combination can't be carried out.The black and white two look demonstrations that had etc., mainly be that granules of pigments is scattered in the low-molecular-weight polyethylene of fused, obtain the layer of polyethylene film by spray-dired method on the surface of granules of pigments again, the one, reduce its density, the 2nd, make the granules of pigments surface charging, and electric field is made response.Utilize this method, higher to equipment requirements on the one hand, be to obtain the particle median size on the other hand at the granules of pigments more than 5 microns, this has limited the size (particle diameter is 30～300 microns) of electron ink microcapsule to a certain extent, thereby in the resolving power that has fundamentally limited electronic ink display.
Summary of the invention the object of the invention provides a kind of red electric ink display material, and its granules of pigments adopts the nanometer red, utilizes new organism film to its modification, can obtain the less red pigment particle of size distribution; Adopt situ aggregation method simultaneously, with the urea-formaldehyde resin is the wall material, the dispersion system of red particle and organic solvent (zellon) composition is coated, prepare the electron ink microcapsule that particle diameter is not more than 100 microns, thereby improve the resolving power of electronic ink display.Preparation is simple for this method, and reaction process is easy to control, and equipment is not had particular requirement.
Embodiment adopts situ aggregation method to prepare electron ink microcapsule.With the above grade raw material of chemical pure: red is a granules of pigments, and zellon is an organic solvent; Distilled water is external phase; Thiocarbamide and mass percent are that 37% formalin is a raw material, and trolamine, Glacial acetic acid and hydrochloric acid are the pH regulator agent, and OP-10 and Span-80 are tensio-active agent, and in-situ polymerization preparation at a certain temperature is the microcapsule of wall material with the urea-formaldehyde resin.The mass ratio of desired raw material is a polyethylene: hexanaphthene=1: 4800; Red: zellon: water: thiocarbamide: formaldehyde=0.9～1.1: 240: 1500～2500: 25: 25.
At first, modification is carried out on bright red part of surface, be about to a certain amount of low-molecular-weight polyethylene 60 ℃～80 ℃ following stirring and dissolving in hexanaphthene, after the cooling, add red particle and an amount of Si Ben-80 (Span-80), ultra-sonic dispersion number minute, stirring 4～12 hours, is precipitation agent with the dehydrated alcohol, with polyethylene reprecipitation and be wrapped in the red particle surface from cyclohexane solution, filter and drying, promptly obtain PE modified red particle.Then, will through the nanometer red ultra-sonic dispersion of surface modification in zellon as capsule heart solution.Thiocarbamide is dissolved in the formaldehyde solution by certain mol proportion, and regulating the pH value with trolamine is that the urea formaldehyde performed polymer was made in 7～8,60 ℃～90 ℃ following reactions in 1 hour; It is that 2～6,60 ℃～90 ℃ following reactions obtain transparent or slightly opaque thick liquid polycondensate that the performed polymer that obtains is regulated pH with Glacial acetic acid.Then, the distilled water of polycondensate and 2～25 times of volumes is mixed, add capsule heart solution, regulating pH with hydrochloric acid is 1～5, reaction is 4 hours under ℃ stirring of room temperature～90, has obtained coating the microcapsule emulsion of nanometer red and zellon.At last, with reacted emulsion high speed centrifugation 10 minutes,, obtain the microcapsule of certain range scale with absolute ethanol washing, drying, screening.
The present invention has made a kind of microcapsule particle diameter less than 100 microns electric ink by adopting the nanometer red.Preparation is simple, with low cost, and equipment is not had particular requirement, and the product separation process realizes easily.
Concrete enforcement of the present invention is described in detail by following examples:
Embodiment one: (using the urea formaldehyde performed polymer)
0.5 gram thiocarbamide is dissolved in 1.4 milliliter 37% the formalin, and regulating pH value with trolamine is 8, reacts 1 hour down at 80 ℃, obtains performed polymer.At room temperature add 25 ml distilled waters, capsule heart solution (containing 3 milliliters of zellons and 20 milligrams of reds) was disperseed 45 minutes.Regulating pH value is 2.5, and is warming up to 80 ℃, react 3 hours, cools off and stirs four hours, obtains microcapsule emulsion, centrifugal, with absolute ethanol washing drying also, obtains capsule grain diameter and be 0.5～4 micron electric ink.
Embodiment two: (using the urea formaldehyde polycondensate)
25 milligrams of polyethylene are dissolved in 150 milliliters of hexanaphthenes under 75 ℃～80 ℃, add 1 Span-80 then, and with 500 milligrams of red ultra-sonic dispersion wherein, stirred 8 hours under the room temperature, with dehydrated alcohol is precipitation agent, filters and drying, obtains the modification red.Get 6 milliliters of zellons, and add 10 Span-80 and 40 milligrams of reds through surface modification, ultra-sonic dispersion 5 minutes obtains capsule heart solution.1 gram thiocarbamide is dissolved in 2.8 milliliter 37% the formalin, and regulating pH value with trolamine is 8, reacts 1 hour down at 80 ℃, obtains performed polymer.Add the Glacial acetic acid about 0.25 milliliter again, regulating the pH value is 4, reacts 1 hour down at 75 ℃, obtains polycondensate.In 25 ml distilled waters, add 4 OP-10 and 3 mass percents and be 3 hydrochloric acid, to be mixed evenly after, add polycondensate again and obtain external phase, the pH value is about 3.At room temperature capsule heart solution is mixed with external phase, stir down elevated temperature to 55 ℃, react after four hours, cool off and stirred four hours, obtain microcapsule emulsion, centrifugal, with absolute ethanol washing and drying, obtain capsule grain diameter and be 1～10 micron electric ink.
Embodiment three:
Press the preparation process of embodiment two, regulate the add-on of OP-10 in the external phase, promptly add 3 OP-10 in 25 ml distilled waters, repeating said process, to obtain capsule grain diameter be 1～20 micron electric ink.
Embodiment four:
Press the preparation process of embodiment two, the add-on of OP-10 and hydrochloric acid in the adjusting external phase, promptly add 4 OP-10 and 1 mass percent and be 3 hydrochloric acid in 25 ml distilled waters, repeating said process, to obtain capsule grain diameter be 20～50 microns electric ink.
Claims (3)
1. red electric ink display material, the granules of pigments of this material is the phenylazo-2-hydroxyl-3-naphthanilide (being commonly called as red) of nanoscale, and dispersion medium is a zellon, and the wall material of microcapsule is a urea-formaldehyde resin; It is characterized in that: this display material is to be scattered in after the modification of polymkeric substance reprecipitation method in the zellon by urea-formaldehyde resin coating formation microcapsule by granules of pigments.
2. a kind of according to claim 1 red electric ink display material, it is characterized in that: granules of pigments is to be obtained with the polyethylene surface modification that is dissolved in hexanaphthene by nanometer phenylazo-2-hydroxyl-3-naphthanilide, and the batching mass ratio is a polyethylene: hexanaphthene=1: 4800.
3. a kind of according to claim 1 red electric ink display material is characterized in that preparation technology may further comprise the steps:
(1) selecting nanometer red, zellon, thiocarbamide, formaldehyde solution for use is raw material; Distilled water is external phase; Trolamine, Glacial acetic acid and hydrochloric acid are the pH regulator agent; OP-10 and Span-80 are tensio-active agent;
(2) the batching mass ratio is a red: zellon: water: thiocarbamide: formaldehyde=0.9～1.1: 240: 1500～2500: 25: 25;
(3) polyethylene being dissolved in the hexanaphthene under 75～80 ℃, adding Span-80 then, and with the red ultra-sonic dispersion wherein, stirred under the room temperature 4～12 hours, is precipitation agent with dehydrated alcohol, filters and drying, obtains the modification red; The red ultra-sonic dispersion of surface modification in zellon, is obtained capsule heart solution;
(4) a certain proportion of thiocarbamide is dissolved in 37% the formalin, regulating pH value with trolamine is 8, reacts 1 hour down at 80 ℃, obtains performed polymer; Be 4,75 ℃ with Glacial acetic acid adjusting pH value again and reacted 1 hour down, obtain polycondensate; In distilled water, add OP-10 and hydrochloric acid, to be mixed evenly after, add polycondensate and obtain external phase, the pH value is 3;
(5) at room temperature capsule heart solution is mixed with external phase, stir down elevated temperature to 55 ℃, react after four hours, cool off and stirred four hours, obtain microcapsule emulsion, centrifugal, with absolute ethanol washing and drying, promptly obtain red electric ink.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02139477 CN1216948C (en) | 2002-10-21 | 2002-10-21 | Red electronic ink display material and its preparing technology |
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|---|---|---|---|
| CN 02139477 CN1216948C (en) | 2002-10-21 | 2002-10-21 | Red electronic ink display material and its preparing technology |
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| Publication Number | Publication Date |
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| CN1491995A CN1491995A (en) | 2004-04-28 |
| CN1216948C true CN1216948C (en) | 2005-08-31 |
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| CN 02139477 Expired - Fee Related CN1216948C (en) | 2002-10-21 | 2002-10-21 | Red electronic ink display material and its preparing technology |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404119C (en) * | 2004-11-03 | 2008-07-23 | 西北工业大学 | Method for preparing quasi-uniform electronic ink micro capsule |
| 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 |
| CN101100571B (en) * | 2007-04-30 | 2012-11-21 | 北京印刷学院 | Electrophoresis display electronic ink |
| CN101633807B (en) * | 2009-08-19 | 2011-09-28 | 郭振荣 | Method for preparing reactive pigment ink with protective group and HDI prepolymer protected by aqueous epsilon-caprolactone |
| CN101819368B (en) * | 2010-04-21 | 2011-06-29 | 天津大学 | Red and white electronic ink microcapsule and preparation method thereof |
| CN102093785B (en) * | 2010-12-20 | 2013-12-11 | 广州奥熠电子科技有限公司 | Electrophoretic display coating fluid and preparation method thereof |
| CN102585676B (en) * | 2011-01-05 | 2014-02-26 | 广州奥熠电子科技有限公司 | Electrophoretic display coating liquid and preparation method thereof |
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2002
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