CN1228401C - Prepn of green electronic ink - Google Patents
Prepn of green electronic ink Download PDFInfo
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- CN1228401C CN1228401C CN 02139591 CN02139591A CN1228401C CN 1228401 C CN1228401 C CN 1228401C CN 02139591 CN02139591 CN 02139591 CN 02139591 A CN02139591 A CN 02139591A CN 1228401 C CN1228401 C CN 1228401C
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Abstract
The present invention provides an electric ink, namely a micro-encapsulation electrophoretic display material. Fine paticles and organic solution are wrapped in a microcapsule, and an electrophoretic display principle is utilized to realize electrophoretic 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 provides a preparation method for a green electronic ink, particularly a preparation method for a green electronic ink for flexible, or flat plate display. The present invention uses stearin amine modification pigment green G (cupric chloride dihydrate phthalocyanine) as pigment granules, uses tetrachloroethylene as a solvent and uses Span-80 as a surface active agent, and capsule core solution is obtained through ultrasonic dispersion; thiourea and formalin solution is used as wall materials, the microcapsule is prepared by an in-situ polymerization method, and a green electronic ink is obtained. The microcapsule prepared by the method is transparent and firm, and the grain size of the microcapsule is 30 to 80 microns.
Description
Technical field the present invention relates to the preparation method of environment-friendly electronic ink, particularly is used for the environment-friendly electronic ink preparation method of flexibility or flat pannel display.
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.
Summary of the invention the present invention seeks to be provided for the preparation method of the environment-friendly electronic ink of flexibility or flat pannel display, be granules of pigments promptly with the modified chlorinated copper phthalocyanine of stearylamine, zellon is an organic solvent, and to adopt urea-formaldehyde resin be the wall material by being that polymerization prepares electron ink microcapsule originally.Its main contents comprise the selection and the preparation method of material.Comprise veridian and surface modification thereof, base fluid and additive, microcapsule wall material and polymerization process, flexible parent metal etc. in the material.The preparation method mainly contains the surface modification of granules of pigments, the preparation of microcapsule etc.
Veridian adopts organic or inorganic pigment, and mineral dye can use but be not limited to iron oxide green; Pigment dyestuff can use but be not limited to phthalocyanines, triarylmethane compound and azo-type metal complex pigment etc., as chlorinated copper phthalocyanine (being commonly called as Phthalocyanine Green G), cupric bromide phthalocyanine (being commonly called as phthalocyanine green 3G).
Utilize inorganics or superpolymer film that granules of pigments is carried out surface modification.Mineral-modified dose can be used but be not limited to titanium dioxide, silicon-dioxide, aluminium sesquioxide, barium titanate etc.Organic modifiers can use but be not limited to polyethylene, polypropylene, polystyrene, tetrafluoroethylene, ABS plastic, polycarbonate, poly-inclined to one side tetrafluoroethylene, polyvinyl chloride, polymethylmethacrylate, urethane, polysiloxane, polymeric amide, ethyl cellulose, polyester etc., and titanate coupling agent, silane coupling agent.In addition, can also use anion surfactant, cats product, polymeric surface active agent etc., as uncle's ammonium salt, alkyl trimethyl ammonium salt, alkyl polyoxyethylene amine, stearate, sylvate, alkyl polyoxyethylene vitriol, sulfonated, sulfonated lignin, alkylphosphonic, polyvinyl alcohol etc.
The method of modifying of granules of pigments has: physics and chemisorption, letex polymerization, in-situ polymerization, single cohesion and complex coacervation etc.
Base fluid adopts organic solvent, can be a kind of, and also two or more solvent complex is to obtain the solvent with the particle Performance Match.Can select aliphatic hydrocarbon, halohydrocarbon, aromatic hydrocarbon, epoxy compounds, siloxanes etc. for use.Additive has tensio-active agent, charge control agent, stablizer etc.
Aliphatic hydrocarbon can use but be not limited to heptane, isoheptane, octane, octane-iso, nonane, decane, undecane, dodecane, tridecane etc.; Aromatic hydrocarbons can use but be not limited to toluene, ethylbenzene, o-Xylol, dodecylbenzene, butyl phenyl ether, butylbenzene, sec-butylbenzene, isobutyl-benzene, naphthalene etc.; Halocarbon can use but be not limited to methylene bromide, glycol dibromide, tetracol phenixin, tetrabromoethane, tetrafluorodibromoethane, trifluorochloroethylene, zellon etc.; Epoxy compounds can use but be not limited to 1,3-dioxane etc.; Siloxanes can use but be not limited to dimethyl siloxane etc.
Tensio-active agent can use nonionogenic tenside, amphoterics etc., as polyoxyethylene fatty acid ester, Voranol EP 2001 class, sorbitan fatty acid ester, sucrose fatty ester, polyglycerol fatty acid ester, N-alkyl-β-An Jibingsuan, N-alkyl sulfonation trimethyl-glycine, N-alkane hydroxyl sulfonation trimethyl-glycine, Yelkin TTS etc.
Charge control agent can be organic sulfate or sulfonate, metallic soap, organic amide, organophosphate or phosphoric acid ester, can also be polymkeric substance and block or graft copolymer and their monomer.
Adopt methods such as chemistry, physico-chemical processes to prepare microcapsule.Chemical method has in-situ polymerization, interfacial polymerization, letex polymerization etc., and physico-chemical processes has single cohesion, complex coacervation, is separated etc.; Operable wall material has water-soluble polymers, oil-soluble polymers, thermosetting polymer, thermal plastic polymer, polyureas, polyamine, urea-formaldehyde resin, Mierocrystalline cellulose and polymkeric substance such as derivative, polyvinyl alcohol thereof.
The spendable polymkeric substance of situ aggregation method has phenol-formaldehyde resin, melamine-formaldehyde resin, urea-formaldehyde resin etc.; Interfacial polymerization can use urethane, polymeric amide, polyureas, polycarbonate, poly(lactic acid), polybutylcyanoacrylate, poly-isobutyl--cyanoacrylate etc.; Emulsion polymerization can be used polymethylmethacrylate, polybutylcyanoacrylate, polystyrene, polyvinyl pyridine, polyacrylic acid and derivative thereof etc.; Polyvinyl alcohol, gelatin, methylcellulose gum, carboxymethyl cellulose, sulfonated polystyrene, phenylethylene-maleic anhydride list coacervation; Gelatin gum arabic complex coacervation etc.
Flexible parent metal adopts organic plastics, as polyethylene, polypropylene, polyimide, polymeric amide, urethane, poly-terephthalic acid-ethylene glycol etc.
Embodiment the present invention is an example to adopt situ aggregation method to prepare the environment-friendly electronic ink micro capsule, and the preparation method of environment-friendly electronic ink is described.With the above grade raw material of chemical pure: chlorinated copper phthalocyanine is a granules of pigments, and zellon is an organic solvent; Thiocarbamide and mass percent are that 37% formalin is a raw material, and hydrochloric acid is catalyzer, 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 stearylamine: dehydrated alcohol=1: 5000～10000, chlorinated copper phthalocyanine: zellon: water: thiocarbamide: formaldehyde=0.9～1.1: 240: 1500～2500: 25: 25.
At first, chlorinated copper phthalocyanine is carried out surface modification, a certain amount of stearylamine is dissolved in the dehydrated alcohol, add the chlorinated copper phthalocyanine particle, ultra-sonic dispersion number minute stirred 12～48 hours, made stearylamine be adsorbed on the chlorinated copper phthalocyanine particle surface, filter and drying, promptly obtain the modified chlorinated copper phthalocyanine particle of stearylamine.Then, be dispersion agent with Span80, will through the chlorinated copper phthalocyanine 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 ℃ of following reactions in 1 hour; The distilled water of performed polymer and 2～25 times of volumes is mixed, add capsule heart solution, stirred 2～40 minutes fast, the capsule heart is disperseed, regulating pH with hydrochloric acid then is 1～5, reaction is 2 hours under stirring at room, and elevated temperature to 60～90 ℃ following curing 2 hours obtained coating the microcapsule emulsion of chlorinated copper phthalocyanine and zellon.At last, with reacted emulsion filtration, washing, dry, screening, obtain the environment-friendly electronic ink micro capsule of certain range scale.
Concrete enforcement of the present invention is described in detail by following examples:
Embodiment: (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 7～8, 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 modified chlorinated copper phthalocyanines of stearylamine) is added and stirring fast, disperseed 5～20 minutes, making capsule heart droplet dia is 30～80 microns.Regulating pH value is 3～3.5, react 1.5～2 hours, and is warming up to 60 ℃, react 2 hours, obtains microcapsule emulsion, and cooling is filtered, and washing, drying are also sieved, and obtains capsule grain diameter and be 30～80 microns environment-friendly electronic ink.
Claims (3)
1. the preparation method of environment-friendly electronic ink, this material is to be granules of pigments with the chlorinated copper phthalocyanine, zellon is a base fluid, is that the wall material prepares the environment-friendly electronic ink micro capsule by situ aggregation method with the urea-formaldehyde resin; It is characterized in that: select for use stearylamine that pigment is implemented surface modification.
2. the preparation method of environment-friendly electronic ink according to claim 1, it is characterized in that: granules of pigments is to carry out surface modification by the stearylamine of chlorinated copper phthalocyanine through being dissolved in dehydrated alcohol to obtain, and the batching mass ratio is a stearylamine: dehydrated alcohol=1: 5000～10000.
3. the preparation method of environment-friendly electronic ink according to claim 1 is characterized in that preparation technology may further comprise the steps:
(1) selecting chlorinated copper phthalocyanine, zellon, thiocarbamide, formaldehyde solution for use is raw material; Distilled water is external phase; Trolamine, hydrochloric acid are the pH regulator agent; Span-80 is a tensio-active agent;
(2) the batching mass ratio is a chlorinated copper phthalocyanine: zellon: water: thiocarbamide: formaldehyde=0.9～1.1: 240: 1500～2500: 25: 25;
(3) stearylamine is dissolved in the dehydrated alcohol, and with the Phthalocyanine Green G ultra-sonic dispersion wherein, stirred under the room temperature 12～48 hours, filter and drying, obtain the modification Phthalocyanine Green G; The Phthalocyanine Green G ultra-sonic dispersion of surface modification in the zellon that contains Span-80, is obtained capsule heart solution;
(4) 0.5 gram thiocarbamide is dissolved in 1.4 milliliter 37% the formalin, regulating pH value with trolamine is 7～8, reacts 1 hour down at 80 ℃, obtains performed polymer; In distilled water, add dilute hydrochloric acid, to be mixed evenly after, add 3 milliliters of capsule heart solution and stir and be dispersed to required particle diameter fast; Add performed polymer, the pH value is 3～3.5;
(5) stirring reaction after two hours at room temperature, elevated temperature to 60 ℃, and stirring 1.5～2 hours obtains microcapsule emulsion, cooling, filter, washing, dry, screening, obtain particle diameter and be 30～80 microns environment-friendly electronic ink micro capsule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02139591 CN1228401C (en) | 2002-12-09 | 2002-12-09 | Prepn of green electronic ink |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02139591 CN1228401C (en) | 2002-12-09 | 2002-12-09 | Prepn of green electronic ink |
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| Publication Number | Publication Date |
|---|---|
| CN1506416A CN1506416A (en) | 2004-06-23 |
| CN1228401C true CN1228401C (en) | 2005-11-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 02139591 Expired - Fee Related CN1228401C (en) | 2002-12-09 | 2002-12-09 | Prepn of green electronic ink |
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Families Citing this family (6)
| 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 |
| CN102649038B (en) * | 2011-07-26 | 2014-06-25 | 京东方科技集团股份有限公司 | Preparation method of inorganic-organic composite electronic iron microcapsules |
| CN102649880B (en) * | 2012-02-14 | 2014-12-17 | 京东方科技集团股份有限公司 | Nanometer pigment and manufacturing method, electronic ink microcapsules and electrophoretic display device |
| CN103834285B (en) * | 2012-11-20 | 2016-05-11 | 广州奥翼电子科技有限公司 | Electrophoresis coating fluid and electrophoresis showed layer and their preparation method |
| CN103666020A (en) * | 2013-11-04 | 2014-03-26 | 铜陵市镜铁粉厂 | Nano iron oxide green for printing ink |
| CN115785721B (en) * | 2022-09-23 | 2023-08-01 | 中国人民解放军国防科技大学 | Composite coating based on zinc phthalocyanine microcapsule |
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