CN101441382B - One-step cover closing method of electronic paper micro-cup and cover closing material - Google Patents
One-step cover closing method of electronic paper micro-cup and cover closing material Download PDFInfo
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- CN101441382B CN101441382B CN2007101776522A CN200710177652A CN101441382B CN 101441382 B CN101441382 B CN 101441382B CN 2007101776522 A CN2007101776522 A CN 2007101776522A CN 200710177652 A CN200710177652 A CN 200710177652A CN 101441382 B CN101441382 B CN 101441382B
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Abstract
The invention relates to an electronic paper micro-cup, in particular to a method for the one-step sealing of the electronic paper micro-cup on flexible basal material in solvent with strong dissolution or swelling such as tetrachlorethylene, and sealing material thereof. According to the invention, unsaturated acrylic ester derivatives are taken as main material to prepare sealing glue liquor together with oligomers, monomers, a photoinitiator, a modifier, a surfactant and conductive material. The sealing glue liquor is mixed with pigment dispersing liquor according to certain proportion and is used for completing the sealing through emulsification and dispersion, delamination, and photo solidification. The sealing thickness can be accurately controlled through the volumetric ratio of the sealing glue liquor and the pigment dispersing liquor. The invention can not only be suitable for sealing electronic ink or liquid crystal to realize flexible or rigid plate display, but also be used for the micro-flow control, cell or tissue culture, synthesis and preparation in the fields of biology, medicine and chemistry.
Description
Technical field
The present invention relates to the electric paper micro-cup of flat pannel display, particularly in the solvent of strong dissolving such as zellon or swelling, realize an one-step cover closing method and the cover closing material of electric paper micro-cup on the flexible parent metal.
Background technology
Electrophoretic display device (EPD) (EPD) is commonly called as Electronic Paper, compare with other flat pannel display, have plurality of advantages, as read comfortable, contrast is high, bistable state power consumption low (outage keep show), high resolving power (＞200dpi), frivolous (0.5 millimeter of thickness), substrate extensively (can flexiblely show), wide viewing angle (180 degree); Thereby have wide practical use, not only will write down relevant industries and bring revolutionary variation, and can hold in e-book, library automation, low consumption and to have wide and profound application prospect aspect display, large-scale outdoor billboard and the folding display device information.
The process that enters the practical stage comparative maturity at present has microcapsules electrophoretype (U.S. Pat 5961804 and the US 5930026 of U.S. E-INK (electric ink) company), little glass of electrophoretype (US20030063370), electronics powder fluid type, cholesteric liquid crystal formation.
The electrophoresis showed ultimate principle: in tiny area (microcapsules or little cup), under direct-current drive between two electrodes (transparency electrode, drive electrode), electrophoretic migration takes place and shows corresponding color in charged particulate (granules of pigments or filler).
There is problems such as easily breaking, wear out, the life-span lacks in microcapsules (US 6017584) because solvent resistance, mechanical property, size and homogeneity are difficult to controlledly, and manufacture difficulty is big; Because little glass of controllable size, material property is stable, has overcome the shortcoming of microcapsules effectively; And because little glass restriction, disturbance reduces greatly to external world, the structure of easier reaching " bistable "; The charge control agent that adds does not lose the electric density that has promptly improved electrophoresis particle, and electrophoresis particle can all accumulate in display plane, has improved contrast.Because wall thickness can be adjusted between little cup, has improved withstand voltage, scratch resistance performance greatly.The method of this little cup-shaped one-tenth is just receiving increasing concern because of its distinctive performance and comparatively practicable production technology.
The Electronic Paper of U.S.'s SiPix Imaging (image) company is to adopt principle of electrophoresis to show in little cup structure; Little glass capping technology is (a United States Patent (USP) 20030063370,20030179437) adopt cover closing material to solidify through means such as illumination, heating, interfacial polymerization or humidity variations, realization is to the capping of the colorant dispersion liquid system of the pigment dye that contains fluorous solvent and fluorination treatment, finishes red, green, blue, black, white, golden multicolor displaying; Described cover closing material is that (methyl) acrylate, cyanoacrylate, vinyl ether, epoxy compound, isocyanates, allyl alcohol etc. have one or more materials in the polymkeric substance of crosslinkable groups.
Contain fluorous solvent and can be used as electrophoretic medium, for example the HT-200 (Ausimont), the FC-43 (Minnesota Mining and Manufacturing Company) that are adopted of U.S. SiPix Imaging (image) company, dichloro trifluoro-benzene etc. are finished little glass of capping; Yet cost an arm and a leg owing to contain fluorous solvent, and need carry out extraordinary processing, make it coupling electrodeposition paint pigments or dyestuff; For example (United States Patent (USP) 20030063370) used colorant such as Chen Xianhai is the phthalocyanine dye of fluoridizing (Minnesota Mining and Manufacturing Company), and with fluorine-containing or perfluoro solvent HT-200 (Ausimont); Liang, Rong-Chang etc. 20030179437 (United States Patent (USP)).
With to contain fluorous solvent different, zellon is a kind of good inexpensive solvent, and its polarity is little, the big (1.6g/cm of density
3), boiling point height, freezing point are suitable, viscosity is little, multiple colorant is had good dispersiveness, electrophoretic velocity is fast; Adapt to the big titania of density (3.8 or 4.2g/cm
3) dispersion and electrophoresis, adapt to also that the little oiliness of density is red, the dispersion and the electrophoresis of various conventional dye pigment systems such as oiliness is blue, phthalocyanine dye, carbon black.
Yet it is the problem that needs solve that zellon is carried out capping as the electric paper micro-cup system of electrophoretic medium.Do not report also that at present both at home and abroad a kind of method can carry out the colorant dispersion liquid as electrophoretic medium such as zellon can and seal with the top layer in little cup of array.
Tetrafluoroethene has following difficult point as the capping of the electric paper micro-cup of electrophoretic medium:
1. for prevent little glass of internal material be cross-linked with each other and contraction causes little cup structure very frangible, the Xianhai Chen of U.S.'s SiPix Imaging (image) company etc. are the stiffness that 8%～15% elastomeric material (as SBR, PBR, NBR etc.) has effectively improved little glass of array by add mass concentration in thermosetting plastic; But because dissolving or swelling can take place in used elastomeric material in the zellon equal solvent, so be not suitable for the capping of the colorant dispersion liquid system that contains zellon.
2. U.S. SiPix Imaging (image) company is used contains fluorous solvent etc., not miscible with the glue of most unsaturated acid ester classes as HT-200 (Ausimont), FC-43, dichloro trifluoro-benzene etc., is easy to capping.
3. zellon is with above-mentioned to contain fluorous solvent different, and it and most of unsaturated acid ester class glue are miscible, under this miscible state, or do not solidify, or whole little glass of inner curing, top layer curing can only not take place; And because the good dissolubility of zellon, can dissolved fat, oils, rubber, natural resin, most of synthetic resin and aromatic organic acid, even take place crosslinked or polymerization and solidifying, postpone for a long time also can be dissolved gradually with forming capping layer; Because the volatility and the strong solubility of zellon, means such as the heating that U.S.'s SiPix Imaging (image) company is adopted, interfacial polymerization or humidity variation are that the colorant dispersion liquid of electrophoretic medium is cured capping and is difficult to implement to zellon in little cup.
4. domestic be engaged in many with Electronic Paper, research that electronic ink is relevant, yet great majority are to imitate company (020139592.6) such as E-ink to do the research of microcapsules aspect, Wang of Zhejiang University is boundless and indistinct, Chen Hongzheng etc. carries out the Primary Study of little glass made from epoxy acrylate on glass baseplate, and flexible parent metal, little glass of capping aspect report not.
The present invention optimizes compound by solvent-proof unsaturated acid ester system, light trigger, auxiliary agent, adopt a step capping method that the electric paper micro-cup unit is carried out capping.Realize the sealing of fast hierarchical and photocuring; Capping layer controllable thickness after the curing, no bubble can stop with the volatilization of tolerance zellon etc. and corrode with swelling, has than stiff stability.
Summary of the invention
The purpose of this invention is to provide the employing UV-curing technology, behind electric paper micro-cup unit can colorant dispersion liquid, implement an one-step cover closing method of electric paper micro-cup.
Another object of the present invention provides the cover closing material that is used for electric paper micro-cup.
The present invention is based on undersaturated acrylate derivative, be mixed with the capping glue with oligomer, monomer, light trigger, modifier, surfactant, conductive material, and with colorant dispersion liquid with certain proportion mix, emulsification dispersion, layering, photocuring finish capping, its thickness is accurately controlled by the volume ratio of capping glue and colorant dispersion liquid.
The present invention is scattered in cover closing material earlier to form mixed liquor in the colorant dispersion liquid in advance, layering rapidly behind the liquid filling electric paper micro-cup to be mixed, and cover closing material floats on the top layer, is light-cured into the capping film at last, and this method may further comprise the steps:
1) preparation capping glue: is to mix 1～30 minute under 0～90 ℃ of lucifuge condition oligomer, monomer, light trigger, modifier, surfactant, conductive material in temperature; Oligomer is that 0～50wt%, monomer are that 10～90wt%, light trigger are that 0.5～5wt%, modifier are that 1～30wt%, surfactant are that 0.2～15wt%, conductive material are 0～50wt% in the described mixed liquor;
2) mixing of capping glue and colorant dispersion liquid: temperature for-25～25 ℃ of conditions under, capping glue that step 1) is obtained and colorant dispersion liquid are to mix in 1: 1～1: 10 to obtain mixed liquor with volume ratio, mixing time is 2～10 minutes; Used colorant dispersion liquid can be the pigment, dyestuff of any commercialization and modification solution or the suspending liquid with arbitrary proportion mixing gained;
3) can mixed liquor: with step 2) mixed liquor that obtains pours in the electric paper micro-cup array on the base material, and described canning means is a kind of methods wherein such as frictioning, dip-coating, spraying, spin coating; The can temperature is-25～25 ℃.
4) standing demix: the base material with electric paper micro-cup array of the glue of filling and capping that step 3) is obtained and the mixed liquor of colorant dispersion liquid left standstill 2～80 seconds at-25～25 ℃, the mixed liquor generation layering in the electric paper micro-cup, and the capping glue floats on the top layer;
5) formation of capping layer: step 4) is left standstill the base material with electric paper micro-cup array that layering takes place in the back, under the uviol lamp of 50～3000W, exposed 5～600 seconds, the capping glue obtains capping layer through photocuring; Used uviol lamp is a kind of in high-pressure sodium lamp, low pressure mercury lamp, the Iodine gallium light etc.
The thickness of described capping layer is 5～20 μ m.
Described base material is silicon substrate, glass baseplate, ITO (tin indium oxide) base material, polyethylene terephthalate (PET) base material, Polyvinylchloride (PVC) base material or polycarbonate (PC) base material.
The cover closing material that is used for electric paper micro-cup of the present invention is the mixed liquor of oligomer, monomer, light trigger, modifier, surfactant, conductive material, wherein, oligomer is that 0～50wt%, monomer are that 10～90wt%, light trigger are that 0.5～5wt%, modifier are that 1～30wt%, surfactant are that 0.2～15wt%, conductive material are 0～50wt% in the mixed liquor.
Described oligomer is the condensate of commercial acrylate, the acrylic polymer of modification or their any mixture.Wherein acrylic ester unit has one or more in the following array structure: 1. contain the structure and/or the ammonium salt structure of acid in the molecule, the acid number scope is 20～400; The structure of the acid that it is contained is one or more in monobasic or polybasic carboxylic acid, sulfonic acid, phosphoric acid, the phosphonic acids; Its contained ammonium salt structure is one or more in the structural units such as monobasic or polybasic carboxylic acid ammonium, ammonium sulphonate, ammonium phosphate, phosphonic acids ammonium; 2. contain in aryl, alkyl, alkoxy, amido, the amino ester segmented structure one or more in the molecule; Described aryl is the phenyl or naphthyl of phenyl, alkyl replacement etc.; Described alkyl chain length is C
1～C
303. molecular structure is one or more in bisphenol A epoxy acrylate, bisphenol-A epoxy methacrylate, phenolic aldehyde epoxy acrylate, phenolic aldehyde epoxy methacrylates, acrylate containing silicone, silicon-containing methacrylate copolymer, urethane acrylate, urethane methacrylate, fluorine-containing or perfluorinated acrylate, the fluorine-containing or perfluoro-methyl acrylic ester array structure, contains in element silicon, fluorine element, epoxide group or the polyurethanyl group one or more in its structure; 4. have 1～6 unsaturated link in the molecule, described unsaturated link structure is one or more in carbon-carbon double bond, carbon-carbon triple bond, carbon-to-nitrogen double bon, the two keys of carbon oxygen etc.
Described monomer is the acrylate of commercial acrylate, modification or their any mixture.Wherein have in the following array structure one or more in the acrylate molecular structure: 1. contain the structure and/or the ammonium salt structure of acid in the molecule, the acid number scope is 20～400; The structure of the acid that it is contained is one or more in monobasic or polybasic carboxylic acid, sulfonic acid, phosphoric acid, the phosphonic acids; Its contained ammonium salt structure is one or more in the structural units such as monobasic or polybasic carboxylic acid ammonium, ammonium sulphonate, ammonium phosphate, phosphonic acids ammonium; 2. contain in aryl, alkyl, alkoxy, amido, the amino ester segmented structure one or more in the molecule; Described aryl is the phenyl or naphthyl of phenyl, alkyl replacement etc.; Described alkyl chain length is C
1～C
303. molecular structure is one or more in bisphenol A epoxy acrylate, bisphenol-A epoxy methacrylate, phenolic aldehyde epoxy acrylate, phenolic aldehyde epoxy methacrylates, acrylate containing silicone, silicon-containing methacrylate copolymer, urethane acrylate, urethane methacrylate, fluorine-containing or perfluorinated acrylate, the fluorine-containing or perfluoro-methyl acrylic ester array structure, contains in element silicon, fluorine element, epoxide group or the polyurethanyl group one or more in its structure; 4. have 1～6 unsaturated link in the molecule, described unsaturated link structure is one or more in carbon-carbon double bond, carbon-carbon triple bond, carbon-to-nitrogen double bon, the two keys of carbon oxygen etc.
Described light trigger is commercial radical photoinitiator, and described radical photoinitiator is one or more the potpourri in alpha-hydroxyalkyl benzophenone type, α-amine alkyl phenones type, dialkoxy acetophenone type, acylphosphine oxide, benzophenone, the thioxanthone.
Described modifier is one or more materials in commercial acrylate, acid anhydrides, the amine; Described acrylate is one or more in hydroxy-ethyl acrylate, hydroxyethyl methylacrylate, the polymerizable acrylic ester; Described acid anhydrides is one or more in maleic anhydride, phthalic anhydride, THPA, HHPA, the glutaric anhydride; Described amine is one or more in the alkyl acrylate of acrylate, amine modification of the diethanolamine that replaces of triethanolamine, alkyl, amine modification; Wherein said alkyl is C
1～C
30Alkyl.
Described surfactant is one or more in commercial macromolecule dispersing agent, acrylic polyol, methacrylic acid polyvalent alcohol, coupling agent, the siliceous or fluorochemical surfactant, play levelling, dispersion, froth breaking, emulsification, can effectively the emulsification of capping glue be disperseed, improve capping glue surface property; Described coupling agent be silane coupling agent, titanate coupling agent, aluminate coupling agent or they arbitrarily than potpourri.
Described macromolecule dispersing agent is commercial molecular weight greater than 10000 less than 3000000 alkane hydroxyl amino acid amides, the interpolymer of carboxylic acid and acrylate, acrylate interpolymer, the polyaminoamide solution of cationic unsaturated polybasic carboxylic acid, the alkylammonium salt solution of acidic polymer, after the polymerization molecular weight greater than 10000 less than 3000000 the polyester and the block copolymerization liquid solution of acrylate, after the polymerization molecular weight greater than 5000 less than in 3000000 the fluorine-containing or siliceous polymkeric substance one or more; Wherein said alkyl is C
1～C
30Alkyl.
Described conductive material is the metal of nano-micro level, metal oxide, organic conductive macromolecule or their compound substance of nano-micro level.The pattern of conductive material is but is not limited in Powdered, spheroid, sheet, bar-shaped, tubulose, two dimension such as netted, hollow, mesoporous and/or the three-dimensional structure one or more, is used to improve the capping layer electric conductivity.
The metal of described nano-micro level is that density is 0.8～1.5g/cm
3, particle diameter is that one or more materials in the aluminium powder, silver powder, copper powder etc. of 50～5000nm are compound.
Described metal oxide is that density is 0.8～1.5g/cm
3, particle diameter is that one or more materials in the tin indium oxide (ITO), zinc paste, tin ash, indium oxide, silicon dioxide, titania etc. of 50～5000nm are compound.
Described organic conductive macromolecule is commercial polyaniline, polyaniline derivative, polythiophene, polythiofuran derivative, polypyrrole or polypyrrole derivant.
The characteristics of electric paper micro-cup one step capping of the present invention:
1. the photo-curing material and other reagent that are used for the electric paper micro-cup capping all have commodity to purchase at home, and photo-curing material is cheap and easy to get.
2. equipment is inexpensive, normal-temperature operation, and method is simple and easy fast, available exposure commonly used, coating apparatus, light sources such as UV-lamp, mercury lamp all can.
3. because the interaction of surfactant and monomer, oligomer makes the capping glue be easy to emulsification, in colorant dispersion liquid, be uniformly dispersed, be convenient to coating technique.
4. because monomer and oligomer structure are not soluble in organic solvent (as zellon), and density is less, and layering is rapid, owing to contain the unsaturated link of polyfunctionality, is easy to quick curing again, and the top layer is solidified rapid, long-term anti-nip.
5. be applicable to electrophoretic mediums such as the capping of multiple solvent as the electric paper micro-cup of electrophoretic medium, particularly zellon, toluene, dimethylbenzene, cyclohexanone, cyclohexane, tetrahydrofuran, dichloro hexane, FC-40 (Minnesota Mining and Manufacturing Company), FC-43 (Minnesota Mining and Manufacturing Company), dichloro trifluoro-benzene.
6. since have in the used molecular structure give material flexibility, what have gives material stiffness, adjusts the ratio between them, takes into account flexibility and rigidity, the wall material of cover closing material and electric paper micro-cup adheres to by force, and the favorable mechanical performance is arranged.
7. the thickness of capping layer can obtain the thick capping layer of 5～20 μ m by the volume ratio control of capping glue and colorant dispersion liquid.
8. owing to contain conductive material in the cover closing material, the conductive material marshalling is regular, interconnect, so capping layer has excellent conducting performance, helps the electrophoresis showed of Electronic Paper.
The present invention is not only applicable to capping electric ink or liquid crystal and realizes the flexibility or rigidity flat pannel display, can be used for the micro-fluidic of biology, medicine, chemical field yet, and cell or tissue is cultivated, aspects such as synthetic preparation.
Description of drawings
Fig. 1. the emulsification mixed liquor stage synoptic diagram in the electric paper micro-cup one step capping flow process of the present invention.
Fig. 2. little glass of array synoptic diagram before the can in the electric paper micro-cup one step capping flow process of the present invention.
Fig. 3. the mixed liquor can stage synoptic diagram in the electric paper micro-cup one step capping flow process of the present invention.
Fig. 4. standing demix stage synoptic diagram after the can in the electric paper micro-cup one step capping flow process of the present invention.
Fig. 5. the capping layer in the electric paper micro-cup one step capping flow process of the present invention forms synoptic diagram.
Reference numeral
1. mixed liquor 2. electric paper micro-cups 3. base materials
4. capping glue 5. colorant dispersion liquids 6. capping layers
Embodiment
The present invention is described further below by specific embodiment.
See also Fig. 1～5.
In the capping glue: light trigger: 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, concentration is 0.5wt%, 2-(4-(2-hydroxy-2-methyl propoxyl group) phenoxy group) acetate, concentration is 0.5wt%, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, concentration is 1wt%, monomer: the methacrylate of maleic anhydride modified, concentration is 8wt%, the methacrylate phosphate, concentration is 3wt%, polyglycol (600) acrylate, concentration is 2wt%, two trimethylolpropene tetraacrylate, concentration is 2wt%, oligomer: SB401 (aromatic acid methacrylic acid half ester) (U.S. Sartomer company), concentration is 5wt%, CN966 (amino ester/acrylate) (U.S. Sartomer company), concentration is 10wt%, conductive material: the hollow aluminium powder of the sheet of 5 μ m, concentration is 50wt%, surfactant: CD9051 (acrylate that contains three unsaturated carbon-carbon double bonds) (U.S. Sartomer company), concentration is 4wt%, BYK115 (molecular weight with pigment affinity groups greater than 10000 less than 3000000 high molecular block copolymerization liquid solution) (German Bi Ke chemical company), concentration is 2wt%, BYK300 (molecular weight is greater than 10000 solution less than 3000000 polyether-modified dimethyl silicone polymer interpolymer) (German Bi Ke chemical company), concentration is 2wt%, modifier: methyldiethanolamine, concentration is 10wt%, and lucifuge stirred 10 minutes under the room temperature;
In 25 ℃ capping glue 4 is mixed with volume ratio with colorant dispersion liquid 5 at 1: 4, stirred 10 minutes under the room temperature, obtain mixed liquor 1;
Scrape fast in the high electric paper micro-cup 2 of 100 μ m on the base material 3 in 25 ℃ of mixed liquor 1 usefulness steel wire scrapers, left standstill 20 seconds in 25 ℃ capping glue and colorant dispersion liquid, in the exposure 600 seconds down of 1000W high-pressure sodium lamp, the thick capping layer 6 of 20 μ m.
With driving circuit and little glass of applying of capping, finish the assembling of whole principle device.
See also Fig. 1～5.
In the capping glue: light trigger: 2-hydroxyl-1-(4-(2-hydroxyl-oxethyl) phenyl)-2-methyl-propyl-1-ketone, concentration is 0.5wt%, 1-hydroxy-cyclohexyl phenyl ketone, concentration is 0.5wt%, monomer: polyglycol (200) acrylate, concentration is 5wt%, glycerine triol triacrylate, concentration is 3wt%, the ethylene glycol double methyl methacrylate, concentration is 2wt%, oligomer: EB2002 (soluble polyurethane acrylate, the special company of U.S.'s cyanogen), concentration is 30wt%, CN2256 (water-soluble polyester acrylic acid, U.S. Sartomer company), concentration is 10wt%, CN972 (the amino ester acrylate of aromatic series) (U.S. Sartomer company), concentration is 10wt%, the silver-plated silica spheres of the sheet of conductive material: 500nm, concentration is 10wt%, polyaniline, concentration is 10wt%, surfactant: silane coupling agent 570, concentration is 1wt%, BYK110 (German Bi Ke chemical company), concentration is 2wt%, BYK154 (molecular weight is greater than 10000 ammonium salt solutions less than 3000000 acrylate interpolymer) (German Bi Ke chemical company), concentration is 1wt%, modifier: dimethylamino ethyl benzoate, concentration is 10wt%, triethanolamine, concentration is 5wt%, and lucifuge stirred 10 minutes under the room temperature;
In 25 ℃ capping glue 4 is mixed with volume ratio with colorant dispersion liquid 5 at 1: 4, stirred 2 minutes under the room temperature, obtain mixed liquor 1;
Scrape in the high electric paper micro-cup 2 of 100 μ m on the base material 3 in 25 ℃ of mixed liquor 1 usefulness steel wire scrapers, left standstill 40 seconds in 0 ℃ capping glue and colorant dispersion liquid, in the exposure 300 seconds down of 1000W high-pressure sodium lamp, the thick capping layer 6 of 20 μ m.
With driving circuit and little glass of applying of capping, finish the assembling of whole principle device.
See also Fig. 1～5.
In the capping glue: light trigger: benzoin dimethylether, concentration is 1wt%, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, concentration is 1wt%, monomer: acrylic acid modified acrylate, concentration is 10wt%, isobornyl acrylate, concentration is 15wt%, two trimethylolpropene tetraacrylate, concentration is 20wt%, oligomer: PE55WN (water-soluble polyester acrylate, BASF Aktiengesellschaft), concentration is 25wt%, CN988 (U.S. Sartomer company), concentration is 7wt%, surfactant: CD9051 (acrylate that contains three unsaturated carbon-carbon double bonds in the molecule) (U.S. Sartomer company), concentration is 1wt%, BYK115 (German Bi Ke chemical company), concentration is 2wt%, BYK181 (molecular weight with anionic/nonionic feature is greater than 10000 solution less than 3000000 alkanol ammonium salt polymkeric substance) (German Bi Ke chemical company), concentration is 5wt%, modifier: glutaric anhydride, concentration is 5wt%, methyldiethanolamine, concentration is 5wt%, dimethylamino ethyl benzoate, concentration are 3wt%, and 60 ℃ of following lucifuges stirred 30 minutes;
In-25 ℃ capping glue 4 is mixed with volume ratio with colorant dispersion liquid 5 at 1: 5, stirred 5 minutes under the room temperature, obtain mixed liquor 1;
Scrape fast in the high electric paper micro-cup 2 of 60 μ m on the base material 3 in-25 ℃ of mixed liquor 1 usefulness steel wire scrapers, left standstill 5 seconds in-25 ℃ capping glue and colorant dispersion liquid, in the exposure 500 seconds down of 50W high-pressure sodium lamp, the thick capping layer 6 of 10 μ m.
With driving circuit and little glass of applying of capping, finish the assembling of whole principle device.
See also Fig. 1～5.
In the capping glue: light trigger: isopropyl thioxanthone, concentration is 0.8wt%, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, concentration is 0.5wt%, 2-hydroxyl-1-(4-(2-hydroxyethyl sulfydryl) phenyl)-2-methyl-propyl-1-ketone, concentration is 0.5wt%, monomer: polyglycol (200) acrylate, concentration is 20wt%, the methacrylate of glutaric anhydride modification, concentration is 30wt%, hot pentanediol double methacrylate, concentration is 20wt%, isobornyl acrylate, concentration is 20wt%, oligomer: SB520 (aromatic series acrylate) (U.S. Sartomer company), concentration is 0.1wt%, EM6225 (organic silicon polyether acrylate, Changxing, Taiwan chemical industry company limited), concentration is 0.1wt%, the hollow ping-pong ball of conductive material: 300nm, concentration is 6.8wt%, surfactant: BYK110 (molecular weight with acidic-group greater than 10000 less than 3000000 polymer copolymerization liquid solution) (German Bi Ke chemical company), concentration is 0.2 wt%, modifier: dimethylamino ethyl benzoate, concentration are 1wt%, and 90 ℃ of following lucifuges stirred 10 minutes;
In-5 ℃ capping glue 4 is mixed with volume ratio with colorant dispersion liquid 5 at 1: 9, stirred 10 minutes under the room temperature, obtain mixed liquor 1;
Scrape in the high electric paper micro-cup of 100 μ m on the base material 3 in-5 ℃ of mixed liquor 1 usefulness steel wire scrapers, left standstill 80 seconds in 0 ℃ capping glue and colorant dispersion liquid, in the exposure 60 seconds down of 1000W high-pressure sodium lamp, the thick capping layer 6 of 15 μ m.
With driving circuit and little glass of applying of capping, finish the assembling of whole principle device.
Embodiment 5
See also Fig. 1～5.
In the capping glue: light trigger: 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, concentration is 0.5wt%, monomer: isobornyl acrylate, concentration is 30wt%, double pentaerythritol C5 methacrylate, concentration is 20wt%, oligomer: EM6225 (Changxing, Taiwan chemical industry company limited), concentration is 5wt%, PE55WN (water-soluble polyester acrylate, BASF Aktiengesellschaft), concentration is 20wt%, CN970 (U.S. Sartomer company), concentration is 10wt%, surfactant: BYK500 (German Bi Ke chemical company), concentration is 2wt%, FC-500 (fluorochemical surfactant, Minnesota Mining and Manufacturing Company), concentration is 2wt%, modifier: methyldiethanolamine, concentration is 5.5wt%, the dimethylamino ethyl benzoate, concentration is 5%, lucifuge stirred 10 minutes under the room temperature;
In 25 ℃ capping glue 4 is mixed with volume ratio with colorant dispersion liquid 5 at 1: 5, stirred 10 minutes under the room temperature, obtain mixed liquor 1;
Scrape fast in the high electric paper micro-cup 2 of 60 μ m on the base material 3 in 0 ℃ of mixed liquor 1 usefulness steel wire scraper, left standstill 5 seconds in 0 ℃ capping glue and colorant dispersion liquid, in the exposure 300 seconds down of 100W high-pressure sodium lamp, the thick capping layer 6 of 10 μ m.
With driving circuit and little glass of applying of capping, finish the assembling of whole principle device.
See also Fig. 1～5.
In the capping glue: light trigger: 2, the 4-diethyl thioxanthone, concentration is 5wt%, monomer: isobornyl acrylate, concentration is 8wt%, pentaerythritol triacrylate, concentration is 10wt%, oligomer: SB401 (aromatic acid methacrylic acid half ester) (U.S. Sartomer company), concentration is 5wt%, IRR210 (the water-soluble acrylic ester that contains three unsaturated carbon-carbon double bonds in the molecule, the special company of U.S.'s cyanogen), concentration is 20wt%, CN963 (U.S. Sartomer company), concentration is 5wt%, the ITO powder of conductive material: 50nm, concentration is 2wt%, surfactant: CD9051 (acrylate that contains three unsaturated carbon-carbon double bonds) (U.S. Sartomer company), concentration is 5wt%, BYK057 (molecular weight greater than 10000 less than 3000000 polymer solution) (German Bi Ke chemical company), concentration is 5wt%, BYK183 (molecular weight of tool pigment affinity groups greater than 10000 less than 3000000 high molecular block copolymerization liquid solution) (German Bi Ke chemical company), concentration is 5wt%, modifier: triethanolamine, concentration is 15wt%, the dimethylamino ethyl benzoate, concentration is 15%, and lucifuge stirred 20 minutes under the room temperature;
In 25 ℃ capping glue 4 is mixed with volume ratio with colorant dispersion liquid 5 at 1: 9, stirred 2 minutes under the room temperature, obtain mixed liquor 1;
Scrape in the high electric paper micro-cup 2 of 100 μ m on the base material 3 in 25 ℃ of mixed liquor 1 usefulness steel wire scrapers, left standstill 30 seconds in 0 ℃ capping glue and colorant dispersion liquid, in the exposure 600 seconds down of 1000W high-pressure sodium lamp, the thick capping layer 6 of 10 μ m.
With driving circuit and little glass of applying of capping, finish the assembling of whole principle device.
Claims (6)
1. an one-step cover closing method of an electric paper micro-cup is cover closing material to be scattered in advance form mixed liquor in the colorant dispersion liquid, layering behind the liquid filling electric paper micro-cup to be mixed, and cover closing material floats on the top layer, is light-cured into the capping film at last, it is characterized in that:
1) preparation capping glue: with the condensate of acrylate, the oligomer of the acrylic polymer of modification or their potpourri, acrylate, the monomer of the acrylate of modification or their potpourri, the light trigger of free radical type, acrylate, acid anhydrides, the modifier of one or more materials in the amine, macromolecule dispersing agent, acrylic polyol, the methacrylic acid polyvalent alcohol, coupling agent, the surfactant of one or more in the siliceous or fluorochemical surfactant and the metal of nano-micro level, the metal oxide of nano-micro level, the conductive material of organic conductive macromolecule or their compound substance is to mix under 0～90 ℃ of lucifuge condition in temperature; Oligomer is that 0～50wt%, monomer are that 10～90wt%, light trigger are that 0.5～5wt%, modifier are that 1～30wt%, surfactant are that 0.2～15wt%, conductive material are 0～50wt% in the described mixed liquor;
2) mixing of capping glue and colorant dispersion liquid: temperature for-25～25 ℃ of conditions under, capping glue that step 1) is obtained and colorant dispersion liquid are to mix in 1: 1～1: 10 with volume ratio, obtain mixed liquor;
3) can mixed liquor: with step 2) mixed liquor that obtains pours in the electric paper micro-cup array on the base material; The can temperature is-25～25 ℃;
4) standing demix: the base material with electric paper micro-cup array of the glue of filling and capping that step 3) is obtained and the mixed liquor of colorant dispersion liquid leaves standstill at-25～25 ℃, the mixed liquor generation layering in the electric paper micro-cup, and the capping glue floats on the top layer;
5) formation of capping layer: step 4) is left standstill the base material with electric paper micro-cup array that layering takes place in the back, expose under ultraviolet light, the capping glue obtains capping layer through photocuring;
Acrylic ester unit in the condensate of described acrylate or the acrylic polymer of modification has one or more in the following array structure: 1. contain the structure and/or the ammonium salt structure of acid in the molecule, the acid number scope is 20～400; 2. contain in aryl, alkyl, alkoxy, amido, the amino ester segmented structure one or more in the molecule; 3. molecular structure is one or more in bisphenol A epoxy acrylate, bisphenol-A epoxy methacrylate, phenolic aldehyde epoxy acrylate, phenolic aldehyde epoxy methacrylates, acrylate containing silicone, silicon-containing methacrylate copolymer, urethane acrylate, urethane methacrylate, fluorine-containing or perfluorinated acrylate, the fluorine-containing or perfluoro-methyl acrylic ester array structure, contains in element silicon, fluorine element, epoxide group or the polyurethanyl group one or more in its structure; 4. have 1～6 unsaturated link in the molecule, described unsaturated link structure is one or more in carbon-carbon double bond, carbon-carbon triple bond, carbon-to-nitrogen double bon, the two keys of carbon oxygen;
Have in the following array structure one or more in the acrylate molecular structure in the described monomer: 1. contain the structure and/or the ammonium salt structure of acid in the molecule, the acid number scope is 20～400; 2. contain in aryl, alkyl, alkoxy, amido, the amino ester segmented structure one or more in the molecule; 3. molecular structure is one or more in bisphenol A epoxy acrylate, bisphenol-A epoxy methacrylate, phenolic aldehyde epoxy acrylate, phenolic aldehyde epoxy methacrylates, acrylate containing silicone, silicon-containing methacrylate copolymer, urethane acrylate, urethane methacrylate, fluorine-containing or perfluorinated acrylate, the fluorine-containing or perfluoro-methyl acrylic ester array structure, contains in element silicon, fluorine element, epoxide group or the polyurethanyl group one or more in its structure; 4. have 1～6 unsaturated link in the molecule, described unsaturated link structure is one or more in carbon-carbon double bond, carbon-carbon triple bond, carbon-to-nitrogen double bon, the two keys of carbon oxygen;
Described radical photoinitiator is one or more the potpourri in alpha-hydroxyalkyl benzophenone type, α-amine alkyl phenones type, dialkoxy acetophenone type, acylphosphine oxide, benzophenone, the thioxanthone;
Acrylate in the described modifier is one or more in hydroxy-ethyl acrylate, hydroxyethyl methylacrylate, the polymerizable acrylic ester;
Described macromolecule dispersing agent is a molecular weight greater than 10000 less than 3000000 alkane hydroxyl amino acid amides, the interpolymer of carboxylic acid and acrylate, acrylate interpolymer, the polyaminoamide solution of cationic unsaturated polybasic carboxylic acid, the alkylammonium salt solution of acidic polymer, after the polymerization molecular weight greater than 10000 less than 3000000 the polyester and the block copolymerization liquid solution of acrylate, after the polymerization molecular weight greater than 5000 less than in 3000000 the fluorine-containing or siliceous polymkeric substance one or more; Wherein said alkyl is C
1～C
30Alkyl;
Described coupling agent is silane coupling agent, titanate coupling agent, aluminate coupling agent or their potpourri;
Described acid anhydrides is one or more in maleic anhydride, phthalic anhydride, THPA, HHPA, the glutaric anhydride; Described amine is one or more in the alkyl acrylate of acrylate, amine modification of the diethanolamine that replaces of triethanolamine, alkyl, amine modification; Wherein said alkyl is C
1～C
30Alkyl;
The metal of described nano-micro level is that density is 0.8～1.5g/cm
3, particle diameter is that one or more materials in the aluminium powder, silver powder, copper powder of 50～5000nm are compound;
Described metal oxide is that density is 0.8～1.5g/cm
3, particle diameter is that one or more materials in the tin indium oxide, zinc paste, tin ash, indium oxide, silicon dioxide, titania of 50～5000nm are compound;
Described organic conductive macromolecule is polyaniline, polyaniline derivative, polythiophene, polythiofuran derivative, polypyrrole or polypyrrole derivant.
2. method according to claim 1 is characterized in that: described is under the uviol lamp at 50～3000W in exposure under the ultraviolet light, exposes 5～600 seconds.
3. method according to claim 1 is characterized in that: the thickness of described capping layer is 5～20 μ m.
4. method according to claim 1 is characterized in that: the structure of the acid in described acrylic ester unit or the acrylate molecular structure is one or more in monobasic or polybasic carboxylic acid, sulfonic acid, phosphoric acid, the phosphonic acids; Described ammonium salt structure is one or more in monobasic or polybasic carboxylic acid ammonium, ammonium sulphonate, ammonium phosphate, the phosphonic acids ammonium structural unit;
Aryl in described acrylic ester unit or the acrylate molecular structure is that phenyl, chain length are C
1～C
30The phenyl or naphthyl that replaces of alkyl;
Alkyl chain length in described acrylic ester unit or the acrylate molecular structure is C
1～C
30
5. method according to claim 1 is characterized in that: the pattern of described conductive material is one or more in spheroid, sheet, bar-shaped, tubulose, netted, hollow, mesoporous two dimension and/or the three-dimensional structure.
6. cover closing material that is used for electric paper micro-cup, it is characterized in that: described cover closing material is the condensate of acrylate, the oligomer of the acrylic polymer of modification or their potpourri, acrylate, the monomer of the acrylate of modification or their potpourri, the light trigger of free radical type, acrylate, acid anhydrides, the modifier of one or more materials in the amine, macromolecule dispersing agent, acrylic polyol, the methacrylic acid polyvalent alcohol, coupling agent, the surfactant of one or more in the siliceous or fluorochemical surfactant, metal with nano-micro level, the metal oxide of nano-micro level, the mixed liquor of the conductive material of organic conductive macromolecule or their compound substance, wherein, oligomer is 0～50wt% in the mixed liquor, monomer is 10～90wt%, light trigger is 0.5～5wt%, modifier is 1～30wt%, surfactant is 0.2～15wt%, conductive material is 0～50wt%;
Acrylic ester unit in the condensate of described acrylate or the acrylic polymer of modification has one or more in the following array structure: 1. contain the structure and/or the ammonium salt structure of acid in the molecule, the acid number scope is 20～400; 2. contain in aryl, alkyl, alkoxy, amido, the amino ester segmented structure one or more in the molecule; 3. molecular structure is one or more in bisphenol A epoxy acrylate, bisphenol-A epoxy methacrylate, phenolic aldehyde epoxy acrylate, phenolic aldehyde epoxy methacrylates, acrylate containing silicone, silicon-containing methacrylate copolymer, urethane acrylate, urethane methacrylate, fluorine-containing or perfluorinated acrylate, the fluorine-containing or perfluoro-methyl acrylic ester array structure, contains in element silicon, fluorine element, epoxide group or the polyurethanyl group one or more in its structure; 4. have 1～6 unsaturated link in the molecule, described unsaturated link structure is one or more in carbon-carbon double bond, carbon-carbon triple bond, carbon-to-nitrogen double bon, the two keys of carbon oxygen;
Have in the following array structure one or more in the acrylate molecular structure in the described monomer: 1. contain the structure and/or the ammonium salt structure of acid in the molecule, the acid number scope is 20～400; 2. contain in aryl, alkyl, alkoxy, amido, the amino ester segmented structure one or more in the molecule; 3. molecular structure is one or more in bisphenol A epoxy acrylate, bisphenol-A epoxy methacrylate, phenolic aldehyde epoxy acrylate, phenolic aldehyde epoxy methacrylates, acrylate containing silicone, silicon-containing methacrylate copolymer, urethane acrylate, urethane methacrylate, fluorine-containing or perfluorinated acrylate, the fluorine-containing or perfluoro-methyl acrylic ester array structure, contains in element silicon, fluorine element, epoxide group or the polyurethanyl group one or more in its structure; 4. have 1～6 unsaturated link in the molecule, described unsaturated link structure is one or more in carbon-carbon double bond, carbon-carbon triple bond, carbon-to-nitrogen double bon, the two keys of carbon oxygen;
Described radical photoinitiator is one or more the potpourri in alpha-hydroxyalkyl benzophenone type, α-amine alkyl phenones type, dialkoxy acetophenone type, acylphosphine oxide, benzophenone, the thioxanthone;
Acrylate in the described modifier is one or more in hydroxy-ethyl acrylate, hydroxyethyl methylacrylate, the polymerizable acrylic ester;
Described macromolecule dispersing agent is a molecular weight greater than 10000 less than 3000000 alkane hydroxyl amino acid amides, the interpolymer of carboxylic acid and acrylate, acrylate interpolymer, the polyaminoamide solution of cationic unsaturated polybasic carboxylic acid, the alkylammonium salt solution of acidic polymer, after the polymerization molecular weight greater than 10000 less than 3000000 the polyester and the block copolymerization liquid solution of acrylate, after the polymerization molecular weight greater than 5000 less than in 3000000 the fluorine-containing or siliceous polymkeric substance one or more; Wherein said alkyl is C
1～C
30Alkyl;
Described coupling agent is silane coupling agent, titanate coupling agent, aluminate coupling agent or their potpourri;
Described acid anhydrides is one or more in maleic anhydride, phthalic anhydride, THPA, HHPA, the glutaric anhydride; Described amine is one or more in the alkyl acrylate of acrylate, amine modification of the diethanolamine that replaces of triethanolamine, alkyl, amine modification; Wherein said alkyl is C
1～C
30Alkyl;
The metal of described nano-micro level is that density is 0.8～1.5g/cm
3, particle diameter is that one or more materials in the aluminium powder, silver powder, copper powder of 50～5000nm are compound;
Described metal oxide is that density is 0.8～1.5g/cm
3, particle diameter is that one or more materials in the tin indium oxide, zinc paste, tin ash, indium oxide, silicon dioxide, titania of 50～5000nm are compound;
Described organic conductive macromolecule is polyaniline, polyaniline derivative, polythiophene, polythiofuran derivative, polypyrrole or polypyrrole derivant.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101776522A CN101441382B (en) | 2007-11-19 | 2007-11-19 | One-step cover closing method of electronic paper micro-cup and cover closing material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101776522A CN101441382B (en) | 2007-11-19 | 2007-11-19 | One-step cover closing method of electronic paper micro-cup and cover closing material |
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| CN101441382B true CN101441382B (en) | 2010-08-04 |
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| KR20150063309A (en) * | 2014-12-03 | 2015-06-09 | 주식회사 나노브릭 | Anti-counterfeit apparatus |
| CN108644125A (en) * | 2018-04-29 | 2018-10-12 | 贝德科技有限公司 | A kind of diesel engine long axis fire pump using seawater corrosion resistance new material |
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|---|---|---|---|---|
| CN1466013A (en) * | 2002-06-24 | 2004-01-07 | ϣ | Improved electrophoretic display and novel process for its mfg. |
| CN1774659A (en) * | 2003-02-21 | 2006-05-17 | 希毕克斯影像有限公司 | Electrophoretic display and process for its manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1466013A (en) * | 2002-06-24 | 2004-01-07 | ϣ | Improved electrophoretic display and novel process for its mfg. |
| CN1774659A (en) * | 2003-02-21 | 2006-05-17 | 希毕克斯影像有限公司 | Electrophoretic display and process for its manufacture |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2001-188268A 2001.07.10 |
| 荣宇,陈红征,汪茫.电泳显示材料及技术的研究进展.材料科学与工程学报21 6.2003,21(6),903-907. |
| 荣宇,陈红征,汪茫.电泳显示材料及技术的研究进展.材料科学与工程学报21 6.2003,21(6),903-907. * |
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