CN101441382B - One-step capping method and capping material for electronic paper microcup - Google Patents

Abstract

The invention relates to an electronic paper microcup displayed on a flat panel, in particular to a one-step capping method and a capping material for realizing the electronic paper microcup on a flexible base material in a strong dissolving or swelling solvent such as tetrachlorethylene. The present invention is mainly based on unsaturated acrylate derivatives, oligomers, monomers, photoinitiators, modifiers, surfactants, conductive materials are formulated into capping glue, and mixed with colorant dispersion liquid Mixing in a certain proportion, emulsification and dispersion, layering, and light curing complete the capping, and its thickness is precisely controlled by the volume ratio of the capping glue and the colorant dispersion. The invention is not only suitable for capping electronic ink or liquid crystal to realize flexible or rigid flat panel display, but also can be used for microfluidic control, cell or tissue culture, synthesis preparation, etc. in the fields of biology, medicine and chemistry.

Description

One-step capping method and capping material for electronic paper microcup

technical field

The invention relates to an electronic paper microcup displayed on a flat panel, in particular to a one-step capping method and a capping material for realizing the electronic paper microcup on a flexible base material in a strong dissolving or swelling solvent such as tetrachlorethylene.

Background technique

Electrophoretic display (EPD), commonly known as electronic paper, has many advantages compared with other flat panel displays, such as comfortable reading, high contrast, low bistable power consumption (power-off display), high resolution (>200dpi), light and thin ( Thickness 0.5 mm), wide substrate (flexible display), wide viewing angle (180 degrees); therefore, it has a wide range of application prospects, not only will bring revolutionary changes to information recording related industries, but also in e-books, e-libraries, There are broad and far-reaching application prospects in low-power sustainable displays, large outdoor billboards, and foldable display devices.

At present, the relatively mature process methods that have entered the practical stage include microcapsule electrophoresis type (US patents US 5961804 and US 5930026 of E-INK (electronic ink) company in the United States), microcup electrophoresis type (US20030063370), electronic powder fluid type, and cholesterol liquid crystal type. .

The basic principle of electrophoretic display: In a tiny area (microcapsule or microcup), under the direct current drive between two electrodes (transparent electrode, driving electrode), charged particles (pigment particles or fillers) undergo electrophoretic migration to display corresponding colors.

Microcapsules (US 6017584) are difficult to control due to solvent resistance, mechanical properties, size and uniformity, and have problems such as easy breakage, aging, and short life. It overcomes the shortcomings of microcapsules; and due to the limitation of microcups, the external disturbance is greatly reduced, and it is easier to achieve a "bistable" structure; the added charge control agent increases the charge density of the electrophoretic particles without loss, and the electrophoretic particles can be fully charged. Gathered on the display plane, the contrast ratio is improved. Since the thickness of the wall of the microcup can be adjusted, the performance of pressure resistance and scratch resistance is greatly improved. This method of microcup formation is receiving more and more attention because of its unique performance and relatively feasible production process.

The electronic paper of SiPix Imaging (image) company in the United States uses the principle of electrophoresis to display in the microcup structure; and other means to solidify, to realize the capping of the color dispersion liquid system of the fluorine-containing solvent and the fluorinated pigment dye, and to complete the multi-color display of red, green, blue, black, white, and gold; the capping material is One or more materials in polymers with crosslinkable groups such as (meth)acrylate, cyanoacrylate, vinyl ether, epoxy compound, isocyanate, allyl alcohol, etc.

Fluorine-containing solvents can be used as electrophoretic media, such as HT-200 (Ausimont), FC-43 (3M Company in the United States), dichlorotrifluorobenzene, etc. used by SiPix Imaging (image) in the United States, to complete the microcup capping; however, due to Fluorine-containing solvents are expensive, and need to carry out special treatment to electrophoretic pigment or dyestuff, make it match; For example Chen Xianhai etc. (U.S. Patent 20030063370,) used colorant is the phthalocyanine dye of fluorination (U.S. 3M Company), and Use fluorine-containing or perfluorinated solvent HT-200 (Ausimont); Liang, Rong-Chang et al. 20030179437 (US patent).

Different from fluorine-containing solvents, tetrachloroethylene is an excellent and cheap solvent, which has low polarity, high density (1.6g/cm ³ ), high boiling point, suitable freezing point, low viscosity, and excellent performance on various colorants. Dispersion, fast electrophoresis; suitable for dispersion and electrophoresis of high-density titanium dioxide (3.8 or 4.2g/cm ³ ), also suitable for low-density oily red, oily blue, phthalocyanine dyes, carbon black, etc. Dispersion and electrophoresis of conventional dye and pigment systems.

However, capping the electronic paper microcup system with tetrachlorethylene as the electrophoretic medium is a problem that needs to be solved. At present, there is no report of a method at home and abroad that can use tetrachlorethylene or the like as the colorant dispersion of the electrophoretic medium to fill and seal the surface in the microcups of the array.

The capping of electronic paper microcups with tetrafluoroethylene as the electrophoretic medium has the following difficulties:

① In order to prevent the microcup structure from being very fragile due to the mutual cross-linking and shrinkage of the internal materials of the microcup, Xianhai Chen from SiPix Imaging (image) company in the United States added a rubber material with a mass concentration of 8% to 15% in the thermosetting plastic. (such as SBR, PBR, NBR, etc.) effectively improve the flexibility of the microcup array; but because the rubber material used will dissolve or swell in solvents such as tetrachloroethylene, it is not suitable for colorants containing tetrachloroethylene Caps for dispersion systems.

② The fluorine-containing solvents used by SiPix Imaging in the United States, such as HT-200 (Ausimont), FC-43, dichlorotrifluorobenzene, etc., are immiscible with most unsaturated ester glues , easy to seal.

③Tetrachlorethylene is different from the above-mentioned fluorine-containing solvents. It is miscible with most unsaturated ester glues. In this miscible state, either no curing occurs, or the entire microcup is cured. Only the surface layer is cured; and because of the excellent solubility of tetrachlorethylene, it can dissolve fat, oil, rubber, natural resin, most synthetic resins and aromatic organic acids, even if it is cured by crosslinking or polymerization, it will not change after a long time. Will form the capping layer to gradually dissolve; due to the volatility and strong solubility of tetrachlorethylene, the methods such as heating, interface polymerization or humidity change adopted by SiPix Imaging (image) company in the United States will use tetrachlorethylene in the microcup as the electrophoretic medium. It is difficult to implement the curing and capping of the pigment dispersion liquid.

④ There are many researches related to electronic paper and electronic ink in China, but most of them follow the example of E-ink and other companies (020139592.6) to do research on microcapsules. Zhejiang University Wang Mang and Chen Hongzheng et al. Acrylic esters were used in the preliminary research on the fabrication of microcups, but there were no reports on flexible substrates and microcup caps.

In the present invention, a solvent-resistant unsaturated ester system, a photoinitiator, and an auxiliary agent are optimized and compounded, and the electronic paper microcup unit is sealed by a one-step sealing method. Realize rapid delamination and light-curing sealing; the thickness of the cured capping layer is controllable, without bubbles, and can block and withstand volatilization and swelling corrosion of tetrachlorethylene, etc., with strong stability.

Contents of the invention

The purpose of the present invention is to provide a one-step capping method for the electronic paper microcup after the electronic paper microcup unit is filled with the colorant dispersion liquid by using ultraviolet light curing technology.

Another object of the present invention is to provide a cover material for an electronic paper microcup.

The present invention is mainly based on unsaturated acrylate derivatives, oligomers, monomers, photoinitiators, modifiers, surfactants, conductive materials are formulated into capping glue, and mixed with colorant dispersion liquid Mixing in a certain proportion, emulsification and dispersion, layering, and light curing complete the capping, and its thickness is precisely controlled by the volume ratio of the capping glue and the colorant dispersion.

In the present invention, the capping material is pre-dispersed in the colorant dispersion liquid to form a mixed liquid, and after the mixed liquid is filled into the electronic paper microcup, the layers are rapidly layered, the capping material floats on the surface, and finally light-cured to form a capping film. Include the following steps:

1) Prepare capping glue: Stir and mix oligomers, monomers, photoinitiators, modifiers, surfactants, and conductive materials for 1 to 30 minutes at a temperature of 0 to 90°C and avoid light; The oligomer in the mixed solution is 0-50wt%, the monomer is 10-90wt%, the photoinitiator is 0.5-5wt%, the modifier is 1-30wt%, the surfactant is 0.2-15wt%, and the conductive material 0～50wt%;

2) Mixing of capping glue and colorant dispersion: at a temperature of -25 to 25°C, mix the capping glue and colorant dispersion obtained in step 1) at a volume ratio of 1:1 to 1: 10 Stir and mix to obtain a mixed solution, the stirring time is 2 to 10 minutes; the used colorant dispersion can be a solution or suspension obtained by mixing any commercialized and modified pigments and dyes in any proportion;

3) Filling the mixed solution: pour the mixed solution obtained in step 2) into the electronic paper microcup array on the substrate, and the filling method is one of scraping, dip coating, spray coating, spin coating, etc. Method; filling temperature is -25 ~ 25 ℃.

4) Static stratification: the base material with the electronic paper microcup array that has been filled with the mixture of capping glue and colorant dispersion obtained in step 3) is allowed to stand at -25 to 25°C for 2 to 80 seconds , the mixed solution in the electronic paper microcup is stratified, and the capping glue floats on the surface;

5) Formation of the capping layer: Expose the substrate with the electronic paper microcup array that delaminated in step 4) under a 50-3000W ultraviolet lamp for 5-600 seconds, and the capping glue solution passes through the light curing to obtain the capping layer; the ultraviolet lamp used is one of high-pressure mercury lamps, low-pressure mercury lamps, iodine-gallium lamps, and the like.

The thickness of the capping layer is 5-20 μm.

The substrate is a silicon substrate, a glass substrate, an ITO (indium tin oxide) substrate, a polyethylene terephthalate (PET) substrate, a polyvinyl chloride (PVC) substrate or a polycarbonate (PC) substrate.

The capping material for the electronic paper microcup of the present invention is a mixed solution of oligomers, monomers, photoinitiators, modifiers, surfactants, and conductive materials, wherein the oligomers in the mixed solution are 0- 50wt%, monomer 10-90wt%, photoinitiator 0.5-5wt%, modifier 1-30wt%, surfactant 0.2-15wt%, conductive material 0-50wt%.

The oligomer is a commercial acrylate polymer, a modified acrylate polymer or any mixture thereof. Among them, the acrylate unit has one or more of the following structures: ①The molecule contains an acid structure and/or an ammonium salt structure, and the acid value ranges from 20 to 400; the acid structure contained in it is a monobasic or polybasic carboxylic acid One or more of sulfonic acid, phosphoric acid, phosphonic acid; the ammonium salt structure contained in it is one or more of structural units such as monobasic or polycarboxylic ammonium, ammonium sulfonate, ammonium phosphate, and ammonium phosphonate ②The molecule contains one or more of aryl, alkyl, alkoxy, amino, and amino ester segment structures; the aryl is phenyl, alkyl-substituted phenyl, or naphthyl, etc. ; The alkyl chain length is C ₁ ~ C ₃₀ ; ③ Molecular structure is bisphenol A epoxy acrylate, bisphenol A epoxy methacrylate, novolac epoxy acrylate, novolac epoxy methacrylate , silicon-containing acrylate, silicon-containing methacrylate, polyurethane acrylate, polyurethane methacrylate, fluorine-containing or perfluoroacrylate, fluorine-containing or perfluoromethacrylate series structure, Its structure contains one or more of silicon elements, fluorine elements, epoxy groups or polyurethane groups; ④ There are 1 to 6 unsaturated bonds in the molecule, and the unsaturated bond structure is a carbon-carbon double bond , carbon-carbon triple bond, carbon-nitrogen double bond, carbon-oxygen double bond, etc. one or more.

Said monomer is commercial acrylate, modified acrylate or any mixture thereof. Among them, the molecular structure of acrylate has one or more of the following structures: ①The molecule contains acid structure and/or ammonium salt structure, and the acid value ranges from 20 to 400; the acid structure contained in it is mono- or multi-element One or more of carboxylic acid, sulfonic acid, phosphoric acid, and phosphonic acid; the ammonium salt structure contained in it is one of the structural units such as monobasic or polybasic carboxylate, ammonium sulfonate, ammonium phosphate, and ammonium phosphonate or more; ②The molecule contains one or more of aryl, alkyl, alkoxy, amino, and amino ester segment structures; the aryl is phenyl, alkyl-substituted phenyl, or naphthalene base, etc.; the alkyl chain length is C ₁ ~ C ₃₀ ; ③ molecular structure is bisphenol A epoxy acrylate, bisphenol A epoxy methacrylate, novolac epoxy acrylate, novolac epoxy methyl One or more of acrylate, silicon-containing acrylate, silicon-containing methacrylate, polyurethane acrylate, polyurethane methacrylate, fluorine-containing or perfluoroacrylate, fluorine-containing or perfluoromethacrylate series The structure contains one or more of silicon element, fluorine element, epoxy group or polyurethane group; ④ There are 1 to 6 unsaturated bonds in the molecule, and the unsaturated bond structure is carbon-carbon One or more of double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, carbon-oxygen double bonds, etc.

The photoinitiator is a commercial free radical photoinitiator, and the free radical photoinitiator is α-hydroxyalkylphenone type, α-aminoalkylphenone type, dialkoxybenzene One or a mixture of acetone, acylphosphine oxide, benzophenone, and thioxanthone.

The modifier is one or more materials in commercial acrylate, acid anhydride, amine; the acrylate is one of hydroxyethyl acrylate, hydroxyethyl methacrylate, polymerizable acrylate one or more kinds; the acid anhydride is one or more of maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, glutaric anhydride; the amine is triethanolamine, alkyl-substituted di One or more of ethanolamine, amine-modified acrylate, and amine-modified alkyl acrylate; wherein the alkyl group is a C ₁ -C ₃₀ alkyl group.

The surfactant is one or more of commercial polymer dispersants, acrylic polyols, methacrylic polyols, coupling agents, silicon-containing or fluorine-containing surfactants. , defoaming and emulsification, can effectively emulsify and disperse the capping glue, improve the surface properties of the capping glue; the coupling agent is a silane coupling agent, titanate coupling agent, aluminate coupling agent or their mixture in any ratio.

The polymer dispersant is a commercially available alkoxyaminoamide with a molecular weight greater than 10,000 and less than 3,000,000, a copolymer of carboxylic acid and acrylate, an acrylate copolymer, a polyaminoamide solution of cationic unsaturated polycarboxylic acid, acidic Alkyl ammonium salt solution of polymer, block copolymer solution of polyester and acrylate with molecular weight greater than 10,000 and less than 3,000,000 after polymerization, fluorine-containing or silicon-containing polymer with molecular weight greater than 5,000 and less than 3,000,000 after polymerization, or Various; wherein the alkyl group is a C ₁ -C ₃₀ alkyl group.

The conductive material is nano-micron-scale metal, nano-micron-scale metal oxide, organic conductive polymer or their composite materials. The morphology of the conductive material is but not limited to one or more of two-dimensional and/or three-dimensional structures such as powder, sphere, flake, rod, tube, mesh, hollow, and mesoporous, used to improve the capping layer Electrical conductivity.

The nano-micron-scale metal is compounded with one or more materials among aluminum powder, silver powder, copper powder and the like with a density of 0.8-1.5 g/cm ³ and a particle size of 50-5000 nm.

The metal oxide is one of indium tin oxide (ITO), zinc oxide, tin dioxide, indium oxide, silicon dioxide, titanium dioxide, etc. with a density of 0.8-1.5 g/cm ³ and a particle size of 50-5000 nm. composite of one or more materials.

The organic conductive polymer is commercialized polyaniline, polyaniline derivatives, polythiophene, polythiophene derivatives, polypyrrole or polypyrrole derivatives.

Features of the one-step capping of the electronic paper microcup of the present invention:

① The light-curing materials and other reagents used for the capping of electronic paper microcups are commercially available in China, and the light-curing materials are cheap and easy to get.

② The equipment is cheap and operated at room temperature. The method is simple and fast. Commonly used exposure and coating equipment, ultraviolet lamps, mercury lamps and other light sources can be used.

③ Due to the interaction between surfactants and monomers and oligomers, the capping glue is easy to emulsify and evenly dispersed in the colorant dispersion, which is convenient for the glue coating process.

④Since the structure of monomers and oligomers is not easily soluble in organic solvents (such as tetrachlorethylene), and the density is small, the layering is rapid, and because it contains multi-functional unsaturated bonds, it is easy to cure quickly, and the surface layer cures quickly. Long-term Resistant to solvent attack.

⑤It is suitable for the capping of electronic paper microcups with various solvents as electrophoretic media, especially tetrachloroethylene, toluene, xylene, cyclohexanone, cyclohexane, tetrahydrofuran, dichlorohexane, FC-40 (US 3M Company), FC-43 (US 3M Company), dichlorotrifluorobenzene and other electrophoretic media.

⑥Because some of the molecular structures used endow the material with flexibility, and some endow the material with rigidity, adjust the ratio between them, taking into account both flexibility and rigidity, the sealing material and the wall material of the electronic paper microcup have strong adhesion and good mechanical properties. performance.

⑦ The thickness of the capping layer can be controlled by the volume ratio of the capping glue and the colorant dispersion, and a capping layer with a thickness of 5-20 μm can be obtained.

⑧Because the capping material contains conductive materials, the conductive materials are neatly arranged and connected to each other, so the capping layer has good conductivity, which is beneficial to the electrophoretic display of electronic paper.

The invention is not only suitable for capping electronic ink or liquid crystal to realize flexible or rigid flat panel display, but also can be used for microfluidic control, cell or tissue culture, synthesis preparation, etc. in the fields of biology, medicine and chemistry.

Description of drawings

Figure 1. Schematic diagram of the emulsified mixed liquid stage in the one-step capping process of the electronic paper microcup of the present invention.

Fig. 2. A schematic diagram of the microcup array before filling in the one-step capping process of the electronic paper microcup of the present invention.

Fig. 3. Schematic diagram of the mixed liquid filling stage in the one-step capping process of the electronic paper microcup of the present invention.

Fig. 4. Schematic diagram of the static stratification stage after filling in the one-step capping process of the electronic paper microcup of the present invention.

Figure 5. Schematic diagram of the formation of the capping layer in the one-step capping process of the electronic paper microcup of the present invention.

reference sign

1. Mixed liquid 2. Electronic paper microcup 3. Substrate

4. Capping glue 5. Pigment dispersion 6. Capping layer

Detailed ways

The present invention will be further described below through specific examples.

Example 1

Please refer to Figures 1-5.

In the capping glue: photoinitiator: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, the concentration is 0.5wt%, 2-(4-(2-hydroxyl-2-methylpropane Oxy)phenoxy)acetic acid at a concentration of 0.5 wt%, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide at a concentration of 1 wt%, monomer: maleic anhydride modified Methacrylate at 8 wt%, Methacrylate Phosphate at 3 wt%, Polyethylene Glycol (600) Acrylate at 2 wt%, Ditrimethylol Propylene Tetraacrylate at 2 wt% %, oligomer: SB401 (aromatic acid methacrylic acid half ester) (Sartomer Company, U.S.), concentration is 5wt%, CN966 (amino ester/acrylic acid ester) (Sartomer Company, U.S.), concentration is 10wt%, Conductive material: 5 μm flake-shaped hollow aluminum powder, concentration is 50wt%, surfactant: CD9051 (acrylic acid ester containing three unsaturated carbon-carbon double bonds) (Sartomer, USA), concentration is 4wt%, BYK115 ( High-molecular-weight block copolymer solution with a molecular weight greater than 10,000 and less than 3,000,000 having pigment-affinity groups) (German BYK Chemical Company), the concentration is 2 wt%, BYK300 (polyether-modified polydimethyl ether with a molecular weight greater than 10,000 and less than 3,000,000 The solution of siloxane interpolymer) (Germany BYK chemical company), concentration is 2wt%, modifier: methyldiethanolamine, concentration is 10wt%, under room temperature, avoid light and stir for 10 minutes;

Mix the capping glue 4 and the colorant dispersion 5 at a volume ratio of 1:4 at 25°C, and stir at room temperature for 10 minutes to obtain a mixed solution 1;

At 25°C, quickly scrape the mixture 1 of the capping glue and the colorant dispersion liquid into the 100 μm high electronic paper microcup 2 on the substrate 3 with a wire scraper, let it stand at 25°C for 20 seconds, and then use a 1000W high-pressure mercury Expose under a lamp for 600 seconds to obtain a capping layer 6 with a thickness of 20 μm.

Attach the driving circuit to the capped microcup to complete the assembly of the entire principle device.

Example 2

Please refer to Figures 1-5.

In the capping glue: photoinitiator: 2-hydroxyl-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropyl-1-one, the concentration is 0.5wt%, 1- Hydroxycyclohexyl phenyl ketone, the concentration is 0.5wt%, monomer: polyethylene glycol (200) acrylate, the concentration is 5wt%, triglycerol triacrylate, the concentration is 3wt%, ethylene glycol bis Methacrylate, concentration is 2wt%, oligomer: EB2002 (water-soluble urethane acrylate, U.S. Cytec), concentration is 30wt%, CN2256 (water-soluble polyester acrylic acid, U.S. Sartomer Company), concentration is 10wt%, CN972 (aromatic amino ester acrylate) (Sartomer, U.S.), concentration is 10wt%, conductive material: 500nm flake silver-coated silica ball, concentration is 10wt%, polyaniline, concentration is 10wt% %, surfactant: silane coupling agent 570, concentration is 1wt%, BYK110 (Germany BYK chemical company), concentration is 2wt%, BYK154 (molecular weight is greater than the ammonium salt solution of the acrylate interpolymer of 10000 less than 3000000) (Germany BYK chemical company), the concentration is 1wt%, modifier: dimethylaminobenzoic acid ethyl ester, the concentration is 10wt%, triethanolamine, the concentration is 5wt%, under room temperature, avoid light and stir for 10 minutes;

Mix the capping glue 4 and the colorant dispersion 5 at a volume ratio of 1:4 at 25°C, and stir at room temperature for 2 minutes to obtain a mixed solution 1;

At 25°C, scrape the mixture 1 of the capping glue and the colorant dispersion liquid into the 100 μm high electronic paper microcup 2 on the substrate 3 with a wire scraper, let it stand at 0°C for 40 seconds, and place it in a 1000W high-pressure mercury lamp. Under exposure for 300 seconds, a capping layer 6 with a thickness of 20 μm was obtained.

Attach the driving circuit to the capped microcup to complete the assembly of the entire principle device.

Example 3

Please refer to Figures 1-5.

In the capping glue solution: photoinitiator: benzoin dimethyl ether, the concentration is 1wt%, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, the concentration is 1wt%, monomer: acrylic acid modified Acrylate, concentration is 10wt%, isobornyl acrylate, concentration is 15wt%, ditrimethylol propylene tetraacrylate, concentration is 20wt%, oligomer: PE55WN (water-soluble polyester acrylate, Germany BASF company ), concentration is 25wt%, CN988 (Sartomer Company of the U.S.), concentration is 7wt%, surfactant: CD9051 (acrylic acid ester containing three unsaturated carbon-carbon double bonds in the molecule) (Sartomer Company of the United States), Concentration is 1wt%, BYK115 (Germany BYK chemical company), concentration is 2wt%, BYK181 (having the molecular weight of anionic/non-ionic character is greater than the solution of the alkanolammonium salt polymer of 10000 less than 3000000) (Germany BYK chemical company) , concentration is 5wt%, modifier: glutaric anhydride, concentration is 5wt%, methyldiethanolamine, concentration is 5wt%, dimethylaminobenzoic acid ethyl ester, concentration is 3wt%, under 60 ℃, avoid light and stir 30 minute;

Mix the capping glue 4 and the colorant dispersion 5 at a volume ratio of 1:5 at -25°C, and stir at room temperature for 5 minutes to obtain the mixed solution 1;

At -25°C, quickly scrape the mixture 1 of the capping glue and the colorant dispersion liquid into the 60 μm high electronic paper microcup 2 on the substrate 3 with a wire scraper, let it stand at -25°C for 5 seconds, and put it under 50W Expose under a high-pressure mercury lamp for 500 seconds to obtain a capping layer 6 with a thickness of 10 μm.

Attach the driving circuit to the capped microcup to complete the assembly of the entire principle device.

Example 4

Please refer to Figures 1-5.

In the capping glue solution: photoinitiator: isopropylthioxanthone, the concentration is 0.8wt%, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, the concentration is 0.5wt%, 2 -Hydroxy-1-(4-(2-hydroxyethylmercapto)phenyl)-2-methylpropyl-1-one, the concentration is 0.5wt%, monomer: polyethylene glycol (200) acrylate, Concentration of 20 wt%, glutaric anhydride modified methacrylate at a concentration of 30 wt%, octapentyl glycol diacrylate at a concentration of 20 wt%, isobornyl acrylate at a concentration of 20 wt%, oligomer: SB520( Aromatic acrylate) (Sartomer Corporation of the U.S.), concentration is 0.1wt%, EM6225 (organic silicon polyether acrylate, Taiwan Changxing Chemical Co., Ltd.), concentration is 0.1wt%, conductive material: the hollow silver ball of 300nm, Concentration is 6.8wt%, surfactant: BYK110 (having the molecular weight of acidic group is greater than 10000 and is less than the macromolecule interpolymer solution of 3000000) (Bick chemical company of Germany), concentration is 0.2wt%, modifier: dimethylamine Ethyl benzoate, the concentration is 1wt%, 90 ℃, dark and stirred for 10 minutes;

Mix the capping glue 4 and the colorant dispersion 5 at a volume ratio of 1:9 at -5°C, and stir at room temperature for 10 minutes to obtain a mixed solution 1;

At -5°C, scrape the mixture 1 of the capping glue and the colorant dispersion liquid into the 100 μm high electronic paper microcup on the substrate 3 with a wire scraper, let it stand at 0°C for 80 seconds, and place it in a 1000W high-pressure mercury lamp Under exposure for 60 seconds to obtain a capping layer 6 with a thickness of 15 μm.

Attach the driving circuit to the capped microcup to complete the assembly of the entire principle device.

Example 5

Please refer to Figures 1-5.

In the capping glue: photoinitiator: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, the concentration is 0.5wt%, monomer: isobornyl acrylate, the concentration is 30wt%, dipentaerythritol Pentaacrylate, concentration is 20wt%, oligomer: EM6225 (Taiwan Changxing Chemical Co., Ltd.), concentration is 5wt%, PE55WN (water-soluble polyester acrylate, Germany BASF company), concentration is 20wt%, CN970 (American sand Dorma company), concentration is 10wt%, surfactant: BYK500 (Bick chemical company of Germany), concentration is 2wt%, FC-500 (fluorosurfactant, U.S. 3M company), concentration is 2wt%, modification Agent: methyldiethanolamine, concentration is 5.5wt%, ethyl dimethylaminobenzoate, concentration is 5%, under room temperature, avoid light and stir for 10 minutes;

Mix the capping glue 4 and the colorant dispersion 5 at a volume ratio of 1:5 at 25°C, and stir at room temperature for 10 minutes to obtain a mixed solution 1;

At 0°C, quickly scrape the mixture 1 of the capping glue and the colorant dispersion liquid into the 60 μm high electronic paper microcup 2 on the substrate 3 with a wire scraper, let it stand at 0°C for 5 seconds, and put it under 100W high-pressure mercury Expose under a lamp for 300 seconds to obtain a capping layer 6 with a thickness of 10 μm.

Attach the driving circuit to the capped microcup to complete the assembly of the entire principle device.

Example 6

Please refer to Figures 1-5.

In the capping glue solution: photoinitiator: 2,4-diethylthioxanthone, the concentration is 5wt%, monomer: isobornyl acrylate, the concentration is 8wt%, pentaerythritol triacrylate, the concentration is 10wt%, Oligomer: SB401 (aromatic acid methacrylic half ester) (Sartomer, USA), concentration is 5wt%, IRR210 (water-soluble acrylate containing three unsaturated carbon-carbon double bonds in the molecule, Cytec Corporation, USA ), the concentration is 20wt%, CN963 (Sartomer, U.S.), the concentration is 5wt%, conductive material: the ITO powder of 50nm, the concentration is 2wt%, surfactant: CD9051 (containing three unsaturated carbon-carbon double bonds Acrylate) (Sartomer, USA), the concentration is 5wt%, BYK057 (polymer solution with molecular weight greater than 10,000 and less than 3,000,000) (German BYK chemical company), the concentration is 5wt%, BYK183 (with pigment affinity group Molecular weight is greater than 10000 and is less than the high molecular weight block interpolymer solution of 3000000) (Bick chemical company of Germany), concentration is 5wt%, modifier: triethanolamine, concentration is 15wt%, ethyl dimethylaminobenzoate, concentration is 15%, stir at room temperature for 20 minutes in the dark;

Mix the capping glue 4 and the colorant dispersion 5 at a volume ratio of 1:9 at 25°C, and stir at room temperature for 2 minutes to obtain a mixed solution 1;

At 25°C, scrape the mixture 1 of the capping glue and the colorant dispersion liquid into the 100 μm high electronic paper microcup 2 on the substrate 3 with a wire scraper, let it stand at 0°C for 30 seconds, and place it in a 1000W high-pressure mercury lamp. Under exposure for 600 seconds, a capping layer 6 with a thickness of 10 μm was obtained.

Attach the driving circuit to the capped microcup to complete the assembly of the entire principle device.

Claims (6)

1. A one-step capping method for an electronic paper microcup is to disperse the capping material in the colorant dispersion liquid in advance to form a mixed solution, and to layer the electronic paper microcup after the mixed solution is filled, and the capping material floats on the surface layer, Finally, it is cured by light into a cover film, which is characterized by: 1) Preparation of capping glue: acrylate polymers, modified acrylate polymers or oligomers of their mixtures, acrylates, modified acrylates or monomers of their mixtures, free Basic photoinitiator, modifier of one or more materials in acrylate, acid anhydride, amine, polymer dispersant, acrylic polyol, methacrylic polyol, coupling agent, containing silicon or fluorine One or more surfactants in the surfactant, and the conductive material of nano-micron metal, nano-micron metal oxide, organic conductive polymer or their composite materials at a temperature of 0-90°C Stirring and mixing under light-shielding conditions; in the mixed solution, oligomers are 0-50wt%, monomers are 10-90wt%, photoinitiators are 0.5-5wt%, modifiers are 1-30wt%, surface activity 0.2-15wt% of the agent, 0-50wt% of the conductive material; 2) Mixing of capping glue and colorant dispersion: at a temperature of -25 to 25°C, mix the capping glue and colorant dispersion obtained in step 1) at a volume ratio of 1:1 to 1: 10 Stir and mix to obtain a mixed solution; 3) Filling the mixed solution: pour the mixed solution obtained in step 2) into the electronic paper microcup array on the substrate; the filling temperature is -25-25°C; 4) Static stratification: the base material with the electronic paper microcup array of the mixture of the filled capping glue and the color dispersion obtained in step 3) is left at -25 to 25°C, and the electronic paper microcup The mixture in the cup is stratified, and the sealing glue floats on the surface; 5) Formation of the capping layer: exposing the substrate with the electronic paper microcup array that has been stratified in step 4) under ultraviolet light, and the capping glue is cured by light to obtain the capping layer; The acrylate unit in the acrylate polymer or the modified acrylate polymer has one or more of the following structures: ① the molecule contains an acid structure and/or an ammonium salt structure, and the acid value ranges from 20 to 400; ②The molecule contains one or more of aryl, alkyl, alkoxy, amino, and amino ester segment structures; ③The molecular structure is bisphenol A epoxy acrylate, bisphenol A epoxy Methacrylate, Novolac Epoxy Acrylate, Novolac Epoxy Methacrylate, Silicone Acrylate, Silicone Methacrylate, Urethane Acrylate, Urethane Methacrylate, Fluorinated or Perfluorinated Acrylate, Containing One or more of fluorine or perfluoromethacrylate series structures, which contain one or more of silicon element, fluorine element, epoxy group or polyurethane group; 6 unsaturated bonds, the unsaturated bond structure is one or more of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-oxygen double bonds; The acrylate molecular structure in the monomer has one or more of the following structures: ①The molecule contains an acid structure and/or an ammonium salt structure, and the acid value ranges from 20 to 400; ②The molecule contains an aromatic One or more of base, alkyl, alkoxy, amino, amino ester segment structure; ③Molecular structure is bisphenol A epoxy acrylate, bisphenol A epoxy methacrylate, novolac epoxy acrylate Ester, novolac epoxy methacrylate, silicon-containing acrylate, silicon-containing methacrylate, polyurethane acrylate, polyurethane methacrylate, fluorine-containing or perfluorinated acrylate, fluorine-containing or perfluoromethacrylate series One or more of the structures, which contain one or more of silicon elements, fluorine elements, epoxy groups or polyurethane groups; ④ There are 1 to 6 unsaturated bonds in the molecule, the said The unsaturated bond structure is one or more of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-oxygen double bonds; The free radical photoinitiator is α-hydroxyalkyl phenone type, α-aminoalkyl phenone type, dialkoxy acetophenone type, acyl phosphine oxide, benzophenone, thioxanthene One or more mixtures of ketones; The acrylate in the modifier is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, and polymerizable acrylate; The polymer dispersant is a polyaminoamide solution of alkylhydroxyaminoamide with molecular weight greater than 10,000 and less than 3,000,000, carboxylic acid and acrylate copolymer, acrylate copolymer, cationic unsaturated polycarboxylic acid polyaminoamide solution, and acidic polymer. One or more of alkyl ammonium salt solution, block copolymer solution of polyester and acrylate with molecular weight greater than 10,000 and less than 3,000,000 after polymerization, fluorine-containing or silicon-containing polymer with molecular weight greater than 5,000 and less than 3,000,000 after polymerization; Wherein said alkyl is C ₁ -C ₃₀ alkyl; The coupling agent is a silane coupling agent, a titanate coupling agent, an aluminate coupling agent or a mixture thereof; The acid anhydride is one or more of maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and glutaric anhydride; the amine is triethanolamine, alkyl-substituted diethanolamine, amine-modified One or more of acrylates and amine-modified alkyl acrylates; wherein the alkyl group is a C ₁ ~C ₃₀ alkyl group; The nano-micron metal is compounded with one or more materials among aluminum powder, silver powder and copper powder with a density of 0.8-1.5 g/cm ³ and a particle size of 50-5000 nm; The metal oxide is one or more of indium tin oxide, zinc oxide, tin dioxide, indium oxide, silicon dioxide, and titanium dioxide with a density of 0.8-1.5 g/cm ³ and a particle size of 50-5000 nm. Material composite; The organic conductive polymer is polyaniline, polyaniline derivatives, polythiophene, polythiophene derivatives, polypyrrole or polypyrrole derivatives. 2. The method according to claim 1, characterized in that: said exposure under ultraviolet light is under a 50-3000W ultraviolet light for 5-600 seconds. 3. The method according to claim 1, characterized in that: the thickness of the capping layer is 5-20 μm. 4. The method according to claim 1, characterized in that: the structure of the acid in the acrylate unit or acrylate molecular structure is one or more of monobasic or polycarboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid Multiple; the ammonium salt structure is one or more of monobasic or polybasic ammonium carboxylate, ammonium sulfonate, ammonium phosphate, and ammonium phosphonate structural units; The aryl group in the acrylate unit or acrylate molecular structure is a phenyl group, a phenyl group or a naphthyl group substituted by an alkyl group with a chain length of C ₁ to C ₃₀ ; The acrylate unit or the alkyl chain length in the acrylate molecular structure is C ₁ -C ₃₀ . 5. The method according to claim 1, characterized in that: the shape of the conductive material is one of sphere, flake, rod, tube, mesh, hollow, mesoporous two-dimensional and/or three-dimensional structure one or more species. 6. A cover material for electronic paper microcups, characterized in that: the cover material is an acrylate polymer, a modified acrylate polymer or an oligomer of their mixture, acrylic acid Monomers of esters, modified acrylates or their mixtures, free radical photoinitiators, modifiers for one or more of acrylates, anhydrides, and amines, polymer dispersants, acrylic multi-component Alcohols, methacrylic acid polyols, coupling agents, one or more surfactants containing silicon or fluorine-containing surfactants, and nano-micron-scale metals, nano-micron-scale metal oxides, organic conductive high A mixture of molecules or conductive materials of their composite materials, wherein the oligomer in the mixture is 0-50wt%, the monomer is 10-90wt%, the photoinitiator is 0.5-5wt%, and the modifier is 1 ～30wt%, surfactant 0.2～15wt%, conductive material 0～50wt%; The acrylate unit in the acrylate polymer or the modified acrylate polymer has one or more of the following structures: ① the molecule contains an acid structure and/or an ammonium salt structure, and the acid value ranges from 20 to 400; ②The molecule contains one or more of aryl, alkyl, alkoxy, amino, and amino ester segment structures; ③The molecular structure is bisphenol A epoxy acrylate, bisphenol A epoxy Methacrylate, Novolac Epoxy Acrylate, Novolac Epoxy Methacrylate, Silicone Acrylate, Silicone Methacrylate, Urethane Acrylate, Urethane Methacrylate, Fluorinated or Perfluorinated Acrylate, Containing One or more of fluorine or perfluoromethacrylate series structures, which contain one or more of silicon element, fluorine element, epoxy group or polyurethane group; 6 unsaturated bonds, the unsaturated bond structure is one or more of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-oxygen double bonds; The acrylate molecular structure in the monomer has one or more of the following structures: ①The molecule contains an acid structure and/or an ammonium salt structure, and the acid value ranges from 20 to 400; ②The molecule contains an aromatic One or more of base, alkyl, alkoxy, amino, amino ester segment structure; ③Molecular structure is bisphenol A epoxy acrylate, bisphenol A epoxy methacrylate, novolac epoxy acrylate Ester, novolac epoxy methacrylate, silicon-containing acrylate, silicon-containing methacrylate, polyurethane acrylate, polyurethane methacrylate, fluorine-containing or perfluorinated acrylate, fluorine-containing or perfluoromethacrylate series One or more of the structures, which contain one or more of silicon elements, fluorine elements, epoxy groups or polyurethane groups; ④ There are 1 to 6 unsaturated bonds in the molecule, the said The unsaturated bond structure is one or more of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-oxygen double bonds; The free radical photoinitiator is α-hydroxyalkyl phenone type, α-aminoalkyl phenone type, dialkoxy acetophenone type, acyl phosphine oxide, benzophenone, thioxanthene One or more mixtures of ketones; The acrylate in the modifier is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, and polymerizable acrylate; The polymer dispersant is a polyaminoamide solution of alkylhydroxyaminoamide with molecular weight greater than 10,000 and less than 3,000,000, carboxylic acid and acrylate copolymer, acrylate copolymer, cationic unsaturated polycarboxylic acid polyaminoamide solution, and acidic polymer. One or more of alkyl ammonium salt solution, block copolymer solution of polyester and acrylate with molecular weight greater than 10,000 and less than 3,000,000 after polymerization, fluorine-containing or silicon-containing polymer with molecular weight greater than 5,000 and less than 3,000,000 after polymerization; Wherein said alkyl is C ₁ -C ₃₀ alkyl; The coupling agent is a silane coupling agent, a titanate coupling agent, an aluminate coupling agent or a mixture thereof; The acid anhydride is one or more of maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and glutaric anhydride; the amine is triethanolamine, alkyl-substituted diethanolamine, amine-modified One or more of acrylates and amine-modified alkyl acrylates; wherein the alkyl group is a C ₁ ~C ₃₀ alkyl group; The nano-micron metal is compounded with one or more materials among aluminum powder, silver powder and copper powder with a density of 0.8-1.5 g/cm ³ and a particle size of 50-5000 nm; The metal oxide is one or more of indium tin oxide, zinc oxide, tin dioxide, indium oxide, silicon dioxide, and titanium dioxide with a density of 0.8-1.5 g/cm ³ and a particle size of 50-5000 nm. Material composite; The organic conductive polymer is polyaniline, polyaniline derivatives, polythiophene, polythiophene derivatives, polypyrrole or polypyrrole derivatives.

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