WO2012083899A1 - Electrophoretic display coating solution and method of preparing same - Google Patents

Electrophoretic display coating solution and method of preparing same Download PDF

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Publication number
WO2012083899A1
WO2012083899A1 PCT/CN2012/071297 CN2012071297W WO2012083899A1 WO 2012083899 A1 WO2012083899 A1 WO 2012083899A1 CN 2012071297 W CN2012071297 W CN 2012071297W WO 2012083899 A1 WO2012083899 A1 WO 2012083899A1
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Prior art keywords
electrophoretic display
microcapsules
display coating
adhesive
water
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PCT/CN2012/071297
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French (fr)
Chinese (zh)
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魏松丽
张磊
杨伟强
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广州奥熠电子科技有限公司
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Publication of WO2012083899A1 publication Critical patent/WO2012083899A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/26—Cellulose ethers
    • C09D101/28—Alkyl ethers
    • C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/26—Cellulose ethers
    • C09D101/28—Alkyl ethers
    • C09D101/286—Alkyl ethers substituted with acid radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09D103/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09D103/04—Starch derivatives
    • C09D103/08—Ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D189/00—Coating compositions based on proteins; Coating compositions based on derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D189/00—Coating compositions based on proteins; Coating compositions based on derivatives thereof
    • C09D189/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C09D189/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
    • G02F1/166—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
    • G02F1/167—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect by electrophoresis
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
    • G02F1/1675—Constructional details
    • G02F1/16757—Microcapsules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles

Definitions

  • the present invention relates to the technical field of electrophoretic display, in particular to an electrophoretic display coating liquid and a preparation method thereof.
  • Electrophoretic image display namely electrophoretic image display
  • It is the phenomenon of using colloidal dispersed particles to migrate under the action of an electric field. Its advantages are high contrast, large viewing angle, high display brightness, low price, and easy realization of large flat display. Its disadvantage is poor reliability, The threshold characteristics are not easy to control, especially the particles in the dispersion system are prone to agglomeration, precipitation, etc., so the life of the EPID display is relatively short.
  • MIT Massachusetts Institute of Technology
  • the media laboratory put forward the concept of encapsulated electrophoretic ink, that is, microencapsulated electrophoretic display technology (encapsulated electrophoretic ink). electrophoretic display).
  • the pigment particles and the dark dye solution are innovatively wrapped in the microcapsule, and the electrophoretic display is realized in the microcapsule.
  • the shortcomings of agglomeration and deposition of the electrophoretic colloidal particles in the range larger than the size of the capsule are suppressed, and its stability is improved, and the service life is prolonged.
  • Electronic ink is an ink-like suspended matter. Under the action of an external electric field, it can realize reversible, bistable, and flexible display. It is a flexible display material and technology that integrates physics, chemistry, electronics and other disciplines. It has the advantages of good visibility, low power consumption, strong information loading ability, convenient carrying, low manufacturing cost, and no electromagnetic radiation, and can fundamentally solve the deficiencies of the existing flat panel display technology.
  • the current electronic ink uses 30-300 Micron spherical transparent and smooth microcapsules are coated with the dielectric suspension, in which there are charged electrophoretic particles. These capsules are distributed in the polyurethane adhesive to form a dispersion system, which is coated or printed on flexible ITO On the conductive film, a principle-type flexible EPID electronic paper is formed.
  • the capsules cannot be dispersed well in the polyurethane adhesive, and there are disadvantages such as agglomeration of the capsules in a larger size range. This makes it difficult to apply when coating methods such as roll coating, screen printing, spraying, etc., the appearance of the coating film is poor, and there are various appearance defects, including voids, scratches, bumps, dead spots, etc. , which makes the yield rate lower.
  • the shrinkage force of the polyurethane during the drying process is not large enough, the capsule is not easy to deform, the gap between the capsule and the capsule is large, the capsule is not spread well on the substrate, and the single-layer arrangement cannot be realized. Performance is poor.
  • the technical problem to be solved by the present invention is to provide an electrophoretic display coating liquid and a preparation method thereof, which can solve the various technical defects mentioned above.
  • the microcapsules have better dispersibility in the electrophoretic display coating liquid. When the display coating liquid is dried, the microcapsules therein will be deformed, thereby effectively improving the photoelectric performance of the electrophoretic display coating liquid.
  • the present invention provides an electrophoretic display coating solution, which contains microcapsules, and the microcapsules contain a suspension and a plurality of charged pigment particles dispersed in the suspension, and the charged pigment particles are under the action of an electric field. Will move in the suspension; the microcapsules are dispersed in an adhesive, the adhesive contains a water-soluble polymer compound and water, wherein the concentration of the water-soluble polymer compound is 5%-20%; when the adhesive is dry, at least one of the microcapsules is deformed.
  • the water-soluble polymer compound is selected from but not limited to: carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, soluble starch, carboxymethyl starch, gum arabic, gelatin, gum , Soybean protein, polyvinyl alcohol, polyethylene glycol, and composite materials composed of two or more of the above materials.
  • the electrophoresis shows that the weight percentage of the adhesive and the microcapsules in the coating solution is 10%-70% More preferably, the weight percentage of the adhesive and the microcapsules in the electrophoretic display coating solution may preferably be 25-50%.
  • the concentration of the water-soluble polymer compound is preferably 7%-15% .
  • the above electrophoresis shows that the particle size distribution of the microcapsules dispersed in the coating solution has a span value of 0.5-0.7.
  • the aforementioned microcapsules may also contain several neutral pigment particles.
  • the present invention also provides a method for preparing an electrophoretic display coating solution, which includes the following steps: A. Dissolve a certain amount of water-soluble polymer compound in water to prepare an adhesive, wherein the concentration of the water-soluble polymer compound is 5%-20%; B. The adhesive is added to the microcapsules, and the electrophoresis display coating solution is prepared after stirring and mixing. Specifically, the above-mentioned electrophoresis shows that the weight percentage of the adhesive and the microcapsules in the coating solution is 10%-70%.
  • the present invention also provides a method for preparing an electrophoretic display assembly, the electrophoretic display assembly includes a transparent substrate with a transparent conductive layer, the preparation method includes: coating the above-mentioned electrophoretic display coating liquid on the transparent conductive layer When the electrophoretic display coating liquid is dried, at least one of the microcapsules is deformed during drying, and after drying, the electrophoretic display coating liquid forms an electrophoretic display layer.
  • the thickness of the electrophoretic display coating liquid coated on the transparent conductive layer in the above steps is about 50-300 ⁇ m ;
  • the thickness after drying and curing is about 20-120 ⁇ m .
  • the electrophoresis shows that the adhesive in the coating solution shrinks and becomes flat when dried; after drying, the cross section of the microcapsule changes from a circular or elliptical shape to a polygonal shape.
  • the adhesive in the electrophoretic display coating solution of the present invention is a water-soluble polymer solution, it is beneficial to the dispersion of microcapsules in water and effectively reduces the agglomeration between microcapsules. It can produce a certain shrinkage stress during drying, thereby deforming the microcapsules dispersed therein.
  • the electrophoretic display coating solution of the present invention can realize a single-layer coating film due to its better adhesive fluidity. , The surface of the coating film is smooth, and the density of microcapsules in the electrophoretic display layer after drying is higher, thereby effectively improving the photoelectric performance of the electrophoretic display coating liquid.
  • FIG. 1 is a drawing of the coating appearance of an existing electrophoretic display coating liquid
  • FIG. 2 is a drawing of the appearance of an electrophoretic display coating liquid in an embodiment of the present invention
  • Fig. 3 is a preparation flow chart of an embodiment of a preparation method of an electrophoretic display assembly of the present invention
  • 4 is a preparation flow chart of an embodiment of a preparation method of an electrophoretic display coating solution of the present invention
  • 5 is a schematic diagram of the structure of the electrophoretic display assembly when the electrophoretic display coating liquid is just coated in step S2 in FIG. 3 of the present invention
  • 6 is a schematic diagram of the structure of the electrophoretic display assembly after the electrophoretic display coating liquid coated in step S2 in FIG. 3 of the present invention is dried.
  • the invention discloses an adhesive material that can be used in an electrophoretic display coating solution.
  • This adhesive is made by dissolving a water-soluble polymer compound in water; previously this material is mainly used in medicine, Industry fields such as tablets and food processing.
  • Water-soluble polymer compounds are also called water-soluble resins or water-soluble polymers.
  • the usually said water-soluble polymer is a highly hydrophilic polymer material that can be dissolved or swelled in water to form an aqueous solution or dispersion system.
  • Water-soluble polymers are generally divided into three categories according to their sources: 1 , Natural water-soluble polymer. Extracted from natural animals and plants; such as starch, cellulose, vegetable glue, animal glue, etc.; 2 1. Chemically modified natural polymers; mainly include modified starch and modified cellulose; such as carboxymethyl starch, acetate starch, hydroxymethyl cellulose, carboxymethyl cellulose, etc.; 3. Synthetic polymers. There are two types of polymer resins and condensation resins, such as Polyacrylamide (PAM), hydrolyzed polyacrylamide (HPAM)), polyvinylpyrrolidone (PVP), etc.
  • PAM Polyacrylamide
  • HPAM hydrolyzed polyacrylamide
  • PVP polyvinylpyrrolidone
  • Water-soluble polymer materials mainly have the following functions: 1 water solubility, 2 dispersion, 3 flocculation, 4 viscosity increasing, 5 Drag reduction effect, 6 rheology.
  • the electrophoresis display coating solution of the present invention contains microcapsules, and the microcapsules contain a suspension and a plurality of charged pigment particles (same polarity or different polarities) dispersed in the suspension. Of course, it can also contain several medium. Charged pigment particles; these microcapsules are uniformly dispersed in the adhesive, and the electrophoretic display coating liquid is coated on the transparent conductive layer (such as ITO), after the electrophoretic display coating solution is dried, it will be on the ITO A very thin electrophoretic display layer is formed on the layer. If a certain voltage is applied to both sides of the electrophoretic display layer, the charged pigment particles in the microcapsules in the electrophoretic display layer will undergo electrophoresis in the suspension to realize electrophoretic display.
  • ITO transparent conductive layer
  • the adhesive used in the present invention is made by dissolving a transparent and glossy powdery granular water-soluble polymer compound in water; this water-soluble polymer compound includes but is not limited to: carboxymethyl cellulose, hydroxyethyl fiber Vegetarian, hydroxypropyl methylcellulose, soluble starch, carboxymethyl starch, gum arabic, gelatin, gum, soy protein, casein, polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyvinylpyrrolidone, etc. Mixtures and derivatives.
  • the water-soluble polymer compound When preparing the adhesive, the water-soluble polymer compound needs to be in the range of 30-70 The concentration of water-soluble polymer compound in the above-mentioned adhesive is 5%-20%; preferably in the range of 7%-15%; the best is 10% about.
  • the adhesive After the adhesive is prepared, it is mixed with the microcapsules in a certain ratio, that is, the microcapsules are dispersed into the prepared adhesive, and the prepared electrophoresis displays the percentage of the adhesive to the microcapsules in the coating solution control in Between 10%-70%, preferably 25%-50%; preferably around 40%.
  • Electrophoresis shows that the microcapsules in the coating solution can be uniformly dispersed in the water-soluble polymer solution (ie, the adhesive), and the particle size distribution span of the dispersed microcapsules is 0.5-0.7; effectively reduce the agglomeration of microcapsules and other problems.
  • the adhesive is dried at room temperature, at least one of the dispersed microcapsules will deform.
  • the present invention also provides a method for preparing an electrophoretic display assembly from the above-mentioned electrophoretic display coating solution.
  • the specific implementation steps of the method are shown in FIG. 3 ; Refer to Figure 5 and Figure 6 for the structure diagram of the electrophoretic display assembly before and after the drying of the coated electrophoretic display liquid.
  • S1 First, coat a transparent conductive layer 22 on a transparent substrate 33.
  • PET can be used as a transparent substrate.
  • ITO Indium Tin Oxide
  • the material can be selected from, but not limited to, epoxy resin, polyurethane, silicone adhesive, polyacrylic and polyacrylate adhesive, and a combination of two or more of the above materials Material.
  • the above-mentioned electrophoresis shows that the water-soluble polymer compound in the coating solution can produce a certain shrinkage stress during the drying process of the adhesive, which can effectively deform the microcapsules, so that the microcapsules can be tightly packed after deformation, as shown in Figure 2. Shown.
  • the density of microcapsules in the electrophoretic display layer formed after drying is greatly increased, which increases the density of electrophoretic particles on the electrode side when an electric field is applied to generate electrophoresis. In this way, the measured black and white reflectivity is also greatly increased, and the contrast is also improved. .
  • the water-soluble polymer compound used in the present invention has a certain surface activity, which can reduce the surface tension of water to a certain extent, help the wetting of the wall of the microcapsule by water, and thus facilitate the dispersion of the microcapsule in water. Effectively reduce the agglomeration between microcapsules.
  • such water-soluble polymer compounds have certain rheological properties, so the prepared electrophoresis shows that the coating liquid has better leveling properties and the coating appearance can be greatly improved, as shown in the figure 2 shown.
  • the electrophoretic display coating liquid prepared with the above-mentioned water-soluble polymer compound has a better appearance and better photoelectric properties. Specifically, the microcapsules can be deformed when the electrophoretic display coating solution is dried, the deformed capsules are tightly packed, the density of electrophoretic particles on the electrode side during electrophoresis increases, and the contrast is improved. Compared with other electrophoretic display coating liquids prepared with polyurethane adhesives, the electrophoretic display coating liquid of the present invention has higher contrast 3-4.
  • the present invention also provides a preparation method of the above-mentioned electrophoresis display coating liquid.
  • the preparation process of the method is simple and feasible, the preparation process is easy to control, and there is no special requirement for equipment.
  • the preparation method of the electrophoretic display coating solution includes the following steps: S01. Dissolve a certain amount of water-soluble polymer materials in water to prepare an adhesive, wherein the concentration of the water-soluble polymer is 5%-20%; S02. Filter the adhesive prepared above to remove impurities in the adhesive; S03. Weigh a certain amount of microcapsules for centrifugation, then add water to adjust the solid content; then mix with the adhesive filtered in step S02; the percentage of adhesive to microcapsules is controlled at 10%-70% Between, preferably 40%; S04. After stirring for a period of time, an electrophoretic display coating solution is prepared.
  • the stirring speed in the above step S04 may specifically be 50-300 revolutions per minute; the best is 250 revolutions per minute.
  • the prepared electrophoretic display coating solution should be at about 30 degrees Celsius (about 20 to 40 degrees Celsius). It can be used for coating only after it is stored for a certain period of time in the ambient temperature within the range of Celsius. The storage time is determined by the total amount of the electrophoresis display coating solution prepared. The more the amount, the longer the time. Generally, it can be stored for about half an hour to two hours.
  • the prepared electrophoresis shows that the coating solution should be stored in 5-10 Generally, it can be stored in a refrigerator or freezer in degrees Celsius for about a week; each time you need to use it, take out the required amount.
  • the electrophoresis display coating solution just taken out needs to pass 30-50 It is dissolved in a water bath at a temperature of degrees Celsius, and then can be used for coating.
  • Electrophoresis shows the preparation process of the coating solution
  • the electrophoretic display coating liquid can be accurately coated or printed on the substrate with a transparent conductive layer by using a coater, and then heated and cured to produce a multi-layer compactly arranged electrophoresis Display layer. Subsequently, the electrophoretic display material layer and the conductive layer are hot pressed together, and a spectrophotometer is used to test the black and white reflectance, contrast and other data of the electrophoretic display film after power-on driving. From the table below 1 It can be seen that the electrophoretic display film prepared from the electrophoretic display coating liquid of the present invention has the advantages of high contrast (greater than 7) and high white reflectivity (greater than 40%).
  • the L* value reflects the reflected light intensity of the display film. The higher the L* value, the stronger the reflectivity; 2.

Abstract

An electrophoretic display coating solution, said solution comprising microcapsules. The microcapsules contain a suspension and a plurality of charged pigment particles dispersed throughout the suspension. The microcapsules are dispersed throughout an adhesive. The adhesive is obtained by dissolving in water a water-soluble macromolecular compound having a density of 5%-20%. When the adhesive dries, at least one of the microcapsules therein changes shape. Also provided is a method of preparing said electrophoretic display coating solution as well as a method of using said same to prepare an electrophoretic display assembly.

Description

一种电泳显示涂布液及其制备方法 Electrophoresis display coating liquid and preparation method thereof
技术领域 Technical field
本发明涉及电泳显示的技术领域，特别涉及一种电泳显示涂布液及其制备方法。 The present invention relates to the technical field of electrophoretic display, in particular to an electrophoretic display coating liquid and a preparation method thereof.
背景技术 Background technique
电泳图象显示 ( EPID , 即 electrophoretic image display) 是利用胶体分散粒子在电场作用下发生泳动的现象 , 其优点是高对比度、大视角、高显示明亮度、低价格、容易实现大平面显示等。其缺点是可靠性差 , 阈值特性不容易控制 , 尤其是分散系中微粒易发生团聚、沉淀等现象 , 所以 EPID 显示的寿命较短。近年来 , 麻省理工学院 (MIT) 媒体实验室提出了电子墨水 (encapsulated electrophoretic ink) 的概念 , 即微胶囊化电泳显示技术 (encapsulated electrophoretic display) 。利用电泳显示原理 , 创新性地把颜料颗粒和深色染料溶液包裹在微囊内 , 在微囊内实现了电泳显示 , 从而抑制了电泳胶粒在大于胶囊尺度范围内的团聚、沉积等缺点 , 提高了其稳定性 , 延长使用寿命。电子墨水是一种墨水状的悬浮物 , 在外电场作用下可以实现可逆、双稳态、柔性显示 , 是一种融合物理、化学、电子学等学科的柔性显示材料和技术 , 具有良好的可视性、低功耗、信息载入能力强、携带方便、制造低廉、无电磁辐射等优点 , 且可以从根本上解决现有平板显示技术的不足。 Electrophoretic image display (EPID, namely electrophoretic image display) It is the phenomenon of using colloidal dispersed particles to migrate under the action of an electric field. Its advantages are high contrast, large viewing angle, high display brightness, low price, and easy realization of large flat display. Its disadvantage is poor reliability, The threshold characteristics are not easy to control, especially the particles in the dispersion system are prone to agglomeration, precipitation, etc., so the life of the EPID display is relatively short. In recent years, the Massachusetts Institute of Technology (MIT) The media laboratory put forward the concept of encapsulated electrophoretic ink, that is, microencapsulated electrophoretic display technology (encapsulated electrophoretic ink). electrophoretic display). Using the electrophoretic display principle, the pigment particles and the dark dye solution are innovatively wrapped in the microcapsule, and the electrophoretic display is realized in the microcapsule. Thereby, the shortcomings of agglomeration and deposition of the electrophoretic colloidal particles in the range larger than the size of the capsule are suppressed, and its stability is improved, and the service life is prolonged. Electronic ink is an ink-like suspended matter. Under the action of an external electric field, it can realize reversible, bistable, and flexible display. It is a flexible display material and technology that integrates physics, chemistry, electronics and other disciplines. It has the advantages of good visibility, low power consumption, strong information loading ability, convenient carrying, low manufacturing cost, and no electromagnetic radiation, and can fundamentally solve the deficiencies of the existing flat panel display technology.
目前的电子墨水采用 30-300 微米的球状透明光滑的微胶囊包覆电介质悬浮液，悬浮液中漂浮着带电电泳颗粒，这些胶囊分布在聚氨酯胶黏剂中构成分散体系，涂布或者印刷在柔性 ITO 导电薄膜上，构成原理型柔性 EPID 电子纸。 The current electronic ink uses 30-300 Micron spherical transparent and smooth microcapsules are coated with the dielectric suspension, in which there are charged electrophoretic particles. These capsules are distributed in the polyurethane adhesive to form a dispersion system, which is coated or printed on flexible ITO On the conductive film, a principle-type flexible EPID electronic paper is formed.
而胶囊在聚氨酯胶黏剂中不能很好的分散，存在着胶囊在较大尺寸范围内的团聚等缺点。这就造成在涂布包括滚涂、丝网印刷、喷涂等涂布方法时很难涂布，涂膜外观较差，存在各种外观缺陷，包括空点、刮痕、凸点、坏点等，从而使得良率较低。另外，用聚氨酯配制的墨水中由于聚氨酯在干燥过程中的收缩力不够大，胶囊不易变形，胶囊与胶囊之间空隙大，胶囊在基材上铺展不好，不能实现单层排布，从而光电性能较差。 However, the capsules cannot be dispersed well in the polyurethane adhesive, and there are disadvantages such as agglomeration of the capsules in a larger size range. This makes it difficult to apply when coating methods such as roll coating, screen printing, spraying, etc., the appearance of the coating film is poor, and there are various appearance defects, including voids, scratches, bumps, dead spots, etc. , Which makes the yield rate lower. In addition, in the ink formulated with polyurethane, the shrinkage force of the polyurethane during the drying process is not large enough, the capsule is not easy to deform, the gap between the capsule and the capsule is large, the capsule is not spread well on the substrate, and the single-layer arrangement cannot be realized. Performance is poor.
发明内容 Summary of the invention
本发明所要解决的技术问题是提供一种电泳显示涂布液及其制备方法，其可以解决上述提到的各种技术缺陷，微胶囊在电泳显示涂布液中的分散性更好，当电泳显示涂布液干燥时其中的微胶囊会产生变形，从而有效提高电泳显示涂布液的光电性能。 The technical problem to be solved by the present invention is to provide an electrophoretic display coating liquid and a preparation method thereof, which can solve the various technical defects mentioned above. The microcapsules have better dispersibility in the electrophoretic display coating liquid. When the display coating liquid is dried, the microcapsules therein will be deformed, thereby effectively improving the photoelectric performance of the electrophoretic display coating liquid.
本发明提供的一种电泳显示涂布液，其包含有微胶囊，所述微胶囊内包含有悬浮液和分散于悬浮液中的多个带电颜料粒子，所述带电颜料粒子在电场的作用下会在悬浮液中移动；所述微胶囊分散在胶黏剂中，该胶黏剂中包含有水溶性高分子化合物和水，其中水溶性高分子化合物的浓度为 5%-20% ；当所述胶黏剂干燥时，所述微胶囊至少有一个发生形变。 The present invention provides an electrophoretic display coating solution, which contains microcapsules, and the microcapsules contain a suspension and a plurality of charged pigment particles dispersed in the suspension, and the charged pigment particles are under the action of an electric field. Will move in the suspension; the microcapsules are dispersed in an adhesive, the adhesive contains a water-soluble polymer compound and water, wherein the concentration of the water-soluble polymer compound is 5%-20%; when the adhesive is dry, at least one of the microcapsules is deformed.
具体地，所述水溶性高分子化合物选自但不限于：羧甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、可溶性淀粉、羧甲基淀粉、阿拉伯胶、明胶、树胶、大豆蛋白、聚乙烯醇、聚乙二醇以及由上述两种或两种以上的材料组成的复合材料。 Specifically, the water-soluble polymer compound is selected from but not limited to: carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, soluble starch, carboxymethyl starch, gum arabic, gelatin, gum , Soybean protein, polyvinyl alcohol, polyethylene glycol, and composite materials composed of two or more of the above materials.
进一步地，所述电泳显示涂布液中胶黏剂与微胶囊的重量百分比为 10%-70% ；更佳地，所述电泳显示涂布液中胶黏剂与微胶囊的重量百分比可以优选为 25-50% 。所述水溶性高分子化合物的浓度优选为 7%-15% 。上述电泳显示涂布液中分散的微胶囊的粒径分布的跨度值为 0.5-0.7 。 Further, the electrophoresis shows that the weight percentage of the adhesive and the microcapsules in the coating solution is 10%-70% More preferably, the weight percentage of the adhesive and the microcapsules in the electrophoretic display coating solution may preferably be 25-50%. The concentration of the water-soluble polymer compound is preferably 7%-15% . The above electrophoresis shows that the particle size distribution of the microcapsules dispersed in the coating solution has a span value of 0.5-0.7.
具体地，上述微胶囊中还可以包含有若干中性颜料粒子。 Specifically, the aforementioned microcapsules may also contain several neutral pigment particles.
本发明还提供了一种电泳显示涂布液的制备方法，其包括以下步骤：
A 、将一定量水溶性高分子化合物溶解在水中，制得胶黏剂，其中水溶性高分子化合物的浓度为 5%-20% ；
B 、将所述胶黏剂加入到微胶囊中，进行搅拌混合后制得所述的电泳显示涂布液。
具体地，上述电泳显示涂布液中胶黏剂与微胶囊的重量百分比为 10%-70% 。The present invention also provides a method for preparing an electrophoretic display coating solution, which includes the following steps:
A. Dissolve a certain amount of water-soluble polymer compound in water to prepare an adhesive, wherein the concentration of the water-soluble polymer compound is 5%-20%;
B. The adhesive is added to the microcapsules, and the electrophoresis display coating solution is prepared after stirring and mixing.
Specifically, the above-mentioned electrophoresis shows that the weight percentage of the adhesive and the microcapsules in the coating solution is 10%-70%.
本发明还提供了一种电泳显示组件的制备方法，该电泳显示组件中包含有带透明导电层的透明基板，该制备方法包括：在所述透明导电层上涂布上述的电泳显示涂布液，待电泳显示涂布液干燥，干燥时其中的至少一个微胶囊发生形变，干燥后电泳显示涂布液形成电泳显示层。 The present invention also provides a method for preparing an electrophoretic display assembly, the electrophoretic display assembly includes a transparent substrate with a transparent conductive layer, the preparation method includes: coating the above-mentioned electrophoretic display coating liquid on the transparent conductive layer When the electrophoretic display coating liquid is dried, at least one of the microcapsules is deformed during drying, and after drying, the electrophoretic display coating liquid forms an electrophoretic display layer.
具体地，上述步骤中在透明导电层上涂布所述电泳显示涂布液的厚度大概为 50-300 μ m ；干燥固化之后的厚度大约为 20-120 μ m 。所述电泳显示涂布液中的胶黏剂在干燥时收缩且展平；干燥之后，其中微胶囊的截面由圆形或椭圆形变为多边形。 Specifically, the thickness of the electrophoretic display coating liquid coated on the transparent conductive layer in the above steps is about 50-300 μm ; The thickness after drying and curing is about 20-120 μ m . The electrophoresis shows that the adhesive in the coating solution shrinks and becomes flat when dried; after drying, the cross section of the microcapsule changes from a circular or elliptical shape to a polygonal shape.
与现有技术相比，由于本发明的电泳显示涂布液中的胶黏剂是一种水溶性高分子的溶液，其有利于微胶囊在水中的分散，有效减少了微胶囊之间的团聚，其在干燥时可以产生一定的收缩应力，从而使得分散在其中的微胶囊变形，本发明的电泳显示涂布液由于其胶黏剂流动性更好，可在涂布时实现单层涂膜，涂膜表面光滑，干燥后的电泳显示层中微胶囊的密度更高，从而有效提高了电泳显示涂布液的光电性能。 Compared with the prior art, since the adhesive in the electrophoretic display coating solution of the present invention is a water-soluble polymer solution, it is beneficial to the dispersion of microcapsules in water and effectively reduces the agglomeration between microcapsules. It can produce a certain shrinkage stress during drying, thereby deforming the microcapsules dispersed therein. The electrophoretic display coating solution of the present invention can realize a single-layer coating film due to its better adhesive fluidity. , The surface of the coating film is smooth, and the density of microcapsules in the electrophoretic display layer after drying is higher, thereby effectively improving the photoelectric performance of the electrophoretic display coating liquid.
附图说明 Description of the drawings
图 1 是现有的一种电泳显示涂布液的涂布外观图；
图 2 是本发明一种电泳显示涂布液在一种实施方式中的涂布外观图；
图 3 是本发明一种电泳显示组件的制备方法在一种实施方式中的制备流程图；
图 4 是本发明一种电泳显示涂布液的制备方法在一种实施方式中的制备流程图；
图 5 是本发明图 3 中步骤 S2 中刚涂布上电泳显示涂布液时电泳显示组件的结构示意图；
图 6 是本发明图 3 中步骤 S2 中涂布的电泳显示涂布液干燥后的电泳显示组件的结构示意图。Figure 1 is a drawing of the coating appearance of an existing electrophoretic display coating liquid;
FIG. 2 is a drawing of the appearance of an electrophoretic display coating liquid in an embodiment of the present invention;
Fig. 3 is a preparation flow chart of an embodiment of a preparation method of an electrophoretic display assembly of the present invention;
4 is a preparation flow chart of an embodiment of a preparation method of an electrophoretic display coating solution of the present invention;
5 is a schematic diagram of the structure of the electrophoretic display assembly when the electrophoretic display coating liquid is just coated in step S2 in FIG. 3 of the present invention;
6 is a schematic diagram of the structure of the electrophoretic display assembly after the electrophoretic display coating liquid coated in step S2 in FIG. 3 of the present invention is dried.
具体实施方式 Detailed ways
本发明公开了一种可用于电泳显示涂布液中的胶黏剂材料，这种胶黏剂是由一种水溶性高分子化合物溶解于水中而制成；之前这种材料主要应用于医药、片剂、食品加工等行业领域。水溶性高分子化合物又称为水溶性树脂或水溶性聚合物。通常所说的水溶性高分子是一种强亲水性的高分子材料，能溶解或溶胀于水中形成水溶液或分散体系。 The invention discloses an adhesive material that can be used in an electrophoretic display coating solution. This adhesive is made by dissolving a water-soluble polymer compound in water; previously this material is mainly used in medicine, Industry fields such as tablets and food processing. Water-soluble polymer compounds are also called water-soluble resins or water-soluble polymers. The usually said water-soluble polymer is a highly hydrophilic polymer material that can be dissolved or swelled in water to form an aqueous solution or dispersion system.
水溶性高分子按来源通常分为三大类： 1 、天然水溶性高分子。以天然动植物为原料提取而得；如淀粉类、纤维素、植物胶、动物胶等； 2 、化学改性天然聚合物；主要有改性淀粉和改性纤维素；如羧甲基淀粉、醋酸淀粉、羟甲基纤维素、羧甲基纤维素等； 3 、合成聚合物。有聚合类树脂和缩合类树脂两类，如 聚丙烯酰胺(PAM) 、水解聚丙烯酰胺 (HPAM)) 、 聚乙烯吡咯烷酮(PVP) 等。 Water-soluble polymers are generally divided into three categories according to their sources: 1 , Natural water-soluble polymer. Extracted from natural animals and plants; such as starch, cellulose, vegetable glue, animal glue, etc.; 2 1. Chemically modified natural polymers; mainly include modified starch and modified cellulose; such as carboxymethyl starch, acetate starch, hydroxymethyl cellulose, carboxymethyl cellulose, etc.; 3. Synthetic polymers. There are two types of polymer resins and condensation resins, such as Polyacrylamide (PAM), hydrolyzed polyacrylamide (HPAM)), polyvinylpyrrolidone (PVP), etc.
水溶性高分子材料主要具有以下功能： ① 水溶性， ② 分散作用， ③ 絮凝作用， ④ 增粘性， ⑤ 减阻作用， ⑥ 流变性。 Water-soluble polymer materials mainly have the following functions: ① water solubility, ② dispersion, ③ flocculation, ④ viscosity increasing, ⑤ Drag reduction effect, ⑥ rheology.
本发明的电泳显示涂布液中包含有微胶囊，微胶囊内包裹有悬浮液和分散于悬浮液中的多个带电颜料粒子（同极性或不同极性），当然也可以包含若干的中性带电颜料粒子；这些微胶囊均匀分散在胶黏剂中，将电泳显示涂布液涂布在带有透明导电层（例如 ITO ）的基板上 , 待电泳显示涂布液干燥之后会在 ITO 层上面形成一层很薄的电泳显示层，若在电泳显示层的两侧加一定的电压，电泳显示层中的微胶囊里面的带电颜料粒子会在悬浮液中发生电泳，从而实现电泳显示。 The electrophoresis display coating solution of the present invention contains microcapsules, and the microcapsules contain a suspension and a plurality of charged pigment particles (same polarity or different polarities) dispersed in the suspension. Of course, it can also contain several medium. Charged pigment particles; these microcapsules are uniformly dispersed in the adhesive, and the electrophoretic display coating liquid is coated on the transparent conductive layer (such as ITO), after the electrophoretic display coating solution is dried, it will be on the ITO A very thin electrophoretic display layer is formed on the layer. If a certain voltage is applied to both sides of the electrophoretic display layer, the charged pigment particles in the microcapsules in the electrophoretic display layer will undergo electrophoresis in the suspension to realize electrophoretic display.
本发明采用的胶黏剂是由一种透明光泽的粉粒状水溶性高分子化合物溶解于水中而制成；这种水溶性高分子化合物包括但不限于：羧甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、可溶性淀粉、羧甲基淀粉、阿拉伯胶、明胶、树胶、大豆蛋白、酪蛋白、聚乙烯醇、聚乙二醇、聚丙烯酰胺、聚乙烯吡咯烷酮等它们的混合物和衍生物。 The adhesive used in the present invention is made by dissolving a transparent and glossy powdery granular water-soluble polymer compound in water; this water-soluble polymer compound includes but is not limited to: carboxymethyl cellulose, hydroxyethyl fiber Vegetarian, hydroxypropyl methylcellulose, soluble starch, carboxymethyl starch, gum arabic, gelatin, gum, soy protein, casein, polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyvinylpyrrolidone, etc. Mixtures and derivatives.
制备胶黏剂时，水溶性高分子化合物需要在 30-70 度的温度范围下溶解，上述胶黏剂中水溶性高分子化合物的浓度为 5%-20% ；优选在 7%-15% 区间；最佳为 10% 左右。制备好胶黏剂之后，将其与微胶囊按一定的比例进行混合，即将微胶囊分散到制备好的胶黏剂中，配好的电泳显示涂布液中，胶黏剂与微胶囊的百分比控制在 10%-70% 之间，优选为 25%-50% 区间；最好为 40% 左右。 When preparing the adhesive, the water-soluble polymer compound needs to be in the range of 30-70 The concentration of water-soluble polymer compound in the above-mentioned adhesive is 5%-20%; preferably in the range of 7%-15%; the best is 10% about. After the adhesive is prepared, it is mixed with the microcapsules in a certain ratio, that is, the microcapsules are dispersed into the prepared adhesive, and the prepared electrophoresis displays the percentage of the adhesive to the microcapsules in the coating solution control in Between 10%-70%, preferably 25%-50%; preferably around 40%.
电泳显示涂布液中的微胶囊在水溶性高分子溶液（即胶黏剂）中可以均匀分散，分散后的微胶囊的粒径分布的跨度值为 0.5-0.7 ；有效减少了微胶囊的团聚等问题。当胶黏剂在室温下干燥时，其中分散的微胶囊至少有一个会发生形变。 Electrophoresis shows that the microcapsules in the coating solution can be uniformly dispersed in the water-soluble polymer solution (ie, the adhesive), and the particle size distribution span of the dispersed microcapsules is 0.5-0.7; effectively reduce the agglomeration of microcapsules and other problems. When the adhesive is dried at room temperature, at least one of the dispersed microcapsules will deform.
本发明还提供了一种由上述的电泳显示涂布液来制成电泳显示组件的制备方法，该方法的具体实施步骤参见图 3 ；涂布的电泳显示液在干燥前后的电泳显示组件的结构示意图参看图 5 和图 6 。 The present invention also provides a method for preparing an electrophoretic display assembly from the above-mentioned electrophoretic display coating solution. The specific implementation steps of the method are shown in FIG. 3 ; Refer to Figure 5 and Figure 6 for the structure diagram of the electrophoretic display assembly before and after the drying of the coated electrophoretic display liquid.
S1: 首先在一层透明的基板 33 上涂布一层透明导电层 22 ，具体可以选用 PET 作为透明基板，在 PET 上涂布一层 ITO( 铟锡氧化物 ) ，待 ITO 干燥； S1: First, coat a transparent conductive layer 22 on a transparent substrate 33. Specifically, PET can be used as a transparent substrate. Coat a layer of ITO (Indium Tin Oxide) on the PET and wait for the ITO to dry;
S2: 然后，在干燥的 ITO 导电层 22 之上涂布一层前文中提到的包含有水溶性高分子化合物的电泳显示涂布液 11 ，大概涂 50-300 μ m 的厚度，在室温条件下（ 25 摄氏度左右）干燥 15 分钟以上，电泳显示涂布液 11 中的胶黏剂 111 在干燥时收缩且展平；干燥之后，其中微胶囊 110 的截面由圆形或椭圆形变为多边形（如图 2 所示）；干燥之后的电泳显示层 11 变薄，厚度大约变为 20-120 μ m 。 S2: Then, in the dried ITO conductive layer 22 Coat a layer of electrophoresis display coating liquid 11 containing water-soluble polymer compounds mentioned above, approximately 50-300 μm thick, and dry at room temperature (about 25 degrees Celsius) 15 For more than minutes, electrophoresis showed that the adhesive 111 in the coating solution 11 shrank and flattened during drying; after drying, the cross section of the microcapsule 110 changed from a circular or elliptical shape to a polygonal shape (as shown in Figure 2). Shown); after drying, the electrophoretic display layer 11 becomes thinner, and the thickness becomes approximately 20-120 μm.
S3: 之后在电泳显示层上再涂布胶水层，该胶水层的体电阻率大概为 105 ～ 1014ohm·cm ，其材料可以选自但不限于环氧树脂类、聚氨酯类、有机硅类粘接剂、聚丙烯酸类及聚丙烯酸酯类的粘接剂、及以上材料中的两种或两种以上的复合材料。 S3: Then apply a glue layer on the electrophoretic display layer. The volume resistivity of the glue layer is about 105 ～ 1014ohm·cm , The material can be selected from, but not limited to, epoxy resin, polyurethane, silicone adhesive, polyacrylic and polyacrylate adhesive, and a combination of two or more of the above materials Material.
S4: 最后在胶水层上方贴附上一层保护层或者铝箔之类的分离片。 S4: Finally, attach a protective layer or a separation sheet such as aluminum foil on top of the glue layer.
上述电泳显示涂布液中的水溶性高分子化合物在胶黏剂干燥过程中能产生一定的收缩应力，可以使微胶囊发生有效的变形，从而使微胶囊变形后能够紧密堆积，如图 2 所示。干燥后形成的电泳显示层中微胶囊的密度大大提高了，使得加电场发生电泳时电极一侧的电泳粒子密度增加，这样，测得的黑白反射率也大大增加，随之对比度也得到了提高。 The above-mentioned electrophoresis shows that the water-soluble polymer compound in the coating solution can produce a certain shrinkage stress during the drying process of the adhesive, which can effectively deform the microcapsules, so that the microcapsules can be tightly packed after deformation, as shown in Figure 2. Shown. The density of microcapsules in the electrophoretic display layer formed after drying is greatly increased, which increases the density of electrophoretic particles on the electrode side when an electric field is applied to generate electrophoresis. In this way, the measured black and white reflectivity is also greatly increased, and the contrast is also improved. .
本发明所用到的水溶性高分子化合物具有一定的表面活性，可以在一定程度上降低水的表面张力，有助于水对微胶囊囊壁的润湿，从而有利于微胶囊在水中的分散，有效减少了微胶囊之间的团聚。同时，此类水溶性高分子化合物有一定的流变性能，从而配制的电泳显示涂布液流平性较好，涂布外观能得到较大提高，如图 2 所示。 The water-soluble polymer compound used in the present invention has a certain surface activity, which can reduce the surface tension of water to a certain extent, help the wetting of the wall of the microcapsule by water, and thus facilitate the dispersion of the microcapsule in water. Effectively reduce the agglomeration between microcapsules. At the same time, such water-soluble polymer compounds have certain rheological properties, so the prepared electrophoresis shows that the coating liquid has better leveling properties and the coating appearance can be greatly improved, as shown in the figure 2 shown.
用上述水溶性高分子化合物所配制的电泳显示涂布液涂布出来的涂膜外观较好，并且有较好的光电性能。具体表现为：微胶囊在电泳显示涂布液干燥时能发生形变，形变后的胶囊紧密堆积，电泳时电极一侧的电泳粒子密度增加，对比度提高。相比于其它采用聚氨酯类胶黏剂配制的电泳显示涂布液，本发明的电泳显示涂布液的对比度要高 3-4 。 The electrophoretic display coating liquid prepared with the above-mentioned water-soluble polymer compound has a better appearance and better photoelectric properties. Specifically, the microcapsules can be deformed when the electrophoretic display coating solution is dried, the deformed capsules are tightly packed, the density of electrophoretic particles on the electrode side during electrophoresis increases, and the contrast is improved. Compared with other electrophoretic display coating liquids prepared with polyurethane adhesives, the electrophoretic display coating liquid of the present invention has higher contrast 3-4.
本发明还提供了上述电泳显示涂布液的配制方法，该方法制备工艺简单易行，配制过程易于控制，对设备无特殊要求。 The present invention also provides a preparation method of the above-mentioned electrophoresis display coating liquid. The preparation process of the method is simple and feasible, the preparation process is easy to control, and there is no special requirement for equipment.
参见图 4 ，该电泳显示涂布液的配制方法包括以下步骤：
S01 、将一定量水溶性高分子的材料溶解于水中，制得胶黏剂，其中水溶性高分子的浓度为 5%-20% ；
S02 、对上述制得的胶黏剂进行过滤处理，以去除胶黏剂中的杂质；
S03 、称取一定量的微胶囊进行离心处理，再加水调节其固含量；然后与步骤 S02 中过滤后的胶黏剂进行混合；其中胶黏剂与微胶囊的百分比控制在 10%-70% 之间，最好为 40%;
S04 、搅拌一段时间后，制得电泳显示涂布液。Referring to Figure 4, the preparation method of the electrophoretic display coating solution includes the following steps:
S01. Dissolve a certain amount of water-soluble polymer materials in water to prepare an adhesive, wherein the concentration of the water-soluble polymer is 5%-20%;
S02. Filter the adhesive prepared above to remove impurities in the adhesive;
S03. Weigh a certain amount of microcapsules for centrifugation, then add water to adjust the solid content; then mix with the adhesive filtered in step S02; the percentage of adhesive to microcapsules is controlled at 10%-70% Between, preferably 40%;
S04. After stirring for a period of time, an electrophoretic display coating solution is prepared.
上述步骤 S04 中的搅拌速度具体可以为每分钟 50-300 转；最佳为每分钟 250 转。 The stirring speed in the above step S04 may specifically be 50-300 revolutions per minute; the best is 250 revolutions per minute.
进一步地，步骤 S04 搅拌混合后，制得的电泳显示涂布液应在 30 摄氏度左右（大约在 20 至 40 摄氏度的范围内）的环境温度中存放一定时间，才可用来涂布。存放的时间根据配制的电泳显示涂布液总量而定，量越多时间就越久，一般存放半个小时至两小时左右即可。 Further, after the stirring and mixing in step S04, the prepared electrophoretic display coating solution should be at about 30 degrees Celsius (about 20 to 40 degrees Celsius). It can be used for coating only after it is stored for a certain period of time in the ambient temperature within the range of Celsius. The storage time is determined by the total amount of the electrophoresis display coating solution prepared. The more the amount, the longer the time. Generally, it can be stored for about half an hour to two hours.
制得的电泳显示涂布液应当储藏在 5 - 10 摄氏度的冰箱或冷藏库中，一般可以保藏一周左右的时间；每次需要用时，取出所需要的量，刚取出的电泳显示涂布液需要经过 30-50 摄氏度温度的水浴溶解，溶解之后才可进行涂布用。 The prepared electrophoresis shows that the coating solution should be stored in 5-10 Generally, it can be stored in a refrigerator or freezer in degrees Celsius for about a week; each time you need to use it, take out the required amount. The electrophoresis display coating solution just taken out needs to pass 30-50 It is dissolved in a water bath at a temperature of degrees Celsius, and then can be used for coating.
下面举例说明上述本发明的构思原理；所举的实例仅用于阐述本发明，本发明的保护范围并不局限于以下所列举的实例。 The following examples illustrate the conception principle of the present invention; the examples cited are only used to illustrate the present invention, and the protection scope of the present invention is not limited to the examples listed below.
1 、电泳显示涂布液的配制过程 1. Electrophoresis shows the preparation process of the coating solution
称取 150g 离心好的微胶囊，将 10g 聚乙二醇（也可以是其他的水溶性高分子化合物）溶解于 80g 水中，将溶解好的聚乙二醇溶液过滤后加入微胶囊中，以 250rpm 的搅拌速度进行搅拌混合，混合 1 小时后制得电泳显示涂布液。 Weigh 150g of centrifuged microcapsules, and dissolve 10g polyethylene glycol (or other water-soluble polymer compounds) in 80g In water, filter the dissolved polyethylene glycol solution and add it to the microcapsules, stir and mix at a stirring speed of 250 rpm, and mix for 1 hour to prepare an electrophoretic display coating solution.
2 、电泳显示涂布液制得的光电性能检测 2. Photoelectric performance detection made by electrophoresis display coating liquid
通过上述方法步骤制得电泳显示涂布液之后，可利用涂布仪将电泳显示涂布液精确涂布或印刷在带透明导电层的基板上，经过加热固化，制得多层紧密排列的电泳显示层。随后将上述电泳显示材料层和导电层热压在一起，用分光光度计来测试加电驱动后电泳显示膜的黑白反射率、对比度等数据。从下面的表 1 可知，由本发明的电泳显示涂布液所制得的电泳显示膜片具有高对比度（大于 7 ）和高白色反射率（大于 40% ）等优点。 After the electrophoretic display coating liquid is prepared by the above method steps, the electrophoretic display coating liquid can be accurately coated or printed on the substrate with a transparent conductive layer by using a coater, and then heated and cured to produce a multi-layer compactly arranged electrophoresis Display layer. Subsequently, the electrophoretic display material layer and the conductive layer are hot pressed together, and a spectrophotometer is used to test the black and white reflectance, contrast and other data of the electrophoretic display film after power-on driving. From the table below 1 It can be seen that the electrophoretic display film prepared from the electrophoretic display coating liquid of the present invention has the advantages of high contrast (greater than 7) and high white reflectivity (greater than 40%).
表 1 电泳显示膜的黑白反射率、对比度测试结果 Table 1 Black and white reflectance and contrast test results of electrophoretic display film
L* 白 L* white L* 黑 L* black R 白 R white R 黑 R black 对比度 Contrast
显示膜 Display film 70.69 70.69 26.63 26.63 41.74 41.74 4.96 4.96 8.41 8.41
注： 1. L* 数值体现了显示膜的反射光强， L* 值越高就意味着反射率越强；
2. R 数值体现了显示膜的反射率数值， R= （（ L*+16 ） /116 ） 3*100% ；
3. 对比度 =R 白 /R 黑。Note: 1. The L* value reflects the reflected light intensity of the display film. The higher the L* value, the stronger the reflectivity;
2. The R value reflects the reflectance value of the display film, R= ((L*+16) /116) 3*100%;
3. Contrast=R white/R black.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉该技术的人在本发明所揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。 The above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited to this. Anyone familiar with the technology can easily think of changes or substitutions within the technical scope disclosed in the present invention. , Should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (14)

  1. 一种电泳显示涂布液，其包含有微胶囊，所述微胶囊内包含有悬浮液和分散于悬浮液中的多个带电颜料粒子，所述带电颜料粒子在电场的作用下会在悬浮液中移动；其特征在于，所述微胶囊分散在胶黏剂中，该胶黏剂中包含有水溶性高分子化合物和水，其中水溶性高分子化合物的浓度为 5%-20% ;当所述胶黏剂干燥时，所述微胶囊至少有一个发生形变。 An electrophoretic display coating liquid, which contains microcapsules, the microcapsules contain a suspension and a plurality of charged pigment particles dispersed in the suspension, the charged pigment particles will be suspended in the suspension under the action of an electric field Mobile; characterized in that the microcapsules are dispersed in an adhesive, the adhesive contains a water-soluble polymer compound and water, wherein the concentration of the water-soluble polymer compound is 5%-20%; When the adhesive is dry, at least one of the microcapsules deforms.
  2. 如权利要求 1 所述的电泳显示涂布液，其特征在于，所述水溶性高分子化合物选自但不限于：羧甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、可溶性淀粉、羧甲基淀粉、阿拉伯胶、明胶、树胶、大豆蛋白、聚乙烯醇、聚乙二醇以及由上述两种或两种以上的材料组成的复合材料。As claimed in claim 1 The electrophoresis display coating solution is characterized in that the water-soluble polymer compound is selected from but not limited to: carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, soluble starch, carboxymethyl cellulose Methyl starch, gum arabic, gelatin, gum, soy protein, polyvinyl alcohol, polyethylene glycol, and composite materials composed of two or more of the above materials.
  3. 如权利要求 1 所述的电泳显示涂布液，其特征在于，所述电泳显示涂布液中胶黏剂与微胶囊的重量百分比为 10%-70% 。The electrophoretic display coating liquid of claim 1, wherein the weight percentage of the adhesive and the microcapsules in the electrophoretic display coating liquid is 10%-70% .
  4. 如权利要求3所述的电泳显示涂布液，其特征在于，所述电泳显示涂布液中胶黏剂与微胶囊的重量百分比为25%-50%。8. The electrophoretic display coating liquid of claim 3, wherein the weight percentage of the adhesive and the microcapsules in the electrophoretic display coating liquid is 25%-50%.
  5. 如权利要求4所述的电泳显示涂布液，其特征在于，所述胶黏剂中水溶性高分子化合物的浓度为7%-15%。8. The electrophoretic display coating solution of claim 4, wherein the concentration of the water-soluble polymer compound in the adhesive is 7%-15%.
  6. 如权利要求4所述的电泳显示涂布液，其特征在于，所述电泳显示涂布液中分散的微胶囊的粒径分布的跨度值为0.5-0.7。The electrophoretic display coating liquid of claim 4, wherein the particle size distribution of the microcapsules dispersed in the electrophoretic display coating liquid has a span value of 0.5-0.7.
  7. 如权利要求1所述的电泳显示涂布液，其特征在于，所述微胶囊中还包含有若干中性颜料粒子.The electrophoretic display coating solution of claim 1, wherein the microcapsules also contain a number of neutral pigment particles.
  8. 一种电泳显示涂布液的制备方法，其特征在于包括以下步骤：A method for preparing an electrophoretic display coating solution, which is characterized in that it comprises the following steps:
    A、将水溶性高分子化合物溶解于水中，制得胶黏剂，其中水溶性高分子化合物的浓度为5%-20%；A. The water-soluble polymer compound is dissolved in water to prepare an adhesive, wherein the concentration of the water-soluble polymer compound is 5%-20%;
    B、将所述胶黏剂加入到微胶囊中，进行搅拌混合后制得所述的电泳显示涂布液。B. The adhesive is added to the microcapsules, and the electrophoresis display coating solution is prepared after stirring and mixing.
  9. 如权利要求8所述的电泳显示涂布液的制备方法，其特征在于，所述水溶性高分子化合物选自但不限于：羧甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、可溶性淀粉、羧甲基淀粉、阿拉伯胶、明胶、树胶、大豆蛋白、聚乙烯醇、聚乙二醇以及由上述两种或两种以上的材料组成的复合材料。8. The method for preparing an electrophoretic display coating solution according to claim 8, wherein the water-soluble polymer compound is selected from but not limited to: carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl Cellulose, soluble starch, carboxymethyl starch, gum arabic, gelatin, gum, soy protein, polyvinyl alcohol, polyethylene glycol, and composite materials composed of two or more of the above materials.
  10. 如权利要求8所述的电泳显示涂布液的制备方法，其特征在于，所述电泳显示涂布液中胶黏剂与微胶囊的重量百分比为10%-70%。8. The method for preparing an electrophoretic display coating liquid according to claim 8, wherein the weight percentage of the adhesive and the microcapsules in the electrophoretic display coating liquid is 10%-70%.
  11. 如权利要求10所述的电泳显示涂布液的制备方法，其特征在于，所述水溶性高分子化合物的浓度为7%-15%。10. The method for preparing an electrophoretic display coating solution according to claim 10, wherein the concentration of the water-soluble polymer compound is 7%-15%.
  12. 一种电泳显示组件的制备方法，该电泳显示组件中包含有带透明导电层的透明基板，其特征在于，所述制备方法包括：在所述透明导电层上涂布权利要求1所述的电泳显示涂布液，待电泳显示涂布液干燥，干燥时其中的至少一个微胶囊发生形变，干燥后电泳显示涂布液形成电泳显示层。A method for preparing an electrophoretic display assembly, the electrophoretic display assembly includes a transparent substrate with a transparent conductive layer, wherein the preparation method comprises: coating the transparent conductive layer with the electrophoresis according to claim 1 When the electrophoretic display coating liquid is dried, at least one of the microcapsules is deformed when the electrophoretic display coating liquid is dried. After drying, the electrophoretic display coating liquid forms an electrophoretic display layer.
  13. 如权利要求12所述的电泳显示组件的制备方法，其特征在于，所述电泳显示涂布液中的胶黏剂在干燥时收缩且展平；所述电泳显示涂布液干燥之后，其中至少一个微胶囊的截面变为多边形。The method for preparing an electrophoretic display assembly according to claim 12, wherein the adhesive in the electrophoretic display coating solution shrinks and flattens when dried; after the electrophoretic display coating solution is dried, at least The cross section of a microcapsule becomes a polygon.
  14. 如权利要求13所述的电泳显示组件的制备方法，其特征在于，所述步骤B中在透明导电层上涂布所述电泳显示涂布液的厚度为50-300μm；干燥固化之后的厚度为20-120μmThe method for preparing an electrophoretic display assembly according to claim 13, wherein the thickness of the electrophoretic display coating liquid coated on the transparent conductive layer in the step B is 50-300 μm; the thickness after drying and curing is 20-120μm
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