WO2019161647A1 - Electrophoretic display diaphragm, electrophoretic display, and electrophoretic display coating liquid - Google Patents

Electrophoretic display diaphragm, electrophoretic display, and electrophoretic display coating liquid Download PDF

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Publication number
WO2019161647A1
WO2019161647A1 PCT/CN2018/102277 CN2018102277W WO2019161647A1 WO 2019161647 A1 WO2019161647 A1 WO 2019161647A1 CN 2018102277 W CN2018102277 W CN 2018102277W WO 2019161647 A1 WO2019161647 A1 WO 2019161647A1
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WIPO (PCT)
Prior art keywords
electrophoretic display
microcapsules
electrophoretic
size
layer
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PCT/CN2018/102277
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French (fr)
Chinese (zh)
Inventor
曾晞
陈宇
马宝光
陈伟楠
苏晶
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广州奥翼电子科技股份有限公司
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Publication of WO2019161647A1 publication Critical patent/WO2019161647A1/en

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    • 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
    • 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 
    • G02F1/13—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 liquid crystals, e.g. single liquid crystal display cells
    • G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Definitions

  • the invention relates to the field of display devices, in particular to an electrophoretic display film, an electrophoretic display and an electrophoretic display coating liquid.
  • Electrophoretic displays are paper-thin, soft and rewritable displays that have gained increasing popularity in billboards and price cards in recent years.
  • electrophoretic display technology mainly includes microcapsule technology and microcup technology.
  • the display effect depends to a large extent on the compactness of the arrangement of the microcapsules, and the degree of compactness of the array is closely related to the size distribution of the microcapsules.
  • the relationship between the size of the relatively reliable microcapsule and the display effect of the electrophoretic display has not been found, so that the production process of the electrophoretic display capable of stably producing the display performance has not been developed accordingly.
  • the mass production and wide application of electrophoretic displays are greatly affected.
  • an object of the present invention is to provide an electrophoretic display film, an electrophoretic display, and an electrophoretic display coating liquid having good display performance.
  • an embodiment of the present invention provides an electrophoretic display film including an electrophoretic display layer, the electrophoretic display layer including a curing medium and a plurality of microcapsules distributed in the curing medium, each The microcapsule contains an electrophoresis liquid and a plurality of electrophoretic pigment particles dispersed in the electrophoresis liquid.
  • the percentage of microcapsules having a size smaller than 30 micrometers is 15% or more, and the percentage of microcapsules having a size larger than 55 micrometers is less than 25%.
  • the percentage of microcapsules having a size of less than 30 microns is greater than or equal to 20%; and/or the percentage of microcapsules having a size greater than 55 microns is less than 15%, preferably less than 10%.
  • the ratio of the number of microcapsules having a size of less than 30 microns to the number of microcapsules having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably greater than 5:1.
  • an electrophoretic display comprising: a transparent substrate, a transparent conductive electrode, a driving substrate, and the electrophoretic display layer of any of the above embodiments, the transparent substrate, the transparent conductive electrode, the electrophoretic display layer, and
  • the driving substrate is sequentially connected in a stack, and the driving substrate is provided with a driving circuit and a driving electrode connected to the driving circuit, and the driving electrode and the transparent conductive electrode are used for applying an electrical signal at both ends of the electrophoretic display layer .
  • the electrophoretic display layer and the transparent conductive electrode and/or the electrophoretic display layer and the driving substrate are connected by an adhesive layer, and the thickness of the electrophoretic display layer and the adhesive layer The thickness ratio is 1-10:1.
  • the electrophoretic pigment particles comprise pigment particles and an organic modified layer formed on a surface of the pigment particles; the organic modified layer is a surfactant layer or a polymer material formed on a surface of the pigment particles
  • the pigment particles have a specific surface area organic content W surf in the range of 0.1 to 2% g/m 2 , and more preferably W surf is in the range of 0.25 to 1.6% g/m 2 .
  • the organically modified layer has a thickness greater than 20 nm, preferably between 30 nm and 100 nm.
  • a further aspect of the present invention provides an electrophoretic display coating liquid comprising a dispersion medium and a plurality of microcapsules dispersed in the dispersion medium, each microcapsule containing an electrophoresis liquid and a plurality of dispersions in the electrophoresis liquid
  • the electrophoretic pigment particles have a percentage of microcapsules having a size of less than 30 micrometers of 15% or more, and a percentage of microcapsules having a size of more than 55 micrometers of less than 25%.
  • the percentage of microcapsules having a size of less than 30 microns is greater than or equal to 20%; and/or the percentage of microcapsules having a size greater than 55 microns is less than 15%, preferably less than 10%.
  • the ratio of the number of microcapsules having a size of less than 30 microns to the number of microcapsules having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably greater than 5:1.
  • the electrophoretic display film, the electrophoretic display and the electrophoretic display coating liquid provided by the embodiments of the present invention are controlled in an appropriate content range by the small-sized microcapsules and the large-sized microcapsules, so that the electrophoretic display layer of the electrophoretic display is
  • the microcapsules can achieve a relatively tight alignment effect, so that the electrophoretic display achieves a better display effect.
  • FIG. 1 to 3 are schematic structural views of an electrophoretic display according to three embodiments of the present invention.
  • FIGS. 4 to 6 are schematic structural views of an electrophoretic display film according to three embodiments of the present invention.
  • FIG. 7 is a microscopic enlarged view of an electrophoretic display layer of an electrophoretic display according to an embodiment of the present invention.
  • Figure 8 is a microscopic enlarged view of an electrophoretic display layer of an electrophoretic display of the comparative example of the present invention.
  • an embodiment of the present invention provides an electrophoretic display including a transparent substrate 13 , a transparent conductive electrode 12 , an electrophoretic display layer 20 , and a driving substrate 30 , a transparent substrate 13 , a transparent conductive electrode 12 , and an electrophoretic display layer. 20 and the drive bottom plate 30 are sequentially laminated and connected.
  • the electrophoretic display layer 20 includes a curing medium and a plurality of microcapsules 21 distributed in the curing medium. Each of the microcapsules 21 includes an electrophoresis liquid and electrophoretic pigment particles suspended in the electrophoresis liquid.
  • the drive substrate 30 is provided with a drive circuit and a drive electrode connected to the drive circuit, and the drive electrode and the transparent conductive electrode 12 are used to apply an electrical signal to both ends of the electrophoretic display layer 20.
  • the transparent substrate 13 may be made of materials such as polyethylene terephthalate (PET), polyethylene (PE), polyimide (PI), and polyethylene naphthalate (PEN). to make.
  • the transparent conductive electrode 12 can be made by growing a material such as an indium tin oxide (ITO) film, a nano silver wire, or a graphene film on the transparent substrate 13.
  • ITO indium tin oxide
  • the electrophoretic pigment particles in the microcapsule 21 may have black particles and white particles or particles of other colors.
  • the electrophoretic pigment particles have electric charges and can move in the electrophoresis liquid under the action of an electric field, and control electrophoretic pigment particles of different colors through different electric signals.
  • the transparent conductive electrode 12 is moved such that the electrophoretic display layer 20 displays patterns and characters.
  • the electrophoretic display layer 20 may be formed by coating an electrophoretic display coating liquid containing a plurality of microcapsules 21 on the transparent conductive electrode 12 and drying the electrophoretic display coating liquid.
  • the electrophoresis after drying shows that the coating liquid forms a curing medium, and the curing medium may contain an adhesive, a thickener, a leveling agent, a surfactant, an antifoaming agent, and the like.
  • the driving substrate 30 can be formed by fabricating a Thin Film Transistor (TFT) driving circuit by a semiconductor process on a substrate such as glass, PI, or PET. Both the drive substrate 30 and the transparent conductive electrode 12 are connected to circuitry for applying electrical signals on both sides of the electrophoretic display layer 20.
  • the driving electrode may be a pixel electrode of the electrophoretic display, and the voltage signal on the driving electrode is controlled by the controller to control the electrophoretic display layer 20 to display the display pattern and the character.
  • the microcapsule 21 may have a plurality of positively charged black electrophoretic pigment particles and a plurality of negatively charged white electrophoretic pigment particles, or a plurality of positively or negatively charged black electrophoretic pigment particles and a plurality of electrons.
  • a dye with a specific color may be added to the microcapsule 21, so that the liquid in the microcapsule 21 has a characteristic color, and the electrophoretic pigment particles therein have a different color from the solution, and one, two or two of them may be present. More than one type of electrophoretic pigment particles.
  • the microcapsule 21 includes a combination of a plurality of positively or negatively charged white electrophoretic pigment particles and dyes of other colors, or a plurality of positively charged black electrophoretic pigment particles and a plurality of negatively charged a combination of white electrophoretic pigment particles and a dye of a third color, or a combination of a plurality of positively or negatively charged black electrophoretic pigment particles and a plurality of electrically neutral white electrophoretic pigment particles and a third color of dye Or a combination of a plurality of electrically neutral black electrophoretic pigment particles and a plurality of positively or negatively charged white electrophoretic pigment particles and a third color dye, or a positively charged red electrophoretic pigment particle, blue
  • the size (i.e., particle diameter) of the microcapsule 21 refers to the maximum size of the microcapsule 21, and for example, when the longitudinal section of the microcapsule 21 has an elliptical shape, the size of the microcapsule 21 is the length of the major axis of the ellipse.
  • the size of the microcapsule 21 refers to the maximum size of the microcapsule 21 in the display plane of the electrophoretic display layer 20 (i.e., the plane closest to the outer surface of the electrophoretic display).
  • the size of the microcapsules 21 is generally about several tens of micrometers.
  • the number of microcapsules having a size of less than 30 ⁇ m is 15% or more, and the percentage of microcapsules having a size larger than 55 ⁇ m is less than 25%.
  • the percentages referred to herein refer to the ratio of the number of microcapsules 21 of corresponding size to the number of all microcapsules 21.
  • the size of the microcapsules 21 of the electrophoretic display layer 20 is preferably controlled within a suitable range. There are two considerations: on the one hand, it is desirable that the size of the microcapsules 21 be small, so that the microcapsules 21 can reach one in the electrophoretic display layer 20.
  • the size of the microcapsules 21 is again increased to a reasonable extent, so that the electrophoretic pigment particles have sufficient space inside the microcapsules 21 to make different colors after the display is driven.
  • the pigment particles can have sufficient space for distribution, and the distribution state of the electrophoretic pigment particles of different colors does not affect the color expression of other electrophoretic pigment particles.
  • the average size of the microcapsules is in the range of 20 to 80 ⁇ m, preferably in the range of 25 to 60 ⁇ m, and more preferably in the range of 30 to 50 ⁇ m.
  • the number of the microcapsules 21 having a large size is not too large, so that a plurality of microcapsules 21 having a large size are not brought close to each other, resulting in a large size between the large-sized microcapsules 21 .
  • the phenomenon of gaps or gaps may easily cause more uneven display areas on the electrophoretic display, resulting in uneven display state, large inconsistencies in small dots, spots, plaques, etc., which may affect the user. Use experience.
  • the number of microcapsules 21 having a size of less than 30 micrometers should occupy a certain proportion, so that the microcapsules 21 having a smaller size can sufficiently fill the gaps between the microcapsules 21 of larger sizes, thereby achieving a tightly arranged effect, thereby realizing the electrophoretic display.
  • Very uniform display the overall display state is very uniform and tidy.
  • the percentage of microcapsules 21 having a size of less than 30 microns is greater than or equal to 20%; and/or the percentage of microcapsules 21 having a size greater than 55 microns is less than 15%, preferably less than 10%.
  • the ratio of the number of microcapsules 21 having a size of less than 30 microns to the number of microcapsules 21 having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably greater than 5:1.
  • the microcapsules 21 in the electrophoretic display layer 20 can achieve a relatively tight alignment effect, thereby achieving a better display effect of the electrophoretic display.
  • the electrophoretic display layer 20 and the transparent conductive electrode 12 and/or the electrophoretic display layer 20 and the driving substrate 30 are connected by an adhesive layer 11, and the thickness t2 of the electrophoretic display layer 20 and the adhesive layer 11 are The ratio of the thickness t1 is 1-10:1.
  • An adhesive may be applied on the surface of the electrophoretic display layer 20, and the adhesive is cured to form an adhesive layer 11.
  • the adhesive layer 20 has a certain electrical conductivity. If the adhesive layer 11 is too thick, the voltage applied to the electrophoretic display layer 20 by the transparent conductive electrode 12 and the drive substrate 30 is lowered.
  • the adhesive layer 11 When the adhesive layer 11 is disposed between the transparent conductive electrode 12 and the electrophoretic display layer 20, the adhesive layer 11 is transparent, and the too thick adhesive layer 11 affects the transparency of the electrophoretic display layer 20 to the surface of the electrophoretic display. , thereby affecting the optical properties of the electrophoretic display. If the adhesive layer 11 is too thin, the connection strength between the electrophoretic display layer 20 and the transparent conductive electrode 12 or the drive substrate 30 is affected, so that the electrophoretic display is easily damaged when subjected to mechanical shock. Therefore, the ratio of the thickness t2 of the electrophoretic display layer 20 to the thickness t1 of the adhesive layer 11 is controlled to 1-10:1, so that the electrophoretic display can have both good electro-optical display performance and good mechanical strength. Generally, the thickness of the electrophoretic display layer 20 is between 20 micrometers and 150 micrometers, and the thickness of the adhesive layer 11 is generally between 15 micrometers and 20 micrometers.
  • the transparent conductive electrode 12 and the electrophoretic display layer 20 are connected by an adhesive layer 11, the electrophoretic display layer 20 includes an adhesive, and the plurality of microcapsules 21 are covered with an adhesive.
  • the adhesive is bonded to the driving bottom plate 30.
  • the transparent conductive electrode 12 may be formed on the transparent substrate 13, the electrophoretic display layer 20 is connected to the driving substrate 30, and then the adhesive is coated on the inner surface of the transparent substrate 13, and the electrophoretic display layer 20 is laminated to On the adhesive, the adhesive is dried and cured to form an adhesive layer 11.
  • an adhesive may be added to the electrophoretic display coating liquid, and the electrophoretic display liquid is cured to form an electrophoretic display layer 20, and the adhesive is bonded to the driving substrate 30, thereby The electrophoretic display layer 20 is fixed to the drive substrate 30.
  • the filler ie, the curing medium
  • the curing medium contains an adhesive.
  • the driving substrate 30 and the electrophoretic display layer 20 are connected by an adhesive layer 11
  • the electrophoretic display layer 20 includes an adhesive
  • the plurality of microcapsules 21 are covered by an adhesive.
  • the adhesive is bonded to the transparent conductive electrode 12.
  • the transparent conductive electrode 12 may be formed on the transparent substrate 13, and then the electrophoretic display coating liquid is coated on the inner surface of the transparent conductive electrode 12, and the electrophoretic display coating liquid is dried and solidified to form the electrophoretic display layer 20. .
  • an adhesive is applied on the upper surface of the driving substrate 30, and the electrophoretic display film composed of the electrophoretic display layer 20, the transparent conductive electrode 12 and the transparent substrate 13 is laminated on the adhesive, and the electrophoretic display layer 20 is adhered to the adhesive.
  • the adhesive is dried and solidified to form an adhesive layer 11.
  • the adhesive layer 11 may be opaque, but still needs to have a certain conductivity.
  • the electrophoretic display coating solution contains an adhesive. After electrophoresis shows that the coating liquid is cured, the adhesive is bonded to the transparent conductive electrode 12, so that the electrophoretic display layer 20 is fixed on the transparent conductive electrode 12. After curing, the filler between the plurality of microcapsules 21 contains an adhesive.
  • the electrophoretic display layer 20 and the transparent conductive electrode 12 and the electrophoretic display layer 20 and the driving substrate 30 are connected by an adhesive layer 11.
  • the preparation process of the electrophoretic display is similar to the above two embodiments, and details are not described herein again.
  • the electrophoretic pigment particles comprise pigment particles and an organically modified layer formed on the surface of the pigment particles; the organically modified layer is a surfactant layer or a layer of polymeric material formed on the surface of the pigment particles.
  • the pigment particles may be pigment particles of inorganic salts or inorganic oxide pigments, including silica, titania, calcium oxide, chromium oxide, zinc dioxide, copper oxide, lead oxide, carbon black, silicate, titanium yellow, chromium.
  • the organic modified layer may be a layer of a polymer material grafted on the surface of the pigment particles or a layer of a surfactant adsorbed on the surface of the pigment particles.
  • a polymerization reaction can be carried out in a solution using a polymer monomer, and the polymer after the reaction is grafted by reacting with a coupling agent existing on the surface of the pigment particles.
  • Common coupling agents include silane coupling agents, titanate coupling agents, aluminate coupling agents, and the like.
  • the polymer monomer can be any compound available for polymerization, including but not limited to octadecyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, ethyl methyl Acrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, styrene, 4-vinylpyridine, N-vinylpyrrolidone, methyl a compound such as trifluoroethyl acrylate or methacrylic acid or a mixture, a complex or a derivative thereof.
  • the organic matter content W surf per unit specific surface area of the electrophoretic pigment particles may be in the range of 0.1 to 2% g/m 2 , and the organic content W surf is defined as follows:
  • the organic matter referred to herein means the organic substance of the organic modified layer, that is, the organic content W surf is used to characterize the content of the organic matter on the surface of the pigment particle.
  • the organic content W surf is used to characterize the content of the organic matter on the surface of the pigment particle.
  • the surfactant layer or the polymer material layer on the surface of the pigment particles causes the electrophoretic pigment particles to have a steric hindrance effect when they are close to each other, thereby isolating van der Waals force or electrostatic force between the electrophoretic pigment particles, thereby Achieve stable dispersion of electrophoretic pigment particles.
  • it is desirable that the organic content per unit surface area W surf is sufficiently high so that the thickness of the organically modified layer is sufficiently large to isolate van der Waals forces and electrostatic attractive forces.
  • the W surf is too high, the thickness of the organic modified layer will be too large, and the electrophoretic pigment particles will bring more resistance when moving under the applied electric field, and reduce the migration of the electrophoretic pigment particles under the electric field.
  • W surf needs to be in a suitable range to provide sufficient dispersibility and stability to the electrophoretic pigment particles without seriously reducing the migration rate of the electrophoretic pigment particles.
  • the electrophoretic pigment particles have a specific surface area organic content W surf further ranging from 0.25 to 1.6% g/m 2 .
  • the thickness of the organically modified layer is greater than 20 nm, and preferably between 30 nm and 100 nm, such that the spacing between the two electrophoretic pigment particles can be maintained above 40 nm, which can reduce the interaction between the electrophoretic pigment particles. Van der Waals' force and electrostatic attraction increase the dispersion and stability of electrophoretic pigment particles in the electrophoretic fluid.
  • the embodiment of the invention further provides an electrophoretic display coating liquid, which can be used to manufacture the electrophoretic display layer 20 in the above embodiment.
  • the electrophoretic display coating liquid comprises a dispersion medium and a plurality of microcapsules dispersed in the dispersion medium, each microcapsule containing an electrophoresis liquid and a plurality of electrophoretic pigment particles dispersed in the electrophoresis liquid, and microcapsules having a size of less than 30 micrometers
  • the percentage of the number of microcapsules greater than or equal to 15% and the size of the microcapsules larger than 55 microns is less than 25%.
  • the size of the microcapsules referred to in the present embodiment refers to the maximum size of the microcapsules in the dispersion medium.
  • the dispersion medium may be an adhesive containing water and a water-soluble polymer compound, wherein the concentration of the water-soluble polymer compound is 5% to 20%, and the weight percentage of the microcapsule may be 10% to 70%.
  • the water-soluble polymer compound mainly includes carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, water-based polyurethane, water-soluble polymer, soluble starch, carboxymethyl starch, gum arabic, gelatin, gum, Soy protein, polyvinyl alcohol, polyethylene glycol, and a composite material composed of two or more of the above materials. After the dispersion medium is dried and solidified, the curing medium described in the above embodiment is formed.
  • the percentage of microcapsules having a size of less than 30 microns is greater than or equal to 20%; and/or the percentage of microcapsules having a size greater than 55 microns is less than 15%, preferably less than 10%.
  • the ratio of the number of microcapsules having a size of less than 30 microns to the number of microcapsules having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably greater than 5:1. Similar to the above embodiment, since the electrophoretic display coating liquid of the present embodiment has an appropriate content of small-sized microcapsules and large-sized microcapsules, the electrophoretic display manufactured by the electrophoretic display coating liquid is in the electrophoretic display layer.
  • the microcapsules can achieve a relatively tight alignment effect, so that the electrophoretic display achieves a better display effect.
  • the embodiment of the invention further provides an electrophoretic display film comprising an electrophoretic display layer 20, the electrophoretic display layer 20 comprises a curing medium and a plurality of microcapsules 21 distributed in the curing medium, each microcapsule 21 containing an electrophoresis liquid And a plurality of electrophoretic pigment particles dispersed in the electrophoresis liquid, the number of microcapsules 21 having a size of less than 30 ⁇ m is 15% or more, and the percentage of the microcapsules 21 having a size larger than 55 ⁇ m is less than 25%.
  • the size of the microcapsule 21 refers to the maximum size of the microcapsule 21 in the display plane of the electrophoretic display layer 20 (i.e., the plane closest to the outer surface of the electrophoretic display).
  • the electrophoretic display coating liquid of the above embodiment may be dried and solidified in a certain carrier or container to form an electrophoretic display layer 20, and then coated on one side or both sides of the electrophoretic display layer 20.
  • the adhesive and the adhesive are cured to form the adhesive layer 11, that is, the electrophoretic display film is obtained.
  • the electrophoresis shows that the dispersion medium in the coating liquid is dried and solidified, the above-mentioned curing medium is formed.
  • the outer surface of the adhesive layer 11 may also be attached with a release film to facilitate the transport of the electrophoretic display film.
  • the release film can be peeled off.
  • the electrophoretic display coating liquid of the above embodiment may be coated on the transparent conductive electrode 12, and then the electrophoretic display coating liquid is dried and solidified to form the electrophoretic display layer 20, that is, The membrane is displayed by electrophoresis.
  • the outer surface of the electrophoretic display layer 20 may also be coated with a release film.
  • the percentage of microcapsules having a size of less than 30 microns is greater than or equal to 20%; and/or the percentage of microcapsules having a size greater than 55 microns is less than 15%, preferably less than 10%.
  • the ratio of the number of microcapsules having a size of less than 30 microns to the number of microcapsules having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably greater than 5:1.
  • the black pigment uses copper chrome black and the white pigment uses titanium dioxide.
  • the surface modification synthesis step of the pigment particles was as follows: In a 1000 ml reaction flask, 200 g of pigment, a certain amount of coupling agent, 200 g of lauryl ester, and 400 g of toluene were added. The mixture was mixed for 20 minutes at a stirring speed of 200 rpm in an inert atmosphere of a nitrogen-filled system. The temperature of the reaction mixture was slowly raised to 50 ° C under a nitrogen atmosphere and a condensing reflux apparatus, and an initiator was added to carry out a reaction for 16 hours. The reaction product was collected by centrifugation at 3,500 RPM, and the product was washed with toluene during the collection.
  • Solvent selection alkane solvent, stabilizer selected polyisoprene (IR), IR has cis structure and trans structure, because considering the practical application, the trans structure IR is insoluble or difficult to dissolve in the alkane solvent, mainly choose cis Structure IR.
  • Electrophoretic display liquid configuration an appropriate amount of white negative electrophoresis pigment particles and black neutral electrophoretic pigment particles, a stabilizer, and a charge control agent are dispersed in an alkane solvent to prepare an electrophoresis liquid, which is uniformly dispersed and used at a certain temperature.
  • a certain amount of deionized water was weighed and added to a 10 L glass sandwich reactor, and a certain amount of gelatin was weighed and added to deionized water to stir and dissolve, and the dissolution temperature was 42 °C.
  • a certain amount of gum arabic and deionized water were weighed and stirred and dissolved in another 4 L glass reactor at a dissolution temperature of 40 °C.
  • the electrophoretic display solution is added, the rotation speed is adjusted, and the dispersion is stirred for 45 minutes, and then the fully dissolved gum arabic solution is added, and the appropriate rotation speed is adjusted to continue stirring and dispersing for 30 minutes.
  • the pH was adjusted to 4.5 with an aqueous solution of 10% by mass of acetic acid, and the appropriate rotation speed was adjusted and stirred for 30 minutes.
  • the reactor temperature was lowered to 10 ° C and the cooling time was 3 h.
  • a glutaraldehyde solution having a mass fraction of 50% was added, and the reaction temperature was raised to 25 ° C, and the microcapsules were cross-linked and cured for 10 hours.
  • the microcapsules are collected, and a micro-capsule of a suitable particle size is selected by using a vibrating sieve method with a microporous filter.
  • the electrophoretic display coating liquid was prepared by stirring, and then the electrophoretic display coating liquid was coated on an ITO film (transparent conductive electrode) to be dried to form an electrophoretic display layer, and the thickness of the electrophoretic display layer was measured to be 28 ⁇ m. Finally, an adhesive layer is further scraped on the electrophoretic display layer, laser cut to a suitable size, and then laminated to the TFT driving substrate to seal, that is, the preparation of the electrophoretic display is completed.
  • the electrophoretic display is driven to the all-white display screen with the specified voltage, and the image is randomly taken under a microscope with a certain magnification ratio, and the size of all the microcapsules in the image is measured, and the actual size data of the microcapsule is converted according to the built-in scale.
  • Fig. 7 and Table 1 respectively show the pictures of the electrophoretic display sample 1 under the microscope (microscopic magnification: 10x) and the corresponding microcapsule size data.
  • Fig. 8 and Table 2 are photographs of the electrophoretic display sample 2 under the microscope as a comparative example (microscopic magnification: 5x) and the corresponding microcapsule size data, respectively.
  • the structure of the display plane of the electrophoretic display layers of the electrophoretic display samples 1 and 2 shown in Figs. 7 and 8 is shown. From the data in Table 1, the display plane of sample 1, the percentage of microcapsules having a size smaller than 30 ⁇ m is 25.40%, the percentage of microcapsules having a size larger than 55 ⁇ m is 3.35%, and the microcapsules having a size smaller than 30 ⁇ m are larger than the size. The percentage of the number of 55 micron microcapsules was 7.57:1. As seen from Fig. 7, the overall display of the electrophoretic display is very uniform and the display effect is good.
  • the display surface of sample 2 the percentage of microcapsules having a size smaller than 30 ⁇ m is 0.46%, the percentage of microcapsules having a size larger than 55 ⁇ m is 43.00%, and the microcapsules having a size smaller than 30 ⁇ m are larger than the size.
  • the percentage of the number of 55 micron microcapsules is 0.01:1.
  • the electrophoretic display has an uneven display overall, and has many spots and plaques with inconsistent colors, and the display effect is poor.
  • Sample 1 shows the size distribution of the surface microcapsules
  • the electrophoretic display film, the electrophoretic display and the electrophoretic display coating liquid provided by the embodiments of the present invention are controlled in an appropriate content range by the small-sized microcapsules and the large-sized microcapsules, so that the electrophoretic display layer of the electrophoretic display is
  • the microcapsules can achieve a relatively tight alignment effect, so that the electrophoretic display achieves a better display effect.

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Abstract

An electrophoretic display diaphragm, an electrophoretic display, and an electrophoretic display coating liquid. The electrophoretic display diaphragm comprises an electrophoretic display layer (20), the electrophoretic display layer (20) comprising a curing medium and a plurality of microcapsules (21) distributed in the curing medium, each microcapsule (21) containing an electrophoretic liquid and a plurality of electrophoretic pigment particles dispersed in the electrophoretic liquid, the percentage of the number of microcapsules (21) having a size less than 30 microns being greater than or equal to 15%, and the percentage of the number of microcapsules (21) having a size greater than 55 microns being less than 25%. By controlling the amount of microcapsules (21) of small sizes and microcapsules (21) of large sizes within appropriate ranges, the effect of close packing of the microcapsules (21) in the electrophoretic display layer (20) of the electrophoretic display can be achieved, so that the electrophoretic display achieves a good display effect.

Description

电泳显示膜片、电泳显示器和电泳显示涂布液Electrophoretic display membrane, electrophoretic display and electrophoretic display coating solution 技术领域Technical field
本发明涉及显示器件领域，尤其是一种电泳显示膜片、电泳显示器和电泳显示涂布液。The invention relates to the field of display devices, in particular to an electrophoretic display film, an electrophoretic display and an electrophoretic display coating liquid.
背景技术Background technique
电泳显示器是一种像纸一样薄、柔软和可擦写的显示器，近年来在广告牌和价格牌上获得越来越广泛的应用。目前电泳显示技术主要包括微胶囊技术、微杯技术等。对于基于微胶囊的电泳显示器来说，其显示效果在很大程度上取决于微胶囊的排列的致密性，而排列的致密程度又与微胶囊的尺寸分布有着密切的关系。现有技术中，人们尚未找出较为可信的微胶囊尺寸与电泳显示器显示效果之间的关联关系，因此尚未能据此研究出能稳定生产显示性能较好的电泳显示器的生产工艺，使电泳显示器的量产及广泛应用受到较大的影响。Electrophoretic displays are paper-thin, soft and rewritable displays that have gained increasing popularity in billboards and price cards in recent years. At present, electrophoretic display technology mainly includes microcapsule technology and microcup technology. For microcapsule-based electrophoretic displays, the display effect depends to a large extent on the compactness of the arrangement of the microcapsules, and the degree of compactness of the array is closely related to the size distribution of the microcapsules. In the prior art, the relationship between the size of the relatively reliable microcapsule and the display effect of the electrophoretic display has not been found, so that the production process of the electrophoretic display capable of stably producing the display performance has not been developed accordingly. The mass production and wide application of electrophoretic displays are greatly affected.
发明内容Summary of the invention
针对现有技术的不足，本发明目的是提供一种显示性能好的电泳显示膜片、电泳显示器和电泳显示涂布液。In view of the deficiencies of the prior art, an object of the present invention is to provide an electrophoretic display film, an electrophoretic display, and an electrophoretic display coating liquid having good display performance.
为解决上述技术问题,本发明实施例一方面提供一种电泳显示膜片，其包括电泳显示层，所述电泳显示层包括固化介质和分布于所述固化介质中的多个微胶囊，每个微胶囊内包含有电泳液和分散于电泳液中的多个电泳颜料粒子，尺寸小于30微米的微胶囊的数量百分比大于等于15％，尺寸大于55微米的微胶囊的数量百分比小于25％。In order to solve the above technical problem, an embodiment of the present invention provides an electrophoretic display film including an electrophoretic display layer, the electrophoretic display layer including a curing medium and a plurality of microcapsules distributed in the curing medium, each The microcapsule contains an electrophoresis liquid and a plurality of electrophoretic pigment particles dispersed in the electrophoresis liquid. The percentage of microcapsules having a size smaller than 30 micrometers is 15% or more, and the percentage of microcapsules having a size larger than 55 micrometers is less than 25%.
优选地，尺寸小于30微米的微胶囊的数量百分比大于等于20％；和/或，尺寸大于55微米的微胶囊的数量百分比小于15％，优选地为小于10％。Preferably, the percentage of microcapsules having a size of less than 30 microns is greater than or equal to 20%; and/or the percentage of microcapsules having a size greater than 55 microns is less than 15%, preferably less than 10%.
优选地，尺寸小于30微米的微胶囊与尺寸大于55微米的微胶囊的数量之比大于2:1，优选地大于3:1，进一步优选地大于5:1。Preferably, the ratio of the number of microcapsules having a size of less than 30 microns to the number of microcapsules having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably greater than 5:1.
本发明实施例另一方面提供一种电泳显示器，其包括透明基板、透明导电电极、驱动底板和上述任一实施例所述的电泳显示层，所述透明基板、透明导电电极、电泳显示层和驱动底板依次层叠连接，所述驱动底板上设置有驱动电路及与所述驱动电路连接的驱动电极，所述驱动电极和所述透明导电电极用于在所述电泳显示层的两端施加电信号。Another embodiment of the present invention provides an electrophoretic display, comprising: a transparent substrate, a transparent conductive electrode, a driving substrate, and the electrophoretic display layer of any of the above embodiments, the transparent substrate, the transparent conductive electrode, the electrophoretic display layer, and The driving substrate is sequentially connected in a stack, and the driving substrate is provided with a driving circuit and a driving electrode connected to the driving circuit, and the driving electrode and the transparent conductive electrode are used for applying an electrical signal at both ends of the electrophoretic display layer .
优选地，所述电泳显示层与所述透明导电电极之间和/或所述电泳显示层与所述驱动底板之间通过胶黏层连接，所述电泳显示层的厚度与所述胶黏层的厚度之比为1-10:1。Preferably, the electrophoretic display layer and the transparent conductive electrode and/or the electrophoretic display layer and the driving substrate are connected by an adhesive layer, and the thickness of the electrophoretic display layer and the adhesive layer The thickness ratio is 1-10:1.
优选地，所述电泳颜料粒子包括颜料颗粒和形成于所述颜料颗粒表面上的有机改性层；所述有机改性层为形成于所述颜料颗粒表面上的表面活性剂层或高分子材料层；所述颜料颗粒单位比表面积的有机物含量W surf在0.1-2％g/m 2的范围，进一步优选地W surf在0.25-1.6％g/m 2。 Preferably, the electrophoretic pigment particles comprise pigment particles and an organic modified layer formed on a surface of the pigment particles; the organic modified layer is a surfactant layer or a polymer material formed on a surface of the pigment particles The pigment particles have a specific surface area organic content W surf in the range of 0.1 to 2% g/m 2 , and more preferably W surf is in the range of 0.25 to 1.6% g/m 2 .
优选地，所述有机改性层的厚度大于20nm，优选地在30nm-100nm之间。Preferably, the organically modified layer has a thickness greater than 20 nm, preferably between 30 nm and 100 nm.
本发明实施例再一方面提供一种电泳显示涂布液，其包括分散介质和分散在分散介质中的多个微胶囊，每个微胶囊内包含有电泳液和分散于电泳液中的多个电泳颜料粒子，尺寸小于30微米的微胶囊的数量百分比大于等于15％，尺寸大于55微米的微胶囊的数量百分比小于25％。A further aspect of the present invention provides an electrophoretic display coating liquid comprising a dispersion medium and a plurality of microcapsules dispersed in the dispersion medium, each microcapsule containing an electrophoresis liquid and a plurality of dispersions in the electrophoresis liquid The electrophoretic pigment particles have a percentage of microcapsules having a size of less than 30 micrometers of 15% or more, and a percentage of microcapsules having a size of more than 55 micrometers of less than 25%.
优选地，尺寸小于30微米的微胶囊的数量百分比大于等于20％；和/或，尺寸大于55微米的微胶囊的数量百分比小于15％，优选地为小于10％。Preferably, the percentage of microcapsules having a size of less than 30 microns is greater than or equal to 20%; and/or the percentage of microcapsules having a size greater than 55 microns is less than 15%, preferably less than 10%.
优选地，尺寸小于30微米的微胶囊与尺寸大于55微米的微胶囊的数量之比大于2:1，优选地大于3:1，进一步优选地大于5:1。Preferably, the ratio of the number of microcapsules having a size of less than 30 microns to the number of microcapsules having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably greater than 5:1.
本发明实施例提供的电泳显示膜片、电泳显示器和电泳显示涂布液，通过将小尺寸的微胶囊与大尺寸的微胶囊控制在适当的含量范围内，使得电泳显示器的电泳显示层中，微胶囊可以实现比较紧密的排列效果，从而使电泳显示器达到比较好的显示效果。The electrophoretic display film, the electrophoretic display and the electrophoretic display coating liquid provided by the embodiments of the present invention are controlled in an appropriate content range by the small-sized microcapsules and the large-sized microcapsules, so that the electrophoretic display layer of the electrophoretic display is The microcapsules can achieve a relatively tight alignment effect, so that the electrophoretic display achieves a better display effect.
附图说明DRAWINGS
图1至3为本发明提供的三个实施例的电泳显示器的结构示意图。1 to 3 are schematic structural views of an electrophoretic display according to three embodiments of the present invention.
图4至6为本发明提供的三个实施例的电泳显示膜片的结构示意图。4 to 6 are schematic structural views of an electrophoretic display film according to three embodiments of the present invention.
图7是本发明实施例的电泳显示器的电泳显示层的显微镜放大图。7 is a microscopic enlarged view of an electrophoretic display layer of an electrophoretic display according to an embodiment of the present invention.
图8是本发明对比例的电泳显示器的电泳显示层的显微镜放大图。Figure 8 is a microscopic enlarged view of an electrophoretic display layer of an electrophoretic display of the comparative example of the present invention.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明所述技术方案作进一步的详细描述，以使本领域的技术人员可以更好的理解本发明并能予以实施，但所举实施例不作为对本发明的限定。The technical solutions of the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments to enable those skilled in the art to understand the invention. .
请参考图1至图8，本发明实施例提供一种电泳显示器，其包括透明基板13、透明导电电极12、电泳显示层20和驱动底板30，透明基板13、透明导电电极12、电泳显示层20和驱动底板30依次层叠连接。电泳显示层20包括固化介质和分布于固化介质中的多个微胶囊21。每个微胶囊21包括电泳液及悬浮于电泳液中的电泳颜料粒子。驱动底板30上设置有驱动电路及与驱动电路连接的驱动电极，驱动电极和透明导电电极12用于在电泳显示层20的两端施加电信号。Referring to FIG. 1 to FIG. 8 , an embodiment of the present invention provides an electrophoretic display including a transparent substrate 13 , a transparent conductive electrode 12 , an electrophoretic display layer 20 , and a driving substrate 30 , a transparent substrate 13 , a transparent conductive electrode 12 , and an electrophoretic display layer. 20 and the drive bottom plate 30 are sequentially laminated and connected. The electrophoretic display layer 20 includes a curing medium and a plurality of microcapsules 21 distributed in the curing medium. Each of the microcapsules 21 includes an electrophoresis liquid and electrophoretic pigment particles suspended in the electrophoresis liquid. The drive substrate 30 is provided with a drive circuit and a drive electrode connected to the drive circuit, and the drive electrode and the transparent conductive electrode 12 are used to apply an electrical signal to both ends of the electrophoretic display layer 20.
具体来说，透明基板13可以由聚对苯二甲酸乙二醇酯(PET)、聚乙烯(PE)、聚酰亚胺(PI)、聚萘二甲酸乙二醇酯(PEN)等材料制成。透明导电电极12可以通过在透明基板13上生长氧化铟锡(ITO)薄膜、纳米银线或者石墨烯薄膜等材料制成。微胶囊21中的电泳颜料粒子可以有黑色粒子和白色粒子或者其他色的粒子，电泳颜料粒子带有电荷，可以在电场作用下在电泳液中移动，通过不同电信号控制不同颜色的电泳颜料粒子向透明导电电极12移动，使得电泳显示层20显示图案和文字。在一些实施例中，可以通过在透明导电电极12上涂布含有多个微胶囊21的电泳显示涂布液，并将电泳显示涂布液烘干，形成电泳显示层20。烘干后的电泳显示涂布液即形成固化介质，固化 介质中可以含有胶黏剂、增稠剂、流平剂、表面活性剂、消泡剂等。驱动底板30可以通过在玻璃、PI、PET等衬底上用半导体制程制作薄膜晶体管(Thin Film Transistor，TFT)驱动电路而形成。驱动底板30和透明导电电极12均连接电路，用于在电泳显示层20的两侧施加电信号。驱动电极可以是电泳显示器的像素电极，通过控制器控制驱动电极上的电压信号，来控制电泳显示层20显示显示图案和文字。Specifically, the transparent substrate 13 may be made of materials such as polyethylene terephthalate (PET), polyethylene (PE), polyimide (PI), and polyethylene naphthalate (PEN). to make. The transparent conductive electrode 12 can be made by growing a material such as an indium tin oxide (ITO) film, a nano silver wire, or a graphene film on the transparent substrate 13. The electrophoretic pigment particles in the microcapsule 21 may have black particles and white particles or particles of other colors. The electrophoretic pigment particles have electric charges and can move in the electrophoresis liquid under the action of an electric field, and control electrophoretic pigment particles of different colors through different electric signals. The transparent conductive electrode 12 is moved such that the electrophoretic display layer 20 displays patterns and characters. In some embodiments, the electrophoretic display layer 20 may be formed by coating an electrophoretic display coating liquid containing a plurality of microcapsules 21 on the transparent conductive electrode 12 and drying the electrophoretic display coating liquid. The electrophoresis after drying shows that the coating liquid forms a curing medium, and the curing medium may contain an adhesive, a thickener, a leveling agent, a surfactant, an antifoaming agent, and the like. The driving substrate 30 can be formed by fabricating a Thin Film Transistor (TFT) driving circuit by a semiconductor process on a substrate such as glass, PI, or PET. Both the drive substrate 30 and the transparent conductive electrode 12 are connected to circuitry for applying electrical signals on both sides of the electrophoretic display layer 20. The driving electrode may be a pixel electrode of the electrophoretic display, and the voltage signal on the driving electrode is controlled by the controller to control the electrophoretic display layer 20 to display the display pattern and the character.
微胶囊21中可以具有多个带正电荷的黑色电泳颜料粒子和多个带有负电荷的白色电泳颜料粒子，或者具有多个带正电荷或者负电荷的黑色电泳颜料粒子和多个呈电中性的白色电泳颜料粒子，或者具有多个呈电中性的黑色电泳颜料粒子和多个带正电荷或者负电荷的白色电泳颜料粒子，或者具有带正电荷的红色电泳颜料粒子、蓝色电泳颜料粒子以及带负电荷的绿色电泳颜料粒子等。同时在微胶囊21中也可以添加带特定颜色的染料，这样微胶囊21内的液体带有特征颜色，而其中的电泳颜料粒子带有与溶液不同的颜色，其中可以有一种、两种或两种以上的电泳颜料粒子。例如微胶囊21中包括一种具有多个带正电荷或者负电荷的白色电泳颜料粒子与其他颜色的染料的组合，或者具有多个带正电荷的黑色电泳颜料粒子和多个带有负电荷的白色电泳颜料粒子与第三种颜色的染料的组合，或者具有多个带正电荷或者负电荷的黑色电泳颜料粒子和多个呈电中性的白色电泳颜料粒子与第三种颜色的染料的组合，或者具有多个呈电中性的黑色电泳颜料粒子和多个带正电荷或者负电荷的白色电泳颜料粒子与第三种颜色的染料的组合，或者具有带正电荷的红色电泳颜料粒子、蓝色电泳颜料粒子以及带负电荷的绿色电泳颜料粒子与第三种颜色的染料的组合，或者其他多种颜料粒子与染料的组合等。The microcapsule 21 may have a plurality of positively charged black electrophoretic pigment particles and a plurality of negatively charged white electrophoretic pigment particles, or a plurality of positively or negatively charged black electrophoretic pigment particles and a plurality of electrons. Sexual white electrophoretic pigment particles, or a plurality of electrically electrophoretic black electrophoretic pigment particles and a plurality of positively or negatively charged white electrophoretic pigment particles, or positively charged red electrophoretic pigment particles, blue electrophoretic pigments Particles and negatively charged green electrophoretic pigment particles. At the same time, a dye with a specific color may be added to the microcapsule 21, so that the liquid in the microcapsule 21 has a characteristic color, and the electrophoretic pigment particles therein have a different color from the solution, and one, two or two of them may be present. More than one type of electrophoretic pigment particles. For example, the microcapsule 21 includes a combination of a plurality of positively or negatively charged white electrophoretic pigment particles and dyes of other colors, or a plurality of positively charged black electrophoretic pigment particles and a plurality of negatively charged a combination of white electrophoretic pigment particles and a dye of a third color, or a combination of a plurality of positively or negatively charged black electrophoretic pigment particles and a plurality of electrically neutral white electrophoretic pigment particles and a third color of dye Or a combination of a plurality of electrically neutral black electrophoretic pigment particles and a plurality of positively or negatively charged white electrophoretic pigment particles and a third color dye, or a positively charged red electrophoretic pigment particle, blue The combination of color electrophoretic pigment particles and negatively charged green electrophoretic pigment particles with a dye of a third color, or a combination of other pigment particles and dyes.
微胶囊21的尺寸(也即粒径)是指微胶囊21的最大尺寸，例如当微胶囊21的纵截面呈椭圆形状时，微胶囊21的尺寸为该椭圆的长轴的长度。为了便于表征，在本实施例中，微胶囊21的尺寸是指电泳显示层20的显示平面(即最靠近电泳显示器外表面的平面)中微胶囊21的最大尺寸。微胶囊21的尺寸一般在几十微米左右。在本实施例中，尺寸小于30微米的微胶囊的数 量百分比大于等于15％，尺寸大于55微米的微胶囊的数量百分比小于25％。此处所指数量百分比，是指相应尺寸的微胶囊21的数量与所有微胶囊21的数量之比。电泳显示层20的微胶囊21的尺寸最好控制在一个合适的范围，这有两方面的考虑：一方面希望微胶囊21的尺寸偏小，这样在电泳显示层20内微胶囊21可以达到一个紧密排列的状态，实现较好的显示效果；另一方面微胶囊21的尺寸又到大到一个合理的程度，这样电泳颜料粒子在微胶囊21内部有足够的空间，使得在显示驱动后不同颜色的颜料颗粒可以有足够的空间来分布，不同颜色的电泳颜料粒子的分布状态不会影响其他电泳颜料粒子的色彩表现力。综合考虑，希望微胶囊的平均尺寸在20-80微米的范围，优选在25-60微米的范围，进一步优选在30-50微米的范围。此外，尺寸较大(大于55微米)的微胶囊21的数量不宜太多，这样不会造成多个尺寸较大的微胶囊21相互接近，从而导致大尺寸的微胶囊21之间有尺寸较大的空隙或缝隙的现象，容易造成电泳显示器出现较多的不均匀显示的区域，造成整体的显示状态不均匀、出现较多显示不一致的小点、斑点、斑块等现象，进而影响到用户的使用体验。尺寸小于30微米的微胶囊21的数量应占有一定的比例，这样尺寸较小的微胶囊21可以充分填充较大尺寸的微胶囊21之间的空隙，实现紧密排列的效果，进而使电泳显示器实现很均匀的显示效果，整体的显示状态非常均匀、整洁。The size (i.e., particle diameter) of the microcapsule 21 refers to the maximum size of the microcapsule 21, and for example, when the longitudinal section of the microcapsule 21 has an elliptical shape, the size of the microcapsule 21 is the length of the major axis of the ellipse. For convenience of characterization, in the present embodiment, the size of the microcapsule 21 refers to the maximum size of the microcapsule 21 in the display plane of the electrophoretic display layer 20 (i.e., the plane closest to the outer surface of the electrophoretic display). The size of the microcapsules 21 is generally about several tens of micrometers. In the present embodiment, the number of microcapsules having a size of less than 30 μm is 15% or more, and the percentage of microcapsules having a size larger than 55 μm is less than 25%. The percentages referred to herein refer to the ratio of the number of microcapsules 21 of corresponding size to the number of all microcapsules 21. The size of the microcapsules 21 of the electrophoretic display layer 20 is preferably controlled within a suitable range. There are two considerations: on the one hand, it is desirable that the size of the microcapsules 21 be small, so that the microcapsules 21 can reach one in the electrophoretic display layer 20. The tightly arranged state achieves a better display effect; on the other hand, the size of the microcapsules 21 is again increased to a reasonable extent, so that the electrophoretic pigment particles have sufficient space inside the microcapsules 21 to make different colors after the display is driven. The pigment particles can have sufficient space for distribution, and the distribution state of the electrophoretic pigment particles of different colors does not affect the color expression of other electrophoretic pigment particles. In general, it is desirable that the average size of the microcapsules is in the range of 20 to 80 μm, preferably in the range of 25 to 60 μm, and more preferably in the range of 30 to 50 μm. Further, the number of the microcapsules 21 having a large size (greater than 55 μm) is not too large, so that a plurality of microcapsules 21 having a large size are not brought close to each other, resulting in a large size between the large-sized microcapsules 21 . The phenomenon of gaps or gaps may easily cause more uneven display areas on the electrophoretic display, resulting in uneven display state, large inconsistencies in small dots, spots, plaques, etc., which may affect the user. Use experience. The number of microcapsules 21 having a size of less than 30 micrometers should occupy a certain proportion, so that the microcapsules 21 having a smaller size can sufficiently fill the gaps between the microcapsules 21 of larger sizes, thereby achieving a tightly arranged effect, thereby realizing the electrophoretic display. Very uniform display, the overall display state is very uniform and tidy.
在优选实施例中，尺寸小于30微米的微胶囊21的数量百分比大于等于20％；和/或，尺寸大于55微米的微胶囊21的数量百分比小于15％，优选地为小于10％。在另一优选实施例中，尺寸小于30微米的微胶囊21与尺寸大于55微米的微胶囊21的数量之比大于2:1，优选地大于3:1，进一步优选地大于5:1。通过控制小尺寸的微胶囊21与大尺寸的微胶囊21的数量之比，使电泳显示层20中的微胶囊21可以实现比较紧密的排列效果，从而使电泳显示器达到比较好的显示效果。In a preferred embodiment, the percentage of microcapsules 21 having a size of less than 30 microns is greater than or equal to 20%; and/or the percentage of microcapsules 21 having a size greater than 55 microns is less than 15%, preferably less than 10%. In another preferred embodiment, the ratio of the number of microcapsules 21 having a size of less than 30 microns to the number of microcapsules 21 having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably greater than 5:1. By controlling the ratio of the small-sized microcapsules 21 to the number of the large-sized microcapsules 21, the microcapsules 21 in the electrophoretic display layer 20 can achieve a relatively tight alignment effect, thereby achieving a better display effect of the electrophoretic display.
在优选实施例中，电泳显示层20与透明导电电极12之间和/或电泳显示层20与驱动底板30之间通过胶黏层11连接，电泳显示层20的厚度t2与胶 黏层11的厚度t1之比为1-10:1。可以在电泳显示层20的表面上涂布胶黏剂，胶黏剂固化后形成胶黏层11。胶黏层20具有一定的导电性。如果胶黏层11太厚，会降低透明导电电极12和驱动底板30施加到电泳显示层20的电压。当胶黏层11设置在透明导电电极12和电泳显示层20之间时，胶黏层11是透明的，太厚的胶黏层11会影响到电泳显示层20到电泳显示器表面的透光性，从而影响电泳显示器的光学特性。如果胶黏层11太薄，则会影响电泳显示层20与透明导电电极12或者驱动底板30之间的连接强度，使得电泳显示器在遭受机械冲击时，容易损坏。因此将电泳显示层20的厚度t2与胶黏层11的厚度t1之比控制为1-10:1，可以使电泳显示器既具有较好的电光显示性能，又具有较好的机械强度。一般来说，电泳显示层20的厚度在20微米-150微米之间，胶黏层11的厚度一般在15微米-20微米之间。In a preferred embodiment, the electrophoretic display layer 20 and the transparent conductive electrode 12 and/or the electrophoretic display layer 20 and the driving substrate 30 are connected by an adhesive layer 11, and the thickness t2 of the electrophoretic display layer 20 and the adhesive layer 11 are The ratio of the thickness t1 is 1-10:1. An adhesive may be applied on the surface of the electrophoretic display layer 20, and the adhesive is cured to form an adhesive layer 11. The adhesive layer 20 has a certain electrical conductivity. If the adhesive layer 11 is too thick, the voltage applied to the electrophoretic display layer 20 by the transparent conductive electrode 12 and the drive substrate 30 is lowered. When the adhesive layer 11 is disposed between the transparent conductive electrode 12 and the electrophoretic display layer 20, the adhesive layer 11 is transparent, and the too thick adhesive layer 11 affects the transparency of the electrophoretic display layer 20 to the surface of the electrophoretic display. , thereby affecting the optical properties of the electrophoretic display. If the adhesive layer 11 is too thin, the connection strength between the electrophoretic display layer 20 and the transparent conductive electrode 12 or the drive substrate 30 is affected, so that the electrophoretic display is easily damaged when subjected to mechanical shock. Therefore, the ratio of the thickness t2 of the electrophoretic display layer 20 to the thickness t1 of the adhesive layer 11 is controlled to 1-10:1, so that the electrophoretic display can have both good electro-optical display performance and good mechanical strength. Generally, the thickness of the electrophoretic display layer 20 is between 20 micrometers and 150 micrometers, and the thickness of the adhesive layer 11 is generally between 15 micrometers and 20 micrometers.
请参考图1，在优选实施例中，透明导电电极12与电泳显示层20之间通过胶黏层11连接，电泳显示层20包括胶黏剂，多个微胶囊21被胶黏剂所包覆，胶黏剂与驱动底板30粘接。制造时，可以先在透明基板13上形成透明导电电极12，将电泳显示层20与驱动底板30连接，然后在透明基板13的内侧表面上涂布胶黏剂，将电泳显示层20层压到胶黏剂上，胶黏剂被烘干固化后，形成胶黏层11。在驱动底板30上制作电泳显示层20时，可以在电泳显示涂布液中加入胶黏剂，电泳显示涂布液固化后形成电泳显示层20，胶黏剂与驱动底板30粘接，从而使电泳显示层20固定在驱动底板30上。固化后，多个微胶囊21之间的填充物(即固化介质)中含有胶黏剂。Referring to FIG. 1, in a preferred embodiment, the transparent conductive electrode 12 and the electrophoretic display layer 20 are connected by an adhesive layer 11, the electrophoretic display layer 20 includes an adhesive, and the plurality of microcapsules 21 are covered with an adhesive. The adhesive is bonded to the driving bottom plate 30. When manufacturing, the transparent conductive electrode 12 may be formed on the transparent substrate 13, the electrophoretic display layer 20 is connected to the driving substrate 30, and then the adhesive is coated on the inner surface of the transparent substrate 13, and the electrophoretic display layer 20 is laminated to On the adhesive, the adhesive is dried and cured to form an adhesive layer 11. When the electrophoretic display layer 20 is formed on the driving substrate 30, an adhesive may be added to the electrophoretic display coating liquid, and the electrophoretic display liquid is cured to form an electrophoretic display layer 20, and the adhesive is bonded to the driving substrate 30, thereby The electrophoretic display layer 20 is fixed to the drive substrate 30. After curing, the filler (ie, the curing medium) between the plurality of microcapsules 21 contains an adhesive.
请参考图2，在另一优选实施例中，驱动底板30与电泳显示层20之间通过胶黏层11连接，电泳显示层20包括胶黏剂，多个微胶囊21被胶黏剂所包覆，胶黏剂与透明导电电极12粘接。制造时，可以先在透明基板13上形成透明导电电极12，然后在透明导电电极12的内侧表面上涂布电泳显示涂布液，将电泳显示涂布液烘干固化后，形成电泳显示层20。然后在驱动底板30的上表面上涂布胶黏剂，将由电泳显示层20、透明导电电极12和透明基板13构成的电泳显示膜片层压到胶黏剂上，电泳显示层20与胶黏剂粘接，胶黏剂被 烘干固化后，形成胶黏层11。在该实施例中，胶黏层11可以是不透明的，但仍需要具有一定的导电性。与上述实施例类似，电泳显示涂布液中含有胶黏剂，电泳显示涂布液固化后，胶黏剂与透明导电电极12粘接，从而使电泳显示层20固定在透明导电电极12上。固化后，多个微胶囊21之间的填充物中含有胶黏剂。Referring to FIG. 2, in another preferred embodiment, the driving substrate 30 and the electrophoretic display layer 20 are connected by an adhesive layer 11, the electrophoretic display layer 20 includes an adhesive, and the plurality of microcapsules 21 are covered by an adhesive. The adhesive is bonded to the transparent conductive electrode 12. When manufacturing, the transparent conductive electrode 12 may be formed on the transparent substrate 13, and then the electrophoretic display coating liquid is coated on the inner surface of the transparent conductive electrode 12, and the electrophoretic display coating liquid is dried and solidified to form the electrophoretic display layer 20. . Then, an adhesive is applied on the upper surface of the driving substrate 30, and the electrophoretic display film composed of the electrophoretic display layer 20, the transparent conductive electrode 12 and the transparent substrate 13 is laminated on the adhesive, and the electrophoretic display layer 20 is adhered to the adhesive. After the agent is bonded, the adhesive is dried and solidified to form an adhesive layer 11. In this embodiment, the adhesive layer 11 may be opaque, but still needs to have a certain conductivity. Similar to the above embodiment, the electrophoretic display coating solution contains an adhesive. After electrophoresis shows that the coating liquid is cured, the adhesive is bonded to the transparent conductive electrode 12, so that the electrophoretic display layer 20 is fixed on the transparent conductive electrode 12. After curing, the filler between the plurality of microcapsules 21 contains an adhesive.
请参考图3，电泳显示层20与透明导电电极12之间和电泳显示层20与驱动底板30之间均通过胶黏层11连接。该电泳显示器的制备工艺与上述两个实施例类似，此处不再赘述。Referring to FIG. 3, the electrophoretic display layer 20 and the transparent conductive electrode 12 and the electrophoretic display layer 20 and the driving substrate 30 are connected by an adhesive layer 11. The preparation process of the electrophoretic display is similar to the above two embodiments, and details are not described herein again.
在优选实施例中，电泳颜料粒子包括颜料颗粒和形成于颜料颗粒表面上的有机改性层；有机改性层为形成于颜料颗粒表面上的表面活性剂层或高分子材料层。颜料颗粒可以为无机盐类或无机氧化物颜料的颜料颗粒，包括二氧化硅、二氧化钛、氧化钙、氧化铬、二氧化锌、氧化铜、氧化铅、炭黑、硅酸盐、钛黄、铬黄、铅铬绿、锰紫、铁蓝、钴蓝、锌白、镉黄、硫酸钡、钼橙、群青、天青蓝、翡翠绿、翠绿以及其他种类的无机盐类或无机氧化物颜料。有机改性层可以为接枝在颜料颗粒表面上的高分子材料层或者吸附在颜料颗粒表面上的表面活性剂层。例如，可以采用聚合物单体在溶液中进行聚合反应，同时反应后的高分子通过与颜料颗粒表面已有的偶联剂反应进行接枝。常见的偶联剂包括硅烷类偶联剂、钛酸酯类偶联剂、铝酸酯类偶联剂等。聚合物单体可以是任何可供聚合反应用的化合物，包括但不限于甲基丙烯酸十八烷基酯、甲基丙烯酸十二烷基酯、甲基丙烯酸十四烷基酯、乙基甲基丙烯酸酯、丁基甲基丙烯酸酯、叔丁基甲基丙烯酸酯、甲基丙烯酸环己酯、甲基丙烯酸异冰片酯、甲基丙烯酸苄基酯、苯乙烯、4-乙烯吡啶、N-乙烯吡咯烷酮、甲基丙烯酸三氟乙酯、甲基丙烯酸等化合物或者他们的混合物、复合物或者衍生物等。In a preferred embodiment, the electrophoretic pigment particles comprise pigment particles and an organically modified layer formed on the surface of the pigment particles; the organically modified layer is a surfactant layer or a layer of polymeric material formed on the surface of the pigment particles. The pigment particles may be pigment particles of inorganic salts or inorganic oxide pigments, including silica, titania, calcium oxide, chromium oxide, zinc dioxide, copper oxide, lead oxide, carbon black, silicate, titanium yellow, chromium. Yellow, lead chrome green, manganese violet, iron blue, cobalt blue, zinc white, cadmium yellow, barium sulfate, molybdenum orange, ultramarine blue, azure blue, emerald green, emerald green and other kinds of inorganic salts or inorganic oxide pigments. The organic modified layer may be a layer of a polymer material grafted on the surface of the pigment particles or a layer of a surfactant adsorbed on the surface of the pigment particles. For example, a polymerization reaction can be carried out in a solution using a polymer monomer, and the polymer after the reaction is grafted by reacting with a coupling agent existing on the surface of the pigment particles. Common coupling agents include silane coupling agents, titanate coupling agents, aluminate coupling agents, and the like. The polymer monomer can be any compound available for polymerization, including but not limited to octadecyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, ethyl methyl Acrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, styrene, 4-vinylpyridine, N-vinylpyrrolidone, methyl a compound such as trifluoroethyl acrylate or methacrylic acid or a mixture, a complex or a derivative thereof.
电泳颜料粒子单位比表面积的有机物含量W surf可以在0.1-2％g/m 2的范围内，有机物含量W surf定义如下： The organic matter content W surf per unit specific surface area of the electrophoretic pigment particles may be in the range of 0.1 to 2% g/m 2 , and the organic content W surf is defined as follows:
Figure PCTCN2018102277-appb-000001
Figure PCTCN2018102277-appb-000001
需要说明的是，此处所指有机物是指有机改性层的有机物，也即有机物含量W surf用于表征的是颜料颗粒表面有机物的含量。在电泳显示中，很多情况下会存在两种甚至多种带有不同表面电荷的颗粒共存在一个溶液中，其中至少有两种不同的颗粒带有相反的表面电荷，即一种颗粒带有正电荷，另外一种颗粒带有负电荷，这样这两种颗粒之间还存在很强的静电吸引力。颜料颗粒表面上的表面活性剂层或高分子材料层，会使电泳颜料粒子在相互接近的时候，产生一种空间位阻的效应，隔离电泳颜料粒子之间的范德华力或者静电作用力，从而实现电泳颜料粒子的稳定分散。一方面，希望单位比表面积的有机物含量W surf足够高，这样有机改性层的厚度足够大，可以隔离范德华作用力和静电吸引力。但是另外一方面，如果W surf过高的话，会造成有机改性层的厚度太大，电泳颜料粒子在外加电场下运动的时候会带来更大的阻力，降低电泳颜料粒子在电场下的迁移速率。这样W surf需要在一个合适的范围，既能给电泳颜料粒子提供足够的分散性和稳定性，又不会严重降低电泳颜料粒子的迁移速率。在优选实施例中，电泳颜料粒子单位比表面积的有机物含量W surf范围进一步为0.25-1.6％g/m 2。 It should be noted that the organic matter referred to herein means the organic substance of the organic modified layer, that is, the organic content W surf is used to characterize the content of the organic matter on the surface of the pigment particle. In electrophoretic display, in many cases, there are two or more kinds of particles with different surface charges coexisting in one solution, at least two different particles carrying opposite surface charges, that is, one particle with positive The charge, another particle, has a negative charge, so there is a strong electrostatic attraction between the two particles. The surfactant layer or the polymer material layer on the surface of the pigment particles causes the electrophoretic pigment particles to have a steric hindrance effect when they are close to each other, thereby isolating van der Waals force or electrostatic force between the electrophoretic pigment particles, thereby Achieve stable dispersion of electrophoretic pigment particles. On the one hand, it is desirable that the organic content per unit surface area W surf is sufficiently high so that the thickness of the organically modified layer is sufficiently large to isolate van der Waals forces and electrostatic attractive forces. On the other hand, if the W surf is too high, the thickness of the organic modified layer will be too large, and the electrophoretic pigment particles will bring more resistance when moving under the applied electric field, and reduce the migration of the electrophoretic pigment particles under the electric field. rate. Thus, W surf needs to be in a suitable range to provide sufficient dispersibility and stability to the electrophoretic pigment particles without seriously reducing the migration rate of the electrophoretic pigment particles. In a preferred embodiment, the electrophoretic pigment particles have a specific surface area organic content W surf further ranging from 0.25 to 1.6% g/m 2 .
在优选实施例中，有机改性层的厚度大于20nm，且优选地在30nm-100nm之间，这样两个电泳颜料粒子的之间的间距可以维持在40nm以上，可以降低电泳颜料粒子之间的范德华作用力和静电吸引力，增加电泳颜料粒子在电泳液中的分散性和稳定性。In a preferred embodiment, the thickness of the organically modified layer is greater than 20 nm, and preferably between 30 nm and 100 nm, such that the spacing between the two electrophoretic pigment particles can be maintained above 40 nm, which can reduce the interaction between the electrophoretic pigment particles. Van der Waals' force and electrostatic attraction increase the dispersion and stability of electrophoretic pigment particles in the electrophoretic fluid.
本发明实施例还提供一种电泳显示涂布液，该电泳显示涂布液可以用于制造上述实施例中的电泳显示层20。该电泳显示涂布液包括分散介质和分散在分散介质中的多个微胶囊，每个微胶囊内包含有电泳液和分散于电泳液中的多个电泳颜料粒子，尺寸小于30微米的微胶囊的数量百分比大于等于15％，尺寸大于55微米的微胶囊的数量百分比小于25％。需要说明的是，在本实施例中所指微胶囊的尺寸，是指微胶囊在分散介质中的最大尺寸。该分散介质可以为包含水和水溶性高分子化合物的胶黏剂，其中水溶性高分子化合物的浓度为5％-20％，而微胶囊的重量百分比可以为10％-70％。水溶性高分子化 合物主要包括羧甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、水性聚氨酯，水溶性高分子、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。分散介质被烘干固化后，即形成上述实施例中所述的固化介质。The embodiment of the invention further provides an electrophoretic display coating liquid, which can be used to manufacture the electrophoretic display layer 20 in the above embodiment. The electrophoretic display coating liquid comprises a dispersion medium and a plurality of microcapsules dispersed in the dispersion medium, each microcapsule containing an electrophoresis liquid and a plurality of electrophoretic pigment particles dispersed in the electrophoresis liquid, and microcapsules having a size of less than 30 micrometers The percentage of the number of microcapsules greater than or equal to 15% and the size of the microcapsules larger than 55 microns is less than 25%. It should be noted that the size of the microcapsules referred to in the present embodiment refers to the maximum size of the microcapsules in the dispersion medium. The dispersion medium may be an adhesive containing water and a water-soluble polymer compound, wherein the concentration of the water-soluble polymer compound is 5% to 20%, and the weight percentage of the microcapsule may be 10% to 70%. The water-soluble polymer compound mainly includes carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, water-based polyurethane, water-soluble polymer, soluble starch, carboxymethyl starch, gum arabic, gelatin, gum, Soy protein, polyvinyl alcohol, polyethylene glycol, and a composite material composed of two or more of the above materials. After the dispersion medium is dried and solidified, the curing medium described in the above embodiment is formed.
在优选实施例中，尺寸小于30微米的微胶囊的数量百分比大于等于20％；和/或，尺寸大于55微米的微胶囊的数量百分比小于15％，优选地为小于10％。在另一优选实施例中，尺寸小于30微米的微胶囊与尺寸大于55微米的微胶囊的数量之比大于2:1，优选地大于3:1，进一步优选地大于5:1。与上述实施例类似，由于本实施例的电泳显示涂布液具有适当含量的小尺寸的微胶囊与大尺寸的微胶囊，因此用该电泳显示涂布液制造的电泳显示器，其电泳显示层中的微胶囊可以实现比较紧密的排列效果，从而使电泳显示器达到比较好的显示效果。In a preferred embodiment, the percentage of microcapsules having a size of less than 30 microns is greater than or equal to 20%; and/or the percentage of microcapsules having a size greater than 55 microns is less than 15%, preferably less than 10%. In another preferred embodiment, the ratio of the number of microcapsules having a size of less than 30 microns to the number of microcapsules having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably greater than 5:1. Similar to the above embodiment, since the electrophoretic display coating liquid of the present embodiment has an appropriate content of small-sized microcapsules and large-sized microcapsules, the electrophoretic display manufactured by the electrophoretic display coating liquid is in the electrophoretic display layer. The microcapsules can achieve a relatively tight alignment effect, so that the electrophoretic display achieves a better display effect.
本发明实施例还提供一种电泳显示膜片，其包括电泳显示层20，电泳显示层20包括固化介质和分布于固化介质中的多个微胶囊21，每个微胶囊21内包含有电泳液和分散于电泳液中的多个电泳颜料粒子，尺寸小于30微米的微胶囊21的数量百分比大于等于15％，尺寸大于55微米的微胶囊21的数量百分比小于25％。在本实施例中，微胶囊21的尺寸是指电泳显示层20的显示平面(即最靠近电泳显示器外表面的平面)中微胶囊21的最大尺寸。请参考图4和图5，可以将上述实施例的电泳显示涂布液在一定载体或者容器中烘干固化，形成电泳显示层20，然后在电泳显示层20的一侧或者两侧涂布胶黏剂，胶黏剂固化形成胶黏层11，即得到该电泳显示膜片。电泳显示涂布液中的分散介质烘干固化后，即形成上述固化介质。胶黏层11的外表面还可贴有离型膜，以便于电泳显示膜片的运输。制作电泳显示器的过程中要使用电泳显示膜片时，撕掉离型膜即可。请参考图6，在另一实施例中，可以在透明导电电极12上涂布上述实施例的电泳显示涂布液，然后将电泳显示涂布液烘干固化，形成电泳显示层20，即得到电泳显示膜片。电泳显示层20的外表面也可以贴有离型膜。The embodiment of the invention further provides an electrophoretic display film comprising an electrophoretic display layer 20, the electrophoretic display layer 20 comprises a curing medium and a plurality of microcapsules 21 distributed in the curing medium, each microcapsule 21 containing an electrophoresis liquid And a plurality of electrophoretic pigment particles dispersed in the electrophoresis liquid, the number of microcapsules 21 having a size of less than 30 μm is 15% or more, and the percentage of the microcapsules 21 having a size larger than 55 μm is less than 25%. In the present embodiment, the size of the microcapsule 21 refers to the maximum size of the microcapsule 21 in the display plane of the electrophoretic display layer 20 (i.e., the plane closest to the outer surface of the electrophoretic display). Referring to FIG. 4 and FIG. 5, the electrophoretic display coating liquid of the above embodiment may be dried and solidified in a certain carrier or container to form an electrophoretic display layer 20, and then coated on one side or both sides of the electrophoretic display layer 20. The adhesive and the adhesive are cured to form the adhesive layer 11, that is, the electrophoretic display film is obtained. After the electrophoresis shows that the dispersion medium in the coating liquid is dried and solidified, the above-mentioned curing medium is formed. The outer surface of the adhesive layer 11 may also be attached with a release film to facilitate the transport of the electrophoretic display film. When using an electrophoretic display diaphragm in the process of making an electrophoretic display, the release film can be peeled off. Referring to FIG. 6, in another embodiment, the electrophoretic display coating liquid of the above embodiment may be coated on the transparent conductive electrode 12, and then the electrophoretic display coating liquid is dried and solidified to form the electrophoretic display layer 20, that is, The membrane is displayed by electrophoresis. The outer surface of the electrophoretic display layer 20 may also be coated with a release film.
在优选实施例中，尺寸小于30微米的微胶囊的数量百分比大于等于20％；和/或，尺寸大于55微米的微胶囊的数量百分比小于15％，优选地为小于10％。在另一优选实施例中，尺寸小于30微米的微胶囊与尺寸大于55微米的微胶囊的数量之比大于2:1，优选地大于3:1，进一步优选地大于5:1。In a preferred embodiment, the percentage of microcapsules having a size of less than 30 microns is greater than or equal to 20%; and/or the percentage of microcapsules having a size greater than 55 microns is less than 15%, preferably less than 10%. In another preferred embodiment, the ratio of the number of microcapsules having a size of less than 30 microns to the number of microcapsules having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably greater than 5:1.
下面简单介绍一下上述电泳显示器的制造步骤：The following briefly describes the manufacturing steps of the above electrophoretic display:
1、电泳颜料粒子的合成1. Synthesis of electrophoretic pigment particles
选用颜料颗粒时，黑色颜料使用铜铬黑，白色颜料使用二氧化钛。颜料颗粒的表面修饰合成步骤如下：在1000毫升反应瓶中，加入200克颜料，一定量的偶联剂，200g月桂酯，400克甲苯。在充氮气保持体系惰性环境，以200rpm的搅拌速度混合20分钟。在氮气环境和冷凝回流装置下，将反应混合物温度缓慢升高至50℃，加入引发剂，反应16个小时。反应产物在3500RPM下离心收集，收集过程中产物用甲苯清洗。When pigment particles are used, the black pigment uses copper chrome black and the white pigment uses titanium dioxide. The surface modification synthesis step of the pigment particles was as follows: In a 1000 ml reaction flask, 200 g of pigment, a certain amount of coupling agent, 200 g of lauryl ester, and 400 g of toluene were added. The mixture was mixed for 20 minutes at a stirring speed of 200 rpm in an inert atmosphere of a nitrogen-filled system. The temperature of the reaction mixture was slowly raised to 50 ° C under a nitrogen atmosphere and a condensing reflux apparatus, and an initiator was added to carry out a reaction for 16 hours. The reaction product was collected by centrifugation at 3,500 RPM, and the product was washed with toluene during the collection.
2、电泳显示液的配置2. Configuration of electrophoretic display liquid
溶剂选择烷烃溶剂，稳定剂选择聚异戊二烯(IR)，IR有顺式结构和反式结构，因考虑到实际应用中，反式结构IR不溶或难溶于烷烃溶剂，主要选择顺式结构IR。Solvent selection alkane solvent, stabilizer selected polyisoprene (IR), IR has cis structure and trans structure, because considering the practical application, the trans structure IR is insoluble or difficult to dissolve in the alkane solvent, mainly choose cis Structure IR.
电泳显示液配置：分别将适量的白色负电电泳颜料粒子和黑色中性电泳颜料粒子、稳定剂、电荷控制剂分散在烷烃溶剂中，配制电泳液，在一定温度下分散均匀使用。Electrophoretic display liquid configuration: an appropriate amount of white negative electrophoresis pigment particles and black neutral electrophoretic pigment particles, a stabilizer, and a charge control agent are dispersed in an alkane solvent to prepare an electrophoresis liquid, which is uniformly dispersed and used at a certain temperature.
3、微胶囊的合成3. Synthesis of microcapsules
称取一定量的去离子水加入到10L玻璃夹层反应釜，再称取一定量的明胶加入到去离子水中搅拌溶解，溶解温度为42℃。同时称取一定量的阿拉伯胶和去离子水，在另一个4L玻璃反应釜中搅拌溶解，溶解温度为40℃。待明胶溶解完全后，加入电泳显示液，调整转速，搅拌分散45min，再加入溶解完全的阿拉伯胶溶液，调整合适转速继续搅拌分散30min。然后用质量分数为10％的醋酸水溶液调节pH值至4.5，调整合适转速再搅拌分散30min。降低反应釜温度至10℃，降温时间为3h。加入质量分数为50％的戊二醛溶液，同 时升高反应温度至25℃，使微胶囊交联固化反应10h。收集微胶囊，采用附微孔过滤网的振动筛法，选择合适粒径的微胶囊使用。A certain amount of deionized water was weighed and added to a 10 L glass sandwich reactor, and a certain amount of gelatin was weighed and added to deionized water to stir and dissolve, and the dissolution temperature was 42 °C. At the same time, a certain amount of gum arabic and deionized water were weighed and stirred and dissolved in another 4 L glass reactor at a dissolution temperature of 40 °C. After the gelatin is completely dissolved, the electrophoretic display solution is added, the rotation speed is adjusted, and the dispersion is stirred for 45 minutes, and then the fully dissolved gum arabic solution is added, and the appropriate rotation speed is adjusted to continue stirring and dispersing for 30 minutes. Then, the pH was adjusted to 4.5 with an aqueous solution of 10% by mass of acetic acid, and the appropriate rotation speed was adjusted and stirred for 30 minutes. The reactor temperature was lowered to 10 ° C and the cooling time was 3 h. A glutaraldehyde solution having a mass fraction of 50% was added, and the reaction temperature was raised to 25 ° C, and the microcapsules were cross-linked and cured for 10 hours. The microcapsules are collected, and a micro-capsule of a suitable particle size is selected by using a vibrating sieve method with a microporous filter.
4、电泳显示器的制备4. Preparation of electrophoretic display
将微胶囊调整到合适的pH值5.0左右，然后以5份重量的胶黏剂、45份重量的微胶囊和50份重量的水混合搅拌均匀，再加入分散剂和增稠剂，在45℃搅拌配制成电泳显示涂布液，然后将电泳显示涂布液涂布在ITO薄膜(透明导电电极)上烘干，即形成电泳显示层，测试电泳显示层的厚度为28微米。最后在电泳显示层上再刮涂一层胶黏层，激光切割至合适的尺寸，再层压到TFT驱动底板上密封，即完成电泳显示器的制备。Adjust the microcapsules to a suitable pH of about 5.0, then mix and mix with 5 parts by weight of adhesive, 45 parts by weight of microcapsules and 50 parts by weight of water, then add dispersant and thickener at 45 ° C. The electrophoretic display coating liquid was prepared by stirring, and then the electrophoretic display coating liquid was coated on an ITO film (transparent conductive electrode) to be dried to form an electrophoretic display layer, and the thickness of the electrophoretic display layer was measured to be 28 μm. Finally, an adhesive layer is further scraped on the electrophoretic display layer, laser cut to a suitable size, and then laminated to the TFT driving substrate to seal, that is, the preparation of the electrophoretic display is completed.
5、电泳显示器微胶囊尺寸的测量5. Measurement of microcapsule size of electrophoretic display
将电泳显示器用指定的电压驱动到全白的显示画面，在显微镜下面用一定的放大比例随机拍摄图片，将图片内所有微胶囊的尺寸测量出来，根据内置的标尺转换为微胶囊的实际尺寸数据。图7和表1分别是显示效果较好的电泳显示器样品1在显微镜下的图片(显微镜放大倍数为10x)和所对应的微胶囊的尺寸数据。图8和表2分别是作为对比例的显示效果较差的电泳显示器样品2在显微镜下的图片(显微镜放大倍数为5x)和所对应的微胶囊的尺寸数据。图7和图8所示的也即电泳显示器样品1和样品2的电泳显示层的显示平面的结构。从表1的数据来看，样品1的显示平面，尺寸小于30微米的微胶囊数量百分比为25.40％，尺寸大于55微米的微胶囊数量百分比为3.35％，尺寸小于30微米的微胶囊与尺寸大于55微米的微胶囊的数量百分比的比例为7.57：1。从图7来看，该电泳显示器整体显示非常均匀，显示效果较好。从表2的数据来看，样品2的显示面，尺寸小于30微米的微胶囊数量百分比为0.46％，尺寸大于55微米的微胶囊数量百分比为43.00％，尺寸小于30微米的微胶囊与尺寸大于55微米的微胶囊的数量百分比的比例为0.01：1。从图8来看，该电泳显示器整体显示不均匀，有许多色彩不一致的斑点和斑块，显示效果较差。The electrophoretic display is driven to the all-white display screen with the specified voltage, and the image is randomly taken under a microscope with a certain magnification ratio, and the size of all the microcapsules in the image is measured, and the actual size data of the microcapsule is converted according to the built-in scale. . Fig. 7 and Table 1 respectively show the pictures of the electrophoretic display sample 1 under the microscope (microscopic magnification: 10x) and the corresponding microcapsule size data. Fig. 8 and Table 2 are photographs of the electrophoretic display sample 2 under the microscope as a comparative example (microscopic magnification: 5x) and the corresponding microcapsule size data, respectively. The structure of the display plane of the electrophoretic display layers of the electrophoretic display samples 1 and 2 shown in Figs. 7 and 8 is shown. From the data in Table 1, the display plane of sample 1, the percentage of microcapsules having a size smaller than 30 μm is 25.40%, the percentage of microcapsules having a size larger than 55 μm is 3.35%, and the microcapsules having a size smaller than 30 μm are larger than the size. The percentage of the number of 55 micron microcapsules was 7.57:1. As seen from Fig. 7, the overall display of the electrophoretic display is very uniform and the display effect is good. From the data in Table 2, the display surface of sample 2, the percentage of microcapsules having a size smaller than 30 μm is 0.46%, the percentage of microcapsules having a size larger than 55 μm is 43.00%, and the microcapsules having a size smaller than 30 μm are larger than the size. The percentage of the number of 55 micron microcapsules is 0.01:1. As seen from FIG. 8, the electrophoretic display has an uneven display overall, and has many spots and plaques with inconsistent colors, and the display effect is poor.
表1：样品1显示面微胶囊的尺寸分布Table 1: Sample 1 shows the size distribution of the surface microcapsules
微胶囊尺寸(微米)Microcapsule size (micron) 微胶囊数量Microcapsule quantity 微胶囊数量百分比Microcapsule percentage
1919 11 0.1597440.159744
21twenty one 33 0.4792330.479233
23twenty three 1717 2.7156552.715655
2525 2727 4.3130994.313099
2727 4545 7.1884987.188498
2929 6666 10.5431310.54313
3131 6666 10.5431310.54313
3333 5858 9.2651769.265176
3535 5050 7.987227.98722
3737 4040 6.3897766.389776
3939 4040 6.3897766.389776
4141 4343 6.869016.86901
4343 3131 4.9520774.952077
4545 3030 4.7923324.792332
4747 3030 4.7923324.792332
4949 1414 2.2364222.236422
5151 21twenty one 3.3546333.354633
5353 1010 1.5974441.597444
5555 1313 2.0766772.076677
5757 1616 2.5559112.555911
5959 11 0.1597440.159744
6161 22 0.3194890.319489
6363 22 0.3194890.319489
表2：样品2显示面微胶囊的尺寸分布Table 2: Sample 2 shows the size distribution of the surface microcapsules
微胶囊尺寸(微米)Microcapsule size (micron) 微胶囊数量Microcapsule quantity 微胶囊数量百分比Microcapsule percentage
23twenty three 11 0.1146790.114679
2525 00 00
2727 00 00
2929 33 0.3440370.344037
3131 99 1.032111.03211
3333 55 0.5733940.573394
3535 1212 1.3761471.376147
3737 1616 1.8348621.834862
3939 23twenty three 2.6376152.637615
4141 3030 3.4403673.440367
4343 2828 3.2110093.211009
4545 3535 4.0137614.013761
4747 6868 7.7981657.798165
4949 5454 6.1926616.192661
5151 5959 6.7660556.766055
5353 7676 8.7155968.715596
5555 7878 8.9449548.944954
5757 7171 8.1422028.142202
5959 6767 7.6834867.683486
6161 5555 6.3073396.307339
6363 5858 6.6513766.651376
6565 3636 4.128444.12844
6767 3333 3.7844043.784404
6969 1818 2.064222.06422
7171 1414 1.6055051.605505
7373 99 1.032111.03211
7575 88 0.9174310.917431
7777 33 0.3440370.344037
7979 11 0.1146790.114679
8181 11 0.1146790.114679
8383 11 0.1146790.114679
本发明实施例提供的电泳显示膜片、电泳显示器和电泳显示涂布液，通过将小尺寸的微胶囊与大尺寸的微胶囊控制在适当的含量范围内，使得电泳显示器的电泳显示层中，微胶囊可以实现比较紧密的排列效果，从而使电泳显示器达到比较好的显示效果。The electrophoretic display film, the electrophoretic display and the electrophoretic display coating liquid provided by the embodiments of the present invention are controlled in an appropriate content range by the small-sized microcapsules and the large-sized microcapsules, so that the electrophoretic display layer of the electrophoretic display is The microcapsules can achieve a relatively tight alignment effect, so that the electrophoretic display achieves a better display effect.
以上所述仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the invention, and the equivalent structure or equivalent process transformations made by the description of the invention and the drawings are directly or indirectly applied to other related The technical field is equally included in the scope of patent protection of the present invention.

Claims (10)

  1. 一种电泳显示膜片，其包括电泳显示层，所述电泳显示层包括固化介质和分布于所述固化介质中的多个微胶囊，每个微胶囊内包含有电泳液和分散于电泳液中的多个电泳颜料粒子，其特征在于，尺寸小于30微米的微胶囊的数量百分比大于等于15％，尺寸大于55微米的微胶囊的数量百分比小于25％。An electrophoretic display film comprising an electrophoretic display layer, the electrophoretic display layer comprising a curing medium and a plurality of microcapsules distributed in the curing medium, each microcapsule containing an electrophoresis liquid and dispersed in the electrophoresis liquid A plurality of electrophoretic pigment particles characterized in that the percentage of microcapsules having a size of less than 30 micrometers is greater than or equal to 15%, and the percentage of microcapsules having a size greater than 55 micrometers is less than 25%.
  2. 如权利要求1所述的电泳显示膜片，其特征在于，尺寸小于30微米的微胶囊的数量百分比大于等于20％；和/或，尺寸大于55微米的微胶囊的数量百分比小于15％，优选地为小于10％。The electrophoretic display film according to claim 1, wherein the percentage of the number of microcapsules having a size of less than 30 μm is 20% or more; and/or the percentage of the number of microcapsules having a size of more than 55 μm is less than 15%, preferably The ground is less than 10%.
  3. 如权利要求1所述的电泳显示膜片，其特征在于，尺寸小于30微米的微胶囊与尺寸大于55微米的微胶囊的数量之比大于2:1，优选地大于3:1，进一步优选地大于5:1。The electrophoretic display film of claim 1 wherein the ratio of the number of microcapsules having a size of less than 30 microns to the number of microcapsules having a size greater than 55 microns is greater than 2:1, preferably greater than 3:1, further preferably More than 5:1.
  4. 一种电泳显示器，其特征在于，包括透明基板、透明导电电极、驱动底板和如权利要求1至3任一项所述的电泳显示层，所述透明基板、透明导电电极、电泳显示层和驱动底板依次层叠连接，所述驱动底板上设置有驱动电路及与所述驱动电路连接的驱动电极，所述驱动电极和所述透明导电电极用于在所述电泳显示层的两端施加电信号。An electrophoretic display, comprising: a transparent substrate, a transparent conductive electrode, a driving substrate, and the electrophoretic display layer according to any one of claims 1 to 3, the transparent substrate, the transparent conductive electrode, the electrophoretic display layer and the driving The bottom plate is sequentially connected in a stack, and the driving substrate is provided with a driving circuit and a driving electrode connected to the driving circuit, and the driving electrode and the transparent conductive electrode are used to apply an electric signal to both ends of the electrophoretic display layer.
  5. 如权利要求4所述的电泳显示器，其特征在于，所述电泳显示层与所述透明导电电极之间和/或所述电泳显示层与所述驱动底板之间通过胶黏层连接，所述电泳显示层的厚度与所述胶黏层的厚度之比为1-10:1。The electrophoretic display according to claim 4, wherein the electrophoretic display layer and the transparent conductive electrode and/or the electrophoretic display layer and the driving substrate are connected by an adhesive layer, The ratio of the thickness of the electrophoretic display layer to the thickness of the adhesive layer is 1-10:1.
  6. 如权利要求4所述的电泳显示器，其特征在于，所述电泳颜料粒子包括颜料颗粒和形成于所述颜料颗粒表面上的有机改性层；所述有机改性层为形成于所述颜料颗粒表面上的表面活性剂层或高分子材料层；所述颜料颗粒单位比表面积的有机物含量W surf在0.1-2％g/m 2的范围，进一步优选地W surf在0.25-1.6％g/m 2。 The electrophoretic display according to claim 4, wherein said electrophoretic pigment particles comprise pigment particles and an organic modified layer formed on a surface of said pigment particles; said organic modified layer being formed on said pigment particles a surfactant layer or a polymer material layer on the surface; the pigment particles have a specific surface area organic content W surf in the range of 0.1 to 2% g/m 2 , and further preferably W surf is in the range of 0.25 to 1.6% g/m 2 .
  7. 如权利要求6所述的电泳显示器，其特征在于，所述有机改性层的厚度大于20nm，优选地在30nm-100nm之间。The electrophoretic display according to claim 6, wherein the organically modified layer has a thickness of more than 20 nm, preferably between 30 nm and 100 nm.
  8. 一种电泳显示涂布液，其包括分散介质和分散在分散介质中的多个微胶囊，每个微胶囊内包含有电泳液和分散于电泳液中的多个电泳颜料粒子，其特征在于，尺寸小于30微米的微胶囊的数量百分比大于等于15％，尺寸大于55微米的微胶囊的数量百分比小于25％。An electrophoretic display coating liquid comprising a dispersion medium and a plurality of microcapsules dispersed in a dispersion medium, each microcapsule containing an electrophoresis liquid and a plurality of electrophoretic pigment particles dispersed in the electrophoresis liquid, wherein The percentage of microcapsules having a size of less than 30 microns is greater than or equal to 15%, and the percentage of microcapsules having a size greater than 55 microns is less than 25%.
  9. 如权利要求1所述的电泳显示涂布液，其特征在于，尺寸小于30微米的微胶囊的数量百分比大于等于20％；和/或，尺寸大于55微米的微胶囊的数量百分比小于15％，优选地为小于10％。The electrophoretic display coating liquid according to claim 1, wherein the percentage of the number of microcapsules having a size of less than 30 μm is 20% or more; and/or the percentage of the number of microcapsules having a size larger than 55 μm is less than 15%. It is preferably less than 10%.
  10. 如权利要求1所述的电泳显示涂布液，其特征在于，尺寸小于30微米的微胶囊与尺寸大于55微米的微胶囊的数量之比大于2:1，优选地大于3:1，进一步优选地大于5:1。The electrophoretic display coating liquid according to claim 1, wherein a ratio of the number of microcapsules having a size of less than 30 μm to the number of microcapsules having a size larger than 55 μm is more than 2:1, preferably more than 3:1, further preferably The ground is greater than 5:1.
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