WO2024026949A1 - 一种双剥离片及其制造方法和应用 - Google Patents

一种双剥离片及其制造方法和应用 Download PDF

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WO2024026949A1
WO2024026949A1 PCT/CN2022/114830 CN2022114830W WO2024026949A1 WO 2024026949 A1 WO2024026949 A1 WO 2024026949A1 CN 2022114830 W CN2022114830 W CN 2022114830W WO 2024026949 A1 WO2024026949 A1 WO 2024026949A1
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Prior art keywords
layer
glue
glue layer
release film
electro
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PCT/CN2022/114830
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English (en)
French (fr)
Inventor
罗裕杰
曾晞
胡典禄
杨伟强
黄金浪
陈宇
Original Assignee
广州奥翼电子科技股份有限公司
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Publication of WO2024026949A1 publication Critical patent/WO2024026949A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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 
    • 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
    • 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

Definitions

  • the present application relates to the technical field of electro-optical components of electro-optical displays, and specifically to a double peeling sheet and its manufacturing method and application.
  • Electro-optical material is a term used herein in its ordinary sense in the art to refer to a material that has at least one first and second display state that differ in optical properties and that changes from its state when an electric field is applied to the material.
  • the first display state changes to its second display state.
  • the optical property is usually the color perceptible to the human eye, but may be another optical property such as optical transmission, reflection, luminescence, or in the case where machine reading displays are desired, reflection at electromagnetic wavelengths outside the visible range Change the perception of pseudo-color.
  • the layer includes a mixture of polymeric binder material and additives selected from the group consisting of salts, polyelectrolytes, polymer electrolytes, solid electrolytes, and combinations thereof. wherein one of the first and second substrates or both the first and second substrates include electrodes.
  • an encapsulated electrophoretic medium containing capsules in a binder is coated onto a flexible substrate including indium tin oxide (ITO) or a similar conductive coating (which is used as the final One electrode of a display) is coated on a plastic film and the capsule/binder coating dries to form an adhesive layer that firmly bonds the electrophoretic medium to the substrate.
  • the conductive layer is conveniently a thin metal layer, for example aluminum or indium tin oxide, or may be a conductive polymer.
  • PET polyethylene terephthalate
  • At least one substrate in the electro-optical component has the conductive layer.
  • the conductive layer is ITO and the substrate is PET.
  • the thickness is generally between 0.01mm and 0.2mm. The applicant believes that if PET can be removed, the display effect can be further improved.
  • the present invention provides an electro-optical material, which is used to form a display component when combined with a functional layer having a transparent conductive layer.
  • the electro-optical material removes the PET part, which can reduce the loss of light energy and effectively improve the efficiency of the display. display effect.
  • the invention provides a double peeling sheet, which includes a first release film and a second release film, and an electro-optical material placed between the first release film and the second release film;
  • the electro-optical materials include:
  • a first glue layer, the first glue layer is formed by a first liquid glue coated on the first release film;
  • Electrophoretic medium layer the electrophoretic medium layer is formed of a liquid electrophoretic medium coated on the first glue layer, the electrophoretic medium includes a plurality of capsules and an adhesive surrounding the capsules, the capsules include capsule walls, a suspension fluid coating the capsule wall and a plurality of electrophoretic pigment particles suspended in the suspension fluid and capable of moving through the fluid when an electric field is applied to the electrophoretic medium, the electrophoretic pigment particles including negatively charged electrophoretic pigment particles and electrically neutral electrophoretic pigment particles; the contact surface between the electrophoretic medium layer and the first glue layer is a flat surface, and the other side of the electrophoretic medium layer presents an uneven surface due to numerous capsule differences;
  • the second glue layer is formed of a liquid second glue covering the step difference between capsules in the electrophoretic medium layer;
  • the functional layer includes at least one or any combination of a color filter layer, a light guide plate, a touch display layer and a protective layer.
  • the volume resistivity of the first glue layer is controlled at 1*10 5 ⁇ 1*10 10 ( ⁇ .cm).
  • the thickness of the first glue layer is 0.1-10 ⁇ m.
  • the thickness of the second glue layer is 0.1-50 ⁇ m.
  • the thickness of the second glue layer is 5-35 ⁇ m.
  • the volume resistivity of the second glue layer is controlled at 1*10 7 ⁇ 1*10 12 ( ⁇ .cm).
  • the first glue and the second glue each include a high molecular polymer, and the high molecular polymer includes a polyurethane polymer or a copolymer of polyurethane and acrylic acid.
  • the polymer molecular weight in the second glue layer is distributed between 10,000 and 100,000.
  • the polymer in the second glue layer includes ionic groups, which refer to carboxyl groups, sulfonic acid groups, amine groups and their salt-forming products.
  • ionic groups refer to carboxyl groups, sulfonic acid groups, amine groups and their salt-forming products.
  • the mass proportion of carboxylic acid groups is 0.1% to 10% of sulfonic acid groups,
  • the mass proportion of amine groups is 0.1% to 1.5%.
  • the molecular weight of the polymer in the first glue layer is distributed between 20,000 and 70,000.
  • the polymer in the first glue layer includes ionic groups, and the ionic groups of the polymer refer to carboxyl groups, sulfonic acid groups, amine groups and their salt-forming products;
  • the ionic group content of the polymer is 0% to 10% by mass of carboxylic acid groups, and 0% to 3% by mass of sulfonic acid groups and amine groups.
  • the release force between the first release film and the electro-optical material is (5-50) gf/inch; further 20-40;
  • the release force between the second release film and the electro-optical material is more than twice the release force between the first release film and the electro-optical material.
  • the first release film has electrical conductivity or does not have electrical conductivity.
  • the second release film has electrical conductivity or does not have electrical conductivity.
  • the present invention also provides a method for manufacturing the double peeling sheet as described above, including:
  • the electrophoretic medium layer and the second glue are laminated so that the second glue covers the inter-capsule steps generated in the electrophoretic medium layer.
  • the present invention also provides a method for manufacturing the double peeling sheet as described above, including:
  • a second glue is coated on the electrophoretic medium layer and dried to form a second glue layer.
  • the second glue layer covers the inter-capsule step difference generated in the electrophoretic medium layer.
  • the present invention also provides an application of the double peeling sheet as mentioned above, including:
  • the first glue layer is in direct contact with the drive base plate.
  • the present invention has the following technical effects:
  • an electro-optical component which includes first and second substrates, a glue layer and an electro-optical material layer located between the first and second substrates.
  • the glue layer includes A mixture of polymeric binder materials and additives selected from the group consisting of salts, polyelectrolytes, polymer electrolytes, solid electrolytes and combinations thereof.
  • one or both of the first and second substrates includes an electrode and PET to which the electrode is attached. Please refer to Figure 1 (original drawing of the original patent publication).
  • the manufacturing method of the electro-optical component includes: (1) coating the electro-optical layer 130 on the substrate 110 with the conductive layer 120, (2) applying the electro-optical layer in a liquid form Laminating adhesive 180 is applied to release sheet 190, conveniently by slot die coating, and the adhesive is dried (or otherwise cured) to form a solid layer (3) Laminating adhesive and release sheet to electro-optical layer 130; This lamination can be conveniently performed using hot roller lamination.
  • a lamination adhesive may be applied over the electro-optical layer 130 and then dried or otherwise cured prior to being covered by the release sheet 190.
  • the release sheet 190 is conveniently a 7 mil (177 ⁇ m) film ; Depending on the nature of the electro-optical medium used, it may be necessary to coat this film with a release agent such as silicone. As illustrated in Figure 1, prior to laminating the FPL 100 to a chassis (not shown) to form the final display, the release sheet 190 is peeled off or otherwise removed from the lamination adhesive 180.
  • FIG. 2 shows an electronic paper display made using the electro-optical component as described above, including the electro-optical component part and the functional layer and TFT drive substrate combined with it.
  • the specific bonding process is as follows: the electro-optical component part includes an electrophoretic medium layer 210 and a substrate 220.
  • the substrate 220 has a transparent conductive layer 221 in direct contact with the electrophoretic medium layer 210; it also includes an OCA layer 240 on the other side of the substrate 220. and a glue layer 230 provided with the electrophoretic medium layer 210 .
  • the OCA layer 240 is combined with the functional layer 250, and the glue layer 230 is combined with the TFT driving base plate.
  • the electro-optical component with a certain functional layer obtained above is limited to being applicable to a certain function. From a practical point of view, the electro-optical component is not as universal as the double peeling sheet of the prior art. The applicant believes that in order to better solve the technical problems in the background art, the process needs to be divided into two parts. One is to obtain a sub-assembly of an electro-optical component that is easy to store and does not contain PET, and then it is necessary to apply the above-mentioned electro-optical component When forming the sub-assembly, attach ITO to the functional layer, and then laminate the electro-optical layer of the electro-optical assembly sub-assembly on the ITO. The above solution can obtain PET-free electro-optical components.
  • the sub-assembly of the electro-optical component includes: a first glue layer, an electrophoretic medium layer and a second glue layer.
  • the first glue layer is formed by a liquid first glue coated on the first release film;
  • the electrophoretic medium is formed by a liquid electrophoretic medium coated on the first glue layer, and the electrophoretic medium includes a plurality of a capsule and a binder surrounding the capsule, the capsule including a capsule wall, a suspension fluid coated in the capsule wall and a plurality of particles suspended in the suspension fluid and capable of moving through the fluid when an electric field is applied to the electrophoretic medium.
  • electrophoretic pigment particles, the electrophoretic pigment particles include negatively charged electrophoretic pigment particles and electrically neutral electrophoretic pigment particles;
  • the second glue layer is a liquid second glue covering the inter-capsule segment difference in the electrophoretic medium layer form.
  • Figure 1 is a schematic structural diagram of a cross-section of an electro-optical component in the prior art
  • Figure 2 is a schematic structural diagram of a cross-section of an electronic paper display in the prior art
  • Figure 3 is a schematic cross-sectional structural diagram of an embodiment of a double peeling sheet in the present invention.
  • Figure 4 depicts a display pattern of diffusion phenomena in an electrophoretic display
  • Figure 5 is a display pattern of an embodiment of an electro-optical component in the present invention.
  • Figure 6 depicts a schematic diagram of the voltage in the glue layer of an electro-optical component
  • Figure 7 is an optical enlargement of the display surface of the control group
  • Figure 8 is an optical enlargement of the display surface of the experimental group.
  • an electro-optical component which includes first and second substrates, a glue layer and an electro-optical material layer located between the first and second substrates.
  • the glue layer Includes a mixture of polymeric binder materials and additives selected from the group consisting of salts, polyelectrolytes, polymer electrolytes, solid electrolytes and combinations thereof.
  • One of the first and second substrates or both the first and second substrates include an electrode and PET to which the electrode is attached.
  • PET release film also called PET silicone oil film, is to apply a layer of silicone oil on the surface of the PET film to reduce the adhesion on the surface of the PET film and achieve a release effect. It can be divided into single-sided release film and double-sided release film. According to the release force, it can be divided into light release film, medium release film and heavy release film. Commonly used thicknesses are:
  • the manufacturing method of the electro-optical component includes: (1) coating the electro-optical layer 130 on the substrate 110 with the conductive layer 120, (2) applying the electro-optical layer in a liquid form Laminating adhesive 180 is applied to release sheet 190, conveniently by slot die coating, and the adhesive is dried (or otherwise cured) to form a solid layer (3) Laminating adhesive and release sheet to electro-optical layer 130; This lamination can be conveniently performed using hot roller lamination.
  • a lamination adhesive may be applied over the electro-optical layer 130 and then dried or otherwise cured prior to being covered by the release sheet 190.
  • the release sheet 190 is conveniently a 7 mil (177 ⁇ m) film ; Depending on the nature of the electro-optical medium used, it may be necessary to coat this film with a release agent such as silicone. As illustrated in Figure 1, prior to laminating the FPL 100 to a chassis (not shown) to form the final display, the release sheet 190 is peeled off or otherwise removed from the lamination adhesive 180.
  • the electro-optical component with a certain functional layer obtained above is limited to being applicable to a certain function. From a practical point of view, the electro-optical component is not as universal as the double peeling sheet of the prior art. The applicant believes that the process needs to be divided into two parts. One is to obtain a sub-assembly of an electro-optical component that is easy to store and does not contain PET. When it is necessary to apply the sub-assembly of the above-mentioned electro-optical component, first on the functional layer The ITO is attached, and the electro-optical layer of the sub-assembly of the electro-optical component is laminated to the ITO. Then PET-free electro-optical components can be obtained.
  • the sub-assembly of the electro-optical component includes: a first glue layer, an electrophoretic medium layer and a second glue layer.
  • the first glue layer is formed by coating the first liquid glue on the first release film, and the contact surface between the first glue layer and the release film is a flat surface; the electrophoretic medium layer is formed by coating on the first release film.
  • a liquid electrophoretic medium is formed on the first glue layer.
  • the electrophoretic medium includes a plurality of capsules and an adhesive surrounding the capsules.
  • the capsules include a capsule wall, a suspended fluid coated in the capsule wall, and a suspended fluid in the suspended fluid.
  • a plurality of electrophoretic pigment particles suspended and capable of moving through the fluid when an electric field is applied to the electrophoretic medium the electrophoretic pigment particles including negatively charged electrophoretic pigment particles and electrically neutral electrophoretic pigment particles;
  • the second The glue layer is formed of a liquid second glue covering the step difference between capsules in the electrophoretic medium layer.
  • an embodiment of an electro-optical material provided by one aspect of the present invention includes: a first glue layer 1 , an electrophoretic medium layer 2 and a second glue layer 3 .
  • the glue used includes polymer binder materials and additives, and the additives are selected from: propylene glycol ether, diethylene glycol butyl ether, methoxymethanol, Ethylene glycol, propylene glycol, glycerol, Texanol, adipic acid, phthalic acid, lusolvan FBH, Coasol, DBE-IB, DPnB, Dowanol PPh, alcohol ester-12, hexylene glycol, commercial compositions thereof and its combination.
  • the additives are selected from: propylene glycol ether, diethylene glycol butyl ether, methoxymethanol, Ethylene glycol, propylene glycol, glycerol, Texanol, adipic acid, phthalic acid, lusolvan FBH, Coasol, DBE-IB, DPnB, Dowanol PPh, alcohol ester-12, hexylene glycol, commercial compositions thereof and its combination.
  • the polymer binder material is selected from: polyurethane, vinyl acetate, vinyl acetate ethylene, epoxy resin ), polyacrylic-based adhesives, commercial compositions thereof (e.g., aqueous polyurethane emulsions), and combinations thereof.
  • the glue layer includes polyurethane.
  • the electro-optical material according to any one of the first aspects of the present invention, wherein the additive accounts for 0.5-20% by weight of the glue layer, preferably 1-20% by weight, preferably 2-20% by weight, preferably 2-15% by weight. % by weight, preferably 2 to 10% by weight, such as about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 7.5% by weight, about 10% by weight, about 15% by weight , about 20% by weight.
  • the glue layer further includes: salt, polyelectrolyte, polymer electrolyte, solid electrolyte, or a combination thereof.
  • the salt is selected from: potassium acetate, tetraalkylammonium salts, tetrabutylammonium chloride, tetrabutylammonium hexafluorophosphate.
  • the polyelectrolyte is selected from the group consisting of alkali metal salts of polyacrylic acid, such as the sodium salt of PPA.
  • the electro-optical material is a solid, meaning that the electro-optical material has a solid outer surface, although the material can (and usually does) have internal liquid or gas-filled spaces, as well as methods of assembling displays using such electro-optical materials.
  • Such displays using solid electro-optical materials may be conveniently referred to below as “solid electro-optical displays”.
  • solid electro-optical display thus includes rotating two-color component displays (see below), encapsulated electrophoretic displays, microaperture electrophoretic displays and encapsulated liquid crystal displays.
  • bistable and “bistable” are used herein in their ordinary sense in the art to mean a display including a display component having at least one first and second display state with different optical properties, and such that after any given component is driven by an addressing pulse of finite duration to assume its first or second display state, that state persists for at least several times, such as at least four times, after terminating the addressing pulse, as required The minimum duration of the addressing pulse to change the state of the display component.
  • some particle-based electrophoretic displays capable of achieving grayscale are stable not only in their extreme black and white states but also in their intermediate gray states, some other types of electro-optical The same goes for monitors. Displays of this type are appropriately termed “multistable” rather than bistable, although for convenience the term “bistable” may be used herein to cover both bistable and multistable displays.
  • electro-optical displays are known.
  • One type of electro-optical display is the rotating dichromatic component type described, for example, in U.S. Patent Nos. 5,808,783; 5,777,782; 5,760,761; 6,054,071; 6,055,091; 6,097,531; 6,128,124; 6,137,467; color ball" display, since the rotating component is not spherical in some of the patents mentioned above, the term "rotating two-color component" is preferred as it is more accurate).
  • Such displays use a large number of small objects (usually spherical or cylindrical) with two or more cross-sections with different optical properties and internal dipoles.
  • Electro-optical media of this type are usually bistable.
  • polymer-dispersed electrophoretic displays in which the electrophoretic medium includes multiple discrete liquids of electrophoretic fluid.
  • the discrete droplets of electrophoretic fluid in such polymer-dispersed electrophoretic displays may be considered capsules or microcapsules, although there is no discrete capsule membrane associated with each individual droplet; See, for example, 2002/0131147 above. Therefore, for the purposes of this application, such polymer-dispersed electrophoretic media are considered to be a subcategory of encapsulated electrophoretic media.
  • Encapsulated electrophoretic displays are generally not subject to the aggregation and settling failure modes of traditional electrophoretic devices and offer further advantages, such as the ability to print or coat displays on a variety of flexible and rigid substrates.
  • printing is intended to include all printing and coating methods, including but not limited to: pre-measured coating such as sheet die coating, slot die or extrusion coating, slide or laminate coating, curtain coating; Roller coating such as knife roller coating, front and rear roller coating; gravure coating; dip coating; spray coating; meniscus coating; dip coating; brush coating; air knife coating; screen printing process; electrostatic printing process: thermal printing process ; inkjet printing process; and other similar technologies). Therefore, the resulting display can be flexible. Additionally, the display media can be printed (using various methods) and the display itself can be manufactured cheaply.
  • electrophoretic media are typically opaque (e.g., because in many electrophoretic media the particles substantially block the propagation of visible light through the display) and operate in a reflective mode
  • many electrophoretic displays can be made to operate in a so-called "gating mode" in which one One display state is basically opaque, and one is light-transmitting. See, for example, U.S. Patent Nos. 6,130,774 and 6,172,798, mentioned above, and U.S. Patent Nos. 5,872,552, 6,144,361, 6,271,823, 6,225,971, and 6,184,856.
  • Dielectrophoretic displays which are similar to electrophoretic displays but rely on changes in electric field strength, can operate in a similar mode; see U.S. Patent No. 4,418,346.
  • electro-optical display uses electrochromic media, for example in the form of a nanochromic film that includes an electrode formed at least partially from a semiconducting metal oxide and is connected to the electrode capable of reversible color change.
  • electrochromic media for example in the form of a nanochromic film that includes an electrode formed at least partially from a semiconducting metal oxide and is connected to the electrode capable of reversible color change.
  • Multiple dye molecules see, for example, O'Regan, B., et al., Nature 1991, 353, 737; and Wood, D., Information Display, 18(3), 24 (March 2002). See also Bach, U., et al., Adv.Mater., 2002, 14(11), 845.
  • Nanochromic films of this type are also described, for example, in U.S. Patent No. 6,301,038, International Patent Publication No. WO 01/27690, and in U.S. Patent Application 2003/0214695. This type of media is also typically bistable.
  • electro-optical display Another type of electro-optical display, which has been the subject of intensive research and development for many years, is particle-based electrophoretic displays, in which multiple charged particles move through a suspended fluid under the influence of an electric field.
  • electrophoretic displays can have properties of good brightness and contrast, wide viewing angles, state bistability, and low energy consumption.
  • long-term image quality problems with these displays have hindered their widespread use. For example, the particles that make up electrophoretic displays tend to settle, resulting in an insufficient shelf life of these displays.
  • electro-optical materials Examples of electro-optical materials will be described below in conjunction with a method for manufacturing the electro-optical material.
  • the method includes:
  • a liquid first glue is coated on the first release film 4, and the first glue layer 1 is formed after drying.
  • a liquid electrophoretic medium is coated on the first glue layer; the coating pressure causes the liquid electrophoretic medium to The capsule on the contact surface of the first glue layer is squeezed and presents a flat surface, while the capsule on the other side of the electrophoretic medium is squeezed by the deformed capsule and presents ups and downs.
  • the electrophoretic medium includes capsules with different particle sizes ranging from 5 ⁇ m to 100 ⁇ m.
  • the purpose is to use capsules with smaller particle sizes to fill the spaces between capsules with larger particle sizes.
  • European patent EP1010036B1 and its Japanese equivalent patent JP4460149 provide an electrophoretic display, which includes a display surface (viewed surface) and a back surface (rear surface). There is a polymer array (Polymer Matrix) between the surface and the back.
  • the lamination operation can be performed while the second glue is not dry, or a softer glue can be used as the second glue.
  • the above-mentioned electrophoretic medium includes a plurality of capsules and a binder surrounding the capsules.
  • the capsules include capsule walls, a suspension fluid coated in the capsule walls and suspended in the suspension fluid and applied to the electrophoretic medium.
  • a plurality of electrophoretic pigment particles that can move through the fluid in an electric field.
  • the electrophoretic pigment particles include negatively charged electrophoretic pigment particles and electrically neutral electrophoretic pigment particles; the first glue and the second glue can be considered to have the same chemical structure.
  • Glues with different chemical structures and compositions are also understood to mean glues with different chemical structures and compositions, including different glue compositions and different thicknesses of the glue layers. The application of glue will be described in detail later in this embodiment.
  • the thickness of the second glue layer is preferably 5-35 ⁇ m.
  • Figure 3 is the pattern of the electro-optical component in the normal display state.
  • the applicant found that when applied to a driver board with a 200dpi or above, edge residual images will appear (as shown in Figure 4). This is mainly because The edge diffusion phenomenon is caused by the thickness and volume resistivity of the glue layer.
  • Figure 5 The voltage on the driving base plate 6 goes from point A to A'. Due to the resistance of the glue layer, the voltage will weaken. For example, the voltage at point A drops from 15V to 7V at point A'. It may also happen that the voltage at point C is 15V and attenuates to 0V when it reaches point B'.
  • the electrophoretic pigment particles at points A' and B' of the electrophoretic medium layer 2 affect their original movement trajectories due to voltage changes, thereby affecting the final display effect and initially showing residual images.
  • the above process can be understood abstractly as the glue layer is a resistor, and its resistance affects the voltage, which further affects the display effect. Since volume resistivity is proportional to resistance, the smaller the volume resistivity, the smaller the voltage loss under ideal conditions. However, the applicant found that when the volume resistivity is reduced to a certain value, the voltage loss increases instead. The reason is that the voltage from A to A' changes to 13V. However, due to the decrease in volume resistivity, the current A to B', the voltage may become 7V. Therefore, the volume resistivity of the glue layer in contact with TFT6 should be controlled between 1*10 10 and 1*10 12 ( ⁇ .cm).
  • R the resistance
  • S the cross-sectional area
  • L the thickness of the glue layer
  • ⁇ the volume resistivity of the glue layer.
  • ⁇ and S are constant, the smaller the thickness L of the glue layer, the smaller the resistance and the smaller the impact on the voltage.
  • the thickness of the first glue layer is 1 to 10 ⁇ m, which is obtained by the applicant through experiments. A thickness greater than 10 ⁇ m will affect the voltage, and a thickness less than 1 ⁇ m will affect the mechanical strength.
  • the applicant proposed a plan to "attach ITO to functional layers that can be applied to displays such as color filter layers, light guide plates, waterproof protective layers, and touch screens. Then the electro-optical layer is coated on the tape On the functional layer with the conductive layer, the electro-optical component with a certain functional layer is obtained by following the operating steps of the existing technology in order, which can be laminated with TFT when necessary.” Based on the foregoing analysis, it can be understood that the electro-optical layer (i.e., the electrophoretic medium in this application) is coated on the transparent conductive layer, and the capsule on the contact surface with the transparent conductive layer is squeezed to present a flat surface, and the capsule on the other side of the electrophoretic medium is deformed.
  • the electro-optical layer i.e., the electrophoretic medium in this application
  • the thickness of the glue layer is preferably 5 to 35 ⁇ m. It is understandable that the thickness of the glue layer will affect the final display effect. Therefore, only by adopting the technical solution of this embodiment, the thickness of the first glue layer can be controlled to 1 to 10 ⁇ m.
  • the second glue layer is used to coat the step difference on the reverse side, that is, it satisfies the pressure-sensitive characteristics of the glue.
  • This application independently synthesizes high molecular polymers, controls the molecular weight of the polymer, controls the content of ionic groups in the molecular structure, and adds some ionic liquids or small molecule polyols to achieve both reduced volume resistivity and pressure-sensitive characteristics.
  • the molecular weight distribution of the polymer in the second glue layer ranges from 10,000 to 50,000. It can be understood that too large a molecular weight will cause the glue layer to become hard and unable to cover the steps between capsules.
  • the polymer in the first glue layer includes ionic groups, which refer to carboxyl groups, sulfonic acid groups, amine groups and their salt-forming products.
  • ionic groups refer to carboxyl groups, sulfonic acid groups, amine groups and their salt-forming products.
  • the mass proportion of carboxylic acid groups is 0.1% to 1.5%
  • the mass proportion of sulfonic acid groups is 0.1% to 1.5%.
  • the resistance of the glue layer can be adjusted within 1*107 ⁇ 1*1010 ( ⁇ .cm).
  • the small molecule polyol refers to a small molecule glycol or its oligomers with a molecular weight of less than 600 and which is liquid at room temperature, usually propylene glycol, ethylene glycol and their oligomers.
  • the addition ratio is 0.1 % to 4%. This ratio can change the TG of the glue mixture, causing the volume resistivity of the glue to slow down with temperature. Excessive addition will affect the bonding force.
  • the first glue specifically selects polyurethane and acrylic monomer materials for polymerization.
  • the mass percentage of the carboxylic acid group of the raw material is 0.3%, and the sulfonic acid and amine groups of the raw material are 0.2%.
  • the degree of polymerization is controlled, and the tested weight average molecular weight Mw is 63,000, add propylene glycol ether at the same time, the addition amount is 2% of the solid content, and the test volume resistivity is 7*10 11 ( ⁇ .cm).
  • the coating thickness is 4 ⁇ m, resulting in products that meet edge diffusion and reliability.
  • the second glue specifically selects the raw materials required for polyurethane for polymerization.
  • the mass percentage of the carboxylic acid group of the raw material is 0.8%, and the sulfonic acid and amine groups of the raw material are 1.3%.
  • the degree of polymerization is controlled, and the tested weight average molecular weight Mw is 30,000.
  • the display structure uses precision slit extrusion equipment to control the coating thickness at 30 ⁇ m, which improves the bubbles in the electro-optical display layer and ensures good optoelectronic demand.
  • Table 1 describes the specific experimental parameters and display effects of this embodiment.
  • the polymer in the first glue layer includes ionic groups.
  • the ionic groups of the polymer refer to carboxyl groups, sulfonic acid groups, amine groups and their salt-forming products. In order to control its volume resistivity at 1*10 10
  • the ionic group content of the polymer described in ⁇ 1*10 12 ( ⁇ .cm) the mass proportion of carboxylic acid groups is 0% to 0.4%, and the mass proportions of sulfonic acid groups and amine groups are 0% to 0.3 %.
  • the molecular weight distribution of the polymer in the first glue layer ranges from 20,000 to 70,000. If the molecular weight is too low, the heat resistance of the glue will be reduced, causing the reliability test to fail.
  • Figure 3 shows that the thickness of the first glue layer is controlled at 1 ⁇ 5um, and the volume resistivity is controlled at 1*10 10 ⁇ 1*10 12 ( ⁇ .cm).
  • a second aspect of the present invention provides a glue layer, which includes a polymer adhesive material and an additive, the additive being selected from the group consisting of: propylene glycol ether, diethylene glycol butyl ether, methoxymethanol, ethylene glycol, propylene glycol, propylene glycol, Triol, Texanol, adipic acid, phthalic acid, lusolvan FBH, Coasol, DBE-IB, DPnB, Dowanol PPh, alcohol ester-12, hexylene glycol, commercial compositions thereof, and combinations thereof.
  • the additive being selected from the group consisting of: propylene glycol ether, diethylene glycol butyl ether, methoxymethanol, ethylene glycol, propylene glycol, propylene glycol, Triol, Texanol, adipic acid, phthalic acid, lusolvan FBH, Coasol, DBE-IB, DPnB, Dowanol PPh
  • the glue layer according to any one of the second aspects of the present invention, wherein the polymer adhesive material is selected from: polyurethane, vinyl acetate, vinyl acetate-ethylene, epoxy resin, polyacrylic acid-based adhesives , commercial compositions thereof (such as water-based polyurethane emulsions) and combinations thereof.
  • the glue layer includes polyurethane.
  • the glue layer according to any one of the second aspects of the present invention, wherein the additive accounts for 0.5-20% by weight of the glue layer, preferably 1-20% by weight, preferably 2-20% by weight, preferably 2-15% by weight %, preferably 2 to 10% by weight, such as about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 7.5% by weight, about 10% by weight, about 15% by weight, About 20% by weight.
  • the additive accounts for 0.5-20% by weight of the glue layer, preferably 1-20% by weight, preferably 2-20% by weight, preferably 2-15% by weight %, preferably 2 to 10% by weight, such as about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 7.5% by weight, about 10% by weight, about 15% by weight, About 20% by weight.
  • the glue layer according to any one of the second aspects of the present invention, wherein the glue layer further includes: salt, polyelectrolyte, polymer electrolyte, solid electrolyte, or a combination thereof.
  • the salt is selected from: potassium acetate, tetraalkylammonium salts, tetrabutylammonium chloride, tetrabutylammonium hexafluorophosphate.
  • the polyelectrolyte is selected from the group consisting of alkali metal salts of polyacrylic acid, such as the sodium salt of PPA.
  • the glue layer according to any one of the second aspects of the present invention, wherein the additive-containing glue layer further includes an optical biasing element.
  • a second aspect of the invention provides an adhesive comprising a polymeric adhesive material and an additive selected from the group consisting of conductive metal powders, ferrofluids, non-reactive solvents, conductive organic compounds and combinations thereof.
  • a second aspect of the present invention provides the use of additives in reducing the volume resistivity of products and/or improving the electro-optical properties of products, including but not limited to electro-optical components, double peel sheets, electrophoretic media, adhesives, Adhesives, electro-optical displays, electro-optical materials, electrophoretic displays, electro-optical media, electronic paper, electronic paper display screens, etc.
  • the additives are selected from: propylene glycol ether, diethylene glycol butyl ether, methoxymethanol, ethylene glycol Alcohol, propylene glycol, glycerin, Texanol, adipic acid, phthalic acid, lusolvan FBH, Coasol, DBE-IB, DPnB, Dowanol PPh, alcohol ester-12, hexylene glycol, commercial compositions thereof, and combinations thereof .
  • the additive is used in combination with a polymer adhesive material selected from: polyurethane, vinyl acetate, vinyl acetate-ethylene, epoxy resin, polyethylene Acrylic-based adhesives, commercial compositions thereof (eg, aqueous polyurethane emulsions), and combinations thereof.
  • a polymer adhesive material selected from: polyurethane, vinyl acetate, vinyl acetate-ethylene, epoxy resin, polyethylene Acrylic-based adhesives, commercial compositions thereof (eg, aqueous polyurethane emulsions), and combinations thereof.
  • the weight ratio of the polymer binder material to the additive is 100: (1-60), preferably 100: (2-50), preferably 100: (2-40), preferably 100: ( 2 ⁇ 25), preferably 100:(2 ⁇ 20), preferably 100:(2 ⁇ 15), preferably 100:(2 ⁇ 10).
  • the term "commercial composition” refers to a composition formulated for commercial use based on the mentioned ingredient as a main ingredient (or one of the main ingredients).
  • products with the trade names NeoRez 9630 and NeoRez 9330 are two polyurethane dispersions purchased from NeoResins, Inc., 730 Main Street, Wilmington MA 01887.
  • aqueous polyurethane emulsion refers to an aqueous emulsion made with polyurethane as the main component.
  • release sheet may also be referred to as a "release sheet.”
  • encapsulation may also be referred to as “encapsulated.”
  • base frame may also be referred to as a "backplane.”
  • polyelectrolytes may also be included in the glue layer.
  • Polyelectrolytes may include, for example, salts of polyacids, such as, but not limited to, alkali metal salts of polyacrylic acid.
  • Glue layers containing additives may provide additional functions in addition to the adhesive function.
  • the glue layer can have differently colored areas and act as a color filter.
  • the glue layer may include optical biasing elements.
  • a salt may also be included in the binder used in the electrophoretic medium.
  • the salt may be, for example, an inorganic salt, an organic salt, or a combination thereof.
  • the salt includes potassium acetate.
  • the salt may include a quaternary ammonium salt, such as a tetraalkylammonium salt, such as tetrabutylammonium chloride or tetrabutylammonium hexafluorophosphate.
  • the polyelectrolyte may include a salt of a polyacid, such as an alkali metal salt of polyacrylic acid.
  • Binders containing additives can provide functions other than that of an adhesive.
  • the adhesive may include optical biasing components.
  • an electrophoretic medium in yet another aspect, includes a plurality of capsules, each capsule including a capsule wall, a suspending fluid enclosed in the capsule walls, and a medium suspended in the suspending fluid and capable of moving therefrom when an electric field is applied to the medium. a plurality of charged particles, the medium further comprising a binder surrounding the capsule, the binder comprising a mixture of polymeric binder material and additives selected from the group consisting of conductive metal powders, ferrofluids, non-reactive solvents, conductive organic compounds and combinations thereof.
  • an adhesive in another aspect, includes a mixture of a polymeric adhesive material and an additive selected from the group consisting of propylene glycol ether, diethylene glycol butyl ether, methoxymethanol, ethylene glycol, propylene glycol, glycerol, Alcohol, Texanol, adipic acid, phthalic acid, lusolvan FBH, Coasol, DBE-IB, DPnB, Dowanol PPh, alcohol ester-12, hexylene glycol, commercial compositions thereof, and combinations thereof.
  • the additive may further be selected from the group consisting of salts, polyelectrolytes, polymer electrolytes, solid electrolytes, and combinations thereof.
  • the adhesive may comprise a polyurethane, vinyl acetate, vinyl acetate-ethylene, epoxy, or polyacrylic based adhesive.
  • an adhesive that includes a mixture of a polymeric adhesive material and an additive selected from the group consisting of conductive metal powders, ferrofluids, non-reactive solvents, conductive organic compounds, and combinations thereof.
  • the polymeric adhesive material may be selected from the group consisting of polyurethane, vinyl acetate, vinyl acetate-ethylene, epoxy resin, polyacrylic based adhesives, and combinations thereof.
  • certain additives are disclosed herein for use in glue layers of electro-optical components and displays, and in adhesives surrounding capsules encapsulating electrophoretic media, to control the volume resistance of the adhesive material. Rate.
  • the glue layers and adhesives disclosed herein are capable of changing the volume resistivity without substantially changing the mechanical properties of the glue layer or adhesive.
  • the glue layers and binders expand the selection of adhesive materials that have the required mechanical properties but cannot otherwise be used because their volume resistivity is not suitable. Therefore, one can "fine tune" the volume resistivity of the glue layer or adhesive, ie, adjust the volume resistivity of the material to the optimal value for a specific display or electrophoretic medium.
  • a salt may also be included in the binder used in the electrophoretic medium.
  • the salt may be, for example, an inorganic salt, an organic salt, or a combination thereof.
  • the salt includes potassium acetate.
  • the salt may include a quaternary ammonium salt, such as a tetraalkylammonium salt, such as tetrabutylammonium chloride or tetrabutylammonium hexafluorophosphate.
  • the polyelectrolyte may include a salt of a polyacid, such as an alkali metal salt of polyacrylic acid.
  • Binders containing additives can provide functions other than that of an adhesive.
  • the adhesive may include optical biasing components.
  • an electrophoretic medium in yet another aspect, includes a plurality of capsules, each capsule including a capsule wall, a suspending fluid enclosed in the capsule walls, and a medium suspended in the suspending fluid and capable of moving therefrom when an electric field is applied to the medium. a plurality of charged particles, the medium further comprising a binder surrounding the capsule, the binder comprising a mixture of polymeric binder material and additives selected from the group consisting of conductive metal powders, ferrofluids, non-reactive solvents, conductive organic compounds and combinations thereof.
  • an adhesive in another aspect, includes a mixture of a polymeric adhesive material and an additive selected from the group consisting of propylene glycol ether, diethylene glycol butyl ether, methoxymethanol, ethylene glycol, propylene glycol, glycerol, Alcohol, Texanol, adipic acid, phthalic acid, lusolvanFBH, Coasol, DBE-IB, DPnB, Dowanol PPh, alcohol ester-12, hexylene glycol, commercial compositions thereof, and combinations thereof.
  • the additive may further be selected from the group consisting of salts, polyelectrolytes, polymer electrolytes, solid electrolytes, and combinations thereof.
  • the adhesive may comprise a polyurethane, vinyl acetate, vinyl acetate-ethylene, epoxy, or polyacrylic based adhesive.
  • an adhesive that includes a mixture of a polymeric adhesive material and an additive selected from the group consisting of conductive metal powders, ferrofluids, non-reactive solvents, conductive organic compounds, and combinations thereof.
  • the polymeric adhesive material may be selected from the group consisting of polyurethane, vinyl acetate, vinyl acetate-ethylene, epoxy, polyacrylic based adhesives, and combinations thereof.
  • certain additives are disclosed herein for use in glue layers of electro-optical components and displays, and in adhesives surrounding capsules encapsulating electrophoretic media, to control the volume resistance of the adhesive material Rate.
  • the glue layers and adhesives disclosed herein are capable of changing the volume resistivity without substantially changing the mechanical properties of the glue layer or adhesive.
  • the glue layers and binders expand the selection of adhesive materials that have the required mechanical properties but cannot otherwise be used because their volume resistivity is not suitable. Therefore, one can "fine tune" the volume resistivity of the glue layer or adhesive, ie, adjust the volume resistivity of the material to the optimal value for a specific display or electrophoretic medium.
  • the glue layer or adhesive includes one or more additives selected from the group consisting of: (a) propylene glycol ether, diethylene glycol butyl ether, methoxymethanol, ethylene glycol, propylene glycol, glycerol, Texanol, adipic acid , phthalic acid, lusolvanFBH, Coasol, DBE-IB, DPnB, Dowanol PPh, alcohol ester-12, hexylene glycol, commercial compositions thereof and combinations thereof; (b) salts, polyelectrolytes, polymer electrolytes, solids Electrolytes and combinations thereof; or (c) conductive metal powders, ferromagnetic fluids, non-reactive solvents, conductive organic compounds and combinations thereof.
  • additives selected from the group consisting of: (a) propylene glycol ether, diethylene glycol butyl ether, methoxymethanol, ethylene glycol, propylene glycol, glycerol, Texano
  • the additive may be a salt such as an inorganic salt, an organic salt, or a combination thereof.
  • exemplary salts include potassium acetate and tetraalkylammonium salts, particularly tetrabutylammonium salts such as chloride.
  • Further examples of salts include lithium salts such as LiCF3SOF3, LiClO4, LiPF6, LiBF4, LiAsF6 and LiN(CF3SO2)3.
  • the currently preferred salt is tetrabutylammonium hexafluorophosphate, primarily due to the stability and inertness of this salt.
  • the polymer electrolyte is a polyelectrolyte.
  • Polyelectrolytes are typically polymers in which about 10% or more of the molecules consist of functional groups capable of ionizing to form charged moieties. Examples of certain functional groups in polyelectrolytes include, but are not limited to, carboxylic acids, sulfonic acids, phosphoric acids, and quaternary ammonium compounds. These polymers can be used in combination with organic or inorganic salts or alone.
  • polyelectrolytes include, but are not limited to, polyacrylic acid, polystyrene sulfonate, poly(2-vinylpyridine), poly(4-vinylpyridine), poly(dimethylammonium chloride), poly(methyl Dimethylaminoethyl acrylate), poly(diethylaminoethyl methacrylate).
  • a preferred polyelectrolyte is the sodium salt of polyacrylic acid (PAA).
  • the additive is a polymer electrolyte.
  • polymer electrolyte as used herein describes a polymer capable of solubilizing salts. The solubility of salts in these polymers can be increased by the presence of oxygen and/or nitrogen atoms in the polymer, which atoms form ethers, carbonyl groups, carboxylic acids, primary, secondary, tertiary and quaternary amino groups, sulfonic acids, etc.
  • polymer electrolytes examples include polyether compounds such as polyepoxy ethane, polyepoxy propane, polytetrahydrofuran (polytetramethyleneoxide), polyamines such as polyethyleneimine, polyvinylpyrrolidone, and polymers containing quaternary ammonium groups such as N +R1R2R3R4, wherein R1, R2, R3 and R4 are each independently H or a linear, branched, or cyclic alkyl group containing 1 to 25 carbon atoms, and wherein the counterion can be selected from any organic or inorganic anion .
  • polyether compounds such as polyepoxy ethane, polyepoxy propane, polytetrahydrofuran (polytetramethyleneoxide), polyamines such as polyethyleneimine, polyvinylpyrrolidone, and polymers containing quaternary ammonium groups such as N +R1R2R3R4, wherein R1, R2, R3 and R4 are each independently
  • the following additives propylene glycol ether, diethylene glycol butyl ether, methoxymethanol, ethylene glycol, propylene glycol, glycerin, Texanol, adipic acid, phthalic acid, lusolvanFBH, Coasol, DBE -IB, DPnB, Dowanol PPh, alcohol ester-12, hexylene glycol, their commercial compositions and combinations thereof, they all have basically the same properties due to their role in contributing to film formation, that is, they can form as a film Auxiliary agents.
  • Still other additives may include conductive metal powders, ferrofluids, and/or non-reactive solvents that may improve or hinder ion mobility in solution.
  • suitable non-reactive solvents include water, diethyl ether, dipropyl ether, diethylene glycol, glyme, diglyme, N-methylpyrrolidone, and the like.
  • conductive organic compounds may be used as additives. Some non-limiting examples of these compounds include polyaniline, polythiophene, polypyrrole, poly-3,4-dioxyethylenethiophene, and derivatives of these materials in their n- or p-doped states.
  • the polymeric binder material used in the glue layer or adhesive may be any polymeric material suitable for the end use application.
  • suitable polymeric adhesive materials include polyurethane, vinyl acetate, vinyl acetate-ethylene, epoxy, polyacrylic-based adhesives, or combinations thereof. These adhesive materials can be solvent-based or water-based. Examples of specific polyurethanes that may be used are described in co-pending U.S. Application Serial No. 10/715,916 filed with Air Products and Chemicals, Inc. on November 18, 2003.
  • Additives introduced into the polymeric binder material can be formed in situ; in other words, one or more precursor materials can be introduced into the polymeric binder material or binder, where the precursor materials can react with each other, or with the polymerization Reaction of a binder or binder, or exposure of a binder material or binder to conditions that cause changes in precursor materials to form the final additive (e.g., exposure to heat, light, or magnetic or electric fields) down to cause changes.
  • precursor materials can react with each other, or with the polymerization Reaction of a binder or binder, or exposure of a binder material or binder to conditions that cause changes in precursor materials to form the final additive (e.g., exposure to heat, light, or magnetic or electric fields) down to cause changes.
  • the binder material or binder may contain components (or other dopants) in addition to additives for adjusting its volume resistivity; for example, the binder material or binder may also contain dyes or other colorants .
  • the binder material or binder may also contain dyes or other colorants .
  • optical biasing components can be provided in the adhesive or laminating adhesive encapsulating electrophoretic displays to adjust the appearance of the display. Providing such optical biasing components can affect the electrical properties of the adhesive or adhesive, and the electrical properties of adhesives or adhesives containing such optical biasing components can be optimized through the use of additives described herein.
  • the optimal amount of additives will vary widely depending on the exact polymeric binder or binder material, the exact additives used, and the desired volume resistivity of the final mixture. Generally, however, it can be stated that additives as described above in this invention are found to be used in amounts which give useful results. As shown in the following examples, the volume resistivity of a binder material generally changes in a predictable manner with the concentration of additives, and therefore the final choice of how much additive should be added to achieve the desired volume resistivity can easily be based on experience Sure.
  • the glue layer is formed by coating a film of a latex or solution of an adhesive material onto a substrate, or onto an electro-optical material, and then drying to form the glue layer, typically
  • the additive is simply dissolved or dispersed in a latex or solution of the binder material prior to coating.
  • Additives may be added neat to the latex or solution, or may be dissolved in aqueous solutions, non-aqueous solutions, or combinations thereof.
  • electrophoretic media are formed by mixing a slurry of capsules in a liquid with a latex or solution of a polymeric binder, coating the resulting mixture onto a substrate, and drying to The electrophoretic medium is formed; the additives are often simply dissolved or dispersed in the latex or solution of the polymeric binder before mixing this latex or solution with the capsules. It is of course necessary to ensure a homogeneous dispersion of the additives throughout the adhesive material in order to prevent changes in conductivity in the final adhesive or binder layer, but those skilled in coating technology are familiar with conventional techniques such as lengthy stirring on a roller kneader to ensure this even dispersion.
  • the choice of the specific additive used is primarily governed by considerations of compatibility with other components of the glue layer and solubility in the adhesive material to which the additive is to be incorporated. If, as is typically the case, additives are to be added to an aqueous latex of the binder material, the additives should be selected to have good water solubility, so that alkali metal salts and substituted ammonium salts are generally preferred among the salts. Care should be taken to ensure that the additives do not cause aggregation of latex particles. Likewise, the additives should be expected not to cause large changes in the pH of the adhesive material, and should not chemically react with the adhesive material or other parts of the final display with which it ultimately contacts (eg, the chassis).
  • the addition of one or more additives greatly expands the range of polymeric materials that can be used as binders and laminating adhesives in electro-optical displays.
  • the addition of one or more additives enables the use of polymeric materials that have highly desirable mechanical properties in electro-optical displays, but whose volume resistivity in their pure state is too high to be used.
  • the addition of one or more additives could be used instead of the non-hygroscopic and/or hydrophobic polymeric materials used heretofore. Water-based polyurethane dispersions for such displays.
  • modified adhesives and binders disclosed herein may be used in applications other than electro-optical displays.
  • a third aspect of the present invention provides a method for manufacturing the above-mentioned electro-optical material, which specifically includes:
  • the electrophoretic medium 2 and the second glue are laminated so that the second glue covers the inter-capsule steps in the electrophoretic medium layer.
  • the thickness of the first glue layer is controlled to be 1 to 10 ⁇ m
  • the volume resistivity of the first glue layer is controlled to be 1*10 10 to 1*10 12 ( ⁇ .cm).
  • the thickness of the second glue layer is controlled to be 5-35 ⁇ m.
  • the volume resistivity of the second glue layer is controlled at 1*10 7 ⁇ 1*10 10 ( ⁇ .cm).
  • the double peelable sheet provided in the fourth aspect of the application can be obtained, which in order includes:
  • the first release film 4 the first glue layer 1, the electrophoretic medium layer 2, the second glue layer 3 and the second release film 5.
  • the release force between the first release film and the electro-optical material is (75-110) gf/inch; the release force between the second release film and the electro-optical material is The molding force is more than twice the molding force between the first release film and the electro-optical material.
  • the first release film has electrical conductivity or does not have electrical conductivity.
  • the second release film has electrical conductivity or does not have electrical conductivity.
  • the above manufacturing process can be achieved by applying a non-conductive release film. Since the double peel sheet needs to be tested during this process, a conductive release film can be used for direct testing.
  • the fifth aspect of the present invention provides a method for electro-optical components manufactured using the above-mentioned double stripping, including:
  • a sixth aspect of the present invention provides an electro-optical component manufactured by applying the above-mentioned manufacturing method of an electro-optical component, including in order: a functional layer, a transparent conductive layer, a first glue layer, an electrophoretic medium layer, a second glue layer and a driving base plate.

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Abstract

一种双剥离片，用于与具有透明导电层的功能层结合形成显示组件。相对于现有技术的电泳显示设备去掉了PET部分，能够减少对光能的损失，有效提高显示效果。双剥离片包括第一离型膜（4）和第二离型膜（5），以及置于第一离型膜（4）和第二离型膜（5）之间的电光学材料；电光学材料包括：第一胶水层（1），第一胶水层（1）为涂布在第一离型膜（4）上液态的第一胶水形成；电泳介质层（2）；第二胶水层（3），第二胶水层（3）为覆盖电泳介质层（2）中胶囊间段差的液态的第二胶水形成；功能层包括彩色滤光层、导光板、触摸显示层和保护层中至少一个或者任意组合。

Description

一种双剥离片及其制造方法和应用 技术领域
本申请涉及电光学显示器的电光学组件技术领域，具体地涉及一种双剥离片及其制造方法和应用。
背景技术
电光学材料是在本文中以本领域通常的意义用于表示如下材料的术语：该材料具有至少一种光学性能不同的第一和第二显示状态，当对材料施加电场时，材料从它的第一显示状态改变到它的第二显示状态。光学性能通常是人眼睛可感受到的颜色，但可以是另一种光学性能，如光学传播、反射、发光，或在希望用于机器阅读显示器的情况下，在可见光范围以外的电磁波长反射中改变感觉中的伪颜色。
申请人于2011年11月23日公开专利CN102253502A，公开了一种电光学组件，包括第一和第二衬底和位于第一和第二衬底之间的胶水层和电光学材料层，胶水层包括聚合物粘合剂材料和添加剂的混合物，该添加剂选自盐、聚电解质、聚合物电解质、固体电解质及其结合物。其中第一和第二衬底之一或第一和第二衬两者包括电极。近来授权公开CN100350323C、CN100357993C、CN100390819C、CN101082752B、CN101271239B、CN101738814B、CN103365018B、CN103424947B、CN103540162B、CN103834285B、CN103045151B、CN103091926B、CN103111208B、CN103173040B、CN104073210B、CN104073109B、CN105807531B、CN105845087B、CN105800363B、CN105097945B、CN105261652B、CN105023951B、CN105070736B、CN106520111B、CN106967379B、CN106883808、CN108059852B、CN108447406B、CN109535355B、CN110111746B、CN111048046B、US9,759,976B2、EP2477066B1、US9,318,059B2、EP2555181B1、JP5607231B2、US10,935,711B2、EP3121628B1和US11124655B2。
例如，在几个上述授权专利文本中，其中将在粘结剂中包含胶囊的封装电泳介质涂覆到包括氧化铟锡(ITO)的柔性衬底上或将相似的导电涂料(它用作最终显示器的一个电极)涂覆在塑料膜上，干燥胶囊/粘结剂涂料以形成电泳介质坚固粘合到衬底的粘附层。导电层方便地是例如，铝或氧化铟锡的薄金属层，或者可以是导电聚合物。由铝或ITO涂覆的聚对苯二甲酸乙二醇酯(Polyethylene terephthalate，PET)膜是可商购得到的，例如来自E.I.du Pont de Nemours&Company，WilmingtonDE的″铝化。
申请人发现，业界普遍该采用上述结构，该电光学组件中至少一个衬底具有该导电层，导电层为ITO，衬底为PET，其厚度一般在0.01mm～0.2mm之间。申请人认为若能将PET去掉，可进一步提高显示效果。
发明内容
本发明提供了一种电光学材料，用于与具有透明导电层的功能层结合形成显示组件，由于该电光学材料相对于现有技术去掉了PET部分，能够减少对光能的损失，有效提高显示效果。
本发明提供的一种一种双剥离片，包括第一离型膜和第二离型膜，以及置于第一离型膜和第二离型膜之间的电光学材料；
所述电光学材料包括：
第一胶水层，所述第一胶水层为涂布在第一离型膜上液态的第一胶水形成；
电泳介质层，所述电泳介质层为涂布在所述第一胶水层上液态的电泳介质形成，所述电泳介质包括多个胶囊和围绕胶囊的粘结剂，所述胶囊包括胶囊壁，包覆在胶囊壁中的悬浮流体和在悬浮流体中悬浮和在对所述电泳介质施加电场时能够通过所述流体移动的多个电泳颜料粒子，所述电泳颜料粒子包括带负电荷的电泳颜料粒子和电中性的电泳颜料粒子；所述电泳介质层与所述第一胶水层接触面为平整表面，所述电泳介质层的另一面因多数的胶囊段差呈现高低不平表面；
第二胶水层，所述第二胶水层为覆盖所述电泳介质层中胶囊间段差的液态的第二胶水形成；
所述功能层包括彩色滤光层、导光板、触摸显示层和保护层中至少一个或者任意组合。
可选的，
所述第一胶水层的体积电阻率控制在1*10 5～1*10 10(Ω.cm)。
可选的，
所述第一胶水层的厚度为0.1～10μm。
可选的，
所述第二胶水层的厚度为0.1～50μm.
可选的，
所述第二胶水层的厚度为5～35μm。
可选的，
所述第二胶水层的体积电阻率控制在1*10 7～1*10 12(Ω.cm)。
可选的，
所述第一胶水和第二胶水均包括高分子聚合物，所述高分子聚合物包括聚氨酯聚合物或聚氨酯与丙烯酸的共聚物。
可选的，
所述第二胶水层中聚合物分子量分布在1～10万。
可选的，
所述第二胶水层中聚合物中包括离子基团，是指羧基、磺酸基、胺基以及它们的成盐产物，羧酸基团质量占比为0.1％～10％磺酸基团、胺基基团质量占比为0.1％～1.5％。
可选的，
所述第一胶水层中聚合物分子量分布在2～7万。
可选的，
所述第一胶水层中聚合物中包括离子基团，聚合物的离子基团，是指羧基、磺酸基、胺基以及它们的成盐产物；
所述聚合物离子基团含量，羧酸基团质量占比为0％～10％，磺酸基团、胺基基团质量占比为0％～3％。
可选的，
所述第一离型膜与所述电光学材料间的离型力为(5-50)gf/inch；进一步20-40；
所述第二离型膜与所述电光学材料间的离型力为第一离型膜与所述电光学材料间的离型力的2倍以上。
可选的，
所述第一离型膜具有导电性或者不具有导电性。
可选的，
所述第二离型膜具有导电性或者不具有导电性。
本发明还提供了一种制造如上所述的双剥离片的方法，包括：
在第一离型膜上涂布液态的第一胶水，经干燥后形成第一胶水层；
在第二离型膜上涂布第二胶水，经干燥后形成第二胶水层；
在所述第一胶水层上涂布液态的电泳介质，经干燥后形成电泳介质层；
将所述电泳介质层与所述第二胶水层压，使第二胶水覆盖电泳介质层中所产生的胶囊间段差。
本发明还提供了一种制造如上所述的双剥离片的方法，包括：
在第一离型膜上涂布液态的第一胶水，经干燥后形成第一胶水层；
在所述第一胶水层上涂布液态的电泳介质，经干燥后形成可显示的电泳介质层；
在电泳介质层上涂布第二胶水，经干燥后形成第二胶水层，第二胶水层覆盖电泳介质层中所产生的胶囊间段差。
本发明还提供了一种如上所述的双剥离片的应用，包括：
剥离所述第一离型膜，将所述第二胶水层与含有所述透明导电层的功能层结合，第二胶水层与透明导电层直接接触；
剥离所述第二离型膜，将所述第一胶水层与驱动底板结合；
第一胶水层与驱动底板直接接触。
本发明相对于现有技术具有如下技术效果：
为了方便批量化生产以及存放，现有技术公开了一种电光学组件，包括第一和第二衬底和位于第一和第二衬底之间的胶水层和电光学材料层，胶水层包括聚合物粘合剂材料和添加剂的混合物，该添加剂选自盐、聚电解质、聚合物电解质、固体电解质及其结合物。其中第一和第二衬底之一或第一和第二衬两者包括电极以及该电极所附着的PET。请参阅图1(原专利公开文本原图)，该电光学组件的制造方法包括：(1)将电光学层130涂覆到带有导电层120的衬底110上，(2)以液体形式方便地由缝模涂覆将层压粘合剂180涂覆到剥离片190上，干燥(或另外固化)粘合剂以形成固体层(3)层压粘合剂和剥离片到电光学层130；此层压可方便地使用热辊层压进行。(或者，但较少需要地可以将层压粘合剂在电光学层130上施加和然后在由剥离片190覆盖之前干燥或另外固化。)剥离片190方便地是7密耳(177μm)膜；依赖于使用的电光学介质的本质，可能需要采用脱模剂，例如硅氧烷涂覆此膜。如在图1中说明的那样，在将FPL 100层压到基架(未显示)以形成最终显示器之前，将剥离片190剥离或另外从层压粘合剂180除去。
图2所示为采用如上所述电光学组件制作的电子纸显示器，包括电光学组件部分和与其结合的功能层与TFT驱动底板。结合过程具体如下：电光学组件部分包括电泳介质层210、衬底220，该衬底220具有与电泳介质层210直接接触的透明导电层221；还包括与衬底220另一面具有的OCA层240和与电泳介质层210具有的胶水层230。OCA层240与功能层250结合，胶水层230与TFT驱动底板结合。
根据现有的两者电光学结构，申请人认为上述结构若要去掉PET，需要改进造作工艺，进一步需要解决以下问题：业界公知应用镀有ITO的PET作为透明导电层，因此ITO与PET是不开分离的。而电光学层需要涂敷在ITO上，因此，在业界ITO、PET和电光学层不可分开是公知常识。若不能正视该技术偏见，将PET去掉则成为不可实现的技术方案。申请人认为若要去掉PET，ITO与PET需要分离，而将ITO附着在如彩色滤光层、导光板、防水保护层以及触摸显示屏等能够应用在显示器上的功能层上。再将电光学层涂覆到带有导电层的功能层上，接着依次按现有技术的操作步骤得到具有某种功能层的电光学组件，用于需要时与TFT层压。
上述得到的具有某种功能层的电光学组件限制了其只能应用于某一种功能，从实用性角度分析该电光学组件并没有现有技术的双剥离片普适性强。申请人认为，为了更好解决背景技术中的技术问题，需要将工艺分为两个部分，一是得到一种方便保存且不含PET的电光学组件的亚组件，再需要应用上述电光学组件的亚组件的时候，在功能层上附着ITO，再将电光学组件亚组件的电光学层于ITO层压。上述方案能够得到不含PET的电光学组件。该电光学组件的亚组件包括：第一胶水层、电泳介质层和第二胶水层。
所述第一胶水层为涂布在第一离型膜上液态的第一胶水形成；所述电泳介质为涂布在所述第一胶水层上液态的电泳介质形成，所述电泳介质包括多个胶囊和围绕胶囊的粘结剂，所述胶囊包括胶囊壁，包覆在胶囊壁中的悬浮流体和在悬浮流体中悬浮和在对所述电泳介 质施加电场时能够通过所述流体移动的多个电泳颜料粒子，所述电泳颜料粒子包括带负电荷的电泳颜料粒子和电中性的电泳颜料粒子；所述第二胶水层为覆盖所述电泳介质层中胶囊间段差的液态的第二胶水形成。
附图说明
图1为现有技术中电光学组件的横截面的结构示意图；
图2为现有技术中电子纸显示器的横截面的结构示意图；
图3为本发明中一种双剥离片实施例的横截面的结构示意图；
图4描绘电泳显示中扩散现象的显示图案；
图5为本发明中一种电光学组件实施例的显示图案；
图6描绘一种电光学组件的胶水层中电压示意图；
图7为对照组显示面光学放大图；
图8为实验组显示面光学放大图。
具体实施方式
为了方便批量化生产以及便于存放，现有技术公开了一种电光学组件，包括第一和第二衬底和位于第一和第二衬底之间的胶水层和电光学材料层，胶水层包括聚合物粘合剂材料和添加剂的混合物，该添加剂选自盐、聚电解质、聚合物电解质、固体电解质及其结合物。其中第一和第二衬底之一或第一和第二衬两者包括电极以及该电极所附着的PET。PET离型膜也叫PET硅油膜，就是在PET薄膜的表面涂上一层硅油，以降低PET薄膜表面的附着力，达离型的效果。可以分为单面离型膜和双面离型膜。按离型力可分为轻离型膜，中离型膜，重离型膜。常用的厚度有：
0.012mm,0.019mm,0.025mm,0.038mm,0.05mm,0.075mm,0.1mm,0.125mm,0.188mm。
请参阅图1(原专利公开文本原图)，该电光学组件的制造方法包括：(1)将电光学层130涂覆到带有导电层120的衬底110上，(2)以液体形式方便地由缝模涂覆将层压粘合剂180涂覆到剥离片190上，干燥(或另外固化)粘合剂以形成固体层(3)层压粘合剂和剥离片到电光学层130；此层压可方便地使用热辊层压进行。(或者，但较少需要地可以将层压粘合剂在电光学层130上施加和然后在由剥离片190覆盖之前干燥或另外固化。)剥离片190方便地是7密耳(177μm)膜；依赖于使用的电光学介质的本质，可能需要采用脱模剂，例如硅氧烷涂覆此膜。如在图1中说明的那样，在将FPL 100层压到基架(未显示)以形成最终显示器之前，将剥离片190剥离或另外从层压粘合剂180除去。
申请人认为上述结构若要去掉PET，需要改进造作工艺，以及解决以下问题：
业界公知的应用镀有ITO的PET作为透明导电层，因此ITO与PET是不开分离的。而电光学层需要涂敷在ITO上。因此，在业界ITO、PET和电光学层不可分开是公知常识。若不能正视该技术偏见，将PET去掉则成为不可实现的技术方案。申请人认为若要去掉PET， ITO与PET需要分离，而将ITO附着在如彩色滤光层、导光板、防水保护层以及触摸显示屏等能够应用在显示器上的功能层上。再将电光学层涂覆到带有导电层的功能层上，接着依次按现有技术的操作步骤得到具有某种功能层的电光学组件，用于需要时与TFT层压。
上述得到的具有某种功能层的电光学组件限制了其只能应用于某一种功能，从实用性角度分析该电光学组件并没有现有技术的双剥离片普适性强。申请人认为，需要将工艺分为两个部分，一是得到一种方便保存且不含PET的电光学组件的亚组件，再需要应用上述电光学组件的亚组件的时候，先在功能层上附着ITO，再将电光学组件的亚组件的电光学层于ITO层压。则能够得到不含PET的电光学组件。该电光学组件的亚组件包括：第一胶水层、电泳介质层和第二胶水层。
所述第一胶水层为涂布在第一离型膜上液态的第一胶水形成，所述第一胶水层与所述离型膜接触面为平整表面；所述电泳介质层为涂布在所述第一胶水层上液态的电泳介质形成，所述电泳介质包括多个胶囊和围绕胶囊的粘结剂，所述胶囊包括胶囊壁，包覆在胶囊壁中的悬浮流体和在悬浮流体中悬浮和在对所述电泳介质施加电场时能够通过所述流体移动的多个电泳颜料粒子，所述电泳颜料粒子包括带负电荷的电泳颜料粒子和电中性的电泳颜料粒子；所述第二胶水层为覆盖所述电泳介质层中胶囊间段差的液态的第二胶水形成。
请参阅图2，本发明一方面提供的一种电光学材料实施例包括：第一胶水层1、电泳介质层2和第二胶水层3。
根据本发明第一方面任一项所述的电光学材料，所使用的胶水包含聚合物粘合剂材料和添加剂，所述添加剂选自：丙二醇醚、二甘醇丁醚、甲氧基甲醇、乙二醇、丙二醇、丙三醇、Texanol、己二酸、邻苯二甲酸、lusolvan FBH、Coasol、DBE-IB、DPnB、Dowanol PPh、醇酯-12、己二醇、其商品化组合物及其组合。
根据本发明第一方面任一项所述的电光学材料，其中所述聚合物粘合剂材料选自：聚氨酯、醋酸乙烯酯、醋酸乙烯酯-乙烯(vinyl acetate ethylene)、环氧树脂(epoxy)、聚丙烯酸基的粘合剂、其商品化组合物(例如水性聚氨酯乳液)及其组合。在一个实施方案中，所述胶水层包含聚氨酯。
根据本发明第一方面任一项所述的电光学材料，其中所述添加剂占所述胶水层的0.5～20重量％，优选1～20重量％，优选2～20重量％，优选2～15重量％，优选2～10重量％，例如约1重量％、约2重量％、约3重量％、约4重量％、约5重量％、约7.5重量％、约10重量％、约15重量％、约20重量％。
根据本发明第一方面任一项所述的电光学材料，其中所述胶水层中所述聚合物粘合剂材料与添加剂的重量比为100∶(1～60)，优选100∶(2～50)，优选100∶(2～40)，优选100∶(2～25)，优选100∶(2～20)，优选100∶(2～15)，优选100∶(2～10)。
根据本发明第一方面任一项所述的电光学材料，其中所述胶水层还包含：盐、聚电解质、聚合物电解质、固体电解质、或其组合。在一个实施方案中，所述盐选自：乙酸钾、 四烷基铵盐、氯化四丁基铵、六氟磷酸四丁基铵。在一个实施方案中，所述聚电解质选自：聚丙烯酸的碱金属盐，例如PPA的钠盐。
该电光学材料是固体，意即该电光学材料具有固体外表面，尽管该材料可以(并且通常是)具有内部液体或气体填充的空间，以及使用此种电光学材料组装显示器的方法。使用固体电光学材料的此类显示器在下文中可方便地称为“固体电光学显示器”。因此，术语“固体电光学显示器”包括旋转双色组件显示器(参见下文)、封装的电泳显示器、微孔电泳显示器和封装的液晶显示器。
术语“双稳态的”和“双稳性”在本文中以本领域通常的意义用于表示包括显示组件的显示器，该显示组件具有至少一种光学性能不同的第一和第二显示状态，并且使得在通过有限持续时间的寻址脉冲驱动任何给定的组件以呈现它的第一或第二显示状态之后，在终止寻址脉冲之后，该状态持续至少几次，例如至少四次，需要寻址脉冲的最小持续时间以改变显示组件的状态。在公开的美国专利申请No.2002/0180687中表明，能够达到灰度的一些粒子基电泳显示器不仅仅在它们的极端黑白状态下稳定而且在它们的中间灰色状态下稳定，一些其它类型的电光学显示器的情况也相同。此类型显示器合适地称为“多稳态”而不是双稳态的，尽管为方便起见术语“双稳态”在本文可用于覆盖双稳态和多稳态显示器两者。
几种类型的电光学显示器是已知的。一种类型的电光学显示器是例如在U.S.专利No.5,808,783；5,777,782；5,760,761；6,054,071；6,055,091；6,097,531；6,128,124；6,137,467和6,147,791中描述的旋转双色组件类型(尽管此类型显示器通常称为“旋转双色球”显示器，由于在以上提及的一些专利中旋转组件不是球形，术语“旋转双色组件”是优选的，因为它更为准确)。此类显示器使用大量小型物体(通常是球形或圆筒形)和内部偶极，所述小型物体具有两个或多个光学特性不同的截面。这些物体在基体中液体填充的空泡中悬浮，空泡由液体填充使得所述物体自由旋转。改变显示器的外观以对其施加电场，因此旋转所述物体到各种位置并改变通过视表面看到的所述物体截面。此类型的电光学介质通常是双稳态的。
许多上述的专利和申请认识到，在封装电泳介质中围绕离散微胶囊的壁可以由连续相替代，因此产生所谓的“聚合物分散的电泳显示器”，其中电泳介质包括电泳流体的多个离散液滴和聚合物材料的连续相，在此种聚合物分散的电泳显示器中的电泳流体的离散液滴可以认为是胶囊或微胶囊，尽管没有离散的胶囊膜与每个单独的液滴相关联；参见例如，上述的2002/0131147。因此，对于本申请的目的，此种聚合物分散的电泳介质认为是封装电泳介质的亚类。
封装的电泳显示器通常不受制于传统电泳器件的聚集和沉降故障模式，并提供了进一步的优点，例如在多种柔性和刚性衬底上印刷或涂覆显示器的能力。(单词“印刷”的使用希望包括所有的印刷和涂覆方式，包括但不限于：预计量的涂覆如片模涂覆、缝模或挤出涂覆、滑动或层叠涂覆、帘涂；辊涂如刀辊上涂覆、前后辊涂；凹版涂覆；浸涂；喷涂；弯液面涂覆；浸涂；刷涂；空气刀涂；丝网印刷工艺；静电印刷工艺：热印刷工艺；喷墨印 刷工艺；和其它相似技术)。因此，获得的显示器可以是柔性的。此外，可以印刷显示介质(使用各种方法)，该显示器自身可以便宜地制造。
尽管电泳介质通常是不透明的(例如，由于在许多电泳介质中，粒子基本阻断可见光通过显示器的传播)并以反射模式操作，可以使许多电泳显示器以所谓的“光闸模式”操作，其中一种显示状态是基本不透明的，一种是透光的。例如参见上述的美国专利Nos.6,130,774和6,172,798，以及美国专利Nos.5,872,552、6,144,361、6,271,823、6,225,971和6,184,856。介电电泳显示器，它类似于电泳显示器但依赖于电场强度的变化，可以采用相似的模式操作；参见美国专利No.4,418,346。
另一种类型的电光学显示器使用电致变色介质，例如以纳米变色膜形式的电致变色介质，该膜包括至少部分从半导金属氧化物形成的电极和连接到该电极能够进行可逆颜色变化的多个染料分子；参见，例如O′Regan，B.，et al.，Nature 1991，353，737；和Wood，D.，Information Display，18(3)，24(March 2002)。亦可参见Bach，U.，et al.，Adv.Mater.，2002，14(11)，845。此类型的纳米变色膜还例如描述于美国专利No.6,301,038，国际专利公开No.WO 01/27690，以及描述于美国专利申请2003/0214695。此类型的介质也通常是双稳态的。
另一种类型的电光学显示器是粒子基电泳显示器，它已经是许多年来深入研究和开发的目标，其中多个带电粒子通过悬浮流体在电场的影响下移动。当与液晶显示器比较时，电泳显示器可具有良好亮度和对比度，宽视角，状态双稳性，和低能耗的属性。然而，这些显示器长期图像质量的问题阻碍了它们的广泛使用。例如，组成电泳显示器的粒子倾向于沉降，导致这些显示器使用期限不足。
下面结合该电光学材料的制造方法，对电光学材料实施例进行说明，该方法包括：
在第一离型膜4上涂布液态的第一胶水，经干燥后形成第一胶水层1，在所述第一胶水层上涂布液态的电泳介质；涂布压力导致液态的电泳介质与第一胶水层接触面的胶囊受到挤压，呈现平整表面，而电泳介质另一面的胶囊受到形变胶囊的挤压呈现高低起落的段差。
需要说明的是，申请人在电泳介质涂布过程中，电泳介质包括粒径大小不一的胶囊粒径范围5μm-100μm，其目的是为了采用粒径较小的胶囊填补粒径较大胶囊之间存在大量缝隙，避免有效的显示面积因胶囊间缝隙而减小。申请人于2019-01-25授权公开的专利文本中记载“例如，欧洲专利EP1010036B1及其日本同族专利JP4460149提供了一种电泳显示器，其包括显示面(viewed surface)和背面(rearsurface)，在显示面和背面之间具有一聚合物阵列(Polymer Matrix)，在该聚合物阵列之中具有若干容纳悬浮液和粒子的洞穴，其中洞穴的宽高比大于1.2。该专利要解决的技术问题是在单层胶囊涂布的情况下，胶囊之间存在大量缝隙，使得实际有效的显示面积变小。该文献声称可以通过机械力或者利用胶黏剂的收缩使洞穴的变得扁平从而能够改善其光学显示性能”。因而，电泳介质另一面的胶囊受到形变胶囊的挤压上层大小不一的胶囊呈现粗糙表面，大小不一的胶囊形成高低起落的段差3-30μm。
在第二离型膜上涂布第二胶水，然后将所述电泳介质与所述第二胶水层压，使第二胶水覆盖电泳介质层中胶囊间段差。上述过程中可以趁第二胶水尚未干燥进行层压操作，或者采用质地较软的胶水作为第二胶水。
需要说明的是，上述电泳介质包括多个胶囊和围绕胶囊的粘结剂，所述胶囊包括胶囊壁，包覆在胶囊壁中的悬浮流体和在悬浮流体中悬浮和在对所述电泳介质施加电场时能够通过所述流体移动的多个电泳颜料粒子，所述电泳颜料粒子包括带负电荷的电泳颜料粒子和电中性的电泳颜料粒子；第一胶水和第二胶水可以认为是相同化学结构和组成的胶水，也理解为不同化学结构和组成胶水，其中包括胶水组成成分不同，以及所构成的胶水层厚度不同。本实施例后续将对胶水的应用进行详细说明。
下面对本发明的电光学材料的实施例进一步说明:
在本实施例中，为了能够较好的覆盖电泳介质层中胶囊间段差，所述第二胶水层的厚度优选为5～35μm。该方案为申请人经过实验所得，若没有消除胶囊间段差直接将电光显示层与透明导电层层压，则会由于透明导电层与电泳介质间存在空隙显示中产生白点，严重影响显示效果。
下面对本发明的电光学材料的实施例进一步说明:
请参阅图3-图5，图3为电光学组件正常显示状态下的图案，申请人发现在应用到200dpi以上的驱动板时，会出现边缘残影(如图4所示)，这主要是由胶水层的厚度及体积电阻率造成的边缘扩散现象。请参阅图5，驱动底板6上电压从A点到A’，因为胶水层的电阻影响，电压将减弱。例如在A点15V到A’降为7V，也可能出现的如C点的电压为15V，到B’点时衰减为0V。电泳介质层2处于A’和B’点处的电泳颜料粒子由于电压变化而影响原有的运动轨迹从而影响最终显示效果初显残影。上述过程可以抽象的理解为胶水层是一个电阻，其阻值影响电压，进一步影响显示效果。由于体积电阻率与电阻成正比，因此在理想状态下体积电阻率越小电压损失越小。但申请人发现，当体积电阻率小到一定值后，电压损失反而增加，其原因是从A到A’电压变为13V，但由于体积电阻率降低，电流A到B’，电压可能变为7V。因此，接触TFT6的胶水层的体积电阻率要控制在1*10 10～1*10 12(Ω.cm)之间。
申请人经分析，体积电阻率公式可以表示为ρ＝RS/L，其中R是电阻，S为横截面积，L为胶水层厚度，ρ为胶水层的体积电阻率。上述公式可以简单变形为R＝ρL/S，在ρ和S一定的情况下，胶水层厚度L越小则电阻越小，对电压的影响越小。优选的，第一胶水层厚度为1～10μm，该厚度为申请人经过实验得到，厚度大于10μm则影响电压，小于1μm则影响机械强度。
本文前面曾说明，申请人提出方案“将ITO附着在如彩色滤光层、导光板、防水保护层以及触摸显示屏等能够应用在显示器上的功能层上。再将电光学层涂覆到带有导电层的功能层上，接着依次按现有技术的操作步骤得到具有某种功能层的电光学组件，用于需要时与TFT层压”。根据前述分析，可以理解的是，电光学层(即本申请中电泳介质)涂覆到 透明导电层，其与透明导电层接触面胶囊受到挤压呈现平整表面，电泳介质另一面的胶囊受到形变胶囊的挤压呈现高低起落的段差。为了能够较好的覆盖电泳介质层中胶囊间段差，该胶水层的厚度优选为5～35μm。可以理解的是，采用该胶水层的厚度则会影响最终显示效果。因此，只有采用本实施例的技术方案中，才能将第一胶水层的厚度控制在1～10μm。
下面继续对本申请的电光学材料实施例进行说明：前文曾说明第二胶水层用于涂覆反面的段差，即满足胶水的压敏特性。本申请通过自主合成高分子聚合物，控制聚合物分子量，控制分子结构中离子基团含量，且添加部分的离子液体，或者小分子多元醇，达到既降低了体积电阻率，又压敏特性。在本实施例中，所述第二胶水层中聚合物分子量分布在1～5万。可以理解为过大的分子量将导致胶水层变硬而无法覆盖胶囊间的段差。
所述第一胶水层中聚合物中包括离子基团，是指羧基、磺酸基、胺基以及它们的成盐产物，羧酸基团质量占比为0.1％～1.5％，磺酸基团、胺基基团质量占比为0.1％～1.5％。可以让上胶水层的电阻在1*107～1*1010(Ω.cm)内调整。
需要说明的是，所述小分子多元醇是指分子量600以下，常温呈液体的小分子二元醇或其低聚物，通常为丙二醇、乙二醇以及它们的低聚物，添加比例为0.1％～4％，此比例可以改变上胶水混合物的TG，使得上胶水的体积电阻率随温度变化减缓，过多的加入量将影响粘结力。
第一胶水具体选取聚氨酯和丙烯酸的单体材料进行聚合，原材料羧酸基团的质量百分比为0.3％，原材料磺酸、胺基的基团在0.2％，控制聚合度，测试重均分子量Mw为6.3万，同时添加丙二醇醚，加入量为固体份的2％，测试体积电阻率为7*10 11(Ω.cm)，将第一胶按照所示结构，采用精密狭缝挤出设备，控制涂布厚度在4μm，得出满足边缘扩散和可靠性产品。
第二胶水具体选取聚氨酯所需原材料进行聚合，原材料羧酸基团的质量百分比为0.8％，原材料磺酸、胺基的基团在1.3％，控制聚合度，测试重均分子量Mw为3万，同时添加丙三醇，加入量为固体份的3％，添加丙三醇，加入量为固体份的1％，测试体积电阻率为2*10 7(Ω.cm)，将第二胶按照所示结构，采用精密狭缝挤出设备，控制涂布厚度在30μm，改善了电光显示层的气泡，保证了良好的光电需求。
表1表述本实施例具体实验参数和显示效果
Figure PCTCN2022114830-appb-000001
Figure PCTCN2022114830-appb-000002
下面继续对本申请的电光学材料实施例进行说明：
所述第一胶水层中聚合物中包括离子基团，聚合物的离子基团，是指羧基、磺酸基、胺基以及它们的成盐产物，为了控制其体积电阻率在1*10 10～1*10 12(Ω.cm)所述聚合物离子基团含量，羧酸基团质量占比为0％～0.4％，磺酸基团、胺基基团质量占比为0％～0.3％。
需要说明的是，所述第一胶水层中聚合物分子量分布在2～7万。分子量过低，会使下胶水的耐热性能下降，造成可靠性测试不通过。图3为第一胶水层厚度控制在1～5um，体积电阻率控制在1*10 10～1*10 12(Ω.cm)，当最终膜片通过下胶水层层压在TFT底板时，由图可见，本实施例明显改善高清模组(300dpi)的边缘扩散效果。
本发明第二方面提供了一种胶水层，其包含聚合物粘合剂材料和添加剂，所述添加剂选自：丙二醇醚、二甘醇丁醚、甲氧基甲醇、乙二醇、丙二醇、丙三醇、Texanol、己二酸、邻苯二甲酸、lusolvan FBH、Coasol、DBE-IB、DPnB、Dowanol PPh、醇酯-12、己二醇、其商品化组合物及其组合。
根据本发明第二方面任一项所述的胶水层，其中所述聚合物粘合剂材料选自：聚氨酯、醋酸乙烯酯、醋酸乙烯酯-乙烯、环氧树脂、聚丙烯酸基的粘合剂、其商品化组合物(例如水性聚氨酯乳液)及其组合。在一个实施方案中，所述胶水层包含聚氨酯。
根据本发明第二方面任一项所述的胶水层，其中所述添加剂占所述胶水层的0.5～20重量％，优选1～20重量％，优选2～20重量％，优选2～15重量％，优选2～10重量％，例如约1重量％、约2重量％、约3重量％、约4重量％、约5重量％、约7.5重量％、约10重量％、约15重量％、约20重量％。
根据本发明第二方面任一项所述的胶水层，其中聚合物粘合剂材料与添加剂的重量比为100∶(1～60)，优选100∶(2～50)，优选100∶(2～40)，优选100∶(2～25)，优选100∶(2～20)，优选100∶(2～15)，优选100∶(2～10)。
根据本发明第二方面任一项所述的胶水层，其中所述胶水层还包含：盐、聚电解质、聚合物电解质、固体电解质、或其组合。在一个实施方案中，所述盐选自：乙酸钾、四烷基铵盐、氯化四丁基铵、六氟磷酸四丁基铵。在一个实施方案中，所述聚电解质选自：聚丙烯酸的碱金属盐，例如PPA的钠盐。
根据本发明第二方面任一项所述的胶水层，其中所述包含添加剂的胶水层具有不同颜色的区域用作滤色器。
根据本发明第二方面任一项所述的胶水层，其中所述包含添加剂的胶水层进一步包括光学偏置元件。
本发明第二方面提供了一种粘合剂，其包含聚合物粘合剂材料和添加剂，该添加剂选自导电金属粉末、铁磁流体、非反应性溶剂、导电有机化合物及其组合。
本发明第二方面提供了添加剂在降低产品的体积电阻率和/或改善产品的电光学性能中的用途，所述产品包括但不限于电光学组件、双剥离片、电泳介质、粘合剂、粘合剂、电 光学显示器、电光学材料、电泳显示器、电光学介质、电子纸、电子纸显示屏等，所述添加剂选自：丙二醇醚、二甘醇丁醚、甲氧基甲醇、乙二醇、丙二醇、丙三醇、Texanol、己二酸、邻苯二甲酸、lusolvan FBH、Coasol、DBE-IB、DPnB、Dowanol PPh、醇酯-12、己二醇、其商品化组合物及其组合。
根据本发明第二方面的用途，其中所述添加剂与聚合物粘合剂材料组合使用，该聚合物粘合剂材料选自：聚氨酯、醋酸乙烯酯、醋酸乙烯酯-乙烯、环氧树脂、聚丙烯酸基的粘合剂、其商品化组合物(例如水性聚氨酯乳液)及其组合。在一个实施方案中，所述聚合物粘合剂材料与添加剂的重量比为100∶(1～60)，优选100∶(2～50)，优选100∶(2～40)，优选100∶(2～25)，优选100∶(2～20)，优选100∶(2～15)，优选100∶(2～10)。
在本发明的任一方面，其中任意两个或更多个实施方案之间所具有的特征可以相互组合，只要它们不会相互矛盾。当然，在相互之间组合时，必要的话可对相应特征作适当修饰。此外，本发明任一方面所涉及的特征，其同样适用于任意其它方面所涉及的相同特征，或者必要的话可对相应特征作适当修饰。
本发明所引述的所有文献，它们的全部内容通过引用并入本文，并且如果这些文献所表达的含义与本发明不一致时，以本发明的表述为准。此外，本发明使用的各种术语和短语具有本领域技术人员公知的一般含义，即便如此，本发明仍然希望在此对这些术语和短语作更详尽的说明和解释，提及的术语和短语如有与公知含义不一致的，以本发明所表述的含义为准。
如本文所述的，术语“商品化组合物”是指以所提及的成分为主要成分(或主要成分之一)配制成的供商品使用的组合物。例如商品名为NeoRez 9630和NeoRez 9330的产品，是两种购自NeoResins，Inc.，730Main street，Wilmington MA 01887的聚氨酯分散体。
如本文所述的，术语“水性聚氨酯乳液”是指以聚氨酯为主要成分制成的水性的乳浊液。
如本文所述的，术语“剥离片”亦可称为“释放片(release sheet)”。
如本文所述的，术语“封装”亦可称为“包覆(encapsulated)”。
如本文所述的，术语“基架”亦可称为“底板(backplane)”。
在一个实施方案中，所述胶水层中还可以包含聚电解质。聚电解质可包括例如，多酸的盐，例如，但不限于，聚丙烯酸的碱金属盐。
包含添加剂的胶水层可提供除粘合剂功能以外的其它功能。例如，该胶水层可具有不同颜色的区域和用作滤色器。或者，该胶水层可包括光学偏置元件。
在一个实施方案中，用于所述电泳介质的粘结剂中还可以包含盐。盐可以是例如，无机盐、有机盐、或其组合。在一个特定的实施方案中，盐包括乙酸钾。在另外的实施方案中，盐可包括季铵盐，例如四烷基铵盐，如氯化四丁基铵或六氟磷酸四丁基铵。
在其中粘结剂中的添加剂是聚电解质的实施方案中，聚电解质可包括多酸的盐，例如聚丙烯酸的碱金属盐。
包含添加剂的粘结剂可提供粘合剂功能以外的其它功能。例如，粘结剂可包括光学偏置组件。
在仍然另一方面，提供一种包括多个胶囊的电泳介质，每个胶囊包括胶囊壁，封装在胶囊壁中的悬浮流体和在悬浮流体中悬浮和在对介质施加电场时能够从其移动的多个带电粒子，介质进一步包括围绕胶囊的粘结剂，粘结剂包括聚合物粘合剂材料和添加剂的混合物，该添加剂选自导电金属粉末、铁磁流体、非反应性溶剂、导电有机化合物及其组合。
在另一方面，提供一种包括聚合物粘合剂材料和添加剂的混合物的粘合剂，该添加剂选自丙二醇醚、二甘醇丁醚、甲氧基甲醇、乙二醇、丙二醇、丙三醇、Texanol、己二酸、邻苯二甲酸、lusolvan FBH、Coasol、DBE-IB、DPnB、Dowanol PPh、醇酯-12、己二醇、其商品化组合物及其组合。在一个实施方案中，该添加剂还可选自：盐、聚电解质、聚合物电解质、固体电解质及其组合。在一个实施方案中，所述粘合剂可包含聚氨酯、醋酸乙烯酯、醋酸乙烯酯-乙烯、环氧树脂、或聚丙烯酸基的粘合剂。
最后，提供一种包括聚合物粘合剂材料和添加剂的混合物的粘合剂，该添加剂选自导电金属粉末、铁磁流体、非反应性溶剂、导电有机化合物及其组合。在此粘合剂中，聚合物粘合剂材料可以选自聚氨酯、醋酸乙烯酯、醋酸乙烯酯-乙烯、环氧树脂、聚丙烯酸基的粘合剂及其组合。
如已经描述过的，本文公开了某些添加剂，其用于电光学组件和显示器的胶水层中，以及用于围绕封装电泳介质的胶囊的粘结剂中，以控制粘合剂材料的体积电阻率。本文公开的胶水层和粘结剂能够改变体积电阻率而基本不改变胶水层或粘结剂的机械性能。通过加入一种或多种添加剂，所述胶水层和粘结剂扩展了粘合剂材料的选择，该粘合剂材料具有所需的机械性能但不能另外使用，因为它们的体积电阻率是不合适的。因此，人们可“细调节”胶水层或粘结剂的体积电阻率，即调节材料的体积电阻率到特定显示器或电泳介质的最优数值。
在一个实施方案中，用于所述电泳介质的粘结剂中还可以包含盐。盐可以是例如，无机盐、有机盐、或其组合。在一个特定的实施方案中，盐包括乙酸钾。在另外的实施方案中，盐可包括季铵盐，例如四烷基铵盐，如氯化四丁基铵或六氟磷酸四丁基铵。
在其中粘结剂中的添加剂是聚电解质的实施方案中，聚电解质可包括多酸的盐，例如聚丙烯酸的碱金属盐。
包含添加剂的粘结剂可提供粘合剂功能以外的其它功能。例如，粘结剂可包括光学偏置组件。
在仍然另一方面，提供一种包括多个胶囊的电泳介质，每个胶囊包括胶囊壁，封装在胶囊壁中的悬浮流体和在悬浮流体中悬浮和在对介质施加电场时能够从其移动的多个带电粒子，介质进一步包括围绕胶囊的粘结剂，粘结剂包括聚合物粘合剂材料和添加剂的混合物，该添加剂选自导电金属粉末、铁磁流体、非反应性溶剂、导电有机化合物及其组合。
在另一方面，提供一种包括聚合物粘合剂材料和添加剂的混合物的粘合剂，该添加剂选自丙二醇醚、二甘醇丁醚、甲氧基甲醇、乙二醇、丙二醇、丙三醇、Texanol、己二酸、邻苯二甲酸、lusolvanFBH、Coasol、DBE-IB、DPnB、Dowanol PPh、醇酯-12、己二醇、其商品化组合物及其组合。在一个实施方案中，该添加剂还可选自：盐、聚电解质、聚合物电解质、固体电解质及其组合。在一个实施方案中，所述粘合剂可包含聚氨酯、醋酸乙烯酯、醋酸乙烯酯-乙烯、环氧树脂、或聚丙烯酸基的粘合剂。
最后，提供一种包括聚合物粘合剂材料和添加剂的混合物的粘合剂，该添加剂选自导电金属粉末、铁磁流体、非反应性溶剂、导电有机化合物及其组合。在此粘合剂中，聚合物粘合剂材料可以选自聚氨酯、醋酸乙烯酯、醋酸乙烯酯-乙烯、环氧树脂、聚丙烯酸基的粘合剂及其组合。
如已经描述过的，本文公开了某些添加剂，其用于电光学组件和显示器的胶水层中，以及用于围绕封装电泳介质的胶囊的粘结剂中，以控制粘合剂材料的体积电阻率。本文公开的胶水层和粘结剂能够改变体积电阻率而基本不改变胶水层或粘结剂的机械性能。通过加入一种或多种添加剂，所述胶水层和粘结剂扩展了粘合剂材料的选择，该粘合剂材料具有所需的机械性能但不能另外使用，因为它们的体积电阻率是不合适的。因此，人们可“细调节”胶水层或粘结剂的体积电阻率，即调节材料的体积电阻率到特定显示器或电泳介质的最优数值。
胶水层或粘结剂包括一种或多种选自如下的添加剂：(a)丙二醇醚、二甘醇丁醚、甲氧基甲醇、乙二醇、丙二醇、丙三醇、Texanol、己二酸、邻苯二甲酸、lusolvanFBH、Coasol、DBE-IB、DPnB、Dowanol PPh、醇酯-12、己二醇、其商品化组合物及其组合；(b)盐、聚电解质、聚合物电解质、固体电解质及其组合；或(c)导电金属粉末、铁磁流体、非反应性溶剂、导电有机化合物及其组合。
在某些实施方案中，所述添加剂可以是盐如无机盐、有机盐、或其组合。示例的盐包括乙酸钾和四烷基铵盐，特别地四丁基铵盐如氯化物。盐的进一步例子包括锂盐如LiCF3SOF3、LiClO4、LiPF6、LiBF4、LiAsF6和LiN(CF3SO2)3。目前优选的盐是六氟磷酸四丁基铵，主要是由于此盐的稳定性和惰性。
在其它的实施方案中，聚合物电解质是聚电解质。聚电解质通常是聚合物，其中约10％或更多的分子由能够电离以形成带电部分的官能团组成。聚电解质中某些官能团的例子包括，但不限于羧酸、磺酸、磷酸、和季铵化合物。这些聚合物可以与有机或无机盐组合或单独使用。聚电解质的例子包括但不限于聚丙烯酸、聚苯乙烯磺酸盐、聚(2-乙烯基吡啶)、聚(4-乙烯基吡啶)，聚(氯化二甲基铵)、聚(甲基丙烯酸二甲基氨基乙酯)、聚(甲基丙烯酸二乙基氨基乙酯)。优选的聚电解质是聚丙烯酸(PAA)的钠盐。
在本发明的进一步实施方案中，所述添加剂是聚合物电解质。本文使用的术语“聚合物电解质”描述能够增溶盐的聚合物。盐在这些聚合物中的溶解度可以由聚合物中氧和/或氮原子的存在提高，该原子形成醚，羰基，羧酸，伯、仲、叔和季氨基，磺酸等。聚合物电解 质的例子包括聚醚化合物如聚环氧树脂乙烷、聚环氧树脂丙烷、聚四氢呋喃(polytetramethyleneoxide)、多元胺如聚乙烯亚胺、聚乙烯基吡咯烷酮、包含季铵基团的聚合物如N+R1R2R3R4，其中R1、R2、R3和R4各自独立地是H或含有1-25个碳原子的直链、支链、或环状烷基，并且其中反荷离子可以选自任何有机或无机阴离子。
在本发明中，例如下列的添加剂：丙二醇醚、二甘醇丁醚、甲氧基甲醇、乙二醇、丙二醇、丙三醇、Texanol、己二酸、邻苯二甲酸、lusolvanFBH、Coasol、DBE-IB、DPnB、Dowanol PPh、醇酯-12、己二醇、其商品化组合物及其组合，它们均因具有有助于膜形成的作用而基本上具有共同的性质，即可以作为膜形成辅助剂。
再其它的添加剂可包括导电金属粉末、铁磁流体、和/或非反应性溶剂，该非反应性溶剂可改进或者阻碍离子在溶液中流动性。合适非反应性溶剂的例子包括水、乙醚、二丙醚、二甘醇、甘醇二甲醚、二甘醇二甲醚、N-甲基吡咯烷酮等。在仍然另一个实施方案中，导电有机化合物可以用作添加剂。这些化合物的一些非限制性例子包括聚苯胺、聚噻吩、聚吡咯、聚-3，4-二氧乙烯噻吩，以及这些材料在它们n-或p-掺杂状态的衍生物。
用于胶水层或粘结剂的聚合物粘合剂材料可以是满足最终用途应用的任何聚合物材料。合适聚合物粘合剂材料的例子包括聚氨酯、醋酸乙烯酯、醋酸乙烯酯-乙烯、环氧树脂、聚丙烯酸基的粘合剂、或其组合。这些粘合剂材料可以是溶剂基或水基的。可以使用的特定聚氨酯的例子描述于2003年11月18日提交和受让于AirProducts andChemicals，Inc的待决美国申请系列No.10/715,916。
引入聚合物粘合剂材料的添加剂可以原位形成；换言之，可以将一种或多种前体材料引入聚合物粘合剂材料或粘结剂中，其中前体材料可以相互反应，或者与聚合物粘合剂或粘结剂反应，或将粘合剂材料或粘结剂曝露在能引起前体材料中变化以形成最终添加剂的条件(例如，对热量、光、或磁场或电场的曝露)下而引起变化。
粘合剂材料或粘结剂可包含除用于调节其体积电阻率的添加剂以外的组分(或其它掺杂剂)；例如，粘合剂材料或粘结剂也可包含染料或其它着色剂。已知通过在显示器的观察表面(观察者通过其观察显示器的表面)上以单层提供滤色器以形成全色电光学显示器，此滤色器包含不同颜色(例如红色、绿色和蓝色)的象素。然而，当滤色器以此方式与电光学材料分隔时，存在当在基本垂直于观察表面的角度下观察彩色图像时图像失真的可能性。为避免这样的问题，原则上需要就在电光学材料自身附近立即放置滤色器。然而，这要求在显示器的电极之间放置滤色器，使得滤色器的电性能影响显示器的性能。这是采用滤色器的特殊问题，原因是，这样的过滤器通常由采用三种不同染料或染料混合物将聚合物基础材料染色以形成红色、绿色和蓝色或其它颜色部分而形成；并且不太可能的是，三种不同染料会以相同方式影响滤色器的电性能。本文所述胶水层和粘结剂可用于抵消不同染料的影响并使滤色器的电性能基本均匀，从而避免由于滤色器中不均匀电性能而在图像上出现的人为现象。
也已知(参见上述2003/0011560)“光学偏置组件”可以提供于封装电泳显示器的粘结剂或层压粘合剂中，以调节显示器的外观。提供此光学偏置组件可影响粘合剂或粘结剂的电性能，并且包含此光学偏置组件的粘合剂或粘结剂的电性能可以通过使用本文所述添加剂来优化。
添加剂的最优量会因确切的聚合物粘结剂或粘合剂材料、使用的确切添加剂、以及最终混合物的期望体积电阻率而宽泛地变化。然而，一般地可以指明，发现如本发明上文所述添加剂的用量可以到有用的结果。如在以下实施例中所示，粘合剂材料的体积电阻率通常以可预测的方式随添加剂的浓度变化，并且因此应当加入多少添加剂以达到所需体积电阻率的最终选择可以容易地根据经验确定。
通常，不要求特殊的过程以将添加剂引入粘合剂材料。如果如在典型的情况下，胶水层由如下方式形成：将粘合剂材料的胶乳或溶液的膜涂覆到衬底上，或涂覆到电光学材料上，再干燥以形成胶水层，通常在涂覆之前，将该添加剂简单地在粘合剂材料的胶乳或溶液中溶解或分散。可以将添加剂净加入到胶乳或溶液中，或者可以溶于水溶液、非水溶液、或其组合中。相似地，如在典型的情况下，电泳介质由如下方式形成：使胶囊在液体中的淤浆与聚合物粘结剂的胶乳或溶液混合、将所得混合物涂覆到衬底上、再干燥以形成电泳介质；在将此胶乳或溶液与胶囊混合之前，通常将添加剂简单地溶于或分散于聚合物粘结剂的胶乳或溶液中。当然必须保证在整个粘合剂材料中均匀分散添加剂，以防止最终粘合剂或粘结剂层中电导率的变化，但涂料技术领域技术人员熟悉常规的技术，如在辊式捏合机上漫长搅拌以保证这种均匀分散。
所用具体添加剂的选择主要由与胶水层其它组分的相容性和在添加剂要加入到其中的粘合剂材料中的溶解度的考虑支配。如果，如在典型的情况下，添加剂要加入到粘合剂材料的含水胶乳中，应当选择添加剂以具有良好的水溶解度，使得在盐中通常优选碱金属盐和取代铵盐。应当注意保证添加剂不引起胶乳粒子的聚集。同样，添加剂应当期望不会引起粘合剂材料的pH的较大变化，并且应当不与粘合剂材料或它最终接触的最终显示器的其它部分(例如基架)发生化学反应。
一种或多种添加剂的加入可极大地扩展聚合物材料的范围，该材料可用作电光学显示器中的粘结剂和层压粘合剂。特别地，一种或多种添加剂的加入能够使用聚合物材料，该材料具有电光学显示器中非常期望的机械性能，但它们纯净状态下体积电阻率太高而不能使用。同样，由于一些电光学显示器，特别是封装的电泳显示器和电致变色显示器对水分敏感，一种或多种添加剂的加入可用于代替迄今为止与非吸湿性和/或疏水性聚合物材料一起用于此类显示器的水基聚氨酯分散体。
应当理解，本文公开的改性粘合剂和粘结剂可用于除电光学显示器以外的应用。
本发明第三方面提供了制造如上述的电光学材料的方法，具体包括：
在第一离型膜4上涂布液态的第一胶水，经干燥后形成第一胶水层1；
在所述第一胶水层1上涂布液态的电泳介质2；
在第二离型膜5上涂布第二胶水；
将所述电泳介质2与所述第二胶水层压，使第二胶水覆盖电泳介质层中胶囊间段差。
在本实施例中，控制所述第一胶水层的厚度为1～10μm，所述第一胶水层的体积电阻率控制在1*10 10～1*10 12(Ω.cm)。控制所述第二胶水层的厚度为5～35μm。所述第二胶水层的体积电阻率控制在1*10 7～1*10 10(Ω.cm)。对于控制第一胶水层和第二胶水层的理由和控制方法在前述实施例中已经说明，在此不做赘述。
在实际涂布流水线上，上述实施例可以理解为进行如下操作：
S1、在第一离型膜上涂布液态的第一胶水，经干燥后形成第一胶水层；
S2、在第一胶水层表面层压保护膜；
S3、对具有保护膜的第一胶水层进行收卷；
S4、在第二离型膜上涂布第二胶水，经干燥后形成第二胶水层；
S5、在第二胶水层表面层压保护膜；
S6、对具有保护膜的第二胶水层进行收卷；
S7、剥离所述第一胶水层上的保护膜；
S8、在所述第一胶水层上涂布液态的电泳介质；
S9、剥离所述第二胶水层上的保护膜；
S10、将所述电泳介质与所述第二胶水层压。
经过上述步骤即可得到本申请第四方面提供的双剥离片，依次包括：
第一离型膜4、第一胶水层1、电泳介质层2、第二胶水层3和第二离型膜5。为了能够满足工艺要求，所述第一离型膜与所述电光学材料间的离型力为(75～110)gf/inch；所述第二离型膜与所述电光学材料间的离型力为第一离型膜与所述电光学材料间的离型力的2倍以上。
在本实施例中，所述第一离型膜具有导电性或者不具有导电性。所述第二离型膜具有导电性或者不具有导电性。一般的，可以应用不导电离型膜即可实现上述制造工艺。由于在此过程中，需要对该双剥离片进行测试，因此采用具有导电性的离型膜可以直接进行测试。
本发明第五方面提供了一种应用上述双剥离制造的电光学组件的方法，包括：
在功能层附着透明导电层；
剥离所述第一离型膜，将所述第二胶水层与所述透明导电层层压；
剥离所述第二离型膜，将所述第一胶水层与驱动底板层压。
本发明第六方面提供了一种应用上述电光学组件的制造方法制造的电光学组件，依次包括：功能层、透明导电层、第一胶水层、电泳介质层、第二胶水层和驱动底板。
通过下面的具体实施例可以对本发明进行进一步的描述。然而，本发明的范围并不限于下述实施例。本领域技术人员能够理解，在不背离本发明的精神和范围的前提下，可以对本发明进行各种变化和修饰。本发明对试验中所使用到的材料以及试验方法进行一般性 和/或具体的描述。虽然为实现本发明目的所使用的许多材料和操作方法是本领域公知的，但是本发明仍然在此作尽可能详细描述。
尽管已描述了本申请的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例作出另外的变更和修改。所以，所附权利要求意欲解释为包括优选实施例以及落入本申请范围的所有变更和修改。
显然，本领域的技术人员可以对本申请进行各种改动和变型而不脱离本申请的精神和范围。这样，倘若本申请的这些修改和变型属于本申请权利要求及其等同技术的范围之内，则本申请也意图包含这些改动和变型在内。

Claims (17)

  1. 一种双剥离片，其特征在于，包括第一离型膜和第二离型膜，以及置于第一离型膜和第二离型膜之间的电光学材料；
    所述电光学材料包括：
    第一胶水层，所述第一胶水层为涂布在第一离型膜上液态的第一胶水形成；
    电泳介质层，所述电泳介质层为涂布在所述第一胶水层上液态的电泳介质形成，所述电泳介质包括多个胶囊和围绕胶囊的粘结剂，所述胶囊包括胶囊壁，包覆在胶囊壁中的悬浮流体和在悬浮流体中悬浮和在对所述电泳介质施加电场时能够通过所述流体移动的多个电泳颜料粒子，所述电泳颜料粒子包括带负电荷的电泳颜料粒子和电中性的电泳颜料粒子；所述电泳介质层与所述第一胶水层接触面为平整表面，所述电泳介质层的另一面因多数的胶囊段差呈现高低不平表面；
    第二胶水层，所述第二胶水层为覆盖所述电泳介质层中胶囊间段差的液态的第二胶水形成；
    所述功能层包括彩色滤光层、导光板、触摸显示层和保护层中至少一个或者任意组合。
  2. 根据权利要求1的双剥离片，其特征在于：
    所述第一胶水层的体积电阻率控制在1*10 5～1*10 10(Ω.cm)。
  3. 根据权利要求1的双剥离片，其特征在于：
    所述第一胶水层的厚度为0.1～10μm。
  4. 根据权利要求1的双剥离片，其特征在于：
    所述第二胶水层的厚度为0.1～50μm.
  5. 根据权利要求1的双剥离片，其特征在于：
    所述第二胶水层的厚度为5～35μm。
  6. 根据权利要求1的双剥离片，其特征在于：
    所述第二胶水层的体积电阻率控制在1*10 7～1*10 12(Ω.cm)。
  7. 根据权利要求1的双剥离片，其特征在于：
    所述第一胶水和第二胶水均包括高分子聚合物，所述高分子聚合物包括聚氨酯聚合物或聚氨酯与丙烯酸的共聚物。
  8. 根据权利要求7的双剥离片，其特征在于：
    所述第二胶水层中聚合物分子量分布在1～10万。
  9. 根据权利要求7的双剥离片，其特征在于：
    所述第二胶水层中聚合物中包括离子基团，是指羧基、磺酸基、胺基以及它们的成盐产物，羧酸基团质量占比为0.1％～10％磺酸基团、胺基基团质量占比为0.1％～1.5％。
  10. 根据权利要求7的双剥离片，其特征在于：
    所述第一胶水层中聚合物分子量分布在2～7万。
  11. 根据权利要求7的双剥离片，其特征在于：
    所述第一胶水层中聚合物中包括离子基团，聚合物的离子基团，是指羧基、磺酸基、胺基以及它们的成盐产物；
    所述聚合物离子基团含量，羧酸基团质量占比为0％～10％，磺酸基团、胺基基团质量占比为0％～3％。
  12. 根据权利要求1-11中任一项所述的双剥离片，其特征在于：
    所述第一离型膜与所述电光学材料间的离型力为(5-50)gf/inch；进一步20-40；
    所述第二离型膜与所述电光学材料间的离型力为第一离型膜与所述电光学材料间的离型力的2倍以上。
  13. 根据权利要求1-11的双剥离片，其特征在于：
    所述第一离型膜具有导电性或者不具有导电性。
  14. 根据权利要求1-11的双剥离片，其特征在于：
    所述第二离型膜具有导电性或者不具有导电性。
  15. 一种制造如权利要求1-14中任一项所述的双剥离片的方法，其特征在于，包括：
    在第一离型膜上涂布液态的第一胶水，经干燥后形成第一胶水层；
    在第二离型膜上涂布第二胶水，经干燥后形成第二胶水层；
    在所述第一胶水层上涂布液态的电泳介质，经干燥后形成电泳介质层；
    将所述电泳介质层与所述第二胶水层压，使第二胶水覆盖电泳介质层中所产生的胶囊间段差。
  16. 一种制造如权利要求1-14中任一项所述的双剥离片的方法，其特征在于，包括：
    在第一离型膜上涂布液态的第一胶水，经干燥后形成第一胶水层；
    在所述第一胶水层上涂布液态的电泳介质，经干燥后形成可显示的电泳介质层；
    在电泳介质层上涂布第二胶水，经干燥后形成第二胶水层，第二胶水层覆盖电泳介质层中所产生的胶囊间段差。
  17. 一种如权利要求1-14中任一项所述的双剥离片的应用，包括：
    剥离所述第一离型膜，将所述第二胶水层与含有所述透明导电层的功能层结合，第二胶水层与透明导电层直接接触；
    剥离所述第二离型膜，将所述第一胶水层与驱动底板结合；
    第一胶水层与驱动底板直接接触。
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JP2012063443A (ja) * 2010-09-14 2012-03-29 Toppan Printing Co Ltd 情報表示装置の製造方法、情報表示装置用の散乱反射型表示体及び情報表示装置
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CN102253502A (zh) * 2011-04-18 2011-11-23 广州奥翼电子科技有限公司 粘合剂及其电光学组件和电泳介质
CN114270254A (zh) * 2019-08-26 2022-04-01 伊英克公司 包含识别标记的电光装置

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