WO2021192868A1 - 両面粘着剤付き光学フィルムおよび画像表示装置 - Google Patents

両面粘着剤付き光学フィルムおよび画像表示装置 Download PDF

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Publication number
WO2021192868A1
WO2021192868A1 PCT/JP2021/008163 JP2021008163W WO2021192868A1 WO 2021192868 A1 WO2021192868 A1 WO 2021192868A1 JP 2021008163 W JP2021008163 W JP 2021008163W WO 2021192868 A1 WO2021192868 A1 WO 2021192868A1
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WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive layer
optical film
image display
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PCT/JP2021/008163
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English (en)
French (fr)
Japanese (ja)
Inventor
伊藤　渉
翔 寳田
崇弘 野中
Original Assignee
日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202180024961.4A priority Critical patent/CN115335739A/zh
Priority to KR1020227035993A priority patent/KR20220146681A/ko
Publication of WO2021192868A1 publication Critical patent/WO2021192868A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to an optical film with a double-sided adhesive having adhesive layers on both sides of the optical film, and an image display device including a rigid transparent plate having a curved surface portion.
  • a polarizing plate is provided on the visible side surface of the image display cell.
  • a hard transparent plate (cover window) made of glass or resin may be provided on the surface of these image display devices for the purpose of preventing damage to the image display panel due to an impact from the outer surface, and is used for mobile applications.
  • This configuration is becoming mainstream for in-vehicle applications.
  • an adhesive layer for adhering to the image display cell on one surface of the polarizing plate In the form of an image display device having a polarizing plate on the visible side surface of the image display cell and a cover window on the visible side surface of the polarizing plate, an adhesive layer for adhering to the image display cell on one surface of the polarizing plate. It has been proposed to use a double-sided pressure-sensitive adhesive film having a pressure-sensitive adhesive layer on the other side for bonding to a cover window (see, for example, Patent Document 1).
  • a flexible optical film (polarizing plate or the like) and an image display cell are attached to a rigid cover window having a curved surface, so that the optical film and the image display cell are formed on the cover window.
  • the curved surface shape is maintained by forming the curved surface shape that follows the curved surface shape.
  • the curvature on the inner surface side (center of curvature side) is smaller than that on the outer surface side, so that mechanical strain is generated at the bonding interface.
  • strain distortion is large, and peeling and wrinkles are likely to occur at the bonding interface.
  • an object of the present invention is to provide an optical film with an adhesive that is less likely to cause peeling or wrinkles at the bonding interface even when applied to an image display device having a curved surface portion.
  • One embodiment of the present invention is an image display device in which at least a part of the screen has a curved surface shape.
  • the image display device includes a rigid transparent plate, an optical film, and a flexible image display cell.
  • the transparent plate has a curved surface-shaped portion with the second main surface inside, and the first main surface of the optical film is bonded to the second main surface of the transparent plate via the first adhesive layer. ..
  • the second main surface of the optical film is bonded to the image display cell via the second adhesive layer.
  • optical film examples include an optically isotropic film and an optically anisotropic film.
  • optically anisotropic film include a polarizer and a retardation plate.
  • the optical film may be a circular polarizing plate or the like in which a polarizing element and a retardation plate are laminated.
  • the image display cell may be an organic EL cell, and the image display device may be an organic EL display device provided with a circular polarizing plate as an optical film on the visible side surface of the organic EL cell.
  • One embodiment of the present invention is an optical film with a double-sided pressure-sensitive adhesive used for forming the above-mentioned image display device, the first main surface of the optical film is provided with a first pressure-sensitive adhesive layer, and the second main surface of the optical film is provided. A second pressure-sensitive adhesive layer is provided on the surface.
  • the first pressure-sensitive adhesive layer used for bonding the optical film and the transparent plate preferably has a strain cross-sectional area S 1 of 800 ⁇ m 2 or less.
  • Second pressure-sensitive adhesive layer for use in bonding of the optical film and the image display cell is preferably a strain cross-sectional area S 2 is 360 .mu.m 2 or less.
  • the thickness T 1 of the first pressure-sensitive adhesive layer may be 25 to 100 ⁇ m, and the thickness T 2 of the second pressure-sensitive adhesive layer may be 5 to 30 ⁇ m.
  • the thickness T 1 of the first pressure-sensitive adhesive layer may be larger than the thickness T 2 of the second pressure-sensitive adhesive layer.
  • Strain sectional area S 1 of the first pressure-sensitive adhesive layer may be larger than the strain sectional area S 2 of the second pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be an acrylic pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive constituting these pressure-sensitive adhesive layers preferably contains a polymer having a crosslinked structure.
  • the strain cross-sectional area of the pressure-sensitive adhesive layer for bonding the members is within a predetermined range, it is possible to suppress peeling and wrinkles of the flexible member in an image display device having a curved surface portion.
  • FIG. 1 is a cross-sectional view schematically showing an optical film with a double-sided adhesive according to an embodiment of the present invention
  • FIG. 2 is a cross-sectional view schematically showing an image display device according to an embodiment of the present invention. Is.
  • the optical film 50 with a double-sided adhesive includes an optical film 10, a first adhesive layer 21 provided on the first main surface of the optical film, and a second adhesive provided on the second main surface of the optical film. It includes a layer 22.
  • the first release film 41 is detachably attached on the first adhesive layer 21 of the optical film 50 with double-sided adhesive, and the second release film 41 is peelably attached on the second adhesive layer 22.
  • the film 42 is detachably attached.
  • the first main surface of the optical film 10 is bonded to the second main surface of the cover window 80 via the first adhesive layer 21, and the second main surface of the optical film 10 is attached. It is attached to the image display cell 70 via the second pressure-sensitive adhesive layer 22.
  • the optical film 50 with a double-sided adhesive and the image display cell 70 are housed in a housing (not shown).
  • the image display device 100 has a curved surface shape in which at least a part of the screen is convex on the viewing side (upper side of the figure).
  • FIG. 2 shows a form in which the entire screen has a spherical curved surface, a part of the screen may be curved and the other portion may be flat.
  • the screen may have a rectangular shape in a plan view, the central portion of the screen may be a flat surface, and the edge portion (the side portion of the rectangle) of the screen may have a curved surface shape that curves downward.
  • the screen of the image display device may have a three-dimensional curved surface shape.
  • a three-dimensional curved surface refers to a shape in which the cross-sectional shape of all surfaces including the normal of the surface is a curved line.
  • a spherical curved surface has an arc cross section on a surface including a normal line (straight line in the radial direction) and is a three-dimensional curved surface.
  • a display device edge display
  • the side portion of the rectangle has a curved surface shape that curves downward
  • two adjacent sides have a curved surface shape that curves downward
  • these It has a three-dimensional curved surface shape at the corner where the two sides intersect.
  • a four-sided edge display in which the entire peripheral edge (all four sides) of a rectangular screen in a plan view is a curved surface has a three-dimensional curved surface shape at four corner portions.
  • the central part of the rectangular side of the edge display has a curved cross section in the direction orthogonal to the side, but the cross section in the direction parallel to the side is a straight line, so the central part of the side is "two-dimensional". It has a curved shape.
  • Image display cell Examples of the image display cell include an organic EL cell. It is preferable to use a flexible image display cell for forming an image display device having a curved surface shape. A flexible substrate is used to form a flexible image display cell.
  • FIG. 3 is an example of a laminated configuration of image display cells, and shows a top emission type organic EL cell.
  • the top emission type organic EL cell is provided with a metal electrode 73, an organic light emitting layer 75, and a transparent electrode 77 in this order on a substrate 71, and the transparent electrode 77 side (upper side in the drawing) is a light emitting surface.
  • a sealing material 79 is laminated on the transparent electrode 77.
  • the encapsulant 79 is preferably provided so as to cover the side surfaces of the electrodes 73 and 77 and the organic light emitting layer 75.
  • the substrate 71 a flexible plastic substrate is preferably used.
  • the substrate 71 does not have to be transparent, and a highly heat-resistant film such as a polyimide film may be used as the substrate 71.
  • a flexible glass plate (glass film) may be used as the substrate 71.
  • the organic light emitting layer 75 may include an electron transport layer, a hole transport layer, and the like, in addition to the organic layer that itself functions as a light emitting layer.
  • the transparent electrode 77 is a metal oxide layer or a metal thin film, and transmits light from the organic light emitting layer 75.
  • the metal electrode 73, the organic light emitting layer 75, and the transparent electrode 77 are all thin films and have a thickness sufficiently smaller than that of the substrate 71. Therefore, if the substrate 71 is flexible, the entire image display cell 70 is flexible.
  • a back sheet (not shown) may be provided on the back surface side of the substrate 71 for the purpose of protecting or reinforcing the substrate.
  • the organic EL cell may be a bottom emission type in which a transparent electrode, an organic light emitting layer, and a metal electrode are laminated in this order on a substrate.
  • a transparent substrate is used, and the substrate is arranged on the visible side (second adhesive layer 22 side).
  • the image display cell is not limited to the organic EL cell, and may be a liquid crystal cell, an electrophoresis-type display cell (electronic paper), or the like.
  • a touch panel sensor (not shown) may be arranged on the visible surface of the image display cell 70.
  • the cover window 80 arranged on the visible side surface of the image display device is a rigid transparent plate, and the first main surface 81 is arranged on the visible side and the second main surface 82 is arranged on the image display cell 70 side.
  • a transparent resin such as an acrylic resin or a polycarbonate resin or glass is used.
  • the thickness of the cover window 80 is, for example, about 50 to 2000 ⁇ m. From the viewpoint of increasing the durability against an external impact, the thickness of the cover window 80 is preferably 200 ⁇ m or more, more preferably 300 ⁇ m or more.
  • the cover window 80 may be integrated with the touch panel sensor.
  • An antireflection layer, a hard coat layer, or the like may be provided on the first main surface 81 of the cover window 80.
  • a light-shielding print layer may be provided on a part of the surface of the cover window 80.
  • the cover window 80 has a curved surface-shaped portion in which the second main surface 82 is inside and the first main surface 81 side is convex in at least a part of the surface.
  • the entire cover window 80 may have a curved surface shape.
  • the curved surface shape may be three-dimensional.
  • the entire cover window has a three-dimensional curved surface shape.
  • the central part of the screen has a planar shape
  • the central part of the side has a two-dimensional curved surface shape
  • the corner part has a three-dimensional curved surface shape. doing.
  • the rigid cover window 80 having a curved surface shape portion and the flexible image display cell 70 are laminated and integrated via an optical film 50 with an adhesive, so that the image display cell 70 covers the image display cell 70. It has a curved surface shape along the second main surface 82 (inner surface) of the window 80.
  • the first main surface 81 of the cover window 80 generally has a curved surface-shaped portion like the second main surface 82, but if the second main surface 82 has a curved surface-shaped portion, The first main surface may be a flat surface.
  • the cover window 80 and the image display cell 70 are laminated and integrated via an optical film 50 with a double-sided adhesive, and the first main surface (viewing side surface) of the optical film 10 is integrated. ) Is attached to the second main surface 82 of the cover window 80.
  • the second adhesive layer 22 arranged on the second main surface of the optical film 10 is attached to the light emitting surface of the image display cell 70.
  • optical film 10 examples include an optically isotropic film and an optically anisotropic film.
  • optically isotropic film a transparent film is preferable.
  • optically anisotropic film include a retardation plate and a polarizer.
  • the optical film may be a laminate of a plurality of films or an optical functional film provided with a coating layer on the film surface.
  • a polarizing plate can be mentioned as an example of a laminated body of a plurality of optical films.
  • the polarizing plate includes a polarizer, and a transparent film as a polarizer protective film is laminated on one side or both sides, if necessary.
  • the polarizer examples include a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, and an ethylene / vinyl acetate copolymerization system partially saponified film, and two colors such as iodine and a bicolor dye.
  • a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, and an ethylene / vinyl acetate copolymerization system partially saponified film
  • two colors such as iodine and a bicolor dye.
  • examples thereof include a uniaxially stretched film by adsorbing a sex substance, a polyene-based oriented film such as a dehydrated product of polyvinyl alcohol and a dehydrogenated product of polyvinyl chloride.
  • a thin polarizer having a thickness of 10 ⁇ m or less can also be used.
  • the thin polarizing element include the polarizers described in JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, Japanese Patent No. 46910205, and Japanese Patent No. 4751481. ..
  • the thin polarizing element is obtained by, for example, a manufacturing method including a step of stretching a polyvinyl alcohol-based resin layer and a stretching resin base material in a laminated state, and a step of dyeing with a dichroic material such as iodine.
  • the polarizer protective film a transparent resin film such as a cellulose resin, a cyclic polyolefin resin, an acrylic resin, a phenylmaleimide resin, or a polycarbonate resin is preferably used.
  • the transparent films 13 and 15 may be films made of the same resin material or may be made of different resin materials.
  • the optical functional film examples include a retardation plate, a viewing angle expanding film, a viewing angle limiting (peeping prevention) film, and a brightness improving film.
  • the optical film 10 may include an optical functional film on one or both surfaces of the polarizer.
  • the optical film 10 may include a touch panel sensor as an optical functional film.
  • the transparent film in contact with the polarizer may have both a function as a polarizer protective film and an optical functional film.
  • the transparent film may also have a function as an electrode substrate film of the touch panel sensor.
  • the metal electrode 73 of the organic EL cell 70 is light reflective. Therefore, when the external light enters the inside of the organic EL cell, the light is reflected by the metal electrode, and the reflected light is visually recognized as a mirror surface from the outside.
  • a circularly polarizing plate as the optical film 10 it is possible to prevent the reflected light from the metal electrode from being emitted again to the outside, and the visibility and design of the screen of the display device are improved. Can be improved.
  • the circularly polarizing plate is provided with a retardation film on the surface of the polarizer on the organic EL cell 70 side.
  • the transparent film arranged adjacent to the polarizer may be a retardation film.
  • the retardation film has a retardation of ⁇ / 4 and the angle between the slow axis direction of the retardation film and the absorption axis direction of the polarizer is 45 °, the polarizer and the retardation film are laminated.
  • the body functions as a circularly polarizing plate for suppressing the re-emission of the reflected light from the metal electrode.
  • the retardation film constituting the circularly polarizing plate may be a laminated film having two or more layers.
  • a broadband circular polarizing plate that functions as a circular polarizing plate over a wide band of visible light can be obtained.
  • a retardation film for example, a stretched resin film is used.
  • the retardation film may be an oriented liquid crystal layer.
  • the first adhesive layer 21 for bonding the optical film 10 and the cover window 80 and the second adhesive layer 22 for bonding the optical film 10 and the image display cell 70 are optically transparent adhesives. It is preferably composed of.
  • the first pressure-sensitive adhesive layer 21 and the second pressure-sensitive adhesive layer 22 may be obtained by laminating a plurality of pressure-sensitive adhesive layers.
  • the pressure-sensitive adhesive layers 21 and 22 are transparent and absorb little visible light.
  • the total light transmittance of the pressure-sensitive adhesive layers 21 and 22 is preferably 85% or more, more preferably 90% or more.
  • the haze of the pressure-sensitive adhesive layers 21 and 22 is preferably 2% or less, more preferably 1% or less.
  • the total light transmittance and haze are measured according to JIS K7136 using a haze meter.
  • the pressure-sensitive adhesives constituting the pressure-sensitive adhesive layers 21 and 22 include acrylic polymers, silicone-based polymers, polyesters, polyurethanes, polyamides, polyvinyl ethers, vinyl acetate / vinyl chloride copolymers, modified polyolefins, epoxy-based, fluorine-based, and rubber-based polymers. Etc. can be appropriately selected and used as a base polymer.
  • an acrylic pressure-sensitive adhesive is preferably used because it has excellent optical transparency, exhibits appropriate wettability, cohesiveness, adhesiveness, and other adhesive properties, and is also excellent in weather resistance, heat resistance, and the like.
  • the content of the acrylic-based base polymer with respect to the total solid content of the pressure-sensitive adhesive composition is preferably 50% by weight or more, more preferably 70% by weight or more, and more preferably 80% by weight or more. Is even more preferable.
  • the acrylic base polymer a polymer having a monomer unit of (meth) acrylic acid alkyl ester as a main skeleton is preferably used.
  • (meth) acrylic means acrylic and / or methacryl.
  • the (meth) acrylic acid alkyl ester a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is preferably used.
  • the (meth) acrylic acid alkyl ester may have a branched alkyl group.
  • the content of the (meth) acrylic acid alkyl ester is preferably 40% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, based on the total amount of the monomer components constituting the base polymer.
  • the acrylic base polymer may be a copolymer of a plurality of (meth) acrylic acid alkyl esters.
  • the arrangement of the constituent monomer units may be random or block.
  • the acrylic base polymer may contain an acrylic monomer having a crosslinkable functional group as a copolymerization component.
  • the gel fraction of the pressure-sensitive adhesive can be easily increased by thermal cross-linking or photocuring of the base polymer.
  • the acrylic monomer having a crosslinkable functional group include a hydroxy group-containing monomer and a carboxy group-containing monomer.
  • Hydroxy group-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and (meth). Examples thereof include 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethyl) cyclohexylmethyl (meth) acrylate.
  • the acrylic base polymer may contain a nitrogen-containing monomer as a monomer component.
  • the nitrogen-containing monomer include N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholin, (meth) acryloylmorpholin, and N-vinyl.
  • vinyl-based monomers such as carboxylic acid amides and N-vinylcaprolactam, and cyanoacrylate-based monomers such as acrylonitrile and methacrylonitrile.
  • N-vinylpyrrolidone and (meth) acryloylmorpholine are preferably used.
  • the monomer component forming the acrylic polymer may contain a polyfunctional polymerizable compound (polyfunctional monomer).
  • polyfunctional polymerizable compound examples include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, bisphenol A ethylene oxide-modified di (meth) acrylate, and bisphenol A.
  • the base polymer can be prepared by a known polymerization method such as solution polymerization, UV polymerization, bulk polymerization, or emulsion polymerization.
  • a polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator may be used depending on the type of polymerization reaction.
  • Chain transfer agents may be used to adjust the molecular weight of the base polymer.
  • the weight average molecular weight of the base polymer is preferably 200,000 to 1,000,000, more preferably 250,000 to 800,000.
  • the molecular weight of the base polymer refers to the molecular weight of the polymer before the introduction of the crosslinked structure.
  • the monofunctional monomer is first polymerized to form a prepolymer composition having a low degree of polymerization (prepolymerization), and the prepolymer is formed.
  • a polyfunctional monomer may be added to the syrup of the composition to polymerize (post-polymerize) the prepolymer and the polyfunctional monomer.
  • a mixture of the prepolymer composition and the unpolymerized monomer component may be applied onto the base material and then post-polymerized on the base material to form a pressure-sensitive adhesive layer.
  • the prepolymer composition has a low viscosity and is excellent in coatability, according to a method in which a pressure-sensitive adhesive composition, which is a mixture of a prepolymer composition and an unpolymerized monomer, is applied and then post-polymerized on a substrate, a pressure-sensitive adhesive layer is used. The productivity of the pressure-sensitive adhesive layer can be increased, and the thickness of the pressure-sensitive adhesive layer can be made uniform.
  • the prepolymer composition is obtained by, for example, partially polymerizing (prepolymerizing) a composition (referred to as a "prepolymer forming composition") in which a monomer component constituting an acrylic base polymer and a polymerization initiator are mixed. Can be prepared.
  • the monomer in the composition for forming a prepolymer is preferably a monofunctional monomer such as a (meth) acrylic acid alkyl ester or a polar group-containing monomer among the monomer components constituting the acrylic polymer.
  • the composition for forming a prepolymer may contain a polyfunctional monomer.
  • a part of the polyfunctional monomer component which is a raw material of the base polymer may be contained in the composition for forming the prepolymer, and the rest of the polyfunctional monomer component may be added after the prepolymer is polymerized to be subjected to post-polymerization.
  • the composition for forming a prepolymer may contain a chain transfer agent or the like, if necessary, in addition to the monomer and the polymerization initiator.
  • the method for polymerizing the prepolymer is not particularly limited, but from the viewpoint of adjusting the reaction time to set the molecular weight (polymerization rate) of the prepolymer in a desired range, polymerization by irradiation with active light such as UV light is preferable.
  • the polymerization initiator and chain transfer agent used for the prepolymerization are not particularly limited.
  • the polymerization rate of the prepolymer is not particularly limited, but is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, from the viewpoint of obtaining a viscosity suitable for coating on a substrate.
  • the polymerization rate of the prepolymer can be adjusted to a desired range by adjusting the type and amount of the photopolymerization initiator, the irradiation intensity and irradiation time of active light such as UV light, and the like.
  • the prepolymer composition is mixed with the rest of the monomer components (post-polymerization monomer) constituting the acrylic base polymer, and if necessary, a polymerization initiator, a chain transfer agent, a silane coupling agent, a cross-linking agent, and the like. , Form the pressure-sensitive adhesive composition.
  • the post-polymerization monomer preferably contains a polyfunctional monomer. As the post-polymerization monomer, a monofunctional monomer may be added in addition to the polyfunctional monomer.
  • the base polymer of the adhesive preferably has a crosslinked structure. Since the base polymer has a crosslinked structure, the creep ratio C of the pressure-sensitive adhesive tends to decrease, and the strain cross-sectional area described later tends to decrease accordingly.
  • a base polymer having a crosslinked structure can be obtained.
  • a cross-linking agent can be added to form a cross-linked structure.
  • commonly used cross-linking agents such as isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, carbodiimide-based cross-linking agents, and metal chelate-based cross-linking agents can be used.
  • the content of the cross-linking agent is usually in the range of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.07 to 2.5 parts by weight with respect to 100 parts by weight of the base polymer. It is a part by weight.
  • the base polymer may contain both a crosslinked structure with a polyfunctional polymerizable compound and a crosslinked structure with a crosslinking agent such as polyisocyanate.
  • the adhesive may contain an ultraviolet absorber.
  • the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine ultraviolet absorber, a salicylate-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and the like.
  • Triazine-based UV absorbers and benzotriazole-based UV absorbers are preferable because they have high UV absorption, excellent compatibility with acrylic polymers, and highly transparent acrylic pressure-sensitive adhesive sheets can be easily obtained. Among them, hydroxyl groups.
  • a triazine-based ultraviolet absorber containing the above, and a benzotriazole-based ultraviolet absorber having one benzotriazole skeleton in one molecule are preferable.
  • the pressure-sensitive adhesives include silane coupling agents, tackifiers, plasticizers, softeners, deterioration inhibitors, fillers, colorants, antioxidants, surfactants, antistatic agents and the like. It may contain an additive.
  • the pressure-sensitive adhesive composition is applied in layers on the base material, and if necessary, the pressure-sensitive adhesive layer is formed by drying the solvent and cross-linking / curing the base polymer.
  • the thickness of the pressure-sensitive adhesive layers 21 and 22 is not particularly limited, and is generally about 5 to 500 ⁇ m.
  • the thickness of the first adhesive layer 21 is preferably 25 ⁇ m or more, preferably 30 ⁇ m or more, in order to have a step absorption property against a printing step. More preferred.
  • the thickness of the first pressure-sensitive adhesive layer 21 may be 35 ⁇ m or more, 40 ⁇ m or more, or 45 ⁇ m or more.
  • the curvature of the image display cell 70 located inside the curved surface is the largest (the radius of curvature is the smallest), and the distortion is large. Therefore, peeling and wrinkles are likely to occur in the portion of the flexible image display cell 70 where the strain is large. In particular, when it has a three-dimensional curved surface shape, omnidirectional strain is generated and it is difficult to release the strain, so that peeling and wrinkles are likely to occur.
  • the first pressure-sensitive adhesive layer 21 and the second pressure-sensitive adhesive layer 22 of the optical film with a double-sided pressure-sensitive adhesive have predetermined creep characteristics, so that peeling and wrinkles between layers in a display device having a curved surface portion are prevented. Can be suppressed.
  • the strain cross-sectional area S 1 of the first pressure-sensitive adhesive layer 21 is preferably 800 ⁇ m 2 or less, and the strain cross-sectional area S s of the second pressure-sensitive adhesive layer 22 is preferably 360 ⁇ m 2 or less.
  • FIG. 4 is an explanatory view of the concept of the strain cross-sectional area of the pressure-sensitive adhesive layer, and a shear load is applied in the arrow direction with one surface of the end portion of the pressure-sensitive adhesive layer 2 bonded to the adherend 1.
  • the cross section of the state is schematically shown. While the cross section of the pressure-sensitive adhesive layer 2 (broken line in FIG. 4) before applying the shear load is rectangular, a constant shear load is applied with the lower surface of the pressure-sensitive adhesive layer 2 fixed to the adherend 1. When the load is applied, the deformation of the upper surface is the largest, and the cross section of the pressure-sensitive adhesive layer is deformed into a parallel quadrilateral shape (solid line in FIG. 4).
  • the creep rate C does not change even if the thickness of the adhesive layer changes.
  • the strain cross-sectional area S is proportional to the creep ratio C and the square T 2 of the thickness. Therefore, when the materials of the pressure-sensitive adhesive layer are the same, the larger the thickness, the larger the strain cross-sectional area.
  • the thickness T of the pressure-sensitive adhesive layer is small.
  • the second adhesive layer 22 used for bonding the optical film 10 and the image display cell 70 is bonded to each other with flexible members, if the strain caused by the curved surface is large, it may cause peeling or wrinkles. It is easy to become.
  • the thickness T 2 of the second pressure-sensitive adhesive layer 22 is preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, further preferably 20 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
  • Strain sectional area S 2 of the second pressure-sensitive adhesive layer 22 is preferably 250 [mu] m 2 or less, more preferably 150 [mu] m 2 or less, more preferably 100 [mu] m 2 or less.
  • S 2 may be 70 ⁇ m 2 or less, 50 ⁇ m 2 or less, 40 ⁇ m 2 or less, or 30 ⁇ m 2 or less.
  • the strain cross-sectional area S 2 of the second pressure-sensitive adhesive layer 22 is as small as possible.
  • the strain cross-sectional area S 2 of the second pressure-sensitive adhesive layer 22 is preferably 1 ⁇ m 2 or more, and more preferably 2 ⁇ m 2 or more.
  • the creep ratio C 2 of the second pressure-sensitive adhesive layer is preferably 80% or less, more preferably 50% or less, still more preferably 40% or less.
  • the smaller the thickness T of the pressure-sensitive adhesive layer and the smaller the creep ratio C the smaller the strain cross-sectional area S.
  • the pressure-sensitive adhesive the higher the molecular weight of the base polymer and the higher the degree of cross-linking, the smaller the creep rate tends to be. Therefore, by increasing the amount of the cross-linking agent and the polyfunctional monomer, a pressure-sensitive adhesive having a small creep rate can be obtained.
  • the higher the glass transition temperature of the base polymer the greater the interaction between the molecular chains such as the entanglement of the molecular chains, so that the creep rate at room temperature tends to decrease.
  • the first pressure-sensitive adhesive layer 21 has a smaller curvature (larger radius of curvature) than the second pressure-sensitive adhesive layer 22. Further, since the first pressure-sensitive adhesive layer 21 adheres the optical film 10 and the cover window 80 which is a rigid member, the pressure-sensitive adhesive layer is not deformed at the interface on the cover window 80 side, which is compared with the second pressure-sensitive adhesive layer 22. It is unlikely to cause wrinkles. Therefore, strain sectional area S 1 of the first pressure-sensitive adhesive layer 21 may be larger than the strain sectional area S 2 of the second pressure-sensitive adhesive layer 22. Further, the thickness T 1 of the first pressure-sensitive adhesive layer 21 may be larger than the thickness T 2 of the second pressure-sensitive adhesive layer 22.
  • the cross-sectional area S 2 strain by reducing the thickness T 2 of the second pressure-sensitive adhesive layer 22, suppressing the occurrence of peeling or wrinkling of the optical film 10 and the image display cell 70 in the curved portion can.
  • the adhesive layer having a relatively large thickness T 1 and a large strain cross-sectional area S 1 as the first adhesive layer 21 the impact resistance against the impact from the surface on the visual side and the second cover window 80 can be obtained. It is possible to provide step absorption to a printing step such as a decorative printing layer provided on the main surface 82.
  • the strain cross-sectional area S 1 of the first pressure-sensitive adhesive layer 21 is preferably 800 ⁇ m 2 or less.
  • S 1 is more preferably 600 .mu.m 2 or less, more preferably 500 [mu] m 2 or less.
  • the thickness T 1 of the first pressure-sensitive adhesive layer is preferably 100 ⁇ m or less, more preferably 90 ⁇ m or less, still more preferably 80 ⁇ m or less.
  • T 1 may be 70 ⁇ m or less, 60 ⁇ m or less, or 50 ⁇ m or less.
  • the storage elastic modulus G'of the first pressure-sensitive adhesive layer 21 at 25 ° C. is preferably 0.35 MPa or less, preferably 0.30 MPa or less. More preferably, 0.25 MPa or less is further preferable.
  • the storage elastic modulus of the first pressure-sensitive adhesive layer 21 at 25 ° C. is preferably 0.05 MPa or more, more preferably 0.10 MPa or more.
  • the storage elastic modulus of the second pressure-sensitive adhesive layer 22 at 25 ° C. is preferably 0.05 MPa or more, more preferably 0.10 MPa or more.
  • the release films 41 and 42 are temporarily adhered to the surfaces of the adhesive layers 21 and 22 as shown in FIG. 1 until they are used for forming the image display cell.
  • the release films 41 and 42 those having a release layer on the surface of the film base material are preferably used.
  • the material of the release layer include a silicone-based release agent, a fluorine-based release agent, a long-chain alkyl-based release agent, a fatty acid amide-based release agent, and the like.
  • a silicone release agent is preferable because it can achieve both adhesion to an acrylic pressure-sensitive adhesive and peelability.
  • Resin materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and (meth) acrylic resins.
  • polyester resins such as polyethylene terephthalate (PET) are particularly preferable.
  • the thickness of the release film is preferably 10 to 200 ⁇ m, more preferably 25 to 80 ⁇ m.
  • the thickness of the first release film 41 and the thickness of the second release film 42 may be the same or different.
  • the image display device 100 is formed by attaching the cover window 80 to the first adhesive layer 21 and attaching the image display cell 70 to the second adhesive layer 22.
  • the order of bonding is not particularly limited, and the cover window 80 may be bonded first, the image display cell 70 may be bonded first, or both may be bonded at the same time.
  • the first pressure-sensitive adhesive layer 21 and the second pressure-sensitive adhesive layer 22 have predetermined characteristics, even in an image display device in which the cover window 80 has a curved surface portion, the layers can be peeled off, and the optical film 10 and the image can be peeled off. The occurrence of wrinkles in the display cell 70 can be suppressed.
  • this prepolymer composition 100 parts by weight of this prepolymer composition, 0.2 parts by weight of a photopolymerization initiator (BASF "Irgacure 651"), and the amount of 1,6-hexanediol diacrylate (HDDA) shown in Table 1 as a polyfunctional monomer.
  • a silane coupling agent (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.): 0.3 parts by weight was added and mixed uniformly to prepare a pressure-sensitive adhesive composition.
  • the above pressure-sensitive adhesive composition is applied to a release-treated surface of a release film (a polyester film whose one side has been release-treated with silicone) so as to have a thickness of 50 ⁇ m to form a coating layer, and this coating layer is formed.
  • the release-processed surface of another release film was laminated on top. After that, UV irradiation was performed with a black light whose position was adjusted so that the irradiation intensity on the irradiation surface directly under the lamp was 5 mW / cm 2 until the integrated light intensity became 3000 mJ / cm 2, and the polymerization was allowed to proceed. An adhesive sheet to which the film was temporarily attached was obtained.
  • ⁇ Adhesives O, P> In the reaction vessel, the monomer (100 parts by weight in total) having the weight ratio shown in Table 1, 233 parts by weight of ethyl acetate, and azobisisobutyronitrile (AIBN): 0.2 parts by weight as the thermal polymerization initiator were charged. , The mixture was stirred for 1 hour in a nitrogen atmosphere at 23 ° C. to perform nitrogen substitution. Then, the reaction was carried out at 65 ° C. for 5 hours, and subsequently at 70 ° C. for 2 hours to prepare a solution of an acrylic polymer having a weight average molecular weight of about 450,000.
  • AIBN azobisisobutyronitrile
  • trimethylolpropane xylylene diisocyanate (“Takenate D110N” manufactured by Mitsui Chemicals, Inc.): 0.27 parts by weight was added as an isocyanate-based cross-linking agent to prepare a pressure-sensitive adhesive composition.
  • the above pressure-sensitive adhesive composition is applied to the release-treated surface of the release film so that the thickness after drying is 50 ⁇ m, heated at 130 ° C. for 3 minutes to remove the solvent, and then placed on the pressure-sensitive adhesive layer.
  • the release-treated surfaces of another release film were overlapped to obtain an adhesive sheet in which the release film was temporarily attached to both sides.
  • Table 1 shows the compositions of the pressure-sensitive adhesives A to P, and the measurement results of the creep modulus and the storage elastic modulus of the pressure-sensitive adhesive sheet having a thickness of 50 ⁇ m.
  • the adhesive sheet 1 is attached to one surface (on the hard coat layer) of the polarizing plate having a thickness of about 75 ⁇ m, and the adhesive sheet 2 is attached to the other surface.
  • Plates (Samples 1-42) were obtained.
  • a triacetyl cellulose film (32 ⁇ m) having a hard coat layer provided on one surface of a polarizing element made of a stretched polyvinyl alcohol film having a thickness of 12 ⁇ m impregnated with iodine is bonded to the other surface of the polarizing element.
  • a triacetyl cellulose film (31 ⁇ m) provided with a coating retardation layer was attached to the film.
  • the adhesive sheets 1 and 2 As the adhesive sheets 1 and 2, the ones shown in Table 2 were used.
  • the pressure-sensitive adhesive types A to P shown in Table 2 are the same as the pressure-sensitive adhesives of the pressure-sensitive adhesive sheets A to P in the above-mentioned production example of the pressure-sensitive adhesive sheet, and the thickness was changed as shown in Table 2.
  • the release film was peeled off from the pressure-sensitive adhesive sheets 2 of Samples 1 to 42, and a polyimide film having a thickness of 25 ⁇ m (“Kapton EN100” manufactured by Toray DuPont) was bonded by roll-to-roll.
  • This sample was cut into a square of 40 mm ⁇ 40 mm, the release film was peeled off from the adhesive sheet 1, and the adhesive sheet 1 was attached to the center of the inner surface of a spherical glass having a thickness of 2 mm, a diameter of 65 mm, and an inner surface with a radius of curvature of 100 mm. ..
  • the bonding was carried out using a vacuum bonding machine at room temperature under the conditions of a vacuum pressure of 100 Pa, a pressing force of 0.2 MPa, and a pressurizing time of 10 seconds. Then, it was treated in an autoclave at 50 ° C. and 0.5 MPa for 15 minutes.
  • the sample after autoclaving was put into a heating oven at 85 ° C. for 240 hours, then the sample was taken out, the bonded state was visually confirmed, and the sample was evaluated according to the following criteria.
  • ⁇ The bonded state of each layer was maintained.
  • ⁇ Wrinkles with a width of less than 5 mm were confirmed.
  • ⁇ Wrinkles or peeling with a width of 5 mm or more were confirmed.
  • Table 2 shows the pressure-sensitive adhesive sheets (type of pressure-sensitive adhesive, thickness and strain cross-sectional area of the pressure-sensitive adhesive sheet) used in Samples 1 to 42, and the bonding evaluation results.
  • the small thickness of the adhesive sheet 1 and the adhesive sheet 2 reduces the strain cross-sectional area, and can suppress peeling and wrinkles when bonded to a curved rigid member.

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  • Physics & Mathematics (AREA)
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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
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  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Theoretical Computer Science (AREA)
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  • Electroluminescent Light Sources (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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