WO2022255155A1 - Stratifié - Google Patents

Stratifié Download PDF

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Publication number
WO2022255155A1
WO2022255155A1 PCT/JP2022/021159 JP2022021159W WO2022255155A1 WO 2022255155 A1 WO2022255155 A1 WO 2022255155A1 JP 2022021159 W JP2022021159 W JP 2022021159W WO 2022255155 A1 WO2022255155 A1 WO 2022255155A1
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WO
WIPO (PCT)
Prior art keywords
layer
laminate
liquid crystal
adhesive layer
adhesive
Prior art date
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PCT/JP2022/021159
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English (en)
Japanese (ja)
Inventor
大▲ショウ▼ 呉
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN202280019217.XA priority Critical patent/CN117015728A/zh
Priority to KR1020237044536A priority patent/KR20240015092A/ko
Publication of WO2022255155A1 publication Critical patent/WO2022255155A1/fr

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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
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • 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
    • 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
    • B32B7/023—Optical 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • 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
    • 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
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining 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
    • H10K59/8793—Arrangements for polarized light emission
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature
    • 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
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

  • the present invention relates to laminates and image display devices.
  • Patent Document 1 discloses a laminate comprising a first protective layer, a first pressure-sensitive adhesive layer, an intervening coating layer, and a second pressure-sensitive adhesive layer in this order.
  • a laminate comprising a first protective layer, a first pressure-sensitive adhesive layer, an intervening coating layer, and a second pressure-sensitive adhesive layer in this order.
  • a laminate that can be bent with the viewer side facing inward is used for a flexible display that can be bent with the viewer side facing inward.
  • a laminate that can be bent with the viewer side surface facing outward as a laminate used in a flexible display that can be bent with the viewer side surface facing outward.
  • a linear polarizing layer, a first adhesive layer, a liquid crystal coating layer, and a second adhesive layer are laminated in this order, and cracks occur when repeatedly bent with the linear polarizing layer side facing outward.
  • the present invention provides the following laminate and image display device.
  • a linear polarizing layer, a first adhesive layer, a liquid crystal coating layer, and a second adhesive layer are laminated in this order,
  • the storage elastic modulus of the first adhesive layer at a temperature of 25 ° C. is G'1 [kPa]
  • the storage elastic modulus of the second adhesive layer at a temperature of 25 ° C. is G'2 [kPa]
  • the following conditions (1 ) the laminate.
  • G'1 ⁇ 1000 kPa and G'2 ⁇ 1000 kPa [2]
  • the laminate according to [1] wherein the linear polarizing layer includes a cured product of a composition containing a polymerizable liquid crystal compound and one or more azo dyes, and an alignment film.
  • the linear polarizing layer, the first adhesive layer, the liquid crystal coating layer, and the second adhesive layer are laminated in this order, and when repeatedly bent with the linear polarizing layer side facing outward, cracks occur. It is possible to provide a laminate in which it is difficult for .
  • FIG. 4 is a schematic cross-sectional view showing another example of the layer structure of the laminate according to the present invention
  • FIG. 4 is a schematic cross-sectional view showing another example of the layer structure of the laminate according to the present invention
  • It is the schematic explaining the method of a flexibility test.
  • a laminate according to one aspect of the present invention includes a linear polarizing layer, a first adhesive layer, a liquid crystal coating layer, and a second adhesive layer laminated in this order, and the storage elastic modulus of the first adhesive layer at a temperature of 25 ° C. is G'1 [kPa], and the storage elastic modulus of the second adhesive layer at a temperature of 25° C. is G'2 [kPa], the following condition (1) is satisfied.
  • FIG. 1 shows a schematic cross-sectional view of a laminate according to one aspect of the present invention.
  • a laminate 100 shown in FIG. 1 includes a linear polarizing layer 10, a first adhesive layer 11, a liquid crystal coating layer 12, and a second adhesive layer 13 laminated in this order. Both the first adhesive layer 11 and the second adhesive layer 13 are arranged in contact with the liquid crystal coating layer 12 .
  • the linear polarizing layer 10 and the first adhesive layer 11 may be arranged in contact with each other.
  • the liquid crystal coating layer 12 does not include a polarizer containing a cured product of a polymerizable liquid crystal compound, which is one form of the linear polarizing layer 10 .
  • the laminate 100 can further include other layers such as a protective layer, a front panel, a third adhesive layer, a bonding layer, an organic EL panel, and a touch sensor.
  • the laminate 100 can be bent with the linear polarizing layer 10 side facing outward with respect to the bending axis (hereinafter also referred to as "outfold"). Being able to bend means that the laminate can be bent without causing cracks in the liquid crystal coating layer and the polarizer layer.
  • Bending includes a form of bending in which a curved surface is formed at the bending portion. In the form of bending, the bending radius of the bent inner surface is not particularly limited. Bending also includes a form of refraction in which the angle of refraction of the inner surface is greater than 0° and less than 180°, and a form of folding in which the radius of curvature of the inner surface is close to zero or the angle of refraction of the inner surface is 0°. .
  • the laminate of the present invention is suitable for flexible displays because it can be bent.
  • the laminate 100 may have a bending radius of, for example, 4 mm, preferably 2 mm, at which cracks are unlikely to occur even when repeatedly bent in an outfold test described later.
  • the number of bending times at which cracks first occur is preferably 200,000 times or more, more preferably 300,000 times or more, and further It is preferably 400,000 times or more, and particularly preferably 500,000 times or more.
  • the thickness of the laminate 100 is not particularly limited because it varies depending on the functions required of the laminate and the application of the laminate. be. In this specification, the thickness of the laminate and each layer can be measured according to the thickness measurement method described in the examples below.
  • the planar shape of the laminate 100 may be, for example, a square shape, preferably a square shape having long sides and short sides, more preferably a rectangle.
  • the length of the long side may be, for example, 10 mm or more and 1400 mm or less, preferably 600 mm or less.
  • the length of the short side is, for example, 5 mm or more and 800 mm or less, preferably 500 mm or less, and more preferably 300 mm or less.
  • Each layer constituting the laminate may have rounded corners, notched ends, or perforated ends.
  • the laminate 100 satisfies the above condition (1).
  • the present inventors have found that by placing a liquid crystal coating layer between two relatively hard adhesive layers with a storage modulus of 1000 kPa or more at a temperature of 25° C., it is possible to repeatedly bend outfold. served.
  • the storage elastic modulus at a temperature of 25° C. can be measured according to the method described in the Examples section below.
  • the storage elastic modulus G′1 [kPa] of the first adhesive layer 11 at a temperature of 25° C. and the storage elastic modulus G′2 [kPa] of the second adhesive layer 13 at a temperature of 25° C. are preferably 1100 kPa or more, more preferably. is 1200 ka or more, more preferably 1300 kPa or more, and particularly preferably 1400 kPa or more.
  • the storage elastic moduli at a temperature of 23° C. of the first adhesive layer 11 and the second adhesive layer 13 may be the same or different.
  • the first adhesive layer 11 and the second adhesive layer 13 are formed from an adhesive composition which will be described later.
  • the storage elastic modulus G′1 [kPa] of the first adhesive layer 11 at a temperature of 25° C. and the storage elastic modulus G′2 [kPa] of the second adhesive layer 13 at a temperature of 25° C. are included in the adhesive composition, for example (
  • the types of monomers that make up the meth)acrylic polymer can be selected, the molecular weight of the (meth)acrylic polymer can be adjusted, and the amount of cross-linking agent added can be used to adjust the cross-linking density and thickness of the adhesive layer. or a combination of these methods.
  • a pressure-sensitive adhesive having a desired storage elastic modulus can be selected and used from commercially available pressure-sensitive adhesives.
  • the laminate 100 can be used, for example, in an image display device or the like.
  • the image display device is not particularly limited, and examples thereof include organic electroluminescence (organic EL) display devices, inorganic electroluminescence (inorganic EL) display devices, liquid crystal display devices, and electroluminescence display devices.
  • the image display device may have a touch panel function.
  • the image display device can preferably be a flexible display.
  • the layered product 100 can be placed in an image display device so that the linear polarizing layer 10 side is on the viewing side.
  • Linear polarizing layer 10 examples include a stretched film or stretched layer to which a dichroic dye is adsorbed, a polarizer layer formed by coating and curing a dichroic dye, and the like.
  • a polarizer layer formed by applying and curing a dichroic dye is preferred because there is no restriction in the bending direction compared to a stretched film or stretched layer to which a dye having anisotropic absorption is adsorbed.
  • Dichroic organic dyes include, for example, azo dyes.
  • azo dyes include C.I. I.
  • Dichroic direct dyes composed of disazo compounds such as DIRECT RED 39, and dichroic direct dyes composed of compounds such as trisazo and tetrakisazo are included.
  • the stretched film to which the dichroic dye is adsorbed is usually produced by the process of uniaxially stretching the polyvinyl alcohol resin film, and the process of dyeing the polyvinyl alcohol resin film with the dichroic dye to adsorb the dichroic dye. , a step of treating a polyvinyl alcohol-based resin film to which a dichroic dye is adsorbed with an aqueous boric acid solution, and a step of washing with water after the treatment with the aqueous boric acid solution.
  • the thickness of the stretched film to which the dichroic dye is adsorbed may be, for example, 2 ⁇ m or more and 40 ⁇ m or less, may be 5 ⁇ m or more, may be 20 ⁇ m or less, further 15 ⁇ m or less, and furthermore may be 10 ⁇ m or less. .
  • Polyvinyl alcohol-based resin is obtained by saponifying polyvinyl acetate-based resin.
  • Polyvinyl acetate-based resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
  • Other monomers copolymerizable with vinyl acetate include, for example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth)acrylamides having an ammonium group.
  • the degree of saponification of the polyvinyl alcohol resin is usually about 85 mol% or more and 100 mol% or less, preferably 98 mol% or more.
  • the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used.
  • the degree of polymerization of the polyvinyl alcohol resin is usually 1000 or more and 10000 or less, preferably 1500 or more and 5000 or less.
  • the stretched layer to which the dichroic dye is adsorbed is usually formed by applying a coating liquid containing the polyvinyl alcohol resin onto the substrate film, uniaxially stretching the resulting laminated film, and uniaxially stretching the laminated film.
  • the base film may be peeled off from the stretching layer to which the dichroic dye is adsorbed.
  • the material and thickness of the base film may be the same as the material and thickness of the thermoplastic resin film described below.
  • the polarizer layer obtained by coating and curing a dichroic dye is a composition containing a polymerizable dichroic dye having liquid crystallinity or a composition containing a polymerizable liquid crystal compound and a dichroic dye as a base material.
  • a polarizer layer containing a cured product of a polymerizable liquid crystal compound, such as a layer obtained by coating and curing a film, may be mentioned.
  • the substrate film may be provided with an alignment film on one surface.
  • the linear polarizing layer 10 is preferably a layer containing a cured product of a composition containing a polymerizable liquid crystal compound and one or more azo dyes, and an alignment film.
  • the thickness of the alignment film may be, for example, 5 nm or more and 1 ⁇ m or less.
  • the linear polarizing layer may be incorporated into the laminate together with the substrate film, or may be incorporated into the laminate by peeling and removing the substrate film from the polarizer layer formed by coating and curing the dichroic dye. .
  • the material and thickness of the base film may be the same as the material and thickness of the thermoplastic resin film described below.
  • a hard coat layer (HC layer) may be formed on at least one surface of the base film as a protective layer, which will be described later.
  • the thickness of the polarizer layer formed by applying and curing a dichroic dye is usually 10 ⁇ m or less, preferably 8 ⁇ m or less, and more preferably 5 ⁇ m or less.
  • the protective layer may be placed on one side or both sides of the linear polarizing layer 10 and have the function of protecting the surface of the linear polarizing layer 10 .
  • the linear polarizing layer laminated with the protective layer may be referred to as a linear polarizing plate.
  • the protective layer can be an organic layer or an inorganic layer.
  • the organic layer or inorganic layer may be a layer formed by coating.
  • the organic layer can be a protective layer-forming composition, for example, a cured resin layer of a (meth)acrylic resin composition, an epoxy resin composition, a polyimide resin composition, or the like.
  • the protective layer-forming composition may be active energy ray-curable or thermosetting.
  • the inorganic layer can be formed of silicon oxide or the like, for example.
  • the protective layer may be called a hard coat layer (HC layer) or an overcoat (OC) layer.
  • the protective layer may be formed directly on the base film described above, or may be formed directly on the linear polarizing layer. After the protective layer is formed on the substrate film described above, the linear polarizing layer can be formed.
  • the protective layer can be produced by, for example, applying an active energy ray-curable composition for forming a protective layer onto the base film and curing it by irradiating it with active energy.
  • the description of the above-mentioned base film is applied to the base film.
  • the protective layer can be incorporated into the laminate after the base film has been peeled off. Examples of the method of applying the protective layer-forming composition include spin coating.
  • the protective layer is an inorganic layer
  • the protective layer can be formed by, for example, a sputtering method, a vapor deposition method, or the like.
  • the thickness of the protective layer may be, for example, 0.1 ⁇ m or more and 10 ⁇ m or less, preferably 5 ⁇ m or less.
  • thermoplastic resin film that is excellent in transparency, mechanical strength, thermal stability, water barrier properties, isotropy, stretchability, etc.
  • thermoplastic resins include cellulose resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyethersulfone resins; polysulfone resins; polycarbonate resins; Resins; polyimide resins; polyolefin resins such as polyethylene, polypropylene, and ethylene/propylene copolymers; cyclic polyolefin resins having cyclo- and norbornene structures (also referred to as norbornene-based resins); (meth)acrylic resins; polyarylate resins; and polyvinyl alcohol resins, as well as mixtures thereof.
  • the two protective layers may be of the same type or of different types.
  • the thickness of the thermoplastic resin film is usually 300 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, still more preferably 50 ⁇ m or less, and even more preferably 30 ⁇ m or less. and is usually 1 ⁇ m or more, and may be, for example, 5 ⁇ m or more or 20 ⁇ m or more.
  • the protective layer is a thermoplastic resin film
  • the thermoplastic resin film can be bonded to the linear polarizing layer 10 via a bonding layer, which will be described later.
  • the bonding layer for bonding the thermoplastic resin film to the linear polarizing layer 10 is preferably an adhesive layer.
  • a linear polarizing layer can be formed on the above protective layer.
  • the laminate 100 preferably has at least one protective layer selected from the group consisting of a thermoplastic resin film and a cured resin layer on the side of the linear polarizing layer 10 opposite to the first adhesive layer 11 .
  • the first adhesive layer 11 may be a layer interposed between the linear polarization layer 10 and the liquid crystal coating layer 12 to bond them.
  • the second adhesive layer 13 can be a layer for bonding, for example, a touch sensor panel, an organic EL panel, or the like to the liquid crystal coating layer 12 side of the laminate 100 .
  • the first adhesive layer 11 and the second adhesive layer 13 may be collectively referred to as an adhesive layer.
  • the adhesive layer may be, for example, a layer composed of an adhesive or a layer obtained by subjecting this layer to some kind of treatment. Adhesives are also called pressure-sensitive adhesives. As used herein, the term "adhesive" refers to an adhesive other than a pressure-sensitive adhesive (pressure-sensitive adhesive), and is clearly distinguished from a pressure-sensitive adhesive.
  • the adhesive layer may consist of one layer or two or more layers, preferably one layer.
  • the adhesive layer can be formed from an adhesive composition.
  • the types of adhesives used for the first adhesive layer 11 and the second adhesive layer 13 may be the same or different.
  • the adhesive layer can be composed of an adhesive composition whose main component is a resin such as (meth)acrylic, rubber, urethane, ester, silicone, or polyvinyl ether. Among them, a pressure-sensitive adhesive composition using a (meth)acrylic resin as a base polymer, which is excellent in transparency, weather resistance, heat resistance, etc., is preferable.
  • the adhesive composition may be active energy ray-curable or heat-curable.
  • Examples of the (meth)acrylic resin (base polymer) used in the adhesive composition include butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, and 2-(meth)acrylate. Polymers or copolymers containing one or more of (meth)acrylic acid esters such as ethylhexyl as monomers are preferably used.
  • the base polymer is copolymerized with a polar monomer.
  • polar monomers examples include (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, glycidyl ( Monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, etc., such as meth)acrylates, can be mentioned.
  • the adhesive composition may contain only the above base polymer, but usually further contains a cross-linking agent.
  • the cross-linking agent is a metal ion having a valence of 2 or more, which forms a carboxylic acid metal salt with a carboxyl group; a polyamine compound, which forms an amide bond with a carboxyl group; Examples include epoxy compounds and polyols that form ester bonds with carboxyl groups; and polyisocyanate compounds that form amide bonds with carboxyl groups. Among them, polyisocyanate compounds are preferred.
  • the active energy ray-curable pressure-sensitive adhesive composition has the property of being cured by being irradiated with an active energy ray such as an ultraviolet ray or an electron beam. It is a pressure-sensitive adhesive composition that can be adhered to an adherend such as the adhesive agent, and that can be cured by irradiation with an active energy ray to adjust the adhesion force.
  • the active energy ray-curable pressure-sensitive adhesive composition is preferably UV-curable.
  • the active energy ray-curable pressure-sensitive adhesive composition further contains an active energy ray-polymerizable compound in addition to the base polymer and the cross-linking agent. Furthermore, if necessary, a photopolymerization initiator, a photosensitizer, and the like may be contained.
  • the adhesive composition contains fine particles for imparting light scattering properties, beads (resin beads, glass beads, etc.), glass fibers, resins other than base polymers, tackifiers, fillers (metal powders and other inorganic powders). etc.), antioxidants, ultraviolet absorbers, dyes, pigments, colorants, antifoaming agents, corrosion inhibitors, antistatic agents, photopolymerization initiators, and other additives.
  • the adhesive layer can be formed by applying an organic solvent-diluted solution of the adhesive composition onto a substrate and drying.
  • an active energy ray-curable pressure-sensitive adhesive composition is used, a cured product having a desired degree of curing can be obtained by irradiating the formed pressure-sensitive adhesive layer with an active energy ray.
  • the first adhesive layer 11 and the second adhesive layer 13 can also be selected from commercially available products so as to satisfy the above condition (1).
  • the thickness of the adhesive layer is, for example, preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 50 ⁇ m or less, and may be 20 ⁇ m or more.
  • the thicknesses of the first adhesive layer 11 and the second adhesive layer 13 may be the same or different.
  • the liquid crystal coating layer 12 is interposed between the first adhesive layer 11 and the second adhesive layer 13 and laminated in contact with the first adhesive layer 11 and the second adhesive layer 13 .
  • the liquid crystal coating layer 12 can be a cured layer of a polymerizable liquid crystal compound.
  • the liquid crystal coating layer consists of one layer or multiple layers. When the liquid crystal coating layer is composed of a plurality of layers, the layers may be laminated via a bonding layer, which will be described later, and preferably via an adhesive layer, which will be described later.
  • the liquid crystal coating layer 12 can be a cured layer of a polymerizable liquid crystal compound.
  • a cured layer of a polymerizable liquid crystal compound can be formed by coating a substrate film with a composition for forming a retardation layer containing a polymerizable liquid crystal compound and curing the composition.
  • coating methods include a coating method and a printing method. Coating methods include bar coating, knife coating, blade coating, die coating, direct gravure coating, reverse gravure coating, roll coating, CAP coating, spin coating, spray coating, screen coating, A slit coat method, a dip coat method, etc. are mentioned.
  • Examples of printing methods include offset printing, gravure printing, screen printing, inkjet printing, and the like.
  • the cured layer of the polymerizable liquid crystal compound can be a retardation layer.
  • the retardation layer can be composed of one layer or two or more layers.
  • the retardation layer may be a positive A plate such as a ⁇ /4 plate, a ⁇ /2 plate, and a positive C plate.
  • the retardation layer is preferably a ⁇ /4 plate.
  • the retardation layer may be a retardation layer laminate composed of a first liquid crystal cured retardation layer and a second liquid crystal cured retardation layer. can.
  • the first liquid crystal-cured retardation layer and the second liquid crystal-cured retardation layer may be laminated via a later-described bonding layer, preferably via an adhesive layer.
  • the first liquid crystal cured retardation layer is preferably a ⁇ /4 plate and the second liquid crystal cured retardation layer is ⁇ /2.
  • a linearly polarizing plate laminated with a retardation layer may be referred to as a circularly polarizing plate.
  • the thickness of the retardation layer is, for example, 0.1 ⁇ m or more and 10 ⁇ m or less, preferably 8 ⁇ m or less, and more preferably 6 ⁇ m or less.
  • the thickness of the liquid crystal coating layer 12 may be, for example, 0.1 ⁇ m or more and 10 ⁇ m or less, preferably 8 ⁇ m or less, and more preferably 6 ⁇ m or less.
  • the front plate forms the outermost surface on the viewing side of the image display device, and can have a function of protecting the front surface (screen) of the image display device.
  • the front plate can be what is called a window film.
  • the material and thickness of the front plate are not limited as long as it is a plate-like body that can transmit light, and it may consist of only one layer or two or more layers. Examples thereof include a plate-like body made of resin (for example, a resin plate, a resin sheet, a resin film, etc.), a plate-like body made of glass (for example, a glass plate, a glass film, etc.), and a touch sensor panel described later.
  • the front panel can be arranged on the viewing side of the laminate 100 .
  • the laminate 100 can include a front plate on the outermost surface of the linear polarizing layer 10 opposite to the first adhesive layer 11 via a third adhesive layer, which will be described later.
  • a laminate 100 having a front panel can be arranged in an image display device such that the front panel constitutes the outermost surface of the image display device.
  • the thickness of the front plate may be, for example, 30 ⁇ m or more and 500 ⁇ m or less, preferably 200 ⁇ m or less, and more preferably 100 ⁇ m or less.
  • the plate-like body made of resin is not limited as long as it can transmit light.
  • the resin constituting the resin plate-like body such as a resin film include triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, polyester, polystyrene, Polyamide, polyetherimide, poly(meth)acrylic, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyetherketone, polyetheretherketone , polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, and
  • the front plate is preferably a film having a hard coat layer (HC layer) provided on at least one surface of the base film.
  • HC layer a hard coat layer
  • the base film a film made of the above resin can be used.
  • the hard coat layer may be formed on one surface of the substrate film, or may be formed on both surfaces.
  • the hard coat layer is, for example, a cured layer of an ultraviolet curable resin. Examples of UV curable resins include acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins.
  • the hard coat layer may contain additives in order to improve strength. Additives are not limited and include inorganic microparticles, organic microparticles, or mixtures thereof.
  • the front plate is a glass plate
  • tempered glass for displays is preferably used as the glass plate.
  • the thickness of the glass plate may be, for example, 50 ⁇ m or more and 1000 ⁇ m or less.
  • the front plate not only has the function of protecting the front surface (screen) of the image display device described above, but also functions as a touch sensor, blue light cut function, and viewing angle adjustment. It may have a function or the like.
  • the front panel preferably has a tensile elastic modulus of 4.0 GPa or more, more preferably 5.0 GPa or more at a temperature of 23° C., from the viewpoint of easily forming the laminate 100 having excellent flexibility. It is more preferably 6.0 GPa or more.
  • the front plate preferably has a tensile elastic modulus of 20 GPa or less at a temperature of 23° C., more preferably 15 GPa or less, from the viewpoint of facilitating formation of a laminate having excellent flexibility.
  • the tensile modulus at a temperature of 23° C. can be measured by the test method described in the Examples section below.
  • the laminate 100 can be repeatedly bent in an outfold even when it has a front plate having a tensile modulus of elasticity of 6.0 GPa at a temperature of 23°C.
  • the base film that constitutes the front plate may be composed of, for example, a resin film, preferably a transparent resin film.
  • the resin constituting the resin film include polyolefins such as polyethylene, polypropylene, norbornene-based polymers, and cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid ester; Cellulose ester such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide; Among them, cyclic olefin resins, cellulose esters and polyimides are preferred.
  • the thickness of the resin film is preferably thin from the viewpoint of thinning the laminate 100, but if it is too thin, it tends to be difficult to ensure impact resistance.
  • the thickness of the resin film may be, for example, 10 ⁇ m or more and 200 ⁇ m or less, preferably 15 ⁇ m or more, and more preferably 20 ⁇ m or more.
  • the base film may have a hard coat layer, an antireflection layer, or an antistatic layer on at least one surface.
  • the third adhesive layer can have the function of bonding the front panel to the laminate 100 .
  • the third adhesive layer can be formed from an adhesive.
  • the adhesive constituting the third adhesive layer may be the same as those exemplified for the adhesive composition constituting the adhesive layer, or other adhesives such as (meth)acrylic adhesive, styrene adhesive, silicone adhesive, rubber adhesive, urethane adhesive, polyester adhesive, epoxy copolymer adhesive, and the like.
  • the storage elastic modulus of the third adhesive layer at a temperature of 25° C. is preferably 50 kPa or less, more preferably 45 kPa or less, and still more preferably 41 kPa or less from the viewpoint that cracks are less likely to occur in the liquid crystal coating layer when bent. be.
  • a lamination layer is a layer comprised from a pressure sensitive adhesive or an adhesive agent.
  • the bonding layer includes, for example, a layer for bonding the front plate and the touch sensor panel, a layer for bonding the laminate and the touch sensor panel, a layer for bonding the linear polarizing layer and the protective layer, and a first liquid crystal curing phase difference. It can be a layer or the like that joins the layer and the second liquid crystal cured retardation layer.
  • the pressure-sensitive adhesive constituting the bonding layer may be the same as those exemplified for the pressure-sensitive adhesive composition constituting the above-described pressure-sensitive adhesive layer, or other pressure-sensitive adhesives such as (meth)acrylic pressure-sensitive adhesives, styrene adhesive, silicone adhesive, rubber adhesive, urethane adhesive, polyester adhesive, epoxy copolymer adhesive, and the like.
  • the laminate 100 may have one bonding layer, or may have two or more bonding layers. When the laminate 100 includes a plurality of bonding layers, the plurality of bonding layers may be the same or different.
  • the adhesive that constitutes the lamination layer for example, one or a combination of two or more of water-based adhesives, active energy ray-curable adhesives, pressure-sensitive adhesives, and the like can be used.
  • water-based adhesives include polyvinyl alcohol-based resin aqueous solutions and water-based two-liquid type urethane-based emulsion adhesives.
  • the active energy ray-curable adhesive is an adhesive that cures when irradiated with an active energy ray such as ultraviolet rays.
  • an active energy ray such as ultraviolet rays.
  • an active energy ray such as ultraviolet rays.
  • one containing a polymerizable compound and a photopolymerization initiator, one containing a photoreactive resin examples include those containing a binder resin and a photoreactive cross-linking agent.
  • Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers, and photocurable urethane monomers, and oligomers derived from these monomers.
  • Examples of the photopolymerization initiator include those containing substances that generate active species such as neutral radicals, anion radicals, and cation radicals upon irradiation with active energy rays such as ultraviolet rays.
  • a pressure-sensitive adhesive layer is used as the lamination layer, it is preferably 1 ⁇ m or more, may be 5 ⁇ m or more, and is usually 200 ⁇ m or less, for example, 150 ⁇ m or less or 100 ⁇ m or less.
  • the thickness of the bonding layer is preferably 0.1 ⁇ m or more, may be 0.5 ⁇ m or more, is preferably 10 ⁇ m or less, and is preferably 5 ⁇ m or less. There may be.
  • the laminate 100 can include an organic EL panel on the side of the second adhesive layer 13 opposite to the liquid crystal coating layer 12 .
  • the organic EL panel preferably has a tensile modulus of 4.0 GPa or more, more preferably 5.0 GPa or more, at a temperature of 23° C., from the viewpoint of facilitating formation of a laminate having excellent flexibility. It is more preferably 6.0 GPa or more.
  • the organic EL panel preferably has a tensile elastic modulus of 20 GPa or less at a temperature of 23° C., more preferably 15 GPa or less, from the viewpoint of facilitating formation of a laminate having excellent flexibility.
  • the laminate 100 can be outfolded and repeatedly flexed even when it includes an organic EL panel having a tensile modulus of elasticity of 6.0 GPa at a temperature of 23°C.
  • the detection method of the touch sensor panel is not limited as long as it is a sensor capable of detecting a touched position, and may be a resistive film method, a capacitance method, an optical sensor method, an ultrasonic method, an electromagnetic induction coupling method, or a sensor method.
  • a surface acoustic wave type touch sensor panel is exemplified.
  • the capacitive touch sensor panel is preferably used in terms of low cost, high response speed, and thin film.
  • the touch sensor panel may include an adhesive layer, a separation layer, a protective layer, etc. between the transparent conductive layer and the base film that supports it.
  • the adhesive layer includes an adhesive layer and an adhesive layer. Examples of the base film supporting the transparent conductive layer include a base film having a transparent conductive layer deposited on one surface, a base film having a transparent conductive layer transferred via an adhesive layer, and the like.
  • An example of a capacitive touch sensor panel is composed of a base film, a transparent conductive layer for position detection provided on the surface of the base film, and a touch position detection circuit.
  • a capacitive touch sensor panel is composed of a base film, a transparent conductive layer for position detection provided on the surface of the base film, and a touch position detection circuit.
  • the transparent conductive layer is grounded via the human body's capacitance at the touched point. be.
  • a touch position sensing circuit senses the grounding of the transparent conductive layer and the touched position is detected.
  • the transparent conductive layer may be a transparent conductive layer made of metal oxide such as ITO, or a metal layer made of metal such as aluminum, copper, silver, gold, or alloys thereof.
  • the transparent electrode layer is formed by a coating method such as a sputtering method, a printing method, or a vapor deposition method.
  • a photosensitive resist is formed on the transparent electrode layer, and then an electrode pattern layer is formed by photolithography.
  • a negative type photosensitive resist or a positive type photosensitive resist is used as the photosensitive resist, and the photosensitive resist may remain or be removed after patterning.
  • the electrode pattern layer can be formed by arranging a mask having an electrode pattern shape and performing sputtering.
  • the separation layer can be a layer formed on a substrate such as glass to separate the transparent conductive layer formed on the separation layer from the substrate together with the separation layer.
  • the separation layer is preferably an inorganic layer or an organic layer. Examples of materials for forming the inorganic layer include silicon oxide.
  • a (meth)acrylic resin composition, an epoxy resin composition, a polyimide resin composition, or the like can be used as a material for forming the organic layer.
  • the separation layer can be formed by coating by a known coating method and curing by thermal curing, UV curing, or a combination thereof.
  • the protective layer can be provided in contact with the transparent conductive layer to protect the conductive layer.
  • the protective layer includes at least one of an organic insulating film and an inorganic insulating film, and these films can be formed by coating methods such as spin coating, sputtering, and vapor deposition.
  • the insulating layer can be formed from, for example, an inorganic insulating material such as silicon oxide, or a transparent organic material such as acrylic resin.
  • the insulating layer can be formed by thermal curing, UV curing, thermal drying, vacuum drying, or the like after application by a known coating method.
  • Base films for touch sensor panels include triacetyl cellulose, polyethylene terephthalate, cycloolefin polymer, polyethylene naphthalate, polyolefin, polycycloolefin, polycarbonate, polyethersulfone, polyarylate, polyimide, polyamide, polystyrene, and polynorbornene.
  • a resin film is mentioned.
  • Polyethylene terephthalate is preferably used from the viewpoint of facilitating formation of a base film having desired toughness.
  • the base film of the touch sensor panel preferably has a thickness of 50 ⁇ m or less, more preferably 30 ⁇ m or less, from the viewpoint of facilitating formation of a laminate having excellent bending resistance.
  • the thickness of the base film of the touch sensor panel may be, for example, 5 ⁇ m or more.
  • a touch sensor panel can be manufactured, for example, as follows.
  • a base film is laminated on a substrate via an adhesive layer.
  • a transparent conductive layer patterned by photolithography is formed on the base film.
  • the substrate and the base film are separated to obtain a touch sensor panel composed of the transparent conductive layer and the base film.
  • the substrate is not particularly limited as long as it maintains flatness and has heat resistance, but is preferably a glass substrate.
  • a material for forming a separation layer is first applied on a substrate to form a separation layer.
  • a protective layer is formed on the separation layer by coating.
  • a protective layer may be formed so that the protective layer is not formed on the portion where the pad pattern layer is formed.
  • a photolithographically patterned transparent conductive layer is formed on the separation layer (or protective layer).
  • An insulating layer is formed on the transparent conductive layer so as to bury the electrode pattern layer.
  • a protective film is laminated on the insulating layer with a peelable adhesive, and the insulating layer and the separation layer are transferred to separate the substrate. By peeling off the peelable protective film, a touch sensor panel having insulating layer/transparent conductive layer/(protective layer)/separation layer in this order is obtained.
  • the thickness of the touch sensor panel may be, for example, 5 ⁇ m or more and 2000 ⁇ m or less, or may be 5 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the touch sensor panel is, for example, 0.5 ⁇ m or more and 10 ⁇ m or less, preferably 5 ⁇ m or less.
  • the layer configuration of the laminate includes, for example, front panel/laminate/touch sensor panel/organic EL panel, front panel/touch sensor panel/laminate. body/organic EL panel and the like.
  • the laminate 200 shown in FIG. 2 includes, from the viewing side, the front panel 21, the third adhesive layer 22, the linear polarizing plate 23, the first adhesive layer 24, the liquid crystal coating layer 25, the second adhesive layer 26, and the organic EL panel 27. They are stacked in this order.
  • the linear polarizing plate 23 has a substrate film 28, an alignment film 29, a linear polarizing layer 30, and a protective layer (OC layer) 31 arranged in this order from the viewing side.
  • the laminate 300 shown in FIG. 3 includes, from the viewing side, a front plate 41, a third adhesive layer 42, a linear polarizing plate 43, a first adhesive layer 44, a liquid crystal coating layer 45, a second adhesive layer 46, and an organic EL panel 47. They are stacked in this order.
  • the linear polarizing plate 43 has a substrate film 48, a protective layer (HC layer) 49, an alignment film 50, a linear polarizing layer 51, and a protective layer (OC layer) 52 arranged in this order from the viewing side.
  • the laminate can be produced by a method including a step of bonding the layers constituting the laminate 100 via an adhesive layer or an adhesive layer.
  • a method including a step of bonding the layers constituting the laminate 100 via an adhesive layer or an adhesive layer.
  • one or both of the laminating surfaces should be subjected to surface activation treatment such as corona treatment in order to improve adhesion. is preferred.
  • the method for producing the linear polarizing layer includes a stretched film or stretched layer to which a dye having the above-mentioned absorption anisotropy is adsorbed. can be manufactured as described in the description.
  • the linear polarizing layer When the linear polarizing layer is a film obtained by coating and curing the dye having the above-mentioned absorption anisotropy, the linear polarizing layer can be formed on the substrate via an alignment film.
  • the linear polarizing layer can be formed by applying and curing a composition for forming a linear polarizing layer containing a dichroic dye and a polymerizable liquid crystal compound.
  • the composition for forming a linear polarization layer preferably further contains a polymerization initiator, a leveling agent and a solvent, and further contains a photosensitizer, a polymerization inhibitor, a leveling agent and the like. It can contain more.
  • the liquid crystal coating layer can be produced by applying a composition for forming a liquid crystal coating layer containing a polymerizable liquid crystal compound onto the substrate and, if present, the alignment film, and polymerizing the polymerizable liquid crystal compound.
  • the liquid crystal coating layer-forming composition further contains a solvent and a polymerization initiator, and may further contain a photosensitizer, a polymerization inhibitor, a leveling agent, and the like.
  • the substrate and alignment film may be incorporated into the liquid crystal coating layer, or may be peeled off from the liquid crystal coating layer and not become a component of the laminate.
  • the application and drying of the composition for forming the linear polarization layer and the composition for forming the liquid crystal coating layer, and the polymerization of the polymerizable liquid crystal compound can be carried out by conventionally known coating methods, drying methods and polymerization methods.
  • wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, and the like can be used as methods for applying the composition for forming a linear polarization layer and the composition for forming a liquid crystal coating layer. can be done.
  • the method of polymerizing the polymerizable liquid crystal compound may be selected according to the type of polymerizable group of the polymerizable liquid crystal compound. If the polymerizable group is a photopolymerizable group, it can be polymerized by a photopolymerization method. If the polymerizable group is a thermally polymerizable group, it can be polymerized by a thermal polymerization method. In the method for producing the liquid crystal coating layer of this embodiment, a photopolymerization method is preferred. Since the photopolymerization method does not necessarily require heating the transparent base material to a high temperature, a transparent base material with low heat resistance can be used.
  • the photopolymerization method is performed by irradiating visible light or ultraviolet light to a film made of a composition for forming a linearly polarized layer or a composition for forming a liquid crystal coating layer containing a polymerizable liquid crystal compound.
  • Ultraviolet light is preferred because it is easy to handle.
  • the adhesive layer can be prepared as an adhesive sheet.
  • the pressure-sensitive adhesive sheet is prepared by dissolving or dispersing the pressure-sensitive adhesive composition in an organic solvent such as toluene or ethyl acetate to prepare a pressure-sensitive adhesive liquid, which is then applied to a release film on which a release treatment has been performed. is formed into a sheet, and another release film is further laminated on the adhesive layer.
  • Each layer can be laminated by a method of laminating an adhesive sheet from which one release film has been peeled off to one layer, then peeling off the other release film, and laminating the other layer.
  • Usual coating techniques using a die coater, a comma coater, a reverse roll coater, a gravure coater, a rod coater, a wire bar coater, a doctor blade coater, an air doctor coater, etc. can be used to apply the adhesive liquid onto the release film. should be adopted.
  • the release film is preferably composed of a plastic film and a release layer.
  • Plastic films include polyester films such as polyethylene terephthalate film, polybutylene terephthalate film and polyethylene naphthalate film, and polyolefin films such as polypropylene film.
  • the release layer can be formed, for example, from a release layer-forming composition.
  • the main component (resin) constituting the release layer-forming composition is not particularly limited, but examples thereof include silicone resins, alkyd resins, acrylic resins, long-chain alkyl resins, and the like.
  • the thickness of the adhesive layer can be adjusted according to the coating conditions of the adhesive liquid. In order to reduce the thickness of the pressure-sensitive adhesive layer, it is effective to reduce the coating thickness.
  • a laminate can be produced by cutting a long film in which a linear polarizing layer and a liquid crystal coating layer are bonded via an adhesive layer to a predetermined size.
  • the laminate can also be produced by laminating a linearly polarizing layer and a liquid crystal coating layer, which have been cut to a predetermined size in advance, with an adhesive layer.
  • An image display device includes the laminate described above.
  • the display device is not particularly limited, and examples thereof include image display devices such as organic EL display devices, inorganic EL display devices, liquid crystal display devices, and electroluminescence display devices.
  • the image display device may have a touch panel function.
  • the laminate is suitable for a flexible display that can be bent or folded.
  • the laminate is arranged on the viewing side of the display element of the image display device with the front panel facing outward (the side opposite to the display element side, that is, the viewing side).
  • the image display device can be used as mobile devices such as smartphones and tablets, televisions, digital photo frames, electronic signboards, measuring instruments and gauges, office equipment, medical equipment, computing equipment, and the like.
  • the image display device has excellent screen visibility because the distortion of the reflected image reflected on the surface of the front panel is suppressed.
  • the storage modulus of the adhesive layer at a temperature of 25°C was measured by the following method.
  • a plurality of adhesive layers used in Examples and Comparative Examples were laminated so as to have a thickness of 0.2 mm.
  • a cylindrical body with a diameter of 8 mm was punched out from the obtained adhesive layer, and this was used as a sample for measuring the storage elastic modulus at a temperature of 25°C.
  • the storage modulus (Pa) at a temperature of 25° C. was measured under the following conditions by the torsional shear method using a viscoelasticity measuring device (manufactured by Physica, MCR300) in accordance with JIS K7244-6. (Measurement condition) Normal Force FN: 1N Distortion ⁇ : 1% Frequency: 1Hz Temperature: 25°C
  • the thickness of the adhesive layer was measured using a contact-type film thickness measuring device ("MS-5C” manufactured by Nikon Corporation). However, the polarizer layer and the alignment film were measured using a laser microscope ("OLS4100” manufactured by Olympus Corporation).
  • the tensile modulus at a temperature of 23°C was measured as follows. A rectangular piece of 110 mm long side ⁇ 10 mm short side was cut out from a front plate or a polyimide film (a substitute equivalent to an organic EL panel) using a super cutter. Then, the upper and lower grips of a tensile tester (manufactured by Shimadzu Corporation, Autograph AG-Xplus testing machine) hold both ends of the measurement sample in the long side direction so that the distance between the grips is 5 cm, and the temperature is 23.
  • a tensile tester manufactured by Shimadzu Corporation, Autograph AG-Xplus testing machine
  • the measurement sample is pulled in the length direction of the measurement sample at a tensile speed of 4 mm / min, and the resulting stress - in the strain curve, from the slope of the straight line between 20 and 40 MPa, the temperature is 23 ° C. , the tensile modulus at 55% relative humidity was calculated.
  • the thickness for calculating the stress was measured by the method described above.
  • the jig 501 is operated in the direction of the arrow A so that the distance D becomes 4.0 mm (bending radius 2R) to bend the measurement sample 500, and then the jig 501 is bent.
  • the tool 501 was operated in the direction of the arrow B to release the bending with the interval D set to 70 mm, and this series of operations was counted as one and was continuously repeated 200,000 times.
  • the moving speed of the jig 501 was 1.32 m/sec, and the time required to repeat 200,000 times was 55.6 hours.
  • the measurement sample was taken out from the bending tester and observed with transmitted light using an optical microscope to confirm the presence or absence of cracks. O: Cracks were generated. x: No cracks occurred.
  • a polyimide film (PI film, total thickness: 40 ⁇ m, tensile modulus of elasticity 6.8 GPa) was prepared as a window film, which is a front plate.
  • Linear polarizing plate A (Base film) A triacetyl cellulose (TAC) film (manufactured by Konica Minolta, Inc., thickness 25 ⁇ m) was prepared as a base film.
  • TAC triacetyl cellulose
  • Polymer 1 is a polymer having a photoreactive group consisting of the following structural units. GPC measurement revealed that the obtained polymer 1 had a number average molecular weight of 28200, Mw/Mn of 1.82, and a monomer content of 0.5%. A solution of polymer 1 dissolved in cyclopentanone at a concentration of 5% by mass was used as a composition for forming an alignment film.
  • the polymerizable liquid crystal compound includes a polymerizable liquid crystal compound represented by formula (1-6) [hereinafter, also referred to as compound (1-6)] and a polymerizable liquid crystal compound represented by formula (1-7) [hereinafter, Also referred to as compound (1-7)] was used.
  • dichroic dye As the dichroic dye, the azo dyes described in the examples of JP-A-2013-101328 represented by the following formulas (2-1a), (2-1b), and (2-3a) were used.
  • composition for forming a linear polarization layer includes 75 parts by mass of compound (1-6), 25 parts by mass of compound (1-7), the above formulas (2-1a) as dichroic dyes (2-1b), (2-1b), ( 2.5 parts by mass each of the azo dyes represented by 2-3a), 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure369, manufactured by BASF Japan Co., Ltd.) as a polymerization initiator ) and 1.2 parts by mass of a polyacrylate compound (BYK-361N, manufactured by BYK-Chemie) as a leveling agent are mixed with 400 parts by mass of toluene as a solvent, and the resulting mixture is heated at 80° C. Prepared by stirring for hours.
  • a polyacrylate compound BYK-361N, manufactured by BYK-Chemie
  • the protective layer composition is composed of 3 parts by weight of polyvinyl alcohol resin powder (manufactured by Kuraray Co., Ltd., average degree of polymerization: 18000, trade name: KL-318) and polyamide epoxy resin (crosslinking agent, resin) per 100 parts by weight of water. Ka Chemtex Co., Ltd., trade name: SR650 (30)) was mixed with 1.5 parts by mass.
  • Polarized UV treatment uses a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.) is transmitted through a wire grid (UIS-27132##, manufactured by Ushio Inc.), and the integrated amount of light measured at a wavelength of 365 nm is 100 mJ/cm 2 . under certain conditions.
  • the thickness of the alignment film was 100 nm.
  • a composition for forming a linear polarization layer was applied onto the formed alignment film by a bar coating method, dried by heating in a drying oven at 120° C. for 1 minute, and then cooled to room temperature.
  • a linearly polarized layer was formed by irradiating the dried film with ultraviolet rays at an integrated light amount of 1200 mJ/cm 2 (365 nm standard) using the above UV irradiation device.
  • the thickness of the obtained linearly polarizing layer was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), it was 1.8 ⁇ m.
  • OLS3000 manufactured by Olympus Corporation laser microscope
  • a protective layer (OC layer) composition was applied onto the formed linear polarizing layer by a bar coating method so that the thickness after drying was 1.0 ⁇ m, and dried at a temperature of 80° C. for 3 minutes.
  • a linear polarizing plate A consisting of "base film/orientation film/linear polarizing layer/protective layer (OC layer)" was obtained.
  • Linear polarizing plate B (Base film) A polyethylene terephthalate (PET) film (thickness: 100 ⁇ m) was prepared as a base film.
  • PET polyethylene terephthalate
  • composition for protective layer 2.8 parts by weight of a dendrimer acrylate having an 18-functional acrylic group (Miramer SP1106, Miwon), 6.6 parts by weight of a urethane acrylate having a hexafunctional acrylic group (Miramer PU-620D, Miwon), and a photopolymerization initiator (Irgacure-184, BASF) 0.5 parts by weight, a leveling agent (BYK-3530, BYK) 0.1 parts by weight, and methyl ethyl ketone (MEK) 90 parts by weight, mixed with a protective layer (HC layer) composition prepared the product.
  • a leveling agent BYK-3530, BYK
  • MEK methyl ethyl ketone
  • compositions for forming the alignment film the composition for forming the linearly polarizing layer, and the composition for forming the protective layer (OC layer), the compositions described in the section [Linearly polarizing plate A] above were used.
  • a protective layer (HC layer) composition was applied to the substrate film by a bar coating method, and dried by heating in a drying oven at 80° C. for 3 minutes.
  • a UV irradiation device SPOT CURE SP-7, manufactured by Ushio Inc.
  • the obtained dry film was irradiated with UV light at an exposure amount of 500 mJ/cm 2 (365 nm standard) to form a protective layer (HC layer). formed.
  • the thickness of the protective layer (HC layer) was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), it was 2.0 ⁇ m.
  • OLS3000 manufactured by Olympus Corporation
  • the protective layer (HC layer) side of the laminate composed of "base film/protective layer (HC layer)” was subjected to corona treatment once.
  • the corona treatment conditions were an output of 0.3 kW and a treatment speed of 3 m/min.
  • the alignment film-forming composition was applied onto the protective layer (HC layer) by a bar coating method, and dried by heating in a drying oven at 80° C. for 1 minute.
  • the resulting dry film was subjected to polarized UV irradiation treatment to form a first alignment film.
  • a composition for forming a linear polarization layer was applied onto the formed alignment film by a bar coating method, dried by heating in a drying oven at 120° C. for 1 minute, and then cooled to room temperature.
  • a linearly polarized layer was formed by irradiating the dried film with ultraviolet rays at an integrated light amount of 1200 mJ/cm 2 (365 nm standard) using the above UV irradiation device.
  • OLS3000 manufactured by Olympus Corporation When the thickness of the obtained linearly polarizing layer was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), it was 1.8 ⁇ m.
  • OLS3000 manufactured by Olympus Corporation
  • a protective layer (OC layer) composition was applied onto the formed polarizing layer by a bar coating method so that the thickness after drying was 1.0 ⁇ m, and dried at a temperature of 80° C. for 3 minutes.
  • a laminate composed of "base film/protective layer (HC layer)/alignment film/linear polarizing layer/protective layer (OC layer)" was obtained.
  • the substrate film was peeled off to obtain a linearly polarizing plate B composed of "protective layer (HC layer)/orientation film/linearly polarizing layer/protective layer (OC layer)".
  • Adhesive layer A As an adhesive sheet A having an adhesive layer A, two release films (heavy separator, light separator) in which one side of a polyethylene terephthalate film (base film) with a thickness of 38 ⁇ m has been subjected to release treatment. A commercially available adhesive sheet sandwiching an acrylic adhesive layer having a thickness of 5 ⁇ m was used.
  • the storage elastic modulus G′1 of the adhesive layer A obtained by removing the release film from the adhesive sheet A at a temperature of 25° C. was 1400 kPa.
  • Adhesive layer B As the adhesive sheet B having the adhesive layer B, an adhesive with a thickness of 25 ⁇ m was applied to each release-treated surface of two release films (heavy separator, light separator) in which one side of the base film was subjected to release treatment.
  • the storage elastic modulus G′2 of the adhesive layer B obtained by removing the release film from the adhesive sheet B at a temperature of 25° C. was 41 kPa.
  • Liquid crystal coating layer (First liquid crystal cured retardation layer)
  • a layer giving a retardation of ⁇ /4 was prepared, which was composed of a layer in which a nematic liquid crystal compound was cured, an alignment layer and a transparent substrate.
  • the total thickness of the layer in which the nematic liquid crystal compound was cured and the alignment layer was 2 ⁇ m.
  • the layer in which the nematic liquid crystal compound was cured was formed by applying a composition for forming a retardation layer containing a nematic liquid crystal compound onto the alignment layer formed on the transparent substrate and curing the composition.
  • a polyethylene terephthalate substrate having a thickness of 38 ⁇ m was used as a transparent substrate, one side of which was coated with a composition for a vertical alignment layer so as to have a thickness of 3 ⁇ m, and an alignment layer was produced by irradiating polarized ultraviolet rays of 20 mJ/cm 2 . .
  • a composition for the vertical alignment layer 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, dipentaerythritol triacrylate, and bis(2-vinyloxyethyl) ether were mixed at a ratio of 1:1:4:5. and 4% of LUCIRIN (registered trademark) TPO was added as a polymerization initiator.
  • a composition for forming a retardation layer containing a photopolymerizable nematic liquid crystal (manufactured by Merck & Co., RMM28B) was applied onto the formed alignment layer by die coating.
  • a liquid crystal composition methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone (CHN) having a boiling point of 155° C. are used as solvents in a mass ratio (MEK:MIBK:CHN) of 35: A mixed solvent mixed at a ratio of 30:35 was used.
  • the composition for forming a retardation layer prepared to have a solid content of 1 to 1.5 g was applied onto the orientation layer so that the coating amount was 4 to 5 g (wet).
  • the retardation layer-forming composition was applied onto the alignment layer, drying was performed at a drying temperature of 75°C and a drying time of 120 seconds. After that, the liquid crystal compound was polymerized by ultraviolet (UV) irradiation to obtain a positive C layer composed of a layer in which the photopolymerizable nematic liquid crystal compound was cured, an alignment layer, and a transparent substrate. The total thickness of the layer in which the photopolymerizable nematic liquid crystal compound was cured and the alignment layer was 4 ⁇ m.
  • UV ultraviolet
  • the first liquid crystal cured retardation layer and the second liquid crystal cured retardation layer are bonded with an ultraviolet curing adhesive so that the surface of each liquid crystal cured retardation layer (the surface opposite to the transparent substrate) becomes the bonding surface. pasted together.
  • ultraviolet rays were irradiated to cure the ultraviolet curing adhesive.
  • the thickness of the cured UV-curable adhesive was 2 ⁇ m.
  • Organic EL panel A polyimide film (PI film, total thickness: 75 ⁇ m, tensile modulus of elasticity 6.96 GPa) was prepared as a substitute for an organic EL panel.
  • Example 1 The adhesive layer A, which was exposed by peeling off the light separator from the adhesive sheet A, was attached to the protective layer 2 side of the linear polarizing plate A to obtain a laminate A1. Both surfaces to be bonded were previously subjected to corona treatment (output: 0.3 kW, speed: 3 m/min).
  • the adhesive layer A which is exposed by peeling off the heavy separator from the laminate A1, is attached to the surface of the liquid crystal coating layer from which the base film used for forming the first liquid crystal cured retardation layer is peeled off, and the laminate A2 is formed. Obtained. Both surfaces to be bonded were previously subjected to corona treatment (output: 0.3 kW, speed: 3 m/min).
  • the adhesive layer A which is exposed by peeling off the light separator from another adhesive sheet A, is attached to the surface where the base film used for forming the second liquid crystal cured retardation layer is peeled from the laminate A2, and the laminate A3 was obtained. Both surfaces to be bonded were previously subjected to corona treatment (output: 0.3 kW, speed: 3 m/min).
  • the third adhesive layer which was exposed by peeling off the light separator from the third adhesive sheet, was attached to the front plate to obtain a laminate A4. Both surfaces to be bonded were previously subjected to corona treatment (output: 0.3 kW, speed: 3 m/min).
  • the heavy separator was peeled off from the laminate A4 and attached to the protective layer 1 side of the laminate A3 to obtain a laminate A5. Both surfaces to be bonded were previously subjected to corona treatment (output: 0.3 kW, speed: 3 m/min).
  • the heavy separator of the laminate A5 was peeled off, and a substitute (polyimide film) equivalent to an organic EL panel was attached to obtain the laminate of Example 1 having the structure shown in FIG. Table 1 shows the results.
  • Example 2 Comparative Examples 1 and 2> Laminates of Example 2 and Comparative Examples 1 and 2 were produced in the same manner as in Example 1, except that the linear polarizing plate and adhesive layer shown in Table 1 were used. Table 1 shows the results.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Theoretical Computer Science (AREA)
  • Engineering & Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention fournit un stratifié obtenu par stratification dans l'ordre d'une couche de polarisation linéaire, d'une première couche adhésive, d'une couche de revêtement à cristaux liquides et d'une seconde couche adhésive, et dans lequel des fissures sont peu susceptibles de se produire dans le cas d'une flexion répétée avec le côté couche de polarisation linéaire pour côté externe. Plus précisément, l'invention concerne un stratifiée dans lequel la couche de polarisation linéaire, la première couche adhésive, la couche de revêtement à cristaux liquides et la seconde couche adhésive sont stratifiées dans cet ordre, et dans lequel lorsque le module d'élasticité de conservation à une température de 25°C de la première couche adhésive est représenté par Ｇ'１［ｋＰａ］, et lorsque le module d'élasticité de conservation à une température de 25°C de la seconde couche adhésive est représenté par Ｇ'２［ｋＰａ］, Ｇ'１≧１０００ｋＰａ et Ｇ'２≧１０００ｋＰａ sont satisfaits.
PCT/JP2022/021159 2021-06-02 2022-05-23 Stratifié WO2022255155A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010044211A (ja) * 2008-08-12 2010-02-25 Sumitomo Chemical Co Ltd 偏光板及びそれを用いた画像表示装置
JP2020060708A (ja) * 2018-10-11 2020-04-16 住友化学株式会社 光学積層体及び表示装置
US20200285093A1 (en) * 2017-10-23 2020-09-10 Samsung Sdi Co., Ltd. Liquid crystal phase difference film, polarizing plate for light-emitting display device including same, and light-emitting display device including same
WO2020195540A1 (fr) * 2019-03-26 2020-10-01 住友化学株式会社 Stratifié et dispositif d'affichage
WO2021070755A1 (fr) * 2019-10-09 2021-04-15 日東電工株式会社 Dispositif d'affichage d'image flexible et stratifié optique destiné à être utilisé dans celui-ci

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7042020B2 (ja) * 2016-08-15 2022-03-25 日東電工株式会社 フレキシブル画像表示装置用積層体、及び、フレキシブル画像表示装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010044211A (ja) * 2008-08-12 2010-02-25 Sumitomo Chemical Co Ltd 偏光板及びそれを用いた画像表示装置
US20200285093A1 (en) * 2017-10-23 2020-09-10 Samsung Sdi Co., Ltd. Liquid crystal phase difference film, polarizing plate for light-emitting display device including same, and light-emitting display device including same
JP2020060708A (ja) * 2018-10-11 2020-04-16 住友化学株式会社 光学積層体及び表示装置
WO2020195540A1 (fr) * 2019-03-26 2020-10-01 住友化学株式会社 Stratifié et dispositif d'affichage
WO2021070755A1 (fr) * 2019-10-09 2021-04-15 日東電工株式会社 Dispositif d'affichage d'image flexible et stratifié optique destiné à être utilisé dans celui-ci

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TW202321036A (zh) 2023-06-01
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