WO2021200364A1 - Multilayer body - Google Patents

Multilayer body Download PDF

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Publication number
WO2021200364A1
WO2021200364A1 PCT/JP2021/011867 JP2021011867W WO2021200364A1 WO 2021200364 A1 WO2021200364 A1 WO 2021200364A1 JP 2021011867 W JP2021011867 W JP 2021011867W WO 2021200364 A1 WO2021200364 A1 WO 2021200364A1
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WO
WIPO (PCT)
Prior art keywords
layer
film
thickness
less
sensitive adhesive
Prior art date
Application number
PCT/JP2021/011867
Other languages
French (fr)
Japanese (ja)
Inventor
▲ビョン▼▲フン▼ 宋
柱烈 張
承柏 洪
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2021039492A external-priority patent/JP2021162855A/en
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN202180025443.4A priority Critical patent/CN115349100A/en
Priority to KR1020227027609A priority patent/KR20220159358A/en
Publication of WO2021200364A1 publication Critical patent/WO2021200364A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10339—Specific parts of the laminated safety glass or glazing being colored or tinted
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
    • B32B17/1044—Invariable transmission
    • B32B17/10458—Polarization selective transmission
    • 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
    • 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
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • 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
    • B32B2331/00—Polyvinylesters
    • B32B2331/04—Polymers of vinyl acetate, e.g. PVA
    • 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
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/206—Organic displays, e.g. OLED
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens

Definitions

  • the present invention relates to a laminated body and further to an image display device including the laminated body.
  • a display device such as a liquid crystal display device or an organic electroluminescence (EL) display device is provided with a colored layer on the outer edge portion in order to prevent the electrode portion and the like from being visually recognized (Patent Document 1).
  • EL organic electroluminescence
  • a laminated body provided with a front plate, a first bonding layer, a coloring member, a second bonding layer, and a circularly polarizing plate in this order, cracks occur in the coloring member when repeated bending is performed with the front plate side inside. There was something. Further, when the appearance of the laminated body is visually observed from the front plate side, rainbow-colored unevenness (hereinafter, also referred to as rainbow unevenness) may be visually recognized due to light interference.
  • An object of the present invention is a laminated body including a front plate, a first bonding layer, a coloring member, a second bonding layer, and a circularly polarizing plate in this order, and the front plate side is turned inside and repeated bending is performed.
  • the present invention provides the following laminate and image display device.
  • the front plate, the first bonding layer, the coloring member, the second bonding layer, and the circularly polarizing plate are included in this order.
  • the ratio Ta / Tb of the thickness Ta of the first bonded layer to the thickness Tb of the second bonded layer is 0.03 or more and less than 50.
  • the laminate according to [1] or [2], wherein the storage elastic modulus G'a of the first bonded layer at a temperature of 25 ° C. is 0.01 MPa or more and 5 MPa or less.
  • the coloring member includes a coloring layer and a separation layer.
  • An image display device comprising the laminate according to any one of [1] to [5].
  • the laminate is provided with a front plate, a first bonding layer, a coloring member, a second bonding layer, and a circular polarizing plate in this order, and is repeatedly bent with the front plate side inside.
  • a laminated body in which cracks are less likely to occur in the colored member and rainbow unevenness is less likely to be observed when the appearance of the laminated body is visually observed from the front plate side.
  • the laminated body of the present invention will be described with reference to FIG.
  • the laminated body 100 shown in FIG. 1 includes a front plate 110, a first bonded layer 120, a coloring member 130, a second bonded layer 140, and a circularly polarizing plate 150 in this order.
  • the first bonding layer 120 and the coloring member 130 are laminated in contact with each other.
  • the second bonding layer 140 and the coloring member 130 are laminated in contact with each other.
  • the laminated body 100 may further have a bonding layer and a touch sensor layer, which will be described later.
  • the laminated body 100 can be bent (hereinafter, also referred to as infold) with the front plate 110 side inward. Being able to bend means that the laminated body can be bent without causing cracks in the coloring member 130. Bending includes a form of bending in which a curved surface is formed on the bent 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 bending angle of the inner surface is greater than 0 ° and less than 180 °, and a form of folding in which the bending radius of the inner surface is close to zero or the bending angle of the inner surface is 0 °. ..
  • the laminate of the present invention is suitable for a flexible display because it can be bent.
  • the laminated body 100 tends to be less likely to crack in the colored member 130 when repeatedly bent with the front plate 110 side inside and a bending radius of 1 mm.
  • the number of times that the colored member 130 is first cracked is preferably 200,000 times or more, more preferably 200,000 times or more. It is 300,000 times or more, more preferably 400,000 times or more, and particularly preferably 500,000 times or more.
  • the laminated body 100 satisfies the conditions (A) and (B).
  • Condition (A) The ratio G'a / G'b of the storage elastic modulus G'a of the first bonded layer 120 at a temperature of 25 ° C. to the storage elastic modulus G'b of the second bonded layer 140 at a temperature of 25 ° C. Less than 50.
  • the laminated body 100 tends to be less likely to crack in the colored member 130 when repeatedly bent with the front plate 110 side inside and a bending radius of 1 mm.
  • G'a / G'b is preferably 10 or less, more preferably 5 or less, still more preferably 2 or less, and particularly preferably 1 or less, from the viewpoint that cracks are less likely to occur in the coloring member 130. It may be less than 1.
  • G'a / G'b may be 0.01 or more.
  • the storage elastic moduli G'a and G'b are measured according to the methods described in the Examples section below. The preferable ranges of the storage elastic moduli G'a and G'b will be described later.
  • Ta and Tb are preferably 1.5 ⁇ m or more and 100 ⁇ m or less, and more preferably 5 ⁇ m or more and 50 ⁇ m or less from the viewpoint of making it difficult to observe rainbow unevenness and enhancing flexibility.
  • Ta is, for example, 10 ⁇ m or more and preferably 20 ⁇ m or more, and for example, 100 ⁇ m or less and preferably 80 ⁇ m or less.
  • Tb is, for example, 1.2 ⁇ m or more, preferably 1.5 ⁇ m or more, and for example, 50 ⁇ m or less, preferably 30 ⁇ m or less.
  • the laminated body 100 preferably further satisfies the condition (C) from the viewpoint that cracks are less likely to occur in the colored member 130 when the laminated body 100 is repeatedly bent with the front plate 110 side inside and the bending radius is 1 mm.
  • the ratio Ta / Tb of the thickness Ta of the first bonding layer to the thickness Tb of the second bonding layer is 0.03 or more and less than 50.
  • Ta / Tb is preferably 0.05 or more and 40 or less, more preferably 1 or more and 30 or less, and further preferably 1 or more and 30 or less.
  • the shape of the laminated body 100 in the plane direction is not particularly limited, but it is preferably a square shape, and more preferably a rectangular shape.
  • the length of the long side may be, for example, 50 mm or more and 300 mm or less, preferably 100 mm or more and 280 mm or less, and the length of the short side is, for example, 30 mm or more and 250 mm or less. It is preferably 60 mm or more and 220 mm or less.
  • the laminated body 100 may be a square shape having rounded corners in which at least one of the corners of the square shape is R-processed, or may be a square shape having a notch on at least one side.
  • the laminated body 100 may be provided with a hole portion penetrating in the laminating direction.
  • the thickness of the laminated body 100 varies depending on the function and application required for the laminated body 100, but can be, for example, 20 ⁇ m or more and 2000 ⁇ m or less, preferably 50 ⁇ m or more and 500 ⁇ m or less.
  • the laminated body 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 an organic electroluminescence (organic EL) display device, an inorganic electroluminescence (inorganic EL) display device, a liquid crystal display device, and an electroluminescence display device.
  • organic EL organic electroluminescence
  • inorganic EL inorganic electroluminescence
  • liquid crystal display device a liquid crystal display device
  • electroluminescence display device an electroluminescence display device.
  • the laminate 100 includes a circularly polarizing plate 150, it can also be used as an antireflection film in, for example, an organic electroluminescence (EL) display device when applied to an image display device.
  • EL organic electroluminescence
  • the material and thickness of the front plate 110 are not limited as long as it is a plate-like body capable of transmitting light, and the front plate 110 may have a single-layer structure or a multi-layer structure, and is a glass plate-like body (for example, glass). Examples thereof include a plate (plate, glass film, etc.), a resin plate (for example, a resin plate, a resin sheet, a resin film, etc.), and a laminate of a resin plate and a glass plate.
  • the front plate 110 can be a layer forming the outermost surface on the visual side of the image display device.
  • the glass plate tempered glass for display is preferably used.
  • the thickness of the glass plate is, for example, 10 ⁇ m or more and 1000 ⁇ m or less, preferably 20 ⁇ m or more and 500 ⁇ m or less.
  • the front plate 110 can have excellent mechanical strength and surface hardness.
  • the resin film is not limited as long as it is a resin film capable of transmitting light.
  • a resin film capable of transmitting light for example, triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, polyester, polystyrene, polyamide, polyetherimide, poly (meth) acrylic, polyimide, polyether.
  • films formed of polymers such as terephthalate, polyethylene naphthalate, polycarbonate and polyamideimide. These polymers can be used alone or in admixture of two or more.
  • a resin formed of a polymer such as polyimide, polyamide, or polyamide-imide, which has excellent flexibility and can be configured to have high strength and high transparency.
  • Films are preferably used.
  • the (meth) acrylic polymer represents at least one selected from the group consisting of an acrylic polymer and a methacryl polymer. The same applies to other terms with "(meta)".
  • the resin film may be a film in which a hard coat layer is provided on at least one surface of the base film to further improve the hardness.
  • the hard coat layer may be formed on one surface of the base film or may be formed on both surfaces.
  • the image display device described later is a touch panel type image display device, the surface of the front plate 110 serves as a touch surface, so a resin film having a hard coat layer is preferably used.
  • the hard coat layer is, for example, a cured layer of an ultraviolet curable resin.
  • the ultraviolet curable resin examples include (meth) acrylic resin, silicone resin, polyester resin, urethane resin, amide resin, epoxy resin and the like.
  • the hard coat layer may contain additives to improve hardness. Additives are not limited and include inorganic fine particles, organic fine particles, or mixtures thereof.
  • the thickness of the resin film is, for example, 30 ⁇ m or more and 100 ⁇ m or less.
  • the front plate 110 not only has a function of protecting the front surface of the image display device, but may also have a function as a touch sensor, a blue light cut function, a viewing angle adjusting function, and the like.
  • the first bonding layer 120 can be a layer for bonding the front plate 110 and the coloring member 130.
  • the first bonding layer 120 is a layer formed of a pressure-sensitive adhesive or an adhesive.
  • the pressure-sensitive adhesive is also referred to as a pressure-sensitive adhesive.
  • the adhesive refers to an adhesive other than the pressure-sensitive adhesive (pressure-sensitive adhesive), and is clearly distinguished from the pressure-sensitive adhesive.
  • the first bonding layer 120 may be one layer or may be composed of two or more layers, but is preferably one layer.
  • the first bonding layer is preferably an adhesive layer.
  • the pressure-sensitive adhesive forming the first bonding layer 120 is composed of a pressure-sensitive adhesive composition containing a resin such as (meth) acrylic, rubber, urethane, ester, silicone, or polyvinyl ether as a main component. be able to. Among them, a pressure-sensitive adhesive composition using a (meth) acrylic resin having excellent transparency, weather resistance, heat resistance and the like as a base polymer is preferable.
  • the pressure-sensitive adhesive composition may be an active energy ray-curable type or a thermosetting type.
  • Examples of the (meth) acrylic resin (base polymer) used in the pressure-sensitive adhesive composition include butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2- (meth) acrylate.
  • a polymer or copolymer having one or more (meth) acrylic acid esters such as ethylhexyl as a monomer is preferably used. It is preferable that the base polymer is copolymerized with a polar monomer.
  • Examples of the polar monomer include (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylamide, N, N-.
  • Examples thereof include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group and the like, such as dimethylaminoethyl (meth) acrylate and glycidyl (meth) acrylate.
  • the pressure-sensitive adhesive composition may contain only the above-mentioned base polymer, but usually further contains a cross-linking agent.
  • the cross-linking agent is a divalent or higher metal ion that forms a carboxylic acid metal salt with a carboxyl group; a polyamine compound that forms an amide bond with a carboxyl group; poly.
  • Epoxy compounds and polyols that form an ester bond with a carboxyl group; polyisocyanate compounds that form an amide bond with a carboxyl group are exemplified. Of these, polyisocyanate compounds are preferable.
  • the active energy ray-curable pressure-sensitive adhesive composition has a property of being cured by being irradiated with active energy rays such as ultraviolet rays and electron beams, and has adhesiveness even before irradiation with active energy rays. It is a pressure-sensitive adhesive composition having the property of being able to adhere to an adherend such as, etc., and being cured by irradiation with active energy rays to adjust the adhesion force.
  • the active energy ray-curable pressure-sensitive adhesive composition is preferably an ultraviolet-curable type.
  • 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. Further, if necessary, a photopolymerization initiator, a photosensitizer, or the like may be contained.
  • the pressure-sensitive adhesive composition includes fine particles for imparting light scattering properties, beads (resin beads, glass beads, etc.), glass fibers, resins other than the base polymer, pressure-sensitive adhesives, fillers (metal powders and other inorganic powders). Etc.), antioxidants, UV absorbers, dyes, pigments, colorants, antifoaming agents, corrosion inhibitors, photopolymerization initiators and other additives can be included.
  • the first bonding layer can be formed by applying an organic solvent diluent of the pressure-sensitive adhesive composition on a substrate and drying the coating film.
  • an organic solvent diluent of the pressure-sensitive adhesive composition When the active energy ray-curable pressure-sensitive adhesive composition is used, a cured product having a desired degree of curing can be obtained by irradiating with active energy rays.
  • the adhesive for example, one or a combination of two or more of water-based adhesives, active energy ray-curable adhesives, and the like can be formed.
  • the water-based adhesive include a polyvinyl alcohol-based resin aqueous solution, a water-based two-component urethane-based emulsion adhesive, and the like.
  • the active energy ray-curable adhesive is an adhesive that cures by irradiating with active energy rays such as ultraviolet rays, and is, for example, an adhesive containing a polymerizable compound and a photopolymerizable initiator, and an adhesive containing a photoreactive resin.
  • Adhesives containing a binder resin and a photoreactive cross-linking agent Adhesives containing a binder resin and a photoreactive cross-linking agent, and the like.
  • the polymerizable compound include photopolymerizable monomers such as a photocurable epoxy monomer, a photocurable acrylic monomer, and a photocurable urethane monomer, and oligomers derived from these monomers.
  • the photopolymerization initiator include compounds containing substances that generate active species such as neutral radicals, anion radicals, and cationic radicals by irradiating them with active energy rays such as ultraviolet rays.
  • the storage elastic modulus G'a of the first bonded layer 120 at a temperature of 25 ° C. may be, for example, 0.01 MPa or more and 5 MPa or less, preferably 0.02 MPa or more and 1 MPa or less, and more preferably 0.03 MPa or more and 0.5 MPa. It is less than or equal to, and may be 0.1 MPa or less.
  • the storage elastic modulus G'a of the first bonded layer 120 can be adjusted, for example, by selecting the material used to form the first bonded layer 120.
  • the coloring member 130 includes a coloring layer in order to shield electrodes, wiring, and the like, and to suppress light leakage from a display unit provided in an image display device.
  • the first bonding layer 120 is laminated in contact with the coloring member 130 on one surface of the coloring member 130, and the second bonding layer 140 is laminated in contact with the coloring member 130 on the other surface of the coloring member 130. Has been done.
  • the coloring member 130 can further include at least one of a separation layer and a protective layer in addition to the coloring layer.
  • the coloring member 130 may include, for example, a protective layer, a coloring layer, and a separation layer in this order, and may include a coloring layer, a protection layer, and a separation layer in this order. ..
  • the coloring member 130 may be laminated so that the coloring layer is closer to the front plate 110 than the separation layer, and the separation layer is closer to the front plate 110 than the coloring layer.
  • the coloring member may include a resin film or glass.
  • a coloring layer is formed on a glass plate via a separation layer, a base material layer (release film) is provided on the coloring layer, and the glass plate is separated from the separation layer to separate the separation layer /. It can be produced by transferring the colored member 130 having the layer structure of the colored layer onto the base material layer.
  • Another base material layer (release film) may be provided on the separation layer obtained by separating and exposing the glass plate. The base material layer is usually removed when the coloring member 130 is incorporated into the laminate 100.
  • the thickness of the coloring member 130 may be, for example, 0.1 ⁇ m or more and 15 ⁇ m or less, preferably 0.5 ⁇ m or more and 10 ⁇ m or less, and more preferably 1 ⁇ m or more and 7 ⁇ m or less.
  • the colored layer can have a shielding property in order to shield electrodes, wiring, and the like, and to suppress light leakage from a display unit provided in an image display device.
  • the shape and color of the colored layer are not limited, and can be appropriately selected depending on, for example, the application and design of the display device using the laminated body.
  • the colored layer may be provided so as to be partially arranged in the plan view of the laminated body, and may be provided, for example, so as to be arranged in the peripheral portion in the plan view of the laminated body.
  • the colored layer may have a single layer structure or a multi-layer structure.
  • the colored layer has a multi-layer structure, at least one of the two or more layers is a colorant-containing layer containing a colorant, and the remaining layer contains the colorant but does not contain the colorant. You may. Examples of the color of the colorant include black, red, white, dark blue, silver, and gold.
  • the color of the colored layer is not particularly limited and may be appropriately selected according to the application, design, etc.
  • Examples of the color of the coloring layer 130 include black, white, red, dark blue, silver, and gold.
  • the thickness of the colored layer may be, for example, 0.1 ⁇ m or more and 5 ⁇ m or less.
  • the thickness of the colored layer is preferably 0.5 ⁇ m or more and 4 ⁇ m or less, more preferably 1 ⁇ m or more and 3 ⁇ m or less, and further preferably 1 ⁇ m or more and 2 ⁇ m or less.
  • the above thickness is the maximum thickness of the colored layer. The thickness of the colored layer is measured by the measuring method described in the column of Examples described later.
  • the optical density of the colored layer may be, for example, 2 or more, preferably 3 or more, more preferably 4 or more, and further preferably 5 or more.
  • the upper limit of the optical density of the colored layer is not particularly limited, but may be, for example, 10 or less, or 7 or less.
  • the colored layer may have an optical density of, for example, 1.8 or more, preferably 2 or more, more preferably 2.5 or more, still more preferably 2.7 or more, per 1 ⁇ m of thickness.
  • the optical density is measured as follows. First, a colored layer is formed on the glass substrate. This sample is set in an optical density measuring instrument (for example, product name: 361T manufactured by X-rite), and the upper light source located on the colored layer side of the sample is turned on to focus on the colored layer of the sample. After turning off the upper light source, the measurement light source located on the substrate side of the sample is turned on, and the optical density is measured with the colored layer as the measurement region.
  • an optical density measuring instrument for example, product name: 361T manufactured by X-rite
  • the colored layer when the colored layer is partially formed, the colored layer can be formed so that the laminated body is distinguished into a display region and a non-display region.
  • the laminate 200 shown in FIG. 2 includes a front plate 110, a first bonding layer 120, a coloring member 130, a second bonding layer 140, and a circularly polarizing plate 150, and the coloring member 130 includes a protective layer 133 and a coloring layer. 131 and the separating layer 132 are included in this order.
  • the laminated body 200 is divided into a display area A and a non-display area B, and the colored layer 131 is provided in the non-display area B.
  • the protective layer 133 of the coloring member 130 and the first bonding layer 120 are laminated in contact with each other, but in another embodiment, either one of the coloring layer and the separation layer of the coloring member 130 or Both and the first bonding layer 120 may be laminated so as to be in contact with each other.
  • FIG. 3 is a schematic top view of the laminated body 200 as viewed from the colored layer side in a plan view.
  • the laminated body 200 is divided into a display area A201 and a non-display area B202.
  • the display area A of the laminated body 200 is an area where the image is visually recognized
  • the non-display area B is an area where the image is not visually recognized. Therefore, it may be required that electrodes, wiring, and the like are arranged in the non-display area B, and that light leakage from a display unit provided in the image display device is suppressed.
  • the colored layer 131 provided in the non-display region B has a concealing property such as electrodes and wiring and a sufficient shielding property to be able to suppress light leakage.
  • the plan view means the view from the thickness direction of the layer.
  • the width W of the colored layer 131 can be, for example, 0.5 mm or more, and is 3 mm or more. It may be 5 mm or more, and usually 80 mm or less, 60 mm or less, 50 mm or less, 30 mm or less, or 20 mm or less. ..
  • the end region of the colored layer 131 of the laminated body 200 on the display region A side may have a tapered portion so that the thickness increases in the direction from the end on the display region A side toward the inside of the colored layer 131. Since the colored layer has a tapered portion, it tends to be easy to suppress the biting of air bubbles when the first bonding layer 120 and the coloring member 130 are bonded to each other.
  • the colored layer 131 can be formed by a photolithography method or the like using an active energy ray-curable resin composition.
  • the composition for forming a colored layer can contain, for example, a colorant, a binder resin, a solvent, and any additive.
  • the composition for forming a colored layer is an active energy ray-curable type, the composition for forming a colored layer further contains an active energy ray-polymerizable compound. Further, if necessary, a photopolymerization initiator, a photosensitizer, or the like may be contained.
  • the colorant examples include carbon black such as acetylene black, iron black, titanium dioxide, zinc flower, petals, chrome vermilion, ultramarine, cobalt blue, yellow lead, titanium yellow and other inorganic pigments; phthalocyanine blue and induslen.
  • Organic pigments or dyes such as blue, isoindolinone yellow, benzidine yellow, quinacridone red, polyazo red, perylene red, aniline black; metal pigments consisting of scaly foil pieces such as aluminum and brass; titanium dioxide-coated mica, basic lead carbonate
  • pearl luster pigments pearl pigments
  • binder resin examples include chlorinated polyolefins (for example, chlorinated polyethylene and chlorinated polypropylene), polyester resins, urethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, and cellulose resins. Be done.
  • the binder resin may be used alone or in combination of two or more.
  • the binder resin may be a heat-polymerizable resin or a photopolymerizable resin.
  • the separation layer 132 has a function for facilitating the separation of the coloring member 130 from the support used in the process of producing the coloring layer 131.
  • the separation layer 132 can be, for example, an inorganic layer or an organic layer. These layers can be formed by a spin coating method, a sputtering method, a vapor deposition method or the like. Examples of the material forming the inorganic layer include silicon oxide. Examples of the material for forming the organic material layer include (meth) acrylic resin compositions, epoxy resin compositions, and polyimide resin compositions.
  • the thickness of the separation layer 132 may be, for example, 0.01 ⁇ m or more and 1 ⁇ m or less, preferably 0.05 ⁇ m or more and 0.5 ⁇ m or less.
  • the protective layer 133 can have a function of protecting the colored layer 131. As shown in FIG. 2, when the protective layer is formed so as to cover the side surface of the colored layer, the protective layer 133 has a function of protecting the colored layer and flattening the step caused by the colored layer 131. Can be done.
  • the protective layer 133 can be an organic layer or an inorganic layer. As the materials for the inorganic layer and the organic layer, the same materials as those shown in the description of the separation layer 132 can be used. These layers can be formed by a spin coating method, a sputtering method, a vapor deposition method or the like.
  • the thickness of the protective layer 133 may be, for example, 0.1 ⁇ m or more and 10 ⁇ m or less, preferably 0.5 ⁇ m or more and 5 ⁇ m or less.
  • the protective layer may be formed between the separation layer and the coloring layer.
  • the second bonding layer 140 is a layer for bonding the coloring member 130 and the circularly polarizing plate 150. In the laminated body 100, the coloring member 130 and the circularly polarizing plate 150 are joined via the second bonding layer 140.
  • the examples and preferable ranges of the adhesive, the pressure-sensitive adhesive and the pressure-sensitive adhesive composition constituting the second bonding layer 140, the examples and the preferable ranges in the description of the first bonding layer 120 are applied.
  • the storage elastic modulus G'b of the second bonded layer 140 at a temperature of 25 ° C. may be, for example, 0.01 MPa or more and 5 MPa or less, preferably 0.02 MPa or more and 3 MPa or less, and more preferably 0.03 MPa or more and 1.5 MPa. It may be 0.1 MPa or more, or 0.2 MPa or more.
  • the storage elastic modulus G'a of the second bonded layer 140 can be adjusted, for example, by selecting the material used to form the second bonded layer 140.
  • the second bonding layer is preferably an adhesive layer.
  • the circular polarizing plate 150 may include a linear polarizing plate and a retardation layer, and the linear polarizing plate may be arranged on the first bonding layer 120 side and the retardation layer may be arranged on the second bonding layer 140 side. can.
  • the circularly polarizing plate 150 can convert light (external light) incident through the laminated body 100 from the visual side of the image display device including the laminated body 100 into circularly polarized light. Further, since the circularly polarizing plate 150 can absorb the external light reflected by the display element in the image display device, the laminated body 100 can be provided with a function as an antireflection film.
  • the linear polarizing plate has a function of selectively transmitting linearly polarized light in a certain direction from unpolarized light rays such as natural light.
  • the linear polarizing plate 130 may include a stretched film on which a dichroic dye is adsorbed, a film coated with a composition containing the dichroic dye and a polymerizable compound, and the like as a polarizer.
  • a composition containing a dichroic dye having a liquid crystal property or a composition containing a dichroic dye and a polymerizable liquid crystal is used as the film obtained by applying and curing the composition containing the dichroic dye and the polymerizable compound.
  • a film or the like having a layer obtained by coating and curing can be used.
  • iodine or a dichroic organic dye can be used as the dichroic dye.
  • dichroic organic dyes C.I. I. Included are dichroic direct dyes made of disuazo compounds such as DIRECT RED 39 and dichroic direct dyes made of compounds such as trisazo and tetrakisazo.
  • a film coated with a composition containing a dichroic dye and a polymerizable compound and cured is preferable because there is no limitation in the bending direction as compared with a stretched film on which a dichroic dye is adsorbed.
  • the stretched film on which the dichroic dye is adsorbed is usually a step of uniaxially stretching the polyvinyl alcohol-based resin film and a step of adsorbing the dichroic dye by dyeing the polyvinyl alcohol-based resin film with the dichroic dye.
  • the stretched film produced by the above step on which the dichroic dye is adsorbed may be used as it is as a linear polarizing plate, or may be used as a linear polarizing plate after a transparent protective film is attached to one or both sides thereof. ..
  • the thickness of the polarizer (stretched film on which the dichroic dye is adsorbed) thus obtained is preferably 2 ⁇ m or more and 40 ⁇ m or less.
  • the polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin.
  • a polyvinyl acetate-based resin in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith is used.
  • examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.
  • the saponification degree of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more.
  • the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal, polyvinyl acetal, etc. modified with aldehydes can be used.
  • the degree of polymerization of the polyvinyl alcohol-based resin is usually about 1000 to 10000, preferably in the range of 1500 to 5000.
  • a film of such a polyvinyl alcohol-based resin By forming a film of such a polyvinyl alcohol-based resin, it is possible to obtain a raw film (that is, a polyvinyl alcohol-based resin film) as a material for a polarizer.
  • the method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method.
  • the film thickness of the polyvinyl alcohol-based resin film can be, for example, about 10 ⁇ m to 150 ⁇ m.
  • the uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, at the same time as dyeing, or after dyeing.
  • the uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment.
  • rolls having different peripheral speeds may be uniaxially stretched, or thermal rolls may be used to uniaxially stretch the rolls.
  • the uniaxial stretching may be a dry stretching in which the stretching is performed in the atmosphere, or a wet stretching in which the polyvinyl alcohol-based resin film is swollen using a solvent.
  • the draw ratio is usually about 3 to 8 times.
  • the thickness of the linear polarizing plate provided with the stretched film as a polarizer may be, for example, 1 ⁇ m or more, 5 ⁇ m or more, or 7 ⁇ m or more.
  • the thickness of the linear polarizing plate provided with the stretched film as a polarizer may be 100 ⁇ m or less, 50 ⁇ m or less, 20 ⁇ m or less, or 10 ⁇ m or less.
  • the material of the transparent protective film to be bonded to one side or both sides of the polarizer is not particularly limited, but for example, a cyclic polyolefin resin film, a cellulose acetate resin film made of a resin such as triacetyl cellulose or diacetyl cellulose, or polyethylene terephthalate. , Polyethylene naphthalate, polyester resin film made of resin such as polybutylene terephthalate, polycarbonate resin film, (meth) acrylic resin film, polypropylene resin film and other films known in the art. .. From the viewpoint of thinning, the thickness of the transparent protective film is usually 300 ⁇ m or less, preferably 200 ⁇ m or less, and more preferably 100 ⁇ m or less. The thickness of the transparent protective film is usually 5 ⁇ m or more, preferably 20 ⁇ m or more. The transparent protective film may or may not have a phase difference.
  • an overcoat layer may be formed on one side or both sides of the polarizer.
  • the overcoat layer can be obtained by applying an adhesive used as a bonding layer described later.
  • the thickness of the overcoat layer is, for example, 10 ⁇ m or less, preferably 5 ⁇ m or less.
  • the thickness of the overcoat layer is, for example, 0.01 ⁇ m or more, preferably 0.1 ⁇ m or more.
  • a linear polarizing plate in which a film obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound serves as a polarizer will be described.
  • a film obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound a composition containing a dichroic dye having a liquid crystal property as described above, or a dichroic dye and a polymerizable liquid crystal may be used.
  • a film having a layer obtained by applying the containing composition on a base film and curing it hereinafter, these are collectively referred to as "film formed from a liquid crystal layer" or the like can be used.
  • An orientation layer may be formed between the base film and the coating layer.
  • the film formed from the liquid crystal layer may be used as a linear polarizing plate by peeling off the base material or used as a linear polarizing plate together with the base material, or may be used as a linear polarizing plate after a transparent protective film is attached to one or both sides thereof. good.
  • the transparent protective film the same material as the transparent protective film in which the above-mentioned stretched film is bonded to a linear polarizing plate serving as a polarizer can be used.
  • the film formed from the liquid crystal layer include the films described in JP2013-37353A, JP2013-33249, and the like.
  • the film formed from the liquid crystal layer is preferably thin, but if it is too thin, the strength tends to decrease and the processability tends to be inferior.
  • the thickness of the film is usually 20 ⁇ m or less, preferably 5 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 3 ⁇ m or less.
  • the thickness of the linear polarizing plate in which the film formed from the liquid crystal layer serves as a polarizer may be, for example, 1 ⁇ m or more and 50 ⁇ m or less.
  • the retardation layer may be one layer or two or more layers.
  • the retardation layer may have an overcoat layer that protects the surface thereof, a base film that supports the retardation layer, and the like.
  • the retardation layer includes a ⁇ / 4 layer, and may further include at least one of a ⁇ / 2 layer and a positive C layer.
  • the retardation layer includes a ⁇ / 2 layer, the ⁇ / 2 layer and the ⁇ / 4 layer are laminated in order from the linear polarizing plate side.
  • the ⁇ / 4 layer and the positive C layer may be laminated in order from the linear polarizing plate side, or the positive C layer and the ⁇ / 4 layer may be laminated in order from the linear polarizing plate side. May be good.
  • the thickness of the retardation layer may be, for example, 0.1 ⁇ m or more and 10 ⁇ m or less, preferably 0.5 ⁇ m or more and 8 ⁇ m or less, and more preferably 1 ⁇ m or more and 6 ⁇ m or less.
  • the retardation layer may be formed from the resin film exemplified as the material of the transparent protective film described above, or may be formed from a layer in which the polymerizable liquid crystal compound is cured.
  • the retardation layer may further include an alignment layer and a base film, and may have a bonding layer described later for bonding the ⁇ / 4 layer, the ⁇ / 2 layer, and the positive C layer. good.
  • the retardation layer When the retardation layer is formed from a layer obtained by curing a polymerizable liquid crystal compound, it can be formed by applying a composition containing the polymerizable liquid crystal compound to a base film and curing it. An orientation layer may be formed between the base film and the coating layer. The material and thickness of the base film may be the same as the material and thickness of the resin film (the transparent protective film).
  • the retardation layer When the retardation layer is formed from a layer obtained by curing a polymerizable liquid crystal compound, the retardation layer may be incorporated into the laminate 100 in the form of having an alignment layer and a base film.
  • the retardation layer can be bonded to the linear polarizing plate via the bonding layer described later.
  • the bonding layer is a layer composed of a pressure-sensitive adhesive or an adhesive.
  • each layer can be bonded in a retardation layer, or a touch sensor panel described later can be bonded to the circularly polarizing plate side of the laminated body.
  • the adhesive or pressure-sensitive adhesive used as the material of the bonding layer the adhesive or pressure-sensitive adhesive exemplified in the description of the first bonding layer 120 can be used.
  • a (meth) acrylic pressure-sensitive adhesive a (meth) acrylic pressure-sensitive adhesive, a styrene-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive, which are different from the materials of other pressure-sensitive adhesives, for example, the first bonding layer 120 and the second bonding layer 140.
  • Urethane-based pressure-sensitive adhesives polyester-based pressure-sensitive adhesives, epoxy-based copolymer pressure-sensitive adhesives, and the like can also be used.
  • the thickness of the bonding layer is not particularly limited, but when the pressure-sensitive adhesive layer is used as the bonding layer, it is preferably 10 ⁇ m or more, 15 ⁇ m or more, 20 ⁇ m or more, 25 ⁇ m or more. It may be usually 200 ⁇ m or less, 100 ⁇ m or less, or 50 ⁇ 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 5 ⁇ m or less. May be good.
  • the laminated body 100 can further include a touch sensor layer 170 on the circularly polarizing plate 150 side.
  • the touch sensor layer 170 can be laminated on the circularly polarizing plate 150 side via the bonding layer 160.
  • the touch sensor layer 170 may be any method as long as it can detect the position touched by the front plate, which will be described later, and an example thereof includes a capacitance coupling method. Capacitive coupling type touch sensor panels are preferably used because of their low cost and high touch sensitivity.
  • An example of a capacitance coupling type touch sensor panel is composed of a base material layer, a translucent electrode layer for position detection provided on the base material layer, and a touch position detection circuit.
  • a capacitance coupling type touch sensor panel for example, when the surface of the front plate described later is touched, the translucent electrode is grounded via the capacitance of the human body at the touched point. Will be done.
  • the touch position detection circuit detects the grounding of the translucent electrode, and the touched position is detected.
  • the touch sensor layer 170 for example, the above-mentioned resistance film type or capacitance coupling type touch sensor panel is formed on a glass plate via a separation layer, and a base material layer (release film) is provided on the touch sensor panel. Later, the glass plate can be separated from the separation layer to manufacture a touch sensor layer having a layer structure of a touch sensor panel / separation layer. This base material layer is usually removed when the touch sensor layer 170 is incorporated into the laminate 100. Another base material layer can be provided on the separation layer obtained by separating and exposing the glass plate.
  • the touch sensor panel may further include a base material layer, an insulating layer, a protective layer, wiring, and a bonding layer.
  • the surface resistance of the translucent electrode layer can be 90 ⁇ / ⁇ or less.
  • the translucent electrode layer may be a translucent electrode layer made of a metal oxide such as ITO (indium tin oxide), and may be aluminum, copper, silver, gold, palladium or an alloy thereof [for example, silver-palladium-copper alloy]. (APC)] or the like may be a metal layer made of a metal.
  • the translucent electrode layer may be patterned by a photolithography method.
  • the touch sensor layer 170 may have one or more translucent electrode layers.
  • the translucent electrode layer may be a single layer or a multi-layer, and when it is a multi-layer, the materials forming each layer may be the same type or different types. From the viewpoint of translucency and surface resistance, the translucent electrode layer is preferably a patterned ITO film, an APC film, or a film in which these are combined.
  • Base layer examples of the base material layer include a base material film in which a translucent electrode layer is vapor-deposited on one surface, a base film in which a translucent electrode layer is transferred via an adhesive layer, and the like.
  • a structure may be configured in which the separation layer described later is used as the base material layer and does not have another base material film.
  • the base film is not limited as long as it is a resin film capable of transmitting light.
  • cyclic polyolefin resin film cellulose acetate resin film made of resins such as triacetyl cellulose and diacetyl cellulose, polyester resin film made of resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, and polycarbonate resin.
  • films known in the art such as films, (meth) acrylic resin films, and polypropylene resin films can be mentioned. Of these, a cyclic polyolefin resin film is preferable.
  • the thickness of the base film is usually 300 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and usually 5 ⁇ m or more, preferably 10 ⁇ m or more.
  • the base material layer may be removed from the touch sensor layer 170 after incorporating the translucent electrode layer into the touch sensor layer 170.
  • the separation layer can be a layer formed on a substrate such as a glass plate and for separating the translucent electrode layer 14 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 the material 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 the material for forming the organic material layer.
  • the separation layer may be removed together with the substrate so that it is not included in the touch sensor layer 170.
  • the insulating layer can be formed so as to cover the translucent electrode layer 14.
  • the insulating layer can be formed from at least one material selected from the group consisting of curable prepolymers, curable polymers and plastic polymers.
  • the insulating layer can also be formed from a film-forming varnish-type material.
  • the varnish type material may include at least one selected from the group consisting of polysilicone, polyimide, and polyurethane materials.
  • the insulating layer may be an adhesive layer described later.
  • the insulating layer may be patterned by a photolithography method.
  • the insulating layer may be a single layer or a multi-layer, and when the insulating layer is a multi-layer, the materials forming each layer may be the same type or different types.
  • the bonding layer can be a layer formed from the adhesive or adhesive described above.
  • the wiring can be arranged in the touch sensor panel to electrically connect the touch position detection circuit and the translucent electrode layer 14.
  • the wiring can be a pattern of metal films.
  • the metal film can be formed by patterning a metal film obtained by forming a metal such as aluminum, copper, silver, gold, or an alloy thereof by a sputtering method or a vapor deposition method by a photolithography method or an etching method.
  • the wiring can be installed on the translucent electrode layer 14.
  • the laminated body 100 is formed by a method including a step of laminating layers constituting the laminated body 100 via a first laminating layer and a second laminating layer composed of an adhesive layer or an adhesive layer, and a bonding layer. Can be manufactured.
  • a surface activation treatment such as a corona treatment to either or both of the bonded surfaces in order to improve the adhesion.
  • the circularly polarizing plate 150 can also be manufactured by directly forming the linear polarizing plate and the retardation layer forming the circularly polarizing plate 150 on the resin film or the base film as described above.
  • the resin film or the base film may be incorporated into the flexible laminated body 100, or may not be peeled off from the circularly polarizing plate 150 to become a component of the flexible laminated body 100.
  • the coloring member 130 can be manufactured, for example, as follows. First, a separation layer is formed on a support such as a glass plate. Next, a colored layer is formed on the separation layer by a photolithography method using an active energy ray-curable resin composition. A peelable resin film is laminated on the outermost surface on the side opposite to the glass plate side, and the colored layer to the separation layer are transferred to the peelable resin film to separate the glass plate. Then, a peelable resin film is attached to the peeled surface of the glass plate. In the photolithography method, the active energy ray-curable resin composition can be applied to the separation layer, the coating film of the photosensitive resin composition can be exposed, then developed, and then fired. As the exposure light source, a mercury vapor arc, a carbon arc, an Xe arc, or the like that emits light having a wavelength of 250 nm or more and 450 nm or less can be used.
  • the touch sensor layer 170 can be manufactured, for example, as follows. First, a separation layer is formed on the glass plate. A translucent electrode layer, wiring, and an insulating layer are formed on the separation layer in this order. A peelable resin film is laminated on the outermost surface on the side opposite to the glass plate side, and the insulating layer to the separation layer are transferred to the peelable resin film to separate the glass plate. Next, a base material layer is prepared, and the base material layer and the separation layer are bonded together via an adhesive layer. By peeling off the peelable resin film, a touch sensor layer 170 having an insulating layer, wiring, a translucent electrode layer, a separating layer, an adhesive layer, and a base material layer in this order can be obtained. It is also possible to form another translucent electrode layer on the insulating layer and form another insulating layer on the other translucent electrode layer.
  • the image display device includes the above-mentioned laminated body.
  • the image display device is not particularly limited, and examples thereof include an image display device such as an organic EL display device, an inorganic EL display device, a liquid crystal display device, and an electroluminescent display device.
  • the image display device may have a touch panel function.
  • the laminate is suitable for a flexible image display device capable of bending or bending. In the image display device, the laminate is arranged on the visual side of the image display device with the front plate facing the outside (the side opposite to the image display element side, that is, the visual recognition side).
  • the image display device according to the present invention can be used as a mobile device such as a smartphone or tablet, a television, a digital photo frame, an electronic signboard, a measuring instrument or an instrument, an office device, a medical device, a computer device, or the like.
  • the image display device according to the present invention has excellent flexibility and is therefore suitable for a flexible display or the like.
  • FIG. 5 is a diagram schematically showing the method of this evaluation test. As shown in FIG. 5, two individually movable mounting tables 501 and 502 were arranged in the gap C1, and the laminated body 500 was fixedly arranged so that the center in the width direction was located at the center of the gap C. (Fig. 5 (a)). At this time, the laminated body 500 was arranged so that the front plate side was on the upper side.
  • the two mounting tables 501 and 502 are rotated 90 degrees upward with the positions P1 and P2 as the centers of the rotation axes, and a bending force is applied to the region of the laminated body 500 corresponding to the gap C of the mounting tables.
  • the distance C2 between the facing front plates is set to 2.0 mm (FIG. 5 (b)).
  • the two mounting tables 501 and 502 were returned to their original positions (FIG. 5 (a)).
  • the number of times the bending force was applied was counted as one.
  • C A crack occurred when the number of bendings was 300,000 or more and less than 400,000.
  • D The number of bendings was less than 300,000, and cracks occurred. I went as.
  • the measurement was performed using a contact type film thickness measuring device (“MS-5C” manufactured by Nikon Corporation). However, the retardation layer and the alignment layer were measured using a laser microscope (LEXT, manufactured by Olympus Corporation).
  • the measurement sample was placed on a rheometer (Anton Parr, MCR-301), and the storage elastic modulus was measured under the conditions of a temperature of 25 ° C., a relative humidity of 50%, a stress of 1%, and a frequency of 1 Hz.
  • the object of measurement was an adhesive layer
  • the adhesive layers were stacked so as to have a thickness of 150 ⁇ m to prepare a sample for measurement.
  • an adhesive was applied onto the glass so as to have a thickness of 5 ⁇ m, and a plate, which is a rheometer jig, was placed on the adhesive. In this state, the adhesive was cured by heating or irradiating ultraviolet rays from the glass side to prepare a sample for measurement.
  • the weight average molecular weight (Mw) of the (meth) acrylic resin was determined by the following size exclusion chromatography (SEC) using tetrahydrofuran as the mobile phase as the polystyrene-equivalent number average molecular weight (Mn).
  • SEC size exclusion chromatography
  • the (meth) acrylic polymer to be measured was dissolved in tetrahydrofuran at a concentration of about 0.05% by mass, and 10 ⁇ L was injected into SEC.
  • the mobile phase was flowed at a flow rate of 1.0 mL / min.
  • PLgel MIXED-B manufactured by Polymer Laboratories
  • a UV-VIS detector (trade name: Agilent GPC) was used as the detector.
  • Adhesive Sheet 1 A mixed solution of 80 parts of ethyl acetate, 70 parts of butyl acrylate, 20 parts of methyl acrylate, and 1.0 part of acrylic acid is charged in a reactor equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and is charged with nitrogen gas. The internal temperature was raised to 55 ° C. while replacing the air in the apparatus with oxygen-free. Then, a total amount of a solution prepared by dissolving 0.2 part of a radical polymerization initiator (2,2'-azobisisobutyronitrile) in 10 parts of acetone was added. One hour after the addition of the initiator, the internal temperature was 54 to 56 ° C.
  • a radical polymerization initiator (2,2'-azobisisobutyronitrile
  • the obtained acrylic resin had a weight average molecular weight Mw of 1,500,000 and Mw / Mn of 5.0.
  • a cross-linking agent (“Coronate L” manufactured by Tosoh Corporation) and 0.5 part of a silane coupling agent (“X-12-981” manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. Ethyl acetate was added so that the total solid content concentration became 10% to obtain a pressure-sensitive adhesive composition.
  • the coating solution of the obtained pressure-sensitive adhesive composition was applied to the release-treated surface of the release-treated polyethylene terephthalate film (release film B) using an applicator so that the thickness after drying was 50 ⁇ m.
  • the coating layer was dried at 100 ° C. for 1 minute to obtain a film having an adhesive layer.
  • another release-treated polyethylene terephthalate film (release film A) was attached onto the exposed surface of the pressure-sensitive adhesive layer. Then, it was cured for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 50% RH.
  • the pressure-sensitive adhesive sheet 1 having the structure of the release film B / the pressure-sensitive adhesive layer (thickness 50 ⁇ m) / the release film A was produced.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 1 is referred to as the pressure-sensitive adhesive layer 1.
  • the storage elastic modulus of the pressure-sensitive adhesive layer 1 at a temperature of 25 ° C. was 0.047 MPa.
  • the obtained acrylic resin had a weight average molecular weight Mw of 1,650,000 and Mw / Mn of 4.1. 100 parts of the obtained acrylic resin (nonvolatile content), 0.2 parts of Coronate L (Tosoh Corporation) as an isocyanate compound, and KBM403 (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) as a silane compound. (Obtained from Co., Ltd.) 0.5 parts were mixed. Ethyl acetate was added so that the total solid content concentration became 10% to obtain a pressure-sensitive adhesive composition.
  • the release film B / adhesive is the same as in the production of the pressure-sensitive adhesive sheet 1, except that the pressure-sensitive adhesive composition is used and the coating solution of the pressure-sensitive adhesive composition is applied so as to have a thickness of 5 ⁇ m after drying.
  • An adhesive sheet 2 having a composition of an agent layer (thickness: 5 ⁇ m) / release film A was prepared.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 2 is referred to as the pressure-sensitive adhesive layer 2.
  • the storage elastic modulus of the pressure-sensitive adhesive layer 2 at a temperature of 25 ° C. was 0.6 MPa.
  • the release film B / adhesive layer (thickness: 25 ⁇ m) / release film is the same as in the production of the pressure-sensitive adhesive sheet 1, except that the coating solution of the pressure-sensitive adhesive composition is applied so that the thickness after drying is 25 ⁇ m.
  • An adhesive sheet 3 having the configuration of A was produced.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 3 is referred to as the pressure-sensitive adhesive layer 3.
  • the storage elastic modulus of the pressure-sensitive adhesive layer 3 at a temperature of 25 ° C. was 0.047 MPa.
  • the pressure-sensitive adhesive sheet 4 having the composition of the release film B / the pressure-sensitive adhesive layer (thickness: 1.7 ⁇ m) / the release film A was produced.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 4 is referred to as the pressure-sensitive adhesive layer 4.
  • the storage elastic modulus of the pressure-sensitive adhesive layer 4 at a temperature of 25 ° C. was 1.5 MPa.
  • Adhesive Sheet 5 81.8 parts of acetone, 70.8 parts of butyl acrylate, 20 parts of methyl methacrylate, 2- (2-phenylethoxy) ethyl acrylate in a reactor equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer. ) A mixed solution of 8 parts, 1.0 part of 4-hydroxybutyl acrylate and 0.2 part of acrylic acid was prepared, and the internal temperature was raised to 55 ° C. while replacing the air in the apparatus with nitrogen gas to make it oxygen-free. I raised it.
  • the release film B / adhesive is the same as in the production of the pressure-sensitive adhesive sheet 1, except that the pressure-sensitive adhesive composition is used and the coating solution of the pressure-sensitive adhesive composition is applied so as to have a thickness of 50 ⁇ m after drying.
  • An adhesive sheet 5 having a composition of an agent layer (thickness: 50 ⁇ m) / release film A was produced.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 5 is referred to as the pressure-sensitive adhesive layer 5.
  • the storage elastic modulus of the pressure-sensitive adhesive layer 5 at a temperature of 25 ° C. was 0.136 MPa.
  • thermosetting adhesive A thermosetting adhesive was prepared.
  • the storage elastic modulus of the thermosetting adhesive layer at a temperature of 25 ° C. was 6.8 MPa.
  • UV curable adhesive The following components were mixed and defoamed to prepare a UV curable adhesive.
  • 3', 4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (trade name: CEL2021P, manufactured by Daicel Co., Ltd.): 70 parts by mass Neopentyl glycol diglycidyl ether (trade name: EX-211, Nagase ChemteX Co., Ltd.) (Manufactured by the company): 20 parts by mass 2-ethylhexyl glycidyl ether (trade name: EX-121, manufactured by Nagase ChemteX Corporation): 10 parts by mass cationic polymerization initiator (trade name: CPI-100, manufactured by San Apro Co., Ltd.): Solid Quantity 2.25 parts by mass (blended as a 50% propylene carbonate solution) 1,4-Diethoxynaphthalene: 2 parts by mass
  • composition 1 for forming a colored layer A composition for forming an active energy ray-curable colored layer containing carbon black (“CR-BK0951L” manufactured by Samsung SDI Co., Ltd.) was prepared.
  • Example 1 Preparation of front plate
  • a transparent base film polyamideimide film, thickness 40 ⁇ m
  • a hard coat layer a transparent base film (polyamideimide film, thickness 40 ⁇ m) prepared according to Example 4 of JP-A-2018-119141 is coated with the following composition for a hard coat layer, and then the solvent is dried to obtain UV.
  • a front plate thickness 50 ⁇ m
  • a hard coat layer having a thickness of 10 ⁇ m formed on one side of the base film was produced.
  • Composition for forming a hard coat layer 30 parts by mass of multifunctional acrylate (MIWON Specialty Chemical, MIRAMER M340), 50 parts by mass of nanosilica sol (particle size 12 nm, solid content 40%) dispersed in propylene glycol monomethyl ether, ethyl acetate 17 A part by mass, 2.7 parts by mass of a photopolymerization initiator (BASF, I184), and 0.3 parts by mass of a fluorine-based additive (Shinetsu Chemical Industry Co., Ltd., KY1203) are blended using a stirrer to mix polypropylene (PP). Manufactured by filtering with a filter of material.
  • MIWON Specialty Chemical, MIRAMER M340 50 parts by mass of nanosilica sol (particle size 12 nm, solid content 40%) dispersed in propylene glycol monomethyl ether, ethyl acetate 17 A part by mass, 2.7 parts by mass of a photopolymerization initiator (BASF
  • a polyvinyl alcohol (PVA) film having an average degree of polymerization of about 2,400, a saponification degree of 99.9 mol% or more, and a thickness of 20 ⁇ m was prepared. After immersing the PVA film in pure water at 30 ° C, it was immersed in an aqueous solution having a mass ratio of iodine / potassium iodide / water of 0.02 / 2/100 at 30 ° C to perform iodine dyeing (iodine dyeing step). ..
  • the PVA film that had undergone the iodine dyeing step was immersed in an aqueous solution having a mass ratio of potassium iodide / boric acid / water of 12/5/100 at 56.5 ° C. to perform boric acid treatment (boric acid treatment step). ..
  • the PVA film that had undergone the boric acid treatment step was washed with pure water at 8 ° C. and then dried at 65 ° C. to obtain a polarizer in which iodine was adsorbed and oriented on polyvinyl alcohol.
  • the PVA film was stretched in the iodine dyeing step and the boric acid treatment step.
  • the total draw ratio of the PVA film was 5.3 times.
  • the thickness of the obtained polarizer was 7 ⁇ m.
  • the polarizer obtained above and a cycloolefin polymer (COP) film (ZF-14, manufactured by Nippon Zeon Corporation, having an in-plane retardation value of 1 nm at a wavelength of 550 nm) having a thickness of 13 ⁇ m are placed on a nip roll via an aqueous adhesive. I pasted them together. While maintaining the tension of the obtained laminate at 430 N / m, it was dried at 60 ° C. for 2 minutes to obtain a linear polarizing plate having a COP film on one side.
  • COP cycloolefin polymer
  • the water-based adhesive is 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol ("Kuraray Poval KL318", manufactured by Kuraray Co., Ltd.) and water-soluble polyamide epoxy resin ("Smiley's resin 650" (solid content concentration 30%). (Aqueous solution) and 1.5 parts (manufactured by Taoka Chemical Industry Co., Ltd.) were added to prepare.
  • the polarizer side of the linear polarizing plate and the retardation layer were bonded to each other via an acrylic pressure-sensitive adhesive layer having a thickness of 5 ⁇ m.
  • the retardation layer has a thickness of 5 ⁇ m
  • the layer structure includes a ⁇ / 2 layer (thickness 2 ⁇ m) including a layer obtained by curing the liquid crystal compound / a UV curable adhesive layer (thickness 2 ⁇ m) / a layer obtained by curing the liquid crystal compound. It was a ⁇ / 4 layer (thickness 1 ⁇ m). In this way, a circularly polarizing plate (thickness 30 ⁇ m, layer structure: COP film / polarizer / retardation layer) was produced.
  • a glass plate (support) was coated with an acrylic resin to form a separation layer (thickness: 2 ⁇ m).
  • the colored layer is partially (frame-shaped) formed on the separation layer by patterning the colored layer on the separation layer by a photolithography method so that the thickness after drying becomes 1.5 ⁇ m using the composition 1 for forming the colored layer. bottom.
  • the surface on the colored layer side was coated with the composition of Example 1 in JP-A-2016-014877 to form a protective layer (thickness: 2 ⁇ m).
  • a colored member having a layer structure of a protective layer / a colored layer / a separated layer was formed on the support.
  • the release film A was laminated on the protective layer.
  • the release film B was attached to the surface from which the glass plate was peeled off to obtain a colored member laminate having a layer structure of the release film A / coloring member (protective layer / coloring layer / separation layer) / release film B.
  • the photolithography method includes a composition coating step for forming a colored layer, an exposure step, a developing step, and a thermosetting step.
  • a glass plate was coated with an acrylic resin to form a separation layer.
  • a translucent electrode layer was formed on the separation layer, and a touch sensor layer (thickness 7 ⁇ m) composed of the translucent electrode layer and the separation layer was produced.
  • the release film A was laminated on the side of the translucent electrode layer opposite to the separation layer side.
  • the release film B was laminated on the surface from which the glass plate was removed to prepare a touch sensor laminate having a layer structure of the release film A / touch sensor layer / release film B.
  • a colored polyimide film (thickness 50 ⁇ m) was laminated on one surface of the colored polyimide film (thickness 35 ⁇ m) via a bonding layer (thickness 25 ⁇ m) composed of an adhesive layer to prepare a substitute for an organic EL panel (thickness 110 ⁇ m). ..
  • This image display device includes a front plate (thickness 50 ⁇ m), an adhesive layer 1 (thickness 50 ⁇ m), a coloring member (thickness 5.5 ⁇ m), an adhesive layer 2 (thickness 5.0 ⁇ m), a circular polarizing plate (thickness 30 ⁇ m), and the like.
  • a bonding layer composed of an adhesive layer (thickness 25 ⁇ m), a touch sensor layer (thickness 7 ⁇ m), a bonding layer composed of an adhesive layer (thickness 25 ⁇ m), and a substitute for an organic EL panel (thickness 110 ⁇ m) are included in this order, and the total thickness thereof is included.
  • the total thickness thereof is included.
  • the pressure-sensitive adhesive layer 1 was laminated so as to be in contact with the transparent base film of the front plate and the protective layer of the coloring member.
  • the pressure-sensitive adhesive layer 2 was laminated so as to be in contact with the separation layer of the coloring member and the COP film of the circularly polarizing plate. That is, the coloring member has a protective layer, a coloring layer, and a separation layer in this order from the front plate side.
  • a flexibility test and an evaluation of rainbow unevenness were performed on the laminated body. The results are shown in Table 1.
  • Example 2 and 3 A laminate was prepared in the same procedure as in Example 1 except that the pressure-sensitive adhesive sheet was changed so that the second bonding layer became the pressure-sensitive adhesive layer shown in Table 1. A flexibility test and an evaluation of rainbow unevenness were performed on the laminated body. The results are shown in Table 1.
  • Example 1 A laminate was prepared in the same procedure as in Example 1 except that the second bonded layer was cured by irradiating it with ultraviolet rays using a UV curable adhesive. A flexibility test and an evaluation of rainbow unevenness were performed on the laminated body. The results are shown in Table 1.
  • thermosetting adhesive was used for the first bonding layer, and heat treatment was performed at 90 ° C. for 1 hour to perform bonding, and the second bonding layer became the pressure-sensitive adhesive layer shown in Table 1.
  • a laminate was prepared in the same procedure as in Example 1 except that the adhesive sheet was changed to.
  • a flexibility test and an evaluation of rainbow unevenness were performed on the laminated body. The results are shown in Table 1.

Abstract

The purpose of the present invention is to provide a multilayer body comprising a front surface plate, a first bonding layer, a colored member, a second bonding layer, and a circular polarizing plate, in the listed order, wherein cracks are not easily formed in the colored member if repeated bending is carried out with the front surface plate side as the inner side, and when visually examining the external appearance of the multilayer body from the front surface plate side, rainbow unevenness is not easily seen. The multilayer body includes the front surface plate, the first bonding layer, the colored member, the second bonding layer, and the circular polarizing plate, and fulfills conditions (A) and (B). Condition (A): The ratio G'a/G'b of the storage modulus G'a of the first bonding layer at a temperature of 25°C to the storage modulus G'b of the second bonding layer at a temperature of 25°C is less than 50. Condition (B): The thickness Ta of the first bonding layer and the thickness Tb of the second bonding layer are both greater than 1.0 μm.

Description

積層体Laminate
　本発明は、積層体に関し、さらにはそれを含む画像表示装置に関する。 The present invention relates to a laminated body and further to an image display device including the laminated body.
　液晶表示装置や有機エレクトロルミネッセンス（ＥＬ）表示装置等の表示装置には、電極部等が視認されないようにするために、外縁部に着色層を設けることが知られている（特許文献１）。 It is known that a display device such as a liquid crystal display device or an organic electroluminescence (EL) display device is provided with a colored layer on the outer edge portion in order to prevent the electrode portion and the like from being visually recognized (Patent Document 1).
特開２０１５－０７６０９５号公報Japanese Unexamined Patent Publication No. 2015-076095
　前面板、第１貼合層、着色部材、第２貼合層及び円偏光板をこの順に備える積層体において、前面板側を内側にして繰返しの屈曲を行った場合、着色部材にクラックが生じることがあった。また、前面板側から積層体の外観を目視した場合、光が干渉して虹色のムラ（以下、虹ムラともいう）が視認されることがあった。 In a laminated body provided with a front plate, a first bonding layer, a coloring member, a second bonding layer, and a circularly polarizing plate in this order, cracks occur in the coloring member when repeated bending is performed with the front plate side inside. There was something. Further, when the appearance of the laminated body is visually observed from the front plate side, rainbow-colored unevenness (hereinafter, also referred to as rainbow unevenness) may be visually recognized due to light interference.
　本発明の目的は、前面板、第１貼合層、着色部材、第２貼合層及び円偏光板をこの順に備える積層体であって、前面板側を内側にして繰返しの屈曲を行った場合に着色部材にクラックが生じにくく、かつ前面板側から積層体の外観を目視で観察したときに虹ムラが視認されにくい積層体を提供することである。 An object of the present invention is a laminated body including a front plate, a first bonding layer, a coloring member, a second bonding layer, and a circularly polarizing plate in this order, and the front plate side is turned inside and repeated bending is performed. In this case, it is an object of the present invention to provide a laminated body in which cracks are less likely to occur in the colored member and rainbow unevenness is less likely to be visually observed when the appearance of the laminated body is visually observed from the front plate side.
　本発明は、以下の積層体及び画像表示装置を提供する。
［１］　前面板、第１貼合層、着色部材、第２貼合層、及び円偏光板をこの順に含み、
　条件（Ａ）及び（Ｂ）を満たす、積層体。
　条件（Ａ）：前記第２貼合層の温度２５℃における貯蔵弾性率Ｇ’ｂに対する前記第１貼合層の温度２５℃における貯蔵弾性率Ｇ’ａの比Ｇ’ａ／Ｇ’ｂは５０未満である。
　条件（Ｂ）：前記第１貼合層の厚みＴａ及び前記第２貼合層の厚みＴｂはいずれも１．０μｍ超である。
［２］　条件（Ｃ）をさらに満たす、［１］に記載の積層体。
　条件（Ｃ）：前記第２貼合層の厚みＴｂに対する前記第１貼合層の厚みＴａの比Ｔａ／Ｔｂが０．０３以上５０未満である。
［３］　前記第１貼合層の温度２５℃における貯蔵弾性率Ｇ’ａは、０．０１ＭＰａ以上５ＭＰａ以下である、［１］又は［２］に記載の積層体。
［４］　前記着色部材は、着色層と分離層とを備える、［１］～［３］のいずれかに記載の積層体。
［５］　前記円偏光板側にタッチセンサ層をさらに備える、［１］～［４］のいずれかに記載の積層体。
［６］　［１］～［５］のいずれかに記載の積層体を備える、画像表示装置。 The present invention provides the following laminate and image display device.
[1] The front plate, the first bonding layer, the coloring member, the second bonding layer, and the circularly polarizing plate are included in this order.
A laminate that satisfies the conditions (A) and (B).
Condition (A): The ratio G'a / G'b of the storage elastic modulus G'a at the temperature of the first bonded layer G'a to the storage elastic modulus G'b at the temperature of the second bonded layer at 25 ° C. Less than 50.
Condition (B): The thickness Ta of the first bonded layer and the thickness Tb of the second bonded layer are both more than 1.0 μm.
[2] The laminate according to [1], which further satisfies the condition (C).
Condition (C): The ratio Ta / Tb of the thickness Ta of the first bonded layer to the thickness Tb of the second bonded layer is 0.03 or more and less than 50.
[3] The laminate according to [1] or [2], wherein the storage elastic modulus G'a of the first bonded layer at a temperature of 25 ° C. is 0.01 MPa or more and 5 MPa or less.
[4] The laminate according to any one of [1] to [3], wherein the coloring member includes a coloring layer and a separation layer.
[5] The laminate according to any one of [1] to [4], further comprising a touch sensor layer on the circularly polarizing plate side.
[6] An image display device comprising the laminate according to any one of [1] to [5].
　本発明によれば、前面板、第１貼合層、着色部材、第２貼合層及び円偏光板をこの順に備える積層体であって、前面板側を内側にして繰返しの屈曲を行った場合に着色部材にクラックが生じにくく、かつ前面板側から積層体の外観を目視で観察したときに虹ムラが観察されにくい積層体を提供することができる。 According to the present invention, the laminate is provided with a front plate, a first bonding layer, a coloring member, a second bonding layer, and a circular polarizing plate in this order, and is repeatedly bent with the front plate side inside. In some cases, it is possible to provide a laminated body in which cracks are less likely to occur in the colored member and rainbow unevenness is less likely to be observed when the appearance of the laminated body is visually observed from the front plate side.
本発明の積層体の一例を模式的に示す概略断面図である。It is the schematic sectional drawing which shows an example of the laminated body of this invention schematically. 本発明の積層体の一例を模式的に示す概略断面図である。It is the schematic sectional drawing which shows an example of the laminated body of this invention schematically. 本発明の積層体の概略上面図である。It is a schematic top view of the laminated body of this invention. 本発明の積層体の一例を模式的に示す概略断面図である。It is the schematic sectional drawing which shows an example of the laminated body of this invention schematically. 屈曲性試験の方法を説明する概略図である。It is the schematic explaining the method of a flexibility test.
　以下、図面を参照しつつ本発明の実施形態を説明するが、本発明は以下の実施形態に限定されるものではない。以下の全ての図面においては、各構成要素を理解し易くするために縮尺を適宜調整して示しており、図面に示される各構成要素の縮尺と実際の構成要素の縮尺とは必ずしも一致しない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments. In all the drawings below, the scale is appropriately adjusted to make it easier to understand each component, and the scale of each component shown in the drawings does not necessarily match the scale of the actual component.
　＜積層体＞
　図１を参照しながら、本発明の積層体について説明する。図１に示す積層体１００は、前面板１１０と、第１貼合層１２０と、着色部材１３０と、第２貼合層１４０と、円偏光板１５０とをこの順に備える。第１貼合層１２０と着色部材１３０とは互いに接して積層されている。また、第２貼合層１４０と着色部材１３０とは互いに接して積層されている。積層体１００は、後述する接合層及びタッチセンサ層をさらに有していてもよい。 <Laminated body>
The laminated body of the present invention will be described with reference to FIG. The laminated body 100 shown in FIG. 1 includes a front plate 110, a first bonded layer 120, a coloring member 130, a second bonded layer 140, and a circularly polarizing plate 150 in this order. The first bonding layer 120 and the coloring member 130 are laminated in contact with each other. Further, the second bonding layer 140 and the coloring member 130 are laminated in contact with each other. The laminated body 100 may further have a bonding layer and a touch sensor layer, which will be described later.
　積層体１００は、前面板１１０側を内側にして屈曲すること（以下、インフォールドともいう）が可能である。屈曲することが可能であるとは、着色部材１３０にクラックを生じさせることなく積層体を屈曲させ得ることを意味する。屈曲には、曲げ部分に曲面が形成される折り曲げの形態が含まれる。折り曲げの形態において、折り曲げた内面の屈曲半径は特に限定されない。また、屈曲には、内面の屈折角が０°より大きく１８０°未満である屈折の形態、および内面の屈曲半径がゼロに近似、または内面の屈折角が０°である折り畳みの形態が含まれる。本発明の積層体は、屈曲することが可能であることからフレキシブルディスプレイに好適である。 The laminated body 100 can be bent (hereinafter, also referred to as infold) with the front plate 110 side inward. Being able to bend means that the laminated body can be bent without causing cracks in the coloring member 130. Bending includes a form of bending in which a curved surface is formed on the bent 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 bending angle of the inner surface is greater than 0 ° and less than 180 °, and a form of folding in which the bending radius of the inner surface is close to zero or the bending angle of the inner surface is 0 °. .. The laminate of the present invention is suitable for a flexible display because it can be bent.
　積層体１００は、前面板１１０側を内側にして屈曲半径が１ｍｍで繰返しの屈曲を行ったとき、着色部材１３０にクラックが生じにくい傾向にある。積層体１００は、前面板１１０側を内側にして屈曲半径が１ｍｍで繰返しの屈曲を行ったとき、着色部材１３０に最初にクラックが生じる屈曲回数が好ましくは２０万回以上であり、より好ましくは３０万回以上であり、さらに好ましくは４０万回以上であり、特に好ましくは５０万回以上である。 The laminated body 100 tends to be less likely to crack in the colored member 130 when repeatedly bent with the front plate 110 side inside and a bending radius of 1 mm. When the laminated body 100 is repeatedly bent with the front plate 110 side inside and a bending radius of 1 mm, the number of times that the colored member 130 is first cracked is preferably 200,000 times or more, more preferably 200,000 times or more. It is 300,000 times or more, more preferably 400,000 times or more, and particularly preferably 500,000 times or more.
　積層体１００は、条件（Ａ）及び（Ｂ）を満たす。
　条件（Ａ）：第２貼合層１４０の温度２５℃における貯蔵弾性率Ｇ’ｂに対する第１貼合層１２０の温度２５℃における貯蔵弾性率Ｇ’ａの比Ｇ’ａ／Ｇ’ｂは５０未満である。
　条件（Ｂ）：第１貼合層１２０の厚みＴａ及び第２貼合層１４０の厚みＴｂはいずれも１．０μｍ超である。
　積層体１００は条件（Ａ）及び（Ｂ）をいずれも満たすことにより、前面板１１０側を内側にして屈曲半径が１ｍｍで繰返しの屈曲を行ったとき、着色部材１３０にクラックが生じにくくなるとともに、前面板側から積層体１００の外観を目視で観察したときに虹ムラが視認されにくくなる。 The laminated body 100 satisfies the conditions (A) and (B).
Condition (A): The ratio G'a / G'b of the storage elastic modulus G'a of the first bonded layer 120 at a temperature of 25 ° C. to the storage elastic modulus G'b of the second bonded layer 140 at a temperature of 25 ° C. Less than 50.
Condition (B): The thickness Ta of the first bonding layer 120 and the thickness Tb of the second bonding layer 140 are both more than 1.0 μm.
By satisfying both the conditions (A) and (B), the laminated body 100 is less likely to cause cracks in the colored member 130 when the laminated body 100 is repeatedly bent with the front plate 110 side inside and a bending radius of 1 mm. When the appearance of the laminated body 100 is visually observed from the front plate side, rainbow unevenness is less likely to be visually recognized.
　［条件（Ａ）］
　積層体１００は、条件（Ａ）を満たすことにより、前面板１１０側を内側にして屈曲半径が１ｍｍで繰返しの屈曲を行ったとき、着色部材１３０にクラックが生じにくくなる傾向にある。Ｇ’ａ／Ｇ’ｂは、着色部材１３０にクラックが生じにくくなる観点から好ましくは１０以下であり、より好ましくは５以下であり、さらに好ましくは２以下であり、特に好ましくは１以下であり、１未満であってもよい。Ｇ’ａ／Ｇ’ｂは、０．０１以上であってもよい。貯蔵弾性率Ｇ’ａ及びＧ’ｂは、後述の実施例の欄において説明する方法に従って測定される。貯蔵弾性率Ｇ’ａ及びＧ’ｂの好ましい範囲については後述する。 [Condition (A)]
By satisfying the condition (A), the laminated body 100 tends to be less likely to crack in the colored member 130 when repeatedly bent with the front plate 110 side inside and a bending radius of 1 mm. G'a / G'b is preferably 10 or less, more preferably 5 or less, still more preferably 2 or less, and particularly preferably 1 or less, from the viewpoint that cracks are less likely to occur in the coloring member 130. It may be less than 1. G'a / G'b may be 0.01 or more. The storage elastic moduli G'a and G'b are measured according to the methods described in the Examples section below. The preferable ranges of the storage elastic moduli G'a and G'b will be described later.
　［条件（Ｂ）］
　積層体１００は、条件（Ｂ）を満たすことにより、積層体１００の前面板側に虹ムラが観察されにくくなる傾向にある。虹ムラは、後述の実施例の欄において説明する方法によって確認される。Ｔａ及びＴｂは、虹ムラが観察されにくくなる観点、および屈曲性を高める観点から好ましくは１．５μｍ以上１００μｍ以下、より好ましくは５μｍ以上５０μｍ以下である。Ｔａは、例えば１０μｍ以上であり、２０μｍ以上であることが好ましく、例えば１００μｍ以下であり、８０μｍ以下であることが好ましい。Ｔｂは、例えば１．２μｍ以上であり、１．５μｍ以上であることが好ましく、例えば５０μｍ以下であり、３０μｍ以下であることが好ましい。 [Condition (B)]
When the condition (B) is satisfied, the laminated body 100 tends to be less likely to have rainbow unevenness on the front plate side of the laminated body 100. Rainbow unevenness is confirmed by the method described in the Examples section below. Ta and Tb are preferably 1.5 μm or more and 100 μm or less, and more preferably 5 μm or more and 50 μm or less from the viewpoint of making it difficult to observe rainbow unevenness and enhancing flexibility. Ta is, for example, 10 μm or more and preferably 20 μm or more, and for example, 100 μm or less and preferably 80 μm or less. Tb is, for example, 1.2 μm or more, preferably 1.5 μm or more, and for example, 50 μm or less, preferably 30 μm or less.
　［条件（Ｃ）］
　積層体１００は、前面板１１０側を内側にして屈曲半径が１ｍｍで繰返しの屈曲を行ったとき、着色部材１３０にクラックが生じにくくなる観点から好ましくは条件（Ｃ）をさらに満たす。
　条件（Ｃ）：第２貼合層の厚みＴｂに対する第１貼合層の厚みＴａの比Ｔａ／Ｔｂが０．０３以上５０未満である。
　Ｔａ／Ｔｂは、好ましくは０．０５以上４０以下、より好ましくは１以上３０以下であり、さらに好ましくは１超３０以下である。 [Condition (C)]
The laminated body 100 preferably further satisfies the condition (C) from the viewpoint that cracks are less likely to occur in the colored member 130 when the laminated body 100 is repeatedly bent with the front plate 110 side inside and the bending radius is 1 mm.
Condition (C): The ratio Ta / Tb of the thickness Ta of the first bonding layer to the thickness Tb of the second bonding layer is 0.03 or more and less than 50.
Ta / Tb is preferably 0.05 or more and 40 or less, more preferably 1 or more and 30 or less, and further preferably 1 or more and 30 or less.
　積層体１００は、面方向の形状は特に限定されないが、方形形状であることが好ましく、長方形形状であることがより好ましい。積層体１００が長方形形状である場合、長辺の長さは、例えば５０ｍｍ以上３００ｍｍ以下であってよく、好ましくは１００ｍｍ以上２８０ｍｍ以下であり、短辺の長さは、例えば３０ｍｍ以上２５０ｍｍ以下であってよく、好ましくは６０ｍｍ以上２２０ｍｍ以下である。積層体１００は、方形形状が有する角の少なくとも１つにＲ加工を施した角丸方形形状であってもよく、少なくとも一辺に切欠き部を有する方形形状であってもよい。積層体１００は、積層方向に貫通する孔部が設けられていてもよい。積層体１００の厚みは、積層体１００に求められる機能および用途等に応じて異なるが、例えば２０μｍ以上２０００μｍ以下とすることができ、好ましくは５０μｍ以上５００μｍ以下とすることができる。 The shape of the laminated body 100 in the plane direction is not particularly limited, but it is preferably a square shape, and more preferably a rectangular shape. When the laminate 100 has a rectangular shape, the length of the long side may be, for example, 50 mm or more and 300 mm or less, preferably 100 mm or more and 280 mm or less, and the length of the short side is, for example, 30 mm or more and 250 mm or less. It is preferably 60 mm or more and 220 mm or less. The laminated body 100 may be a square shape having rounded corners in which at least one of the corners of the square shape is R-processed, or may be a square shape having a notch on at least one side. The laminated body 100 may be provided with a hole portion penetrating in the laminating direction. The thickness of the laminated body 100 varies depending on the function and application required for the laminated body 100, but can be, for example, 20 μm or more and 2000 μm or less, preferably 50 μm or more and 500 μm or less.
　積層体１００は、例えば画像表示装置等に用いることができる。画像表示装置は特に限定されず、例えば有機エレクトロルミネッセンス（有機ＥＬ）表示装置、無機エレクトロルミネッセンス（無機ＥＬ）表示装置、液晶表示装置、電界発光表示装置等が挙げられる。積層体１００を屈曲することが可能である場合、積層体１００は、フレキシブルディスプレイに好適である。 The laminated body 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 an organic electroluminescence (organic EL) display device, an inorganic electroluminescence (inorganic EL) display device, a liquid crystal display device, and an electroluminescence display device. When the laminate 100 can be bent, the laminate 100 is suitable for a flexible display.
　積層体１００は、円偏光板１５０を備えているため、画像表示装置に適用した場合、例えば有機エレクトロルミネッセンス（ＥＬ）表示装置における反射防止フィルムとして用いることもできる。 Since the laminate 100 includes a circularly polarizing plate 150, it can also be used as an antireflection film in, for example, an organic electroluminescence (EL) display device when applied to an image display device.
　［前面板］
　前面板１１０は、光を透過可能な板状体であれば、材料および厚みは限定されず、また単層構造であっても多層構造であってもよく、ガラス製の板状体（例えばガラス板、ガラスフィルム等）、樹脂製の板状体（例えば樹脂板、樹脂シート、樹脂フィルム等）、及び樹脂製の板状体とガラス製の板状体のとの積層体が例示される。前面板１１０は、画像表示装置の視認側の最表面を構成する層であることができる。 [Front plate]
The material and thickness of the front plate 110 are not limited as long as it is a plate-like body capable of transmitting light, and the front plate 110 may have a single-layer structure or a multi-layer structure, and is a glass plate-like body (for example, glass). Examples thereof include a plate (plate, glass film, etc.), a resin plate (for example, a resin plate, a resin sheet, a resin film, etc.), and a laminate of a resin plate and a glass plate. The front plate 110 can be a layer forming the outermost surface on the visual side of the image display device.
　ガラス板としては、ディスプレイ用強化ガラスが好ましく用いられる。ガラス板の厚みは、例えば１０μｍ以上１０００μｍ以下であり、好ましくは２０μｍ以上５００μｍ以下である。ガラス板を用いることにより、前面板１１０は、優れた機械的強度および表面硬度を有することができる。 As the glass plate, tempered glass for display is preferably used. The thickness of the glass plate is, for example, 10 μm or more and 1000 μm or less, preferably 20 μm or more and 500 μm or less. By using a glass plate, the front plate 110 can have excellent mechanical strength and surface hardness.
　樹脂フィルムとしては、光を透過可能な樹脂フィルムであれば限定されない。例えば、トリアセチルセルロース、アセチルセルロースブチレート、エチレン－酢酸ビニル共重合体、プロピオニルセルロース、ブチリルセルロース、アセチルプロピオニルセルロース、ポリエステル、ポリスチレン、ポリアミド、ポリエーテルイミド、ポリ（メタ）アクリル、ポリイミド、ポリエーテルスルホン、ポリスルホン、ポリエチレン、ポリプロピレン、ポリメチルペンテン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、ポリビニルアセタール、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリメチル（メタ）アクリレート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、ポリアミドイミド等の高分子で形成されたフィルムが挙げられる。これらの高分子は、単独でまたは２種以上混合して用いることができる。積層体１００をフレキシブルディスプレイに用いる場合には、優れた可撓性を有し、高い強度および高い透明性を有するように構成可能な、ポリイミド、ポリアミド、ポリアミドイミド等の高分子で形成された樹脂フィルムが好適に用いられる。（メタ）アクリルの高分子とは、アクリルの高分子およびメタクリルの高分子よりなる群から選ばれる少なくとも１種を表す。その他の「（メタ）」を付した用語においても同様である。 The resin film is not limited as long as it is a resin film capable of transmitting light. For example, triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, polyester, polystyrene, polyamide, polyetherimide, poly (meth) acrylic, polyimide, polyether. Sulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl (meth) acrylate, polyethylene terephthalate, polybutylene Examples thereof include films formed of polymers such as terephthalate, polyethylene naphthalate, polycarbonate and polyamideimide. These polymers can be used alone or in admixture of two or more. When the laminate 100 is used in a flexible display, a resin formed of a polymer such as polyimide, polyamide, or polyamide-imide, which has excellent flexibility and can be configured to have high strength and high transparency. Films are preferably used. The (meth) acrylic polymer represents at least one selected from the group consisting of an acrylic polymer and a methacryl polymer. The same applies to other terms with "(meta)".
　前面板１１０が樹脂フィルムである場合、樹脂フィルムは、基材フィルムの少なくとも一方の面にハードコート層を設けて硬度をより向上させたフィルムであってもよい。ハードコート層は、基材フィルムの一方の面に形成されていてもよいし、両方の面に形成されていてもよい。後述する画像表示装置がタッチパネル方式の画像表示装置である場合には、前面板１１０の表面がタッチ面となるため、ハードコート層を有する樹脂フィルムが好適に用いられる。ハードコート層を設けることにより、硬度及び耐スクラッチ性を向上させた樹脂フィルムとすることができる。ハードコート層は、例えば、紫外線硬化型樹脂の硬化層である。紫外線硬化型樹脂としては、例えば、（メタ）アクリル系樹脂、シリコーン系樹脂、ポリエステル系樹脂、ウレタン系樹脂、アミド系樹脂、エポキシ系樹脂等が挙げられる。ハードコート層は、硬度を向上させるために、添加剤を含んでいてもよい。添加剤は限定されることはなく、無機系微粒子、有機系微粒子、またはこれらの混合物が挙げられる。樹脂フィルムの厚みは、例えば３０μｍ以上１００μｍ以下である。 When the front plate 110 is a resin film, the resin film may be a film in which a hard coat layer is provided on at least one surface of the base film to further improve the hardness. The hard coat layer may be formed on one surface of the base film or may be formed on both surfaces. When the image display device described later is a touch panel type image display device, the surface of the front plate 110 serves as a touch surface, so a resin film having a hard coat layer is preferably used. By providing the hard coat layer, a resin film having improved hardness and scratch resistance can be obtained. The hard coat layer is, for example, a cured layer of an ultraviolet curable resin. Examples of the ultraviolet curable resin include (meth) acrylic resin, silicone resin, polyester resin, urethane resin, amide resin, epoxy resin and the like. The hard coat layer may contain additives to improve hardness. Additives are not limited and include inorganic fine particles, organic fine particles, or mixtures thereof. The thickness of the resin film is, for example, 30 μm or more and 100 μm or less.
　前面板１１０は、画像表示装置の前面を保護する機能を有するのみではなく、タッチセンサとしての機能、ブルーライトカット機能、視野角調整機能等を有するものであってもよい。 The front plate 110 not only has a function of protecting the front surface of the image display device, but may also have a function as a touch sensor, a blue light cut function, a viewing angle adjusting function, and the like.
　［第１貼合層］
　第１貼合層１２０は、前面板１１０と着色部材１３０とを貼合するための層であることができる。第１貼合層１２０は、粘着剤又は接着剤から形成される層である。本明細書において、粘着剤とは、感圧式接着剤とも呼ばれるものである。一方、接着剤とは、粘着剤（感圧式接着剤）以外の接着剤をいい、粘着剤とは明確に区別される。第１貼合層１２０は、１層であってもよく、または２層以上からなるものであってもよいが、好ましくは１層である。第１貼合層は、好ましくは粘着剤層である。 [1st bonding layer]
The first bonding layer 120 can be a layer for bonding the front plate 110 and the coloring member 130. The first bonding layer 120 is a layer formed of a pressure-sensitive adhesive or an adhesive. In the present specification, the pressure-sensitive adhesive is also referred to as a pressure-sensitive adhesive. On the other hand, the adhesive refers to an adhesive other than the pressure-sensitive adhesive (pressure-sensitive adhesive), and is clearly distinguished from the pressure-sensitive adhesive. The first bonding layer 120 may be one layer or may be composed of two or more layers, but is preferably one layer. The first bonding layer is preferably an adhesive layer.
　第１貼合層１２０を形成する粘着剤は、（メタ）アクリル系、ゴム系、ウレタン系、エステル系、シリコーン系、ポリビニルエーテル系のような樹脂を主成分とする粘着剤組成物で構成することができる。中でも、透明性、耐候性、耐熱性等に優れる（メタ）アクリル系樹脂をベースポリマーとする粘着剤組成物が好適である。粘着剤組成物は、活性エネルギー線硬化型、熱硬化型であってもよい。 The pressure-sensitive adhesive forming the first bonding layer 120 is composed of a pressure-sensitive adhesive composition containing a resin such as (meth) acrylic, rubber, urethane, ester, silicone, or polyvinyl ether as a main component. be able to. Among them, a pressure-sensitive adhesive composition using a (meth) acrylic resin having excellent transparency, weather resistance, heat resistance and the like as a base polymer is preferable. The pressure-sensitive adhesive composition may be an active energy ray-curable type or a thermosetting type.
　粘着剤組成物に用いられる（メタ）アクリル系樹脂（ベースポリマー）としては、例えば、（メタ）アクリル酸ブチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸２－エチルヘキシルのような（メタ）アクリル酸エステルの１種または２種以上をモノマーとする重合体または共重合体が好適に用いられる。ベースポリマーには、極性モノマーを共重合させることが好ましい。極性モノマーとしては、例えば、（メタ）アクリル酸、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、グリシジル（メタ）アクリレートのような、カルボキシル基、水酸基、アミド基、アミノ基、エポキシ基等を有するモノマーを挙げることができる。 Examples of the (meth) acrylic resin (base polymer) used in the pressure-sensitive adhesive composition include butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2- (meth) acrylate. A polymer or copolymer having one or more (meth) acrylic acid esters such as ethylhexyl as a monomer is preferably used. It is preferable that the base polymer is copolymerized with a polar monomer. Examples of the polar monomer include (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylamide, N, N-. Examples thereof include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group and the like, such as dimethylaminoethyl (meth) acrylate and glycidyl (meth) acrylate.
　粘着剤組成物は、上記ベースポリマーのみを含むものであってもよいが、通常は架橋剤をさらに含有する。架橋剤としては、２価以上の金属イオンであって、カルボキシル基との間でカルボン酸金属塩を形成するもの；ポリアミン化合物であって、カルボキシル基との間でアミド結合を形成するもの；ポリエポキシ化合物やポリオールであって、カルボキシル基との間でエステル結合を形成するもの；ポリイソシアネート化合物であって、カルボキシル基との間でアミド結合を形成するものが例示される。中でも、ポリイソシアネート化合物が好ましい。 The pressure-sensitive adhesive composition may contain only the above-mentioned base polymer, but usually further contains a cross-linking agent. The cross-linking agent is a divalent or higher metal ion that forms a carboxylic acid metal salt with a carboxyl group; a polyamine compound that forms an amide bond with a carboxyl group; poly. Epoxy compounds and polyols that form an ester bond with a carboxyl group; polyisocyanate compounds that form an amide bond with a carboxyl group are exemplified. Of these, polyisocyanate compounds are preferable.
　活性エネルギー線硬化型粘着剤組成物とは、紫外線や電子線のような活性エネルギー線の照射を受けて硬化する性質を有しており、活性エネルギー線照射前においても粘着性を有してフィルム等の被着体に密着させることができ、活性エネルギー線の照射によって硬化して密着力の調整ができる性質を有する粘着剤組成物である。活性エネルギー線硬化型粘着剤組成物は、紫外線硬化型であることが好ましい。活性エネルギー線硬化型粘着剤組成物は、ベースポリマー、架橋剤に加えて、活性エネルギー線重合性化合物をさらに含有する。さらに必要に応じて、光重合開始剤や光増感剤等を含有させることもある。 The active energy ray-curable pressure-sensitive adhesive composition has a property of being cured by being irradiated with active energy rays such as ultraviolet rays and electron beams, and has adhesiveness even before irradiation with active energy rays. It is a pressure-sensitive adhesive composition having the property of being able to adhere to an adherend such as, etc., and being cured by irradiation with active energy rays to adjust the adhesion force. The active energy ray-curable pressure-sensitive adhesive composition is preferably an ultraviolet-curable type. 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. Further, if necessary, a photopolymerization initiator, a photosensitizer, or the like may be contained.
　粘着剤組成物は、光散乱性を付与するための微粒子、ビーズ（樹脂ビーズ、ガラスビーズ等）、ガラス繊維、ベースポリマー以外の樹脂、粘着性付与剤、充填剤（金属粉やその他の無機粉末等）、酸化防止剤、紫外線吸収剤、染料、顔料、着色剤、消泡剤、腐食防止剤、光重合開始剤等の添加剤を含むことができる。 The pressure-sensitive adhesive composition includes fine particles for imparting light scattering properties, beads (resin beads, glass beads, etc.), glass fibers, resins other than the base polymer, pressure-sensitive adhesives, fillers (metal powders and other inorganic powders). Etc.), antioxidants, UV absorbers, dyes, pigments, colorants, antifoaming agents, corrosion inhibitors, photopolymerization initiators and other additives can be included.
　第１貼合層は、上記粘着剤組成物の有機溶剤希釈液を基材上に塗布し、その塗膜を乾燥させることにより形成することができる。活性エネルギー線硬化型粘着剤組成物を用いた場合は、活性エネルギー線を照射することにより所望の硬化度を有する硬化物とすることができる。 The first bonding layer can be formed by applying an organic solvent diluent of the pressure-sensitive adhesive composition on a substrate and drying the coating film. When the active energy ray-curable pressure-sensitive adhesive composition is used, a cured product having a desired degree of curing can be obtained by irradiating with active energy rays.
　接着剤としては、例えば水系接着剤、活性エネルギー線硬化型接着剤等のうち１種または２種以上を組み合わせて形成することができる。水系接着剤としては、例えばポリビニルアルコール系樹脂水溶液、水系二液型ウレタン系エマルジョン接着剤等を挙げることができる。活性エネルギー線硬化型接着剤は、紫外線等の活性エネルギー線を照射することによって硬化する接着剤であり、例えば重合性化合物及び光重合性開始剤を含む接着剤、光反応性樹脂を含む接着剤、バインダー樹脂及び光反応性架橋剤を含む接着剤等を挙げることができる。上記重合性化合物としては、光硬化性エポキシ系モノマー、光硬化性アクリル系モノマー、光硬化性ウレタン系モノマー等の光重合性モノマー、及びこれらモノマーに由来するオリゴマー等を挙げることができる。上記光重合開始剤としては、紫外線等の活性エネルギー線を照射して中性ラジカル、アニオンラジカル、カチオンラジカルといった活性種を発生する物質を含む化合物を挙げることができる。 As the adhesive, for example, one or a combination of two or more of water-based adhesives, active energy ray-curable adhesives, and the like can be formed. Examples of the water-based adhesive include a polyvinyl alcohol-based resin aqueous solution, a water-based two-component urethane-based emulsion adhesive, and the like. The active energy ray-curable adhesive is an adhesive that cures by irradiating with active energy rays such as ultraviolet rays, and is, for example, an adhesive containing a polymerizable compound and a photopolymerizable initiator, and an adhesive containing a photoreactive resin. , Adhesives containing a binder resin and a photoreactive cross-linking agent, and the like. Examples of the polymerizable compound include photopolymerizable monomers such as a photocurable epoxy monomer, a photocurable acrylic monomer, and a photocurable urethane monomer, and oligomers derived from these monomers. Examples of the photopolymerization initiator include compounds containing substances that generate active species such as neutral radicals, anion radicals, and cationic radicals by irradiating them with active energy rays such as ultraviolet rays.
　第１貼合層１２０の温度２５℃における貯蔵弾性率Ｇ’ａは、例えば０．０１ＭＰａ以上５ＭＰａ以下であってよく、好ましくは０．０２ＭＰａ以上１ＭＰａ以下、より好ましくは０．０３ＭＰａ以上０．５ＭＰａ以下であり、０．１ＭＰａ以下であってもよい。第１貼合層１２０の貯蔵弾性率Ｇ’ａは、例えば第１貼合層１２０を形成するのに用いる材料の選定により調節することができる。 The storage elastic modulus G'a of the first bonded layer 120 at a temperature of 25 ° C. may be, for example, 0.01 MPa or more and 5 MPa or less, preferably 0.02 MPa or more and 1 MPa or less, and more preferably 0.03 MPa or more and 0.5 MPa. It is less than or equal to, and may be 0.1 MPa or less. The storage elastic modulus G'a of the first bonded layer 120 can be adjusted, for example, by selecting the material used to form the first bonded layer 120.
　［着色部材］
　着色部材１３０は、電極や配線等を遮蔽したり、画像表示装置に設けられる表示ユニットからの光漏れを抑制したりするために着色層を含む。着色部材１３０の一方の面には、第１貼合層１２０が着色部材１３０に接して積層され、着色部材１３０の他方の面には、第２貼合層１４０が着色部材１３０に接して積層されている。 [Coloring member]
The coloring member 130 includes a coloring layer in order to shield electrodes, wiring, and the like, and to suppress light leakage from a display unit provided in an image display device. The first bonding layer 120 is laminated in contact with the coloring member 130 on one surface of the coloring member 130, and the second bonding layer 140 is laminated in contact with the coloring member 130 on the other surface of the coloring member 130. Has been done.
　着色部材１３０は着色層に加えて、分離層および保護層の少なくとも１つをさらに含むことができる。着色部材１３０が分離層および保護層を含む場合、着色部材１３０は、例えば保護層と着色層と分離層とをこの順に含んでよく、着色層と保護層と分離層とをこの順に含んでよい。着色部材１３０が分離層および保護層を含む場合、着色部材１３０は、着色層が分離層より前面板１１０に近くなるように積層されてよく、分離層が着色層より前面板１１０に近くなるように積層されてよく、好ましくは、前面板１１０に近い順に保護層、着色層、分離層となるように積層されるか、又は前面板１１０に近い順に着色層、保護層、分離層となるように積層される。着色部材は、樹脂フィルムまたはガラスを備えていてもよい。 The coloring member 130 can further include at least one of a separation layer and a protective layer in addition to the coloring layer. When the coloring member 130 includes a separation layer and a protective layer, the coloring member 130 may include, for example, a protective layer, a coloring layer, and a separation layer in this order, and may include a coloring layer, a protection layer, and a separation layer in this order. .. When the coloring member 130 includes a separation layer and a protective layer, the coloring member 130 may be laminated so that the coloring layer is closer to the front plate 110 than the separation layer, and the separation layer is closer to the front plate 110 than the coloring layer. It may be laminated so as to be a protective layer, a colored layer, and a separating layer in the order closer to the front plate 110, or to be a colored layer, a protective layer, and a separating layer in the order closer to the front plate 110. It is laminated on. The coloring member may include a resin film or glass.
　着色部材１３０は、例えばガラス板上に分離層を介して着色層を形成し、着色層上に基材層（剥離フィルム）を設け、ガラス板を分離層との間で分離して分離層／着色層の層構成を有する着色部材１３０を基材層上に転写することで製造することができる。ガラス板を分離して露出させた分離層上に別の基材層（剥離フィルム）を設けることもできる。基材層は通常、着色部材１３０を積層体１００に組込む際に除去される。 In the coloring member 130, for example, a coloring layer is formed on a glass plate via a separation layer, a base material layer (release film) is provided on the coloring layer, and the glass plate is separated from the separation layer to separate the separation layer /. It can be produced by transferring the colored member 130 having the layer structure of the colored layer onto the base material layer. Another base material layer (release film) may be provided on the separation layer obtained by separating and exposing the glass plate. The base material layer is usually removed when the coloring member 130 is incorporated into the laminate 100.
　着色部材１３０の厚みは、例えば０．１μｍ以上１５μｍ以下であってよく、好ましくは０．５μｍ以上１０μｍ以下であり、より好ましくは１μｍ以上７μｍ以下である。 The thickness of the coloring member 130 may be, for example, 0.1 μm or more and 15 μm or less, preferably 0.5 μm or more and 10 μm or less, and more preferably 1 μm or more and 7 μm or less.
　［着色層］
　着色層は、電極や配線等を遮蔽したり、画像表示装置に設けられる表示ユニットからの光漏れを抑制したりするために遮蔽性を有することができる。 [Colored layer]
The colored layer can have a shielding property in order to shield electrodes, wiring, and the like, and to suppress light leakage from a display unit provided in an image display device.
　着色層の形状および色は限定されることはなく、例えば積層体を用いる表示装置の用途やデザインに応じて適宜選択し得る。着色層は、積層体の平面視において部分的に配置されるように設けられていてよく、例えば積層体の平面視において周縁部に配置されるように設けられていてよい。 The shape and color of the colored layer are not limited, and can be appropriately selected depending on, for example, the application and design of the display device using the laminated body. The colored layer may be provided so as to be partially arranged in the plan view of the laminated body, and may be provided, for example, so as to be arranged in the peripheral portion in the plan view of the laminated body.
　着色層は単層構造であってよく、多層構造であってよい。着色層が多層構造である場合、２以上の層の内、少なくとも１層は着色剤を含む着色剤含有層であり、残りの層は着色剤を含んでいても、着色剤を含んでいなくてもよい。着色剤の色としては、黒色、赤色、白色、紺色、銀色、金色などが例示される。 The colored layer may have a single layer structure or a multi-layer structure. When the colored layer has a multi-layer structure, at least one of the two or more layers is a colorant-containing layer containing a colorant, and the remaining layer contains the colorant but does not contain the colorant. You may. Examples of the color of the colorant include black, red, white, dark blue, silver, and gold.
　着色層の色は特に限定されず、用途やデザイン等に応じて適宜選択すればよい。着色層１３０の色としては、黒色、白色、赤色、紺色、銀色、金色等が挙げられる。 The color of the colored layer is not particularly limited and may be appropriately selected according to the application, design, etc. Examples of the color of the coloring layer 130 include black, white, red, dark blue, silver, and gold.
　着色層の厚みは、例えば０．１μｍ以上５μｍ以下であってよい。着色層の厚みが余りに大きい場合、着色層を積層体の平面視において部分的に形成した場合、積層体表面に段差が生じやすくなる傾向にある。一方、着色層の厚みが余りに小さい場合、十分な遮光性が得られにくくなる傾向にある。着色層の厚みは、好ましくは０．５μｍ以上４μｍ以下であり、より好ましく１μｍ以上３μｍ以下であり、さらに好ましく１μｍ以上２μｍ以下である。上記厚みは、着色層の最大厚みのことである。着色層の厚みは後述の実施例の欄に説明する測定方法により測定される。 The thickness of the colored layer may be, for example, 0.1 μm or more and 5 μm or less. When the thickness of the colored layer is too large, when the colored layer is partially formed in a plan view of the laminated body, a step tends to be easily generated on the surface of the laminated body. On the other hand, if the thickness of the colored layer is too small, it tends to be difficult to obtain sufficient light-shielding properties. The thickness of the colored layer is preferably 0.5 μm or more and 4 μm or less, more preferably 1 μm or more and 3 μm or less, and further preferably 1 μm or more and 2 μm or less. The above thickness is the maximum thickness of the colored layer. The thickness of the colored layer is measured by the measuring method described in the column of Examples described later.
　着色層の光学密度は、例えば２以上であってよく、好ましくは３以上であり、より好ましくは４以上であり、さらに好ましくは５以上である。着色層の光学密度の上限は特に限定されないが、例えば１０以下であってもよいし、７以下であってもよい。着色層は、厚み１μｍ当たりの光学密度が例えば１．８以上であってよく、好ましくは２以上であり、より好ましくは２．５以上であり、さらに好ましくは２．７以上である。 The optical density of the colored layer may be, for example, 2 or more, preferably 3 or more, more preferably 4 or more, and further preferably 5 or more. The upper limit of the optical density of the colored layer is not particularly limited, but may be, for example, 10 or less, or 7 or less. The colored layer may have an optical density of, for example, 1.8 or more, preferably 2 or more, more preferably 2.5 or more, still more preferably 2.7 or more, per 1 μm of thickness.
　光学密度は、次のようにして測定される。まずガラス基材上に着色層を形成する。このサンプルを光学密度測定器（例えば、Ｘ－ｒｉｔｅ社製の製品名：３６１Ｔ）にセットし、サンプルの着色層側に位置する上部の光源を点灯して、サンプルの着色層に焦点を合わせる。上部の光源を消灯した後、サンプルの基材側に位置する測定用の光源を点灯し、着色層を測定領域として光学密度を測定する。 The optical density is measured as follows. First, a colored layer is formed on the glass substrate. This sample is set in an optical density measuring instrument (for example, product name: 361T manufactured by X-rite), and the upper light source located on the colored layer side of the sample is turned on to focus on the colored layer of the sample. After turning off the upper light source, the measurement light source located on the substrate side of the sample is turned on, and the optical density is measured with the colored layer as the measurement region.
　平面視において、着色層が、部分的に形成される場合、着色層は、積層体が表示領域と非表示領域とに区別されるように形成されることができる。図２に示す積層体２００は、前面板１１０と第１貼合層１２０と着色部材１３０と第２貼合層１４０と円偏光板１５０とを備え、着色部材１３０は、保護層１３３と着色層１３１と分離層１３２とをこの順に含んでいる。平面視において、積層体２００は、表示領域Ａと非表示領域Ｂとに区別され、着色層１３１は非表示領域Ｂに設けられている。積層体２００は、着色部材１３０の保護層１３３と第１貼合層１２０とが互いに接して積層されているが、別の実施形態においては、着色部材の着色層及び分離層のいずれか一方又は両方と第１貼合層１２０とが互いに接して積層されていてもよい。 In a plan view, when the colored layer is partially formed, the colored layer can be formed so that the laminated body is distinguished into a display region and a non-display region. The laminate 200 shown in FIG. 2 includes a front plate 110, a first bonding layer 120, a coloring member 130, a second bonding layer 140, and a circularly polarizing plate 150, and the coloring member 130 includes a protective layer 133 and a coloring layer. 131 and the separating layer 132 are included in this order. In a plan view, the laminated body 200 is divided into a display area A and a non-display area B, and the colored layer 131 is provided in the non-display area B. In the laminated body 200, the protective layer 133 of the coloring member 130 and the first bonding layer 120 are laminated in contact with each other, but in another embodiment, either one of the coloring layer and the separation layer of the coloring member 130 or Both and the first bonding layer 120 may be laminated so as to be in contact with each other.
　図３は、積層体２００を、平面視において着色層側からみた概略上面図である。積層体２００は、表示領域Ａ２０１と非表示領域Ｂ２０２とに区別される。積層体２００が画像表示装置を構成する場合、積層体２００の表示領域Ａは、画像が視認される領域となり、非表示領域Ｂは画像が視認されない領域となる。そのため、非表示領域Ｂには、電極や配線等が配置されたり、画像表示装置に設けられる表示ユニットからの光が漏れる光漏れを抑制したりすることが求められる場合がある。この場合、非表示領域Ｂに設けられる着色層１３１は、電極や配線等の隠蔽性とともに光漏れの抑制が実現できる程度に十分な遮蔽性を有していることが好ましい。本明細書において、平面視とは層の厚み方向から見ることを意味する。 FIG. 3 is a schematic top view of the laminated body 200 as viewed from the colored layer side in a plan view. The laminated body 200 is divided into a display area A201 and a non-display area B202. When the laminated body 200 constitutes an image display device, the display area A of the laminated body 200 is an area where the image is visually recognized, and the non-display area B is an area where the image is not visually recognized. Therefore, it may be required that electrodes, wiring, and the like are arranged in the non-display area B, and that light leakage from a display unit provided in the image display device is suppressed. In this case, it is preferable that the colored layer 131 provided in the non-display region B has a concealing property such as electrodes and wiring and a sufficient shielding property to be able to suppress light leakage. In the present specification, the plan view means the view from the thickness direction of the layer.
　図３に示すように、平面視において、積層体の周縁部に着色層１３１が形成される場合、着色層１３１の幅Ｗは、例えば０．５ｍｍ以上とすることができ、３ｍｍ以上であってもよく、５ｍｍ以上であってもよく、また、通常８０ｍｍ以下であり、６０ｍｍ以下であってもよく、５０ｍｍ以下であってもよく、３０ｍｍ以下であってもよく、２０ｍｍ以下であってもよい。 As shown in FIG. 3, when the colored layer 131 is formed on the peripheral edge of the laminated body in a plan view, the width W of the colored layer 131 can be, for example, 0.5 mm or more, and is 3 mm or more. It may be 5 mm or more, and usually 80 mm or less, 60 mm or less, 50 mm or less, 30 mm or less, or 20 mm or less. ..
　積層体２００の着色層１３１の表示領域Ａ側の端部領域は、表示領域Ａ側の端部から着色層１３１の内側に向かう方向において厚みが大きくなるようにテーパー部を有することができる。着色層がテーパー部を有することにより、第１貼合層１２０と着色部材１３０とを貼合するときに気泡の噛込みを抑制し易くなる傾向にある。 The end region of the colored layer 131 of the laminated body 200 on the display region A side may have a tapered portion so that the thickness increases in the direction from the end on the display region A side toward the inside of the colored layer 131. Since the colored layer has a tapered portion, it tends to be easy to suppress the biting of air bubbles when the first bonding layer 120 and the coloring member 130 are bonded to each other.
　着色層１３１は、活性エネルギー線硬化性樹脂組成物を用いて、フォトリソグラフィ法などにより形成することができる。着色層形成用組成物は、例えば着色剤、バインダー樹脂、溶媒、任意の添加剤を含むことができる。着色層形成用組成物が活性エネルギー線硬化型である場合、着色層形成用組成物は、活性エネルギー線重合性化合物をさらに含有する。さらに必要に応じて、光重合開始剤や光増感剤等を含有させることもある。 The colored layer 131 can be formed by a photolithography method or the like using an active energy ray-curable resin composition. The composition for forming a colored layer can contain, for example, a colorant, a binder resin, a solvent, and any additive. When the composition for forming a colored layer is an active energy ray-curable type, the composition for forming a colored layer further contains an active energy ray-polymerizable compound. Further, if necessary, a photopolymerization initiator, a photosensitizer, or the like may be contained.
　着色剤としては、例えば、アセチレンブラック等のカーボンブラック、鉄黒、二酸化チタン、亜鉛華、弁柄、クロムバーミリオン、群青、コバルトブルー、黄鉛、チタンイエロー等の無機顔料；フタロシアニンブルー、インダスレンブルー、イソインドリノンイエロー、ベンジジンイエロー、キナクリドンレッド、ポリアゾレッド、ペリレンレッド、アニリンブラック等の有機顔料または染料；アルミニウム、真鍮等の鱗片状箔片からなる金属顔料；二酸化チタン被覆雲母、塩基性炭酸鉛等の鱗片状箔片からなる真珠光沢顔料（パール顔料）等が挙げられる。 Examples of the colorant include carbon black such as acetylene black, iron black, titanium dioxide, zinc flower, petals, chrome vermilion, ultramarine, cobalt blue, yellow lead, titanium yellow and other inorganic pigments; phthalocyanine blue and induslen. Organic pigments or dyes such as blue, isoindolinone yellow, benzidine yellow, quinacridone red, polyazo red, perylene red, aniline black; metal pigments consisting of scaly foil pieces such as aluminum and brass; titanium dioxide-coated mica, basic lead carbonate Examples thereof include pearl luster pigments (pearl pigments) made of scaly foil pieces such as.
　バインダー樹脂としては、塩素化ポリオレフィン（例えば、塩素化ポリエチレン、塩素化ポリプロピレン）、ポリエステル系樹脂、ウレタン系樹脂、アクリル系樹脂、酢酸ビニル樹脂、塩化ビニル－酢酸ビニル共重合体、セルロース系樹脂が挙げられる。バインダー樹脂は、単独で用いてもよく２種以上を併用してもよい。バインダー樹脂は、熱重合性樹脂であっても、光重合性樹脂であってもよい。 Examples of the binder resin include chlorinated polyolefins (for example, chlorinated polyethylene and chlorinated polypropylene), polyester resins, urethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, and cellulose resins. Be done. The binder resin may be used alone or in combination of two or more. The binder resin may be a heat-polymerizable resin or a photopolymerizable resin.
　［分離層］
　分離層１３２は、着色層１３１の作製過程において用いる支持体から着色部材１３０を分離しやすくするための機能を有する。分離層１３２は、例えば無機物層または有機物層であることができる。これらの層は、スピンコート法、スパッタリング法、蒸着法等によって形成することができる。無機物層を形成する材料としては、例えばシリコン酸化物が挙げられる。有機物層を形成する材料としては、例えば（メタ）アクリル系樹脂組成物、エポキシ系樹脂組成物、ポリイミド系樹脂組成物等が挙げられる。分離層１３２の厚みは、例えば０．０１μｍ以上１μｍ以下であってよく、好ましくは０．０５μｍ以上０．５μｍ以下である。 [Separation layer]
The separation layer 132 has a function for facilitating the separation of the coloring member 130 from the support used in the process of producing the coloring layer 131. The separation layer 132 can be, for example, an inorganic layer or an organic layer. These layers can be formed by a spin coating method, a sputtering method, a vapor deposition method or the like. Examples of the material forming the inorganic layer include silicon oxide. Examples of the material for forming the organic material layer include (meth) acrylic resin compositions, epoxy resin compositions, and polyimide resin compositions. The thickness of the separation layer 132 may be, for example, 0.01 μm or more and 1 μm or less, preferably 0.05 μm or more and 0.5 μm or less.
　［保護層］
　保護層１３３は、着色層１３１を保護する機能を有することができる。図２に示されるように、保護層が着色層の側面を被覆するように形成される場合、保護層１３３は、着色層を保護すると共に着色層１３１により生じる段差を平坦化する機能を有することができる。保護層１３３は、有機物層または無機物層であることができる。無機物層及び有機物層の材料としては、分離層１３２の説明で示した材料と同様のものを用いることができる。これらの層は、スピンコート法、スパッタリング法、蒸着法等によって形成することができる。保護層１３３の厚みは、例えば０．１μｍ以上１０μｍ以下であってよく、好ましくは０．５μｍ以上５μｍ以下である。保護層は、分離層と着色層との間に形成されてもよい。 [Protective layer]
The protective layer 133 can have a function of protecting the colored layer 131. As shown in FIG. 2, when the protective layer is formed so as to cover the side surface of the colored layer, the protective layer 133 has a function of protecting the colored layer and flattening the step caused by the colored layer 131. Can be done. The protective layer 133 can be an organic layer or an inorganic layer. As the materials for the inorganic layer and the organic layer, the same materials as those shown in the description of the separation layer 132 can be used. These layers can be formed by a spin coating method, a sputtering method, a vapor deposition method or the like. The thickness of the protective layer 133 may be, for example, 0.1 μm or more and 10 μm or less, preferably 0.5 μm or more and 5 μm or less. The protective layer may be formed between the separation layer and the coloring layer.
　［第２貼合層］
　第２貼合層１４０は、着色部材１３０と円偏光板１５０とを貼合するための層である。
積層体１００において、着色部材１３０と円偏光板１５０とは第２貼合層１４０を介して接合される。 [Second bonding layer]
The second bonding layer 140 is a layer for bonding the coloring member 130 and the circularly polarizing plate 150.
In the laminated body 100, the coloring member 130 and the circularly polarizing plate 150 are joined via the second bonding layer 140.
　第２貼合層１４０を構成する接着剤、粘着剤及び粘着剤組成物の例及び好ましい範囲は、第１貼合層１２０の説明における例及び好ましい範囲が適用される。 As the examples and preferable ranges of the adhesive, the pressure-sensitive adhesive and the pressure-sensitive adhesive composition constituting the second bonding layer 140, the examples and the preferable ranges in the description of the first bonding layer 120 are applied.
　第２貼合層１４０の温度２５℃における貯蔵弾性率Ｇ’ｂは、例えば０．０１ＭＰａ以上５ＭＰａ以下であってよく、好ましくは０．０２ＭＰａ以上３ＭＰａ以下、より好ましくは０．０３ＭＰａ以上１．５ＭＰａ以下であり、０．１ＭＰａ以上であってもよいし、０．２ＭＰａ以上であってもよい。第２貼合層１４０の貯蔵弾性率Ｇ’ａは、例えば第２貼合層１４０を形成するのに用いる材料の選定により調節することができる。第２貼合層は、好ましくは粘着剤層である。 The storage elastic modulus G'b of the second bonded layer 140 at a temperature of 25 ° C. may be, for example, 0.01 MPa or more and 5 MPa or less, preferably 0.02 MPa or more and 3 MPa or less, and more preferably 0.03 MPa or more and 1.5 MPa. It may be 0.1 MPa or more, or 0.2 MPa or more. The storage elastic modulus G'a of the second bonded layer 140 can be adjusted, for example, by selecting the material used to form the second bonded layer 140. The second bonding layer is preferably an adhesive layer.
　［円偏光板］
　円偏光板１５０は、直線偏光板及び位相差層を備えることができ、直線偏光板を第１貼合層１２０側に配置し、位相差層を第２貼合層１４０側に配置することができる。円偏光板１５０は、積層体１００を備える画像表示装置の視認側から積層体１００を通って入射する光（外光）を円偏光に変換することができる。さらに円偏光板１５０は、画像表示装置中の表示素子で反射した外光を吸収することができるため、積層体１００に反射防止フィルムとしての機能を付与することができる。 [Circular polarizing plate]
The circular polarizing plate 150 may include a linear polarizing plate and a retardation layer, and the linear polarizing plate may be arranged on the first bonding layer 120 side and the retardation layer may be arranged on the second bonding layer 140 side. can. The circularly polarizing plate 150 can convert light (external light) incident through the laminated body 100 from the visual side of the image display device including the laminated body 100 into circularly polarized light. Further, since the circularly polarizing plate 150 can absorb the external light reflected by the display element in the image display device, the laminated body 100 can be provided with a function as an antireflection film.
　［直線偏光板］
　直線偏光板は、自然光等の非偏光な光線から、ある一方向の直線偏光を選択的に透過させる機能を有する。直線偏光板１３０は、二色性色素を吸着させた延伸フィルム、又は二色性色素および重合性化合物を含む組成物を塗布し硬化させたフィルム等を偏光子として備えることができる。二色性色素および重合性化合物を含む組成物を塗布し硬化させたフィルムとしては、液晶性を有する二色性色素を含む組成物、または二色性色素と重合性液晶とを含む組成物を塗布し硬化させて得られる層を有するフィルム等を用いることができる。二色性色素として具体的には、ヨウ素または二色性の有機染料を用いることができる。二色性有機染料には、Ｃ．Ｉ．ＤＩＲＥＣＴ　ＲＥＤ　３９等のジスアゾ化合物からなる二色性直接染料、トリスアゾ、テトラキスアゾ等の化合物からなる二色性直接染料が包含される。二色性色素および重合性化合物を含む組成物を塗布し硬化させたフィルムは、二色性色素を吸着させた延伸フィルムに比べて、屈曲方向に制限がないため好ましい。 [Linear polarizing plate]
The linear polarizing plate has a function of selectively transmitting linearly polarized light in a certain direction from unpolarized light rays such as natural light. The linear polarizing plate 130 may include a stretched film on which a dichroic dye is adsorbed, a film coated with a composition containing the dichroic dye and a polymerizable compound, and the like as a polarizer. As the film obtained by applying and curing the composition containing the dichroic dye and the polymerizable compound, a composition containing a dichroic dye having a liquid crystal property or a composition containing a dichroic dye and a polymerizable liquid crystal is used. A film or the like having a layer obtained by coating and curing can be used. Specifically, iodine or a dichroic organic dye can be used as the dichroic dye. For dichroic organic dyes, C.I. I. Included are dichroic direct dyes made of disuazo compounds such as DIRECT RED 39 and dichroic direct dyes made of compounds such as trisazo and tetrakisazo. A film coated with a composition containing a dichroic dye and a polymerizable compound and cured is preferable because there is no limitation in the bending direction as compared with a stretched film on which a dichroic dye is adsorbed.
　以下、二色性色素を吸着させた延伸フィルムが偏光子となる直線偏光板について説明する。二色性色素を吸着させた延伸フィルムは、通常、ポリビニルアルコール系樹脂フィルムを一軸延伸する工程、ポリビニルアルコール系樹脂フィルムを二色性色素で染色することにより、その二色性色素を吸着させる工程、二色性色素が吸着されたポリビニルアルコール系樹脂フィルムをホウ酸水溶液で処理する工程、およびホウ酸水溶液による処理後に上記二色性色素が吸着されたポリビニルアルコール系樹脂フィルムを水洗する工程を経ることにより製造される。上記工程により製造された二色性色素を吸着させた延伸フィルムを、そのまま直線偏光板として用いてもよく、その片面または両面に透明保護フィルムを貼合した上で直線偏光板として用いてもよい。こうして得られる偏光子（二色性色素を吸着させた延伸フィルム）の厚みは、好ましくは２μｍ以上４０μｍ以下である。 Hereinafter, a linear polarizing plate in which a stretched film on which a dichroic dye is adsorbed serves as a polarizer will be described. The stretched film on which the dichroic dye is adsorbed is usually a step of uniaxially stretching the polyvinyl alcohol-based resin film and a step of adsorbing the dichroic dye by dyeing the polyvinyl alcohol-based resin film with the dichroic dye. , A step of treating the polyvinyl alcohol-based resin film on which the dichroic dye is adsorbed with an aqueous boric acid solution, and a step of washing the polyvinyl alcohol-based resin film on which the dichroic dye is adsorbed with water after the treatment with the boric acid aqueous solution. Manufactured by The stretched film produced by the above step on which the dichroic dye is adsorbed may be used as it is as a linear polarizing plate, or may be used as a linear polarizing plate after a transparent protective film is attached to one or both sides thereof. .. The thickness of the polarizer (stretched film on which the dichroic dye is adsorbed) thus obtained is preferably 2 μm or more and 40 μm or less.
　上記ポリビニルアルコール系樹脂は、ポリ酢酸ビニル系樹脂をケン化することによって得られる。ポリ酢酸ビニル系樹脂としては、酢酸ビニルの単独重合体であるポリ酢酸ビニルのほか、酢酸ビニルとそれに共重合可能な他の単量体との共重合体などが用いられる。
酢酸ビニルに共重合可能な他の単量体としては、例えば不飽和カルボン酸類、オレフィン類、ビニルエーテル類、不飽和スルホン酸類、アンモニウム基を有する（メタ）アクリルアミド類等が挙げられる。 The polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith is used.
Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.
　ポリビニルアルコール系樹脂のケン化度は、通常８５～１００モル％程度であり、好ましくは９８モル％以上である。ポリビニルアルコール系樹脂は変性されていてもよく、例えばアルデヒド類で変性されたポリビニルホルマール、ポリビニルアセタール等を使用することができる。ポリビニルアルコール系樹脂の重合度は、通常１０００～１００００程度であり、好ましくは１５００～５０００の範囲である。 The saponification degree of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal, polyvinyl acetal, etc. modified with aldehydes can be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually about 1000 to 10000, preferably in the range of 1500 to 5000.
　このようなポリビニルアルコール系樹脂を製膜することにより、偏光子の材料となる原反フィルム（すなわちポリビニルアルコール系樹脂フィルム）を得ることができる。ポリビニルアルコール系樹脂を製膜する方法は、特に限定されるものでなく、公知の方法で製膜することができる。ポリビニルアルコール系樹脂フィルムの膜厚は、例えば１０μｍ～１５０μｍ程度とすることができる。 By forming a film of such a polyvinyl alcohol-based resin, it is possible to obtain a raw film (that is, a polyvinyl alcohol-based resin film) as a material for a polarizer. The method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based resin film can be, for example, about 10 μm to 150 μm.
　ポリビニルアルコール系樹脂フィルムの一軸延伸は、二色性色素による染色の前、染色と同時、または染色の後で行うことができる。一軸延伸を染色の後で行う場合、この一軸延伸は、ホウ酸処理の前に行ってもよいし、ホウ酸処理中に行ってもよい。さらに、これらの複数の段階で一軸延伸を行うことも可能である。一軸延伸にあたっては、周速の異なるロール間で一軸に延伸してもよいし、熱ロールを用いて一軸に延伸してもよい。一軸延伸は、大気中で延伸を行う乾式延伸であってもよいし、溶剤を用い、ポリビニルアルコール系樹脂フィルムを膨潤させた状態で延伸を行う湿式延伸であってもよい。延伸倍率は、通常３～８倍程度である。 The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, at the same time as dyeing, or after dyeing. When the uniaxial stretching is performed after dyeing, the uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. Furthermore, it is also possible to perform uniaxial stretching in these a plurality of steps. In uniaxial stretching, rolls having different peripheral speeds may be uniaxially stretched, or thermal rolls may be used to uniaxially stretch the rolls. The uniaxial stretching may be a dry stretching in which the stretching is performed in the atmosphere, or a wet stretching in which the polyvinyl alcohol-based resin film is swollen using a solvent. The draw ratio is usually about 3 to 8 times.
　上記延伸フィルムを偏光子として備える直線偏光板の厚みは、例えば１μｍ以上であってもよく、５μｍ以上であってもよく、７μｍ以上であってもよい。上記延伸フィルムを偏光子として備える直線偏光板の厚みは、１００μｍ以下であってもよく、５０μｍ以下であってもよく、２０μｍ以下であってもよく、１０μｍ以下であってもよい。 The thickness of the linear polarizing plate provided with the stretched film as a polarizer may be, for example, 1 μm or more, 5 μm or more, or 7 μm or more. The thickness of the linear polarizing plate provided with the stretched film as a polarizer may be 100 μm or less, 50 μm or less, 20 μm or less, or 10 μm or less.
　偏光子の片面または両面に貼合される透明保護フィルムの材料は、特に限定されないが、例えば環状ポリオレフィン系樹脂フィルム、トリアセチルセルロース、ジアセチルセルロースのような樹脂からなる酢酸セルロース系樹脂フィルム、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレートのような樹脂からなるポリエステル系樹脂フィルム、ポリカーボネート系樹脂フィルム、（メタ）アクリル系樹脂フィルム、ポリプロピレン系樹脂フィルム等の本技術分野において公知のフィルムを挙げることができる。透明保護フィルムの厚みは、薄型化の観点から、通常３００μｍ以下であり、２００μｍ以下であることが好ましく、１００μｍ以下であることがより好ましい。
透明保護フィルムの厚みは、通常５μｍ以上であり、２０μｍ以上であることが好ましい。透明保護フィルムは、位相差を有していても、有していなくてもよい。 The material of the transparent protective film to be bonded to one side or both sides of the polarizer is not particularly limited, but for example, a cyclic polyolefin resin film, a cellulose acetate resin film made of a resin such as triacetyl cellulose or diacetyl cellulose, or polyethylene terephthalate. , Polyethylene naphthalate, polyester resin film made of resin such as polybutylene terephthalate, polycarbonate resin film, (meth) acrylic resin film, polypropylene resin film and other films known in the art. .. From the viewpoint of thinning, the thickness of the transparent protective film is usually 300 μm or less, preferably 200 μm or less, and more preferably 100 μm or less.
The thickness of the transparent protective film is usually 5 μm or more, preferably 20 μm or more. The transparent protective film may or may not have a phase difference.
　透明保護フィルムの代わりに、オーバーコート層を偏光子の片面または両面に形成してもよい。オーバーコート層は、後述の貼合層として用いられる接着剤を塗工することで得られる。オーバーコート層の厚みは、例えば１０μｍ以下であり、５μｍ以下であることが好ましい。オーバーコート層の厚みは、例えば０．０１μｍ以上であり、０．１μｍ以上であることが好ましい。 Instead of the transparent protective film, an overcoat layer may be formed on one side or both sides of the polarizer. The overcoat layer can be obtained by applying an adhesive used as a bonding layer described later. The thickness of the overcoat layer is, for example, 10 μm or less, preferably 5 μm or less. The thickness of the overcoat layer is, for example, 0.01 μm or more, preferably 0.1 μm or more.
　次に、二色性色素および重合性化合物を含む組成物を塗布し硬化させたフィルムが偏光子となる直線偏光板について説明する。二色性色素および重合性化合物を含む組成物を塗布し硬化させたフィルムとしては、上述のように液晶性を有する二色性色素を含む組成物、または二色性色素と重合性液晶とを含む組成物を基材フィルム上に塗布し硬化させて得られる層を有するフィルム（以下、これらを「液晶層から形成されたフィルム」と総称する）等を用いることができる。基材フィルムと塗布層との間に配向層を形成してもよい。
液晶層から形成されたフィルムは、基材を剥離してまたは基材とともに直線偏光板として用いてもよく、あるいはその片面または両面に透明保護フィルムを貼合した上で直線偏光板として用いてもよい。当該透明保護フィルムとしては、上記した延伸フィルムが偏光子となる直線偏光板に貼合される透明保護フィルムと同じ材料を用いることができる。 Next, a linear polarizing plate in which a film obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound serves as a polarizer will be described. As a film obtained by applying and curing a composition containing a dichroic dye and a polymerizable compound, a composition containing a dichroic dye having a liquid crystal property as described above, or a dichroic dye and a polymerizable liquid crystal may be used. A film having a layer obtained by applying the containing composition on a base film and curing it (hereinafter, these are collectively referred to as "film formed from a liquid crystal layer") or the like can be used. An orientation layer may be formed between the base film and the coating layer.
The film formed from the liquid crystal layer may be used as a linear polarizing plate by peeling off the base material or used as a linear polarizing plate together with the base material, or may be used as a linear polarizing plate after a transparent protective film is attached to one or both sides thereof. good. As the transparent protective film, the same material as the transparent protective film in which the above-mentioned stretched film is bonded to a linear polarizing plate serving as a polarizer can be used.
　上記液晶層から形成されたフィルムとしては、具体的には、特開２０１３－３７３５３号公報または特開２０１３－３３２４９号公報等に記載のフィルムが挙げられる。 Specific examples of the film formed from the liquid crystal layer include the films described in JP2013-37353A, JP2013-33249, and the like.
　液晶層から形成されたフィルムは薄い方が好ましいが、薄すぎると強度が低下し、加工性に劣る傾向がある。当該フィルムの厚みは、通常２０μｍ以下であり、好ましくは５μｍ以下であり、より好ましくは０．５μｍ以上３μｍ以下である。液晶層から形成されたフィルムが偏光子となる直線偏光板の厚みは、例えば１μｍ以上５０μｍ以下であってよい。 The film formed from the liquid crystal layer is preferably thin, but if it is too thin, the strength tends to decrease and the processability tends to be inferior. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less. The thickness of the linear polarizing plate in which the film formed from the liquid crystal layer serves as a polarizer may be, for example, 1 μm or more and 50 μm or less.
　［位相差層］
　位相差層は、１層であってもよく２層以上であってもよい。位相差層は、その表面を保護するオーバーコート層、及び位相差層を支持する基材フィルム等を有していてもよい。
位相差層は、λ／４層を含み、さらにλ／２層またはポジティブＣ層の少なくともいずれかを含んでいてもよい。位相差層がλ／２層を含む場合、直線偏光板側から順にλ／２層及びλ／４層を積層する。位相差層がポジティブＣ層を含む場合、直線偏光板側から順にλ／４層及びポジティブＣ層を積層してもよく、直線偏光板側から順にポジティブＣ層及びλ／４層を積層してもよい。位相差層の厚みは、例えば０．１μｍ以上１０μｍ以下であってよく、好ましくは０．５μｍ以上８μｍ以下であり、より好ましくは１μｍ以上６μｍ以下である。 [Phase difference layer]
The retardation layer may be one layer or two or more layers. The retardation layer may have an overcoat layer that protects the surface thereof, a base film that supports the retardation layer, and the like.
The retardation layer includes a λ / 4 layer, and may further include at least one of a λ / 2 layer and a positive C layer. When the retardation layer includes a λ / 2 layer, the λ / 2 layer and the λ / 4 layer are laminated in order from the linear polarizing plate side. When the retardation layer contains a positive C layer, the λ / 4 layer and the positive C layer may be laminated in order from the linear polarizing plate side, or the positive C layer and the λ / 4 layer may be laminated in order from the linear polarizing plate side. May be good. The thickness of the retardation layer may be, for example, 0.1 μm or more and 10 μm or less, preferably 0.5 μm or more and 8 μm or less, and more preferably 1 μm or more and 6 μm or less.
　位相差層は、上述した透明保護フィルムの材料として例示した樹脂フィルムから形成してもよいし、重合性液晶化合物が硬化した層から形成してもよい。位相差層は、さらに配向層及び基材フィルムを含んでいてもよく、λ／４層と、λ／２層及びポジティブＣ層とを貼合するために後述の接合層を有していてもよい。 The retardation layer may be formed from the resin film exemplified as the material of the transparent protective film described above, or may be formed from a layer in which the polymerizable liquid crystal compound is cured. The retardation layer may further include an alignment layer and a base film, and may have a bonding layer described later for bonding the λ / 4 layer, the λ / 2 layer, and the positive C layer. good.
　位相差層は、重合性液晶化合物を硬化してなる層から形成する場合、重合性液晶化合物を含む組成物を、基材フィルムに塗布し硬化させることにより形成することができる。基材フィルムと塗布層との間に配向層を形成してもよい。基材フィルムの材料および厚みは、上記樹脂フィルム（上記透明保護フィルム）の材料及び厚みと同じであってよい。位相差層は、重合性液晶化合物を硬化してなる層から形成する場合、配向層及び基材フィルムを有する形態で積層体１００に組み込まれてもよい。 When the retardation layer is formed from a layer obtained by curing a polymerizable liquid crystal compound, it can be formed by applying a composition containing the polymerizable liquid crystal compound to a base film and curing it. An orientation layer may be formed between the base film and the coating layer. The material and thickness of the base film may be the same as the material and thickness of the resin film (the transparent protective film). When the retardation layer is formed from a layer obtained by curing a polymerizable liquid crystal compound, the retardation layer may be incorporated into the laminate 100 in the form of having an alignment layer and a base film.
　さらに位相差層は、後述の接合層を介して直線偏光板と貼合することができる。 Further, the retardation layer can be bonded to the linear polarizing plate via the bonding layer described later.
　［接合層］
　接合層は、粘着剤又は接着剤から構成される層である。接合層は、位相差層において各層を貼合したり、後述のタッチセンサパネルを積層体の円偏光板側に貼合したりすることができる。接合層の材料となる接着剤や粘着剤は、第１貼合層１２０の説明において例示した接着剤や粘着剤を用いることができる。粘着剤として、他の粘着剤、例えば第１貼合層１２０及び第２貼合層１４０の材料とは異なる（メタ）アクリル系粘着剤、スチレン系粘着剤、シリコーン系粘着剤、ゴム系粘着剤、ウレタン系粘着剤、ポリエステル系粘着剤、エポキシ系共重合体粘着剤等を用いることもできる。 [Joining layer]
The bonding layer is a layer composed of a pressure-sensitive adhesive or an adhesive. As the bonding layer, each layer can be bonded in a retardation layer, or a touch sensor panel described later can be bonded to the circularly polarizing plate side of the laminated body. As the adhesive or pressure-sensitive adhesive used as the material of the bonding layer, the adhesive or pressure-sensitive adhesive exemplified in the description of the first bonding layer 120 can be used. As the pressure-sensitive adhesive, a (meth) acrylic pressure-sensitive adhesive, a styrene-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and a rubber-based pressure-sensitive adhesive, which are different from the materials of other pressure-sensitive adhesives, for example, the first bonding layer 120 and the second bonding layer 140. , Urethane-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, epoxy-based copolymer pressure-sensitive adhesives, and the like can also be used.
　接合層の厚みは特に限定されないが、接合層として粘着剤層を使用する場合、１０μｍ以上であることが好ましく、１５μｍ以上であってもよく、２０μｍ以上であってもよく、２５μｍ以上であってもよく、通常２００μｍ以下であり、１００μｍ以下であってもよく、５０μｍ以下であってもよい。接合層として接着剤層を使用する場合、接合層の厚みは、０．１μｍ以上であることが好ましく、０．５μｍ以上であってもよく、１０μｍ以下であることが好ましく、５μｍ以下であってもよい。 The thickness of the bonding layer is not particularly limited, but when the pressure-sensitive adhesive layer is used as the bonding layer, it is preferably 10 μm or more, 15 μm or more, 20 μm or more, 25 μm or more. It may be usually 200 μm or less, 100 μm or less, or 50 μm or less. When an adhesive layer is used as the bonding layer, the thickness of the bonding layer is preferably 0.1 μm or more, may be 0.5 μm or more, is preferably 10 μm or less, and is 5 μm or less. May be good.
　［タッチセンサ層］
　図４に示すように、積層体１００は、円偏光板１５０側にタッチセンサ層１７０をさらに備えることができる。タッチセンサ層１７０は接合層１６０を介して円偏光板１５０側に積層されることができる。タッチセンサ層１７０としては、後述の前面板でタッチされた位置を検出可能な方式であればよく、その例として静電容量結合方式が挙げられる。低コスト及び高いタッチ感度であることから、静電容量結合方式のタッチセンサパネルは好適に用いられる。 [Touch sensor layer]
As shown in FIG. 4, the laminated body 100 can further include a touch sensor layer 170 on the circularly polarizing plate 150 side. The touch sensor layer 170 can be laminated on the circularly polarizing plate 150 side via the bonding layer 160. The touch sensor layer 170 may be any method as long as it can detect the position touched by the front plate, which will be described later, and an example thereof includes a capacitance coupling method. Capacitive coupling type touch sensor panels are preferably used because of their low cost and high touch sensitivity.
　静電容量結合方式のタッチセンサパネルの一例は、基材層と、基材層上に設けられた位置検出用透光性電極層と、タッチ位置検知回路とにより構成されている。静電容量結合方式のタッチセンサパネルを設けた画像表示装置においては、例えば後述の前面板の表面がタッチされると、タッチされた点で人体の静電容量を介して透光性電極が接地される。タッチ位置検知回路が、透光性電極の接地を検知し、タッチされた位置が検出される。 An example of a capacitance coupling type touch sensor panel is composed of a base material layer, a translucent electrode layer for position detection provided on the base material layer, and a touch position detection circuit. In an image display device provided with a capacitance coupling type touch sensor panel, for example, when the surface of the front plate described later is touched, the translucent electrode is grounded via the capacitance of the human body at the touched point. Will be done. The touch position detection circuit detects the grounding of the translucent electrode, and the touched position is detected.
　タッチセンサ層１７０は、例えばガラス板上に分離層を介して上記の抵抗膜方式又は静電容量結合方式のタッチセンサパネルを形成し、タッチセンサパネル上に基材層（剥離フィルム）を設けた後、ガラス板を分離層との間で分離してタッチセンサパネル／分離層の層構成を有するタッチセンサ層を製造することができる。この基材層は通常、積層体１００にタッチセンサ層１７０を組込む際に除去される。ガラス板を分離して露出させた分離層上に別の基材層を設けることもできる。タッチセンサパネルは、透光性電極層に加えて、基材層、絶縁層、保護層、配線及び接合層をさらに含んでいてもよい。 For the touch sensor layer 170, for example, the above-mentioned resistance film type or capacitance coupling type touch sensor panel is formed on a glass plate via a separation layer, and a base material layer (release film) is provided on the touch sensor panel. Later, the glass plate can be separated from the separation layer to manufacture a touch sensor layer having a layer structure of a touch sensor panel / separation layer. This base material layer is usually removed when the touch sensor layer 170 is incorporated into the laminate 100. Another base material layer can be provided on the separation layer obtained by separating and exposing the glass plate. In addition to the translucent electrode layer, the touch sensor panel may further include a base material layer, an insulating layer, a protective layer, wiring, and a bonding layer.
　（透光性電極層）
　透光性電極層は、表面抵抗が９０Ω／□以下であることができる。透光性電極層は、ＩＴＯ（酸化インジウム錫）等の金属酸化物からなる透光性電極層であってもよく、アルミニウムや銅、銀、金、パラジウム又はこれらの合金［例えば銀パラジウム銅合金（ＡＰＣ）］等の金属からなる金属層であってもよい。透光性電極層は、フォトリソグラフィ法によりパターン化されていてもよい。タッチセンサ層１７０は、１又は２以上の透光性電極層を有していてもよい。透光性電極層は、単層又は多層であってよく、多層である場合、各層を形成する材料は同種であってもよいし異種であってもよい。透光性電極層は、透光性及び表面抵抗の観点から好ましくはパターン化されたＩＴＯ膜、ＡＰＣ膜及びこれらを組合わせた膜が好ましい。 (Translucent electrode layer)
The surface resistance of the translucent electrode layer can be 90 Ω / □ or less. The translucent electrode layer may be a translucent electrode layer made of a metal oxide such as ITO (indium tin oxide), and may be aluminum, copper, silver, gold, palladium or an alloy thereof [for example, silver-palladium-copper alloy]. (APC)] or the like may be a metal layer made of a metal. The translucent electrode layer may be patterned by a photolithography method. The touch sensor layer 170 may have one or more translucent electrode layers. The translucent electrode layer may be a single layer or a multi-layer, and when it is a multi-layer, the materials forming each layer may be the same type or different types. From the viewpoint of translucency and surface resistance, the translucent electrode layer is preferably a patterned ITO film, an APC film, or a film in which these are combined.
　（基材層）
　基材層としては、一方の表面に透光性電極層が蒸着形成されている基材フィルム、接着層を介して透光性電極層が転写された基材フィルム等が挙げられる。あるいは、後述の分離層を基材層として別の基材フィルムを有しない構造としてもよい。 (Base layer)
Examples of the base material layer include a base material film in which a translucent electrode layer is vapor-deposited on one surface, a base film in which a translucent electrode layer is transferred via an adhesive layer, and the like. Alternatively, a structure may be configured in which the separation layer described later is used as the base material layer and does not have another base material film.
　基材フィルムとしては、光を透過可能な樹脂フィルムであれば限定されることはない。
例えば、環状ポリオレフィン系樹脂フィルム、トリアセチルセルロース、ジアセチルセルロースのような樹脂からなる酢酸セルロース系樹脂フィルム、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレートのような樹脂からなるポリエステル系樹脂フィルム、ポリカーボネート系樹脂フィルム、（メタ）アクリル系樹脂フィルム、ポリプロピレン系樹脂フィルムなど、当分野において公知のフィルムを挙げることができる。中でも環状ポリオレフィン系樹脂フィルムが好ましい。基材フィルムの厚みとしては、通常３００μｍ以下であり、２００μｍ以下であることが好ましく、１００μｍ以下であることがより好ましく、また、通常５μｍ以上であり、１０μｍ以上であることが好ましい。基材層は、透光性電極層をタッチセンサ層１７０に組み込んだ後、タッチセンサ層１７０から除去されてもよい。 The base film is not limited as long as it is a resin film capable of transmitting light.
For example, cyclic polyolefin resin film, cellulose acetate resin film made of resins such as triacetyl cellulose and diacetyl cellulose, polyester resin film made of resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, and polycarbonate resin. Examples of films known in the art such as films, (meth) acrylic resin films, and polypropylene resin films can be mentioned. Of these, a cyclic polyolefin resin film is preferable. The thickness of the base film is usually 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less, and usually 5 μm or more, preferably 10 μm or more. The base material layer may be removed from the touch sensor layer 170 after incorporating the translucent electrode layer into the touch sensor layer 170.
　（分離層）
　分離層は、ガラス板等の基板上に形成されて、分離層上に形成された透光性電極層１４を分離層とともに、基板から分離するための層であることができる。分離層は、無機物層又は有機物層であることが好ましい。無機物層を形成する材料としては、例えばシリコン酸化物が挙げられる。有機物層を形成する材料としては、例えば（メタ）アクリル系樹脂組成物、エポキシ系樹脂組成物、ポリイミド系樹脂組成物等を用いることができる。分離層はタッチセンサ層１７０中に含まれないように基板と共に除去されてもよい。 (Separation layer)
The separation layer can be a layer formed on a substrate such as a glass plate and for separating the translucent electrode layer 14 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 the material forming the inorganic layer include silicon oxide. As the material for forming the organic material layer, for example, a (meth) acrylic resin composition, an epoxy resin composition, a polyimide resin composition, or the like can be used. The separation layer may be removed together with the substrate so that it is not included in the touch sensor layer 170.
　（絶縁層）
　絶縁層は、透光性電極層１４を覆うように形成することができる。絶縁層は、硬化性プレポリマー、硬化性ポリマーおよびプラスチックポリマーからなる群から選択される少なくとも１つの材料から形成することができる。絶縁層は、フィルム形成可能なワニス型材料から形成することもできる。ワニス型材料は、ポリシリコーン、ポリイミド、およびポリウレタン材料からなる群から選択される少なくとも１つを含み得る。絶縁層は後述の接着剤層とすることもできる。絶縁層は、フォトリソグラフィ法によりパターン化されていてもよい。絶縁層は単層又は多層であってよく、多層である場合、各層を形成する材料は同種であってもよいし異種であってもよい。
　（接合層）
　接合層は、上述の粘着剤または接着剤から形成される層であることができる。 (Insulation layer)
The insulating layer can be formed so as to cover the translucent electrode layer 14. The insulating layer can be formed from at least one material selected from the group consisting of curable prepolymers, curable polymers and plastic polymers. The insulating layer can also be formed from a film-forming varnish-type material. The varnish type material may include at least one selected from the group consisting of polysilicone, polyimide, and polyurethane materials. The insulating layer may be an adhesive layer described later. The insulating layer may be patterned by a photolithography method. The insulating layer may be a single layer or a multi-layer, and when the insulating layer is a multi-layer, the materials forming each layer may be the same type or different types.
(Joining layer)
The bonding layer can be a layer formed from the adhesive or adhesive described above.
　（配線）
　配線は、タッチセンサパネル内にタッチ位置検知回路と透光性電極層１４とを電気的に接続するために配置されることができる。配線は、金属膜をパターン化したものであることができる。金属膜は、アルミニウムや銅、銀、金、またはこれらの合金等の金属をスパッタリング法や蒸着法により形成した金属膜をフォトリソグラフィ法及びエッチング法によりパターン化して形成することができる。配線は、透光性電極層１４上に設置されることができる。 (wiring)
The wiring can be arranged in the touch sensor panel to electrically connect the touch position detection circuit and the translucent electrode layer 14. The wiring can be a pattern of metal films. The metal film can be formed by patterning a metal film obtained by forming a metal such as aluminum, copper, silver, gold, or an alloy thereof by a sputtering method or a vapor deposition method by a photolithography method or an etching method. The wiring can be installed on the translucent electrode layer 14.
　［積層体の製造方法］
　積層体１００は、粘着剤層又は接着剤層などからなる第１貼合層および第２貼合層、並びに接合層を介して積層体１００を構成する層同士を貼合する工程を含む方法によって製造することができる。層同士を貼合する際は、密着性を高めるために、貼合面のいずれか一方または両方に対し、例えばコロナ処理等の表面活性化処理を施すことが好ましい。 [Manufacturing method of laminated body]
The laminated body 100 is formed by a method including a step of laminating layers constituting the laminated body 100 via a first laminating layer and a second laminating layer composed of an adhesive layer or an adhesive layer, and a bonding layer. Can be manufactured. When the layers are bonded to each other, it is preferable to apply a surface activation treatment such as a corona treatment to either or both of the bonded surfaces in order to improve the adhesion.
　円偏光板１５０は、これをなす直線偏光板および位相差層を、上述のように樹脂フィルムまたは基材フィルム上に直接形成することにより製造することも可能である。この樹脂フィルムまたは基材フィルムは、フレキシブル積層体１００に組み込まれてもよいし、円偏光板１５０から剥離されてフレキシブル積層体１００の構成要素とはならなくてもよい。 The circularly polarizing plate 150 can also be manufactured by directly forming the linear polarizing plate and the retardation layer forming the circularly polarizing plate 150 on the resin film or the base film as described above. The resin film or the base film may be incorporated into the flexible laminated body 100, or may not be peeled off from the circularly polarizing plate 150 to become a component of the flexible laminated body 100.
　着色部材１３０は、例えば以下のようにして製造することができる。まずガラス板等の支持体上に分離層を形成する。次いでこの分離層上に活性エネルギー線硬化性樹脂組成物を用いてフォトリソグラフィ法により着色層を形成する。ガラス板側とは反対側の最外面に剥離可能な樹脂フィルムを積層し、着色層から分離層までを剥離可能な樹脂フィルムに転写して、ガラス板を分離する。その後、ガラス板を剥離した面に、剥離可能な樹脂フィルムを貼合する。フォトリソグラフィ法では、活性エネルギー線硬化性樹脂組成物を分離層に塗布し、感光性樹脂組成物の塗膜を露光し、次いで現像し、その後、焼成を行うことができる。露光光源としては、波長が２５０ｎｍ以上４５０ｎｍ以下の光を発散する水銀蒸気アーク、炭素アーク、Ｘｅアークなどを使用することができる。 The coloring member 130 can be manufactured, for example, as follows. First, a separation layer is formed on a support such as a glass plate. Next, a colored layer is formed on the separation layer by a photolithography method using an active energy ray-curable resin composition. A peelable resin film is laminated on the outermost surface on the side opposite to the glass plate side, and the colored layer to the separation layer are transferred to the peelable resin film to separate the glass plate. Then, a peelable resin film is attached to the peeled surface of the glass plate. In the photolithography method, the active energy ray-curable resin composition can be applied to the separation layer, the coating film of the photosensitive resin composition can be exposed, then developed, and then fired. As the exposure light source, a mercury vapor arc, a carbon arc, an Xe arc, or the like that emits light having a wavelength of 250 nm or more and 450 nm or less can be used.
　タッチセンサ層１７０は、例えば以下のようにして製造することができる。まずガラス板上に分離層を形成する。分離層上に、透光性電極層、配線及び絶縁層をこの順に形成する。ガラス板側とは反対側の最外面に剥離可能な樹脂フィルムを積層し、絶縁層から分離層までを剥離可能な樹脂フィルムに転写して、ガラス板を分離する。次に基材層を準備し、基材層と分離層とを接着剤層を介して貼合する。剥離可能な樹脂フィルムを剥離することで、絶縁層と配線と透光性電極層と分離層と接着剤層と基材層とをこの順に有するタッチセンサ層１７０が得られる。絶縁層上に別の透光性電極層を形成し、その別の透光性電極層上に別の絶縁層を形成することもできる。 The touch sensor layer 170 can be manufactured, for example, as follows. First, a separation layer is formed on the glass plate. A translucent electrode layer, wiring, and an insulating layer are formed on the separation layer in this order. A peelable resin film is laminated on the outermost surface on the side opposite to the glass plate side, and the insulating layer to the separation layer are transferred to the peelable resin film to separate the glass plate. Next, a base material layer is prepared, and the base material layer and the separation layer are bonded together via an adhesive layer. By peeling off the peelable resin film, a touch sensor layer 170 having an insulating layer, wiring, a translucent electrode layer, a separating layer, an adhesive layer, and a base material layer in this order can be obtained. It is also possible to form another translucent electrode layer on the insulating layer and form another insulating layer on the other translucent electrode layer.
　＜画像表示装置＞
　本発明に係る画像表示装置は、上記積層体を含む。画像表示装置は特に限定されず、例えば有機ＥＬ表示装置、無機ＥＬ表示装置、液晶表示装置、電界発光表示装置等の画像表示装置が挙げられる。画像表示装置はタッチパネル機能を有していてもよい。積層体は、屈曲又は折り曲げ等が可能な可撓性を有する画像表示装置に好適である。画像表示装置において、積層体は、前面板を外側（画像表示素子側とは反対側、すなわち視認側）に向けて、画像表示装置の視認側に配置される。 <Image display device>
The image display device according to the present invention includes the above-mentioned laminated body. The image display device is not particularly limited, and examples thereof include an image display device such as an organic EL display device, an inorganic EL display device, a liquid crystal display device, and an electroluminescent display device. The image display device may have a touch panel function. The laminate is suitable for a flexible image display device capable of bending or bending. In the image display device, the laminate is arranged on the visual side of the image display device with the front plate facing the outside (the side opposite to the image display element side, that is, the visual recognition side).
　本発明に係る画像表示装置は、スマートフォン、タブレット等のモバイル機器、テレビ、デジタルフォトフレーム、電子看板、測定器や計器類、事務用機器、医療機器、電算機器等として用いることができる。本発明に係る画像表示装置は、優れたフレキシブル性を有するため、フレキシブルディスプレイ等に好適である。 The image display device according to the present invention can be used as a mobile device such as a smartphone or tablet, a television, a digital photo frame, an electronic signboard, a measuring instrument or an instrument, an office device, a medical device, a computer device, or the like. The image display device according to the present invention has excellent flexibility and is therefore suitable for a flexible display or the like.
　以下、実施例により本発明をさらに詳細に説明する。例中の「％」及び「部」は、特記のない限り、質量％及び質量部である。 Hereinafter, the present invention will be described in more detail with reference to Examples. Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.
　［屈曲性試験］
　各実施例および比較例において得られた積層体について、屈曲評価設備（Ｓｃｉｅｎｃｅ　Ｔｏｗｎ社製、ＳＴＳ－ＶＲＴ－５００）を用いて、２５℃の温度において、曲げに対する耐久性を確認する評価試験を行った。図５は、本評価試験の方法を模式的に示す図である。図５に示すように、個別に移動可能な二つの載置台５０１，５０２を、間隙Ｃ１で配置し、間隙Ｃの中心に幅方向の中心が位置するように積層体５００を固定して配置した（図５（ａ））。このとき、前面板側が上方となるように積層体５００を配置した。そして、二つの載置台５０１，５０２を位置Ｐ１および位置Ｐ２を回転軸の中心として上方に９０度回転させて、載置台の間隙Ｃに対応する積層体５００の領域に曲げの力を付加し、対向する前面板同士の間隔Ｃ２が２．０ｍｍとなるようにした（図５（ｂ））。その後、二つの載置台５０１，５０２を元の位置に戻した（図５（ａ））。以上の一連の操作を完了して、曲げの力の付加回数を１回とカウントした。曲げの力の付加回数を積み重ねて、載置台５０１，５０２の間隙Ｃに対応する積層体５００の着色部材の領域におけるクラックの発生の有無を確認し、着色部材にクラックが発生した時点で曲げの力の付加を停止し、クラックが発生したときの曲げの力の付加回数を記録した。載置台５０１，５０２の移動速度、曲げの力の付加のペースは、いずれの積層体に対する評価試験においても同一の条件とした。屈曲性試験の評価基準を以下に示す。Ａ、ＢまたはＣの評価を合格とする。
　Ａ：屈曲回数が５０万回に達しても、クラックが発生していない。
　Ｂ：屈曲回数が４０万回以上５０万回未満で、クラックが発生した。
　Ｃ：屈曲回数が３０万回以上４０万回未満で、クラックが発生した。
　Ｄ：屈曲回数が３０万回未満で、クラックが発生した。
として行った。 [Flexibility test]
The laminates obtained in each Example and Comparative Example were subjected to an evaluation test for confirming bending durability at a temperature of 25 ° C. using a bending evaluation facility (STS-VRT-500, manufactured by Science Town). rice field. FIG. 5 is a diagram schematically showing the method of this evaluation test. As shown in FIG. 5, two individually movable mounting tables 501 and 502 were arranged in the gap C1, and the laminated body 500 was fixedly arranged so that the center in the width direction was located at the center of the gap C. (Fig. 5 (a)). At this time, the laminated body 500 was arranged so that the front plate side was on the upper side. Then, the two mounting tables 501 and 502 are rotated 90 degrees upward with the positions P1 and P2 as the centers of the rotation axes, and a bending force is applied to the region of the laminated body 500 corresponding to the gap C of the mounting tables. The distance C2 between the facing front plates is set to 2.0 mm (FIG. 5 (b)). After that, the two mounting tables 501 and 502 were returned to their original positions (FIG. 5 (a)). After completing the above series of operations, the number of times the bending force was applied was counted as one. By accumulating the number of times the bending force is applied, it is confirmed whether or not cracks are generated in the region of the colored member of the laminated body 500 corresponding to the gap C of the mounting tables 501 and 502, and when the colored member is cracked, the bending is performed. The force application was stopped and the number of times the bending force was applied when a crack occurred was recorded. The moving speed of the mounting tables 501 and 502 and the pace of application of the bending force were set to the same conditions in the evaluation test for all the laminated bodies. The evaluation criteria for the flexibility test are shown below. Pass the evaluation of A, B or C.
A: No cracks have occurred even when the number of bends reaches 500,000.
B: A crack occurred when the number of bendings was 400,000 or more and less than 500,000.
C: A crack occurred when the number of bendings was 300,000 or more and less than 400,000.
D: The number of bendings was less than 300,000, and cracks occurred.
I went as.
　［虹ムラの評価］
　積層体の有機ＥＬパネルの代用品側に黒板を接合後、前面板側から、３波長形蛍光を照射して虹ムラを目視で評価した。以下に評価基準を示す。ＡまたはＢの評価を合格とする。
　Ａ：虹ムラが見えない。
　Ｂ：虹ムラがほとんど見えない。
　Ｃ：弱い虹ムラが見える。
　Ｄ：強い虹ムラが見える。 [Evaluation of rainbow unevenness]
After joining the blackboard to the substitute side of the organic EL panel of the laminated body, the rainbow unevenness was visually evaluated by irradiating the front plate side with three-wavelength fluorescence. The evaluation criteria are shown below. Pass the evaluation of A or B.
A: I can't see the rainbow unevenness.
B: I can hardly see the rainbow unevenness.
C: Weak rainbow unevenness can be seen.
D: Strong rainbow unevenness can be seen.
　［層の厚み］
　接触式膜厚測定装置（株式会社ニコン製「ＭＳ－５Ｃ」）を用いて測定した。ただし、位相差層及び配向層については、レーザー顕微鏡（ＬＥＸＴ、オリンパス株式会社製）を用いて測定した。 [Layer thickness]
The measurement was performed using a contact type film thickness measuring device (“MS-5C” manufactured by Nikon Corporation). However, the retardation layer and the alignment layer were measured using a laser microscope (LEXT, manufactured by Olympus Corporation).
　［貯蔵弾性率の測定］
　測定用サンプルを、レオメーター（Ａｎｔｏｎ　Ｐａｒｒ、ＭＣＲ－３０１）に配置し、温度２５℃、相対湿度５０％、応力１％、周波数１Ｈｚの条件で、貯蔵弾性率の測定を行った。測定の対象が粘着剤層である場合、粘着剤層を厚み１５０μｍになるように積み重ねて、測定用のサンプルを作製した。測定の対象が接着剤層である場合、ガラス上に厚みが５μｍになるように接着剤を塗布し、接着剤上にレオメーターの治具であるプレートを重ねた。この状態で、加熱して又はガラス側から紫外線を照射して、接着剤を硬化させて、測定用のサンプルを作製した。 [Measurement of storage elastic modulus]
The measurement sample was placed on a rheometer (Anton Parr, MCR-301), and the storage elastic modulus was measured under the conditions of a temperature of 25 ° C., a relative humidity of 50%, a stress of 1%, and a frequency of 1 Hz. When the object of measurement was an adhesive layer, the adhesive layers were stacked so as to have a thickness of 150 μm to prepare a sample for measurement. When the object of measurement was an adhesive layer, an adhesive was applied onto the glass so as to have a thickness of 5 μm, and a plate, which is a rheometer jig, was placed on the adhesive. In this state, the adhesive was cured by heating or irradiating ultraviolet rays from the glass side to prepare a sample for measurement.
　［重量平均分子量（Ｍｗ）の測定］
　（メタ）アクリル樹脂の重量平均分子量（Ｍｗ）は、ポリスチレン換算の数平均分子量（Ｍｎ）として、移動相にテトラヒドロフランを用い、下記のサイズエクスクルージョンクロマトグラフィー（ＳＥＣ）により求めた。
　測定する（メタ）アクリル系ポリマーを約０．０５質量％の濃度でテトラヒドロフランに溶解させ、ＳＥＣに１０μＬ注入した。移動相は、１．０ｍＬ／分の流量で流した。カラムとして、ＰＬｇｅｌ　ＭＩＸＥＤ－Ｂ（ポリマーラボラトリーズ製）を用いた。検出器にはＵＶ－ＶＩＳ検出器（商品名：Ａｇｉｌｅｎｔ　ＧＰＣ）を用いた。 [Measurement of weight average molecular weight (Mw)]
The weight average molecular weight (Mw) of the (meth) acrylic resin was determined by the following size exclusion chromatography (SEC) using tetrahydrofuran as the mobile phase as the polystyrene-equivalent number average molecular weight (Mn).
The (meth) acrylic polymer to be measured was dissolved in tetrahydrofuran at a concentration of about 0.05% by mass, and 10 μL was injected into SEC. The mobile phase was flowed at a flow rate of 1.0 mL / min. PLgel MIXED-B (manufactured by Polymer Laboratories) was used as a column. A UV-VIS detector (trade name: Agilent GPC) was used as the detector.
　［粘着シート１の作製］
　冷却管、窒素導入管、温度計及び攪拌機を備えた反応器に、酢酸エチル８０部、アクリル酸ブチル７０部、アクリル酸メチル２０部、アクリル酸１．０部の混合溶液を仕込み、窒素ガスで装置内の空気を置換して酸素不含としながら、内温を５５℃に上げた。その後、ラジカル重合開始剤（２，２’－アゾビスイソブチロニトリル）０．２部をアセトン１０部に溶かした溶液を全量添加した。開始剤添加１時間後に、単量体を除くアクリル樹脂の濃度が３５％になるよう、添加速度１７．３部／時でアセトンを連続的に反応器に添加しながら、内温５４～５６℃で１２時間保温し、最後に酢酸エチルを添加して、アクリル樹脂の濃度が２０％となるように調節した。得られたアクリル樹脂は、重量平均分子量Ｍｗが１，５００，０００、Ｍｗ／Ｍｎが５．０であった。得られたアクリル樹脂に、架橋剤（東ソー株式会社製「コロネートＬ」）０．３部、シランカップリング剤（信越化学工業株式会社製「Ｘ－１２－９８１」）０．５部を混合し、全体固形分濃度が１０％になるように酢酸エチルを添加して、粘着剤組成物を得た。 [Preparation of Adhesive Sheet 1]
A mixed solution of 80 parts of ethyl acetate, 70 parts of butyl acrylate, 20 parts of methyl acrylate, and 1.0 part of acrylic acid is charged in a reactor equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and is charged with nitrogen gas. The internal temperature was raised to 55 ° C. while replacing the air in the apparatus with oxygen-free. Then, a total amount of a solution prepared by dissolving 0.2 part of a radical polymerization initiator (2,2'-azobisisobutyronitrile) in 10 parts of acetone was added. One hour after the addition of the initiator, the internal temperature was 54 to 56 ° C. while continuously adding acetone to the reactor at an addition rate of 17.3 parts / hour so that the concentration of the acrylic resin excluding the monomer became 35%. The mixture was kept warm for 12 hours, and finally ethyl acetate was added to adjust the concentration of the acrylic resin to 20%. The obtained acrylic resin had a weight average molecular weight Mw of 1,500,000 and Mw / Mn of 5.0. To the obtained acrylic resin, 0.3 part of a cross-linking agent (“Coronate L” manufactured by Tosoh Corporation) and 0.5 part of a silane coupling agent (“X-12-981” manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. Ethyl acetate was added so that the total solid content concentration became 10% to obtain a pressure-sensitive adhesive composition.
　得られた粘着剤組成物の塗布溶液を離型処理されたポリエチレンテレフタレートフィルム（剥離フィルムＢ）の離型処理面に、アプリケーターを利用して乾燥後の厚みが５０μｍになるように塗布した。塗布層を１００℃で１分間乾燥して、粘着剤層を備えるフィルムを得た。その後、粘着剤層の露出面上に、別の離型処理されたポリエチレンテレフタレートフィルム（剥離フィルムＡ）を貼合した。その後、温度２３℃、相対湿度５０％ＲＨの条件で７日間養生させた。このようにして、剥離フィルムＢ／粘着剤層（厚み５０μｍ）／剥離フィルムＡの構成からなる粘着シート１を作製した。粘着シート１の粘着剤層を粘着剤層１とする。粘着剤層１の温度２５℃における貯蔵弾性率は、０．０４７ＭＰａであった。 The coating solution of the obtained pressure-sensitive adhesive composition was applied to the release-treated surface of the release-treated polyethylene terephthalate film (release film B) using an applicator so that the thickness after drying was 50 μm. The coating layer was dried at 100 ° C. for 1 minute to obtain a film having an adhesive layer. Then, another release-treated polyethylene terephthalate film (release film A) was attached onto the exposed surface of the pressure-sensitive adhesive layer. Then, it was cured for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 50% RH. In this way, the pressure-sensitive adhesive sheet 1 having the structure of the release film B / the pressure-sensitive adhesive layer (thickness 50 μm) / the release film A was produced. The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 1 is referred to as the pressure-sensitive adhesive layer 1. The storage elastic modulus of the pressure-sensitive adhesive layer 1 at a temperature of 25 ° C. was 0.047 MPa.
　［粘着シート２の作製］
　冷却管、窒素導入管、温度計及び攪拌機を備えた反応器に、アセトン８１．８部、アクリル酸ブチル６８部、及びメタクリル酸メチル３０部、アクリル酸１．０部、及びアクリル酸２－ヒドロキシエチル１．０部の混合溶液を仕込み、窒素ガスで装置内の空気を置換して酸素不含としながら、内温を５５℃に上げた。その後、アゾビスイソブチロニトリル（重合開始剤）０．１４部をアセトン１０部に溶かした溶液を全量添加した。開始剤添加１時間後に、単量体を除くアクリル樹脂の濃度が３５％になるよう、添加速度１７．３部／時でアセトンを連続的に反応器に添加しながら、内温５４～５６℃で１２時間保温し、最後に酢酸エチルを添加して、アクリル樹脂の濃度が２０％となるように調節した。得られたアクリル樹脂は、重量平均分子量Ｍｗが１，６５０，０００、Ｍｗ／Ｍｎが４．１であった。得られたアクリル樹脂１００部（不揮発分）と、イソシアネート系化合物として、コロネートＬ（東ソー株式会社）０．２部と、シラン系化合物としてＫＢＭ４０３（３－グリシドキシプロピルトリメトキシシラン、信越化学工業株式会社より入手）０．５部とを混合した。全体固形分濃度が１０％になるように酢酸エチルを添加して、粘着剤組成物を得た。 [Preparation of adhesive sheet 2]
81.8 parts of acetone, 68 parts of butyl acrylate, 30 parts of methyl methacrylate, 1.0 part of acrylic acid, and 2-hydroxyacrylate in a reactor equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer. A mixed solution of 1.0 part of ethyl was charged, and the internal temperature was raised to 55 ° C. while replacing the air in the apparatus with nitrogen gas to make it oxygen-free. Then, a total amount of a solution prepared by dissolving 0.14 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of acetone was added. One hour after the addition of the initiator, the internal temperature was 54 to 56 ° C. while continuously adding acetone to the reactor at an addition rate of 17.3 parts / hour so that the concentration of the acrylic resin excluding the monomer became 35%. The mixture was kept warm for 12 hours, and finally ethyl acetate was added to adjust the concentration of the acrylic resin to 20%. The obtained acrylic resin had a weight average molecular weight Mw of 1,650,000 and Mw / Mn of 4.1. 100 parts of the obtained acrylic resin (nonvolatile content), 0.2 parts of Coronate L (Tosoh Corporation) as an isocyanate compound, and KBM403 (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) as a silane compound. (Obtained from Co., Ltd.) 0.5 parts were mixed. Ethyl acetate was added so that the total solid content concentration became 10% to obtain a pressure-sensitive adhesive composition.
　上記粘着剤組成物を用いたこと、及び粘着剤組成物の塗布溶液を乾燥後の厚みが５μｍになるように塗布したこと以外は、粘着シート１の作製と同様にして、剥離フィルムＢ／粘着剤層（厚さ：５μｍ）／剥離フィルムＡの構成からなる粘着シート２を作製した。粘着シート２の粘着剤層を粘着剤層２とする。粘着剤層２の温度２５℃における貯蔵弾性率は、０．６ＭＰａであった。 The release film B / adhesive is the same as in the production of the pressure-sensitive adhesive sheet 1, except that the pressure-sensitive adhesive composition is used and the coating solution of the pressure-sensitive adhesive composition is applied so as to have a thickness of 5 μm after drying. An adhesive sheet 2 having a composition of an agent layer (thickness: 5 μm) / release film A was prepared. The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 2 is referred to as the pressure-sensitive adhesive layer 2. The storage elastic modulus of the pressure-sensitive adhesive layer 2 at a temperature of 25 ° C. was 0.6 MPa.
　［粘着シート３の作製］
　粘着剤組成物の塗布溶液を乾燥後の厚みが２５μｍになるように塗布したこと以外は、粘着シート１の作製と同様にして、剥離フィルムＢ／粘着剤層（厚さ：２５μｍ）／剥離フィルムＡの構成からなる粘着シート３を作製した。粘着シート３の粘着剤層を粘着剤層３とする。粘着剤層３の温度２５℃における貯蔵弾性率は、０．０４７ＭＰａであった。 [Preparation of adhesive sheet 3]
The release film B / adhesive layer (thickness: 25 μm) / release film is the same as in the production of the pressure-sensitive adhesive sheet 1, except that the coating solution of the pressure-sensitive adhesive composition is applied so that the thickness after drying is 25 μm. An adhesive sheet 3 having the configuration of A was produced. The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 3 is referred to as the pressure-sensitive adhesive layer 3. The storage elastic modulus of the pressure-sensitive adhesive layer 3 at a temperature of 25 ° C. was 0.047 MPa.
　［粘着シート４の作製］
　アクリル酸ｎ－ブチル４５質量部、アクリル酸２－エチルヘキシル４５質量部およびアクリル酸４－ヒドロキシブチル１０質量部を共重合させて、アクリル樹脂を調製した。このアクリル樹脂の重量平均分子量（Ｍｗ）は１５万であった。上記工程で得られたアクリル樹脂１００質量部（固形分換算値；以下同じ）と、熱架橋剤としてのトリメチロールプロパン変性キシリレンジイソシアネート（綜研化学社製、製品名「ＴＤ－７５」）０．０２質量部、およびシランカップリング剤としての３－グリシドキシプロピルトリメトキシシラン（信越化学工業社製、製品名「ＫＢＭ４０３」）０．２質量部とを混合し、十分に撹拌して、メチルエチルケトンで希釈することにより、粘着剤組成物の塗布溶液を得た。 [Preparation of adhesive sheet 4]
An acrylic resin was prepared by copolymerizing 45 parts by mass of n-butyl acrylate, 45 parts by mass of 2-ethylhexyl acrylate and 10 parts by mass of 4-hydroxybutyl acrylate. The weight average molecular weight (Mw) of this acrylic resin was 150,000. 100 parts by mass of acrylic resin obtained in the above step (solid content conversion value; the same applies hereinafter) and trimethylolpropane-modified xylylene diisocyanate as a thermal cross-linking agent (manufactured by Soken Kagaku Co., Ltd., product name "TD-75") 0. Mix 02 parts by mass and 0.2 parts by mass of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM403") as a silane coupling agent, and stir well to make methyl ethyl ketone. By diluting with, a coating solution of the pressure-sensitive adhesive composition was obtained.
　上記粘着剤組成物を用いたこと、粘着剤組成物の塗布溶液を乾燥後の厚みが１．７μｍになるように塗布したこと、及び塗布層を９０℃で１分間乾燥したこと以外は、粘着シート１の作製と同様にして、剥離フィルムＢ／粘着剤層（厚さ：１．７μｍ）／剥離フィルムＡの構成からなる粘着シート４を作製した。粘着シート４の粘着剤層を粘着剤層４とする。粘着剤層４の温度２５℃における貯蔵弾性率は、１．５ＭＰａであった。 Adhesive except that the above pressure-sensitive adhesive composition was used, the coating solution of the pressure-sensitive adhesive composition was applied so that the thickness after drying was 1.7 μm, and the coating layer was dried at 90 ° C. for 1 minute. In the same manner as in the production of the sheet 1, the pressure-sensitive adhesive sheet 4 having the composition of the release film B / the pressure-sensitive adhesive layer (thickness: 1.7 μm) / the release film A was produced. The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 4 is referred to as the pressure-sensitive adhesive layer 4. The storage elastic modulus of the pressure-sensitive adhesive layer 4 at a temperature of 25 ° C. was 1.5 MPa.
　［粘着シート５の作製］
　冷却管、窒素導入管、温度計及び攪拌機を備えた反応器に、アセトン８１．８部、アクリル酸ブチル７０．８部、及びメタクリル酸メチル２０部、アクリル酸２－（２－フェニルエトキシ）エチル）８部及びアクリル酸４－ヒドロキシブチル１．０部、アクリル酸０．２部の混合溶液を仕込み、窒素ガスで装置内の空気を置換して酸素不含としながら、内温を５５℃に上げた。その後、アゾビスイソブチロニトリル（重合開始剤０．１４部）をアセトン１０部に溶かした溶液を全量添加した。開始剤添加１時間後に、単量体を除くアクリル樹脂の濃度が３５％になるように添加速度１７．３部／時でアセトンを連続的に反応器に添加しながら、内温５４～５６℃で１２時間保温し、最後に酢酸エチルを添加して、アクリル樹脂の濃度が２０％となるように調節した。得られたアクリル樹脂は、重量平均分子量Ｍｗが１，５００，０００、Ｍｗ／Ｍｎが４．３であった。得られたアクリル樹脂１００部（不揮発分）と、イソシアネート系化合物として、コロネートＬ（東ソー株式会社）０．２部と、シラン系化合物としてＫＢＭ４０３（３－グリシドキシプロピルトリメトキシシラン、信越化学工業株式会社より入手）０．５部とを混合した。全体固形分濃度が１０％になるように酢酸エチルを添加して、粘着剤組成物を得た。 [Preparation of Adhesive Sheet 5]
81.8 parts of acetone, 70.8 parts of butyl acrylate, 20 parts of methyl methacrylate, 2- (2-phenylethoxy) ethyl acrylate in a reactor equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer. ) A mixed solution of 8 parts, 1.0 part of 4-hydroxybutyl acrylate and 0.2 part of acrylic acid was prepared, and the internal temperature was raised to 55 ° C. while replacing the air in the apparatus with nitrogen gas to make it oxygen-free. I raised it. Then, a total amount of a solution prepared by dissolving azobisisobutyronitrile (0.14 part of the polymerization initiator) in 10 parts of acetone was added. One hour after the addition of the initiator, the internal temperature was 54 to 56 ° C. while continuously adding acetone to the reactor at an addition rate of 17.3 parts / hour so that the concentration of the acrylic resin excluding the monomer became 35%. The mixture was kept warm for 12 hours, and finally ethyl acetate was added to adjust the concentration of the acrylic resin to 20%. The obtained acrylic resin had a weight average molecular weight Mw of 1,500,000 and Mw / Mn of 4.3. 100 parts of the obtained acrylic resin (nonvolatile content), 0.2 parts of Coronate L (Tosoh Corporation) as an isocyanate compound, and KBM403 (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) as a silane compound. (Obtained from Co., Ltd.) 0.5 parts were mixed. Ethyl acetate was added so that the total solid content concentration became 10% to obtain a pressure-sensitive adhesive composition.
　上記粘着剤組成物を用いたこと、及び粘着剤組成物の塗布溶液を乾燥後の厚みが５０μｍになるように塗布したこと以外は、粘着シート１の作製と同様にして、剥離フィルムＢ／粘着剤層（厚さ：５０μｍ）／剥離フィルムＡの構成からなる粘着シート５を作製した。粘着シート５の粘着剤層を粘着剤層５とする。粘着剤層５の温度２５℃における貯蔵弾性率は、０．１３６ＭＰａであった。 The release film B / adhesive is the same as in the production of the pressure-sensitive adhesive sheet 1, except that the pressure-sensitive adhesive composition is used and the coating solution of the pressure-sensitive adhesive composition is applied so as to have a thickness of 50 μm after drying. An adhesive sheet 5 having a composition of an agent layer (thickness: 50 μm) / release film A was produced. The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 5 is referred to as the pressure-sensitive adhesive layer 5. The storage elastic modulus of the pressure-sensitive adhesive layer 5 at a temperature of 25 ° C. was 0.136 MPa.
　［熱硬化型接着剤］
　熱硬化型接着剤を準備した。熱硬化型接着剤層の温度２５℃における貯蔵弾性率は、６．８ＭＰａであった。 [Thermosetting adhesive]
A thermosetting adhesive was prepared. The storage elastic modulus of the thermosetting adhesive layer at a temperature of 25 ° C. was 6.8 MPa.
　［ＵＶ硬化型接着剤］
　以下の成分を混合し、脱泡してＵＶ硬化型接着剤を調整した。
３’，４’－エポキシシクロヘキシルメチル　３，４－エポキシシクロヘキサンカルボキシレート（商品名：ＣＥＬ２０２１Ｐ、株式会社ダイセル製）：７０質量部
ネオペンチルグリコールジグリシジルエーテル（商品名：ＥＸ－２１１、ナガセケムテックス株式会社製）：２０質量部
２－エチルヘキシルグリシジルエーテル（商品名：ＥＸ－１２１、ナガセケムテックス株式会社製）：１０質量部
カチオン重合開始剤（商品名：ＣＰＩ－１００、サンアプロ株式会社製）：固形分量２．２５質量部（５０％プロピレンカーボネート溶液として配合した。）
１，４－ジエトキシナフタレン：２質量部 [UV curable adhesive]
The following components were mixed and defoamed to prepare a UV curable adhesive.
3', 4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (trade name: CEL2021P, manufactured by Daicel Co., Ltd.): 70 parts by mass Neopentyl glycol diglycidyl ether (trade name: EX-211, Nagase ChemteX Co., Ltd.) (Manufactured by the company): 20 parts by mass 2-ethylhexyl glycidyl ether (trade name: EX-121, manufactured by Nagase ChemteX Corporation): 10 parts by mass cationic polymerization initiator (trade name: CPI-100, manufactured by San Apro Co., Ltd.): Solid Quantity 2.25 parts by mass (blended as a 50% propylene carbonate solution)
1,4-Diethoxynaphthalene: 2 parts by mass
　［着色層形成用組成物１］
　カーボンブラックを含有する活性エネルギー線硬化型着色層形成用組成物（Ｓａｍｓｕｎｇ　ＳＤＩ社製「ＣＲ－ＢＫ０９５１Ｌ」）を準備した。 [Composition 1 for forming a colored layer]
A composition for forming an active energy ray-curable colored layer containing carbon black (“CR-BK0951L” manufactured by Samsung SDI Co., Ltd.) was prepared.
　〔実施例１〕
　（前面板の準備）
　特開２０１８－１１９１４１号公報の実施例４に従って作製した透明基材フィルム（ポリアミドイミドフィルム、厚み４０μｍ）の一方の表面に、以下のハードコート層用組成物をコーティングした後、溶剤を乾燥させＵＶ硬化することで、基材フィルムの片面に厚み１０μｍのハードコート層が形成された前面板（厚み５０μｍ）を作製した。
　ハードコート層形成用組成物：多機能アクリレート（ＭＩＷＯＮスペシャルティーケミカル、ＭＩＲＡＭＥＲ　Ｍ３４０）３０質量部、プロピレングリコールモノメチルエーテルに分散したナノシリカゾル（粒子径１２ｎｍ、固形分４０％）５０質量部、エチルアセテート１７質量部、光重合開始剤（ＢＡＳＦ社、Ｉ１８４）２．７質量部、フッ素系添加剤（信越化学工業株式会社、ＫＹ１２０３）０．３質量部を攪拌機を利用して配合し、ポリプロピレン（ＰＰ）材質のフィルターを用いて濾過することにより製造した。 [Example 1]
(Preparation of front plate)
One surface of a transparent base film (polyamideimide film, thickness 40 μm) prepared according to Example 4 of JP-A-2018-119141 is coated with the following composition for a hard coat layer, and then the solvent is dried to obtain UV. By curing, a front plate (thickness 50 μm) having a hard coat layer having a thickness of 10 μm formed on one side of the base film was produced.
Composition for forming a hard coat layer: 30 parts by mass of multifunctional acrylate (MIWON Specialty Chemical, MIRAMER M340), 50 parts by mass of nanosilica sol (particle size 12 nm, solid content 40%) dispersed in propylene glycol monomethyl ether, ethyl acetate 17 A part by mass, 2.7 parts by mass of a photopolymerization initiator (BASF, I184), and 0.3 parts by mass of a fluorine-based additive (Shinetsu Chemical Industry Co., Ltd., KY1203) are blended using a stirrer to mix polypropylene (PP). Manufactured by filtering with a filter of material.
　（円偏光板の準備）
　平均重合度約２，４００、ケン化度９９．９モル％以上、厚み２０μｍのポリビニルアルコール（ＰＶＡ）フィルムを準備した。ＰＶＡフィルムを３０℃の純水に浸漬した後、ヨウ素／ヨウ化カリウム／水の質量比が０．０２／２／１００の水溶液に３０℃で浸漬してヨウ素染色を行った（ヨウ素染色工程）。ヨウ素染色工程を経たＰＶＡフィルムを、ヨウ化カリウム／ホウ酸／水の質量比が１２／５／１００の水溶液に、５６．５℃で浸漬してホウ酸処理を行った（ホウ酸処理工程）。ホウ酸処理工程を経たＰＶＡフィルムを８℃の純水で洗浄した後、６５℃で乾燥して、ポリビニルアルコールにヨウ素が吸着配向している偏光子を得た。ＰＶＡフィルムの延伸は、ヨウ素染色工程とホウ酸処理工程において行った。ＰＶＡフィルムの総延伸倍率は５．３倍であった。得られた偏光子の厚みは７μｍであった。 (Preparation of circularly polarizing plate)
A polyvinyl alcohol (PVA) film having an average degree of polymerization of about 2,400, a saponification degree of 99.9 mol% or more, and a thickness of 20 μm was prepared. After immersing the PVA film in pure water at 30 ° C, it was immersed in an aqueous solution having a mass ratio of iodine / potassium iodide / water of 0.02 / 2/100 at 30 ° C to perform iodine dyeing (iodine dyeing step). .. The PVA film that had undergone the iodine dyeing step was immersed in an aqueous solution having a mass ratio of potassium iodide / boric acid / water of 12/5/100 at 56.5 ° C. to perform boric acid treatment (boric acid treatment step). .. The PVA film that had undergone the boric acid treatment step was washed with pure water at 8 ° C. and then dried at 65 ° C. to obtain a polarizer in which iodine was adsorbed and oriented on polyvinyl alcohol. The PVA film was stretched in the iodine dyeing step and the boric acid treatment step. The total draw ratio of the PVA film was 5.3 times. The thickness of the obtained polarizer was 7 μm.
　上記で得られた偏光子と、厚み１３μｍのシクロオレフィンポリマー（ＣＯＰ）フィルム（ＺＦ－１４、日本ゼオン株式会社製、波長５５０ｎｍにおける面内位相差値が１ｎｍ）とを水系接着剤を介してニップロールで貼り合わせた。得られた貼合物の張力を４３０Ｎ／ｍに保ちながら、６０℃で２分間乾燥して、片面にＣＯＰフィルムを有する直線偏光板を得た。なお、水系接着剤は水１００部に、カルボキシル基変性ポリビニルアルコール（「クラレポバール　ＫＬ３１８」、株式会社クラレ製）３部と、水溶性ポリアミドエポキシ樹脂（「スミレーズレジン６５０」（固形分濃度３０％の水溶液）、田岡化学工業株式会社製）１．５部とを添加して調製した。 The polarizer obtained above and a cycloolefin polymer (COP) film (ZF-14, manufactured by Nippon Zeon Corporation, having an in-plane retardation value of 1 nm at a wavelength of 550 nm) having a thickness of 13 μm are placed on a nip roll via an aqueous adhesive. I pasted them together. While maintaining the tension of the obtained laminate at 430 N / m, it was dried at 60 ° C. for 2 minutes to obtain a linear polarizing plate having a COP film on one side. The water-based adhesive is 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol ("Kuraray Poval KL318", manufactured by Kuraray Co., Ltd.) and water-soluble polyamide epoxy resin ("Smiley's resin 650" (solid content concentration 30%). (Aqueous solution) and 1.5 parts (manufactured by Taoka Chemical Industry Co., Ltd.) were added to prepare.
　直線偏光板の偏光子側と、位相差層とを、厚みが５μｍのアクリル系粘着剤層を介して貼合した。位相差層は、厚みが５μｍであり、層構成が液晶化合物が硬化した層を含むλ／２層（厚み２μｍ）／ＵＶ硬化型接着剤層（厚み２μｍ）／液晶化合物が硬化した層を含むλ／４層（厚み１μｍ）であった。このようにして円偏光板（厚み３０μｍ、層構成：ＣＯＰフィルム／偏光子／位相差層）を作製した。 The polarizer side of the linear polarizing plate and the retardation layer were bonded to each other via an acrylic pressure-sensitive adhesive layer having a thickness of 5 μm. The retardation layer has a thickness of 5 μm, and the layer structure includes a λ / 2 layer (thickness 2 μm) including a layer obtained by curing the liquid crystal compound / a UV curable adhesive layer (thickness 2 μm) / a layer obtained by curing the liquid crystal compound. It was a λ / 4 layer (thickness 1 μm). In this way, a circularly polarizing plate (thickness 30 μm, layer structure: COP film / polarizer / retardation layer) was produced.
　（着色部材積層体の準備）
　アクリル系樹脂をガラス板（支持体）にコーティングして分離層（厚み：２μｍ）を形成した。分離層上に、着色層形成用組成物１を用いて乾燥後の厚みが１．５μｍになるように着色層をフォトリソグラフィ法によりパターニングして、着色層を部分的に（額縁状に）形成した。次いで形成した着色層側の面に、特開２０１６－０１４８７７号公報における実施例１の組成物をコーティングして保護層（厚み：２μｍ）を形成した。このようにして、保護層／着色層／分離層の層構成を有する着色部材を支持体上に形成した。その後、保護層上に剥離フィルムＡを貼合した。ガラス板を剥離した面に剥離フィルムＢを貼合し、剥離フィルムＡ／着色部材（保護層／着色層／分離層）／剥離フィルムＢの層構成を有する着色部材積層体を得た。なお、フォトリソグラフィ法は着色層形成用組成物塗布工程、露光工程、現像工程および熱硬化工程を含む。 (Preparation of colored member laminate)
A glass plate (support) was coated with an acrylic resin to form a separation layer (thickness: 2 μm). The colored layer is partially (frame-shaped) formed on the separation layer by patterning the colored layer on the separation layer by a photolithography method so that the thickness after drying becomes 1.5 μm using the composition 1 for forming the colored layer. bottom. Next, the surface on the colored layer side was coated with the composition of Example 1 in JP-A-2016-014877 to form a protective layer (thickness: 2 μm). In this way, a colored member having a layer structure of a protective layer / a colored layer / a separated layer was formed on the support. Then, the release film A was laminated on the protective layer. The release film B was attached to the surface from which the glass plate was peeled off to obtain a colored member laminate having a layer structure of the release film A / coloring member (protective layer / coloring layer / separation layer) / release film B. The photolithography method includes a composition coating step for forming a colored layer, an exposure step, a developing step, and a thermosetting step.
　（タッチセンサ積層体の準備）
　アクリル系樹脂をガラス板にコーティングして分離層を形成した。次いで分離層上に透光性電極層を形成し、透光性電極層と分離層とからなるタッチセンサ層（厚み７μｍ）を作製した。その後、透光性電極層の分離層側とは反対側に剥離フィルムＡを積層した。ガラス板を取り除いた面に剥離フィルムＢを積層し、剥離フィルムＡ／タッチセンサ層／剥離フィルムＢの層構成を有するタッチセンサ積層体を作製した。 (Preparation of touch sensor laminate)
A glass plate was coated with an acrylic resin to form a separation layer. Next, a translucent electrode layer was formed on the separation layer, and a touch sensor layer (thickness 7 μm) composed of the translucent electrode layer and the separation layer was produced. Then, the release film A was laminated on the side of the translucent electrode layer opposite to the separation layer side. The release film B was laminated on the surface from which the glass plate was removed to prepare a touch sensor laminate having a layer structure of the release film A / touch sensor layer / release film B.
　（有機ＥＬパネルの代用品の準備）
　有色ポリイミドフィルム（厚み３５μｍ）の一方の面に粘着剤層からなる接合層（厚み２５μｍ）を介して有色ポリイミドフィルム（厚み５０μｍ）を積層し、有機ＥＬパネルの代用品（厚み１１０μｍ）を作製した。 (Preparation of substitute for organic EL panel)
A colored polyimide film (thickness 50 μm) was laminated on one surface of the colored polyimide film (thickness 35 μm) via a bonding layer (thickness 25 μm) composed of an adhesive layer to prepare a substitute for an organic EL panel (thickness 110 μm). ..
　（積層体の作製）
　上記部材を積層することにより、積層体を作製した。この画像表示装置は、前面板（厚み５０μｍ）、粘着剤層１（厚み５０μｍ）、着色部材（厚み５．５μｍ）、粘着剤層２（厚み５．０μｍ）、円偏光板（厚み３０μｍ）、粘着剤層からなる接合層（厚み２５μｍ）、タッチセンサ層（厚み７μｍ）、粘着剤層からなる接合層（厚み２５μｍ）、有機ＥＬパネルの代用品（厚み１１０μｍ）をこの順に含み、その合計厚みが３０７．５μｍであった。各部材を貼合する際は、貼合面にコロナ処理を施した。なお、粘着剤層１は、前面板の透明基材フィルム及び着色部材の保護層に接するように積層した。粘着剤層２は、着色部材の分離層及び円偏光板のＣＯＰフィルムに接するように積層した。すなわち、着色部材は、前面板側から、保護層、着色層、及び分離層をこの順に有する。積層体について屈曲性試験及び虹ムラの評価を行った。結果を表１に示す。 (Preparation of laminate)
A laminated body was produced by laminating the above members. This image display device includes a front plate (thickness 50 μm), an adhesive layer 1 (thickness 50 μm), a coloring member (thickness 5.5 μm), an adhesive layer 2 (thickness 5.0 μm), a circular polarizing plate (thickness 30 μm), and the like. A bonding layer composed of an adhesive layer (thickness 25 μm), a touch sensor layer (thickness 7 μm), a bonding layer composed of an adhesive layer (thickness 25 μm), and a substitute for an organic EL panel (thickness 110 μm) are included in this order, and the total thickness thereof is included. Was 307.5 μm. When the members were bonded together, the bonded surface was subjected to corona treatment. The pressure-sensitive adhesive layer 1 was laminated so as to be in contact with the transparent base film of the front plate and the protective layer of the coloring member. The pressure-sensitive adhesive layer 2 was laminated so as to be in contact with the separation layer of the coloring member and the COP film of the circularly polarizing plate. That is, the coloring member has a protective layer, a coloring layer, and a separation layer in this order from the front plate side. A flexibility test and an evaluation of rainbow unevenness were performed on the laminated body. The results are shown in Table 1.
　〔実施例２及び３〕
　第２貼合層が表１に記載の粘着剤層となるように粘着シートを変えたこと以外は、実施例１と同様の手順で積層体を作製した。積層体について屈曲性試験及び虹ムラの評価を行った。結果を表１に示す。 [Examples 2 and 3]
A laminate was prepared in the same procedure as in Example 1 except that the pressure-sensitive adhesive sheet was changed so that the second bonding layer became the pressure-sensitive adhesive layer shown in Table 1. A flexibility test and an evaluation of rainbow unevenness were performed on the laminated body. The results are shown in Table 1.
　〔比較例１〕
　第２貼合層にＵＶ硬化型接着剤を用い、紫外線を照射して硬化させたこと以外は、実施例１と同様の手順で積層体を作製した。積層体について屈曲性試験及び虹ムラの評価を行った。結果を表１に示す。 [Comparative Example 1]
A laminate was prepared in the same procedure as in Example 1 except that the second bonded layer was cured by irradiating it with ultraviolet rays using a UV curable adhesive. A flexibility test and an evaluation of rainbow unevenness were performed on the laminated body. The results are shown in Table 1.
　〔比較例２〕
　第１貼合層に熱硬化型接着剤を用い、９０℃にて１時間の熱処理を行って貼合を行ったこと、及び第２貼合層が表１に記載の粘着剤層となるように粘着シートを変えたこと以外は、実施例１と同様の手順で積層体を作製した。積層体について屈曲性試験及び虹ムラの評価を行った。結果を表１に示す。 [Comparative Example 2]
A thermosetting adhesive was used for the first bonding layer, and heat treatment was performed at 90 ° C. for 1 hour to perform bonding, and the second bonding layer became the pressure-sensitive adhesive layer shown in Table 1. A laminate was prepared in the same procedure as in Example 1 except that the adhesive sheet was changed to. A flexibility test and an evaluation of rainbow unevenness were performed on the laminated body. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　１００，２００，５００　積層体、１１０　前面板、１２０　第１貼合層、１３０　着色部材、１３１　着色層、１３２　分離層、１３３　保護層、１４０　第２貼合層、１５０　円偏光板、１６０　接合層、１７０　タッチセンサ層、２０１　表示領域Ａ、２０２　非表示領域Ｂ、５０１，５０２　載置台、Ｗ　着色層の幅。 100, 200, 500 laminate, 110 front plate, 120 first bonded layer, 130 colored member, 131 colored layer, 132 separation layer, 133 protective layer, 140 second bonded layer, 150 circular polarizing plate, 160 bonding layer , 170 touch sensor layer, 201 display area A, 202 non-display area B, 501,502 mounting table, W width of colored layer.

Claims (6)

  1. 前面板、第１貼合層、着色部材、第２貼合層、及び円偏光板をこの順に含み、
    条件（Ａ）及び（Ｂ）を満たす、積層体。
    　条件（Ａ）：前記第２貼合層の温度２５℃における貯蔵弾性率Ｇ’ｂに対する前記第１貼合層の温度２５℃における貯蔵弾性率Ｇ’ａの比Ｇ’ａ／Ｇ’ｂは５０未満である。
    　条件（Ｂ）：前記第１貼合層の厚みＴａ及び前記第２貼合層の厚みＴｂはいずれも１．０μｍ超である。     The front plate, the first bonding layer, the coloring member, the second bonding layer, and the circularly polarizing plate are included in this order.
    A laminate that satisfies the conditions (A) and (B).
    Condition (A): The ratio G'a / G'b of the storage elastic modulus G'a at the temperature of the first bonded layer G'a to the storage elastic modulus G'b at the temperature of the second bonded layer at 25 ° C. Less than 50.
    Condition (B): The thickness Ta of the first bonded layer and the thickness Tb of the second bonded layer are both more than 1.0 μm.
  2. 条件（Ｃ）をさらに満たす、請求項１に記載の積層体。
    　条件（Ｃ）：前記第２貼合層の厚みＴｂに対する前記第１貼合層の厚みＴａの比Ｔａ／Ｔｂが０．０３以上５０未満である。     The laminate according to claim 1, further satisfying the condition (C).
    Condition (C): The ratio Ta / Tb of the thickness Ta of the first bonded layer to the thickness Tb of the second bonded layer is 0.03 or more and less than 50.
  3. 前記第１貼合層の温度２５℃における貯蔵弾性率Ｇ’ａは、０．０１ＭＰａ以上５ＭＰａ以下である、請求項１又は２に記載の積層体。 The laminate according to claim 1 or 2, wherein the storage elastic modulus G'a of the first bonded layer at a temperature of 25 ° C. is 0.01 MPa or more and 5 MPa or less.
  4. 前記着色部材は、着色層と分離層とを備える、請求項１～３のいずれか一項に記載の積層体。 The laminate according to any one of claims 1 to 3, wherein the coloring member includes a coloring layer and a separation layer.
  5. 前記円偏光板側にタッチセンサ層をさらに備える、請求項１～４のいずれか一項に記載の積層体。 The laminate according to any one of claims 1 to 4, further comprising a touch sensor layer on the circularly polarizing plate side.
  6. 請求項１～５のいずれか一項に記載の積層体を備える、画像表示装置。 An image display device comprising the laminate according to any one of claims 1 to 5.
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